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25‐26 November 2013Cádiz, Spain

TOWARDS A BETTER UNDERSTANDING OF THE LINKS BETWEEN STRESSORS,

HAZARD ASSESSMENT AND ECOSYSTEM SERVICES UNDER WATER SCARCITY

4th SCARCEInternational Conference

Esmeralda Ramos

4th SCARCE

International Conference

TOWARDS A BETTER UNDERSTANDING OF THE LINKS BETWEEN STRESSORS, HAZARD ASSESSMENT AND ECOSYSTEM SERVICES UNDER WATER SCARCITY

25‐26 November 2013, Cádiz, Spain

Scientific Committee

• Julián Blasco, ICMAN‐CSIC, Puerto Real, Spain • Alícia Navarro‐Ortega, IDAEA‐CSIC, Barcelona, Spain • Damià Barceló, IDAEA‐CSIC, Barcelona and ICRA, Girona, Spain • Ralf Ludwig, Ludwig Maximilians Universität, München, Germany • Ignacio Rodríguez Iturbe, Princeton University, New Jersey, USA • Klement Tockner, IGB, Berlin, Germany

ORGANIZERS

SUPPORTING ORGANIZATIONS

INSTITUTO DE CIENCIAS MARINASDE ANDALUCÍA

INSTITUTO DE CIENCIAS MARINASDE ANDALUCÍA

Book of abstracts of the 4th SCARCE International Conference Edition 2012 Editors: Alícia Navarro Ortega and Damià Barceló Cullerés With contributions of all conference participants Edited by Asociación Ibérica de Limnología ISBN 978-84-937882-6-1 This work has been supported by the Ingenio-Consolider 2010 project SCARCE (CSD2009-00065) from the Spanish Ministry of Economy and Competitiveness.

5 Preface

4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and

ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain

Preface Water scarcity and quality are the main problems of humanity in the current scenarios in relation to water resources. In a next future, this situation can be even worse, because the global population is growing and the demand for different water uses are increasing. It should be taken into account that problems are not only related with the available amount but also with its quality. To understand the links between stressor, hazard assessment and ecosystem services, water management must improve to guarantee its supply to everybody in sufficient amount and quality. Some stressors such as water scarcity can limit biodiversity and economic activities in entire regions. In addition of being a stressor on its own, water scarcity can drive the effects of other stressors acting upon river ecosystems. It leads to intermittency in water flow, and therefore has implications for hydrologic connectivity, negative side-effects on biodiversity, water quality, and river ecosystem functioning. Water scarcity can amplify the effects of water pollution by reducing the natural diluting capacity of rivers. Interactions between stressors may be exacerbated by climate change. For instance, warmer temperatures and reduced river flows will likely increase the physiological burden of pollution on the aquatic biota, and biological feedback between stressors (e.g. climate change and nutrient pollution) may produce unexpected outcomes. Degradation of drainage basins, destruction of natural habitats, over-exploitation of fish populations and other natural resources, or the establishment of invasive species, are factors whose impacts combine and may give rise to synergistic effects, especially during periods of water shortage. The effects of these stressors are very relevant for the chemical and ecological status of water bodies as well as for the sustainability of ecosystem services they provide

Water scarcity is a key stressor with direct and indirect effects. The relevance of water scarcity as a stressor is most important in semi-arid regions such as the Mediterranean basin, characterized by highly variable river flows and the periodic occurrence of low flows and even no-flows. Climate change previsions forecast an increase in the frequency and magnitude of extreme events. Although extremes are part of the normal hydrologic behaviour in Mediterranean-type rivers, many already show a consistent trend towards decreased discharge. Finally, we should consider as well that the research to support the management has to take into account the complexity of the problems, their multi- and interdisciplinary nature and how to transfer the gathered knowledge to managers and authorities.

The Spanish funded project SCARCE wants to tackle water scarcity in our country. To solve this problem it will assess and predict the effects of global change on water quantity and quality and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their impact on society and economy. The project has assembled a multidisciplinary team in different fields (hydrology, chemistry, ecology, ecotoxicology, economy and modelling) to transform the obtained scientific knowledge into effective and sustainable water management tools. In order to guarantee practical application of the research results, water authorities and stakeholders are involved in the project. The topic of this project is of great relevance and reaches beyond national borders. Thus, an international perspective is fundamental to understand water problems and to find the solutions. These facts give an international dimension to the project and the meeting.

After the success of the three previous SCARCE International Conferences, which were held, in Girona (2010), Madrid (2011) and Valencia (2012), this meeting is focused on the understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity. The participation of researchers from different disciplines but with an

6 Preface

4th SCARCE International Conference Towards a better understanding of the links between stressors, hazard assessment and ecosystem services under water scarcity 25‐26 November 2013, Cádiz, Spain

integrative approach of water problems will give support to a new vision, tools and strategies to achieve an oriented solution of current and future water quality problems and the role of the ecosystem services in management policies.

The topics of this 4th SCARCE International Conference are:

• Monitoring network for chemical and biological data. Legacy and emerging POPs, pharmaceuticals and tools for integration and improvement of risk assessment

• Global change and water

• Multiple stressors and risk assessment

• Socioeconomic issues and water management

• Last FP7 EU call on water resources: multistressors and toxicants

This SCARCE Conference will provide a forum to present and discuss water related issues from a multi- and interdisciplinary perspective. This meeting encourages communications with an integrative perspective on issues related to the links between the occurrence of stressors in water, the hazard assessment and ecosystem services in water scarcity scenarios. The participation of anyone interested in sharing knowledge about water resources and the improvement in their management for sustainability is welcome.

The three previous SCARCE International Conferences led to special issues in the Environmental Science and Pollution Research (19(4) 2012), Science of the Total Environment (440(1) 2012) and Journal Hazardous Material (2013). A special journal issue associated with the 4th edition will be published in Science of the Total Environment. All participants are encouraged to submit their contributions to this special issue.

We are pleased to welcome you to Cadiz. We hope you will have a good experience and your participation in this meeting will give you the opportunity to share your knowledge and experience and to interact with colleagues in an exciting environment for science. We would like to thank the speakers, participants, supporters and sponsors for their contributions that will make this event an unforgettable meeting. We acknowledge the support of the Spanish Ministry of Economy and Competitiveness to SCARCE project.

Julián Blasco and Damià Barceló

Cádiz, November 25th, 2013



Final Programme

9 Final programme



Monday, 25th November 2013

9.00 – 9.30 Registration 9.30 – 9.50 Welcome

Eduardo González Mazo1, Marina Villegas2 and Damià Barceló3,4 1 Chancellor of the University of Cadiz, Cadiz, Spain 2 Deputy Director of Research Projects, Ministry of Economy and Competitiveness, Government of Spain

3 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 4 Catalan Institute for Water Research (ICRA), Girona, Spain

Introduction to global change and water scarcity Chairperson: Julián Blasco 9.50 – 10.20 Water research and innovation strategy in Horizon 2020, the State Plan

of Spain and the Water JPI Marina Villegas1,2 1 Deputy Director of Research Projects, Ministry. of Economy and Competitiveness, Government of Spain 2 President of the Governing Board of the Water JPI, Ministry of Economy and Competitiveness, Government of Spain

10.20 – 10.50 The Joint Programming Initiative on Water: a Pilot call for proposals

Enrique Playán1 1 Coordinator of the Water JPI, Ministry of Economy and Competitiveness, Government of Spain

10.50 – 11.10 SCARCE: Snapshots on recent results and achievements Dec2009-Nov

2013 Damià Barceló1,2 and Alícia Navarro-Ortega1


11.10 – 11.40 Poster session/Coffee break

Session I: Monitoring network for chemical and biological data. Legacy and emerging POPs Chairperson: Peter D. Hansen 11.40 – 12.10 Changes in the distributions of persistent organic pollutants and

mercury in freshwater ecosystems under changing climate conditions Joan O. Grimalt Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain

10 Final programme


12.10 – 12.40 Monitoring Perfluorinated Compounds in the Xúquer River Julián Campo1, Francisca Pérez2, Ana Masia1, Marinel.la Farré2, Yolanda Pico1 and Damià Barceló2,3

1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain 2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 3 Catalan Institute of Water Research (ICRA) Girona, Spain

12.40 – 13.00 First report of pyrethroids in river fish: a case study in Iberian river

basins (Spain) Cayo Corcellas1, Ethel Eljarrat1 and Damià Barceló1,2 1 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

13.00 – 13.20 Priority and emerging pollutants in southern Spain: overview of some

case studies from the Anquimed research group Irene Aparicio, Julia Martín, Dolores Camacho-Muñoz, Juan Luís Santos and Esteban Alonso Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville, Seville, Spain

13.20 – 15.00 Lunch

Session II: Monitoring network for chemical and biological data. Pharmaceuticals and other emerging compounds Chairperson: Mira Petrovic 15.00 – 15.30 Uptake and Bioaccumulation of Endocrine Disruptors and

Pharmaceutical compounds in Biofilm, Macroinvertebrates, and Fish in four Mediterranean Rivers Belinda Huerta1, Victoria Osorio2, Marina Gorga2, Anna Jakimska3, Nuria de Castro4, Lidia Ponsati1, Isabel Muñoz4, Sandra Pérez2, Mira Petrovic1,5, Sergi Sabater1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2

1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 3 Departmen. of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology, Gdansk, Poland 4 Department of Ecology, Facultat de Biologia, University of Barcelona, Barcelona, Spain 5 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

15.30 – 15.50 Methodological challenges for the determination of endocrine disruptor

compounds in the environment. Comparison of different analytical strategies Marina Gorga1, Belinda Huerta2, Sara Rodríguez-Mozaz2, Mira Petrovic2,3 and Damià Barceló1,2

1 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain 3 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

11 Final programme



15.50 – 16.10 A monitoring survey of pharmaceuticals in wastewater treatment plants and river water in four Iberian river basins Victoria Osorio1, Jaume Aceña1, Sandra Pérez1 and Damià Barceló1,2 1 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

16.10 – 16.30 Sediment core analysis as a tool for reconstructing the contamination

history of aquatic systems. Case study: Jamaica Bay (NY) Pablo A. Lara-Martín1,2, Eduardo González-Mazo1, and Bruce J. Brownawell2

1 Department of Physical Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto Real, Spain 2 School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York, United States


Session III: Monitoring network for chemical and biological data. Tools for integration and improvement of risk assessment Chairperson: Werner Brack 17.00 – 17.30 Chemicals of emerging concern in Iberian rivers. Analysis of sources and

environmental exposure Mira Petrovic1,2, Maja Kuzmanovic3, Damia Barceló1,3and Antoni Ginebreda3 1 Catalan Institute for Water Research (ICRA), Girona, Spain. 2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain. 3 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain

17.30 – 17.50 Occurrence and in-stream attenuation of wastewater derived

pharmaceuticals in Iberian rivers Vicenç Acuña1, Daniel von Schiller1, María Jesús García-Galán1, Sara Rodríguez-Mozaz1, Lluís Corominas1, Ignasi Aymerich1, Mira Petrovic1,2, Manel Poch1,3, Damià Barceló1,4 and Sergi Sabater1,5 1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 3 Laboratory of Chemical and Environmental Engineering (LEQUIA). University of Girona, Girona, Spain 4 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 5 Institute of Aquatic Ecology, University of Girona, Girona, Spain

17.50 – 18.10

Effects of food limitation and pharmaceuticals compounds on the larval development of a marine invertebrate Enrique González-Ortegón1, Julián Blasco2, Lewis LeVay1 and Luis Giménez1 1 School of Ocean Sciences, Bangor University, Menai Bridge, UK 2 Instituto de Ciencias Marinas de Andalucía, CSIC, Puerto Real, Spain

12 Final programme


18.10 – 18.30 Preliminary results of effects of pharmaceuticals on fresh water organisms Gabriela V. Aguirre-Martínez1,2,4, C. Okello1,3, María José Salamanca1, C. Garrido2, T.B. Henry4,5,6, Tomás A. Del Valls1 and María Laura Martín-Díaz1,2

1 Cátedra UNESCO/UNITWIN/WiCop, Facultad Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real, Spain 2 Andalusian Center of Marine Science and Technology (CACYTMAR), Puerto Real, Spain 3 Integrated Geoscience Research Group (IGRG), Interdepartmental Centre for Environmental Sciences Research (CIRSA), University of Bologna, Ravenna, Italy 4 School of Biomedical and Biological Sciences/Marine Institute, University of Plymouth, Plymouth, United Kingdom 5 Center for Environmental Biotechnology, University of Tennessee, Knoxville, USA 6 Department of Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, USA

18.30 – 18.50 Assessment of the water purification ecosystem service regarding in-

stream pharmaceutical residues: exploring the GREAT-ER model parameters based on data uncertainty Laurie Boithias1, Rafael Marcé1, Vicenç Acuña1, Joana Aldekoa2, Vicky Osorio3, Mira Petrović1,4, Felix Francés2, Antoni Ginebreda3 and Sergi Sabater1,5

1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Universitat Politècnica de València, Valencia, Spain 3 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 4 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 5 Institute of Aquatic Ecology, University of Girona, Girona, Spain

19.30 – 21.00 Touristic route 21:00 Joint Dinner

Tuesday, 26th November 2013

Session IV: Global change and water Chairperson: Joan Grimalt 9.00 – 9.30 Climate Change, Water and Security in the Mediterranean - implications

for science and policy (a perspective from the CLIMB project) Ralf Ludwig and the CLIMB consortium Department of Geography, Ludwig-Maximilians-Universität Munich, Munich, Germany

9.30 – 10.00 Spring snowfall decadal variability over the Alps

Matteo Zampieri1, Enrico Scoccimarro1,2 and Silvio Gualdi1,2 1 EuroMediterranean Center for Climate Change (CMCC), Bologna, Italy 2 INGV, Bologna, Italy

13 Final programme



10.00 – 10.30 Analysis of climate change effects on water and sediment cycle in a Mediterranean catchment Gianbattista Bussi1, Félix Francés1, José Andrés López-Tarazón2,3and Ramón J. Batalla3,4,5

1 Research Institute of Water and Environmental Engineering, Universitat Politècnica de València, Spain 2 School of Natural Sciences and Psychology, Liverpool John Moores University, UK 3 Department of Environment and Soil Sciences, University of Lleida, Spain 4 Catalan Institute for Water Research (ICRA), Girona, Spain 5 Forest Science Centre of Catalonia, Solsona, Spain

10.30 – 10.50 Sediment dynamics response under global change: Sensitivity Analysis in

a Mediterranean watershed María Sánchez-Canales1, Alfredo López1, Vicenç Acuña2 and F. Javier Elorza1 1 Univ. Politécnica de Madrid, Escuela Técnica Sup. de Ingenieros de Minas, Madrid, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

10.50 – 11.20 Measuring wetlands level using historical remot sensing imaginery

Victor Juan Cifuentes Sanchez1, Rosario Escudero Barbero2 and María Jose Checa Alonso2 1 Confederacion Hidrografica del Gaudalquivir, Sevilla, Spain 2 Empresa Pública TRAGSATEC, Madrid, Spain


Session V: Multiple stressors and risk assessment Chairperson: Ralf Ludwig 11.50 – 12.20 From chemical exposure to ecosystem effects: a critical view of the risk

assessment process Antoni Ginebreda Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain

12.20 – 12.40 Multiple stressor effects on river biofilms. Searching the ruling factor

Lídia Ponsatí1, Mira Petrovic1,2, Yolanda Picó3, Antoni Ginebreda4, Elisabet Tornés1,5, Natàlia Corcoll1, Helena Guasch5, Damià Barceló1,4 and Sergi Sabater1,5

1 Catalan Institute for Water Research (ICRA), Girona Spain 2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 3 Laboratori de Nutrició i Bromatologia, Univerisity of València, Burjassot, Spain 4 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 5 Institue of Aquatic Ecology, University of Girona, Girona, Spain

12.40 – 13.00 Ecological screening indicators of stress and risk for the Llobregat river

water Ramón López-Roldán1, Irene Jubany2, Vicenç Martí2,3, Susana González1 and Jose Luis Cortina1,3 1 CETaqua, Cornellà, Barcelona, Spain 2 CTM Technological Centre Foundation, Manresa, Spain 3 Department of Chemical Engineering, BarcelonaTech (UPC), Barcelona, Spain

14 Final programme


13.00 – 13.20 Habitat quality assessment in river basins considering terrestrial and aquatic threats Marta Terrado1, Guy Ziv2, Lisa Mandle2, Becky Chaplin-Kramer2, Richard Sharp2, Sergi Sabater1,3 and Vicenç Acuña1 1 Catalan Institute for Water Research, Girona, Spain 2 The Natural Capital Project, Woods Institute for the Environment, Stanford Univ, CA, USA 3 Institute of Aquatic Ecology, University of Girona, Spain

13.20 – 15.00 Lunch

Session VI: Socioeconomic issues and water management Chairperson: Antoni Ginebreda

15.00 – 15.30 Evaluation strategy and data processing of indicator values and risk

assessment – a sustainable logic indicator system for planning, constructions, materials and scenarios in semi arid areas Peter-D. Hansen1, B. Gabriel2 and R. vom Lehn2 1 TU Berlin (Berlin Institute of Technology - BIT), Dept. Ecological Impact Research and Ecotoxicology 2TU-Campus Wedding (TIB), Master´s Programme Real Estate Management, Berlin, Germany

15.30 – 16.00 The role of e-Infrastructures: Linking biodiversity and ecosystems

through the deployment of new water quality technologies in river basins Juan Miguel González Aranda1, Antonio José Sáenz Albanés2, Jesús Marco de Lucas3 and Benjamín Sánchez Gimeno4 1 Ministry of Economy and Competitiveness, Madrid, Spain 2Andalusian Institute of Technology-IAT, Seville, Spain 3Institute of Physics of Cantabria-IFCA, CSIC-UC, Santander, Spain 4Ministry of Economy and Competitiveness, Madrid, Spain

16.00 – 16.20 Integrating Action Assessment and Knowledge Exchange in Combating

Desertification: The PRACTICE Integrated Protocol Susana Bautista1, Barron J. Orr2, and V. Ramón Vallejo3 1 Department of Ecology, University of Alicante, Alicante, Spain 2 Office of Arid Lands Studies, University of Arizona, Tucson, USA 3 Departmment of Plant Biology, University of Barcelona, Barcelona, Spain

16.20 – 16.40 The use of deliberative scenarios for WES appraisal and identification of

measures in two Mediterranean case studies: Noguera de Tor and Anoia river basins Francesc La Roca1, Graciela Ferrer1 and Joserra Díez2

1 University of Valencia, Department for Applied Economics, Valencia, Spain 2 University of the Basque Country, Department of Mathematics and Experimental Sciences Didactics, Vitoria-Gasteiz, Spain


15 Final programme



Session VII: Last FP7 EU call on water resources: multiestressors and toxicants Chairperson: Damià Barceló 17.10 – 17.40 SOLUTIONS for present and future emerging pollutants in land and

water resources management Werner Brack Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany

17.40 – 18.10 Managing Aquatic ecosystems and water Resources under multiple

Stress (MARS) Christian K. Feld1,2, Sebastian Birk1 and Daniel Hering1,2 1 Depar. of Aquatic Ecology, Faculty of Biology, Univ. of Duisburg-Essen, Essen, Germany 2 Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Essen, Germany

18.10 – 18.40 GLOBAQUA: Managing the effects of multiple stressors on aquatic

ecosystems under water scarcity Sergi Sabater1, Alícia Navarro-Ortega2 and Damià Barceló1,2

1Catalan Institute for Water Research (ICRA), Girona, Spain

2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain

Final remarks and closure of the meeting 18.40 – 18.50 Final remarks and closure of the meeting 18.50 End of meeting

In italics, invited presentations

16 Final programme


Posters Monitoring network for chemical and biological data. Legacy and emerging POPs 1.- Development and optimization of configuration IT-SPME coupled to UHPLC-MS/MS

to the analysis of organic pollutants in water samples Ana Masiá1, Yolanda Moliner-Martínez2, María Muñoz-Ortuño2, Yolanda Picó1 and Pilar Campíns-Falcó2 1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain 2 Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, Burjassot, Spain

2.- Analysis of organic persistent pollutants compounds by gas chromatography

tandem mass spectrometry in biota samples from four spanish rivers Elena Martínez1, Àngels Quiroga1 and Damià Barceló1,2


3.- Stir bar sorptive extraction of 100 micropollutants from aqueous samples and

determination by gas chromatography-mass spectrometry: electrospray ionization vs atmospheric pressurized gas chromatography Marina G. Pintado-Herrera1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1

1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of International Excellence of the Sea (CEI.MAR), Puerto Real, Spain

4.- Screening of perfluorinated compounds in water, sediment and biota of the

Llobregat River basin (NE Spain) Julián Campo1, Francisca Pérez2, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3

1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain


5.- Occurrence of perfluorinated compounds in Spanish sewage treatment plants and

determination of their removal efficiencies Julián Campo1, Ana Masiá1, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3

1 Food and Environmental Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain. 2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 3 Catalan Institute of Water Research (ICRA), Girona, Spain

6.- Seasonal inputs of polyethoxylated compounds to a Mediterranean coastal lagoon

through surface watercourses Juan M. Traverso-Soto1, Pablo A. Lara-Martín1, Eduardo González-Mazo1 and V. M. León2

1 Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Campus de Excelencia Internacional del Mar (CEI·MAR), Universidad de Cádiz, Puerto Real, Spain 2 Instituto Español de Oceanografía, Centro Oceanográfico de Murcia, San Pedro del Pinatar, Spain

17 Final programme



7.- Seasonal changes in the concentration of synthetic surfactants in groundwater from aquifer systems (Cadiz, SW Spain) Carmen Corada-Fernández1, Nivis Torres-Fuentes1, Pablo A. Lara-Martín1, L. Candela2 and Eduardo González-Mazo1 1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto Real, Spain 2 Department of Geotechnical Engineering and Geosciences, UPC, Barcelona, Spain

8.- Geographical distribution of pesticides in waters of the river Júcar, Spain

Juan Antonio Pascual Aguilar1,2, Vicente Andreu1, Ana Masiá3 and Yolanda Picó3 1 Environmental forensic and Landscape Chemistry Group, Centro de Investigaciones sobre Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain 2 Centro para el Conocimiento del Paisaje, Matet, Spain 3 Food and Environmental Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

9.- Study of the occurrence, spatial and temporal distribution of pesticides in water,

sediment and biota from Llobregat River Basin Ana Masiá, Julián Campo, Cristina Blasco and Yolanda Picó Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

10.- Occurrence of siloxanes in fish samples from the Júcar River

Josep Sanchís1, Francisca Pérez1, Marinella Farré1 and Damià Barceló1,2


11.- Study of Silver Nanoparticles in aqueous solutions by Capillary Reversed-Phase

Liquid Chromatography, Transmission Electron Microscopy and UV-Vis techniques Rodrigo A. Gonzalez-Fuenzalida, Yolanda Moliner-Martínez, Jorge Verdú-Andrés and Pilar Campíns-Falcó Department of Analytical Chemistry, University of Valencia, Burjassot, Spain

12.- Cost effective methodology as analytics tools for DEHP and their degradation

products in waters Neus Jornet-Martinez, María Muñoz-Ortuño, Yolanda Moliner-Martínez, Rosa Herráez-Hernández, A. Argente-García and Pilar Campíns-Falcó Department of Analytical Chemistry, University of Valencia, Burjassot, Spain

13.- Incidence and distribution of heavy metals in sediments of the Turia River basin

Vicente Andreu1, Eugenia Gimeno2 and Juan A. Pascual1 1 Centro de Investigaciones sobre Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain 2 Fundación Universidad de Valencia. CIDE, Moncada, Spain

14.- Levels of free and combined chlorine found in indoor swimming pools, both in

bathing water and air Javier Pla-Tolós1, Carmen Molins-Legua1, Jorge Verdú-Andres1, Yolanda Moliner-Martínez1, Rosa Herráez-Hernández1, Pilar Campins-Falcó1 and Salvador Llana2 1 Department of Analytical Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain 2 Dpto. de Educación Física y Deportiva, Universidad de Valencia

18 Final programme


15.- Development of new supports for in situ estimation of nitrogen containing compounds in atmospheres of wastewater treatment plants Neus Jornet-Martinez, Yolanda Moliner-Martínez, Jorge Verdú Andrés, Carmen Molins-Legua, Rosa Herráez Hernández and Pilar Campíns-Falcó Department of Analytical Chemistry, Chemistry Faculty, University of València, Burjassot, Spain

16.- Fat determination in effluents of dairy industries by preconcentration in nylon

membranes and ATR-IR María Muñoz-Ortuño, Yolanda Moliner-Martinez, Rosa Herráez-Hernández and Pilar Campíns-Falcó Department of Analytical Chemistry, Chemistry Faculty, University of València, Burjassot, Spain

17.- Determination of lactose in effluents of dairy industries

María Muñoz-Ortuño1, Yolanda Moliner-Martinez1, Rosa Herráez-Hernández1, M.T. Picher2 and Pilar Campíns-Falcó1 1 Department of Analytical Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain 2 Department of Organic Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain

18.- Greenhouse gas emissions in two coastal systems in Cadiz Bay (SW Spain):

relationship with organic matter inputs Macarena Burgos, A. Sierra, Teodora Ortega and Jesús Forja CACYTMAR, Dep. Química-Física, Puerto Real, Spain

19.- Anthropogenic effects on greenhouse gas emissions in the Guadalete River

Estuary Macarena Burgos, A. Sierra, Teodora Ortega and Jesús Forja CACYTMAR, Dpto. Química-Física, Puerto Real, Spain

Monitoring network for chemical and biological data. Pharmaceuticals and other emerging compounds 20.- Hourly variations in the occurrence of several pharmaceuticals and surfactants in

urban and industrial wastewater Dolores Camacho-Muñoz, Julia Martín, Juan L. Santos, Irene Aparicio and Esteban Alonso Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville, Seville, Spain

21.- Multi-residue analysis of pharmaceutically active compounds (PhACs) in aqueous

matrices by liquid chromatography -quadrupole - time-of-flight - mass spectrometry Rosa M. Baena-Nogueras, Gabriela Aguirre-Martínez, L. Alves-Maranho, María Laura Martín-Díaz, Eduardo González-Mazo and Pablo A. Lara-Martín

Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real, Spain

22.- Sorption of 3 pharmaceuticals in agricultural soils: hydrochlorothiazide,

metoprolol and clarithromycin Nivis Torres-Fuentes1, Carmen Corada-Fernández1, Eduardo González-Mazo1, Pablo A. Lara-Martín1 and Diana Álvarez-Muñoz1,2

1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of International Excellence (CEI•MAR), Puerto Real, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

19 Final programme



23.- Evaluation of a simple method for the analysis of pharmaceuticals in seafood Diana Álvarez-Muñoz1, Belinda Huerta1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2 1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain

24.- High-resolution mass spectrommetry applications in the identification and detection of transformation products in the aquatic environment Bozo Zonja1, Sandra Pérez1 and Damià Barceló1,2

1 Water and soil quality research group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute of Water Research (ICRA), Girona, Spain

25.- Pharmaceutical compounds in sludge from different sludge stabilization

processes: occurrence and environmental risk assessment after sludge application onto soils Juan L. Santos, Julia Martín, Dolores Camacho-Muñoz, A. Santos, Irene Aparicio and Esteban Alonso Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville, Seville, Spain

25b.- Green and cheap alternative for the determination of 5-nitroimidazoles in river

and well waters based on Cation Selective Exhaustive Inyection and Sweeping Micellar Electrokinetic Chromatography (CSEI-sweeping-MEKC) Diego Airado-Rodríguez, Maykel Hernández-Mesa, Carmen Cruces-Blanco and Ana M. García-Campaña Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain

26.- Temporal trends of illicit drugs in WWTPs in Valencia, Spain

María Jesús Andrés-Costa1, Ana Masiá1, Vicente Andreu2 and Yolanda Picó1 1 Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia. Burjassot, Spain 2 Reserch Centre of Desertification (CIDE, CSIC-UV-GVA). Moncada, Valencia, Spain

27.- Emerging illicit drugs in waste and surface waters in the Turia River Basin

María Jesús Andrés-Costa1, Ana Masiá1, Cristina Blasco1, Vicente Andreu2 and Yolanda Picó1 1 Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia. Burjassot, València, Spain 2 Reserch Centre of Desertification (CIDE, CSIC-UV-GVA). Moncada, Valencia, Spain

28.- Occurrence and environmental risk assessment of drugs of abuse in four Spanish

river basins Nicola Mastroianni1, Miren López de Alda1 and Damià Barceló1,2 1 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

28b.- Investigation of drugs of abuse in river water from the Granada Province by

means of UHPLC-MS/MS in combination with dispersive liquid-liquid microextraction (DLLME) as environmentally-friendly sample treatment Diego Airado-Rodríguez, Manuel Lombardo-Agüí, Ana M. García-Campaña and Carmen Cruces-Blanco Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain

20 Final programme


Monitoring network for chemical and biological data. Tools for integration and improvement of risk assessment 29.- Assessment of pharmaceutical Diclofenac occurrence in the Llobregat river via

Monte Carlo sensitivity analysis of several parameters using GREAT-ER model Zoran Banjac1, Laurie Boithias2, Antoni Ginebreda1, Rafa Marce2, Victoria Osorio1, Sandra Pérez1, Damià Barceló1,2, Sergi Sabater2 and Vicenç Acuña2


30.- Application of ArcGIS software to display the occurrence and risk of chemical

pollutants Maja Kuzmanović1, Antoni Ginebreda1, Mira Petrović2,3 and Damià Barceló1,2

1 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain. 3 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

31.- Improving the WFD purposes by the incorporation of ecotoxicity tests

Neus Roig1,2, Jordi Sierra1,3, Martí Nadal2, Ignacio Moreno4, Elena Nieto4, Miriam Hampel4, Julián Blasco , Marta Schuhmacher1,2 and Jose Luis Domingo2 1 Environmental Engineering Laboratory, Departament d'Enginyeria Quimica, Universitat Rovira i Virgili, Tarragona, Spain 2 Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira i Virgili, Reus, Spain 3 Laboratori d’Edafologia, Facultat de Farmàcia, Universitat de Barcelona, Barcelona, Spain 4 Departamento Ecología y Gestión Costera, Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Cadiz, Spain

32.- A chemical determination of the sediment fluxes at the Barasona Reservoir

José A. López-Tarazón1,2, Pilar López3, Damià Vericat2,4,5 Isabel Muñoz3 and Ramon J. Batalla2,4,6 1 School of Natural Sciences and Psychology, Liverpool John Moores University, Liverpool, UK 2 Departament de Medi Ambient i Ciències del Sòl (DMACS), Universitat de Lleida, Lleida, Spain 3 Departament d’Ecologia, Universitat de Barcelona, Barcelona, Spain 4 Centre Tecnològic Forestal de Catalunya, Solsona, Spain 5 Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, Wales, UK 6 Catalan Institute for Water Research (ICRA), Girona, Spain

33.- Exposure to human pharmaceuticals produces differential transcriptome

expression fingerprints in the brain of the seabream, Sparus aurata Miriam Hampel1,2, Massimo Milan1, Julián Blasco1, Serena Ferraresso1 and Luca Bargelloni3 1 Instituto de Ciencias Marinas de Andalucía (ICMAN-CSIC), Puerto Real, Spain 2 Department of Comparative Biomedicine and Food Science, University of Padova, Legnaro, Italy

34.- Environmentally relevant concentrations of three human pharmaceuticals alter

the liver transcriptome of the Atlantic salmon, Salmo salar Miriam Hampel1, Esteban Alonso2, Irene Aparicio2, James Bron2, Juan Luis Santos2, John Taggart1 and Michael Leaver1 1 Institute of Aquaculture, University of Stirling, Stirling, Scotland, UK 2 Department of Analytical Chemistry, University of Seville, Seville, Spain

21 Final programme



35.- Temperature forcing and pharmaceuticals occurrence as proxy of global change. Subtlethal effects (osmoregulatory capacity, ingestion and respiration rates) in the freshwater crustacean, A. desmarestii Elena Nieto, Miriam Hampel, Enrique González-Ortegón, Pilar Drake and Julián Blasco Institute for Marine Science of Andalusia, Department of Ecology and Coastal Management, Campus Universitario Rio San Pedro s/n, Puerto Real, Spain

35b.- A comparative study of recirculation and continuous mode for pollutant ions

exchange from pretreated olive mill wastewater M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2 and A. Martínez-Férez1

1 Chemical Engineering Department, University of Granada, 18071 Granada, Spain 2 Molecular Biology & Biochemical Engineering Department, University Pablo de Olavide, 14013 Seville

35c.- Effect of ions concentration on the remediation of sodium and iron from olive

mill effluent by ion exchange technique M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2, L. Martínez-Nieto1 and A. Martínez-Férez1

1 Chemical Engineering Department, University of Granada, Granada, Spain 2 Molecular Biology & Biochemical Engineering Department, University Pablo de Olavide, Seville

35d.- Comparing different nanofiltration and reverse osmosis membranes for final

remediation of olive mill wastewater J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2, L. Martínez-Nieto1 and A. Martínez-Férez1


35e.- Steady-state performance enhancement of a diafiltration reverse osmosis system

for final salinity rejection of olive mill wastewater J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2 and A. Martínez-Férez1


Global change and water 36.- Freshwater scarcity effects on the different components of a European estuary

from Mediterranean-climate zone Enrique González-Ortegón1, Alberto Arias1, Francisco Baldó2, José Antonio Cuesta1, Carlos Fernández-Delgado3, César Vilas4 and Pilar Drake1 1 Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Spain 2 Instituto Español de Oceanografía, Cádiz, Spain 3 Departamento Biología Animal, Universidad de Córdoba, Córdoba, Spain 4 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

22 Final programme


Multiple stressors and risk assessment 37.- Effects of stream habitat complexity and biodiversity on leaf litter decomposition

Lorea Flores1, R. A. Bailey2,3, Arturo Elosegi1, Aitor Larrañaga1, B. R. Rall4 and J. Reiss5 1 Fac. of Science and Technology; University of the Basque Country, Leioa, Spain 2 Mathematical Sciences Institute, Queen Mary University, London, UK 3 School of Mathematics and Statistics, University of St Andrews, St Andrews, UK 4 J. F. Blumenbach, Institute of Zoology and Anthropology, University of Goettingen, Goettingen, Germany 5 Dept. of Life Sciences, Whitelands College, Roehampton University, London, UK

38.- The effects of a mixture of pharmaceuticals compounds at environmental

concentrations on epilithic biofilms: constant flow vs water intermittency conditions Natàlia Corcoll1, Maria Casellas1, Belinda Huerta1, Helena Guasch2, Sara Rodríguez-Mozaz1, Albert Serra2, Damià Barceló1,3 and Sergi Sabater1,2 1 Catalan Institute for Water Research (ICRA), Girona Spain 2 Institue of Aquatic Ecology, University of Girona, Girona, Spain 3 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain

39.- Invertebrate community response to water and sediment chemical composition in

Mediterranean rivers Núria de Castro-Català1, Damià Barceló2,3, Sandra Pérez2, Mira Petrovic3, Yolanda Picó4 and Isabel Muñoz1 1 Department of Ecology, University of Barcelona, Barcelona, Spain. 2 Water and Soil Quality Research Group, IDAEA-CSIC, Barcelona, Spain 3 Catalan Institute for Water Research (ICRA), Girona, Spain. 4 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

40.- Effects of water abstraction on large river ecosystem metabolism

Maite Arroita, Ibon Aristi and Arturo Elosegi Faculty of Science and Technology, the University of the Basque Country, Bilbao, Spain

41.- Effects of restoring stream dead wood on reach-scale storage and decomposition

of organic matter Aitor Larrañaga1, Lorea Flores1, Ibon Aristi1, Inmaculada Arostegui1, Maite Arroita1, Joserra Díez2 and Arturo Elosegi1 1 Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain 2 University college of Teacher Training, University of the Basque Country, Vitoria-Gasteiz, Spain

42.- Effects of WWTP effluent on the metabolism of a Mediterranean river

Ibon Aristi1, Maite Arroita1, Lydia Ponsati2, Sergi Sabater2,3, Daniel von Schiller2, Arturo Elosegi1 and Vicenç Acuña2 1 Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain 3 Institute of Aquatic Ecology, University of Girona, Girona, Spain

23 Final programme



43.- An assessment of environmental factors influencing species distribution in a temperate estuary: a binomial approach Enrique González-Ortegón1, César Vilas4, Alberto Arias1, Francisco Baldó2, José Antonio Cuesta1, Carlos Fernández-Delgado3 and Pilar Drake1 1 Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Spain 2 Instituto Español de Oceanografía, Cádiz, Spain 3 Dpto Biología Animal, Universidad de Córdoba, Córdoba, Spain 4 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

44.- Effect of black poplar plantations in the base river flow in a Mediterranean

stream Núria Ferrer and Albert Folch Hydrogeology Group, Dept. of Geotechnical Engineering and Geo-Sciences, Universitat Politècnica de Catalunya-BarcelonaTech, Barcelona, Spain

Socioeconomic issues and water management 45.- Water management in a restored wetland influences trophic links and species

composition in the aquatic macroinvertebrate community Enrique González-Ortegón1, M.E.M. Walton1, Bushra Moghaddam1, Cesar Vilas2, Ana Prieto 2, H.A. Kennedy1, J. Pedro Cañavate2 and Lewis Le Vay1

1 School of Ocean Sciences, College of Natural Sciences, Bangor University, Menai Bridge, UK 2 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

46.- Integrated Water Resources Management and related indicators

Andrea Momblanch, Joaquín Andreu and Javier Paredes Universitat Politècnica de València

47.- WaterDiss2.0: Disseminating Water Research across the European Union

Beatriz Medina1, C. Roberts2, T. Simms2, U. Stein3 and G. Nion4

1 Amphos 21, Spain 2 The Chancellor, masters and Scholars of the University of Oxford, UK 3 Ecologic, Germany, UK 4 Office International del L’Eau, France

24 Final programme




Oral presentations

27 Oral presentations



Water research and innovation strategy in Horizon 2020, the State Plan of Spain and the Water JPI

Marina Villegas1,2

1 Deputy Director of Research Projects, Ministry of Economy and Competitiveness, Government of Spain

2 President of the Governing Board of the Water JPI, Ministry of Economy and Competitiveness, Government of Spain

Introduction

In this presentation, three research and innovation programmes devoting significant investments to water research and innovation will be discussed. One of them is the State Plan of Spain, covering the period 2013-2016, while the other two have a European dimension. Horizon 2020 is the successor of the seventh Framework Programme, and represents a completely new approach to research and innovation in the period 2014-2020. Finally, the Joint Programming Initiative “Water Challenges for a Changing World” (the Water JPI) represents an effort of European countries to coordinate efforts in water research and innovation. All three programmes represent the main funding opportunities for Spanish researchers and innovators, and use complementary approaches to cover a wide range of activities and to fund actors located in different points along the knowledge value chain.

In this document, water is referred to in the terms used in the Water Framework Directive, article 1: “inland surface waters, transitional waters, coastal waters and groundwater”.

Horizon 2020, the research and innovation programme of the European Commission

Horizon 2020 is the financial instrument implementing the Innovation Union, a Europe 2020 flagship initiative aimed at securing Europe's global competitiveness. Horizon 2020 is part of the political drive to create new growth and jobs in Europe. Upon its start, on January 1st 2014, the programme will combine all research and innovation funding currently provided through the Framework Programmes for Research and Technical Development, the innovation related activities of the Competitiveness and Innovation Framework Programme (CIP) and the European Institute of Innovation and Technology (EIT).

Horizon 2020 will strengthen the EU’s position in science, strengthen industrial leadership in innovation, and address major concerns shared by all Europeans by tackling societal challenges. The programme will help bridge the gap between research and the market. This market-driven approach will include creating partnerships with the private sector and Member States to bring together the resources needed. International cooperation will be an important cross-cutting priority of Horizon 2020. Horizon 2020 will be complemented by further measures to complete and further develop the European Research Area by 2014. These measures will aim at breaking down barriers to create a genuine single market for knowledge, research and innovation.

Water Research and Innovation (R&I) will be addressed in virtually all areas of Horizon 2020. However, the area where it will receive dedicated attention is the Societal Challenges. Water issues are partially addressed under Challenge 2 “food security, sustainable agriculture and forestry, marine and maritime and inland water research and the bioeconomy”. In this challenge, water issues are considered in areas such as water and soil biodiversity, low water agricultural production or inland aquaculture.

The most important share of water R&I in Horizon 2020 is under Challenge 5 “climate action, environment, resource efficiency and raw materials”. One of its objectives is to achieve a water efficient economy and society. According to the formulation of this challenge, water challenges in the rural, urban and industrial environments need to be addressed to promote water system innovation and resource efficiency and to protect aquatic ecosystems. This challenge aims at protecting the environment,



sustainably managing natural resources, water, biodiversity and ecosystems.

The State Plan for scientific and technological research and for innovation, 2013-2016

This Plan will simultaneously and continuously face the design of interventions aimed at the promotion and coordination of Research, Development and Innovation (RDI) activities, ranging from the generation of ideas to market access in the form of new products and / or processes, improving quality of life, citizen well-being and contributing to economic development. It is addressed to all the agents of the Spanish Science, Technology and Innovation sector responsible for:

• RDI execution;

• RDI management; and

• RDI deployment for scientific, technological and innovation progress of the entire Spanish society and economy.

The State Plan is the instrument allowing the implementation of public policies of the General Administration of Spain addressing the coordination of RDI activities. Therefore, public funds are awarded through competition processes. The selection of RDI proposals to be funded is made taking into account technical and scientific criteria. If relevant, internationally validated technological, business and commercial viability criteria are additionally used. In all cases, standardized and transparent assessment processes based on peer review are implemented.

The State Plan is aligned with Horizon 2020 - the research and innovation programme of the European Commission – in order to capitalize synergies and to facilitate the passage of researchers and technologists from one programme to the other.

The State Plan is divided in State Programmes and Subprogrammes covering a number of areas related to human resources, blue sky research, support to companies, societal challenges and strategic areas. There is no specific programme on water, but virtually all programmes are developing activities related to water research.

The State Programme on RDI supporting societal challenges is the programme most directly related to Water. This section of the State Plan is in tight coordination with Horizon 2020. Challenge 5 under this Programme “Climate Change, resource efficiency and raw materials” is the area most directly focusing on water RDI. Research on societal challenges will be implemented through a series of activities, such as projects, accompanying measures, and support to Joint Programming Initiatives, such as the Water JPI, whose activities are described in the next section.

The Water JPI, coordinating the research and innovation efforts of European Countries

In 2008 the European Commission presented a new policy: ‘Towards joint programming in research’ with the meaningful subtitle ‘Working together to tackle common challenges more effectively”, challenging countries to develop initiatives on joint programming with the purpose of increasing the efficiency and impact of national public funding in strategic areas. Joint programming targets public research programmes first and foremost, which means public-public cooperation in the direction of the definition and implementation of common research agendas with jointly agreed-upon multi–annual activities and funding mechanisms. Joint Research Initiatives are a relative new but important mechanism in the European Research Area. The Joint Programming process is to pool national efforts at a large scale and to make better use of Europe's RDI resources to tackle major challenges effectively. It is a strategic process whereby Member States agree, on voluntary basis and in a partnership approach, on common visions and strategic research agendas. National resources are put together on the basis of collaboration between national programmes.

The JPI “Water challenges for a changing world” deals with research in the field of water and




hydrological sciences. The availability of water in sufficient quantities and adequate quality is indeed a public issue of high priority and addresses a pan-European and global environmental challenge.

The Council of the European Union decided to launch the Joint Programming Initiative “Water Challenges for a Changing World” on 6 December 2011 as a contribution to the reduction of fragmentation of efforts by Member States and mobilisation of skills, knowledge and resources, with a view to strengthening Europe's leadership and competitiveness on water research and innovation.

Europe invests an estimated amount of 500 million € per year to fund public research and innovation activities in water. While European countries invest 370 million €, the European Commission invests 130 million €. The Joint Programming Initiative will actively cooperate with the European Commission to provide the European society with the maximum return of these investments. The Initiative responds to the grand challenge of “Achieving Sustainable Water Systems for a Sustainable Economy in Europe and Abroad”. No single European country can address this challenge by itself, due to the magnitude of the needed operations and to the geographical variation of the water problems. Responding to the grand challenge requires a joint multi-disciplinary approach, since outstanding economic, ecological, technological and societal challenges are to be addressed.

The objectives of the Water JPI are described in its Vision Document:

• Involving water end-users for effective RDI results uptake;

• Attaining critical mass of research programmes;

• Reaching effective, sustainable coordination of European water RDI;

• Harmonising National water RDI agendas in Partner Countries;

• Harmonising National water RDI activities in Partner Countries; and

• Supporting European leadership in science and technology.

The Strategic Research and Innovation Agenda establishes five research and innovation challenges:

• Maintaining Ecosystem Sustainability;

• Developing Safe Water Systems for the Citizens;

• Promoting Competitiveness in the Water Industry:

• Implementing a Water-Wise Bio-Based Economy

• Closing the Water Cycle Gap

These challenges are being implemented through different activities. Calls for proposals for collaborative projects are an important type of activities in the Water JPI. A pilot call on “Emerging water contaminants – anthropogenic pollutants and pathogens” has been preannounced and will be published on November 1st, 2013.



The Joint Programming Initiative on Water: a Pilot call for proposals

Enrique Playán1

1 Coordinator of the Water JPI, Ministry of Economy and Competitiveness, Government of Spain

The Water JPI

The Joint Programming Initiative “Water Challenges for a Changing World” (the Water JPI) started its development in 2008, and was endorsed by the European Council in December 2011. This is an intergovernmental initiative, currently formed by 19 partner countries plus the European Commission. Five additional countries are participating as observers. The Water JPI published its Vision Document in 2011, and its Strategic Research and Innovation Agenda (SRIA) in 2013. The Water JPI SRIA lists five specific challenges, which are in turn divided into a total of 11 subchallenges. The Water JPI has listed a number of possible instruments which can be used to address these challenges. Among them, the support for and use of networks (hubs) of institutions or teams, systematic reviews, think tanks, coordination of ongoing national or EU projects, calls for proposals on collaborative projects, training and mobility activities, Public-Private partnerships workshops, conferences, and infrastructure. A Pilot activity has been formulated by the Water JPI in the form of a call for proposals on collaborative projects.

A Pilot Call for Proposals

The Pilot Call for Proposals was pre-announced on September 20th, 2013, and will be published on November 1st, 2013. The call topic is “Emerging water contaminants – anthropogenic pollutants and pathogens”. This topic responds to Water JPI SRIA specific challenge 2 (Developing Safe Water System for Citizens), and more specifically to subchallenge 2.1 (Emerging Pollutants: Assessing their Effects on Nature and Humans, their Behaviour and Treatment Opportunities). The deadline for proposal submission is 19th December 2013 at 12.00 (CET). Funding decisions will be announced by May-October 2014, and projects are expected to start in autumn 2014. A one-stage application procedure will be used in this call. Proposals (in English language) must be submitted electronically via the Academy of Finland online services.

This Pilot Call for proposals aims to enable multi-national, collaborative research, development and innovation projects. The overarching aim of this Pilot Call of the Water JPI is to identify new ways to efficiently assess, prevent, control and remove emerging pollutants and pathogens and thereby prevent human health risks and secure ecological functions of water ecosystems now and in the future. The call also intends to stimulate mobility of researchers between participating countries, consequently enhancing European collaborative research during the project life and beyond. Within each selected consortium funding of the participating researchers will be provided by their respective national funding organisation according to their normal terms and conditions for project funding. The amount of public funding available for transnational collaborative research projects through this call is estimated almost up to 9 M Euros. Funding organizations from 10 countries will contribute to the call: RPF Cyprus; DCSR Denmark; AKA Finland; ONEMA France; BMBF Germany; EPA Ireland; MIUR Italy; RCN Norway; FCT Portugal; MINECO and CDTI Spain. In the case of Spain, MINECO and CDTI will support respectively the participation of public research institutions and industries.

At least one of the following three themes shall be addressed by applicants:

1. Identification and prevention of emerging freshwater contaminants including but not limited to:

• Identification of new contaminants as well as their sources; • Prediction of environmental behaviour in surface water, sediments, soil, groundwater,

aquatic food web, as well as in wastewater or drinking water systems;




• Assessing the transfer time of the different contaminants between various environmental compartments as well as understanding the processes suffered during transfer;

• Modelling transport and fate of emerging contaminants as well as the propagation of antimicrobial resistance;

• Development of reliable, sensitive, innovative, and rapid analysis and detection systems; • Development of comparable and validated data sets on the prevalence and distribution of

major contaminants in the freshwater environments; and • Assessing the formation of transformation products (TP) and elucidating the processes

leading to these TPs.

2. Control, mitigation and methods for treatment and removal including but not limited to:

• Development, implementation and evaluation of management measures and technologies to control and reduce the dispersal and impact of emerging contaminants on water quality, especially under the aspect of water reuse;

• Development of technologies for a more efficient removal of these contaminants at source or in urban or rural water treatment system;

• Evaluation of treatment efficiency and implementation of existing and novel techniques. Including monitoring/sensor technologies; and

• Development, implementation and evaluation of mitigation options.

3. Impacts on ecosystem services and human health including but not limited to:

• Impact assessment of emerging contaminants on ecosystem services (ecotoxicology) and human health (toxicology) at different scales, considering short-term and long-term aspects;

• Development of integrated risk assessment methodologies for emerging contaminants; especially for those acting at sub-lethal level;

• Estimation of health risks resulting from new water management practices, such as water reuse in urban areas; and

• Understanding and predicting the environmental behaviour of emerging contaminants in surface water, sediments, soil, groundwater and in freshwater food webs.

(Bullet points are only meant as examples).

Proposals with duration of 24-36 months may be submitted by Universities, higher education institutions; public research institutes, industries, companies and SMES. Tackling societal challenges always requires a multidisciplinary approach. Therefore, all submitted applications should emphasize participation of stakeholders and dissemination and exploitation of results. Consortia must include a minimum of three partners from three different Water JPI partner countries contributing to the funding of this call. Researchers from 1) Water JPI partner countries not funding this call; 2) Water JPI observer countries; or 3) Third countries can participate in the consortia at their own expense.

Further activities

The Water JPI is currently preparing additional activities in cooperation with Horizon 2020. Among them, a call to be published in 2014 is under preparation on the topic “developing technological solutions and services for water distribution and measurement, waste water treatment and reuse, desalination, floods and droughts, etc.” This call for proposals will probably be performed under an ERA-NET from Horizon 2020, so as to obtain additional funds for selected projects. Information on this and other forthcoming activities will be published at the Water JPI web site.



SCARCE: Snapshots on recent results and achievements (Dec2009-Nov 2013)

Damià Barceló1,2 and Alícia Navarro-Ortega1

1 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain

2 Catalan Institute for Water Research (ICRA), Girona, Spain

The Mediterranean basin is one of the regions of the world most vulnerable to global change (Barceló and Sabater 2010), and one of the "hot spots" for oncoming problems in water availability (Giorgi and Lionello 2008). The main panels on climate change predict a future scenario of increasing frequency of floods and extended droughts in the Iberian Peninsula, mostly in the Mediterranean basin (IPCC 2007). Low summer flow and large floods in autumn and winter are characteristics of rivers under Mediterranean climate (Gasith and Resh 1999), but the forecasted scenarios suggest several points of concern, including decreased hydrological connectivity and increased concentration of pollutants during droughts, changes in biological communities as a result of harsher environmental conditions, and decreased of biological processes like nutrient uptake, primary production, or decomposition .In addition, water resources in Spain are subjected to rising pressures, related to the socioeconomic activities of an increasing human population, expressed by accelerated land use changes, and the specific climate characteristic of Mediterranean countries. This will be added to the currently existing problems, and will probably affect the available water resources, their quality, the functioning of associated ecosystems, especially rivers and their aquifers, and the ecosystem services they provide.

In such context, SCARCE (Assessing and predicting effects on water quantity and quality in Iberian Rivers caused by global change – www.scarceconsolider.es), which is a Consolider-Ingenio 2010 project from the Spanish Ministry of Economy and Competitiveness, aims to describe and predict the relevance of global change impacts on water availability, water quality and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their impacts on the human society and economy (Navarro-Ortega et al. 2012). Hence, the project has assembled a multidisciplinary team of leading scientists in the fields of hydrology, geomorphology, chemistry, ecology, ecotoxicology, economy, engineering and modelling, in an unknown effort in the CONSOLIDER framework. The project also considers the active involvement of Water Authorities and other relevant agents as stakeholders.

SCARCE has two complementary objectives. The first tackles basic research questions and will define the long-term patterns and the mechanisms that operate in the hydrology, water quality, habitat dynamics, and ecosystem structure and function of Mediterranean basins. The second objective is related to the effects of climate and human footprint (taken both as key elements of global change) that provide on the ecosystem services, rivers and streams, as well as the urgent need to implement and eventually refine the water management policies demanded by the EU Water Framework Directive (WFD). Therefore, the project emphasizes linking basic research and management practices in a single framework. The project is structured in ten thematic work packages (WPs), each of them dealing with one scientific discipline, from hydrology, chemistry and biology to modelling, economy and river management. Many interactions have been established between the different WPs in order to allow a complete flow of results between WPs. The final goals of SCARCE are to complete the monitoring and to advance in modelling of several issues. Regarding monitoring, WP4 QUALITY analyses the biological and chemical quality through extensive monitoring campaigns. WP3 MORPH deals with the morphological and sediment characterization of the river basins. WP5 PROCESS details on the ecosystem responses to hydrological, geomorphological and chemical disturbances and WP2 HYDRO deals with the hydrology of the selected basins and the connection to aquifers. These monitoring data and others available from the water authorities (assembled by WP1 DATA) feed models of WP6 UPSCALE and WP8 SERVICES. Finally socioeconomic scenarios




are considered in the WP7 ECONOMY.

Four basins have been selected (Llobregat, Ebro, Júcar and Guadalquivir) because of their representativeness of the different factors operating in the Mediterranean area. Most of these basins were included in EU projects (the Llobregat in MODELKEY, the Ebro in AquaTerra or the Guadalquivir in AQUAMONEY and RAMWASS).

Two extensive field campaigns have been undertaken at different flow conditions (high and low-medium) in 77 sampling sites along the four basins. The levels of over 250 compounds belonging to different groups have been determined in water, sediments and fish. The macroinvertebrates, diatomees and biofilm have been studied in all the sites and a morphological characterization of the sites has taken place together with the characterization of sediments, vegetation, ecosystem processes and impacts. The results obtained from the sampling campaigns have been related with the historical ones coming from the river Management authorities and transferred for its use in different models that consider from hydrological variables to emerging contaminants, water quality management or climate change impacts. The amount of data generated in the monitoring campaigns, together with the application of a variety of models will generate attractive management tools aimed to improve the river basin management plans demanded by the WFD.

SCARCE is a 5-year project that has been active since December 2009. With this international conference the fourth year of project is closed. The scientific objectives included in the project have been accomplished as it is reflected in the more than 200 articles published in peer reviewed journals and three special issues in Environmental Science and Pollution Research, Science of the Total Environment and Journal of Hazardous Materials respectively. The amount of scientists involved in the project has also increased from the initial 72 to the present 161 which means more than double the active involvement in the project. Active participation is visible as well from the number of PhD thesis associated to the SCARCE. All these indicators reflect the importance of the project and its high impact in the scientific community by increasing the knowledge of the Mediterranean river basins of the Iberian Peninsula.

Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the project Consolider-Ingenio 2010 CSD2009-00065. Special thanks to all partners of the Scarce consortium and the peer review panel for ensuring quality results and good collaboration within the project.

References

Barceló, D. and S. Sabater (2010). "Water quality and assessment under scarcity: Prospects and challenges in Mediterranean watersheds." Journal of Hydrology 383(1-2): 1-4.

Gasith, A. and V. H. Resh (1999). "Streams in Mediterranean climate regions: Abiotic influences and biotic responses to predictable seasonal events." Annual Review of Ecology and Systematics 30: 51-81.

Giorgi, F. and P. Lionello (2008). "Climate change projections for the Mediterranean region." Global and Planetary Change 63(2-3): 90-104.

IPCC (2007). Fourth Assessment Report: Climate Change 2007. Cambridge, UK, Cambridge University Press.

Navarro-Ortega, A., V. Acuña, R. J. Batalla, J. Blasco, C. Conde, A. Elosegi, F. Francés, F. La-Roca, I. Muñoz, M. Petrovic, Y. Picó, S. Sabater, X. Sanchez-Vila, M. Schuhmacher and D. Barceló (2012). "Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins." Environmental Science and Pollution Research 9: 918-933.



Changes in the distributions of persistent organic pollutants and mercury in freshwater ecosystems under changing climate conditions

Joan O. Grimalt

Department of Environmental Chemistry, IDÆA-CSIC, Barcelona, Spain

Urban, industrial and agricultural processes release to the atmosphere toxic substances such as organochlorine compounds (OCs) such as polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) and DDTs, which are semi-volatile, chemically stable and largely hydrophobic, a group of properties that define these compounds as persistent organic pollutants (POPs). Polycyclic aromatic hydrocarbons (PAHs) and some trace metals (e.g. mercury, cadmium and lead) are also released to the atmosphere as consequence of these activities. After emission, these pollutants are dispersed widely and are deposited onto waterbodies (Tables 1-3). They can enter the food web where they bioaccumulate and become toxic to aquatic and terrestrial organisms. Many of the diverse aspects of climate change (e.g. temperature increase, variations in rainfall, wind patterns and dust deposition) affect the distribution and mobility of toxic substances in freshwater systems.

Table 1 Concentrations of OCs in waters from remote sites (mean ± standard deviation; pg L-1) (from Vilanova et al., 2001a; Fernandez et al., 2005)

Location HCB α-HCH γ-HCH α-Endosulfanß-Endosulfan Endosulfan sulfate

Ladove Lake Sept. 2000 8.5 ± 3.2 68 ± 35 139 ± 89 nd nd 280 ± 65 Lake Redon May 2000 6.0 ± 2.4 313 ± 120 1760 ± 606 207 ± 88 157 ± 51 1246 ± 293 Lake Redon (1996-8) 8.4 ± 11 410 ± 220 2500 ± 1090 60 ± 38 84 ± 46 1000 ± 540 Lake Gossenkölle (1996-7) 4.0 ± 1.8 64 ± 53 930 ± 850 44 ± 28 28 ± 24 92 ± 72 Øvre Neådalsvatn (1998) 6.2 ± 1.0 110 ± 52 200 ± 76 nd nd 120 ± 16 Amituk Lake (1994, Arctic) 630 169 28 Sea water (Antarctica) 3.4 0.7 Arctic Ocean (1990, 1992-4) 14-18 870-4700 180-700 2.0-7.2 0.35-5.3 Lake Malawi (1996-8) 4.4 ± 1.6 9.8 ± 6.2 14 ± 8.7 3.3 ± 6.2 Bow Lake (2000) 21 210 130 19 23 Kananaskis (2000) 15 160 140 15 17

Table 2 Concentrations of PCBs and DDTs in waters from remote sites (mean ± standard deviation) (from Vilanova et al., 2001a; Fernandez et al., 2005)

PCBs (pg L-1) DDTs (pg L-1)Location Total Particulate Dissolved % in SPM Total Ladove Lake Sept. 2000 64 ± 30 33 ±8 31 ± 31 59 ± 19 12 ± 3 Lake Redon Nov. 2000 79 53 26 67 9.6 Lake Redon May 2000 56 ± 11 28 ± 8 29 ± 8 7.1 ± 2.9 Lake Redon (1996-8)(a) 62 ± 44 16 ± 28 Lake Gossenkölle (1996-7) 110 ± 64 14 ± 6.3 Øvre Neådalsvatn (1998) 26 ± 5.4 0.59 ± 0.40 Amituk Lake (1994, Arctic) 372 27 Arctic Ocean (1990, 1992-4) 1.0 ± 0.30* Easthwaite Water Lake (1996-7) 680±190 Lakes in Southern Sweden (1997) 8-144




Although many toxic substances introduced into the environment by human activity have been banned or restricted in use, many persist, especially in soils and sediments, and either they remain in contact with food webs or can be eventually re-mobilised and taken up by aquatic biota (Catalan et al., 2004; Vives et al., 2005). The high levels of metals (e.g Hg) and OCs in the tissue of freshwater fish in arctic and alpine lakes (Grimalt et al., 2001; Vives et al., 2004a) attest to the mobility and transport of these substances in the atmosphere (Figure 1; Carrera et al., 2002; Fernandez et al., 2002; 2003; van Drooge et al., 2004) and their concentration in cold regions (Fernandez and Grimalt, 2003).



Figure 1 Geometric mean concentrations of various OCs in gas phase (bars) compared to mean ambient temperature (points). The warmest periods generally correlate with higher concentrations of the compounds in the gas phase. This trend is clearest for the least volatile compounds and at the site of lowest temperatures (Skalnate Pleso) (based on van Drooge et al., 2004).

Table 3 Concentrations of PAHs in waters from remote sites (mean ± standard deviation) (from Vilanova et al., 2001b; Fernandez et al., 2005).

Location PAH particulate

PAH dissolved

PAH total

Ladove Lake Sept. 2000 8.5 ± 0.7 3.4 ± 0.4 12 ± 1.0 Lake Redon May 2001 0.18 ±0.03 0.58 ± 0.2 0.77 ± 0.20 Lake Redon (1996-8) 0.41 ± 0.13 0.27 ± 0.19 0.70 ± 0.21 Lake Gossenkölle (1996-7) 0.57 ± 0.34 0.35 ± 0.19 0.86 ± 0.44 Øvre Neådalsvatn (1998) 0.50 ± 0.08 0.56 ± 0.06 1.1 ± 0.1 Esthwaite Water Lake 92 ± 32 Raritan Bay (New Jersey) 7.0 – 7.1 3.2 – 7.4 10 – 15 Hamilton Harbour (Lake

Ontario) 45 ± 4

Niagara River 17 ± 5 Danube Estuary 0.13 – 1.25 0.18 – 0.21 Northern Chesapeake Bay 8.7 – 14

Southern Chesapeake Bay Hampton (urban) York River (semiurban) Elizabeth River (industrial)

2.9 5.2 23

3.2 5.2 43

Baltic Sea 0.07 – 0.33 0.57- 0.74 0.64 – 1.08

The IPCC (2007) predicts that precipitation will increase in northern Europe and decrease in the Mediterranean zones by 10 to 20% due to climatic change, and will become more unpredictable (Cristensen et al., 2007). This translates to an increase in the frequency of extreme hydrological phenomena such as major droughts and flash floods. These changes in precipitation patterns will influence the transport and distribution of pollutants as well as their impact on aquatic environments.

For OCs, greater deposition is observed for volatile contaminants (primarily HCH, HCB, and the most volatile congeners of PCBs, DDEs and DDTs) at higher levels of wet deposition as exemplified in at Teide in Tenerife (Fig. 8.11) (van Drooge et al., 2001). These results are consistent with the differences in atmospheric deposition observed in other sites such as Redon Lake, Øvre Neadålsvatn and Gossenkölesee (Fig. 8.7) (Carrera et al., 2002). Hence, any future decrease in precipitation would imply a drop in the amounts of these contaminants that enter water bodies.

In contrast, PAH deposition is primarily controlled by particle settling, followed by wet precipitation, and lastly, air temperature. The two first aspects are fundamental for high molecular weight hydrocarbons, whereas temperature is most important for the low molecular weight ones (Fernandez et al., 2003).

Volatile heavy metals and POPs present much more cryptic problems than those of habitat change, acidification or eutrophication. Their effects on communities are largely unknown and difficult to trace, because they are generally sub-lethal. Health implications for fish and their human consumers are nonetheless clear and the volatility and condensation effects make it very likely that a warmer climate in particular will increase their transfer to polar and mountain regions. One of the more poignant observations of recent years has been that of the widespread contamination even of Antarctic ecosystems with these substances (Borghini et al., 2005; Bargagli 2008).

However, in the areas closer to emission sites, warmer temperatures may result in higher concentrations




of these compounds in air than at present. This change will increase the dispersion capacity of hydrophobic organic pollutants and mercury, leading to higher rates of toxification of humans and higher organisms through respiration. This effect will also be important for PAHs although in this case the ultimate environmental impact will depend on the balance between improved combustion sources and future energy demands, which may increase following population and wealth growth. The implications of increased temperatures will be similar for mercury. Transformation into methylmercury may be enhanced at higher temperatures due to increased microbial activity. Higher temperatures in Arctic and northern environments, where cold conditions currently limit methylation and mercury mobility, are of concern. In Scandinavia, thousands of lakes have fish with mercury levels above the health guidelines. The projected decreases in atmospheric precipitation, e.g. rain and snow may further increase these levels due to higher proportions of groundwater percolating through mercury-rich soils. Acknowledgements

Financial support was provided by the EU Projects EUROLIMPACS (GOCE-CT-2003-505540) and ArcRisk (FP7-ENV-2008-1-226534) and GRACCIE (CSD2007-00067). Financial support from the Generalitat de Catalunya (Research Group 2009SGR1178) is also acknowledged.

References

Bargagli, R. (2008) Environmental contamination in Antarctic ecosystems. The Science of the Total Environment 400, 212-26.

Carrera, G., Fernandez, P., Grimalt, J.O. et al. (2002) Atmospheric deposition of organochlorine compounds to remote high mountain lakes of Europe. Environmental Science and Technology 36, 2581-2588.

Catalan, J., Ventura, M., Vives, I. & Grimalt, J.O. (2004) The roles of food and water in the bioaccumulation of organochlorine compounds in high mountain lake fish. Environmental Science and Technology 38, 4269-4275.

Christensen, J.H., Hewitson, B., Busuioc, A. et al (2007) Regional Climate Projections. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., Qin, D., Manning, M. et al. (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA.

Fernandez, P. & Grimalt, J.O. (2003) On the global distribution of persistent organic pollutants. Chimia 57, 514-521.

Fernandez, P., Carrera, G. & Grimalt, J.O. (2005) Persistent organic pollutants in remote freshwater ecosystems. Aquatic Sciences 67, 263-273.

Fernandez, P., Carrera, G., Grimalt, J.O. et al. (2003) Factors governing the atmospheric deposition of polycyclic aromatic hydrocarbons to remote areas. Environmental Science and Technology 37, 3261-3267.

Fernandez, P., J.O. Grimalt & R.M. Vilanova (2002) Atmospheric Gas-Particle Partitioning of Polycyclic Aromatic Hydrocarbons in High Mountain Regions of Europe. Environmental Science and Technology 36, 1162-1168.

Grimalt, J.O., Fernandez, P., Berdié, L. et al. (2001) Selective trapping of organochlorine compounds in mountain lakes of temperate areas. Environmental Science and Technology 35, 2690-2697.

van Drooge, B.L., Grimalt, J.O., Torres-García, C.J. & Cuevas, E. (2001) Deposition of semi-volatile organochlorine compounds in the free troposphere of the Eastern North Atlantic Ocean. Marine Pollution Bulletin 42, 628-634.

van Drooge, B.L., Grimalt, J.O., Camarero, L., Catalan, J., Stuchlik, E. & Torres Garcia, C.J. (2004) Atmospheric semivolatile organochlorine compounds in European high-mountain areas (Central Pyrenees and High Tatras). Environmental Science and Technology 38, 3525-3532.

Vilanova, R., Fernández, P., Martinez, C. & Grimalt, J.O. (2001a) Organochlorine pollutants in remote mountain lake waters. Journal of Environmental Quality 30, 1286-1295.

Vilanova, R.M., Fernandez, P., Martinez, C. & Grimalt, J.O. (2001b) Polycyclic aromatic hydrocarbons in remote mountain lake waters. Water Research 35, 3916-3926.

Vives, I., Grimalt, J.O., Catalan, J., Rosseland, B.O. & Battarbee, R.W. (2004a) Influence of altitude and age in the accumulation of organochlorine compounds in fish from high mountain lakes. Environmental Science and Technology 38, 690-698.

Vives, I., Grimalt, J.O., Ventura, M. & Catalan, J. (2005) Distribution of polycyclic aromatic hydrocarbons in the food web of a high mountain lake, Pyrenees, Catalonia, Spain. Environmental Toxicology and Chemistry 24, 1344-1352 (2005)



Monitoring Perfluorinated Compounds in the Xúquer River

Julián Campo1, Francisca Pérez2, Ana Masia1, Marinel.la Farré2, Yolanda Pico1 and Damià Barceló2,3

1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain 2 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain


Introduction

Perfluorinated compounds (PFCs) are synthetic chemicals with long fluorocarbon chains headed by different functional groups (carboxylic, sulfonate, sulphonamide, alcohol, etc). Their chemical properties provide them strong water and oil repellency, thus, PFCs and their precursors are widely used in industrial and commercial applications, such as electrical wire insulation, specialist circuit boards, plumbers tape, waterproof membranes for garments (such as Gore-Tex), surgical implants, dental floss, engine protector additives, non-stick coatings, moulded parts and coatings for use in a wide range of chemically hostile environments (Liu et al. 2013, Pico et al. 2011). The strength of the carbon-fluorine bonds confer to PFCs high thermal and chemical stabilities making them highly persistent in the environment, where they can bio-accumulate and potentially produce adverse effects on human beings and wildlife (Xu et al. 2013). Because of this, compounds such as perfluorooctane sulfonate (PFOS) and its precursor, Perfluorooctyl sulfonyl fluoride (POSF), were the first group of PFCs included as Persistent Organic Pollutants by the Stockholm Convention. The European Union also published a Directive prohibiting its use since June 2008 (Liu et al. 2013).

Although the International and European Legislations attempt to decrease PFCs levels in the environment, a clear declining trend in their pollution has not been observed since there is a still growing demand for substances with their unique properties. However, other short-chain PFCs are replacing PFOS. Over the last decade, advances in analytical techniques have resulted in studies describing the occurrence of PFCs in water (including drinking water), sediments, air, organisms, and even in ice caps (Llorca et al. 2010, 2011, 2012a, Wang et al. 2013). Contamination of aquatic ecosystems with PFCs results from a combination of point and non-point sources. Some reports suggest that non-point inputs are responsible for much of the pollution, other state that the most important contribution are point sources such as sewage treatment plant discharges, as these plants appear to be ineffective eliminating PFCs (Llorca et al. 2012a, Pico et al 2012).

The aim of the present study was to determine the distribution of 21 PFCs in water, sediments and biota samples collected in the Xúquer River (East of Spain) to describe the current quality of this Spanish Mediterranean basin in order to understand the possible effects of global change on ecosystem services. This river basin host large cities (Cuenca, Requena, Valencia) and, until recently, has suffer uncontrolled wastewater discharge of both, industrial and human origin.

Experimental

Screened PFCs were chosen after a thorough study of the existing literature considering their solubility and their possible presence in the matrices analysed. Twenty-one PFCs were selected including 14 perfluorocarboxylic acids (from 4 to 18 carbons), 6 perfluorosulfonates (from 4 to 10 carbons) and one perfluorosulfonamide. The Júcar basin was designated as a European Pilot River Basin for the implementation of the WFD and is located in the east of Spain. It has an area of 21,632km2, a main stream length of approximately 500 km, and an average precipitation of 510 mm/year. Urban water use is 118.64hm3/year for 1,030,979 people, and irrigated area is 187,855ha, consuming 1,394hm3/year. It is a much regulated basin, with a total reservoir capacity of 2,643hm3. Main industry located in the basin includes several sectors (automotive, furniture, tiles, etc.).




Fig.1. Location of the sampling points at the Jucar River Basin

Grab water and sediment samples were collected. PFCs were extracted from sediments with acidified methanol by ultrasonication and cleaned up by solid-phase extraction (SPE) and from water by SPE using STRATA X reversed mode cartridges and methanol as eluent (Picó et al. 2012). The chromatographic instrument was an HP1200 series LC combined with an Agilent 6410 triple quadrupole (QQQ) mass spectrometer, equipped with an electrospray ionization (ESI) interface working in negative ionization mode. For fish extraction, the sample was digested using potassium hydroxide in methanol on an orbital shaker at room temperature. Samples were then centrifuged, and supernatants were directly injected into the turbulent flow chromatographic system that uses two columns in tandem for clean-up (Llorca et al. 2012b). The triple quadrupole mass spectrometer Thermo Scientific TSQ Vantage (Thermo Fisher Scientific, San Jose, CA), equipped with a Turbo Ion Spray source was used for analytical purposes.

The recoveries were in the range of 69–110%, 62–103% and 87-110 % for water, sediment and biota with RSDs (%) ≤ 20 %. LOQs ranged from 0.01 to 2 ng/L for water, from 0.04 to 8 ng/g for sediments, and from 0.02 to 2.26 pg/µL for biota. A strict quality control was carried out to check the results. So, every 15 samples analysed a procedural blank and a positive control sample were injected. Each water, sludge and biota samples were analyzed in triplicate and the average concentration is reported

Results and discussions In terms of detection frequency, most of the PFCs were detected at least once. From the 21 analytes included in this study, 11 were detected in water and sediment and 14 in biota samples. PFOS, perfluoropentonic acid (PFPeA) and the perfluorobutanoic acid (PFBA) were the most frequent, being the sulfonate present in all the biota samples and the acid in all the sediment samples. In fact all samples were contaminated with at least one PFC. Table 1 summarizes the results of the water monitoring. Of the 21 analytes screened, 10 were not detected. Most of the PFCs were found in less of 30% of the samples. However, PFBA, PFPeA and perfluoroctanoic acid (PFOA) showed high frequencies (≥ 50 %). PFBA, perfluorodecanoic acid (PFDA) and PFOS showed concentrations higher than 100 ng/L, as the 644.19 ng/L of PFBA. Also, in the case of the sediments, 10 compounds were not detected. PFBA, PFPeA, PFOA, perfluorobutane sulfonate (PFBS), PFOS were in more than 50 % of the samples. Concentrations were from 0.05 ng/g d.w. for PFHxs to 29.19 ng/g d.w. for perfluorobutane sulfonate (PFBS). The partition coefficients of PFCs between sediment and surface water were estimated using the concentration of PFCs in the sediment and in the overlaying water at the same sampling sites always that possible showing an appropriate correlation as previously described (Pico et al. 2012).



Table 1. Minimum and maximum concentration, mean levels and frequency of PFCs in waters of the Xúquer River Basin.

Concentration ng/L Perfluorinted compounds Min a Max Mean b Mean c

Frequency (%)

Perfluorocarboxilic acids (PFA) Pefluorobutanoic acid (PFBA) 5,21 644,19 49,87 83,12 60 Pefluoropentanoic acid (PFPeA) 0,08 2,82 0,38 0,64 60 Perfluorohexanoic acid (PFHxA) 1,44 18,74 3,82 9,55 40 Pefluoroheptanoic acid (PFHpA) 0,64 20,14 2,22 5,55 40 Perfluoroctanoic acid (PFOA) 0,07 52,15 4,36 8,18 53 Perfluorononanoic acid (PFNA) 0,85 19,80 2,31 8,67 27 Pefluorodecanoic acid (PFDA) 0,09 213,01 14,21 71,06 20 Perfluoroundecanoic acid (PFUdA) 0,62 0,62 0,04 0,62 7 Perflurotridecanoic acid (PFTrDA) 0,04 0,04 0,00 0,04 7 Perfluorotetradecanoic acid (PFTeDA) 0,03 0,04 0,01 0,04 13 Perfluorosulfonates Perfluorohexane sulfonate (L-PFHxS) 12,07 36,70 3,25 24,38 13 Perfluoroctane sulfonate (L-PFOS) 0,01 127,98 11,29 28,23 40 a Values different from zero b Considering non-detected as zero c Considering only positive results

In biota, PFOA was the prevalent compound, it was found in 56% of the samples and also it was at a higher concentrations ranging from 26 to 151 ng/g wet weight. Other compounds found in the majority of the fish samples were PFOS and PFHxA.

Figure 1. Cumulative concentrations of PFCs in each sampling point of the Xúquer River Basin (A)

sediment and (B) water

On the spatial distribution of PFCs in the Júcar River, Figure 1 shows the cumulative concentration in each sampling point for water and sediment. The highest concentrations in water were at the points

A B




located in main cities such as Cuenca (JUC2) and Sueca (JUC8), both characterized by the presence of industrial belts. PFOS was important in water only at the point JUC7 and JUC8, suggests localized sources that are unique to the study region at this time. Concentrations of PFCs measured in Júcar River Basin (all ng/L level) did not approach the numerical water quality criteria (all > several μg/L), viz. either the criteria maximum concentration (CMC) or criteria continuous concentration (CCC) values The pattern in sediments was different. There is an accumulation of perfluorinated sulfonates in comparison with water. The accumulation of PFCs in sediments is related to the TOC (Pico et al. 2012), which ranges from 0.64 (JUC8) to 3,685 (MAG2). The Magro tributary has been historically affected by regular and episodic sewage inputs (domestic and industrial) on the water quality. Perfluorosulfonates in biota were at concentrations similar to those found in sediments. The mean value for PFOS in fish was 46 ng/g wet weight. The values of perfluorosulfonates were also higher than the values for perfluocarboxylic acids, such as PFOA with a mean concentration of 33 ng/g wet weight. In summary, all compartment examined in this survey contained measurable concentrations of PFCs. PFBA, PFBS and PFPeA were typically the most abundant PFC across all sample types.

Conclusion

Methodologies used in this research proved to be feasible and efficient ways for systematic PFCs determination in different matrices. All samples were contaminated with at least one PFC, 11 were detected in water and sediment and 14 in biota samples. The higher concentrations in the water samples located at the most highly inhabited cities, offers some support to the idea that a proportion of the PFC contamination in Spanish cities is likely to arise from the use and disposal of consumer goods containing these compounds. Despite the fact that production of L-PFOS ceased in 2002, the results of this study indicate that it still exists in the marketplace and is actively used. PFCs were detected in different compartments of the ecosystem where they are bio-accumulating and, potentially, would produce adverse effects on humans Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio 2010 CSD2009, and CGL2011-29703-C02-02.

References

Liu, C.H., Chang, V.W.C. and Gin K.Y.H. Environmental toxicity of PFCs: An enhanced integrated biomarker assessment and structure-activity analysis. Environ. Toxicol. Chem.. (2013) 32, 2226-2233.

Llorca, M., Farre, M., Pico, Y., Teijon, M.L., Alvarez, J.G. and Barcelo, D. Infant exposure of perfluorinated compounds: Levels in breast milk and commercial baby food. Environ.Int. (2010) 36, 584-592.

Llorca, M., Farre, M., Pico, Y. and Barcelo, D. Analysis of perfluorinated compounds in sewage sludge by pressurized solvent extraction followed by liquid chromatography-mass spectrometry. J. Chromatogr. A (2011) 1218, 4840-4846.

Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T.P. and Barcelo, D. Analysis of perfluoroalkyl substances in waters from Germany and Spain. Sci. Total Environ. (2012a) 431, 139-150.

Llorca, M., Pérez, F., Farré, M., Agramunt, S., Kogevinas,M. and Barceló, D. Analysis of perfluoroalkyl substances in cord blood by turbulent flow chromatography coupled to tandem mass spectrometry. Sci. Total Environ. (2012b) 433, 151-160

Pico, Y., Farre, M., Llorca, M. and Barcelo, D. Perfluorinated Compounds in Food: A Global Perspective. Crit. Rev. Food Sci. Nut. (2011) 51, 605-625.

Pico, Y., Blasco, C., Farre, M., Barcelo, D. Occurrence of perfluorinated compounds in water and sediment of L'Albufera Natural Park (Valencia, Spain). Environ. Sci. Pollut. Res. (2012), 19, 946-957.

Wang SL, Wang H, Deng WJ. Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the Yellow River Estuary, China. Environ. Monit. Assess. (2013) 185,8517-8524.

Xu J, Tian YZ, Zhang Y, et al. Source apportionment of perfluorinated compounds (PFCs) in sediments: Using three multivariate factor analysis receptor models. J. Hazard. Mat. (2013), 260, 483-488



First report of pyrethroids in river fish: a case study in Iberian river basins (Spain)

Cayo Corcellas1, Ethel Eljarrat1 and Damià Barceló1,2

Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain


Introduction

Pyrethrins are natural insecticides produced by certain species of chrysanthemum. In order to increase their stability in the environment, some different derivates have been synthesized. These semi-synthetic compounds are named pyrethroids. They contain 2-3 chiral centers depending on their structure, so each pyrethroid could contain 2 or 4 enantiomer pairs and different diastereoisomers.

In last decades the usage of pyrethroids has increased widely in the indoor as household insecticides, insect-control products, pet shampoos and lice treatments, and in the outdoor as agricultural pesticides and for pest control. Because of that, they are almost ubiquitous and, as long as they are dumped continuously, they will be always present in the environment. Some authors have already determined levels of pyrethroid in rivers, in both water and sediment. (Feo, Ginebreda, Eljarrat, & Barcelo, 2010; Rocha, Ribeiro, Cruzeiro, Figueiredo, & Rocha, 2012).

Despite the assumption that these insecticides are converted to non-toxic metabolites by hydrolysis in mammals, recent studies showed their presence in dolphins or even in human breast milk (Alonso et al., 2012; Corcellas et al., 2012). These studies point out a potential bioaccumulation of these insecticides. Besides, even when their toxicity was supposed low for non-target organisms, it is known the high toxicity in fish (Feo, Eljarrat, & Barcelo, 2010).

With that background, our study involves for the first time the determination of pyrethroid in fishes and their isomeric characterization. The fishes were collected from four different Iberian River Basins, e.g. the Ebro, the Llobregat, the Júcar and the Guadalquivir.

Sampling and methodology

48 samples of different fish species and different size were collected at selected sampling points along each basin river. Inside each river basin, one selected species of fish was monitored in four, five or even six sampling points along the river. Besides, diverse species were fished in each sampling point in order to have more information about that point. The analyzed species were barbels (Luciobarbus sclateri, L. graellsii, Barbus guiraonis), carps (Cyprinus carpio), trouts (Salmo trutta), gudgeons (Gobio Lozanoi) and catfishes (Silurus glanis).

Whole fishes were analysed. Each sample corresponded to pool of individuals. Pool samples were homogenized, freeze-dried and stored until analyses at -20ºC. Sample preparation consisted in an extraction with hexane:dichloromethane (2:1) and a tandem SPE cleanup with alumina and C18 cartridges. Finally, pyrethroids were determined by a GC-MS-MS system working with negative chemical ionization. The analytical method included 12 different pyrethroids: bifenthrin, cifluthrin, cypermethrin, cyhalothrin, deltamethrin, fluvalinate, fenvalerate, permethrin, phenothrin, resmethrin, tetramethrin and tralomethrin. The samples were analysed twice, first with an achiral GC column and second with a chiral one.

Results

The first remarkable result was that pyrethroids were detected in all the tested samples, indicating the bioavailability and bioaccumulation of these pesticides by river fish. Concentrations of pyrethroids in




fishes ranged between 12 and 4938 ng/g lipid weight (lw), with the highest levels being found in areas with greater agricultural impact. Table 1 summarizes the general results obtained.

Table 1: Pyrethroid levels in fishes from Iberian river basins (ng/g lw).

Monitored species Other species River basin (N) Species Range Mean Species (N) Mean

L. graellsii (4) 114 Ebro (5) C. carpio 46-1017 307

Silurus glanis (2) 238

L. graellsii (2+1*) 356 Llobregat (5+1*) C. carpio 152-1508 551

Salmo trutta (1*) 4938

Guadalquivir (4) L. sclateri 20-843 608 C. carpio (1) 140

B. guiraonis (2) 68 Júcar (5) G. Lozanoi 114-670 327

Salmo trutta (2) 481

N: number of sampling points.

* This sampling point corresponds to a reservoir.

Moreover, these river basins are in different geographical areas, so the pyrethroid usage is assumed to be different. In that sense, we considered important to evaluate and characterize the individual presence of each analysed pyrethroid. Generally, the most abundant pyrethroids were permethrin and cypermethrin, with a maximum contribution of 75 and 72% to the total pyrethroid contamination. In contrast, fluvalinate, phenothrin and resmethrin were never detected. The following Figure 1 shows the pyrethroid distribution for each river basin. It is easy to check the different pattern for each river basin, even when for Ebro and Llobregat were similar. For instance, permethrin is the most abundant pyrethroid in Ebro and Llobregat basins but cypermethrin is in Guadalquivir and tetramethrin in Júcar River Basin.



Figure 1: Distribution of pyrethroids through each River Basin.

Since pyrethroid isomerism could affect toxicology, isomeric and enantiomeric studies have been also carried out in order to determine potential isomeric- and/or enantiomeric-selective accumulation processes by fish. For that purpose, an additional analysis through a chiral GC column was performed. Some differences between species were found in the enantiomer distribution in samples from the same sampling point. Figure 2 shows an example of that fact. In it, cypermethrin chromatogram with a chiral column is represented for a sample of catfish and a sample of barbel both corresponding to the same sampling point of the Ebro river. It is clear that the trans- isomers (the two not-shadowed peaks) represent less than the 10% of the total cypermethrin but the cys- isomers (the four shadowed peaks) present different profiles. Concretely in this case, the first two enantiomers are in an almost racemic mixture in barbels but catfishes bioaccumulate more of one of these enantiomers.

As a result of this characterization, we could conclude that these enantiomeric profiles depended on the species but not so much on the sampling point or even the river sampled. That means that there is a selective accumulation in each species.

Conclusions

This report evaluates for the first time the presence of pyrethroids in fishes. The levels reached up to 4938 ng/g lw. There are significative differences in the distribution pattern of the 13 pyrethroids among river basins and even among species from the same sampling point. Different enantiomeric profiles were described for each species. This could imply a selective accumulation depending on the species.




a)

b)

Figure 2: Chromatograms of the enantiomeric separation of cypermethrin in a) barbel sample and b) catfish sample of the Ebro River. (cys-isomers shadowed)

Acknowledgements

This research was founded by the Spanish Ministry of Science and Innovation through the project SCARCE (Consolider Ingenio 2010 CSD2009-00065). This work has also been partly funded by the Generalitat de Catalunya (Consolidated Research Group Water and Soil Quality Unit 2009-SGR-965).

References

Alonso, M. B., Feo, M. L., Corcellas, C., Vidal, L. G., Bertozzi, C. P., Marigo, J., Barcelo, D. (2012). Pyrethroids: A new threat to marine mammals? Environment International, 47, 99-106. doi: 10.1016/j.envint.2012.06.010

Corcellas, C., Feo, M. L., Paulo Torres, J., Malm, O., Ocampo-Duque, W., Eljarrat, E., & Barcelo, D. (2012). Pyrethroids in human breast milk: Occurrence and nursing daily intake estimation. Environment International, 47, 17-22. doi: 10.1016/j.envint.2012.05.007

Feo, M. L., Eljarrat, E., & Barcelo, D. (2010). Determination of pyrethroid insecticides in environmental samples. Trac-Trends in Analytical Chemistry, 29(7), 692-705. doi: 10.1016/j.trac.2010.03.011

Feo, M. L., Ginebreda, A., Eljarrat, E., & Barcelo, D. (2010). Presence of pyrethroid pesticides in water and sediments of Ebro River Delta. Journal of Hydrology, 393(3-4), 156-162. doi: 10.1016/j.jhydrol.2010.08.012

Rocha, M. J., Ribeiro, M. F. T., Cruzeiro, C., Figueiredo, F., & Rocha, E. (2012). Development and validation of a GC-MS method for determination of 39 common pesticides in estuarine water - targeting hazardous amounts in the Douro River estuary. International Journal of Environmental Analytical Chemistry, 92(14), 1587-1608. doi: 10.1080/03067319.2011.581366



Priority and emerging pollutants in southern Spain: overview of some case studies from the Anquimed research group

Irene Aparicio, Julia Martín, Dolores Camacho-Muñoz, Juan Luís Santos and Esteban Alonso

Department of Analytical Chemistry, Escuela Politécnica Superior, University of Seville, Seville, Spain

Introduction

Nowadays, thousands of organic compounds end up into the environment as a result of their production, applications or consumption rates. Some of these compounds, such as polycyclic aromatic hydrocarbons, pesticides and polychlorinated biphenyls, have been classified as priority pollutants and are regulated by legislation. However, there is less information about of other compounds, which are also continuously discharged to the environment, mainly due to the lack of analytical methodologies for their determination at low concentrations in complex matrices. Among the emerging contaminants are pharmaceutically active compounds, surfactants such as linear alkylbenzene sulfonates and nonylphenol ethoxylates, perfluorinated compounds and flame retardants.

Since its founding in 2004, the research group "Análisis Químico Industrial y Medioambiental" (Anquimed) from the University of Seville has focused its studies on the occurrence of priority and emerging contaminants in the environment. The main activities of the group are the development of analytical methods, environmental monitoring studies, degradation studies and the evaluation of wastewater treatments in the removal of emerging pollutants.

Development of analytical methods

One of the main challenges, to obtain information about the presence of emerging pollutants in the environment, is to develop analytical methodologies that allow their determination at low concentration levels in the complex environmental matrices. Our research group has contributed to this field in three ways: (i) the development of reliable analytical methods that combine appropriate analytical properties and low-cost for the routine determination of emerging contaminants in the environment, (ii) the development of analytical methods for the determination of new groups of significant pollutants, of great environmental concern, for which the availability of analytical methods is still limited and (iii) the development of novel sample treatment methods.

The methodologies developed for the routine determination of emerging pollutants involved solid-phase extraction, for aqueous samples, and ultrasonic-assisted extraction, for solid samples, and determination by liquid chromatography with diode-array and fluorescence detectors. These methods allowed the determination of 17 of the most significant pharmaceutically active compounds in wastewater and surface water (Camacho-Muñoz et al., 2009) and in sewage sludge, soils and sediments (Martín et al., 2010), as well as the determination of some of the most problematic emerging pollutants (linear alkybenzene sulfonates, nonylphenol ethoxylates and di(2-ethylhexyl)phthalate) in sewage sludge and in sludge-amended soil (González et al., 2010). The developed methodologies allowed high recoveries (up to 123 % for aqueous samples and up to 107 % for solid samples) and low limits of quantification (lower than 1 μg/L in aqueous samples and lower than 360 μg/kg in solid samples). The methods developed of the determination of novel pollutants employed liquid chromatography coupled to triple-quadrupole-mass spectrometry for the analysis of cytostatic drugs (Martín et al., 2011a) and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry for the analysis of classical and novel antidibetic drugs (Martín et al., 2012a). Due to their low consumption rates, these compounds are present in the environment at low concentrations so the use of advanced analytical tools is necessary for their determination. The limits of quantitation of the developed methods were 0.1 ng/L and




0.4 ng/L, for the analysis of the cytostatic and antidiabetic drugs, respectively. The developed methods are suitable to be applied to the evaluation of the occurrence and the ecotoxicological risk of these problematic compounds in aqueous environmental samples such as wastewater or surface water.

The evaluation and development of alternative sample treatment techniques to solid-phase extraction was studied in order to improve the speed, economy and efficiency of sample treatment and to reduce interferences from the matrix. Dispersive liquid–liquid microextraction was evaluated showing to be a useful tool for the determination of organic pollutants in aqueous samples (Martín et al., 2013) with recoveries up to 80 %. The main advantages of the proposed method, with regards to SPE methods, are that sample management is facilitated because of the low sample and solvent volumes required, and the treatment is easier and faster to perform.

Environmental monitoring studies

The analytical methods developed by the group have been applied to the monitorization of emerging pollutants in several environmental compartments such as wastewater, surface water, sludge, soil and sediment in order to evaluate their occurrence not only in the aquatic and terrestrial environment but also in the main sources of releasing emerging pollutants into the environment: urban and industrial wastewater.

Among the natural systems studied are the unique ecosystems of Doñana National Park (Camacho et al., 2010a; 2010b; Camacho-Muñoz et al., 2013a)) and Guadalquivir River basin (Martín et al., 2011b). These studies showed the presence of pharmaceutically active compounds at concentrations up to 4.55 μg/L and 52 μg/kg in surface water and sediments, respectively, from Doñana National Park and up to 0.75 μg/L in surface water from Guadalquivir River. The antiinflammatory drugs were the therapeutic group at the highest concentrations, followed by lipid regulators, nervous stimulant and antiepileptic drugs. This distribution is similar to that observed in effluent wastewater, so effluent wastewater discharges can be considered as the main source of these compounds to Doñana National Park and Guadalquivir River.

Pharmaceutically active compounds had been monitored in wastewater treatment plants during one-year period (Santos et al., 2009). The seasonal evolution of the concentrations observed, conditioned to the therapeutic group, could be related with their human consumption. The potential industrial and urban sources of pharmaceutically active compounds and other emerging contaminants to the environment have been studied through their monitorization in wastewater collection systems (Camacho-Muñoz et al., 2014). This study showed that urban activities were the main source of pharmaceutically active compounds and linear alkylbenzene sulfonates to the environment while industrial activities contributed significantly to the discharges of nonylphenol ethoxylates and salicylic acid. Different discharge patterns were observed: while pharmaceutically active compounds were present at their highest concentration at the first hours in the morning others, such as linear alkylbenzene sulfonates, nonylphenol ethoxylates and salicylic acid, showed an hourly distribution similar to water consumption.

Anquimed research group has also carried out monitorization studies of several emerging contaminants in sewage sludge from wastewater treatment plants (Aparicio et al., 2009; Martín et al., 2012b, 2012c; González et al., 2010). These studies, carried out in more than 20 wastewater treatment plants from Andalusia region, showed the presence of linear alkylbenzene sulfonates and nonylphenol ethoxylates at high concentrations, being, in most of the studied sludge samples, higher than the limit values set by the European Union Sludge Directive draft published in April 2000 (higher than 78 % in the case of nonylphenol ethoxylates).

Degradation studies

Degradation studies are of great concern since they do not only provide information about the distribution of the contaminants in the environment, but also about their persistence in different environmental compartments. Our research group has performed degradation studies of anionic and non-ionic surfactants in a typical Mediterranean soil amended with sewage sludge applying winter (12.7 ºC) and summer (22.4



ºC) conditions (González et al., 2012). The results showed the influence of the temperature in the degradation of these compounds. The half-life time of linear alkylbenzene sulfonates were lower than 14 days at 12.7 ºC and lower than 7 days at 22.4 ºC. The concentrations were reduced to 5% of the initial concentration 49 and 21 days after sludge-application to the soil at 12.7 ºC and 22.4 ºC, respectively. In the case of nonylphenol ethoxylates, an increase of the concentration was observed during the first days of the experiment as consequence of the degradation of the nonylphenol polyethoxylate compounds. Their concentrations were reduced to 5% after 63 and 70 days at 12.7 ºC and 22.4 ºC, respectively.

Wastewater treatment evaluation

After their use or consumption, emerging contaminants are discharged to wastewater treatment plants through sewer systems. The knowledge about their occurrence in wastewater treatments is of great interest in order to assess the entry of these contaminants into the environment and their potential environmental effects. Our research group has evaluated the removal of emerging pollutants in different wastewater treatment systems including conventional (Santos et al., 2009), low-cost (Camacho-Muñoz et al., 2012a) and tertiary processes (Camacho-Muñoz et al., 2012b).

The occurrence of pharmaceutically active compounds, linear alkylbenzene sulfonates and nonylphenol ethoxylates has been studied in 17 wastewater treatment plants based on conventional activated sludge processes (n=4), oxidation ditches (n=8), trickling filter beds (n=1), lagooning (n=2) and constructed wetlands (n=2) (Camacho-Muñoz et al., 2012a), as well as, in membrane bioreactor technologies operating with flat sheet, hollow fibre membranes and with reverse osmosis (Camacho-Muñoz et al., 2012b). Mean removal rates of pharmaceutically active compounds in conventional wastewater treatments were slightly higher (64%) than those achieved in low-cost treatments (55%). Ibuprofen, naproxen, salicylic acid and caffeine were the pharmaceutical compounds most efficiently removed, regardless the wastewater treatment applied, with removal rates up to 99%. Anaerobic lagooning was the less effective treatment for the removal of the most persistent compounds: carbamazepine and propranolol.

Mean removal rates of pharmaceutical compounds achieved by membrane bioreactor technologies were ranged between 7 % (carbamazepine after flat sheet membranes) and 97 % (caffeine after flat sheet membranes). No significant difference in effectiveness was found among flat sheet and hollow fibre membranes. However, improvement was obtained for most of the studied organic compounds with the addition of a reverse osmosis module. In comparison to conventional activated sludge process, membrane bioreactor technologies allowed higher removal rates for all the studied compounds, except for linear alkylbenzene sulfonates homologues.

Nowadays, the research of Anquimed group in the topic of wastewater treatments is focused in the evaluation of new treatment technologies for the removal of emerging pollutants from wastewater. These technologies include a combination of integrated fixed-film activated sludge and membrane bioreactor technology followed by reverse osmosis for the achievement of a high-quality effluent, as well as environmental and sustainable technologies for the removal of emerging contaminants of great environmental concern from hospital residues. References

Aparicio, I., Santos, J.L., Alonso, E. Limitation of the concentration of organic pollutants in sewage sludge for agricultural purposes: a case of study in south Spain. Waste Management (2009), 29, 1747–1753.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. An affordable method for the simultaneous determination of the most studied pharmaceutical compounds as wastewater and surface water pollutants. Journal of Separation Science (2009), 32, 3064-3073.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence, temporal evolution and risk assessment of pharmaceutically active compounds in Doñana Park (Spain). Journal of Hazardous Materials (2010a), 183, 602-608.

Camacho-Muñoz, D., Santos, J.L., Aparicio, I., & Alonso, E. Presence of pharmaceutically active compounds in Doñana Park




(Spain) main watersheds. Journal of Hazardous Materials (2010b), 177, 1159-1162.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Effectiveness of conventional and low-cost wastewater treatments in the removal of pharmaceutically active compounds. Water, Air and Soil Pollution (2012a), 223, 2611-2621.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Alonso, E., Aparicio, I., De La Torre, T., Rodriguez, C., Malfeito, J.J. Effectiveness of three configurations of membrane bioreactors on the removal of priority and emergent organic compounds from wastewater: comparison with conventional wastewater treatments. Journal of Environmental Monitoring (2012b), 14, 1428-1436.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso E. Distribution and risk assessment of pharmaceutical compounds in river sediments from Doñana Park (Spain). Water, Air and Soil Pollution (2013a), 224, 1665-1679.

Camacho-Muñoz, D., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence of surfactants in wastewater: Hourly and seasonal variations in urban and industrial wastewaters from Seville (Southern Spain). Science of the Total Environment (2014), 468–469, 977-984.

González, M.M., Santos, J.L., Aparicio, I., Alonso, E. Method for the simultaneous determination of the most problematic families of organic pollutants in compost and compost-amended soil.Analytical and Bioanalytical Chemistry (2010a), 397, 277-285

González, M.M., Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Occurrence and risk assessment of nonylphenol and nonylphenol ethoxylates in sewage sludge from different conventional treatment processes. Science of the Total Environment (2010b), 408, 563-570.

González, M.M., Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Degradation and environmental risk of surfactants after the application of compost sludge to the soil. Waste Management (2012), 32, 1324-1331.

Martín, J., Santos, J.L., Aparicio, I., Alonso, E. Multi-residue method for the analysis of pharmaceutical compounds in sewage sludge, compost, and sediments by sonication-assisted extraction and LC determination. Journal of Separation Science (2010) 33, 1760-1766.

Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Simultaneous determination of a selected group of cytostatic drugs in water using high-performance liquid chromatography-triple-quadrupole mass spectrometry. Journal of Separation Science (2011a), 34, 3166-3177.

Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment. Journal of Environmental Monitoring (2011b), 13, 2042-2049.

Martín, J., Buchberger, W., Santos, J.L., Aparicio, I., Alonso, E. High-performance liquid chromatography quadrupole time-of-flight mass spectrometry method for the analysis of antidiabetic drugs in aqueous environmental samples. Journal of Chromatography B, (2012a), 895-896, 94-101.

Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Occurrence of pharmaceutical compounds in wastewater and sludge from wastewater treatment plants: removal and ecotoxicological impact of wastewater discharges and sludge disposal. Journal of Hazardous Materials (2012b), 239-240, 40-47.

Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Distribution and temporal evolution of pharmaceutically active compounds alongside sewage sludge treatment. Risk assessment of sludge application onto soils. Journal of Environmental Management (2012c), 102, 18-25.

Martín, J., Camacho-Muñoz, D., Santos, J.L., Aparicio, I., Alonso, E. Determination of priority pollutants in aqueous samples by dispersive liquid–liquid microextraction. Analytica Chimica Acta (2013), 773, 60-67.

Santos, J.L., Aparicio, I., Callejón, M., Alonso, E. Occurrence of pharmaceutically active compounds during 1-year period in wastewaters from four wastewater treatment plants in Seville (Spain). Journal of Hazardous Materials (2009), 164, 1509-1516.



Uptake and Bioaccumulation of Endocrine Disruptors and Pharmaceutical compounds in Biofilm, Macroinvertebrates, and Fish in

four Mediterranean Rivers

Belinda Huerta1, Victoria Osorio2, Marina Gorga2, Anna Jakimska3, Nuria de Castro4, Lidia Ponsati1, Isabel Muñoz4, Sandra Pérez2, Mira Petrovic1, 5, Sara Rodríguez-Mozaz1 and Damià

Barceló 1,2

1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain

3 Department of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology, Gdansk, Poland 4 Departament d’Ecologia, Facultat de Biologia, Universitat de Barcelona (UB), Barcelona, Spain

5 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

Introduction

Many contaminants have been detected in wastewater effluents and surface water in recent years, including pharmaceuticals (PhACs) and endocrine disrupting compounds (EDCs). Many of these compounds are not completely removed in the wastewater treatment plants (WWTPs) and are released to the environment (Gros et al., 2006; Halling-Sørensen et al., 1998; Kolpin et al., 2002; Osorio et al., 2012). This situation is of special concern in Mediterranean regions, where the WWTP effluents may represent a high percentage of some streams flow, particularly under water scarcity (Coogan et al., 2007). In surface waters heavily impacted by WWTP effluents PhACs and EDCs may be present at concentrations that might cause adverse effects in the aquatic organisms (Garcia et al., 2012). Moreover, as they are continuously introduced into surface waters, chronic exposure of the affected biota may occurs during a complete life cycle, and in some cases, in successive generations (Pascoe et al., 2003). PhACs are designed to modify physiological or biochemical functions in target organisms but the exposure to them by non-target organisms could also have severe consequences. In the case of EDCs, they are already defined as compounds able to disrupt endocrine system in many organisms and may also have unexpected effects in non-target organisms. A better understanding of how these compounds are transferred from water to biota could help to determine the potential of ecosystem damage associated with the discharge of WWTP effluent containing these contaminants (Kinney et al., 2008).

It is generally accepted that substances with octanol-water partition coefficient (log KOW) values higher than or equal to 3 have the potential to bioaccumulate in biological tissues. Many PhACs and EDCs have a log KOW < 3, and thus, are not expected to bioaccumulate. However, some of these compounds are lipid soluble and therefore potentially bioaccumulative in the environment (Howard and Muir, 2011). Moreover, when considering bioaccumulation of PhACs and EDCs in aquatic organisms, one must take other factors into consideration, such as the different rates of metabolism in various organisms, the accumulation behaviour of their metabolites, and the uptake and depuration kinetics.

This work describes the presence and bioaccumulation of PhACs and EDCs in aquatic organisms from different trophic levels – biofilm (basal resource), two macroinvertebrates: Hydropsyche sp, (collector-filterer insect larvae) and Dreissena polymorpha (zebra mussel), and fish – collected from four rivers basins in Spain: Ebro, Llobregat, Júcar and Guadalquivir.

Materials and methods

Sampling was performed in 5 points in each of four rivers with Mediterranean fluvial regime (Ebro, Llobregat, Júcar and Guadalquivir) to achieve a pollution gradient, from the upper points to the lower points of the rivers. A total of 20 sites were sampled during the summer of 2010 for the analysis of up to 43 multi-class pharmaceuticals and 21 EDCs in aquatic organisms from different trophic levels: biofilm,




insect larvae, mussels and fish (see Table 1). Samples were homogenized, composited into a single sample, freeze-dried and kept at minus 20 °C until analysis.

Table 1. Total number of biota samples collected in 2010.Fish sampling included several species in site (number indicated in parenthesis)

EBRO LLOBREGAT JÚCAR GUADALQUIVIR

Biofilm 4 5 - -

Insect larvae 2 4 3 3

Zebra mussel 2 - - -

Fish (nº species) 20 (3) 20 (2) 20 (7) 20 (2)

Biofilm samples were extracted according to the method developed by Huerta et al (in preparation). Briefly, 200 mg of freeze-dried sample was extracted in an automated solvent extractor system (ASE® 350, Dionex), using a mixture of acetonitrile/citric buffer (pH=4) (1:1, v/v) as extraction solvent. Extracts were further purified using solid phase extraction (SPE) with Oasis HLB cartridges (6 ml, 200 mg).

Macroinvertebrate samples were extracted according to the method developed by Huerta et al (in preparation). Briefly, samples (200 mg) were placed in a 50-mL Falcon tube with 3 ml of methanol and vortexed. A sonication tip was applied in 3 cycles of 120 s, with amplitude (intensity) of 30 %. Extracts were centrifuged at 11000 rpm, for 5 min. Supernatant was collected and 1.5 ml of the extract was taken for further purification. Extracts were redissolved in 750 μl of H2O/ACN (1:3, 1 % HCOOH, v/v). OstroTM 96-well plate was placed in a manifold and wells were added 750 of fresh solvent and then carefully mixed with the extract in the well. After extraction by vacuum, purified extracts were collected.

Fish and mussel samples were extracted according to the method developed by Huerta et al (Huerta et al., 2013) for the analysis of pharmaceuticals Briefly, approximately 1 g and 0.5 g, respectively, of freeze-dried sample was extracted in an automated solvent extractor system (ASE® 350, Dionex), using methanol as extraction solvent. Extracts were evaporated to 1 ml and then 250 μl was passed through a preparative column in a gel permeation chromatography system for lipid removal. For the analysis of EDCs a QuEChERS procedure developed by Jamiska et al was applied (Jakimska et al., 2013). Briefly, 0.5 g of homogenized and freeze-dried sample was transferred to a 50-mL centrifuge tube and vortex for 30 s. Then a ceramic homogenizer and water was added and vortexed for 30 s. After vortexing for 1 min with subsequent addition of ACN, an extraction salt was added directly to the tube and then the mixture was immediately manually shaken for 1 min. Samples were centrifuged at 11,000 rpm for 4 min. The ACN layer was transferred to the polypropylene tube containing dSPE sorbents, vortexed for 1 min and centrifuged for 15 min at 5000 rpm. Supernatant was collected and evaporated to dryness.

Final extracts were collected and redissolved in methanol/water (10:90 (PhACs), 50:50 (EDCs)) for the analysis by ultra-rapid liquid chromatography tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) operating in both positive and negative ion mode, according to the method developed by Gros et al (Gros et al., 2012) for pharmaceuticals and Jakimska et al (Jakimska et al., 2013) for EDCs. Ultra performance liquid chromatography (UPLC Acquity, Waters, Mildford, USA) coupled to a QTRAP® 5500 (AB SCIEX, Framingham, USA) was used for instrumental analysis.



Results and Discussion

In the case of EDCs, 12 compounds, out of 18 detected in water and sediment, were also found in biota samples. Table 2 shows the number of compounds detected in each river basin and organism in relation to the number of compounds analyzed for each sample’s type. Bisphenol A, propylparaben, TCEP and triclosan were detected in all the biofilm samples analyzed, TBEP compound in all the macroinvertebrate samples, and in 95 % of the fish samples. These compounds are also some of the most prevalent compounds in water and sediment (detected in more than 70 % samples). Compounds like caffeine and tolyltriazole, although persistently detected in water at considerable concentration in the majority of the sampling points (up to 572.2 ng/L and 874.9 ng/L, respectively), was only detected in one biota sample at very low concentration.

Table 2. Number of EDCs detected in aquatic organisms from four Mediterranean rivers.

Compounds detected (compounds analyzed)


Biofilm 7 (17) 7 (14) - -

Insect larvae 2 (21) 3 (21) 4 (21) 3 (21)

Zebra Mussels 2 (19) - - -

Fish 7 (19) 5 (19) 7 (19) 7 (19)

In the case of PhACs, 20 compounds, out of 77 found in water and sediment, were also detected in aquatic organisms. Table 3 illustrates the number of compounds detected in each river basin and trophic level in relation to the number of compounds analyzed for each sample’s type. Most prevalent compound in biofilm was the antibiotic azythromycin, found in 44 % of the samples. In contrast, the anti-inflammatory drug diclofenac was the most ubiquitous compound in fish, as it was detected in different fish species and in all the river basins. Compounds frequently detected in water, such as acetaminophen and ibuprofen, with concentrations around 150 ng/L in some sampling sites, were not detected in any aquatic organism.

Table 3. Number of PhACs detected in aquatic organisms from four Mediterranean rivers.

Compounds detected (compounds analyzed)


Biofilm 0 (43) 15 (43) - -

Insect larvae 1 (41) 1 (41) 1 (41) 1 (41)

Zebra Mussels 3 (20) - - -

Fish 4 (20) 2 (20) 2 (20) 1 (20)




Acknowledgements

This study has been co-financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065) the EU Project ECSafeSEAFOOD [FP7-KBBE 311820] and by the European Union through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965).

References

Coogan MA, Edziyie RE, La Point TW, Venables BJ. Algal bioaccumulation of triclocarban, triclosan, and methyl-triclosan in a North Texas wastewater treatment plant receiving stream. Chemosphere 2007; 67: 1911-1918.

Garcia SN, Foster M, Constantine LA, Huggett DB. Field and laboratory fish tissue accumulation of the anti-convulsant drug carbamazepine. Ecotox. Environ. Safe. 2012; 84: 207-211.

Gros M, Petrovic M, Barceló D. Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 2006; 70: 678-690.

Gros M, Rodríguez-Mozaz S, Barceló D. Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. J. Chromatogr. A 2012; 1248: 104-121.

Halling-Sørensen B, Nors Nielsen S, Lanzky PF, Ingerslev F, Holten Lützhøft HC, Jørgensen SE. Occurrence, fate and effects of pharmaceutical substances in the environment: A review. Chemosphere 1998; 36: 357-393.

Howard PH, Muir DC. Identifying new persistent and bioaccumulative organics among chemicals in commerce II: pharmaceuticals. Environ Sci Technol 2011; 45: 6938-46.

Huerta B, Jakimska A, Gros M, Rodriguez-Mozaz S, Barcelo D. Analysis of multi-class pharmaceuticals in fish tissues by ultra-high-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 2013; 1288: 63-72.

Jakimska A, Huerta B, Barganska Z, Kot-Wasik A, Rodriguez-Mozaz S, Barcelo D. Development of a liquid chromatography-tandem mass spectrometry procedure for determination of endocrine disrupting compounds in fish from Mediterranean rivers. J Chromatogr A 2013; 1306: 44-58.

Kinney CA, Furlong ET, Kolpin DW, Burkhardt MR, Zaugg SD, Werner SL, et al. Bioaccumulation of pharmaceuticals and other anthropogenic waste indicators in earthworms from agricultural soil amended with biosolid or swine manure. Environ Sci Technol 2008; 42: 1863-70.

Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, et al. Pharmaceuticals, Hormones, and Other Organic Wastewater Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance. Environ. Sci. Technol. 2002; 36: 1202-1211.

Osorio V, Marcé R, Pérez S, Ginebreda A, Cortina JL, Barceló D. Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions. Sci.Total Environ. 2012; 440: 3-13.

Pascoe D, Karntanut W, Müller CT. Do pharmaceuticals affect freshwater invertebrates? A study with the cnidarian Hydra vulgaris. Chemosphere 2003; 51: 521-528.



Methodological challenges for the determination of endocrine disruptor compounds in the environment. Comparison of different

analytical strategies

Marina Gorga1, Belinda Huerta2, Sara Rodríguez-Mozaz2, Mira Petrovic2,3, Damià Barceló1,2

1 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain


Introduction

The Mediterranean river basins are one of the most vulnerable regions of the world to the global change due to their climatic conditions and their characteristic topographical regions1. Moreover, the high activity close to the Mediterranean rivers, either industrial or agricultural, intensive use of the water resources, and the high population density in these zones, are the principals arguments to evaluate the water quality of these rivers. Focusing our attention on the group of endocrine disruptor compounds (EDCs), during the last 3 years and within the multipurpose SCARCE project, the occurrence, spatial distribution and partitioning of this organic contaminants has been evaluated in four river basins of the Iberian Peninsula.

In the literature, there are several analytical methodologies already available for the determination of EDCs and related organic contaminants in different matrices with acceptable limits of detection (LODs). These techniques involve different preconcentration or extraction approaches and multi-step clean-up protocols. Moreover, the analysis of EDCs or related groups of organic micropollutants, combines the offline analysis with online instrumental techniques in order to minimize the time of analysis, sample manipulation or reduce the ion suppression.

The objective of this work was the evaluation and comparison of the different techniques used for the analysis of EDCs in the principal matrices analyzed under the multidisciplinary SCARCE project with high number of samples and matrices; river water and sediment, waste water and sewage sludge and fish-tissue samples.

First approach consisted of an automated online method using Thermo Scientific EQuan/TurboFlowTM

liquid chromatography coupled to a triple quadrupole mass spectrometer (TSQ Vantatge) with an ESI source for mass spectrometry detection in tandem (LC-LC-MS/MS). EQuanTM methodology2 was used as a preconcentration technique in less complex water samples (such as groundwater or surface water), allowing to inject high volumes of samples decreasing considerably the detection limits. TurboFlowTM technology was used as a purification approach in the case of water samples where the matrix effects were important (such as waste water or effluents). This methodology is also applied as a clean-up step in the case of solid matrices, specifically in sediments, sewage sludge and fish.

For the analysis of EDCs in fish a QuEChERS procedure developed by Jakimska et al.3 (2013) was applied. The performance of this method was compared to the one developed by Huerta4 (2013) et al. for the analysis of pharmaceuticals in fish and based on a gel permeation chromatography (GPC).

Therefore, a thorough comparison of different approaches was performed in order to select the most appropriate method for the analysis of EDCs in different types of environmental samples. Figure 1 showed a schematic diagram of the different techniques for the preconcentration or extraction and clean up applied for the analysis of EDCs in different matrices.




Extraction

Solid Phase Extraction (SPE)

Preconcentration

EQuanTM

technique

TurboFlowTM technique Gel Permeation chromatography

(GPC)

Solid Phase clean up

UltraSonicExtraction

(USE)

Pressurized Liquid

Extraction (PLE)

QuEChERSmethod

Purification

Water samples Dirty water samples Solid samples

Methods applied for the analysis of EDCs in the different matrices

Methods tested and discarded for the analysis of EDCs in the different matrices

Alternative methods applied for the analysis of EDCs in the different matrices

River water

Effluent water

Influent waste water


Analysis by liquid chromatography separation coupled to mass spectrometry detection (LC-MS/MS)

Purification

Sediment

Sediment and sludge

Sediment and sludge

Fish

Fish River water

Effluent water


M1 M2

M4

M5

M3

M6

M8

M7

Figure 1. Schematic diagram of the different techniques applied for the preconcentration or extraction

and clean up analysis of EDCs in different matrices

Sample collection and methods

River water and sediment samples were collected during two sampling campaigns (2010 and 2011) at 77 sites from Iberian rivers: 24, 14, 15 and 24 sampling points in Ebro, Llobregat, Júcar and Guadalquivir river basins, respectively. Wastewater and sludge samples were collected during two sampling campaigns (2010 and 2011) from 16 wastewater treatment plants (WWTPs): 6, 3, 2 and 5 major WWTPs in Ebro, Llobregat, Júcar and Guadalquivir river basins, respectively. Fish sampling was performed in 5 point in each of four rivers. A total of 20 sites were samples during the summer of 2010.

The methodology applied for the simultaneous determination of EDCs in water samples is a fully automated method based on column switching using EQuanTM columns (M2) for an integrated sample preconcentration and liquid chromatography coupled to tandem mass spectrometry (LC-LC-MS/MS).

A Hypersil GOLDTM Aqua and a C18 reversed-phase column were used as preconcentration and analytical columns respectively. The injection volume was set at 5mL for river water and 2 mL in the case of wastewater. The flow-rate through loading column was 1.75 mL/min during the charge step and in the transfer step its flow rate down to 0.3 mL/min. Chromatographic separation of compounds detected under NI conditions was performed under gradient elution condition using water and methanol. Compounds detected under PI conditions were separated with the same gradient program used above and solvents were water-methanol with 20 mM of ammonium formiate and 0.1% of acetic acid. For a comparison an offline preconcentration method based on a classical solid phase extraction (SPE) was performed (M1).

For the determination of EDCs in sediments, sewage sludge and fish samples 2g, 1g and 1g of dried weight (dw) samples were extracted using a pressurized liquid extraction (PLE) fully automated ASE 200 system (Dionex, Sunnyvale, CA, USA). The extraction solvent employed was water:methanol:acetone (1:2:1) mixture, the temperature 50ºC and the pressure reached 1500 psi. The resulting extract volume was about 20 mL. This extract was reduced and re-dissolved with 1mL of methanol in the case of



sediment samples, for sludge and fish samples the redissolution was with 10 mL of methanol. Then, 20 µl of these extracts were injected into the LC-LC-MS/MS system. In parallel a UltraSonic Extraction (USE) with the same solvents was used for sediment samples (M4).

For the purification of these samples, an online TurboFlowTM system was applied (M5). Consisted of two LC columns, one for purification of the sample (Cyclone) and the second for the analytical separation. The Aria™ TLX system was programmed to control the loading and eluting pump and the LC-LC conditions for the sample purification and subsequent separation of the target compounds. Furthermore, an off-line solid phase purification of the extracts of sediment and sludge samples with an SPE oasis HLB cartridges was also performed for comparison purposes (M6).

As a modification of the technique explained above, a purification online technique for the analysis of water samples was applied. During the loading step 250 µl of sample was directly injected onto the TurboFlowTM column at 1mL/min, and the analytes were retained. The other steps were similar to the others presented before (M3).

Finally, different methodologies developed for the analysis of fish were compared. M7 was based on the method adapted for the determination of EDCs using a QuEChERS procedure developed by Jamiska et al. (2013), where 0.5 g of dw sample was transferred to a 50-mL centrifuge tube and vortex for 30 s. Then a ceramic homogenizer and water was added and vortexed for 30 s. After vortexing with subsequent addition of ACN, an extraction salt was added directly and shaken for 1 min, samples were centrifuged and ACN layer was transferred to the polypropylene tube containing dSPE sorbents, vortexed for 1 min and centrifuged for 15 min at 5000 rpm. Supernatant was collected and evaporated to dryness. Final extracts were collected and redissolved in methanol/water (50:50, v/v) for the analysis by ultra-rapid-LC-MS/MS with an Ultra performance liquid chromatography (UPLC Acquity, Waters, Mildford, USA) coupled to a QTRAP® 5500 (AB SCIEX, Framingham, USA). This method was compared to the one developed by Huerta et al. for the analysis of pharmaceuticals in fish (M8).

Results

The new online methodologies (M2, M5, and M3) showed lower limits of detection than the classical approaches (M2, M5 and M3) for the determination of EDCs in environmental matrices, minimizing the matrix effects and the time of analysis. Moreover, in general the on-line methodology was capable of improving the recoveries for all the target compounds analyzed.

Focusing in water samples and comparing the two different online methodologies (M2 and M3), lower LODs and LOQs were obtained with EQuanTM methodology in the case of river water samples for all compounds, confirming that this preconcentration technique was appropriate for samples without complex matrices. For wastewater samples, the best online methodology was the TurboFlowTM approach, except for: E2 (influent), E1 (influent, effluent), TCC (influent), BPA (influent), OP1EC (effluent, influent). Table 1 showed LODs of these techniques.

For the analysis of EDCs in water samples an EQuanTM (M2) approach was applied during two campaigns. Water TurboFlowTM methodology was only applied during the sampling campaign in 2011 in waste water. Comparing M2 and M3, in general, the results were in the same range, in addition we detected about 7% more positive results in waste water (2011) due to the lower limit of detection of this technique.

Fish samples were analyzed using QuEChERS procedure, but applying the TurboFlowTM approach with lower limits of detection for important EDCs compounds such as hormones, except for E1, a new complementary results could be obtained, depending of the target compound analyzed and the species of fish. Table 1 showed LODs of these techniques.




Table 1. LODs for the determination of EDCs in wastewaters and in different species of fish

Compound M2 EQuan (ng/L) M3 TurboFlow (ng/L) QuEChERS M7 (ng/g) M5 PLE

extraction/TurboFlow purification (ng/g)

Surface

river water

Effluent water

Influent water

Surface river water

Effluent water

Influent water

Barbus graellisii

Cyprinus carpio

Silurus glanis Silurus glanis

Natural and synthetic estrogens and conjugates

Estradiol (E2) 0.037 0.59 5.4 0.61 0.62 3.5 3.09 2.77 0.34 0.36

Estrone (E1) 0.05 0.14 0.14 0.25 0.27 0.28 0.35 0.34 0.06 0.45

Estriol (E3) 0.17 2.3 3.1 0.59 0.63 0.57 3 2.88 2 0.62

Ethinylestradiol (EE2) 0.14 3.8 4.2 0.34 0.45 1.8 0.62 0.81 0.6 0.49

Diethylstilbestrol (DES) 0.043 1.2 2.7 0.57 0.72 0.84 0.01 0.02 0.03 0.015

Estrone 3-sulfate (E1-3S) 0.0038 0.21 0.35 0.054 0.054 0.12

Estriol 3-sulfate (E3-3S) 0.03 0.75 0.99 0.15 0.18 0.18

Estradiol 17-glucuronide (E2-17G) 0.46 2.9 4.2 0.58 0.61 4.3

Estrone 3-glucuronide (E1-3G) 0.056 0.96 3.1 0.2 0.24 0.57

Estriol 16-glucuronide(E3-16G) 0.059 2 7.5 0.42 0.42 0.47

Antimicrobials/Disinfectants

Triclosan (TCS) 0.17 1.5 2.1 0.39 0.45 0.46 0.27 0.3 0.25 0.22

Triclorocaraban (TCC) 0.036 0.14 0.18 0.16 0.18 0.22

Preservatives

Methylparaben (MeP) 0.2 0.59 1.5 0.23 0.25 0.27 0.04 0.04 0.005 0.064

Ethylparaben (EtP) 0.27 1.2 1.4 0.084 0.10 0.16 0.04 0.05 0.004 0.11

Propylparaben (PrP) 0.021 0.35 0.94 0.075 0.10 0.1 0.004 0.01 0.002 0.098

Benzylparaben (BeP) 0.031 0.12 1 0.15 0.2 0.37 0.01 0.02 0.003 0.027

Bisphenol A (BPA) 0.11 0.69 1.4 0.57 0.61 1.7 0.01 0.01 0.003 0.087

Alkylphenolic compounds

Octylphenol (OP) 0.14 1.6 2.9 0.41 0.44 1.1

Nonylphenol (NP) 0.013 0.3 0.71 0.44 0.55 0.59

Octylphenol monocarboxylate (OP1EC) 0.065 0.64 0.87 0.28 0.34 0.4

Nonylphenol monocarboxylate (NP1EC) 0.034 0.076 0.11 0.052 0.06 0.068

Octylphenol monoethoxylate (OP1EO) 17 20 33 37 18 27

Nonylphenol monoethoxylate (NP1EO) 62 125 187 89 105 135

Octylphenol diethoxylate (OP2EO) 0.011 0.092 0.2 0.087 0.091 0.097

Nonylphenol diethoxylate (NP2EO) 0.013 0.11 0.12 0.075 0.084 0.093

Anticorrosives

1H-Benzotriazole (BT) 0.072 0.16 0.54 0.16 0.17 0.17 0.1 0.06 0.04 0.029 Tolytriazol (TT) 0.013 0.1 0.21 0.082 0.1 0.14 0.12 0.15 0.09 0.0057 Organophosphorus flame retardants

Tris(butoxyethyl) phosphate (TBEP) 0.0024 0.053 0.082 0.041 0.045 0.071 0.06 0.45 0.02 0.0075 Tris(chloroisopropyl) phosphate (TCPP) 0.0025 0.063 0.55 0.11 0.13 0.14 0.5 0.09 0.2 0.0011 Tris(2-chloroetyhl) phosphate (TCEP) 0.034 0.098 0.36 0.084 0.091 0.35 0.1 0.25 0.13 0.0034

Acknowledgements

This work was supported by the Spanish Ministry of Economy and Competitivity through the Consolider-Ingenio 2010 CSD2009-00065 project and SGR 2009-SGR00796 of Generalitat de Catalunya. Marina Gorga acknowledges the European Social Fund and AGAUR (Generalitat de Catalunya, Spain) for their financial support through the FI pre-doctoral grant. Thermo Scientific and Merck are acknowledged for the gift of LC columns. Marina Gorga acknowledges Alícia Navarro Ortega (SCARCE project manager) for your coordination of sampling campaigns that it has made possible this study.

References

1. Petrovic M, Ginebreda A., Acuña V., et al. Combined scenarios of chemical and ecological quality under water scarcity in Mediterranean rivers. TrAC Trends in Analytical Chemistry (2011) 30(8), 1269-1278.

2. Gorga, M., Petrovic, M., Barceló, D. Multi-residue analytical method for the determination of endocrine disruptors and



related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry. J Chromatogr A 2013; 1295: 57-66

3. Jakimska A, Huerta B, Barganska Z, Kot-Wasik A, Rodriguez-Mozaz S, Barcelo D. Development of a liquid chromatography-tandem mass spectrometry procedure for determination of endocrine disrupting compounds in fish from Mediterranean rivers. J Chromatogr A 2013; 1306: 44-58.

4. Huerta B, Jakimska A, Gros M, Rodriguez-Mozaz S, Barcelo D. Analysis of multi-class pharmaceuticals in fish tissues by ultra-high-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 2013; 1288: 63-72.




A monitoring survey of pharmaceuticals in wastewater treatment plants and river water in four Iberian river basins

Victoria Osorio1, Jaume Aceña1, Sandra Pérez1 and Damià Barceló1,2

1 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain


Introduction

There are 3,936 different pharmaceutically active compounds (PhACs) approved in the worldwide market for human medicine. The majority of them enter into the aquatic environment from two main routes: the excretion by humans and the direct disposal through domestic wastewater. Despite its previous treatment in wastewater treatment plants (WWTPs), depending on the efficiency and chemical properties of the compound, PhACs are able to reach surface and ground waters. Therefore, PhACs are widespread pollutants. More than 150 PhACs have been detected in the aquatic environment at levels in the ng/L range. However, little attention has been paid to the behaviour of PhACs in surface waters.

Iberian river basins are characterized by high flow variability, which is strongly influenced by seasonal rainfall. High levels of emerging organic contaminants have been detected for instance in the Llobregat river, in which a trend of rising concentrations was paralleled by an increasing number of WWTP outlets and increasing population density when approaching the river mouth. As a result of global hydrological change, when water scarcity periods occur, water flow and dilution capacity of the river are reduced and consequently wastewater effluent constitutes large percentage of the total river flow. On the other hand, floods contribute to remobilization of pollutants from sediments. As a consequence of both events, the potential environmental risk of pollutants is expected to increase[1].

Objectives

In this context, the goals of this work were (a) to study the role of WWTPs in PhACs removal, (b) to assess the importance of WWTPs as source of contaminants in the aquatic environment, (c) to determine the occurrence of the contaminants at river basin scale and, (d) to investigate their distribution between water and solid phase. Two extensive field campaigns have been undertaken at different flow conditions (high and low-medium). Surface waters and sediments were taken in 77 sampling sites along four representative basins (Llobregat, Ebro, Júcar and Guadalquivir), together with influent and effluent sewage water from 15 WWTPs. The levels of over 70 pharmaceuticals belonging to different therapeutic groups were determined. Based on published literature about occurrence and distribution in the aquatic environment, a list of 70 prescription drugs was defined, classified by its different therapeutic activity namely, analgesics and anti-inflammatories, histamine H1 and H2 receptor antagonists, b-blockers, anti-platelet agents, treatment of asthma, anticoagulants, lipid regulators, antibiotics, diuretics, psychiatric drugs, anti-hypertensives, anti-diabetics, x-ray contrast agents and veterinary treatment.

Experimental

To investigate on the fate and distribution of the pollutants in the river basins, surface and sediment samples were analyzed in both sampling campaigns. Analysis of the pharmaceuticals was performed with a method adapted from Gros et al.[2] using a multi-residue method based on liquid chromatography coupled to mass spectrometry after solid-phase extraction. Quantification of pharmaceuticals was carried out in Multiple Reaction Monitoring (MRM) mode monitoring two transitions per analyte.

Results

Levels of PhACs were detected in the range of ng/L in surface waters, low ng/g range in sediment and



ng/L to µg/L range in wastewaters. It was observed that the highest levels PhACs were determined in the Llobregat river basin, followed by the Ebro, Guadalquivir and Júcar. The most widespread and abundant therapeutic groups in the surface water and sediment samples were analgesics and anti-inflammatories, followed by diuretics, psychiatric drugs and veterinary pharmaceuticals. Representativeness of therapeutic groups was different among the four river basins indicating patterns of consumption in the different areas of study (Figure 1).

Figure 1: Occurrence of PhACs in surface water of the four Iberian river basins

Conclusions

Concerning the elimination study of PhACs in the WWTPs, most of the compounds were detected both in influent and effluent wastewater. The elimination rates varied largely and were strongly compound-dependent but cumulative levels indicate that the water treatment did not completely eliminate the contaminants and some compounds remain in significant concentrations in the treated effluents. Considering WWTPs as emission source of PhACs in the Iberian river basins, these compounds were quantified in surface water and sediment samples in order to gain further insight of the fate and behaviour of these compounds from the emission source to the control point.

Acknowledgements

Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065). SP acknowledges the contract from the Ramón y Cajal Program of the Spanish Ministry of Economy and Competitiveness.

References

[1] V. Osorio, S. Pérez, A. Ginebreda, D. Barceló, Environmental Science and Pollution Research 19 (2012) 1013. [2] M. Gros, S. Rodríguez-Mozaz, D. Barceló, Journal of Chromatography A 1248 (2012) 104.




Sediment core analysis as a tool for reconstructing the contamination history of aquatic systems. Case study: Jamaica Bay (NY)

Pablo A. Lara-Martín1,2, Eduardo González-Mazo1, and Bruce J. Brownawell2

1 Department of Physical Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto

Real, Spain 2 School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York, United States

1. Introduction

Aquatic systems are often subjected to the influence of urban and/or industrial wastewater discharges, which may contain significant amounts of organic contaminants. In spite of their low concentration in the water column (often sub-ppb levels), these chemicals may cause damage to the ecosystem in the long term due to chronic exposure. Among them, personal care products and pharmaceutically active compounds (PPCPs) and some other emerging contaminants have been the focus of many researchers within the last decade. Most of these studies deal with the identification and distribution of these chemicals in water bodies [1,2]. Data on the presence of PPCPs in particulate matter and sediments are still scarce mainly because further analytical method development is required and the sorption capacity of many of these compounds is very low. In this sense, the present study deals with the identification, distribution and fate of PPCPs in the sedimentary column; this offers a new insight that allows reconstructing the history of the contamination of an aquatic system by these compounds.

2. Materials and methods

Sediment sampling was carried out in Jamaica Bay, located on the Southwestern shore of Long Island, NY. Six waste water treatment plants (WWTPs) discharge roughly 1.1x109 L/day biologically treated sewage, constituting by far the largest input of freshwater to the Bay. Tidal exchange of water in this estuarine embayment is restricted by the single opening to the greater New York Bight. Nine surface sediment samples were collected from stations A to I (Fig. 1). A sediment core was sampled in 2008 in the deepest area of the Bay (up to 15 m) (station B), which is characterized by high rates of sediment deposition (1-2 cm/year), as well as the highest levels of organic wastewater contaminants within Jamaica Bay in both sediments and overlying waters [2-4]. The sediment core was sectioned at 2 cm intervals, dried in an oven at 35 °C, and stored at room-temperature pending analysis. 137Cs, derived from global fallout from atmospheric testing of nuclear weapons was used for dating. 7Be, a short-lived (t1/2 = 53 days) natural radionuclide, was detected only in the surface (0-2 cm) sample indicating deposition within about a year of core collection. The bottom of the core dated to approximately 1948.

Figure 1: location of sampling stations (A-I) at Jamaica Bay (NY). Sediment cores were

collected at station B.

70 different pharmaceutically active compounds (PhACs) were analyzed in these samples, including a variety of different analgesics, antiimflammatories, antihypertensives, lipid regulators, antibiotics and



psichyatric drugs. Linear alkylbenzene sulfonate (LAS), an anionic surfactant widely used in personal care products and cleaners, was also considered, as well as polyethyleneglycols (PEGs), widely used in all kind of household products and as an excipient in medicine. The analytical protocol, modified from ref. 5, includes the extraction and purification of PPCPs in sediment samples in order to perform a later identification and quantification by liquid chromatography – tandem mass spectrometry (LC-MS-MS). Briefly, samples (1 g) are extracted by pressurized liquid extraction (PLE) using water/methanol 2:1 as solvent. Three extraction cycles (5 min each) are performed at 100ºC. Later, the extracts (25-30 mL) are evaporated and redissolved in 100 mL of HPLC water. Solid phase extraction (SPE) is carried out then, using Oasis HLB cartridges and methanol (10 mL) as eluting solvent. Recoveries are usually above 70% for most compounds, except those which are most hydrophobic (and therefore harder to be eluted, e.g., some antibiotics such as tamoxifen) or those which are too polar to be properly retained in the SPE sorbent. Limits of detection were usually below 0.1 ng/g.

3. Results and discussion

Analysis of surface samples showed that highest levels of target compounds belonged to stations A and B, up to 80 ng/g of PhACs and 9.5 mg/kg of LAS. Therefore, station B was selected to sample the sediment core. First, the vertical distribution of LAS along the sedimentary column was investigated in order to confirm the dating of the sediment core by radionuclides (Fig. 2), and also to study changes over time in the WWTP efficiencies and inputs. Sediments from the sampling area (Jamaica Bay) are characterized by very high burial rates, virtually no benthic infauna, and little biological or physical mixing, with anoxic or hypoxic conditions prevailing in the near-bottom waters that favour preservation of LAS and other potentially labile organic contaminants such as pharmaceuticals in these sediments. The vertical profile for LAS concentration indicates a first appearance of this compound in the sediment record around 1960, when it started replacing the poorly biodegradable branched alkylbenzene sulfonates (BAS) [7] (also detected in the sediment core from 1954 to 1967). Two different maxima are observed in the time history of LAS concentration corresponding to the mid-late-1980s (75 μg/g), and the mid-1960s (250 μg/g). These changes over time are attributed to upgrades in treatment performance of the local Jamaica WWTP that occurred in 1963 and 1978 [3]. The profile of LAS concentration remains fairly stable following 1978, so any changes in the concentration of any other organic contaminants are interpreted as resulting primarily from changing inputs to the WWTPs surrounding Jamaica Bay, which cover largely residential portions of Queens and Brooklyn Boroughs of New York City.

Figure 2: vertical profiles showing the distribution of radionuclides and anionic surfactants (LAS and

BAS) in sediment cores from station B.




With respect to pharmaceuticals, their concentrations are much lower (< 100 ng/g) than those for anionic surfactants (up to 250 µg/g) in the same samples, mainly as a consequence of their lower production and consumption. However, PhACs, as well as PEGs, show a growing trend over the last decades, in agreement with the continuous increase in the production and use of these chemicals (Fig. 3). Only 16 of the 70 pharmaceuticals that were analyzed could be detected. Their sediment records are consistent with first use dates for pharmaceuticals. Some examples are illustrated in Fig. 3. Thus, ibuprofen is an anti-inflammatory drug that was first sold in 1974, and it has been very popular since then, so its presence can be observed in sediments from that date until today showing an average concentration of 10 ng/g. Beta-blockers such as metoprolol and propanolol are used for hypertension treatment. Propanolol was the first beta-blocker successfully developed in the 1960s, but then it was replaced during the 1980s for more effective compounds such as metoprolol (developed in 1978). This is in agreement with the concentration profiles that we can observe for both compounds along the sediment core. Thus, concentration of propanolol increases to 3 ng/g from 1977 to 1985, and then it decreases towards the surface of the core. Moreover, metoprolol became a generic product in 2006, which improved its sales recently and can explain the exponential increase in its concentration from 5 to 35 ng/g over the last decade. This is true also for some other pharmaceuticals, such as the antibiotic clarithromycin, developed in 1991 and gone generic in 2005 (its maximum concentration was detected in the core surface, being 16 ng/g). Psychiatric drugs, such as carbamazepine or fluoxetine, which are slowly biodegraded in the water column, can be also detected in sediments in spite of their high solubility. Carbamazepine was released in 1974 and it is still widely used in epilepsy treatment (average concentration in sediment is 2 ng/g), whereas fluoxetine (Prozac) is among the most popular antidepressants. It went generic in 2001 and, although their sales have decreased over the last decade, it is still widely used despite the availability of newer agents (its concentration is above 10 ng/g in recent sediments).

Figure 3: concentration vertical profiles showing the distribution of PEGs and pharmaceuticals in

sediment cores from station B.



4. Conclusions

Surfactants and some pharmaceuticals undergo sorption onto sediments and can be preserved under anoxic conditions in the sedimentary column. In this study, 16 of 70 pharmaceuticals were detected in sewage impacted marine sediments, reaching concentrations up to 97 ng/g. Concentrations for LAS and PEG were significantly higher (> 100 µg/g) due to their more extensive use. Analyzing PPCPs in dated sediment cores collected from sewage polluted areas allows obtaining historical records of these contaminants. This can be considered as a powerful tool for monitoring the exposure of aquatic systems to PPCPs during several decades, an also reflects any changes that may occur in their use and consumption by nearby populations.

Acknowledgements

The authors thank the funds provided by fellowships from the Marie Curie FP7 Program (ref. 228616, BADEPAS) and from the Spanish Ministry of Science and Education / Fulbright Commission

References

[1] Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT. 2002. Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. Streams, 1999-2000: a national reconnaissance. Environ Sci Technol 36: 1202-1211.

[2] Benotti MJ, Bronwawell BJ. 2007. Distributions of pharmaceuticals in an urban estuary during both dry- and wet-weather conditions. Environ Sci Technol 41: 5795-5802.

[3] Ferguson PL, Bopp RF, Chillrud SN, Aller RC, Brownawell BJ. 2003. Biogeochemistry of nonylphenol ethoxylates in urban estuarine sediments. Environ Sci Technol 37: 3499-3506.

[4] Lara-Martín PA, Li X, Bopp RF, Brownawell BJ. 2010. Occurrence of alkyltrimethylammonium compounds in urban estuarine sediments: behentrimonium as a new emerging contaminant. Environ Sci Technol 44: 7569-7575.

[5] Jelic A, Petrovic M, Barceló D. 2009. Multi-residue method for trace level determination of pharmaceuticals in solid samples using pressurized liquid extraction followed by liquid chromatography/quadrupole linear ion trap mass spectrometry. Talanta 80: 363-371.




Chemicals of emerging concern in Iberian rivers. Analysis of sources, environmental exposure and risk

Mira Petrovic1,2, Maja Kuzmanovic3, Damia Barcelo1,3 and Antoni Ginebreda3


2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 3 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain

Introduction

The identification and determination of emerging contaminants in the aquatic environment has seen a dramatic progress in recent years along with a rapid development of new analytical techniques. Several extensive national and multinational monitoring programs have been launched in the last few years in order to provide comprehensive reconnaissance of the occurrence of various contaminants, with a special emphasis on pharmaceuticals, hormones and other polar organic wastewater contaminants. Within the project SCARCE an extensive sampling of water, sediment and biota from four Iberian river basins has been undertaken in two monitoring campaigns (2010 and 2011). A total of 77 samples of water, 75 sediments, and 63 pools of fish were collected for chemical characterization. At selected locations in the Llobregat, Ebro, Jucar and Guadalquivir River Basins the levels of over 300 compounds belonging to different groups of priority (polycyclic aromatic hydrocarbons, organochlorine pesticides, and alkylphenols), and emerging contaminants (pharmaceuticals, drugs of abuse, personal care products, polar pesticides, perfluorinated compounds, endocrine disrupting compounds, halogenated flame retardants, and nanoparticles) have been determined using advanced analytical techniques based on gas chromatography- tandem mass spectrometry and liquid chromatography- tandem and hybrid mass spectrometry.

This work presents a synthesis and critical evaluation of levels for 244 organic emerging contaminants found in water phase and provides a basis for assessing the risk of exposure to these contaminants. In order to get better insight into the spatial distribution of contaminants and to pinpoint hot spots impacted by human and agricultural waste sources, a site-specific Geographical Information Systems (GIS) model was created, combining sampling site locations and analytical data from each of those sampling points. ArcMap Software, as the main component of Esri's ArcGIS suite of geospatial processing programs has been used to create the maps which show the occurrence of organic pollutants along 77 sites located in 4 Iberian river basins measured in SCARCE project, well as their risk to ecosystem at given locations.

Results

156 of the 244 targeted organic chemicals were detected in at least one water sample. The most frequently detected chemicals (all detected at more than 80% sampling points) were contaminants of industrial origin phosphate flame retardants and anticorrosive agents benzotriazols, followed by personal care products parabens, degradation products of industrial detergents alkyphenol exthoxylates, some pharmaceuticals such as azitromycin, valsartan, gemfibrozil and desloratidine, and pesticides chlorphyriphos and diazinon, as shown in Fig. 1.



Fig 1. Frequency of detection (at all sampling points)

Typically >50 compounds were detected per site indicating that the targeted chemicals generally occur in mixtures in the environment and likely originate from a variety of animal and human uses and waste sources.

Fig. 2. Compounds detected at the highest average concentrations




In terms of concentrations the compounds found at the highest average concentrations were: nonylphenol monocarboxylate (NP1EC), tolyltriazole (TT), tris(chloroisopropyl)phosphate (TCPP) found at average concentrations above 100 ng/L, followed by other 5 contaminants found at average concentrations higher than 50 ng/L: perfluorobutanoate (PFBA), 1H-benzotriazole, tris(butoxyethyl) phosphate (TBEP), diuretic hydrocholorthiazide and imazalil, a fungicide widely used in agriculture, particularly in the growing of citrus fruits (see Fig. 2).

Regarding the spatial distribution of organic emerging contaminants, the Llobregat river was found to be the most contaminated river basin, showing clear and significant increase in concentrations downstream the river being the sites near the mouth of the river the ones with the highest contaminants load, as shown in Fig. 3. In the Ebro river basin several hot spots can be identified, such as sited downstream of main cities Zaragoza, Pamplona and Vitoria where effluents from wastewater treatment plant are discharged into the river or its smaller tributaries. Of four studied river basin, Jucar showed to be the least contaminated.

Fig. 3. Spatial distribution of total organic contaminants

Risk posed by chemical pollutants, expressed in terms of hazard quotient (HQ), by referring concentrations to acute EC50 (Daphnia, fish, algae) is also estimated. This allows to identifying both hot spots and priority compounds. Fig. 4. shows spatial distribution of sampling points and corresponding total HQ for algae distributed among four main group of contaminants (pesticides, pharmaceuticals,



endocrine disrupters and related compounds and perfluorinated compounds). At majority of sampling sites pesticides contribute to the major extent to the overall HQ, with the exception of lower Llobregat where significant contribution from perfluorinated compound and smaller from pharmaceuticals is observed and several points at Guadalquivir with significant contribution from EDCs of industrial origin (such as alkylphenols).

Fig. 4. Hot spots: Sampling sites with highest HQ

In terms of individual compounds posing the highest risk several contaminants were identified showing HQ>1 (for algae) such as prochloraz, an imidazole fungicide, herbicide diuron and triclosan an antibacterial and antifungal agent.

In summary, this study confirmed the presence of complex mixtures of unregulated contaminants of various origins in Iberian rivers, thus raising concern about their potential interactive effects. Acknowldegment

Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065)




Occurrence and in-stream attenuation of wastewater derived pharmaceuticals in Iberian rivers

Vicenç Acuña1, Daniel von Schiller1, María Jesús García-Galán1, Sara Rodriguez-Mozaz1, Lluís

Corominas1, Ignasi Aymerich1, Mira Petrovic1,2, Manel Poch1,3, Damià Barceló1,4 and Sergi Sabater1,5


2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 3Laboratory of Chemical and Environmental Engineering (LEQUIA). University of Girona, Girona, Spain

4 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 5 Institute of Aquatic Ecology, University of Girona, Girona, Spain

A multitude of pharmaceuticals enter surface waters mainly via discharges of wastewater treatment plants (WWTPs), and many rise environmental and health concerns (Schwarzenbach et al. 2006, Gros et al. 2007, Pal et al. 2010). Chemical fate models predict the pharmaceutical concentrations along river networks using estimates of mass loading, dilution and in-stream attenuation (Huset et al. 2008, Alder et al. 2010). However, current comprehension of the attenuation rates remains a limiting factor for the development and calibration of predictive models.

We assessed in-stream attenuation of 75 pharmaceuticals in 4 river segments affected by WWTPs and differing in environmental factors, aiming to characterize the effects of both physicochemical properties of pharmaceuticals and local environmental factors on the attenuation rates. The study sites encompassed considerable ranges in terms of hydrogeomorphological and physicochemical characteristics (Table 1). To estimate the in-stream attenuation rates of nutrients and pharmaceuticals, we calculated the mass-transfer coefficient (vf) for each compound at each site following the intrinsic tracers approach (O’Conner et al. 1988, Writer et al. 2011).The vf is a scale-free parameter accounting for discharge and water depth differences among sites which has units of length / time and may be thought of as the theoretical velocity at which a solute moves towards the location of immobilization (i.e., the water / sediment interface; Stream Solute Workshop 1990).

Table 1. River segments characteristics and impact of the WWTP on them, as ratios of flow and load of NH4

+ between the WWTP effluent (e) and the upstream river station (u). Note that means and standard deviations are based on 4 locations (d1-d4).



Our results revealed that in-stream attenuation was highly variable among pharmaceuticals and river segments (Figure 1). The variability among vf values might be attributed to both the physicochemical properties of the pharmaceutical compounds and the local environmental variables. The first was reflected in differences in the mean values among pharmaceutical as well as on the differences among river segments, and the second in the variability of vf among river segments for each pharmaceutical (Figure 1).

Figure 1: Mean and standard deviations of the mass transfer coefficients (vf) of 34 pharmaceuticals plus

TDN, TDP and DOC (n = 4, study river segments).

Thus, differences in the mean values of vf among pharmaceuticals highlight the relevance of their physicochemical properties on their in-stream attenuation rates, but none of the considered physicochemical properties of pharmaceuticals proved to be relevant in determining the mean attenuation rates. Instead, log Kow influenced the variability of rates among river segments (Figure 2). A plausible explanation for such a behaviour is that in the case of hydrophobic compounds (with higher log Kow) sorption to suspended particles and sediment is a dominant process leading to in-stream attenuation (reduction of concentration in the aqueous phase along the water segment) and as such those compounds are less exposed to other biotic (biodegradation) and abiotic (photolysis, volatilization) transformation processes and therefore become the least affected by the variation of environmental conditions. Despite the low number of river segments included in this study, the environmental differences among sites introduced large variability in vf values of the pharmaceuticals. Thus, the differences between sites in vf of pharmaceuticals with low to mid log Kow were mainly driven by phosphorus indicating a coupling to phosphorus attenuation.

Following results from our first survey, we more thoroughly investigated the in-stream attenuation of a selection of pharmaceuticals in one of the river segments (Puigcerdà) using a more sophisticated mechanistic-modelling approach that integrates both the WWTP and the receiving river. Results from this study allowed us to better comprehend the linkages among biogeochemical and attenuation processes as well as the role of the mixing zone in water purification.

Together, our results urge scientist to consider in-stream attenuation in rivers driven by processes other




than dilution, which should be considered in models when aiming to predict loads and concentrations of pharmaceuticals.

Figure 1: Linear regression between coefficient of variation of the mass transfer coefficients and log Kow.

Dotted lines indicate 95% confidence intervals. Acknowledgements

This research was supported by a Marie Curie European Reintegration Grant (PERG07-GA-409 2010-259219) and by a Marie Curie Career Integration Grant (PCIG9-GA-2011-293535) within the 7th European Community Framework Programme, as well as by the Spanish Ministry of Economy and Competitiveness through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and ENDERUS (CTM-2009-13018), and the postdoctoral grants “Juan de la Cierva” (jci-2009-05604 and jci-2010-06397), and by the European Union through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965). Prof. Barceló acknowledges King Saud University for his visiting professorship.

References

Schwarzenbach, R. P., Escher, B. I., Fenner, K., Hofstetter, T. B., Johnson, A.,von Gunten, U. and Wehrli, B. The challenge of micropollutants in aquatic systems. Science (2006), 313, 1072–1077.

Gros, M., Petrović, M. and Barceló, D. Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro basin (Northeast Spain). Environmental toxicology and chemistry (2007), 26, 1553–1562.

Pal, A., Gin, K. Y.-H., Lin, A. Y.-C. and Reinhard, M. Impacts of emerging organic 436 contaminants on freshwater resources: review of recent occurrences, sources, fate and effects. The Science of the Total Environment (2010), 408, 6062–6069.

Huset, C. A., Chiaia, A. C., Barofsky, D. F., Jonkers, N., Kohler, H.-P. E., Ort, C., Giger, D. W. and Field, J. A. Occurrence and mass flows of fluorochemicals in the Glatt Valley watershed, Switzerland. Environmental Science & Technology (2008), 42, 6369–6377.

Alder, A. C., Schaffner, C., Majewsky, M., Klasmeier, J. and Fenner, K. Fate of betablocker human pharmaceuticals in surface water: comparison of measured and simulated concentrations in the Glatt Valley Watershed, Switzerland. Water Research (2010), 44, 936–948.

Writer, J. H., Keefe, S. K., Ryan, J. N., Ferrer, I., Thurman, M. E. and Barber, L. B. Methods for evaluating in-stream attenuation of trace organic compounds. Applied Geochemistry (2011), 26, 344–345.

O’Conner, D. J. Models of sorptive toxic substances in freshwater systems. I. Basic equations. Journal of Environmental Engineering (1988), 114, 507–532.

Stream Solute Workshop. Concepts and methods for assessing solute dynamics in stream ecosystems. Journal of the North American Benthological Society (1990), 9, 95–119.



Effects of food limitation and pharmaceuticals compounds on the larval development of a marine invertebrate

Enrique González-Ortegón1, Julián Blasco2, Lewis LeVay1 and Luis Giménez1

1 School of Ocean Sciences, Bangor University, Menai Bridge, UK

2 Instituto de Ciencias Marinas de Andalucía, CSIC, Puerto Real, Spain

We studied the combined effects of pharmaceutical compounds and food limitation on growth, development and body mass of larval stages of the marine shrimp Palaemon serratus. Effects of emergent compounds on growth and development of early life stages may be stronger when organisms are under some additional stress (González-Ortegón et al 2013). Coastal marine organisms such as the marine shrimp Palaemon serratus develop in a heterogeneous environment characterised by variations in food conditions (Mann & Lazier 2006). Under food limited conditions larvae of this marine species developed through an increased number of stages, especially in warmer waters, resulting in increased duration of development (González-Ortegón and Giménez 2013).

For practical reasons, investigations of pollution effects on larvae are conducted without taking into account environmental variability. However, multiple-stressor approaches are necessary to study and model the effect of emergent compounds on larvae of marine coastal species. Previous results on larvae of Palaemon serratus under different combinations of temperature and salinity conditions demonstrate that the effects on survival and larval growth were compound-specific and depended on salinity (González-Ortegón et al 2013). Following the multiple-stressor approach, we now studied the effect of three common pharmaceuticals (Diclofenac, Clofibric Acid and Clotrimazole) on larval development under food limitation. We hypothesised that the previous effects of these pharmaceuticals on larval survival, growth and development should be magnified under food limited conditions.

The pharmaceuticals compounds tested were the anti-inflammatory and analgesic Diclofenac Sodium (DS), the lipid regulator Clofibric Acid (CA) and the fungicide Clotrimazole (CLZ). The larvae were exposed to concentrations 2 times higher than found in natural habitats (validated concentrations: DS: 70 µg/l, CA: 40 µg/l and CLZ: 0.07 µg/l) and also concentrations 20 times higher than those found in nature (700, 400 and 4 µg/l, respectively). Larvae were reared at 24˚C and full salinity seawater (32 PSU). ). Freshly hatched Artemia sp. nauplii was added and removed with the culture water after a period of 4 h (food limited condition) or 24 hours (permanent access to prey).

Clotrimazole had toxic effect at lower concentrations than the others two compounds. Survival varied between 56 and 96% and was reduced by 30% under the combined effect of food limitation and all pharmaceuticals treatments (exception: Clofibric Acid at low concentration). The duration of larval development and number of instars required to reach the juvenile stage was affected by feeding condition. While food limitation doubled the larval duration of development, the pharmaceuticals did not have any significant effect. By contrast, the number of stages tended be fewer in larvae exposed to all tested pharmaceuticals especially in those growing under food limitation. Significant reductions (31%) in the number of stages were found when larvae were exposed to Clotrimazole at high concentration and to Clofibric Acid at high concentration under food limitation. The reduction in the number of stages without any significant variation in the developmental time in larvae exposed to Clotrimazole can be explained by an increment in the intermoult duration. Growth rate was reduced by Clotrimazole at high concentrations. However, the significant increase in the intermoult duration under the exposure of Clotrimazole with respect the rest of treatments explained why juvenile body mass was not affected.




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In conclusion, the study identifies the toxic effects of Clotrimazole in the marine environment and shows that the effects of emergent compounds on larval survival appear to be stronger under food limitation.

Acknowledgements

This work was carried out while E. González-Ortegón was in the tenure of a Marie Curie Pstdoctoral Fellowship from the European Comission.Furhter financial support was provided by SCARCE (Consolider-Ingenio 2010 CSD2009-00065).

References

González-Ortegón, E., Blasco, J., Le Vay, L. and Giménez, L. A multiple stressor approach to study the toxicity and sublethal effects of pharmaceutical compounds on the larval development of a marine invertebrate, J. Hazard. Mater. (2013), http://dx.doi.org/10.1016/j.jhazmat.2013.09.041

González-Ortegón, E. and Giménez, L Environmentally-Mediated Phenotypic Links And Performance In Larvae of a Marine Invertebrate, Marine Ecology Progress Series (submitted).

Mann, K.H. and Lazier, J.R.N. Dynamics of Marine Ecosystems: Biological–Physical Interactions in the Oceans, (2006) Blackwell Publishing.




Preliminary results of effects of pharmaceuticals on fresh water organisms

Gabriela V. Aguirre-Martínez1,2,4, C. Okello1,3, María José Salamanca1, C. Garrido2, T.B.

Henry4,5,6, Tomás A. Del Valls1 and María Laura Martín-Díaz1,2

1 Cátedra UNESCO/UNITWIN/WiCop. Facultad Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real,

Cádiz, Spain 2 Andalusian Center of Marine Science and Technology (CACYTMAR), Puerto Real. Cádiz. Spain

3 Integrated Geoscience Research Group (IGRG), Interdepartmental Centre for Environmental Sciences Research (CIRSA), University of Bologna, Ravenna, Italy

4 School of Biomedical and Biological Sciences/Marine Institute, University of Plymouth, Plymouth, United Kingdom 5 Center for Environmental Biotechnology, University of Tennessee, Knoxville, USA

6 Department of Forestry, Wildlife and Fisheries, University of Tennessee, Knoxville, USA

Pharmaceuticals are designed with the intention of performing a biological effect to target organisms (Henschel et al., 1997), a concept that cannot be ignored on the fate and effect of these compounds towards non-target organisms in the environment that continue to be exposed (Fent et al., 2006). The continuous entry of pharmaceuticals into the aquatic media via sewage treatment plants (STP) might cause adverse effects to non-target micro and macro organisms from different taxa. The aim of this research was to evaluate the effect of six drugs of common occurrence in STPs including caffeine (CAF), ibuprofen (IBU), carbamazepine (CBZ), novobiocin (NOV), methotrexate (MTX) and tamoxifen (TMX) on freshwater biota. The toxicity of these compounds were examined in the laboratory to assess acute and chronic toxicity using as bioindicators the freshwater microalgae Selenastrum capricornotum (Clorophyta), the clam Corbicula fluminea (Mollusca), and the fish Danio rerio (Chordata) in order to assess potential sublethal responses after short and long-term exposure to different concentrations of these drugs (environmental and no-environmental concentrations), including growth inhibition in microalgae, lysosomal membrane stability (LMS) measured in clams and cyp1a gene expression in zebrafish larvae.

Growth inhibition test using S. capricornutum was performed following the methodology described by Garrido et al. (2008). Microalgae was exposed to pharmaceutical concentrations of 0.000001, 0.00005, 0.00001, 0.00005, 0.0005, 0.001, 0.005, 0.15, 0.05, 0.5, 5, 50, 100 and 500 mg·L-1. The experiment was perfomed in triplicate under laboratory conditions. The optical density at a width length of 690 nm was checked at 0, 24, 48, 72, 96, 120, 144, 168 and 240 hour marks to measure the absorbance signifying growth. LMS was analyzed in clams heamolymph after 21 days of exposure in laboratory controled conditions to CAF (0.1, 5, 15, 50 µg·L-1), IBU (0.1, 5, 10, 50 µg·L-1), CBZ, NOV and MTX (0.1, 1, 10, 50 µg·L-1), using the methodology described by Martín-Díaz et al.,(2008). LMS was evaluated using the neutral red retention time assay (NRRA) following the methodology reported in detail by Martínez-Gómez et al. (2008) and adapted to the species used in this study. Gene expression analysis was performed in zebrafish larvae from age 72 to 168 hour post fertilization. Larvae was exposed to CAF, IBU, CBZ (0.05 and 5 μM) and TMX (0.003 and 0.3 μM) during 96 h in triplicate. Total RNA was extracted from 30-35 larvae per beaker following q-RT-PCR gene expression analysis (Reinardy et al., 2013). The relative fold change in cyp1a expression was calculated following Livak and Schmittgen (2001).

Results indicated that growth rate of S. capricornutum (Fig. 1) was barely affected by CBZ, IBU, NOV,CAF, TMX and MTX at environmental concentrations.However, CAF at 500 mg·L-1 and MTX at 100 and 500 mg·L-1 affected significantly microalgal growth (p < 0.01). Significant inhibition was also observed when S. Carpicornotum was exposed to TMX at 50, 100 and 500 mg·L-1 (p < 0.01) being this drug the most toxic tested. Nevertheless the concentration that provoked an adverse effect on growth rate on this species of microalgae are not likely to occur in the environment. The EC50 calculated is indicated in table 1. Results of LMS are shown in figure 2. No diferences were observed between control (120 min)



and solvent control DMSO (115 min). Environmental concentrations of CAF, IBU, NOV, CBZ and TMX reduced significantly the NRRT compared with controls and DMSO treatment. At the end of 21 days of the experiment LMS in C. fluminea was reduced up to 42 % when exposed to 50 μg L-1 of CAF; 53 % when exposed to 50 μg L-1 of IBU; 58,3 % when exposed to CBZ at 10 and 50 μg L-1; 55 % when exposed to 0.1 and 10 μg L-1of NOV and 65 % when exposed to 1 μg L-1 of TAM. In addittion, clams exposed to CBZ and TMX at 1,10 and 50 μg·L-1 were considered to present a diminished health status (retention time < 45 min). Regarding zebrafish larvae exposed to pharmaceuticals (Fig. 3), it was observed a significant down-regulation of cyp1a gene expression when larvae were exposed to CAF, CBZ, and IBU at environmental range (0.05 μM) and at higher concentration range (5 μM) compared to controls organisms (p < 0.05)(Fig. 2). cyp1a gene expression was also significantly down regulated in zebrafish exposed to TMX at 0.003 and 0.03 μM.

To conclude, environmental concentrations of selected pharmaceuticals are able to excert adverse effect in C. fluminea and D. rerio larvae. On the other hand, only high concentrations of pharmaceuticals in the range of mg·L-1 had an effect in S. capricornotum growth rate. Furthermore endpoints applied in this study showed the necessity of using more sensitive responses such as LMS and gene expression analysis, when assessing risk of pharmaceuticals in freshwater environments, since endpoints applied in current guidelines such as growth inhibition may not be suitable.

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Figure 1: Growth inhibition of Selenastum Capricornotum exposed 240 h to selected drugs.




Table 1. EC50 of S. Caprocornutum exposed to selected drugs. (nc= no calculated)

Pharmaceutical EC 50

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tamoxifen (TMX) and ibuprofen (IBU) at a low and high environmental relevant concentration. Asterisks indicate significant differences with control (n = 2; p < 0.05).

Acknowledgements

This work was conducted under the framework of the project P09-RNM-5136 (Government of Andalusia, Spain),. Gabriela Aguirre-Martínez would like to thank the financial support from BECAS CHILE (Government of Chile) and Junta de Andalucia (Govenrment of Andalucia Spain)

References

Fent, K., Weston, A.A., Caminada, D. Ecotoxicology of human pharmaceuticals, Aquatic Toxicology, (2006), 122-159.

Garrido-Perez, M. C., Perales-VargasMachuca, J. A., Nebot-Sanz, E. & Sales-Marquez, D. Effect of the test media and toxicity of LAS on the growth of Isochrysis galbana, Ecotoxicology, (2008), 17 (8), 738-746.

Henschel, K.,P.,. Wenzel, A., Diedrich, M., Fliedner, A. Environmental Hazard Assessment of Pharmaceuticals. Regulatory Toxicology and Pharmacology, (1997), 25, 220–225.

Livak, K.J., Schmittgen, T.D. Analysis of relative gene expression data using real-timequantitative PCR and the 2(T) (−Delta Delta C) method. Methods, (2001, )25, 402–408.

Martín-Díaz M.L., Jiménez-Tenorio N., Sales D., DelValls T.A. Accumulation and histopathological damage in the clam Ruditapes philippinarum and the crab Carcinus maenas to assess sediment toxicity in Spanish ports. Chemosphere, (2008) 71, 1916–1927

Martínez-Gómez, C., Benedicto, J., Campilloa, J.A. and Moore M. Application and evaluation of the neutral red retention (NRR) assay for lysosomal stability in mussel populations along the Iberian Mediterranean coast. Journal of Environmental Monitoring, (2008), 10, 490-499.

Reinardy, H.C., Scarlett, A.G., Henry, T.B., West, C. E., Hewitt, L.M., Frank, R.A., Rowland, S.J. Aromatic Naphthenic Acids in Oil Sands Process-Affected Water, Fully Resolved by GCxGC-MS, Weakly Induce the Gene for Vitellogenin Production in Zebrafish (Danio rerio) Larvae. Environmental Science and Technology, (2013),47 (12), 6614–6620




Assessment of the water purification ecosystem service regarding in-stream pharmaceutical residues: exploring the GREAT-ER model

parameters based on data uncertainty

Laurie Boithias1, Rafael Marcé1, Vicenç Acuña1, Joana Aldekoa2, Vicky Osorio3, Mira Petrović1,4, Felix Francés2, Antoni Ginebreda3 and Sergi Sabater1,5

1 Catalan Institute for Water Research (ICRA), Girona, Spain 2 Universitat Politècnica de València, Valencia, Spain

3 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 4 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

5 Institute of Aquatic Ecology, University of Girona, Girona, Spain

Introduction

The attenuation of pharmaceutical residues contamination in the aquatic environment depends on various complementary processes such as dilution, sorption to sediments, and degradation (i.e. photodegradation and biodegradation). One of the environmental parameters driving the attenuation of pharmaceutical contamination is therefore water flow (Petrović et al., 2011). Water scarcity thus poses not only a water quantity hazard (Boithias et al., 2013), but also a water quality risk, as contaminants become more concentrated. The removal of pharmaceutical residues within waste water treatment plants (WWTP) (Gros et al., 2010, 2007; Jelic et al., 2012, 2011; Radjenović et al., 2009, 2007) and the assessment of the risk posed by pharmaceutical residues in rivers (e.g. Ginebreda et al., 2014, 2010) are already extensively documented. Very little literature exists that describes the transport and the fate of pharmaceuticals in surface waters and river networks (Aldekoa et al., 2013; Osorio et al., 2012). Consequently, little is known about the ability of aquatic ecosystem to provide the water purification ecosystem service which concerns to pharmaceutical residues removal, included the impact of water scarcity. The objective of this preliminary study is to assess the ability of the steady-state spatially explicit GREAT-ER model (Boeije and Koormann, 2003) to simulate the concentration of 5 ubiquitous pharmaceutical compounds (ketoprofen, diclofenac, carbamazepine, naproxen and acetaminophen) throughout the Llobregat basin in two contrasted hydrological conditions. Using an uncertainty analysis approach, we evaluated the ability of the GREAT-ER model when using a 3-parameters model (WWTP and river removal rates, annual emissions).

Material and method

Study area

The Llobregat River is located in NE Spain, draining an area of 4948 km2. Altitude ranges from 1260 m at its source in the Pyrenees to 0 m at its mouth in the Mediterranean Sea after a 156 km course. Two main tributaries join the Llobregat: the Cardener and the Anoia Rivers (Fig. 1). Mean annual precipitation is 3330 hm3, and mean annual discharge is 693 hm3, the mean discharge at the catchment outlet being 19 m3 s-1. Throughout the basin, the grey water of 59 waste water treatment plants (WWTP) flow into the river network, together with the effluents of several industrial plants such as potash-mining activities in the Cardener River (137 hm3 yr-1, 92% coming from the WWTP), therefore sometimes constituting a significant part of the river flow. The lower course flows through the densely populated area of Barcelona (>3 million inhabitants), which human-use water is supplied from diverting water from the Cardener and the Llobregat upstream river courses. To ensure water supply during low flow periods three dams were built in the upstream sections of the Cardener and the Llobregat rivers (Fig. 1). About 30% of the mean annual flow in the Llobregat basin is diverted for human uses (Aldekoa et al., 2013; Ginebreda et al., 2010).



Fig. 1 Study area (from Aldekoa et al., 2013)

Discharge and pharmaceutical data

Two extensive field campaigns were carried out at different flow conditions in September 2010 and 2011 (with high and low-medium river flow respectively). Daily flow discharges were gathered from the Catalan Water Agency for 14 gauging stations throughout the basin and for entry and exit flows from the three reservoirs in the catchment, and for each campaign. Water flow values were calculated for every river stretch through a water balance considering measured flow levels in 14 points, discharged water from WWTPs, extracted water for supplying drinking or irrigation water, and the natural water contribution. Velocity values in every stretch were calculated relating water flow, slope and drained area with Manning empirical formula using geomorphologic information supplied by the Catalan Water Agency and from Aguilera et al. (2012). Samples were collected at the 14 gauged sites throughout the basin. Water sampling and pharmaceutical laboratory analysis were performed as described by Aldekoa et al. (2013). In addition, pharmaceutical data were gathered from Gros et al. (2010, 2007) and Jelic et al. (2011) to calculate both the compound removal efficiency in WWTP and the annual emission per inhabitant (percentiles and average; Table 1).

Table 1 Uncertainty ranges of ketoprofen, diclofenac, carbamazepine, naproxen and acetaminophen annual emission and WWTP removal rate (REwwtp) in North-Eastern Spain; literature uncertainty range

of the removal rates of the 5 molecules in aquatic environment (REriver)

Emission (kg cap-1 yr-1) REwwtp (%) REriver (h-1) Percentiles Percentiles Percentiles 0.025 0.5 0.975 mean n 0.025 0.5 0.975 mean n 0.025 0.5 0.975 mean n Ketoprofen 0E+00 8E-05 3E-04 1E-04 40 6 84 100 78 36 3E-04 7E-02 1E+00 3E-01 11

Diclofenac 5E-06 6E-05 2E-04 7E-05 40 5 51 100 54 31 1E-03 5E-02 3E+00 4E-01 20

Carbamazepine 1E-06 1E-05 1E-04 2E-05 40 1 25 84 31 20 6E-05 4E-04 6E-02 10E-03 15

Naproxen 4E-05 3E-04 9E-04 3E-04 40 35 91 100 83 38 1E-03 5E-03 3E+00 5E-01 12

Acetaminophen 2E-04 2E-03 6E-03 2E-03 7 100 100 100 100 6 3E-03 2E-02 6E-02 2E-02 10




Modelling approach for pharmaceutical fate modelling

GREAT-ER embeds the spatially explicit flow data previously described. For this exploratory study, we selected the model “0” of GREAT-ER, where only 3 parameters are involved: the annual emission, and the WWTP and river rates of pharmaceutical removal (respectively REwwtp and REriver).

Uncertainty analysis and calibration

The uncertainty analysis was performed by propagating the minimal and the maximal values from the ranges reported in Table 1 for the 5 compounds’ annual emission, REwwtp and REriver. The minimal value was calculated as the 0.025 percentile whereas the maximal value was calculated as the 0.975 percentile. The Root Mean Square Error (RMSE) was calculated to quantify the goodness-of-fit between simulated and observed data at the 14 sampling sites.

Results and discussion

The range of values of the simulated concentrations at the 14 gauging sites varies depending on the inputs (Fig. 2 and Table 2). The RMSE values highlight that in general for the 5 compounds, the emission value probably ranges between the median (similar to mean except for naproxen) and the 0.025 percentile. RMSE differences also appear between 2010 and 2011. As we assume that emission doesn’t change depending on the climate conditions, the possible calibration levers are REwwtp and REriver whose efficiencies change with hydraulic retention time (HRT) in WWTP and rivers (Sui et al., 2011). The RMSE is not sensitive to REwwtp because REwwtp is expressed as a fraction, and changes are therefore linear.

Table 2 Root Mean Square Error (RMSE, in ng L-1) of the simulated concentrations of ketoprofen, diclofenac, carbamazepine, naproxen and acetaminophen compared to observed concentrations. Grey

boxes corresponds either to Emission = 0 or to REwwtp = 100%: outputs are null in both cases.

KETOPROFEN DICLOFENAC CARBAMAZEPINE NAPROXEN ACETAMINOPHENCase # Emission RE wwtp RE river 2010 2011 2010 2011 2010 2011 2010 2011 2010 2011

0.5 perc. 0.5 perc. 0.5 perc. 16 122 16 84 14 29 155 616 70 3

1 0.025 perc. 0.025 perc.

0.025 perc. 48 44 38 74 856 1 11 61 120 599

2 0.025 perc. 0.025 perc.

0.975 perc. 48 44 41 82 560 1 26 34 80 408

3 0.025 perc. 0.975 perc.

0.025 perc. 48 44 41 83 856 1 27 36 70 1

4 0.025 perc. 0.975 perc.

0.975 perc. 48 44 41 83 560 1 27 36 70 1

5 0.975 perc. 0.025 perc.

0.025 perc. 208 44 122 516 64 303 642 34 67 15

6 0.975 perc. 0.025 perc.

0.975 perc. 49 44 26 84 35 198 71 36 68 10

7 0.975 perc. 0.975 perc.

0.025 perc. 48 44 41 83 64 303 27 36 70 1

8 0.975 perc. 0.975 perc.

0.975 perc. 48 44 41 83 35 198 27 36 70 1

MEAN MEAN MEAN 24 127 24 91 9 47 90 36 69 4



Fig. 2 Simulated and observed pharmaceutical concentrations (ng L-1) in 2010 and 2011 campaigns for

the cases described in Table 2. Limits Of Quantifications (LOQ) are also reported.

Concluding remarks and future work

This preliminary study showed that it is relevant to parameterize the GREAT-ER “0” model using the median values of gathered parameter data for most of the compounds. The next step will be to estimate the weight of both the WWTP and the aquatic ecosystem in attenuating the pharmaceutical concentrations, depending on hydrological conditions. Therefore, a sensitivity analysis will be performed. To generalize the conclusion, the study will also include several additional pharmaceutical compounds. Acknowledgments

This project was funded by the Spanish Ministry of Science and Innovation (Consolider-Ingenio 2010 CSD2009-00065), and by a Marie Curie European Reintegration Grant (PERG07-GA-2010-259219) within the 7th European Community Framework Programme.

References Aguilera, R., Sabater, S., Marcé, R., 2012. In-Stream Nutrient Flux and Retention in Relation to Land Use in the Llobregat River Basin, in: Sabater, S., Ginebreda, A., Barceló, D. (Eds.), The Llobregat. Springer Berlin Heidelberg, Berlin, Heidelberg, pp. 69–92.

Aldekoa, J., Medici, C., Osorio, V., Pérez, S., Marcé, R., Barceló, D., Francés, F., 2013. Modelling the emerging pollutant diclofenac with the GREAT-ER model: Application to the Llobregat River Basin. J. Hazard. Mater.

Boeije, G., Koormann, F., 2003. GREAT-ER II�: Chemical Fate Models. 39p.

Boithias, L., Acuña, V., Vergoñós, L., Ziv, G., Marcé, R., Sabater, S., 2013. Assessment of the water supply-demand ratios in a




Mediterranean basin under different global change scenarios and mitigation alternatives. Sci. Total Environ. In Press.

Ginebreda, A., Kuzmanovic, M., Guasch, H., de Alda, M.L., López-Doval, J.C., Muñoz, I., Ricart, M., Romaní, A.M., Sabater, S., Barceló, D., 2014. Assessment of multi-chemical pollution in aquatic ecosystems using toxic units: Compound prioritization, mixture characterization and relationships with biological descriptors. Sci. Total Environ. 468-469, 715–723.

Ginebreda, A., Muñoz, I., de Alda, M.L., Brix, R., López-Doval, J., Barceló, D., 2010. Environmental risk assessment of pharmaceuticals in rivers: Relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain). Environ. Int. 36, 153–162.

Gros, M., Petrović, M., Barceló, D., 2007. Wastewater treatment plants as a pathway for aquatic contamination by pharmaceuticals in the Ebro river basin (northeast Spain). Environ. Toxicol. Chem. 26, 1553–1562.

Gros, M., Petrović, M., Ginebreda, A., Barceló, D., 2010. Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environ. Int. 36, 15–26.

Jelic, A., Fatone, F., Di Fabio, S., Petrovic, M., Cecchi, F., Barceló, D., 2012. Tracing pharmaceuticals in a municipal plant for integrated wastewater and organic solid waste treatment. Sci. Total Environ. 433, 352–361.

Jelic, A., Gros, M., Ginebreda, A., Cespedes-Sánchez, R., Ventura, F., Petrović, M., Barceló, D., 2011. Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Res. 45, 1165–1176.

Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L., Barceló, D., 2012. Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions. Science of The Total Environment 440, 3–13.

Petrović, M., Ginebreda, A., Acuña, V., Batalla, R.J., Elosegi, A., Guasch, H., López de Alda, M., Marcé, R., Muñoz, I., Navarro-Ortega, A., Navarro, E., Vericat, D., Sabater, S., Barceló, D., 2011. Combined scenarios of chemical and ecological quality under water scarcity in Mediterranean rivers. TrAC Trends in Analytical Chemistry 30, 1269–1278.

Radjenović, J., Petrović, M., Barceló, D., 2007. Analysis of pharmaceuticals in wastewater and removal using a membrane bioreactor. Anal. Bioanal. Chem. 387, 1365–1377.

Radjenović, J., Petrović, M., Barceló, D., 2009. Fate and distribution of pharmaceuticals in wastewater and sewage sludge of the conventional activated sludge (CAS) and advanced membrane bioreactor (MBR) treatment. Water Res. 43, 831–841.

Sui, Q., Huang, J., Deng, S., Chen, W., Yu, G., 2011. Seasonal Variation in the Occurrence and Removal of Pharmaceuticals and Personal Care Products in Different Biological Wastewater Treatment Processes. Environmental Science & Technology 45, 3341–3348.



Climate Change, Water and Security in the Mediterranean - implications for science and policy (a perspective from the CLIMB

project)

Ralf Ludwig and the CLIMB consortium

Ludwig-Maximilians-Universität Munich, Department of Geography, Munich, Germany The Mediterranean region is experiencing a broad range of threats to water security. According to latest climate projections, as published in the 5th Assessment Report of the Intergovernmental Panel on Climate Change (IPCC 2013) or the European Environmental Agency (EEA 2012), the region is at risk due to its pronounced susceptibility to changes in the hydrological budget and extremes, which is expected to have strong impact on the management of water resources and on key strategic sectors of regional economies. Related developments have the capacity to exacerbate tensions, and intra- and inter-state conflict among social, political, ecological and economic actors. Effective adaptation and prevention policy measures call for multi-disciplinary analysis and action.

In order to better assess the manifold consequences and uncertainties in climate impact on man-environment systems, a coordinated topic has been programmed in EU-FP7, bringing together the three projects CLICO (SSH), WASSERMed (ENV) and CLIMB (ENV) to establish the research cluster CLIWASEC (Climate Change, Water and Security; www.cliwasec.eu), to improve scientific synergy and policy outreach.

The current state of the art on climate change research for the Mediterranean region shows large scientific consensus that climate change is impacting the area in a manifold and distinct fashion. Recently observed trends and projections from climate model ensembles indicate a strong susceptibility to change in hydrological regimes, an increasing general shortage of water resources and consequent threats to water availability and management. Our comprehensive summary highlights threats resulting from decreasing groundwater resources, strongly increasing drought risk for flash floods, advancing sea-level rise, and their impact on key strategic sectors of regional economies with consequent macroeconomic and social implications. It shows that the magnitude of change contains a strong capacity to aggravate tensions that may lead into conflict among different socio-economic actors. However, it must be clearly stated that current uncertainties in climate projections and subsequent (hydrological) model chains, a yet incomplete understanding of the impact of a climate change signal on (micro- and macro-) economic mechanisms, and the lack of an elaborate and integrated human security conceptual framework are imposing strong limitations on water-related decision-making under conditions of climate change. This is particularly true due to the general lack of regional data and the yet unresolved mismatch of spatial and temporal scales of operation from different scientific perspectives (Ludwig et al. 2011).

The clustering of projects can help push forward current understanding of the interactions of climate change impacts on ecological, economic and social components of human-environment systems. This is essential for advancing towards optimized regional solutions for water resources management under climate change.

The findings from the three projects clearly indicate that climate change is progressing at an unprecedented pace, increasing the pressures of water scarcity on ecological, economic and social levels. The cluster approach of working in multiple case studies around the Mediterranean, the Middle East and Sub-Saharan Africa provides substantial knowledge about the heterogeneity and variability of climate change impacts. Triggered mostly by a strong increase in temperature and a moderate to strong reduction and seasonal re-distribution of precipitation, impacts will mostly be felt in water resources management, agriculture, tourism and its consequent implications on security. Further, CLIMB and the CLIWASEC




cluster have made substantial progress in assessing the uncertainties in climate change research. An example for interdisciplinary CLIWASEC research will be illustrated for the common case study in the Lower Nile Delta, Egypt (Susnik et al. 2013).

The presentation will highlight on a Joint Policy Position Paper, recently published by the three projects, and intended to discuss and exchange on related implications on policy and decision making from international, national and regional perspectives. The presentat summarizes the findings of the cluster and provides recommendations for an improved adaptation to climate change and related threats to water security in the region.

Finally, CLIMB will launch its GeoPortal, a web-based, public platform to access CLIMB results and interpretations. The GeoPortal will provide decision makers with a specifically designed tool to better assess local and regional climate change impacts and related threats to security in high resolution. Acknowledgements

The contribution from all partners in the CLIMB consortium (GA: 244151), the WASSERMed project (GA: 244255) and the CLICO project (GA: 244443) is gratefully acknowledged.

References

European Environmental Agency (2012): Climate Change, Impact and Vulnerability in Europe. EEA Report No 12/2012. 304 p.

Intergovernmental Panel on Climate Change (2013): Climate Change 2013. The Physical Science Basis. Summary for Policy Makers.Working Group 1 contribution to the IPCC Fifth Assessment Report (WG1 AR5). [Stocker, T. F., D. Qin, G.-K. Plattner, M. Tignor, S. K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex and P. M. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, in press.

Ludwig, R., Roson, R., Zografos, C. and G. Kallis (2011): Towards an inter-disciplinary research agenda on climate change, water and security in Southern Europe and Neighbouring countries. In: Environmental Science and Policy. doi:10.1016/j.envsci.2011.04.003

Susnik, J., Vamvakeridou-Lyroudia, L., Gebert, N., Kloos, J., Renaud, F., Lajeunesse, I., Mabrouk, B., Savic, D., Kapelan, Z., Ludwig, R., Fischer, G., Roson, R. and C. Zografos (2013): Interdisciplinary assessment of water-related climate change impacts on the Lower Nile River, Egypt. Proceedings of the 13th Int. Conf. on Env. Sc. and Tech., Athens; CEST2013.ref: cest13_0382.



Spring snowfall decadal variability over the Alps

Matteo Zampieri1, Enrico Scoccimarro1,2 and Silvio Gualdi1,2

1 EuroMediterranean Center for Climate Change (CMCC), Bologna, Italy 2 INGV, Bologna, Italy

Introduction

The Alps are often called the ‘water towers’ of Europe. In fact, they are the most important freshwater supply of continental Europe: the Rhine, Po, Rhone and several tributaries of the Danube originate here. Due to their high elevation, the hydrological cycle of the Alps is largely affected by snow, with important repercussions for the environment and society (Beniston 2012, Barnett et al 2005). In fact, snow acts as an insulator of the underlying soil (Clark et al 1999), determining the vegetation distribution and phenology (Keller et al 2005) and reducing the surface temperature by reflecting solar radiation (Groisman et al 1994). In the Alps, snow is present from late autumn to spring at a wide range of altitudes, allowing ski-related tourism (Toeglhofer et al 2011) and determining the seasonality of hydropower production through the runoff originating from the spring snowmelt (Hanggi and Weingartner 2012). In the past, potential factors determining snowfall and snow cover variations have been extensively studied. Temperature variations can alter the partition of solid to liquid precipitation (Serquet et al 2011, Eccel et al 2012) and the spring snowmelt timing, determining the length of the snowy season (Laternser and Schneebeli 2003). Therefore, long-term global warming is likely responsible for the observed reduction of snowfall (Serquet et al 2011) and for the possible continuation of this trend in the future (Beniston 2012). The potential economic damage to the tourism-related industry could be quite significant (Elsasser and Messerli 2001). Moreover, climate change can alter the seasonality of hydropower generation (Finger et al 2012) and hazard related risks (Marty and Blanchet 2012).

Decadal variations in teleconnections considerably complicate the interpretation of the climate change signal. Therefore, the snowfall trend computed over a few decades can be larger than the effects that might be attributed solely to climate change. This was evidenced in connection with the retreat of glaciers in the tropics (Francou et al 2003, Kaser et al 2004). In the Alps, the recent rapid warming and the associated circulation change have largely contributed to the general reduction of snowfall amount and snow cover duration observed in the past few decades (Hantel and Hirtl-Wielke 2007, Serquet et al 2011).

The change of circulation affecting winter snowfall over the Alps is well known. In fact, the recent tendency toward a predominantly positive phase of the North Atlantic Oscillation (NAO; Hurrell 1995) corresponded to high-pressure, warm and dry weather conditions unfavorable to snow over the Alps, which has decreased particularly since the 1980s at elevations below 1500–2000 m (see e.g. Bartolini et al 2001, Beniston 1997, Laternser and Schneebeli 2003, Marty 2008, Durand et al 2009, Valt and Cianfarra 2010). In this short paper we focus on spring snowfall, which determines the length of the snowy season. We show that spring snowfall low-frequency (multi-decadal) variability over the Alps is modulated by the Atlantic Multi-decadal Oscillation (AMO; Schlesinger and Ramankutty 1994). In fact, the AMO has been recently identified as one of the main natural drivers of the low-frequency variability of the European climate in spring, summer and autumn (Sutton and Dong 2012) and of the mass balance of Alpine glaciers (Huss et al 2010). Similarly, we report the occurrence of synchronous shifts of the AMO phase and spring snowfall amount.

Results

Figure 1 shows the long-term anomalies of temperature (first column), total precipitation (second column) and solid precipitation (third and fourth columns) related to the AMO phase transitions (displayed in the different rows) computed on the HISTALP dataset (Auer et al. 2007, Brunetti et al. 2009, Chimani et al. 2011) In each row we list the periods over which we computed the differences, which correspond to




period of positive (warm) and negative (cold) AMO phase (Suttom and Dong 2012, Einfeld et al 2001). As for temperature (first column), statistically significant changes are found in the shifts toward warm AMO in the 1990s and around 1930 (first and third rows of figure 1, respectively). These transitions correspond to warming of the Alps, more marked on the western side. The largest warming, of about 1.5 C, is recorded during the last AMO transition. Warm to cold AMO transitions that occurred in the early 1960s and around 1900 are displayed in the second and fourth rows, respectively.

Figure 1: From left to right: differences of HISTALP spring temperature, total precipitation observations

and spring snowfall reconstruction (in absolute values and in percentage) due to the four AMO transitions that occurred in the past 150 years. The periods over which we computed the differences are

listed in each row of the plot. Shading is applied over areas where the statistical significance of the differences is below the 95% threshold level according to the Mann–Whitney test.

The same analysis conducted for precipitation is shown in the second column of figure 1. With respect to temperature, precipitation is not characterized by a significant long-termtrend. Despite the larger spatial variability, the precipitation variations show a relatively similar pattern in every transition. In fact, every AMO- to AMO+ change (both forward an backward in time) is characterized by a reduction of total precipitation up to 1 mm/day in the western Alps, i.e, over the French and Swiss territory and northwestern Italy. A similar signal is found for the southeastern Alps, but with smaller amplitude and not always statistically significant. In particular, the difference in precipitation is less significant in the last AMO transition (top panel), most likely because of the shorter period available to compute the averages.

Snowfall (third and last columns) offers the most consistent picture. In fact, snowfall changes are quite similar for every AMO phase shift. In the cold to warm transition, especially in the last episode, snowfall inherits the statistical significance of the temperature change. In fact, the temperature rise occurring during the cold to warm transitions produces statistically significant snowfall reduction at low altitudes. On the other hand, the snowfall increase, passing from warm to cold AMO periods, is more confined at higher elevations. Again, the most significant and robust changes of spring snowfall due to AMO shifts are in the western Alps, where the associated pattern is characterized by a reduction (increase) of about 1 mm/day passing from cold to warm (warm to cold) periods, corresponding to 20–30% of the mean spring snowfall. The signal is weaker and less significant going back in time, but always consistent in terms of the spatial pattern.

Sutton and Dong (2012) show that spring precipitation anomalies connected to the AMO in the last two



transitions were due to a change of circulation, consisting of a ridge of high mean sea level pressure (MSLP) over central Europe, sandwiched between two troughs (low MSLP) over the northeast Atlantic Ocean and northeastern Europe. Here, we explore this dynamical link and its physical consequences over Western Europe for all the AMO transitions in the past 150 years using the 20th Century Reanalysis (Compo et al. 2011).

Figure 2: Same as figure 1, but computed on the 20th Century Reanalysis 2 meters temperature,

precipitation, mean sea level pressure and cloudiness, plotted on a larger area (30W–30E, 35N–65N).

Figure 2 shows the anomalies of temperature, precipitation, MSLP and cloudiness associated with each shift. Results for temperature and precipitation are consistent with HISTALP, particularly in the western Alps, and they confirm the presence of a teleconnection pattern between the North Atlantic basin and the European continent, which, affecting the atmospheric circulation, contributes to the low-frequency changes of precipitation. It is worth noting that our results appear to beless significant and stable from the statistical point of view in the case of the oldest transition. Sutton and Dong (2012) attributed the temperature anomalies in Western Europe mainly to advection of Northern Atlantic air. In addition to this effect, we report statistical significant cloudiness anomalies that might explain a portion of the surface temperature variability related to the AMO.

Althought. It is not possible to extrapolate this results for the future, the next AMO shift could be expected for the 2020s and it migh profoundly affect the climate of Alps and of Europe. Acknowledgements

This research has been funded by the Italian Ministry of Education, University and Research and the Italian Ministry of Environment, Land and Sea under the GEMINA and NEXTDATA projects

References

Auer I et al 2007 HISTALP—historical instrumental climatological surface time series of the greater Alpine region 1760–2003 Int. J. Climatol. 27 17–46

Barnett T P, Adam J C and Lettenmaier D P 2005 Potential impacts of a warming climate on water availability in snow-dominated regions Nature 438 303–9




Bartolini E, Claps P and D’Odorico P 2001 Connecting European snow cover variability with large scale atmospheric patterns Adv. Geosci. 26 93–7

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Beniston M 2012 Is snow in the Alps receding or disappearing? Wiley Interdiscip. Rev. Clim. Change 3 349–58

Brunetti M, Lentini G, Maugeri M, Nanni T, Auer I, Böhm R and Schöner W 2009 Climate variability and change in the Greater Alpine Region over the last two centuries based on multi-variable analysis Int. J. Climatol. 29 2197–225

Chimani B, Böhm R, Matulla C and Ganekind M 2011 Development of a longterm dataset of solid/liquid precipitation Adv. Sci. Res. 6 39–43

Clark M P, Serreze M C and Robinson D A 1999 Atmospheric controls on Eurasian snow extent Int. J. Climatol. 19 27–40

Compo G P et al 2011 The twentieth century reanalysis project Q. J. R. Meteorol. Soc. 137 1–28

Durand Y, Giraut G, Laternser M, Etchevers P, Merindol L and Lesaffre B 2009 Reanalysis of 47 years of climate in the French Alps (1958–2005): climatology and trends for snow cover J. Appl. Meteorol. Climatol. 48 2487–512

Eccel E, Cau P and Ranzi R 2012 Data reconstruction and homogenization for reducing uncertainties in high-resolution climate analysis in Alpine regions Theor. Appl. Climatol. 110 345–58

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Hanggi P and Weingartner R 2012 Variations in discharge volumes for hydropower generation in Switzerland Water Resources Manag. 26 1231–52

Hantel M and Hirtl-Wielke L M 2007 Sensitivity of Alpine snow cover to European temperature Int. J. Climatol. 27 1265–75

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Huss M, Hock R, Bauder A and Funk M 2010 100-year mass changes in the Swiss Alps linked to the Atlantic Multidecadal Oscillation Geophys. Res. Lett. 37 L10501

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Analysis of climate change effects on water and sediment cycle in a Mediterranean catchment

Gianbattista Bussi1, Félix Francés1, José Andrés López-Tarazón2,3 and Ramón J. Batalla3,4,5

1 Research Institute of Water and Environmental Engineering, Universitat Politècnica de València, Spain

2 School of Natural Sciences and Psychology, Liverpool John Moores University, UK 3 Department of Environment and Soil Sciences, University of Lleida, Spain

4 Catalan Institute for Water Research (ICRA), Girona, Spain 5 Forest Science Centre of Catalonia, Solsona, Spain

Introduction

In the last years, the analysis of climate change impact on water resources has been a key environmental research target. A broadly shared conclusion is that, in Mediterranean areas, average temperature is expected to increase while average precipitation is expected to decrease. Extreme events are also expected to increase their magnitude and frequency (Alpert et al., 2002). Nevertheless, little is known about the impact of climate change on water and sediment cycles at the catchment scale. Past studies focused this problem, although climate change impact quantification is still a quite difficult task. Given the high complexity of rainfall – runoff transformation, soil detachment and sediment transport phenomena, physically based distributed hydrological and environmental modelling is proposed as a tool to estimate the effect of climate change on water and sediment cycle. In this study, the TETIS hydrological and sedimentological model (Francés et al., 2007; Bussi et al., 2013) is coupled with climatological model scenarios in order to obtain climate change-affected series of several hydrological and sedimentological variables, which are later analysed in order to understand the impact of future climatological evolutions on hydrology and sediment transport of a highly erodible Mediterranean catchment.

Methods

The TETIS model was implemented at the Ésera River catchment, a medium size catchment (1510 km2) draining to the Barasona reservoir (storage volume 92.2 Hm3). It is located in the Central Southern Pyrenees (Spain), in an area characterized by high reliefs and slopes (Fig. 1). Main land uses are pine forest, shrubland, and arable land. The climate is strongly influenced by the Mediterranean Sea, with dry winters and torrential rainfall episodes in summer.

Figure 1: Ésera River catchment location




The catchment is defined as a highly erodible catchment (López-Tarazón et al., 2009), as it shows frequent badlands areas in its central part. Due to this characteristic, the Barasona reservoir is experiencing severe siltation since its building (1932). Several bathymetries were carried out since 1984 in order to control the reservoir storage volume. Flushing and dredging operation were also carried out along the reservoir life, although the extracted volume is unknown.

The TETIS model was implemented at the Éserva River catchment. Meteorological data (precipitation and temperature) was taken from Spain02 gridded dataset (Herrera et al., 2010). The hydrological sub-module was calibrated by adjusting simulated water discharge at the Capella station (Fig. 1) in order to reproduce observed water discharge records provided by the CEDEX (Experimental Studies Centre). The hydrological sub-model showed a satisfactory behaviour, as calibration Nash and Sutcliffe efficiency was 0.72 and spatio-temporal validation at the Barasona reservoir obtained an efficiency of 0.71.

The sediment sub-model was calibrated by adjusting simulated total load in order to reproduce the sediment volume accumulated at the bottom of the Barasona reservoir. The sediment trap efficiency of the Barasona reservoir was taken into account by using the Brune curves, which provided trap efficiency raging between 82% and 88%. The deposit dry bulk density was computed by means of the Miller formula, using Lane and Koelzer coefficients, and validated with measured density values. The chosen calibration period was from 1998 to 2008. During this period, three bathymetries were carried out, allowing splitting this period into two sub-series, one used for calibration and the other for validation. The results are shown in Fig. 2. The model obtained a validation volume error of 23%.

Figure 2: observed vs simulated evolution of the reservoir storage capacity.

The TETIS model was subsequently coupled with meteorological output (precipitation and temperature) produced by the ARPEGE atmospheric regional model in the framework of the PRUDENCE project (Christensen et al., 2007). Three climatological scenarios were simulated: a control scenario (1961-1990), representing the current climate, A2 scenario (2071-2100) and B2 scenario (2071-2100), both representing two different future climate evolution (elaborated within the Special Report on Emissions Scenarios). A2 scenario forecasts a stronger temperature increase and precipitation decrease tan B2. Previous to their use, climatological precipitation and temperatura were corrected in order to reproduce more precisely the Ésera River catchment climate. The correction was done base on quantiles plots (q-q plots), as suggested, for example, by Déqué (2007). The results are presented as follows.

Results and conclusions

The Ésera River catchment TETIS model was run using as input the daily temperature and precipitation series produced by the ARPEGE model. TETIS provided daily series of several hydrosedimentological variables, such as mean catchment precipitation and temperature, water and sediment discharge, mean catchment soil moisture and water-equivalent snow depth. Results, presented in Tab. 1, show that precipitation tends to decrease and temperature tends to increase, as expected. The variation is more



pronounced for A2 scenario, which is more pessimistic than B2 scenario. These variations cause a strong decrease in both soil saturation and snow depth. All these hydrometeorological variables affect total water yield, which is expected to decrease by 40% under A2 scenario and by 35% under B2 scenario. Nevertheless, sediment yield does not follow the same trend, as it is expected to strongly decrease under A2 scenario and to increase under B2 scenario. Given the highly non-linear relationship between water and sediment discharge, an analysis of extreme values is needed in order to understand this apparent contradiction.

Table 1: model results, averaged on the whole 31-year series and over the entire catchment.

Variable Control A2 variation

B2 variation

Precipitation (mm/year) 686 596 607 Temperature (ºC) 7.99 12.06 11.01 Soil saturation (%) 74 54 57 Snow depth (mm eq.) 49 15 19 Water yield (Hm3/year) 690 418 446 Sediment yield (ton/ha/year) 6.33 3.62 7.04

In Fig.3 the Gumbel distribution functions of annual maximum of daily precipitation, water discharge and sediment discharge are shown. They show that extreme values do not behave accordingly to mean values observed in Tab. 1. This is because extreme precipitation is expected to increase (i.e. precipitation is expected to become more torrential, as pointed out for example by Alpert et al., 2002). This increase is not sufficient to obtain increasing values of extreme water discharge, given that the decrease in soil moisture compensates this effect. Nevertheless, extreme sediment discharge values show an increase under B2 scenario and a decrease under A2 scenario. This is because B2 scenario is more torrential than A2 scenario, as can be seen in the extreme daily precipitation plot in Fig. 3.

Figure 3: Gumbel distribution functions of annual maximum daily precipitation, water discharge and

sediment discharge.

Another interesting phenomenon, which can be noted analysing the model results, is the time compression alteration. Time compression describes the contribution of largest events to the total load. In this case study, the 5 largest events accounted for 39.6%, 36.9% and 49.8% of total sediment yield for control, A2 and B2 scenario respectively, the 10 largest events for 52.7%, 54.8% and 65.1% and the 20 largest events for 62.0%, 70.2% and 78.8%. This indicates that time compression is expected to increase, following model results, and, as a consequence, the Ésera River sediment cycle is expected to become more large event-dependent in the future, regardless of total sediment load.




Another interesting feature that model results allow analysing is the spatial variation of soil erosion (Fig. 4). The most affected zones are located in the northern part of the catchment, due to high slopes and badland presence. Soil erosion is expected to expand under B2 scenario and to reduce under A2 scenario. The main sources of sediments are located in the badland areas in the central part of the catchment for all scenarios, although for scenario B2 the surface of badland zones appears to increase and for scenario A2 to decrease.

Figure 4: spatial variation of soil erosion (from left to right: control period, A2 scenario and B2

scenario). Acknowledgements

This study was funded by the research projects SCARCE-CONSOLIDER (ref. CSD2009-00065) and ECOTETIS (ref. CGL2011-28776-C02-01). Meteorological data was provided by the Spanish Meteorological Agency (AEMET).

References

Alpert, P., Ben-Gai, T., Baharad, A., Benjamini, Y., Yekutieli, D., Colacino, M., Diodato, L., Ramis, C., Homar, V., Romero, R., Michaelides, S., Manes, A. The paradoxical increase of Mediterranean extreme daily rainfall in spite of decrease in total values. Geophysical Research Letters (2002), 29(11), 1536, doi:10.1029/2001GL013554.

Bussi, G., Rodríguez-Lloveras, X., Francés, F., Benito, G., Sánchez-Moya, Y., and Sopeña, A. Sediment yield model implementation based on check dam infill stratigraphy in a semiarid Mediterranean catchment. Hydrology and Earth System Sciences (2013), 17(8), 3339–3354, doi:10.5194/hess-17-3339-2013.

Christensen, J. H., Carter, T. R., Rummukainen, M., and Amanatidis, G. Evaluating the performance and utility of regional climate models: the PRUDENCE project. Climatic Change (2007), 81(S1), 1–6, doi:10.1007/s10584-006-9211-6.

Déqué, M. Frequency of precipitation and temperature extremes over France in an anthropogenic scenario: Model results and statistical correction according to observed values (2007). Global and Planetary Change, 57(1-2), 16–26, doi:10.1016/j.gloplacha.2006.11.030.

Francés, F., Vélez, J.I., and Vélez, J.J.. Split-parameter structure for the automatic calibration of distributed hydrological models. Journal of Hydrology (2007), 332(1-2), 226–240, doi:10.1016/j.jhydrol.2006.06.032.

Herrera, S., Gutiérrez, J.M., Ancell, R., Pons, M.R., Frías, M.D., and Fernández, J.. Development and analysis of a 50-year high-resolution daily gridded precipitation dataset over Spain (Spain02). International Journal of Climatology (2010), 32, 74–85, doi:10.1002/joc.2256.

López-Tarazón, J.A., Batalla, R.J., Vericat, D., and Francke, T., Suspended sediment transport in a highly erodible catchment: The River Isábena (Southern Pyrenees). Geomorphology (2009), 109, 210–221, doi:10.1016/j.geomorph.2009.03.003.



Sediment dynamics response under global change: Sensitivity Analysis in a Mediterranean watershed

María Sánchez-Canales1, Alfredo López1, Vicenç Acuña2 and F. Javier Elorza1

1 Universidad Politécnica de Madrid, Escuela Técnica Superior de Ingenieros de Minas, Calle Ríos Rosas 21, 28003

Madrid, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

Erosion and sediment transport processes are sensitive to Global change, because of their close links to land cover use and the hydrology of a river basin, both climate and land cover change and to a wide range of human activities influence erosion and sediment mobilisation and transport (Walling, 2008). The sediment transport in a watershed is controlled by many factors, including precipitation patterns, variations in land uses or/and soil characteristics, and slope patterns of erosion and sediment runoff.

We carry out a research concerning the different factors implied in sediment dynamics and their importance in order to try to deduce the most effective mitigation strategies to respond to global change effects, with respect to sedimentation, in Mediterranean areas. To address this, we perform a sensitivity analysis of the InVEST Sediment Retention model (Tallis et al., 2013) in the Llobregat basin (a Mediterranean region basin in northeastern Spain) for total sediment export and also for total sediment retained with two different benefits (avoided reservoir sedimentation and water quality).

The service erosion protection, which is the relative contribution of the different parts of the landscape to sediment retention, is estimated considering the land use patterns that affect sedimentation in downstream reservoirs. The function sediment retention is calculated as the difference from received (from upstream cells) and exported sediment. Eroded soil from each cell is estimated using the Universal Soil Loss Equation (USLE) (Wischmeier & Smith 1978), while the retained amount of sediment by each cell is a function of the retention coefficients associated to vegetation covers.

After the model is calibrated (Terrado et al., 2012 and briefly description in section ‘supplementary information’) it is essential to make the model sensitivity analysis. The sensitivity analysis used here is the Morris method (Morris, 1991), which is a one-at-a-time (OAT) sensitivity analysis method that aims at isolating the influential parameters from a large number of input parameters. As all SA methods, the goal of the Morris screening method is to determine the relative influence of each input (xi) on the output (y). To achieve this, it determines the statistical information of the random variable ∂y/∂xi and uses the mean (μ) and standard deviation (σ) of ∂y/∂xi at several points in the sample space to deduce the sensitivity of y to xi. In an extension of the base Morris approach a different sensitivity measure was defined by Campolongo et al. 2007, it is μ*.

With the sensitivity analysis of the model, we determine which factors of the sediment retention model are more relevant for the outcome of the model through a sensitivity analysis in order to know which factors involved in global change affect more sediment dynamics at the Mediterranean basin of Llobregat. The evaluation of these factors is essential at highly pressured basins in semi-arid Mediterranean area. We were interested in determining which factors should have more adjusted data to feed the model and above all, in which ones human management can mitigate sediment erosion.

The results show that, in all cases, any change in climate factors (such as precipitation erosivity or soil erodibility factors) leads to significant changes in sediment dynamics. However, changes in other factors as crop-vegetation and management factor or support practice factor, in some cases, might make it possible to totally or partly compensate the changes in sediment dynamics due to climate change. References

Campolongo F, Cariboni J and Saltelli A. An effective screening design for sensitivity analysis of large models. Environmental




Modelling & Software 22 (2007) 1509-1518.

Morris MD, Factorial sampling plans for preliminary computational experiments. Technometric 33 (1991), 161-174.

Tallis HT, Ricketts T, Guerry AD,Wood SA, Sharp R, Nelson, E, Ennaanay D, Wolny S, Olwero N, Vigerstol K, Pennington D, Mendoza G, Aukema J, Foster J, Forrest J, Cameron D, Arkema K, Lonsdorf E, Kennedy C, Verutes G, Kim CK, Guannel G, Papenfus M, Toft J, Marsik M, Bernhardt J and Griffin R. InVEST 2.4.2 User’s Guide. The Natural Capital Project, Stanford (2013).

Terrado M, Honey-Rosés J, Acuña V, Sabater S. Ecosystem Services in an Impacted Watershed. The Handbook of Environmental Chemistry 21 (2012) 347-368.

Walling DE. Studying the impact of Global Change on erosion and sediment dynamics: current progress and future challenges. Discussion document. ISI Workshop, IRTCES, Beijing (2008).

Wischmeier WH and Smith DD. Predicting rainfall erosion losses-a guide to conservation planning. Vol 537. U.S. Department of Agriculture (1978).



Measuring wetlands level using historical remot sensing imaginery

Victor Juan Cifuentes Sanchez1, Rosario Escudero Barbero2 and María Jose Checa Alonso2

1 Confederacion Hidrografica del Gaudalquivir, Sevilla, Spain 2 Empresa Pública TRAGSATEC, Madrid, Spain

Level recorder devices are the equivalent in lakes of gauge stations. However, lake measuring networks have been neglected until recently. As a result, data is incomplete and fragmentarian. Problem arises when a "reference hydrogram" is required in order to determine if present oscillations are in the range of natural varation.

A possible approach, tested in the present work, is making use of historical images of the LANDSAT program, which are easily available, often in the files of institutions.

The aim of the study is to determinate the level of accuracy which can be attained by calculating lake level from the the water surface using historical images, in lakes where the level was measured and recorded and then comparing the field and the remote sensing measured data.

As test area, the lagoons of South of Cordoba have been used. This group of lagoons have recorded level series up to thirty years long. Most of them are included in the Ramsar List.

Figure 1: Extension of the water layer (Laguna de los Jarales)

The works compress the selection of reliable algorithms that make possible to discrimite between water and dry terrain, and more difficult indeed, between vegetation on dry terrain and vegetation on flooded terrain (Figure 1).

The results shows that remote sensing can be an useful and reliable tool that can be used to recover never recorded data and in order to generate sintetical historical series (Figure 2).




Figure 2. Historical vs Remote Sensing measured data

Acknowledgements

To the managers and staff of the Reserva Natural de lagunas del sur de Cordoba, specially to Baldomero Moreno and Rafael Vega,

References

Lei Ji, Li Zhang y Bruce Wylie. Analysis of Dynamic Thresholds for the Normalized Difference Water Index. Photogrammetric Engineering & Remote Sensing 2009.

J. Bustamante; R, Diaz-Delgado y D. Aragonés. Determinación de las características de masas de aguas someras en las marismas de Doñana mediante teledetección. XI Congreso Nacional de Teledetección. Puerto de la Cruz 2005.

Lic.Gloria Y. Bolívar Durán, Dr. Manoel Araújo de Sousa Junior, MSc. Silvia Midori Saito. Uso de Técnica Tasseled Cap y de los índices NDWI y MNDWI para la delimitación de áreas propensas a inundación _ Estado Guárico, Venezuela.

Emilio Chuvieco y Stijn Hantson, 2010. PNT de Media Resolución. Procesamiento de imágenes Landsat. Documento técnico de algoritmos a aplicar.

José A. Torres Esquivias. Lagunas del sur de Córdoba. Córdoba 2004. Ed. Diputación de Córdoba.

Aljibe (Consultores s.l.l.). Estudio hidrogeológico de las lagunas del Sur de Córdoba. Lagunas del Rincón y Santiago, Lagunas Amarga y Dulce. Net 291875/1.Diciembre 2005. Life-Naturaleza conservación y restauración de humedales andaluces. Life Nat 03/E/000055.

José Manuel Moreira (coord.). Caracterización ambiental de humedales de Andalucía. Consejería de Medio Ambiente. 2005.

Comparativa Profundidades (Rincón)

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From chemical exposure to ecosystem effects: A critical view of the risk assessment process

Antoni Ginebreda1, Maja Kuzmanovic1, Mira Petrovic2 and Damià Barceló1,2

1 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain


Pollution in surface waters is considered one of the main causes of impairment of aquatic ecosystems and biodiversity loss [1]. Risk could be broadly defined [2] as the combination of a probability of occurrence of some event multiplied by its hazard effects:

RISK = OCCURRENCE x ECOSYSTEM EFFECTS

Estimating the risk posed by chemical pollution to the ecosystem thus requires paying attention to both factors, i.e., the exposure to chemicals and the potential or actual effects caused.

‘Occurrence’ or environmental exposure is usually expressed in terms of environmental concentration.Advances in environmental chemistry [3] have shown that typical environmental scenarios are characterised by continuous exposure to many contaminants. This is due not only to the high number of chemicals used that can potentially be released into the environment (In the European Union there are more than 100 000 registered chemicals listed by EINECS of which 30 000 to 70 000 are in daily use) [4], but also to the biotic and abiotic transformations that they may undergo once there. Therefore, parent compounds, transformation products and other non-targeted compounds yield complex mixtures whose composition can only be partially identified by monitoring, while a substantial proportion essentially remains unknown [5].

As regards to ‘effects’, two approaches are typically used (Fig. 1): Adverse effects to the ecosystem, can be indirectly estimated through some intrinsic properties of the pollutants concerned, typically their Ecotoxicity (but also their Persistence and Bioaccumulation), and assuming that they are translated into ecosystem effects. On the other hand, effects of pollution can be perhaps more realistically considered by direct measurement of ecological descriptors covering both structural and functional ecosystem aspects. Whereas indirect methods can be better related to each single pollutant, their extrapolation to the whole ecosystem is not straightforward. On the other hand, direct ecological measurements provide a better insight on the actual ecosystem status but conversely, the role played by every specific chemical remains largely unknown. The situation is even more complicated if one considers that in addition to pollution, other geographic and hydrologic factors are also and simultaneously concurring.




Figure 1: Direct vs. Indirect estimation of ecosystem effects

Overall, and quoting Hendriks [6], we are facing a complex scenario in which “>100,000 compounds × >100,000 end points × >100,000 sites” should be considered together. This is a big scientific challenge that calls for new and imaginative approaches.

Depending on which part of the problem we want to focus, the three blocks of variables can be treated on a detailed basis or instead on an integrative or global form.

Here we argue that the method of choice in the risk assessment process will strongly depend on the question we are interested to answer. If, for instance, we wish to focus our study on what are the most relevant chemicals (prioritization) or what are the most sensitive species to pollution on a given site, a detailed description of the part concerned is required, while others can be handled as global.

Along the presentation we will discuss, with the aid of specific examples, different possible methodological alternatives, showing their advantages and drawbacks, as well as, some ongoing new research possibilities. References

1. Vorosmarty, C.J. ; McIntyre, P.B. ; Gessner, M.O. ; Dudgeon, D.; Prusevich, A.; Green, P.; Glidden, S. ; Bunn, S.E. ; Sullivan, C.A.; Liermann, C.R. ; Davies; P.M.. Nature, 2010, 468, 334

2. D. Guillén , A. Ginebreda, M. Farré, R.M. Darbra, M. Petrovic, M. Gros, D. Barceló. Prioritization of chemicals in the aquatic environment based on risk assessment:Analytical, modeling and regulatory perspective. Science of the Total Environment 440 (2012) 236–252

3. D. Barceló; M. Petrovic. Challenges and achievements of LC-MS in environmental analysis: 25 years on. Trends Anal. Chem. 2007, 26(1), 2-11

4. D.C.G Muir, P.H. Howard. Are there other persistent organic pollutants? A challenge for environmental chemists. Environ Sci Technol 2006;40:7157–66.

5. Daughton, C.G. Non-regulated water contaminants: emerging research. Env. Imp. Assess. Res. 2004, 24, 711-732.

6. A.J. Hendriks. How to deal with 100,000+ Substances, Sites and Species: Overarching Principles in Environmental Risk Assessment. Env. Sci. Technol. 2013; 47, 3546-3547



Multiple stressor effects on river biofilms. Searching the ruling factor

Lídia Ponsatí1, Mira Petrovic1,2, Yolanda Picó3, Antoni Ginebreda4, Elisabet Tornés1,5, Natàlia Corcoll1, Helena Guasch5, Damià Barceló1,4 and Sergi Sabater1,5

1 Catalan Institute for Water Research (ICRA), Girona Spain

2 Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain 3 Laboratori de Nutrició i Bromatologia, Univerisity of València, Burjassot, Spain

4 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 5 Institue of Aquatic Ecology, University of Girona, Girona, Spain

Introduction

Increasing concentrations of nutrients and contaminants (organic and inorganic) are progressively detected in river waters enhancing the potential toxicity risk on epilithic biofilms (Sabater et al., 2007; Ricart et al., 2010; Corcoll et al., 2012). Concentrations in water are variable in time and space depending on the source of pollution (diffuse or point sources), hydrological conditions, and their transformation processes. Chemical compounds from point sources can be diluted during high flows, while those from diffuse sources such as watershed runoff may increase (Guasch et al. 2010; Boithias et al. 2011). Mediterranean rivers have large floods in autumn and winter (Gasith and Resh 1999). Forecasted scenarios of climate change predict an increase of droughts and flood episodes (IPCC 2007). Also dams, that are ubiquitous structures on many rivers, may alter the natural hydrological dynamics of rivers (Cazaubon et al., 1999). Natural conditions determine the biomass dynamics of river biofilms (Bouletreau et al., 2006; Uehlinger et al., 1996) and may be altered by high water flows (Cazaubon et al., 1999; Robinson et al., 2004). These structural changes may also modulate the biofilm sensitivity to toxicants, and mature and thick biofilms may perform as a barrier against chemical toxicity, reducing the accessibility to chemicals (Ivorra et al., 2000; Guasch et al., 2003). The present study evaluates the respective relevance of environmental factors (light, temperature, water flow) and chemical stressors (nutrients, pharmaceuticals, endocrine disruptors, pesticides, perfluorinated compounds and heavy metals) in the structure and functioning of epilithic biofilms in four Mediterranean watersheds. Stressors co-occur and interact in specific manners, and the respective relevance of one or another in the response of the biota may be altered also by the flow regime.

Material and Methods

The study was conducted in four Mediterranean river basins: Llobregat, Ebro, Júcar and Guadalquivir. Five locations were selected in each river according an up- to downstream pollution gradient in each basin. Sampling was performed in two different hydrological periods, expecting differences in water flow: autumn 2010 (C1, with high flow or flood events) and autumn 2011 (C2, with basal or constant flow). Water samples were taken for physical (e.g. discharge, temperature, light) and chemical analysis. Chemical analyses included nutrients such as dissolved inorganic nitrogen (DIN), total phosphorus (TP) and dissolved organic carbon (DOC), heavy metal concentrations (including Cu, Zn, Co, Ni, Cd, Pb and As), and organic priority and emerging compounds (including 175 compounds grouped in 4 groups: pesticides, pharmaceuticals, endocrine disrupters and perfluorinated compounds).

The biofilm was analyzed for its community composition (based on diatom species), the algal biomass (Chl-a), photosynthetic capacity (Ymax), non-photochemical quenching (NPQ), the bacterial density (Bacteria), and the extracellular enzymatic activity alkaline phosphatase (AP). Attribution of main stressors on biofilm response was carried out by means of variance partition analysis (Redundancy analysis), therefore differentiating specific responses of biofilms in each watershed and period.




Results and Discussion

The first axis of the principal component analyses (PCA) performed with the diatom communities separated sensitive vs tolerant species to pollution. The scores were later used for further RDA analyses. The first axis of PCA explained the highest (38 % of the variance) and separated upstream sites of Júcar, Ebro and Guadalquivir rivers (on the right site) to downstream sites of Llobregat, Ebro and Guadalquivir rivers (on the left site). The species composing communities of upstream sites (Achananthes minutissima, A. biasolettiana or Cymbella microchephala) were associated to good water quality conditions. In contrast, those composing communities from downstream sites (Navicula subminuscula, N. recens, Nitzchia insconspicua, N. palea or N. frustulum) are tolerant to pollution. The second PCA axis explains less variance (14%), separates mainly upstream sites (in positive sites) to downstream sites (negative positions) of the Júcar River. The diatoms assemblage in this river was of higher water quality than that of other rivers.

An RDA was performed that could predict the biofilm variables (including the diatoms) from the environmental variables (the main physical and chemical descriptors, heavy metals, and priority and emerging contaminants) for all four watersheds studied (Fig.2). According to partitioning variance analyses, most of the variance was explained by physicochemical factors (17.2%). Conductivity, DIN and TP were the most significant. Other pollution sources explained a 5.1% of the variance, being endocrine disruptors and metals the most significant toxicants. The first axis of RDA (Fig.2) showed a gradient of

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pollution, where sites with higher conductivity, presence of endocrine disruptors and high phosphorus (downstream sites in the Ebro, Guadalquivir and Llobregat rivers) contrasted with sites in the Júcar River. In the former, higher levels of pollution co-occur with more tolerant diatom communities. These sites had algal communities with a higher photosynthetic capacity, mostly green-algae. Biofilm communities were made up of species sensitive to pollution, showed high algal biomass and high alkaline phosphatase activity.

High flows characterized the summer-autumn 2010 hydrology (Fig. 3A), particularly in the Llobregat River. Instead, summer 2011 had conditions close to basal flow. The RDA based on Llobregat river data (Fig. 3B) defines the two sampling campaigns in the first axis (29.1% variance), while the second axis (17.4% of variance) represents a gradient of pollution. During high flows, algal biomass was low and bacteria abundance high, as it corresponds to initial stages of biofilm development. Probably, new biofilm colonization was occurring after the flood event. Pharmaceutical pollution was the most relevant type of pollution in this situation. Their inputs can be associated to waste water treatment plant effluents. During basal flows biofilm communities had higher algal biomass, characteristic of mature communities. In this situation, pesticides concentration was higher than in summer 2010. Dominant pesticides in the Llobregat were probably derived from urban activities, and pesticides can be more concentrated in the water column. Diatom sensitive species characterized the upstream sites of Llobregat River, however, pollution tolerant ones, were typical of downstream sites. Both the type of toxicants pollution detected in Llobregat River (pharmaceuticals and urban pesticides) and the observed up- to downstream increasing gradient of pollution, may be explained by the high proportion of urban land uses in downstream sites of this watershed.

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of Llobregat river based on biofilm structural and functional metrics and environmental factors, including physicochemical parameters and toxicants. Nonte: c1 (sampling autumn 2010) and c2

(sampling autumn 2011).

RDA analyses based on Ebro River data showed that biofilm responses were mainly linked to an excess of nutrients (dissolved inorganic nitrogen) and agricultural pesticides in water. The increasing pollution up to downstream was parallel to co-occurring increasing agricultural land uses. Pesticides concentrations in water were higher during high flow (summer 2010) than with basal flow (summer 2011), supporting that pesticide inputs were coming from the agricultural areas runoff. In the Ebro structural biofilm responses to water flow were comparable to those observed in Llobregat River (Fig. 3B).

Redundancy analyses based on Guadalquivir River data showed that biofilm responses were mainly attributed to an excess of organic matter (DOC) and endocrine disruptors occurrence, increasing from up- to down-stream sites, related to the increasing agricultural and urban land uses in downstream sites. In




summer 2010, slightly high flow was detected in this river when comparing to summer 2011. During basal flow, endocrine disruptors were higher indicating their origin of point sources (such as WWTP). Biofilm responses of Guadalquivir River to changes in water flow were comparable to those observed in the Llobregat River (Fig. 3B). The sensitivity of diatoms species to water pollution also allowed characterize up- and donwnstream sites of the Guadalquivir River according to a gradient of pollution.

Redundancy analyses based on Júcar River data showed that biofilm responses were mainly attributed to a joint gradient increasing conductivity, total phosphorus, and metals from up- to downstream sites. This gradient of pollution co-occurs with an increasing gradient of agricultural areas from up- to downstream sites. No significant differences in water flow were detected among sampling campaigns, since hydrology in this river is highly regulated by dams. Biofilm communities from upstream sites presented a higher abundance of diatoms species sensitive to pollution and a higher abundance of bacteria than those from downstream sites. The biofilm also showed a higher non-photochemical quenching and alkaline phosphatase activity in the upstream sites, indicating their higher efficiency than those from downstream sites. Acknowledgements

This study was financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and by the European Union through the European Regional Development Fund (FEDER).

References

Boithias, L., Sauvage, S., Taghavi, L., Merlina, G., Probst, J.-L., & Pérez, J. M. S. 2011. Occurrence of metolachlor and trifluralin losses in the Save river agricultural catchment during floods. Journal of hazardous materials196, 210–9.

Bouletreau, S., Garabetian, F., Sauvage, S., Sanchez-Perez, J.-M., 2006. Assessing the importance of a self-generated detachment process in river biofilm models. Freshwater Biology 51, 901–912.

Cazaubon, A., Giudicelli, J., Continentales, E., 1999. Impact of the residual flow on the physical characterics and benthic community (algae, invertebrate) of a regulated Mediterranean river: the Durance, France. Regulated Rivers: Research and Management 461, 441–461.

Corcoll, N., Bonet, B., Morin, S., Tlili, A., Leira, M., Guasch, H., 2012. The effect of metals on photosynthesis processes and diatom metrics of biofilm from a metal-contaminated river: A translocation experiment. Ecological Indicators 18, 620–631.

Gasith, A. and V. H. Resh. 1999. Streams in Mediterranean climate regions: Abiotic influences and biotic responses to preditable seasonal events. Annual Review of Ecology and Systematics 30:51-81.

Guasch, H., Admiraal, W., Sabater, S., 2003. Contrasting effects of organic and inorganic toxicants on freshwater periphyton. Aquatic Toxicology 64, 165–175.

Guasch, H., Güluzar, A., Bonet, B., Corcoll, N., Leira, M., Serra, A. 2010. Discharge and the response of biofilms to metal exposure in Mediterranean rivers. Hydrobiologia 657:143–157.

Ivorra, N., Bremer, S., Guasch, H., Kraak, M.H.S., Admiraal, W., 2000. Differences in the Sensitivity of Benthic Microalgae To Zn and Cd Regarding Biofilm Development and Exposure History. Environmental Toxicology and Chemistry 19, 1332.

IPCC, 2007. Fourth Assessment Report: Climate Change 2007. Cambrigde UK, Cambridge University Press.

Ricart, M., Guasch, H., Barceló, D., Brix, R., Conceição, M.H., Geiszinger, A., Alda, M.J.L. De, López-Doval, J.C., Muñoz, I., Postigo, C., Romaní, A.M., Villagrasa, M., Sabater, S., 2010. Primary and complex stressors in polluted mediterranean rivers: Pesticide effects on biological communities. Journal of Hydrology 383, 52–61.

Robinson, C.T., Uehlinger, U., Monaghan, M.T., 2004. Stream ecosystem response to multiple experimental floods from a reservoir. River Research and Applications 20, 359–377.

Sabater, S., Guasch, H., Ricart, M., Romaní, A., Vidal, G., Klünder, C., Schmitt-Jansen, M., 2007. Monitoring the effect of chemicals on biological communities. The biofilm as an interface. Analytical and bioanalytical chemistry 387, 1425–34.

Uehlinger, U.R.S., Bu, H., Federal, S., Science, E., Eawag, T., Du, C.-, 1996. Periphyton dynamics in a floodprone prealpine river: evaluation of significant processes by modelling 249–263.



Ecological screening indicators of stress and risk for the Llobregat river water

Ramón López-Roldán1, Irene Jubany2, Vicenç Martí2,3, Susana González1 and Jose Luis

Cortina1,3

1 CETaqua, Cornellà, Barcelona, Spain 2 CTM Technological Centre Foundation, Manresa, Spain

3 Department of Chemical Engineering, Universitat Politècnica de Catalunya, BarcelonaTech (UPC), Barcelona, Spain

Abstract

The objective is to develop and apply several simple and rough indicators for river aquatic ecosystems assessment in order to screen potential chemical stressors. Several indicators, based on toxicity (PNEC) and on legislation levels (EQS) have been developed. All these indicators are ratios that were calculated by using public and private data of concentrations of a large list of compounds during a period of five years, including metals and organic compounds in the lower part of the Llobregat River basin at the intake of the Drinking Water Treatment Plant. Additionally, new campaigns were executed for increasing the information available on the presence of compounds not routinely analysed, such as some other pesticides and pharmaceuticals. In the case of inorganic pollutants, the indicators obtained in this river section showed significant risk especially for zinc, but also for copper, nickel and barium. For organic pollutants, the pesticides terbuthylazine, diazinon, 2-methyl-4-chlorophenoxyacetic (MCPA), and in a few cases, chlorpyrifos and lindane, also showed indexes above the threshold. Among the pharmaceuticals, the antibiotics clarithromycin and ciprofloxacin were the only ones with risk indicators adverse to ecosystems.The specific values of the indexes obtained rely on the quantity and quality of the data available, so their interpretation should take into account that some values can be high due to the use of too conservative toxicological information.

Introduction

Degradation of water bodies has been a key issue in Europe during last years. Water Framework Directive (WFD, Directive 2000/60/EC) (1) imposes the achievement of good ecological status of water bodies. Environmental objectives should preserve quality of water bodies beyond the potential uses for industry, agriculture, urban and recreational uses, integrating preservation of the health of ecosystems, their functioning and structure. Indexes for physico-chemical and biological status are relatively easy to implement. Measurements are based in data that can be obtained by analysis or by identification and counting of species.

National administrations, like River Basin authorities, should deal with indexes that could be easily used to give an indication of the good chemical, hydromorphological and biological status of each specific water body according to their local characteristics.

The idea of establishing comprehensive indexes is to provide indicators on water quality for the environmental managers. This effort of simplicity can be very useful but the information on the impact on single parameters is lost. Present work is focusing on giving simple indicators on the impact on every pollutant that are can be found in Llobregat river waters, considering its effect on aquatic and vertebrate organisms.

Case study

The proposed ratios were calculated using data of concentrations of a list of contaminants in the Llobregat river water. The Llobregat river basin is situated in Catalonia (NE, Spain) and covers a catchment area of




about 5000 km2 but in the present study, a specific location has been selected close to the mouth of the river, just before the intake of the biggest DWTP supplying water to the Barcelona Metropolitan. The site has been selected for two main reasons. As it is in the lower part of the Llobregat basin, the river is receiving discharges from urban and industrial wastewater treatment plants, sewer overflows and diffuse pollution from agricultural fields, being the area with the highest impact along the river. The location before the DWTP gives information on potential impact on health for consumers. This location is not only advantageous for this double objective of protecting environmental and human health, but for the higher intensity of existing monitoring programmes.

Ecological screening risk indicators

New indexes have been proposed for the calculation of environmental risk for a large list of compounds commonly found in the Llobregat River. Those indexes are based on analytical results on the concentration of these compounds on surface water (Predicted Environmental Concentration, PEC) and reported effects (Predicted Non Effect Concentration, PNEC). For those compounds with no PNEC reported, calculations for obtaining PNEC values have been performed based on available data. The methodology for deriving these standards is based, among others, on the concepts of Ecological Risk Assessment (ERA) based on PNEC and PEC (2).

Taking PECj as the concentration of a contaminant j measured in water, a risk indicator of aquatic organisms, I ao,j is defined as follows:

j

jjao PNEC

PECI =,

PNECj is derived from toxicological values in water, basically NOEC (No Observed Effect Concentration) of crustaceans, algae, and fishes, and the proper safety factor (assessment factor, AF).

For the list of priority substances, according to Directive 2008/105/CE, Environmental Quality Standars (EQS) are defined to give a concentration that supposes impact on aquatic media. In these cases, where threshold concentration for pollutants is legislated, an indicator of aquatic impact Iam,j can be calculated replacing the PNEC by the legislative value EQS (CREF,j):

jREF

jjam C

PECI =,

The protection of terrestrial vertebrates (mammals and birds) that are predators of aquatic organisms are also part of the aquatic ecosystem and could be assessed by comparing concentration of contaminants in aquatic organisms (PECfood) with the value of PNEC expressed in food basis. PECfood,j could be expressed by using the transference Bioconcentration Factor (BCF) that measures the ratio concentration of contaminant in small aquatic organisms (considered food) (PECfood, j) divided by the concentration of contaminant in water (PECj). In this way, an indicator of terrestrial vertebrates risk, Itv,j could be obtained with the following expression:

jjfood

jjtv BCFPNEC

PECI

/,, =

BCFj values could be obtained from empirical studies or, in case of organic compounds, from correlations with log Kow (Octanol-Water Partition Coefficient).

The above mentioned expressions show that, having the concentration of the contaminants in water (PECj), the calculation of all the exposed indicators can be performed. For all these indicators, a target value of 1 was taken as the limit of correct environmental situation.



Results

Up to date, new indexes have been calculated for ecological risk assessment. Risk indicators for aquatic organisms give significant values (index value above 1) for all metals studied, in this case, barium, copper, nickel and zinc. Figure 1 shows indexes based on Water Catalan Agency data. Concerning organic compounds, the most significant indexes for aquatic organisms are referred to the herbicide terbuthylazine, a chlorotriazine, and the nonsystemic organophosphate insecticide diazinon. For terrestrial vertebrates, as seen in Figure 2, the only compound showing an impact according to the index calculated is zinc. The indexes calculated for terrestrial vertebrates for these organic compounds are showing no significant impact.

Figure 1: Monthly risk indicators for aquatic organisms at selected site of Llobregat River (2006-2010) for metals (left) and organic compunds (right) based on Water Catalan Agency (ACA) data bases

Figure 2: Monthly risk indicators for terrestrial vertebrates at selected site of Llobregat River (2006-2010) for organic compunds based on Water Catalan Agency (ACA) data bases

Uncertainty of indicators is mainly due to PNEC values derivation. As mentioned, contaminants that have few representative data have a high value of AF and use deterministic approach, and thus PNEC values could be very conservative, giving indicators of one order of magnitude or more respect to the case when many representative data have been used. When the derived PNEC is based in distributed approach has less uncertainty than in the case of deterministic approach. In the case of these metals with the range of confidence interval and range of AF (1 to 5) a variation of less than order of magnitude in PNEC is obtained.

As a general tendency, risk indexes calculated for aquatic organisms tends to be higher than those indexes calculated for terrestrial organisms for the same compounds as BCF are considered in the second ones. As both indexes are based on the same PEC, monthly variations of those indexes follow the same pattern.

Concerning extra campaigns for pesticides (3) and pharmaceutical compunds (4), the indexes shown in Figure 3 have been calculated on average concentrations for each compound on each campaign. The only pesticides showing indexes above 1 are diazinon, MCPA and terbuthylazine. The indexes for the former three compounds have been calculated using very low reference values. This is one of the reasons why




non-regulated pesticides show higher risk indexes than the legislated ones.

In pharmaceutical compunds, the antibiotics clarithromycin and ciprofloxacin the index is above 1 posing a risk to ecosystems. If indexes based on maximum concentration values are observed, the anti-inflammatory drug diclofenac, the lipid regulators gemfibrozil and fenofibrate, and the antibiotics enrofloxacin and sulfamethoxazole, presents values between 1 and 10.

Figure 3. Risk indicators for pesticides (a) and pharmaceutical compounds (b) at selected site of Llobregat River (special campaigns 2009-2010)

Conclusions

The combination of several indicators is crucial for the assessment of the river pressure based on chemical contaminants, but still there is a lack of information on reliable PNEC values. PNEC values are usually very conservative if they are not derived with the proper quantity and quality data, even though they allow establishing the possibility of rejecting the negative effect of some contaminants if they do not exceed the target value.

New studies in the future will lead to more information on toxicological effects of substances that will lead to more accurate PNEC calculations and toxicological information on new compounds not available nowadays. After this initial diagnosis, more detailed studies on the effect of the potential chemicals that pose risk need to be performed in order to establish cause-effect relationships. Acknowledgements

This work was supported by the Spanish Ministry of Economy and Competitiveness through WATMATIN project (CTM2010-21182) and the former Spanish Ministry of Environment through the VIECO project (MARM009/RN08/01.1). AGBAR is acknowledged for the data supplied.

References

(1) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy

(2) Joint Research Centre, Technical Guidance Document on Risk Assessment in support of Commission Directive 93/67/EEC on Risk Assessment for new notified substances Commission Regulation (EC) No 1488/94 on Risk Assessment for existing substances Directive 98/8/EC of the European Parliament and of the Council concerning the placing of biocidal products on the market Part II, 2003

(3) Köck-Schulmeyer, M., Ginebreda, A., González, S., Cortina, J.L., de Alda, M.L. and Barceló, D. Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain), Chemosphere (2012), 86, 8-16.

(4) Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L. and Barceló, D. Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions, Sci. Total Environ. (2012) 440, 3-13.



Habitat quality assessment in river basins considering terrestrial and aquatic threats

Marta Terrado1, Guy Ziv2, Lisa Mandle2, Becky Chaplin-Kramer2, Richard Sharp2, Sergi

Sabater1,3 and Vicenç Acuña1

1 Catalan Institute for Water Research, Girona, Catalunya, Spain 2 The Natural Capital Project, Woods Institute for the Environment, Stanford University, CA, USA

3 Institute of Aquatic Ecology, University of Girona, Catalunya, Spain

Introduction

The loss and degradation of natural habitat quality constitutes a primary cause of the loss of biodiversity (Fuller et al., 2007). Land use change is considered the most severe driver of change in biodiversity (Sala et al., 2000), but other threats such as the construction of infrastructure (i.e., roads, hydropower generation plants, wastewater treatment plants), or the introduction of exotic species, are also responsible of biodiversity decline (Gleick, 2003, Ricciardi and Rasmussen, 1999). Mediterranean ecoregions host exceptional species diversity, but are poorly protected, highly degraded, and exposed to multiple persistent threats. Consequently, they have been ranked among the world’s highest conservation priorities (Myers et al., 2000).

Efforts to preserve biodiversity in the European Union (EU) have been directed towards the designation of protected areas under the Habitats Directive (92/43/ECC). Aquatic habitats are also regulated under the EU Water Framework Directive (WFD, 2000/60/EC), which aims to attain the good ecological status for all EU water bodies by year 2015. Both Directives require that EU Member States evaluate the conservation status of the protected areas and species listed every six years. Our goal is to provide a tool that could be used by environmental managers to better assess the effects of ongoing threats and management actions on habitat quality- biodiversity.

Methods

We used the ecosystem service tool InVEST or Integrated Valuation of Environmental Services and Tradeoffs (Kareiva et al., 2011; Tallis et al., 2011), which has a biodiversity module to assess terrestrial habitat quality combining information on land use-land cover (LULC) and threats to biodiversity (anthropogenic pressures). We modified the existing terrestrial habitat quality module for it to be able to simultaneously assess aquatic habitat quality. The idea behind the followed approach is that areas with high quality habitat will better support all levels of biodiversity, and that decreases in habitat extent and quality mean a decline in biodiversity persistence and resilience. The model runs in a gridded map in which each cell is assigned a habitat type. Considering biodiversity in general, each type of habitat can provide habitat for a different number of species, meaning that it has higher or lower habitat suitability (Hj) for biodiversity. Ten habitat types were considered in the Llobregat river basin (Figure 1a). Four terrestrial and five aquatic threats were included in the model (Figure 1b-j). The source of each threat was mapped on a raster in which the value of the grid cell, normalized between 0 and 1, indicated the intensity of the threat within the cell. Whereas terrestrial threats were considered to be able to impact all habitat types, aquatic threats only affected aquatic habitat types. The impact of threats on the habitat in a grid cell was mediated by three factors: i) the distance between the cell and the threat’s source (to account for that, a maximum distance over which the threat affected habitat quality was defined); ii) the relative weight of each threat (importance of one threat referred to the others); and iii) the relative sensitivity of each habitat type to the threat. Land-originated threats could initially propagate in all directions of the landscape. However, the behavior of aquatic threats needed to be defined differently, since the sense of propagation should follow the direction of the flow. The more sensitive a habitat type was to a threat, the more degraded it would be by the threat. Eventually, the sum of the total threat level in a grid cell gave a




degradation score for the cell which could be translated into a score of habitat quality.

We validated the model results with available biodiversity data from the area of study. Macroinvertebrate diversity data from the Catalan Water Agency (ACA) for years 2010-2011 was used to validate aquatic habitat quality, whereas an index of floral richness from the Barcelona’s Council accounting for the number of species of vascular plants per habitat was used for terrestrial habitat quality.

Figure 1: Maps of habitat types (a) and location and magnitude of the terrestrial (b-e) and aquatic (f-j) threats in the Llobregat river basin. Considered threats: (b) urbanization, (c) agriculture, (d) roads, (e)

mines, (f) dams, (g) wastewater treatment plants, (h) water abstractions, (i) channelling, (j) invasive species.

Results

Habitat quality in the Llobregat river basin was heterogeneously distributed (Figure 2a). According to the obtained results, urban settlements are one of the main environmental drivers of habitat degradation in the basin. Even though some threats already exist in the Northern part, the lowest habitat quality is mostly detected in the South of the basin, where two factors interact: the higher presence of urban settlements, and an accumulation of threats from upstream. Scores displayed in Figure 2 are relative values differentiating areas according to their higher or lower habitat quality and, therefore, to their higher or lower capacity to host biodiversity. Values are relative because they are referred to forest as the potentially best habitat for terrestrial ecosystems, and to the highest-order streams as the potentially best habitat for aquatic ecosystems.

In general terms, aquatic habitat in the Llobregat basin tended to be more degraded than terrestrial habitat (Figure 2b). We already expected that since aquatic habitat is affected by a higher number of



threats.Moreover, habitat quality scores were more heterogeneous for terrestrial than for aquatic habitat, the latter with values of habitat quality mainly concentrated around 0.5. Low habitat scores [0.1-0.5] occurred majorly in aquatic ecosystems, whereas high habitat scores [0.6-0.9] were more frequent in terrestrial ecosystems. Only were habitat quality scores < 0.1 more important for terrestrial ecosystems.

Figure 2: Habitat quality in the Llobregat river basin: (a) landscape distribution of habitat quality; (b)

histogram of aquatic and terrestrial habitat quality.

Habitat quality in the study area was related to biodiversity (Figure 3). Terrestrial habitat quality appeared to be strongly related to the index of floral richness. Less vascular plant species were found in areas of low habitat quality, and the number of plant species increased as habitat quality improved (Figure 3a). Aquatic habitat quality was also related to macroinvertebrate diversity in water (Figure 3b). Even though the relationship was weaker in this case, it was still significant (p<0.0001). Aquatic habitat quality was in accordance with the assessment of threats performed periodically by the Catalan Water Agency in water bodies (ACA, 2005). A decreasing trend in aquatic habitat quality was observed when the level of total threats increased. Habitat quality was always high when the level of threats was low, but their values were more dispersed as habitat quality became lower as a result of threats increase.




Figure 3: Relationship between biodiversity and predicted habitat quality in the Llobregat river basin:

(a) floral richness versus terrestrial habitat quality; (b) macroinvertebrate Shannon diversity (H’) versus aquatic habitat quality.

Here we improved the existing habitat quality assessment tool of InVEST by including the assessment of aquatic habitats, and we tested its reliability by comparing the results of the model with terrestrial and aquatic biodiversity values in a case study basin affected by multiple threats. We also propose a tool to be used for environmental managers to better assess the effects of ongoing threats and management actions.

Acknowledgements

This research was supported by the Spanish Ministry of Science and Innovation through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065), by the Spanish Ministry of Education and Science through the Juan de la Cierva program (JC2011-09116 – to M Terrado), by a Marie Curie European Reintegration Grant within the 7th European Community Framework Programme (PERG07-GA-2010-259219), as well as by the European Union through the European Regional Development Fund (FEDER). References

ACA (Catalan Water Agency). Characterization of water bodies and analysis of the risk of non-accomplishment of the objectives of the Water Framework Directive (2000/60/CE) in Catalunya (Catalan). Department of Environment and Housing, Catalan Government (2005).

Fuller, T., Sanchez-Cordero, V., Illoldi-Rangel, P., et al. The cost of postponing biodiversity conservation in Mexico. Biol Conserv (2007), 134, 593-600.

Gleick, P.H. Global freshwater resources: soft-path solutions for the 21st century. Science (2003), 302, 1524-28.

Kareiva, P., Tallis, H., Ricketts, T., et al. Natural Capital: Theory and practice of mapping ecosystem services. Oxford University Press, New York (2011).

Myers, N., Mittermeier, R.A., Mittermeier, C.G., et al. Biodiversity hotspots for conservation priorities. Nature (2000), 403, 853-58.

Ricciardi, A. and Rasmussen, J.B. Extinction rates of North American freshwater fauna. Conserv Biol (1999), 13, 1220-22.

Sala, O.E., Chapin III, F.S., Armesto, J.J., et al. Global biodiversity scenarios for the year 2100. Science (2000), 287, 1770-74.

Tallis, H., Ricketts, T., Guery, A.D., et al. InVEST 2.4.4 User's Guide. The Natural Capital Project, Stanford, CA (2011).



Evaluation strategy and data processing of indicator values and risk assessment – a sustainable logic indicator system for planning,

constructions, materials and scenarios in in semi arid areas

Peter-D. Hansen1, B. Gabriel2 and R. vom Lehn2

1 TU Berlin (Berlin Institute of Technology - BIT), Dept. Ecological Impact Research and Ecotoxicology 2 TU-Campus Wedding (TIB), Master´s Programme Real Estate Management, Berlin, Germany

Executive Summary

Process orientated Indicator values are helpful tools for net working, visualization and for understanding of complex systems. A evaluation and monitoring system is internationally needed and accepted according to the International Standards and Indicators used by the BNB/DGNB, BREEAM, LEED, African Green City Index (GCI), Asian GCI, European GCI, ESTIDIMA (Pearls), GREEN Pyramids. The newly established Eva.S evaluation tool represents a challenge as much as a competent opportunity and toolbox for project development, assessment and management of the project progresses.

A comprehensive strategy is necessary to enable a relevant, scientific monitoring to capture and assess qualitative and quantitative effects related indicators of the measures planned and/or realized the first time by Eva.S and the YC-Project. The YC-project working phases were attended during data mining by evaluation matrices and visualization of results by so-called radar diagrams from the beginning on.

The development and realization of a project is a process in several distinct project-phases and this will certainly not end with its implementation. Sectorial considerations and therefore possibly inefficient measures in case of changes in the project can be prevented because the presented interaction and feed back effects in a within the evaluation and monitoring strategy is integrated from the beginning on of the project with the focus on the analysis of work flow and rating checks.

The now available evaluation tool Eva.S serves as an instrument for the project participants to handle and present their dimensions (fields of action), categories i.e. CO2, energy efficiency, sustainability, work packages and finally to present the overall results in a clear and manageable way. Because of the numerous projects and possibilities of Eva.S and its multiple applications and visualization of the processes for interpretation and competent communication to public the indicators values and the investigated evaluation strategy are of significant relevance and acceptance for planning, construction and process orientated monitoring as well as “grade of achievements” for Megacities, New Towns and New Urban Settlements.

Data sets, handling of data and the data bank

The project relevant data are processed in a format of quantitative and qualitative indicators selected in categories like CO2, Energy, Water, Air Quality, Water and Land Use, Socio-cultural, Economy, Environmental Management. The sustainability has to be proved by social-cultural quality, ecological quality and economic quality after the classical technical qualities of sustainability. This operation is resulting in a set of project specific Indicators. The effect related indicators and measures selected are finally proved and visualized as results and rated in a radar diagram. The indicator concept includes a rating system 1-10.




Tab. 1: Rating level 1-10 ___________________________________________________________________

Definition 1-2 = best practice

Definition 5 = accepted average value

Definition 8-9 = most worse rating

Definition 10 = failure / criteria to prove a failure

The rating 3, 4, 6, 7 reflects to project specific refinements ___________________________________________________________________

The rating system is similar to the common rating tables of the International Standards (ISO, CEN) to demonstrate in particular the “grade of achievement” of the measures.

Original data sets were mined and organized in a matrix by the topics: strategic dimensions, work packages (WP), objectives, measures, impact, input Indicators (data of initial situation), objective indicators, target values (qualitative and quantitative) and measuring methods. At this time the data bank contains 135 original data sets. In the individual data sets the project rating is always implemented. The 26 Dimensions were condensed and evaluated according to three fields of action (FoA): Reduction of Resources - Consumption, Energy and Climate and Sustainability. For feeding and editing Eva.S a solid data base of the dimensions and a set of relevant and productive evaluation criteria for the field of actions is of fundamental importance. The mining of the data was in close connection to the given objectives as well as to the work packages of the YC project and feed back by the project teams.

The work flow for managing the data:

Step 1: data mining, organization project data in matrices and Indicator sheets

Step 2: data feeding the Eva.S evaluation tool by project data sets

Step 3: data check by a multi array grid (processor) for sustainability criteria

Step 4: monitoring and decision loop, resulting products and alternative strategies

Step 5: dissemination of results, rating of results and visualization

The Eva.S evaluation tool is working in the background linked to the data bank and the given objectives and achievements of the project progress. This can be monitored and demonstrated at any time and at any place / location in the web: http://yc.liebrenz.info/refina/index.php

In this YC-example the results in the three fields of actions “Reduction of Resources Consumption”, “Energy and Climate” and “Sustainability” are visualized by a radar diagram

(Fig. 1, 2, 3).



Figure 1: Dissemination of Project Results. Field of Action: Reduction of Resource – Consuption

Figure 2: Dissemination of Project Results. Field of Action: Energy and Climate

Figure 3: Dissemination of Project Results. Field of Action: Sustainability




Conclusion

The Eva.S evaluation tool was developed in the Young Cities Project by the Evaluation and Monitoring group. But from the first beginning on it was designed also for other applications and potential projects and test runs were consequently performed. Because the YC-project data bank was build up slowly but constantly. Finally we discussed proved applications of Eva.S at the communal authorities level. There will be a training and application of Eva.S for legal frame work.

The risk analysis and monitoring studies (Hansen 1983, 1997, 2007, Hansen et al 2013) were an added values for the project development, evaluation and monitoring according to the well accepted International Standards.The risk analysis part of Eva.S was tested and optimized by the “MORIX feasibility studies” in the REM (Real Estate Management) Master Courses of the Technische Universität Berlin (BIT – Berlin Institute of Technology). Many new aspects and directions for future applications and new perspectives of Eva.S are discussed in ZIA (2013) and will be certainly applied in the near future. The YC-databank and Eva.S are present in the web by the following address: http://yc.liebrenz.info/refina/index.php

Summary

1. Eva.S data bank is serving (administrate) the Megacity - YC-project by 135 data sets, 3 Fields of Action (FoA: Reduction of Resources - Consumption, Energy and Climate and Sustainability) and 25 Work Packages.

2. Eva.S is easy to feed by a Drop-Down menu.

3. Eva.S is Open Source / Microsoft Office

4. Eva.S is not an E-book – it is a evaluation tool

5. Eva.S is from now on a web based application and has access world wide: http://yc.liebrenz.info/refina/index.php

6. The Eva.S project data are evaluated by qualitative and quantitative project specific indicators proved by the classical dimensions of sustainability: socio-cultural quality, economic and ecological quality.

7. The dynamic and constantly up-dated Eva.S evaluation tool has many potential applications in the field of evaluation and monitoring. Stakeholders are project developer, political decision maker of municipal authorities.

Acknowledgements

The authors thanks the Young Cities Project Center of the world wide Megacities project for data mining and updating of the data sets. We thank the members of the Evaluation Working Group of the YC Project for competent contributions in stimulating many frontiers approaches and evaluation concepts. The authors gratefully acknowledge the BMBF for funding the Young Cities Project – research for sustainable development of the megacities of tomorrow – energy and climate-efficient structures in urban growth centres

References

Hansen, P.-D. 1983. Regulatory Significance of Toxicological Monitoring by Ed. Mervyn Richardson, VCH Publishers, New York 1993

Hansen, P.-D. 1997. Ecotoxicology and Landscape Planning. Quality Assurance, 5,3 231-241

Hansen, P.-D. 2007. Risk assessment of emerging contaminants in aquatic systems. Trends Anal. Chem. (TRAC), Vol. 26, No 11, 1095-1099

ZIA 2013 Real Estate Industry Perspectives – Sustainability, 3rd Revised and Amended Edition – March 2013

Hansen, P.-D. Gabriel, B., Liebrenz, H., Herig, S. and vom Lehn, R. 2013, A sustainable logic indicator system for planning, constructions, materials and scenarios, uwf UmweltWirtschaftsForum- Springer, in press.



The role of e-Infrastructures: Linking biodiversity and ecosystems through the deployment of new water quality technologies in river

basins

Juan Miguel González Aranda1, Antonio José Sáenz Albanés2, Jesús Marco de Lucas3 and Benjamín Sánchez Gimeno4

1 Ministry of Economy and Competitiveness-MINECO, Madrid, Spain

2Andalusian Institute of Technology-IAT, Seville, Spain 3Institute of Physics of Cantabria-IFCA, CSIC-UC, Santander, Spain 4Ministry of Economy and Competitiveness-MINECO, Madrid, Spain

Rationale

Biodiversity Ecosystem Functioning (BEF) is one of the “Big Five” Hot Ecological Topics, jointly with Climate Change, Habitat Fragmentation/loss, Species Invasions, and Compound Impacts. This “Big Five” develops within a global worldwide context, where several high level initiatives aim to deepen into these issues through: (a) The creation of the Intergovernmental Science-Policy Platform on Biodiversity and Ecosystems Services (IPBES, doing what IPCC did for Climate Change for Biodiversity); (b) The definition of the Nagoya 2010 CBD Targets in order to take effective and urgent action to halt the loss of Biodiversity in order to ensure that by 2020 ecosystems are resilient and continue to provide essential services; and (c) the fundamentals of the Economics of Ecosystems and Biodiversity (TEEB-2010), among others. It is clear that all these topics meet in River Basins, where Decision Makers, Researchers, different socio-economic Stakeholders (mainly from Agro-food, Water and Energy sectors) and rest of Citizens (in general terms), come together as members of Communities of Practice sharing these common concerns (González-Aranda et al., 2006) not only at their regional/local river basin, but also at international level (González-Aranda, 2010). Monitoring, modelling and understanding River Basins is a real challenge that requires the experience and knowledge cumulated along many decades, but today it can greatly benefit of the new streams of information, like high resolution satellites images, or real time monitoring sensors, and also from more complex and accurate models covering from global climate to local hydrological and water quality predictions. Therefore, the provision of proper service-oriented e-Infrastructures, integrating the whole chain from instrumentation and databases to supercomputers where models can be executed, taking benefift of the “state-of-art” of the Information Society Tecnologies, will support to understand the environmental limits, ecosystem resilience and relationship between Biodiversity & Essential Ecosystem Services. This contribution shows a set of on-going case studies and initiatives based on the framework of the ESFRI LIFEWATCH, putting in practice many of these concepts.

About the ESFRI LIFEWATCH e-Infrastructure

The European Strategy Forum on Research Infrastructures (ESFRI) is a strategic instrument to develop the scientific integration of Europe and to strengthen its international outreach. The competitive and open access to high quality Research Infrastructures supports and benchmarks the quality of the activities of European scientists, and attracts the best researchers from around the world. Environmental sciences are also considered in ESFRI, through initiatives such as LIFEWATCH “Infrastructure for Research on the Protection, Management and Sustainable Use of Biodiversity”. LIFEWATCH is a distributed e-Infrastructure as it is cooperating with “distributed” Centres in European Union cooperating countries. In fact, Spain (Seville) is the Statutory Seat, responsible of the ICT Core developments and coordinator and manager of the distributed construction operations of this e-Infrastructure. These Centres (initially, the Common facilities also located in Italy, The Netherlands and Belgium) are developing and operating virtual and physical media and other components that give access to (1) distributed observatories/sensor




networks; (2) interoperable databases & warehouses; (3) existing (data-)networks, using accepted standards; (4) computational power; (5) software & tools for visualization, analysis and modelling. Their main aim is to address new research fields, test innovative hypothesis, deepen scientific knowledge and above all, to provide solutions for environmental policy and management issues (see Figure 1).

Figure 1: LIFEWATCH ESFRI connecting Science with Environmental policy & management

Therefore, the proper operation of this e-Infrastructure demands that the development of new “toolboxes” and users’ interfaces is adequately planned. The application of these principles may be exemplified within the context of the research and management of river basin areas as can be derived from the conceptual layer-based Architecture shown in Figure 2. This conceptual framework will provide policy makers, river basin-related managers and other users with available research data, analyses and lessons learned from particular cases, specially those involving multi- and inter-disciplinary work across different research lines. This information will help decision-making processes related with water quality, biodiversity and ecosystem protection, or land and adaptive management.

Figure 2: LIFEWATCH ESFRI distributed e-Infrastructure conceptual Architecture

Thus, such an e-infastructure should ensure in first place the access to validated data from monitoring activities and other reliable sources of data, by establishing and strengthening its relationships with existing scientific and data provider bodies. For instance, a new generation of smarter complex sensing platforms are already integrating water quality measurements and many other relevant environmental measurements (atmospheric variables, solar radiation and spectrum) with high sampling frequency and mobility plus profiling capability (Coterillo, 2012). In addition, the e-infrastructure should enable the integration of accurate hydrological models describing baseline conditions (like thermocline evolution) with those models that could predict relevant events like algae bloom (Monteoliva, 2013). The access to harmonized and consolidated data, such as those systematically provided by river basin authorities (Lassaletta et al., 2009) and integrated modelling will enable the researchers on water-related issues to establish interlinkages with other environmental drivers, such as climate change or anthropic impacts, and



even to work at different temporal and spatial scales (Aguilera el al., 2013 a and b; Lassaletta et al., 2010 and 2013). Finally, the new knowledge built from the use of those tools will provide a new set of criteria for policy makers and environmental managers that will enable them to take decisions based on the best available scientific knowledge. AQUALIFE Advanced Surveillance Environmental & Decision Support System for River Basins The LIFEWATCH e-Infrastructure based AQUALIFE (Sáenz-Albanés, 2013) initiative involves the design, construction and maintenance of an Advanced Surveillance Environmental & Decision Support System for River Basins. Its testing pilot prototypes are being developed in the scenario of the Guadalquivir River Basin (including the Doñana Natural Area), under the auspices of the Guadalquivir River Basin Authorities Body (“Confederación Hidrográfica del Guadalquivir”-CHG), and in tightly cooperation with the Andalusian Institute of Technology (IAT). It is structured in 5 Work Packages, where “cutting-edge” technologies on Remote Sensing (Satellite Images,etc.), sensor networks, interoperability and semantics of big (meta-) data resources and decision support systems (including the so-called “virtual labs”) are initially foreseen to be put at the disposal of the Managers & Decision Makers, Researchers and Citizens dealing with Guadalquivir River Basin area and then, to be opened-up to the rest of ESFRI LIFEWATCH Community of Practice.

Figure 3: AQUALIFE - LIFEWATCH funcionalities & planned e-services features

The expected impacts of AQUALIFE developments in regards to the Public Administration will be especially focused on the establishment of a new generation Organizational Knowledge and Information Management System which allows to coordinate and manage into both “in real time” and “on-demand” ways, the (e-) services requested by the River Basins users. These (e-) services are schematically shown in Figure 3. Moreover, the expected improvement of the coordination among River Basin managers at regional, national and international level, which are sharing common EC Directives (e.g., Water Framework Directive, Directive 2007/60/EC on the assessment and management of flood risk,etc.), River Restoration practices, etc. Moreover, a big impact in Agro-food sector is also expected, as this system will provide with cost and energy saving recommendations, as well as other useful informations related to crops. Moreover, citizens will be aware of their active participation on River Basin Integrated Water Resource Management process, mainly by transmitting their opinions and suggestions in regards to water conflict, gender, and River Basin preservation and restoration. All these, by means of the establishment of proper dissemination mechanisms, though the use of the so-called mobility devices (smartphones, etc.), and portal web public areas (see Figure 4). In summary, these systems will be ideal instruments to support River Basin Authorities for the adaption, application and monitoring of the river basins, including efficient early risk management subsystems, the setting of territory plans and to guarantee a proper dissemination strategy of their activities.




Figure 4: Conceptual Frame of the AQUALIFE - LIFEWATCH Information System Architecture

References

Aguilera, E., Lassaletta, L., Sanz-Cobena, A., Garnier, J. & Vallejo, A., 2013a. The potential of organic fertilizers and water management to reduce N2O emissions in Mediterranean climate cropping systems. A review. Agriculture, Ecosystems & Environment 164, 32-52.

Aguilera, E., Lassaletta L., Gattinger A. & Gimeno B.S. 2013b. Managing soil carbon for climate change mitigation and adaptation in Mediterranean cropping systems. A meta-analysis. Agriculture Ecosystems & Environment 168, 25-36.

Coterillo et al. 2012. Integrating a Multisensor Mobile System in the Grid Infrastructure, in Remote Instrumentation for EScience and Related Aspects. Springer, 2012.

EMoSEM Ecosystem models as support to eutrophication management in the North Atlantic Ocean Project http://www.seas-era.eu/np4/20.html.

González-Aranda, J.M., Rodríguez-Clemente, R., Lozano S. 2010. E-Research in International Cooperation Networks in Science & Technology Research. Pags. 167-199. Chapter in book: E-Research Collaboration: Theory, Techniques and Challenges. Springer. 2010. ISBN 978-3-642-12256-9.

González-Aranda, J.M. 2006. Creating and nurturing the MELIA (Mediterranean Dialogue on Integrated Water Management) Community of Practice: A strategic Coordination Action for the establishment of an Information and Knowledge Management, Sharing and Dissemination Platform for IWRM in the Mediterranean Area. In Book of Abstracts of “EUROPE International Network of Basin Organizations - INBO 2006”, Megève (France) September 2006.

Lassaletta, L., García-Gómez, H., Gimeno, B.S., Rovira, J.V. 2009. Agriculture-induced in nitrate concentrations in stream waters of a large Mediterranean catchment over 25 years (1981-2005). Science of the Total Environment: 407: 6034-604; IF (2009).

Lassaletta, L., García-Gómez, H., Gimeno, B.S., Rovira J.V. 2010. Headwater streams: neglected ecosystems in the EU Water Framework Directive. Implications for nitrogen pollution control. Environmental Science and Policy 13: 423-433.

Lassaletta, L., Billen, G., Romero, E., Garnier, J. & Aguilera, E. 2013. How changes in diet and trade patterns have shaped the N cycle at the national scale: Spain (1961–2009). Regional Environmental Change. Accepted DOI 10.1007/s10113-013-0536-1.

Monteoliva, A. et al., 2013-2015, ROEM+ Project: http://www.roemplus-life.eu/.

Sáenz-Albanés, A.J., 2013. AQUALIFE Technical Annex. Andalusian Institute of Technology, Seville, Spain.



Integrating Action Assessment and Knowledge Exchange in Combating Desertification: The PRACTICE Integrated Protocol

Susana Bautista1, Barron J. Orr2 and V. Ramón Vallejo3

1 Department of Ecology, University of Alicante, Alicante, Spain

2 Office of Arid Lands Studies, University of Arizona, Tucson, USA 3 Departmment of Plant Biology, University of Barcelona, Barcelona, Spain

Introduction

There is an increasing demand for the development and implementation of appropriate assessment methods to measure progress on managingdrylands and combating desertification (UNCCD 2009). The adoption of best management practices requires a good use of the existing scientific and local knowledge, as well as improved understanding on the impacts of the strategies and techniques applied on the target socio-ecological systems. Both requirements can be met through the systematic and participatory evaluation of the actions applied and further dissemination of the results.

Approaches to the assessment and monitoring of dryland management range from those that focus on particular biophysical properties of the system (e.g., soil erosion) to those that emphasize socio-economics (e.g., cost-benefit analysis). In recent years, focus has shifted to socio-ecological assessment, which recognizes the complex and dynamic relationships between humans and ecosystems (MA 2005). Particular challenges are the integration of biophysical and socio-economic fields; the identification and selection of a set of indicators that capture key sustainability issues, that are manageable and simple enough to be applied consistently and affordably in different regions over long periods of time, but also relevant for each specific ecological and socio-economic context assessed; and the development of participatory approaches that integrate scientific and local knowledge, as well as the variety of stakeholder perspectives (Bautista and Alloza 2009).

The participation of stakeholders and the incorporation of local knowledge in the assessment of environmental problems and potential solutions have been increasingly demanded by international institutions. Conventional environmental assessments tend to be expert-led, top-down activities that generate knowledge for understanding the impacts of management actions. However, these approaches suffer poor adoption rates in part because the engagement of local stakeholders is unidirectional and often limited to defining the context at the beginning and delivering the findings upon completion. Participatory assessment has the potential to engender social learning among all stakeholders, including scientists, which then has the potential to increase collaboration (Reed et al. 2008). Assessment approaches that promote the identification and selection of assessment criteria by the stakeholders, ensure a link between stakeholder perspectives and what is measured and create the demand on the part of the stakeholder for accurate and representative data that are relevant to their local realities and constraints.

PRACTICE integrated assessment protocol, IAPro

PRACTICE IAPro links the evaluation of management actions with knowledge exchange and social learning through a participatory process. IAPro is based on (1) key common indicators that represent key ecosystem services in drylands, and that are also relevant for the objectives of CBD and UNFFC, and (2) site-specific indicators identified by local stakeholders that are relevant to the objectives and the particular context conditions.

IAPro provides guidance on how to engage a comprehensive and representative set of stakeholders interested in actions to combat desertification. It provides a means to capture baseline stakeholder perspectives on management actions and assessment indicators, and then facilitates knowledge exchange and social learning among stakeholders.




The basic assumptions underlying IAPro evaluation method are: (1) Participatory assessment increases adoption. (2) Assessment improves by linking scientific and local knowledge. (3) Assessment must be supported by accurate monitoring data. (4) There are not absolute best practices. Evaluation of practices depends on tradeoffs between criteria, individual stakeholder perspectives and interests, as well as dynamic socio-environmental contexts. (5) Dryland social-ecological systems are coupled, and therefore the assessment of management options must simultaneously consider both biophysical and socio-economic attributes.

IAPro is structured as a sequence of steps that offers a path for knowledge exchange among the variety of stakeholders and between scientists and stakeholders. Some of the modules are full participatory activities (Steps 1 to 3 and 6), while Steps 4 and 5 represent scientific and technical work to be performed by the local assessment team (Fig. 1).

2. Baseline evaluation of actions & selection

of site-specific indicators

1. SHPIdentification & engagement

5. Integrating data and perspectives.

MCDA

3. Integrating &weighting general and site-specific indicators

6. Collective integrated

assessment

Social learning

4. Data gathering

Science-based suite of general (common)

indicators

Figure 1: IAPro structure. Flowchart of the protocol steps

The suite of science-based criteria and indicators in IAPro aims to represent a well-balanced basket of ecosystem services, covering the four broad categories of provisioning, regulatory, supporting, and cultural services, and focusing on key services in drylands (MA, 2005). Table 1 summarizes the criteria proposed, including potential indicators for their assessment. These criteria and indicators, which aim to capture the overall functioning of dryland systems, are combined with additional site-specific indicators identified by local stakeholders that are relevant to the objectives and the particular context conditions.



Table 1. Science-based common criteria and indicators for the assessment of management and restoration actions to combat land degradation in drylands.

Criteria Indicators

Income; personal/family wealth Site-specific

Provisioning Services: Goods (food, fiber, timber, forage..) Productivity; Productivity value

Water and soil conservation Plant cover and pattern; Soil surface condition Regulating & Supporting Services: Carbon sequestration Soil organic carbon; Above-ground biomass

Cultural Services: Landscape and cultural heritage Site specific (e.g., aesthetic value; spiritual l )Biodiversity Diversity of vascular plants

The protocol begins with the identification and engagement of the site-specific stakeholder platform (Step 1). This step aims to identify and involve a comprehensive and representative set of stakeholders who can contribute to the evaluation process. It is essential not to assume a priori knowledge of all stakeholders. The stakeholder identification method to be used is a form of “chain referral” where initial key respondents (potential stakeholders) are interviewed to obtain information and referrals of other potential stakeholders.

Step 2 aims to capture the baseline stakeholder perspectives on (1) the actions applied to combat desertification and (2) the site-specific indicators for the assessment of these and other potential actions. This step provides two crucial elements for participatory assessment and social learning. On the one hand, it captures and makes explicit the individual stakeholder baseline perspectives, which can be later contrasted with monitoring data and other stakeholders’ perspectives, leading eventually to the production of new knowledge and learning. On the other hand, it provides stakeholders the opportunity for participating in the definition of the assessment method itself, by proposing site-specific indicators that are relevant for the local conditions.

Step 3 aims to establish both individual and integrated stakeholder perspectives on the relative importance of the indicators selected in previous steps. Step 3 is designed to gather information on stakeholder preferences on both the indicators suggested by different stakeholders and the common indicators suggested by IAPro. Therefore, Step 3 offers opportunities for social learning and the integration of scientific and local knowledge. The final outcome from Step 3 is a set of collective weights for the list of selected indicators. The weights elicited are then incorporated (See Step 5) into a Multi-Criteria Decision Analysis (MCDA) applied to the data collected for each indicator and action assessed. There are several approaches and methods available for weighting indicators and criteria. IAPro proposes a revised version of a procedure known as SIMOS procedure (Figueira and Roy 2002). It is an exercise that uses a ‘card playing’ format in which different criteria (indicators) are classified and ranked.

Step 4 addresses the collection of data for each of the indicators proposed in previous IAPro steps. Data gathering must rely on the expertise of local researchers and technicians, who are responsible for choosing the most appropriate metrics and survey methods, yet participation of stakeholders in the process is desirable and encouraged.

IAPro Step 5 applies MCDA to integrating the stakeholder perspectives on the assessment method (through the selection of indicators and definition of their relative importance) and the data gathered for each of the selected indicators. The final result of the procedure is a partial or ordinal ranking of options, which helps visualize the alternatives that perform at least as good as the others in most of the criteria.

Step 6 represents the end of a process where the combination of science and local knowledge, monitoring data and stakeholder perspectives converge into a collective evaluation of the actions implemented to




combat land degradation. This step brings what scientists have learned from the stakeholders from previous steps back to them and brings the science (the approach and the data) to the stakeholders so that they can make a more informed assessment of the management actions through social learning and other forms of informal learning. Step 6 is conducted in a framework of a workshop with the SHP that targets the integrated evaluation of the management actions to combat land degradation.

Policy oriented recommendations

Sustainable management can benefit from participatory assessment methods that incorporate the knowledge and perspectives of scientists and the stakeholder community. Participatory assessments that promote social learning have a great potential to increase adoption of good practices. Methods that result in social learning also result in engagement, a necessary precursor to collaborative decision making and collective action.

Implementation of IAPro facilitates knowledge exchange and learning through the participatory assessment of management actions to combat desertification. This approach has been successfully tested in 18 dryland sites distributed across eleven countries, demonstrating its potential for the consistent but also adaptive assessment of a large variety of management actions to combat desertification. The PRACTICE-IAProl can be used at larger scales, for instance, to help identifying best policies at a national level. Spatial and temporal scale would be determined by the stakeholder platform and the actions and programmes being evaluated. Since IAPro indicators are also Sustainable Land Management (SLM) indicators, the protocol can be used to SLM assessment. Similarly, the participatory approach could be adjusted for a priori exploration of alternatives.

Dissemination of lessons learned among local communities, and among different sites and the larger desertification community is crucial to further promote knowledge exchange and learning. PRACTICE Netweb (http://practice-netweb.eu/) is a place where people involved in or affected by actions to combat desertification/land degradation can connect, share their stories and learn from each other. Acknowledgements

The authors thank the collaborative work done by the partnership of PRACTICE Project, funded by the European Commission under the FP7-ENV Program, which greatly contributed to the development and testing of PRACTICE Protocol.

References

Bautista S. and Alloza, J.A. Evaluation of forest restoration. In S. Bautista, S., Aronson, J., Vallejo, V.R. (eds), Land Restoration to Combat Desertification. Innovative Approaches, Quality Control and Project Evaluation. Fundación CEAM, Paterna, Spain (2009), pp. 47-72.

Figueira, J. and Roy, B. Determining the weights of criteria in the ELECTRE type methods with a revised Simos’ procedure. European Journal of Operational Research (2002), 139, 317–326.

Millennium Ecosystem Assessment, MA. Ecosystems and Human Well-being: Synthesis. Island Press, Washington, DC. (2005).

Reed, M.S., Dougill, A.J. and Baker, T.R. Participatory indicator development: what can ecologists and local communities learn from each other? Ecological Applications (2008), 18, 1253-1269.

Steins, N.A. and Edwards, V.M. Platforms for collective action in multiple-use common pool resource management. Agriculture and Human Values (1999), 16, 241-255.

UNCCD. UNCCD 1st Scientific Conference: Synthesis and recommendations. ICCD/COP(9)/CST/INF.3. UN Convention to Combat Desertification (2009), http://www.unccd.int/en/programmes/Science/Conferences/Pages/1st-Scientific-Conference.aspx



The use of deliberative scenarios for WES appraisal and identification of measures in two Mediterranean case studies: Noguera de Tor and

Anoia river basins

Francesc La Roca1, Graciela Ferrer1 and Joserra Díez2

1 University of Valencia, Department for Applied Economics, Valencia, Spain 2 University of the Basque Country, Department of Mathematics and Experimental Sciences Didactics, Vitoria-

Gasteiz, Spain

Introduction

In the last decades, human activities have intensified the use of natural resources giving rise to deep transformations of ecosystems and natural processes (Vitousek, 1994; IPPC, 2007). Fresh water ecosystems are particularly vulnerable to these changes, specially, in arid zones like the Mediterranean (CBD, 2010; EEA 2010). The state of water ecosystems is seriously affected by the combined effect of climate change and a wide range of human’s pressures and impacts –e.g. pollution, channelling, flow regulation, loss of riparian forests (Sabater, 2008). The deterioration of water ecosystems impairs their capacity for supplying natural resources and services which are basic for human wellbeing (MEA, 2005).

Implementing mitigation and adaptation measures to deal with the causes and effects of global change requires a shared diagnosis of local issues and identification of context adapted actions (Ostrom et al., 2007) to conserve ecosystem services (ES) in the medium and long run. Participation of users and interested parties in such activities is necessary due to the complex and uncertain nature of the issues to be dealt with (Funtowicz and Ravetz, 1990; WFD-CIS, 2002) and the necessary involvement of such actors in measures implementation for reducing pressures on the environment (WFD-CIS, 2002).

Our interest is to explore how global environmental change affects water ecosystem services (WES) at local scale now and for the 2050 horizon, and to understand how society appraises them. This implies the articulation of a plurality of points of views, values and interests to understand complex relationship among different knowledge domains, spatial scales and time-horizons, as well as anticipatory and strategic thinking (Kay et al., 1999). In this context, we propose the development of deliberative scenarios in small scale case studies as an interesting research tool, as they are suitable instruments for articulation of a plurality of views –including lay people- and fruitful thinking around complex issues, tackling uncertainty, and allow reflection on a concrete socio-economic and spatial context (Pahl-Wostl, 2008; Lebel et al., 2005). In this paper we present the results obtained in the two case studies where we applied this methodology.

Methods

Selection of case studies

The two case studies selected were Noguera de Tor river basin (Ebro river basin) and Anoia river basin (Llobregat river basin). Noguera de Tor is a small mountain river basin (312 km2) located in the southwest Catalan Pyrenees (1800 – 850 m.o.s.l). Its main channel is Noguera de Tor (30 km length, 244 hm3/year), a third order tributary to the Ebro river. The valley has a low population density and the main economic activities are hydropower generation and residential and familiar tourism linked to snow and active sports, nature and historical heritage. Ecosystems have a good status of conservation –a main part of the river basin is included in the National Park “Aigüestortes i Llac de Sant Maurici”- although fluvial ecosystems suffer from high hydromorphological pressures due to intense intervention –dam, weirs, diversions, etc.- on the fluvial channels and over river flows to produce electricity.

Anoia is a river basin (930 km2) located near to the Metropolitan Area of Barcelona. The stream (65 km




length, 60 hm3/year) flows from the Catalan Central Depression (700 m.o.s.l.) through the Prelitoral mountain to Sant Sadurní d’Anoia, to join the Llobregat river in Martorell (56 m.o.s.l.). In natural conditions, the Anoia supplies the 9% of Llobregat river’s water resources. Population concentrates in middle sized cities (Igualada and Martorell) close to the main river channel in the middle river basin and in the confluence of Anoia and Llobregat rivers. Main economic activities are industry and services. Industrial activities –paper, tanneries, textile, automotive, etc.- have a long tradition in the area (Anoia county), historically taking advantage from water and potential energy of Anoia’s river and from pumping Carme-Capellades’ groundwater. Since the mid-eighties traditional industrial sectors have declined influenced by market globalization, however population living in the basin has increased as a result of the Barcelona’s urban sprawl. Non-irrigated agriculture is important in the lower basin (Alt Penedès county), where vineyards are predominant and the production of cava is concentrated. Surface water bodies do not reach good chemical and ecological status due to industrial and urban pollution, hydromorphological alterations –channelling, weirs, and agricultural and urban occupation of fluvial banks. Groundwater bodies are in bad status due to overpumping and chemical pollution. Water provisioning for an important part of urban and industrial uses depends on water transfers from Ter-Llobregat system.

The deliberative scenarios exercise

A deliberative scenarios exercise has been developed to explore the impacts of global environmental change on WES at the local scale for the horizon 2050, and values hold by the local society around WES. It consist of a set of three workshops per case study aimed to define (1) the present situation of WES at the local scale; (2) plausible future situations of WES at local scale taking into account the foreseen impacts of climate change on the hydrological cycle and two alternative socio-economic and institutional contexts –one market driven and another socio-environmental friendly; and, (3) policy actions that should be taken to retain WES in the future situation (La Roca et al., 2011b).

The first workshop was devoted to contrasting the project team identification of WES with local people (La Roca et al., 2011a), and to the identification of WES trade-off derived from current socio-economic activities in each case study river basin.

In a second workshop a scenario of qualitative expected effects of climate change on the hydrological cycle was presented to participants in each case study, taking as reference the downscaling of climate change effects over climatic variables for Catalonia (Barrera-Escoda and Cunillera, 2011). In this context participants identified the most vulnerable current uses and WES. Then, they worked in two groups imagining how their river basin would be in the next 40 years, introducing two contextual socio-economic and institutional scenarios in form of story-lines: one where development is understood as mere economic growth (called “Economic competence”); and the other, where development implies a balance among social values, environmental restrictions and economic growth (called “Socio-environmental integration”). These narratives are based on the global scenario story lines “Market first” and “Sustainability first” of the GEO-4 Report (UNEP 2007) and “Global Orchestration”, “Adapting Mosaic” and “Techno-Garden” of the Millenium Ecosystem Assessment (Cork, Peterson, et al., 2005). Finally, they identified the most relevant WES for future local wellbeing, whatever the contextual socio-economic scenario will be.

In the third workshop participants were asked to select and propose the measures they identified as the relevant ones for future local wellbeing through the conservation or improvement of WES. They identified opportunities and drawbacks for their implementation.

Methodologies applied for the development of workshops included the presentation and contrast of information collected through desk research, structured debate around proposed questions and group work to build up schematic representations of future visions –forecasting approach- and measures –backcasting approach (Van Notten et al., 2003). Each workshop session took between 2 to 3 hours throughout 2012-2013. In each case study interested parties were identified and contacted –telephonically and via e-mail- to invite them to participate. After each workshop, a report on the development and contents treated



during the workshop was sent to participants.

Results

Attendance to workshops was irregular, noting a very low participation in the Anoia case study. In Noguera de Tor there was predominant participation of local actors with environmental sensitivity and the absence of the main economic users of water. In Anoia, there was a scarce participation of local and county authorities and representatives of economic users of water, and a bias to environmentally aware participants.

Identification of current WES uses and trade-offs

Participants in the Noguera de Tor case study identified the highly intense provision of water for energy production as the main source of deterioration of ES (hydrological regime, maintenance the ecosystem integrity, recreational and aesthetic services and provisioning of water for livestock farming).

Participants in the Anoia workshop highlighted the overuse of the provisioning service of water for domestic uses and for industrial activities and the overuse of self-purification service as the main cause of deterioration of regulation, habitat, and cultural/aesthetic services. Such overuse has required the import of these services through Ter-Llobregat system. Participants also stressed that this situation is aggravated by urban, infrastructural or agricultural occupations of fluvial space that deteriorates services of protection against extreme climatic events, soil and sediment dynamics and hydrological regime, which in turn, reduce the provision of habitat, recreational and aesthetic services.

Identification of the most vulnerable uses and WES to climate change

As consequence of climate change expected changes in the case study’s river basins are reductions of surface and groundwater resources, increase of evapotranspiration, a reduced number of snow days –in the case of Pyrenees zone-, and the alteration of the fluvial metabolism, affecting the ecosystem’s ability for fluvial self-purification and for biodiversity support (ACA, 2009).

In the Noguera de Tor, participants considered traditional ranching and snow tourism the most vulnerable current uses; while they consider hydropower generation highly resilient because of existence of room for efficiency improvements and the strong firm’s negotiation power. Participants underlined new economic options: new climate adapted crops and re-orientation of touristic offer towards summer tourism. As a consequence, increased pressure on provisioning and regulation WES is expected. Growing conflicts among water for hydropower production and competing provisioning services are foreseen.

In the case of Anoia river basin, participants identified non-irrigated agriculture, small irrigated gardens, industrial uses and livestock farming as the most vulnerable current uses. Drinking and domestic uses of water is not considered vulnerable because its institutional highest priority of supply. An increase of pressures on all currently used and affected WES is expected, as well as growing dependence on external resources for supplying water provision services to urban and industrial uses.

Identification of WES considered as the most important for the future

In the case of Noguera de Tor, participants considered that the most important WES for local people in the future will be provisioning of water for livestock farming and for other economic activities –tourism, in particular- and the provision of recreational and educational and scientific services. For enjoying these services, they considered the conservation of hydrological regime and the maintenance of ecosystem integrity services as a strategic issue.

In the case of Anoia, participants considered that the most important WES for local people in the future will be the provisioning of water for drinking and domestic purposes, the hydrological regime and the maintenance of ecological integrity, together with self-purification.




Suggested mix of measures for conserving or recovering WES1

In the case of Noguera de Tor, participants identified five action lines: (1) political coordination; (2) land planning integration; (3) water use rationalization; (4) economic instruments; (5) knowledge & education.

In the case of Anoia, participants identified six action lines: (1) water use rationalization; (2) land and urban planning integration; (3) economic instruments; (4) transparency and knowledge; (5) pollution prevention; (6) ecological restoration.

Discussion

Identification of ES is a useful tool to conceptually frame the mapping of human-ecosystem evolving relationship. It enriches the reflection on natural resources management making evident the interdependence of direct uses of natural resources and services with ecological processes and functions that provide them.

Participants perceived provisioning and cultural/aesthetic ES as direct services from ecosystem, with a direct effect on human wellbeing. However, the ES approach allowed people to easily realize that the enjoyment of such ES implies a double relationship with regulation and habitat ES. On the one hand, intensification of provisioning and cultural/aesthetic services can erode the capacity of ecosystem for supplying regulation and habitat ES. On the other hand, provisioning and cultural/aesthetic services heavily depend on the capacity of ecosystems for providing regulation and habitat services. This fact makes people value regulation and habitat ES not only from the perspective of an environmental abstract responsibility but also from a material linkage between human wellbeing to ecosystem health. One of the results of this experience is that workshop’s participants identified regulation and habitat ES as cornerstones for future human wellbeing and, accordingly, a main part of measures they suggested were addressed to improve or guarantee the ecosystems capacity to provide them. This approach is promising to communicate and get social support to measures addressed to achievement of environmental goals in water management –e.g. good status of water bodies under the WFD.

Distributional issues emerged repeatedly in both case studies. Spatial or temporal asymmetries between ES production and use were made evident. Participants pointed out the asymmetry between who assumes the costs for ES production (in form of trade-offs) and who enjoy the benefits. They stressed the need for a more equitable regulation of natural commons –including economic compensations and use restriction’s thresholds- that accounts for local people wellbeing and avoids or minimizes spatial or temporal transference of impacts. The integration of ES conservation as a goal in sector oriented policies –rationalization of demands- and the need of coordination among different political and administrative scales and policies was emphasized as a necessary requirement to effectively conserve or improve ES.

The use of scenarios in a deliberative way allowed participants’ creative and strategic thinking under high uncertainty –the future under global change conditions. Deliberative scenarios are a useful tool for dealing with complexity, addressing multidimensional aspects, their interdependencies and the articulation of mix of measures. Participatory techniques give the opportunity for mutual learning and shared reflection, however participatory processes are time consuming for participants and promoters. Low participation is a weakness in our experiment. Willingness to participate is much related to potential participants’ personal motivation. The lack of practical outcomes in terms of influence on decision making discouraged the attendance of economic and political actors, while introduced an environmental bias as a majority of participants in workshops had an environmentalist sensibility. This fact reduced the inclusiveness of discourses. Acknowledgment This research has been developed in the framework of the SCARCE Project (Consolider-Ingenio 2010 Project CSD2009-00065),

1 Annex 1 contains an example of the expected effects of suggested measures on the capacity of Noguera de Tor river basin’s water ecosystems for providing selected WES. The case of Anoia is not included due to space limitations.



funded by the Spanish Ministry of the Economy and Competitiveness. References ACA – Agència Catalana de l’Aigua. Agua y cambio climático, Generalitat de Catalunya (2009), 1-329. Barrera-Escoda, A. i J. Cunillera. Primer informe sobre la generació d'escenaris climàtics regionalitzats per a Catalunya durant el segle XXI, Servei Meteorològic de Catalunya (2011). CBD - Secretariat of the Convention on Biological Diversity. Year in Review 2009. Montreal (2010), 1-42. Cork, S., G. Peterson and G. Petschel-Held (coords.) Four Scenarios. In MEA. Ecosystems and Human Well-being: Scenarios. Volume 2, (2005), Island Press, USA, 223-294. EEA – European Environment Agency. The European environment. State and Outlook 2010. Synthesis. EEA, Copenhagen, (2010) 1-228. Funtowicz S.O. and J. Ravetz. Science for a post-normal age. Futures (1993), 25, 735–55. IPCC. Climate change 2007: the physical science basis. World Meteorological Organization (2007). Kay, J. J., H.A. Regier, M. Boyle, and G. Francis. An ecosystem approach for sustainability: addressing the challenge of complexity. Futures (1999), 31, 721–742. La Roca, F., G. Ferrer and M. Gual. Scenario building of possible futures: changing the costs structure and new priorities setting, Deliverable 7.2. SCARCE Project (2011), 1-57 La Roca, F., G. Ferrer, M. Gual and S. Farhal. Analysis of the present contribution of water related ecosystem services to the human well-being at the water body scale, Deliverable 7.1. SCARCE Project (2011), 1-185 Lebel, L., P. Thongbai and K. Kok (coord.). Sub-global scenarios. In MEA. Ecosystems and human wellbeing: multiscale assessments. Volume 4, (2005), Island Press, USA, 229-259. MEA - Millennium Ecosystem Assessment. Ecosystems and human well-being: biodiversity synthesis. World Resources Institute (2005). Ostrom, E., M.A. Janssen and J.M. Anderies. 2007. Going beyond panaceas. PNAS (2007), 104(39), 15176-15178. Pahl-Wostl, C. Participation in Building Environmental Scenarios, in Alcamo, J. (ed). Environmental Futures: the practices of environmental scenario analysis. (2008), Elsevier, 105-122 UNEP-United Nations Environmental Programme. Global Environment Outlook GEO4 – Environment for development. (2007), UNEP, Malta. Sabater S. Alterations of the global water cycle and their effects on river structure, function and services. Freshwater Review (2008), 1, 75–88. Van Notten, P.W.F., J. Rotmans, M.B.A. van Asselt and D.S. Rothman. An updated scenario typology. Futures (2003), 35: 423-443. Vitousek, P.M. Beyond global warming-ecology and global change. Ecology (1994), 75(7), 1861–76. WFD-CIS – Water Framework Directive Common Implementation Strategy. Guidance on public participation in relation to the Water Framework Directive, European Commission – DG Environment (2002), 1-66.

Annex 1.

Table 1. Expected effects of participant’s measures on the capacity of Noguera de Tor river basin’s water ecosystems for providing selected WES (grey cells indicate the participant’s selection of WES to be retained for the future wellbeing of river basin inhabitants). Source: own elaboration based on the III Workshop.

Measures (1) (2) (3) (4) (5) (6) (7) Voluntary agreement for WES protection - + + + + + + Land use limitations - - - + + + + Ecosystems connectivity - - + + + + Review of water use rights - + + + + Ecological flows - - - + + + + Payment for water provision for hydropower generation - + + + Payment for self-purification and provision of good quality water + + Payment for recreational uses of protected areas - + + Research on impacts of global change on biodiversity + + + + Knowledge transfer + + + + + + Environmental education + +

Notes: (1) Water for hydropower generation; (2) Water for livestock farming; (3) Water for other economic activities (tourism); (4) Recreational services; (5) Educational and scientific services; (6) Hydrological regime; (7) Maintenance of ecosystem integrity.




SOLUTIONS for present and future emerging pollutants in land and water resources management

Werner Brack

Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany

There is evidence that many European surface waters will not achieve the good ecological and chemical status till 2015 as required by the Water Framework Directive (WFD). Many studies suggest that the contamination with chemicals significantly contribute to this problem, while it is getting more and more obvious that priority substances alone do not explain this phenomenon. So-called emerging pollutants play an important role. They lack regulation but often also appropriate tools for their detection and understanding and models for exposure, effect and risk assessment.

The large scale FP7 Collaborative Project SOLUTIONS addresses this problem. Starting in October 2013 with 39 partners from all over Europe, but also with partners from China, Australia and Brazil, the 5 years project wants to provide solutions for the early detection, identification, prioritization, assessment and abatement of emerging pollutants.

Overall concept

While the chemical status of WFD considers only 33 priority substances together with 8 other chemicals, we are confronted with a dramatically diverse chemosphere. At present more than 70 million chemicals are registered in the Chemical Abstract System (CAS), about 14 million chemicals are commercially available and in typical environmental samples we are able to detect ten thousands of compounds. Thus, it is not astonishing that priority substances often do not explain observed effects. However, despite the multitude of chemicals in general, typically much smaller numbers of chemicals are causing the majority of toxicity, if we focus on distinct toxicological endpoints, organisms or populations. This was shown by Kortenkamp & Faust (SOLUTIONS proposal) for anti-androgenic effects. Based on monitoring data from 2005 they could show that only 5 chemicals including heterocyclic fungicides, butylparabene and plasticizers were responsible for 80 % of anti-androgenicity. Only one of them is a priority substance according to WFD. It is obvious that proper risk assessment has to be well informed on the chemicals that actually cause a risk. These chemicals however, may be highly variable on the time scale, e.g. due to the enormous dynamics in the chemicals market. This holds for example for pesticides, such as the fungicides mentioned above, which are frequently replaced by others because they lose their registration or because pest become resistant. To properly reflect these dynamics, SOLUTIONS provides an exhaustive conceptual framework for legacy chemicals, chemicals that are presently in use but also future chemicals. This framework integrates effect-based and chemical monitoring tools for the early detection and identification of hazardous chemicals that already accumulated in the environment with modeling tools based on compound structure, properties and emission data to predict exposure and risks of chemicals in use. This approach will be also used for future chemicals on the basis of scenarios and predictions. Large scale case studies are performed to demonstrate the novel tools and models and to mutually validate them.

Tools and Models

SOLUTIONS will provide analytical tools for high-sensitivity determination of chemicals with low PNECs including novel passive and active sampling tools and advanced methods for sample preparation and analysis. A second focus is on the development of non-target workflows for compound identification and structure elucidation based on LC-MS/MS techniques in combination with computer tools. Effect-directed analysis integrating chemical information and effect patterns via fractionation or multivariate statistics will help to identify those chemicals that cause measurable effects. The development of multi-endpoint effect-based monitoring tools for the early detection of hazardous chemicals in the aquatic



environment is a key issue in SOLUTIONS. Effect-based tools follow the concept of Adverse Outcome Pathways (AOP) and strive to provide appropriate tools for different levels of biological organization. Effect-based monitoring tools will be supplemented with trait-based ecological tools to detect ecosystem degradation that may be caused by toxicants.

An integrated system of models and databases will be established to understand and predict exposure to emerging pollutants and related risks. Emission estimation modeling will be combined with multi-compartment modeling of fate and transport and distributed modeling on a basin scale in order to estimate pollutant concentrations in European surface waters. Key factors will be together with spatial data for river basin characterization the physico-chemical properties of the compounds that determine exposure. Structure-based modeling of substance properties will fill the significant data gaps. A specific focus is given on ionic, polar and multifunctional compounds where traditional approaches e.g. based on log KOW fail. Mode-of-action specific toxicity prediction and mixture effects modeling will be interlinked with exposure modeling to predict ecosystem and human health risks.

Case studies

SOLUTIONS tools will be demonstrated in three case studies including the Danube basin, the Rhine basin and the river basin under SCARCE. The major focus of the Danube basin case study is on the establishment of River Basin Specific Pollutants. The SOLUTIONS investigations are closely linked to Joint Danube Survey 3, which provides SOLUTIONS with samples and data and will benefit from the new evaluation tools. The Rhine case study will have a specific focus on abatement options in waste and drinking water management. The case study in Spanish rivers will evaluate SOLUTIONS tools under water scarcity conditions and will integrate and evaluate SCARCE and SOLUTIONS approaches.

Products

Solutions for prioritization, assessment and management of emerging pollutants will include

• user-friendly guidelines for innovative monitoring and modeling tools • a solution-oriented computer tool to support decisions • abatement options in waste and drinking water management • a common knowledge base on a wide range of toxicants • scenarios and solutions for upcoming risks and • potential opportunities and obstacles for cooperation of WFD with other policies




Managing Aquatic ecosystems and water Resources under multiple Stress (MARS)

Christian K. Feld1,2, Sebastian Birk1 and Daniel Hering1,2

1 Department of Aquatic Ecology, Faculty of Biology, University of Duisburg-Essen, Essen, Germany

2 Centre for Water and Environmental Research (ZWU), University of Duisburg-Essen, Essen, Germany

Summary

Managing Aquatic ecosystems and water Resources under multiple Stress (MARS) is an Integrated Research Project, funded by the European Union within the Seventh Framework Programme. MARS will have a duration of four years and will start on February 1st, 2014. Within MARS, nearly 100 scientists and practitioners, representing 24 partner institutions in 16 European countries, will address the effects of multiple stressors in surface water and groundwater bodies and its management.

The MARS workplan is organised at the scales of water bodies, river basins and all-Europe, with a direct link to water authorities and decision makers at each scale. Nested within this spatial structure, the project will employ a suite of flume and mesocosm experiments to gain a better understanding of the effects of selected stressors and its combinations, with one focus on hydrological and thermal extremes. This research will lead to a Europe-wide overview of environmental stressors, their present and future impact on ecological status and aquatic ecosystems services.

MARS is composed of eight workpackages addressing the development of tools, concepts and scenarios for river basin management under multiple stressors, and synthesising the empirical research findings across experimental, river basin and all-Europe scales. To transfer MARS’ research findings into applied river basin management, amongst others a wiki information system will be set up to disseminate the MARS outcome among different groups of end users. Eventually, MARS will frequently communicate the outcome with representatives of river basin districts and the Common Implementation Strategy (CIS) groups and will advise the WFD revision.

Multiple stressors are largely unaddressed in operational monitoring

Multiple stressors impact Europe’s water resources and aquatic ecosystems (Schinegger et al. 2012), with often complex effects on ecological and chemical status, water quantity and ecosystem functions and services. Many existing assessment methods (Birk et al. 2012) focus on the assessment of hydromorphological degradation, which itself is composed already of multiple hydrologic (flow, water abstraction, habitat), hydraulic (sheer stress) and morphological (straightening, barriers, damming, bank fixation) impairments (ETC-ICM 2012). In recent years, agricultural land use at the catchment scale has increasingly been addressed in bio-indication (e.g. Feld 2013), yet this particular land use actually bears a cocktail of ‘pollution’ stressors, composed of nutrient pollution (from fertilisers), fine sediment pollution (from surface run-off) and toxic pollution (from pesticides).

While present indicator systems usually detect these combined effects of the stressors, they fail at disentangling the hierarchy and effects of the various stress components. Knowledge of the latter, however, is fundamentally important to manage river basins, i.e. to reduce and mitigate the individual stressors in order of their importance for the overall ecological status. Further, there is knowledge already from previous research that multiple stressors may interact synergistically or antagonistically (Wagenhoff et al. 2011). Therefore, the investigation of the effects of multiple stressors on ecological status, but also on ecosystem functions and services is timely and urgently required to inform the management of



Europe’s waters.

Objectives of MARS

In a pre-project survey of Europe’s river basin management plans, MARS identified a set of major obstacles with regard to multiple stressors:

• Little is known about the combined effects of multiple stressors—although the majority of water bodies in Europe is affected by more than one stressor.

• Simple dose-response relationships between stress intensity and biological effects are not sufficient under multiple-stress conditions for developing appropriate management measures.

• There is a weak understanding of how multiple stressors affect degradation and restoration.

• There is a weak knowledge of the order of importance of individual stressors. This knowledge is required to prioritise restoration and mitigation measures.

Further, the implementation of measures requires convincing arguments beyond the concept of ecological status, in order to better inform society about the need for—and the benefits of—restoration. The value of ecological restoration is difficult to communicate to policy and decision makers and to the public in general, especially in times of the economic crisis in Europe. Therefore, supplementary indicators targeting ecosystem services are required to inform the public about the benefits of ecologically intact ecosystems.

MARS aims at overcoming these obstacles and filling these gaps in river basin management. New research as well as the synthesis of existing knowledge will be conducted to disentangle the impacts of multiple stressors on three response categories: i) ecological status ii) functions and iii) services of surface and ground waters in Europe. New indicators will be developed to predict the implications of river basin management on the three response groups. The outcome will feed into a toolbox to provide end users with an enhanced understanding of the ecosystem processes underlying degradation and recovery. This will help end users quantify the links between the status of aquatic ecosystems and their functioning and services. The MARS tools will make use of existing prototypes and aim to contribute to the toolbox proposed in the Blueprint to Safeguard Europe’s Water Resources.

Conceptual approach

Alike the spatial organisation of river basin management plans, the MARS research activities are organised at different spatial scales. At the water body scale, mesocosm and flume experiments will help enhance the mechanistic understanding of how stressors interact and impact upon water resources. This new experimental data will allow to identify threshold responses to optimise stress reductions. A focus will be on the effect of extreme climate events such as heavy rainfall, heatwaves, water scarcity and the effects of environmental flows.

At the river basin scale, relationships between multiple stressors and ecological responses, functions, services and water resources will be identified. The effects of land use change and mitigation scenarios will be predicted. Altogether, 16 river basins in Europe, chosen to represent a wide range of multiple stress conditions, will be investigated based on existing data from the catchments (Table 1).

At the European scale, the relationships among stress intensity, ecological status and service provision will be investigated, with a special focus on large, transboundary rivers, lakes and fish as sentinels of multiple stressor impacts on biodiversity and direct providers of ecosystem services.




Table 1. River basin case studies of MARS including data availability. Stressors: E=Eutrophication/Organic pollution, F=Fisheries, H=Hydrology/Water scarcity, I=Invasives/Pathogens L=Temperature/Light, O=Morphology/Shipping, T=Toxics. Multiple stressor groups: 1=Hydrology/temperature, 2=Hydrology, morphology, nutrients, 3=Water scarcity, flow alterations. Ecosystem Services: E=Ecological Flows, F=Fisheries, H=Hydropower, R=Recreation, S=Water supply, W=Water purification. Water category: L=Lake, G=Groundwater, T=Transitional water, R=River. Numbers in columns six to ten indicate the number of samples available for each quality element..

Bas

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Sorraia South EHLMT 3 EFSW 30 30 30 70 30 LGT Nervion Ibaizabal South EMT 3 RS 31 31 31 31 31 T Pinios South EHLMT 3 HSW 89 - 80 - - L Beysehir South EHL 3 FRS 16 3 - 80 2 LG Lower Danube South EHIM 3 FR 28 300 18 18 18 R Thames Central EHILT 2 EFSW 597 180 250 900 20 LGT Regge and Dinkel Central EHLM 2 S 428 30 1192 1003 117 G Odense Central EHMT 2 RW 100 20 113 40 27 LT Elbe Central EHM 2 FW 140 100 300 45 90 G Ruhr Central EHMT 2 SW 400 300 1600 50 50 R Drava Central HM 2 EFH 140 40 40 12 12 R Welsh basins North EHLMT 1 FRSW 400 200 400 50 100 R Vansjø-Hobøl North EIT 1 HRS 15 2 5 5 8 L Otra North HILT 1 FHR 30 10 10 10 8 R Kokemäenjoki North EHMT 1 HRWS 30 20 20 20 20 LG Võrtsjärv North EFHT 1 FRW 37 37 37 27 37 L

The MARS model

MARS establishes a framework that explicitly links the assessment of risk, status and ecosystem services within the framework of RBMPs, therefore providing a close integration of stressors, ecosystems and services (Fig. 1). Risk assessment combines the level of a single stressor—or of a combination of stressors—with an indicator’s response sensitivity to the stressor(s). The ecological status assessment centrally fits into the Driver-Pressure-State-Impact-Response (DPSIR) framework: Drivers (e.g. society’s food demand) cause Pressures (equivalent to stressors, e.g. land use) and consequently affect water body State (e.g. through enhanced nutrient levels). This has Impacts on ecological State and ecosystem functioning (e.g. loss of filter feeding taxa and its related filtering of particulate organic matter) and can cause the reduction or entire loss of ecosystem services (e.g. the self-purification capacity of a stream section). Eventually, society’s Response is required, for example through environmental regulation policies (e.g. restoration). Ecosystem services are generally considered through the ‘cascade model’, which links the structure, functions and processes of ecosystems to a specific service. The service may be translated into societal benefits or values associated to human well-being. Indicators link between the three frameworks (Fig. 1). Further, management decisions (Response) are not only based on the State-Impact chain through the DPSIR model, but must consider ecosystem service values, too. MARS will use this linked model to support management decisions and scenario-testing.



Figure 1. The MARS conceptual model for an integrated assessment framework.

Dissemination of MARS outcome

MARS will officially start on February 1st, 2014 and will be kicked off at the first consortium meeting in mid-February. A detailed description of MARS and frequent updates on its progress will be provided soon at www.mars-project.eu. A blog will complement the project website to more frequently address project features and invite the public to discuss those with members of the MARS consortium. The MARS Wiki will provide more detailed information and background knowledge on both the impacts of multiple stressors on the aquatic environment and suited measures to address their management. Acknowledgements

Managing Aquatic ecosystems and water Resources under multiple Stress (MARS) is a EU-funded integrated project within Framework Programme 7, Theme ENV.2013.6.2-1: Water resources management under complex, multi-stressor conditions (contract No. 603378).

References

Birk, S., Bonne, W., Borja, A., Brucet, S., Courrat, A., Poikane, S., Solimini, A., van de Bund, W., Zampoukas, N. and Hering, D. Three hundred ways to assess Europe's surface waters: An almost complete overview of biological methods to implement the Water Framework Directive. Ecological Indicators (2012), 18, 31–41.

ETC-ICM. Hydromorphological alterations and pressures in European rivers, lakes, transitional and coastal waters. ETCICM Technical Report 2/2012, European Topic Centre on Inland, Coastal and Marine waters, Prague.

Feld, C.K. Response of three lotic assemblages to riparian and catchment-scale land use: implications for designing catchment monitoring programmes. Freshwater Biology (2012), 58, 715–729.

Schinegger, R., Trautwein, C., Melcher, A. and Schmutz, S. Multiple human pressures and their spatial patterns in European running waters. Water and Environment Journal (2012), 26, 261–273.

Wagenhoff, A., Townsend, C.R., Philipps, N. and Matthaei, C.D. Subsidy-stress and multiple-stressor effects along gradients of deposited fine sediment and dissolved nutrients in a regional set of streams and rivers. Freshwater Biology (2011), 56, 1916–1936.




GLOBAQUA: Managing the effects of multiple stressors on aquatic ecosystems under water scarcity

Sergi Sabater1, Alícia Navarro-Ortega2 and Damià Barceló1,2

1Catalan Institute for Water Research (ICRA), Girona, Spain

2 Water and Soil Quality Research Group, Department of Analytical Chemistry, IDAEA-CSIC, Barcelona, Spain

Introduction

Water is the most essential of all natural resources and consequently water and water-related services are major components of the human wellbeing and major factors of socio-economic development in Europe. Nowadays, freshwater ecosystems are under threat due to a great variety of stressors that can have deleterious effects on them, including organic and inorganic pollution, geomorphological alterations, land cover change, water abstraction, invasive species and pathogens and water scarcity (Vörösmarty et al., 2010). Most of our current knowledge is based on the effects of single stressors on the chemical and ecological status (Maltby, 1999) and ecosystem functionality. This limits our capacity to understand ecosystem responses to multiple stressors. Water scarcity is a structural, persistent drought affecting resources and aquatic ecosystems, with implications in water quality and societal needs, that occurs when water demand exceeds the water resources exploitable under sustainable conditions (Sabater and Barceló, 2010). It can be a stressor on its own because of its structural character but it can also drive the effects of other stressors (e.g., increasing concentrations of pollutants in rivers resulting from a constant input of pollution and decreasing water availability (Petrovic et al., 2011)). Water scarcity is therefore a key stressor because of its direct and indirect effects in terms of the chemical and ecological status, but also in terms of the sustaining of ecosystem services (Heathwaite, 2010). Water scarcity is among the main problems to be faced by many societies in the 21st century because water use has been growing at more than twice the rate of population increase in the last century. In particular water scarcity has long formed an integral part of the Mediterranean environment, but today exponential demographic growth, climate change and pollution form a growing threat to the resource. As a semi-arid region, water scarcity is present in natural conditions in the Mediterranean are due to the characteristic highly variable river flows and occurrence of low flows of the Mediterranean climate. In addition, the Mediterranean basin is one of the most sensitive areas of the world regarding possible consequences of the present climate change (Barceló and Sabater, 2010) as well as one of the most impacted because of human water demand. Water scarcity is not only a simple matter of available resources for the human necessities. The natural systems also need good quality to guarantee their viability and functioning. To forget their necessities increases the danger in their existence but also in the quality of the services that they deliver.

Fig 1. Conceptual links considered in the projects



In order to properly address the effect of stressors in policy terms, a coordinated effort on the research that considers multiple perspectives is needed. A range of national and EU-funded research projects are directly or indirectly supporting water and climate policies, in particular the scientific challenges posed by the EU Water Framework Directive (WFD) and other policies. Within this context GLOBAQUA project has assembled a multidisciplinary team of leading scientist in the fields of hydrology, chemistry, ecology, ecotoxicology, economy, sociology, engineering and modelling in order to study the interaction of multiple stressors within the frame of strong pressure on water resources. The aim is to achieve a better understanding on how current management practices and policies could be improved by identifying the main drawbacks and alternatives (Fig. 1).

GLOBAQUA project

As one of the last FP7 projects (European Commission), GLOABAQUA, with the full title “Managing the effects of multiple stressors on aquatic ecosystems under water scarcity” is a 5-year project that will start on February 2014 as a follow up of SCARCE project. The consortium is composed of 21 European partners from 8 countries (including 1 SME) and 2 non-EU partners from Morocco and Canada. The institutional experience of the Consortium covers a range of disciplines: chemistry, biology, ecology, geomorphology, hydrology, economics and sociology, including hydrological, biophysical and ecological modelling, socio-economics and governance science, knowledge brokerage and policy advocacy. Scientific management of the project is carried out by the Water and Soil Quality Research Group of the Institute of Environmental Assessment and Water Research of the Spanish Council for Scientific Research of Barcelona (IDAEA-CSIC). The GLOBAQUA team includes practitioners and policymakers (Stakeholder Panel) who will ensure that the project is highly relevant to end-user needs. By bringing together researchers with strong international experience and end-users with key expertise in the region, a critical mass of experience and knowledge will be mobilized to carry out the project activities. The partnership is a result of cooperation of several initiatives, existing networks and research projects.

GLOBAQUA has two major complementary objectives. The first objective deals with fundamental research questions: improvement of our knowledge on relationships between multiple stressors, to identify potentially synergistic linkages and to assess how these interactions might determine changes in the chemical and ecological status. In this sense, special attention will be given to the role of water scarcity as a central stressor and to the relationships between biota (different level of biological organization) and stressors. This envisages a holistic approach that would range from the assessment of effects on water quality, organisms and ecosystems to the effects on socio-economical regional development. Our aim is to establish cause-effect relationships between multiple levels using integrative modelling. The second objective address the urgent need to improve water management practice and policies by taking into consideration the influence of multiple stressors; this should especially comprise the WFD (2000/60/EC) and other related regulations. The objective will be performed through analysis of current policies and scenario analysis of alternative management practices and policies.

Structure of GLOBAQUA

To answer the integrated questions posed within GLOBAQUA, a cross-scale approach will be applied in several representative basins. The basic research element will be the kilometre-scale river reach, including the river channel, the alluvial plain and associated groundwater. GLOBAQUA structure offers a strong interdisciplinary team, facilitating the knowledge transfer between the research and stakeholder sectors. The project is organised through highly integrated fourteen WPs, which are grouped in five main Modules (Fig. 4):

• Module STRESSORS: is defined to understand the mechanisms behind the multiple stressors acting in each case study, WP1-DATA will collect existing data from basin authorities and previous research projects, and will gather experimental data generated within the project. WP2-SCENARIOS will generate climatic, socioeconomic and land-use scenarios to provide drivers for the impact




modelling. Its results will set the boundary conditions for the subsequent modelling WPs. WP3-HYDROL, WP4-GEOMORPH and WP5-QUALITYCHEM will analyse surface and groundwater hydrological patterns, sediment and pollutant transport, and quality of the physical habitat and the fate of inorganic and organic pollutants, respectively.

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WP13-DISSEMINATIONWP14-MANAGE

WP3-HYDROL WP4-GEOMORPH WP5-QUALITYCHEM

WP8-SERVICES

WP12-POLICY

Fig 4. GLOBAQUA project structure and interaction between WPs

• Module RECEPTORS: will analyse the effects of the stressors on biodiversity (WP6-BIOL) and ecosystem functioning (WP7-ECOSYSTEM). Research will be based on manipulative laboratory experiments using artificial streams, reach-scale measurements, and basin-scale surveys, aiming to understand effects of single and multiple stressors at different scales and to feed models dealing with the data at either the reach or basin scales. Results at the lab and reach-scale will be used to feed mechanistical models at the reach scale, whereas basin-scale results will be used to feed statistical integrative models at the basin scale.

• Module IMPLICATIONS: On one hand, WP8-SERVICES will integrate the information generated by WP6-BIOL and WP7-ECOSYSTEM on the effects of stressors on receptors (biodiversity and ecosystem functioning) into integrative models at the reach or basin scales. These models will therefore relate changes in stressors with changes in diversity and ecosystem functioning and, in turn, with ecosystem services in biophysical terms. On the other hand, WP9-SOCIOECON will characterize the socioeconomical setting of case-study basins to support the ecosystem services valuation performed by WP10-VALUATION. Finally, impact of the changes in ecosystem services in economic terms on the socioeconomic development will be assessed by WP10-VALUATION. This will help to identify environmentally and socioeconomically sustainable management of water resources.

• Module ENVIRONMENTAL MANAGEMENT: includes two WPs dealing with relevant issues associated to the impact of multiple stressors on water quality, quantity, and ecosystems, as well as on the potential implementation of the major findings on European policy. Therefore, WP11-INTEGRATION will develop a model framework to assess scenarios affecting availability, quality and demand of water at the European scale. This WP will integrate the most relevant results of the previous WPs in other modules to define a manageable perspective on the multistressor consequences for European river basins. The implications of the stressors interactions and their opportunities for the



related policy making will be analyzed in WP12-POLICY. Therefore this WP is defined as a real interface between the scientific results obtained all along the project with their policy definition and development.

• Module PROJECT COORDINATION AND DISSEMINATION: these WPs (WP13-DISSEMINATION and WP14-MANAGE) will run during the whole project duration to guarantee (i) communication of the results to specific target groups (researchers, policy makers, water managers, land planners, …), stimulation of their use through relations with stakeholders and end-users, training programs for different end-users, screening of IPR potential and (ii) efficient coordination of all activities, day-to-day technical management, overall financial and administrative management of the GLOBAQUA consortium and cooperation with stakeholder and scientific panels.

Study basins

Three representative basins from the Mediterranean European region, where water scarcity is the main problem, as well as one Southern Mediterranean basin (North Africa), have been selected to obtain a complete Mediterranean perspective and an expanded vision of the water scarcity implications. In order to achieve a full European dimension, one Alpine and one UK river basin, where scarcity is a growing issue, have been also included among the case studies. In total six basins have been selected, in which several studies will take place in order to answer the integrated questions that have been put forward in GLOBAQUA. Based on the use of both surface and groundwater resources, the selected basins encompass a rich set of socio-ecological conditions (forested mountainous areas, highly populated watersheds relying on water transfers, agricultural areas and industrial clusters), and a complete geographic coverage, therefore facilitating the necessary vision to understand the European reality on the combined effects of multiple stressors on ecosystems and humans. The effect of multiple stressors on water availability and quality, and their effects on the chemical and ecological status will be examined, and the existing dysfunctions identified. Each basin will focus on a specific set of stressors to illustrate different management scenarios. The selected river basins for GLOBAQUA are: Ebro (Spain), Sava (Slovenia, Croatia, Bosnia and Herzegovina and Serbia), Evrotas (Greece), Souss Massa (morocco), Anglian (UK) and Adige (Italy) (Fig. 5). In four of them (Adige, Sava, Ebro and Evrotas) an extensive field work will be done in order to collect information on different stressors (pollution, pathogens, invasive species, geomorphological and flow regime alterations), while in two of them (Anglian river basin district and Souss Massa) the existing data will be used to evaluate different management scenarios.

Fig. 5 The six Basins studied in GLOBAQUA




Final remarks

GLOBAQUA aims at addressing the fundamental need of connecting the occurrence of multiple stressors in a situation of water scarcity with the policy implementation in European river basins bringing together a large group of researchers, stakeholders and policy makers across a wide range of disciplines. This challenge is met by communication tools including an Internet Platform for data Exchange but also many scientific meetings among the various groups. The structure of the project into WPs allows sharing responsibilities between researchers who are specialists in their respective fields. The work performed by the different WPs expands through different scales, starting from the monitoring and modeling studies to the river basin scale. The achievement of an overall good status of European water bodies until 2015 (according to the WFD timetable demands) poses a crucial challenge not only to water management agents but also to policy makers on different scales, the scientific community and the society in general. Management approaches to tackle EU water challenges will only work in the framework of cross border actions integrating all relevant stakeholders and by making use of cutting-edge scientific knowledge. The added value of this collaboration lies in the possibility of addressing the problems arising from the scarcity and multiple stressors pressures and their effects on the ecosystem services, and the overall effects of global change. Taking into account the interaction between all main environmental compartments and processes involved, a complete picture of the situation can be obtained, and possible solutions are visualized at different levels. Other benefits are mutual enrichment, methodological knowledge transfer, etc. Overall, the synergy of the different groups arises from their different expertise that complements each other to get a holistic picture of the problem, as well as potential solutions. Acknowledgements

This work has been supported by the Spanish Ministry of Science and Innovation through the project SCARCE of Consolider-Ingenio 2010 program (CSD2009-00065). It has also received funding from the European Comunities 7th Framework Programme under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua. Special thanks are due to all partners of the SCARCE and GLOBAQUA consortium and the peer review panels for ensuring quality results and fruitful collaboration within the projects.

References

Barceló D, Sabater S. Water quality and assessment under scarcity: Prospects and challenges in Mediterranean watersheds. Journal of Hydrology 2010;383: 1-4

Heathwaite AL. Multiple stressors on water availability at global to catchment scales: understanding human impact on nutrient cycles to protect water quality and water availability in the long term. Freshwater Biology 2010;55: 241-257

Maltby L. Studying stress: The importance of organism-level responses. Ecological Applications 1999;9: 431-440

Petrovic M, Ginebreda A, Acuna V, Batalla RJ, Elosegi A, Guasch H, Lopez de Alda M, Marce R, Munoz I, Navarro-Ortega A, Navarro E, Vericat D, Sabater S, Barcelo D. Combined scenarios of chemical and ecological quality under water scarcity in Mediterranean rivers. Trac-Trends in Analytical Chemistry 2011;30: 1269-1278

Sabater S, Barceló D (2010). Volume preface. Water Scarcity in the Mediterranean. Perspectives Under Global Change. Sabater S, Barceló D, Springer Berlin Heidelberg

Vörösmarty CJ, McIntyre PB, Gessner MO, Dudgeon D, Prusevich A, Green P, Glidden S, Bunn SE, Sullivan CA, Liermann CR, Davies PM. Global threats to human water security and river biodiversity (vol 467, pg 555, 2010). Nature 2010;468: 334-334



Poster sessions

143 Poster sessions



Development and optimization of configuration IT-SPME coupled to UHPLC-MS/MS to the analysis of organic pollutants in water samples

Ana Masiá1, Yolanda Moliner-Martínez2, María Muñoz-Ortuño2, Yolanda Picó1 and Pilar

Campíns-Falcó2

1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain 2 Department of Analytical Chemistry, Faculty of Chemistry, University of Valencia, Burjassot, Spain

In-Tube Solid Phase Microextraction (IT-SPME) is a mode of SPME which typically uses a GC capillary column with a proper coating to extract the analytes, becoming a useful approach for on-line enrichment of analytes without any previous sample treatment [1]. The aim of this work was to couple IT-SPME with UHPLC-MS/MS system, reaching the selectivity and sensitivity necessary to determine organic pollutants at sub-µg/L level in water samples according to the maximum concentration levels established in the legislation.

For this configuration, two six port valves were used for sample preparation to prevent the high back pressures of the UHPLC column, which could negatively affect the IT-SPME system. Water samples (4.0 mL) were passed through the capillary in valve 1 by means of a 1.0 mL precision Hamilton syringe. Then, 40 µL of methanol were injected in valve 1 to desorb the analytes from the extractive phase of the GC capillary, and the second valve was manually rotated to INJECT position, so the analytes were transferred to the analytical column by the mobile phase for separation and detection (see Figure 1)

Figure 1: Configuration of IT-SPME-UHPLC-QqQ-MS/MS

Separation was carried out on a UHPLC C18 column (1.7 µm, 2.10 × 50 mm) using a gradient elution profile of mobile phase consisting of 10 mM ammonium formate in both methanol and water. Then, analytes were detected with a mass spectrometer using an electrospray ionisation (ESI) source in positive mode. The two most intense precursor ion → product ion transitions were monitored to obtain unambiguous confirmation of the compound identity, excepting for trifluoralin.

The described method offers good accuracy and reproducibility and a high enrichment factor (ca. 15), lineal answer (r > 0.99) and precision (RSD < 20%) are reached, suitable to control the surface water quality for different pollutants. Moreover, this technique allows simplifying the sample preparation, to diminish the sample volume needed, the number of off-line steps and the amount of solvents employed. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects SCARCE (CSD2009-665), CGL2011-29703-C02-02 and CTQ 2011-26760. YM-M expresses her gratitude for the JdC (Ministerio de Ciencia e Innovación) research contract

References

Masiá, A., Moliner-Martínez, Y., Muñoz-Ortuño, M., Picó, Y. and Campíns-Falcó, P. Multiresidue analysis of organic pollutants by in-tube solid phase microextraction coupled to ultra-high performance liquid chromatography-electrospray-tandem mass spectrometry, J. Chromatogr. A (2013), 1306, 1-11.

INJECTION

Open Capillary columnTRB-35

Water sample + µl methanol

MS/MSPump

Waste

Internalloop 5µl

Analytical column

VALVE 1

VALVE 2LOAD

LOAD

Water sample + µl methanol

DESORPTION

Open Capillary columnTRB-35

MS/MSAnalytical columnPump

Internalloop 5µl

VALVE 1

VALVE 2LOAD

INJECT

144 Poster sessions


Analysis of organic persistent pollutants compounds by gas chromatography tandem mass spectrometry in biota samples from four

Spanish rivers

Elena Martínez1, Àngels Quiroga1 and Damià Barceló1,2

1 1 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain


In this work, legacy organic persistent pollutants (POPs), such as organochlorinated compounds (OCs) have been studied in fish samples collected in four Spanish rivers: Ebro, Llobregat, Guadalquivir and Jucar.

The extraction and clean-up was performed using a multi-residue method based on homogenization and lyophilisation of the samples followed by ultrasonic assisted extraction and purification via acidic attack with H2SO4conc. The final extracts were obtained by liquid-liquid extraction with hexane, concentration under a nitrogen stream and reconstitution to a final volume of 300 μl. The potentials losses during this step were corrected by the use of labelled subrogate internal standards.

The extracts were subsequently analysed by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) using a triple quadrupole analyser (QqQ) working in selected reaction monitoring (SRM) mode. Separation was achieved using a capillary column HP-5MS of 30m x 0.25 mm i.d. with 0.25 µm film thicknesses from J&W Scientific (Folsom, CA, USA).

The limits of detection (LODs) and limits of quantification (LOQs) of the method were calculated by analysis of spiked biota with minimum concentrations of each individual compound at a signal-to-noise ratio of 3 and 10, respectively.

The optimized method showed an adequate sensitivity and robustness to be applied in the analysis of selected compounds in complex samples as biota. The method limit of detection and quantification (MLODs and MLOQs) in biota these were in the range between 0.075 and 0.600ng/g and between 0.600 and 8ng/g, respectively. The recovery ranges were between 65% and 102% for all the compounds.

The results of this study showed that the group of DDTs were the predominant compounds and were in general detected in the range between the MLOQ and 15 ng/gw.w. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio 2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA and ICMAN for taking the samples.

145 Poster sessions



Stir bar sorptive extraction of 100 micropollutants from aqueous samples and determination by gas chromatography-mass spectrometry:

electrospray ionization vs atmospheric pressurized gas chromatography

Marina G. Pintado-Herrera1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1

1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of

International Excellence of the Sea (CEI.MAR), Puerto Real, Spain

This work presents the development, optimization and validation of a new multi-residue method (100 analytes) for the simultaneous determination of emerging contaminants, such as fragrances, UV filters, repellents, endocrine disruptors and biocides (40 analytes) and regulated pollutants (polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), organochlorine and organophosphorus pesticides, triazines and pyrethroids) (60 analytes) in aqueous matrices. Water samples were processed using the stir bar sorptive extraction technique (SBSE). Several parameters were optimized for this technique, such as extraction time, ionic strength, presence of organic modifiers, pH, concentration of humic acids, and volume of the derivatization agent. Briefly, 10 mm stir bars coated with polydimethylsiloxane (PDMS) were placed in a flask containing water samples (100 mL) with acetic anhydride, sodium carbonate and sodium chloride, and stirred for 5-6 hours at room temperature. Target compounds were extracted from the bars either by thermal (TD) or by liquid desorption (LD) using a reduced amount of solvent (200 μL). Water samples were analyzed then by means of gas chromatography coupled to two different mass spectrometry analyzers, therefore comparing their sensitivity and selectivity: single quadrupole (GC-MS) and time of flight (GC-ToF-MS). Two types of ionization sources were also tested: electronic impact (EI) and atmospheric pressure gas chromatography (APGC). The optimized protocol showed acceptable recovery percentages (50-100%) for most of the analytes, and limits of detection were often below 1 ng/L. Several micropollutants were identified and quantified in several environmental aquatic compartments, such as seawater, sewage effluent, river and groundwater. Additionally, using unique features provided by GC-APGC-ToF-MS, several non-target compounds such as new emerging organophosphorus flame retardants were identified. This is the first time that this technique has been applied for the analysis of contaminants in environmental matrices, showing significant advantages over more widely used EI such as “soft” ionization and accurate mass measurement of molecular ions and their fragments. Acknowledgements

This study was carried out within the two projects funded by the Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía (RNM 5417 and RNM 6613)

146 Poster sessions


Screening of perfluorinated compounds in water, sediment and biota of the Llobregat River basin (NE Spain)

Julián Campo1, Francisca Pérez2, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3

1 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

2 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

PFCs present significant thermal and chemical stability being persistent in the environment, where they can bio-accumulate and adversely affect humans and wildlife (Llorca et al., 2012). Human exposure to PFCs is of concern since PFCs tend to be associated with fatty acid binding proteins in the liver or albumin proteins in blood, and have been detected in human serum, urine, saliva, seminal plasma and breast milk (Sundstrom et al., 2011). This study is aimed at the screening of 21 perfluorinated compounds (PFCs) in environmental samples by high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS). The main objective is to identify target compounds at low levels in water, sediments and biota of the Llobregat River (2010), second longest river in Catalonia and one of Barcelona’s major drinking water resources. PFCs were extracted from water samples by Solid Phase Extraction (SPE); from sediment by ultrasonication with acidified methanol followed by an off-line SPE procedure (Picó et al., 2012), and from biota (fish) with alkaline digestion, clean-up by TurboFlow™ on line technology coupled to LC-MS/MS (Llorca et al., 2012).

The limits of detection (LODs) and limits of quantification (LOQs) of the method were calculated by analysis of spiked river water, sediment, and biota with minimum concentrations of each individual compound at a signal-to-noise ratio of 3 and 10, respectively. The LODs and LOQs of the method in river water ranged between 0.004 and 0.8 ng L−1 and between 0.01 and 2 ng L−1, respectively. In sediment LODs were 0.013-2.667 ng g−1 dry weight (dw) and LOQs were 0.04-8 ng g−1 dw, meanwhile in biota these were 0.006-0.7 pg μL-1 and 0.02-2.26 pg μL-1, respectively. Recoveries ranged between 65% and 102% for all target compounds. The method was applied to study the spatial distribution of these compounds in the Llobregat River basin. For this, a total of 40 samples were analysed (14 water, 14 sediments, 12 fishes). Of the 21 target compounds, 13 were identified in water samples (PFBA, PFDA, PFHpA, PFHxA, PFHxDA, PFNA, PFOA, PFPeA, PFTrDA, PFUdA, L-PFBS, L-PFHxS and L-PFOS), and their concentrations ranged between 0. 1 ng L−1 (PFNA) and 2709 ng L−1 (L-PFOS). Similarly, PFBA, PFDA, PFDoA, PFHpA, PFNA, PFOA, PFPeA, PFTrDA, PFUdA, L-PFBS, L-PFHxS, L-PFOS and PFOSA were identified in sediments samples, with concentrations ranging from 0.147 ng g−1 dw (L-PFOS) to 13 ng g−1 dw (PFBA). In biota similar PFC were detected, with values between 0.03 and 1738.06 ng g−1. According to this study, PFCs were detected in different compartments of the ecosystem where they are bio-accumulating and, potentially, would produce adverse effects on humans. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio 2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA for taking the samples.

References

Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T. P., Barcelo, D., 2012. Analysis of perfluoroalkyl substances in waters from Germany and Spain. Sci. Total Environ. 431, 139-150.

Llorca, M., Pérez, F., Farre, M., Agramunt, S., Kogevinas, M., Barceló, D., 2012. Analysis of perfluoroalkyl substances in cord blood by turbulent flow chromatography coupled to tandem mass spectrometry. Sci. Total Environ. 433, 151-160.

Pico, Y., Blasco, C., Farre, M., Barcelo, D., 2012. Occurrence of perfluorinated compounds in water and sediment of L'Albufera Natural Park (Valencia, Spain). Environ.Sci.Pollut.Res. 19, 946-957.

Sundstrom, M., Ehresman, D. J., Bignert, A., Butenhoff, J. L., Olsen, G. W., Chang, S. C., Bergman, A., 2011. A temporal trend study (1972-2008) of perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorooctanoate in pooled human milk samples

from Stockholm, Sweden. Environ. Inter. 37, 178-183.

147 Poster sessions



Occurrence of perfluorinated compounds in Spanish sewage treatment plants and determination of their removal efficiencies

Julián Campo1, Ana Masiá1, Yolanda Picó1, Marinel.la Farré2 and Damià Barceló2,3

1 Food and Environmental Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

2 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

1. Introduction

Sewage treatment plant (STP) effluents are currently reused with different purposes (agricultural and industrial purposes, to recharge aquifers or it can be directly discharged into rivers or the sea). However, STPs seem to be ineffective removing non-regulated so-called emerging contaminants, among which the presence of perfluorinated compounds (PFCs) is causing high environmental concern (Arvaniti et al., 2012). In fact, PFCs as Perfluorooctane sulfonate (L-PFOS) and its synthetic starting material, perfluorooctyl sulfonyl fluoride (L-POSF), were the first PFCs to be listed as persistent organic pollutants at the Stockholm Convention, (United Nations Environment Programme, 2010) and the EU also published a directive prohibiting their use after June 2008 (European Parliament and Council, 2006). Monitoring data are available worldwide, indicating that municipal sewage discharges are significant sources of these compounds to the aquatic environment, potentially reaching treated water for human consumption (Ma and Shih, 2010). PFCs are now considered as persistent, bio-accumulative and toxic, which make them a potential hazard to human health. However, there are very few peer-reviewed articles analysing concentrations of PFCs in Spanish wastewaters (Llorca et al., 2011; 2012), and even less reporting their removal efficiency. Accordingly, the main objective of this study is to improve the knowledge about the causes of aquatic environment pollution considering the STPs as point sources of PFCs in some Spanish Mediterranean basins.

2. Materials and methods

2.1. Description of the study area and sampling

The Ebro, Guadalquivir, Jucar and Llobregat rivers are between the 15 longest rivers in Spain (928, 657, 498 and 170 Km) and were selected because of their economic and environmental importance. This work presents the results of an extensive survey carried out in 2010 in STPs of Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (2) Rivers (Figure 1). A total of 21 PFCs have been monitored, among which there are 14 perfluorocarboxylates (PFCAs), 6 perfluorosulfonates (PFASs) and 1 perfluorosulfonamide (PFSAs) (Table 1). PFCs concentrations have been analysed in influent, effluent and dehydrated sludge samples of these STPs and removal efficiencies have been calculated.

2.2. Sample preparation and instrumental analysis

An off-line solid-phase extraction (SPE) procedure was used for the pre-concentration of fortified water samples (Pico et al., 2012), using STRATA-X Polymeric Reversed Phase cartridges (previously preconditioned). Cartridges were air-dried and analytes eluted. Extracts were evaporated to dryness, re-constituted and analysed.

Sludge samples were homogenized, vortexed, ultra-sounded and centrifuged using different acidified solvents, and recovering the supernatants according to Pico et al. (2012). The extraction was completed following the process described in the section 2.2.1. Moisture content was also calculated to report concentrations in dry weight.

148 Poster sessions


Figure 1. Location of the STPs along the course of the different Rivers

Table 1. PFCs selected in this study, their family, acronym, CAS number and formula Family Compound Acronym CAS Nº Formula Perfluorocarboxylic acids PFCA

Perfluorobutanoic acid PFBA 375-22-4 C3F7COOH Perfluoropentanoic acid PFPeA 2706-90-3 C4F9COOH Perfluorohexanoic acid PFHxA 307-24-4 C5F11COOH Perfluoroheptanoic acid PFHpA 375-85-9 C6F13COOH Perfluorooctanoic acid PFOA 335-67-1 C7F15COOH Perfluoro-7-methyloctanoic acid i,p-PFNA Perfluorononanoic acid PFNA 375-95-1 C8F17COOH Perfluorodecanoic acid PFDA 335-76-2 C9F19COOH Perfluoroundecanoic acid PFUdA 2058-94-8 C10F21COOH Perfluorododecanoic acid PFDoA 307-55-1 C11F23COOH Perfluorotridecanoic acid PFTrDA 72629-94-8 C12F25COOH Perfluorotetradecanoic acid PFTeDA 376-06-7 C13F27COOH Perfluorohexadecanoic acid PFHxDA 67905-19-5 C15F31COOH Perfluorooctadecanoic acid PFODA 16517-11-6 C17F35COOH Perfluorosulfonates PFAS Perfluorobutane sulfonate L-PFBS 375-73-5 C4F9SO2O Perfluorohexane sulfonate L-PFHxS 355-46-4 C6F13SO2O Perfluoroheptane sulfonate L-PFHpS 375-92-8 C7F15SO2O Perfluorooctane sulfonate L-PFOS 1763-23-1 C8F17SO2O Perfluoro-7-methyloctane

sulfonate i,p-PFNS

Perfluorodecane sulfonate L-PFDS 335-77-3 C10F21SO2O Perfluoro sulfonamides PFSA Perfluorooctane sulfonamide PFOSA 754-91-6 C8F17SO2NH2

The chromatographic instrument was an HP1200 series LC - with an automatic injector, a degasser, a quaternary pump and a column oven- combined with an Agilent 6410 triple quadrupole (QqQ) mass spectrometer, equipped with an electrospray ionization (ESI) interface (Agilent Technologies, Waldbronn, Germany). Data were processed using a MassHunter Workstation Software for qualitative and quantitative (internal standard methodology based on peak areas) analysis (A GL Sciences, Tokyo, Japan).

149 Poster sessions



0

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i,p-P

FNA

L-PF

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L-PF

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L-PF

OS

PFO

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PFO

SA

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FNS

PFB

A

PFD

A

PFD

oA

PFH

pA

PFH

xA

PFH

xDA

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A

PFO

A

PFPe

A

PFTe

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dA

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HpS

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HxS

L-PF

OS

PFO

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PFO

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PFPe

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PFTr

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PFU

dA

2010 2011

Max

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con

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ratio

n (n

g L-1

)

IN OUT

In water samples, recoveries ranging from 55 to 94%, with relative standard deviations between 8%-18% were obtained; and low limits of quantification (0.01-2.00 ng L-1) were achieved for all selected PFCs. For sludge samples, recoveries were between 79 and 111 % and, relative standard deviation was in all cases below 20 % at the limits of quantification (0.04-8.00 ng g-1). Calibration curves were prepared daily obtaining R2 >0.98.

3. Results and discussion

From 21 analytes screened, 15 were found in influent and effluent samples. In fact, the waste-waters of all STPs were contaminated with at least one PFC. The PFCAs most frequent were PFBA, PFNA and PFPeA, and the PFAS, L-PFOS and L-PFBS. In the Ebro STPs, the maximum concentration in the influent samples was observed for L-PFOS with 689.20 ng L-1. Among the PFCAs, the highest value was for PFBA (86.72 ng L-1). The concentration of these analytes in the effluent samples was reduced between 30 and 70%, with values of 501.10 ng L-1 and 26.29 ng L-1 for L-PFOS and PFBA, respectively (Figure 2). These decreases could be attributed to their sorption onto the activated sludge, which could explain their high concentrations those samples.

Figure 2. Maximum PFCs concentration detected in Ebro STPs influent (IN) and effluent (OUT) samples

The highest concentration was measured in the Guadalquivir basin, with 5600.00 ng L-1 of PFHxA in Cordoba’s influent. Concentration of other analytes as L-PFOS (24.88 ng L-1) and PFBA (23.39 ng L-1) were lower. In the effluent samples, PFBA (27.02 ng L-1) kept similar concentration, meanwhile PFHxA and L-PFOS showed decreased values (around 1.00 ng L-1). The Jucar STP samples presented the lowest PFCs concentrations, up to 150.00 ng L-1. The highest value detected was for the PFDA, which reached 128.40 ng L-1 in influent and 102.90 ng L-1 in effluent, followed by L-PFOS with 52.50 and 35.10 ng L-1, respectively. In the Llobregat STPs, the highest concentration in the influent samples was for L-PFOS (213.49 ng L-1), followed by PFOA (51.49 ng L-1). Their maximum concentrations in the effluent samples were 31.44 and 55.42 ng L-1, respectively.

Regarding the sludge samples, 13 PFCs were detected. The PFCAs most frequently detected were PFBA and PFPeA, and the PFAS, L-PFOS and L-PFBS. PFCs were not detected in Guadalquivir sludge samples, while those of the Llobregat STPs presented high concentrations, showing 1790.25 ng g-1 in dry weight (dw) of L-PFOS, and 149.34 ng g-1 dw of PFBA. The concentration of PFASs in the influent was high. Their adsorption onto the activated sludge (which always presented high concentrations) accounted for its apparent decrease in the effluent. According to Schultz et al. (2006), there is no known biodegradation pathway for this class of fluorochemicals. The PFC residue levels in the STPs of the Jucar

689/501

150 Poster sessions


River were low, reaching the highest level at 175.44 ng g-1 dw (L-PFBS). In the Ebro STP sludge samples, the highest concentration detected was for PFBA (442.38 ng g-1 dw), followed by that of L-PFOS (57.01 ng g-1 dw).

The removal efficiency of PFCs was calculated from the analyte concentration in influent (Cin) and effluent (Cef) : [(Cin-Cef)/Cin] x 100%. According to this equation, the elimination of PFCAs ranged from -557% (PFNA) to 100% (PFPeA, PFUdA), meanwhile the removal of PFASs was in the range 0% (L-PFBS, L-PFHxS and L-PFHpS) to 100% (L-PFOS). The less efficient STP in the Ebro River was Logroño, with 0% of PFBA, PFPeA and L-PFBS elimination, and the most efficient was Tortosa, with 99% of i,p-PFNS removal (Fig. 3). In the Guadalquivir basin, Ranilla showed very low (-557% of PFNA) and very high (100% of PFPeA) elimination efficiencies, although removals of 100% were also calculated for L-PFOS in Loja and Copero. In the Jucar River STPs, the efficiencies were between -121% of PFBA, in Alzira, and 82% of PFOA, in Cuenca. Finally, in the Llobregat basin, the removal ranged from -11% of PFHpA to 100% of PFPeA and PFUdA, all in Manresa.

4. Conclusions

Wastewater samples of all STPs contained at least one PFCs residue. Up to 15 PFCs were found in influent and effluent, and 13 in sludge samples. The PFCs most frequently detected were PFBA, PFNA, PFPeA, L-PFOS and L-PFBS, with concentrations up to 5600 ng/L of PFHxA in the samples of Guadalquivir’s STPs, 128 ng/L of PFDA in those of Jucar River and 689 ng/L and 213 ng/L of L-PFOS in those of Ebro and Llobregat Rivers. 67% of PFCs removal efficiencies analysed in this study do not achieve the 50%. All these data confirm that most of the PFCs are only partially eliminated during the secondary treatment, commonly used in Spanish STPs, suggesting that they can constitute a focal point of contamination to the rivers, where they can bio-accumulate and, potentially, produce adverse effects on humans. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio 2010 CSD2009-00065 and CGL2011-29703-C02-02. We also thank the persons of IDAEA and ICMAN for taking the samples.

References

Ahrens, L., Felizeter, S., Sturm, R., Xie, Z., Ebinghaus, R., 2009. Polyfluorinated compounds in waste water treatment plant effluents and surface waters along the River Elbe, Germany. Mar. Pollut. Bull. 58, 1326-1333.

Arvaniti, O. S., Ventouri, E. I., Stasinakis, A. S., Thomaidis, N. S., 2012. Occurrence of different classes of perfluorinated compounds in Greek wastewater treatment plants and determination of their solid-water distribution coefficients. J. Hazard. Mater. 239-240, 24-31.

European Parliament and Council, 2006. Directive 2006/122/ECOF.

Ma, R., Shih, K., 2010. Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong. Environ. Pollut. 158, 1354-1362.

Llorca, M., Farre, M., Pico, Y., Barcelo, D., 2011. Analysis of perfluorinated compounds in sewage sludge by pressurized solvent extraction followed by liquid chromatography-mass spectrometry. J. Chromatogr. A 1218, 4840-4846.

Llorca, M., Farre, M., Pico, Y., Muller, J., Knepper, T. P., Barcelo, D., 2012. Analysis of perfluoroalkyl substances in waters from Germany and Spain. Sci. Total Environ. 431, 139-150.

United Nations Environment Programme, 2010. New POPs SC-4/17: listing of perfluorooctane sulfonic acid, its salts and perfluorooctane sulfonyl fluoride. United Nations Envrioment Programme: Stockholm Convention on Persistent Organic Pollutants (POPs), Geneva, Switzerland.

Pico, Y., Blasco, C., Farre, M., Barcelo, D., 2012. Occurrence of perfluorinated compounds in water and sediment of L'Albufera Natural Park (Valencia, Spain). Environ.Sci.Pollut.Res. 19, 946-957.

151 Poster sessions



Seasonal inputs of polyethoxylated compounds to a Mediterranean coastal lagoon through surface watercourses

Juan M. Traverso-Soto1, Pablo A. Lara-Martín1, Eduardo González-Mazo1 and V. M. León2

1 Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Campus de Excelencia Internacional del Mar (CEI·MAR), Universidad de Cádiz, Puerto Real, Spain

2 Instituto Español de Oceanografía, Centro Oceanográfico de Murcia, San Pedro del Pinatar, Spain

Nowadays, alcohol ethoxylates (AEOs) are the most important group of nonionic surfactants, being used in a wide range of applications such as household cleaners and detergents. Commercial AEOs consist of a mixture of several homologues of varying carbon chain length (Cn) and degree of ethoxylation (EOm). The major disposal route of these compounds is down the drain to municipal wastewater treatment plants, where they are efficiently removed. In spite of that, significant amounts of AEOs and their metabolites (polyethylene glycols, PEGs, which are nonionic synthetic water-soluble polymers of ethylene oxide that are also used in many other applications) reach the aquatic environments, being eliminated from the water column by degradation and sorption processes. In this work we have monitored the seasonal occurrence, levels and behavior of AEOs and PEGs in waters and sediments from Mar Menor Lagoon (SE, Spain), as well as in a wastewater treatment plant (WWTP) that discharges in this area. Determination of the concentration of the analytes in both aqueous and particulate phases has been carried out by liquid chromatography-mass spectrometry (LC-MS) after accelerated solvent and solid phase extractions. Regarding the WWTP, there were significant differences in the concentrations of the target compounds depending on the season and the day of the week, with maximum values being detected during the weekend. Average AEO and PEG concentrations in the lagoon were 0.07 and 8.8 mg kg-1 for sediments, and 0.35 and 5 μg/L in water, respectively. Levels for both compounds were significantly higher in samples collected near the shore than those measured inside the lagoon itself. The distribution of AEOs and PEGs could be better explained due to a combination of multiple sources, not only due to discharges from the nearby WWTP, but also from the surrounding populations, small creeks which flow directly into the Mar Menor after collecting treated and untreated urban wastewaters, the input of surfactants used such as adjuvants in pesticides through surface and groundwaters, and/or from cleaning products used in ports. Data on these analytes are the first ever known in this area and it is remarkable that concentrations of PEGs, which are relatively polar metabolites, exceeded by two orders of magnitude those found for AEOs in sediment samples. In this sense, the highest concentrations were detected close to the San Javier-Murcia airport, where PEGs are commonly used in aircraft cleaning products. Acknowledgements

This work was supported by Petroquímica Española S.A. (ref. OT2008/071) and the Spanish Inter-Ministerial Science and Technology Commission “DECOMAR” Project (CICYT, CTM2008-01832).

152 Poster sessions


Seasonal changes in the concentration of synthetic surfactants in groundwater from aquifer systems (Cadiz, SW Spain)

Carmen Corada-Fernández1, Nivis Torres-Fuentes1, Pablo A. Lara-Martín1, L. Candela2 and

Eduardo González-Mazo1

1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Puerto Real, Spain

2 Department of Geotechnical Engineering and Geosciences, UPC, Barcelona, Spain Nowadays, soil and groundwater contamination is a worldwide environmental problem with disastrous consequences. As a consequence of this and other environmental issues (e.g., biomagnification), the use and production of some of the most dangerous contaminants, such as pesticides and polychlorinated biphenyls (PCBs) are regulated in most developed countries. However, there are thousands of different chemical products that have not being studied yet, many of them known as “emerging contaminants”, which are also being discharged into aquatic and terrestrial environments. In this work we have determined the presence and temporal distributions of synthetic surfactants (mostly used in the formulation of detergents, personal care products, industrial processes, pesticide adjuvants…) in groundwater samples from two aquifers: Jerez de la Frontera (062.009) and Alluvial Guadalete (062.008). These hydrogeological units are located surrounding the urban area of Jerez de la Frontera (207.500 inhabitants, 2009) in Andalusia (SW, Spain). The aquifers are affected by agricultural pollution sources, as nitrate concentrations up to 65.8 mg L-1 and several pesticides (chlorfenvinphos, chlorpyriphos, prometryn and triazines) have been detected in a previous study (Perez-Carrera et al., 2009). The proximity of several urban areas that may discharge non-treated urban wastewater in the system (Corada-Fernández et al., 2011, 2013) is also relevant. We carried out two different sampling campaigns in the area during dry season (summer) and rainy season (winter). 25 wells were selected, measuring temperature (T), pH, conductivity (E.C.), dissolved oxygen (D.O.) and redox potential (Eh). Water samples were taken from these wells for later analysis of 4 surfactants: linear alkylbenzene sulfonate (LAS) and alkyl ethoxysulfates (AES) (anionics), and alcohol polyethoxylates (AEOs) and nonylphenol polyethoxylates (NPEOs) (non-ionics) (Lara-Martín et al., 2006). In both aquifers, oxic conditions prevailed and pH ranges were between 6.5 and 9. Surfactants were found in a range between 5-165 and 1-665 μg L-1 for LAS and AES, respectively, and, for AEOs and NPEOs, between 4-140 and 2-6 μg L-1, respectively. Highest surfactant concentrations were detected in those wells directly affected by urban sewage infiltration and during the rainy season. Those homologues/ethoxymers being most hydrophilic were predominant. Presence of anionic surfactants was attributed to the irrigation of crops with river water mixed with wastewater from Jerez de la Frontera sewage treatment plant, as well as to the application of sludge from that plant. The distribution of nonionic surfactants, however, was better related to the use of pesticides in the area. Acknowledgements

This study has been supported by the CICYT Projects (CGL2008-05598 and CGL2011-27349), and with the help of a FPI fellowship from the Spanish Ministry of Education (ref. BES/2006/12304).

References

Corada-Fernández, C., Lara-Martín, P.A., Candela, L. and González-Mazo E. Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants, J. Environ. Monit.(2011), 13, 2010-2017. Corada-Fernández, C., Lara-Martín, P.A., Candela, L. and González-Mazo E. Vertical distribution profiles and diagenetic fate of synthetic surfactants in marine and freshwater sediments, Sci. Tol. Environ. (2013), 461-462, 568-575. Lara-Martín, P.A., Gómez-Parra, A. and González-Mazo, E. Development of a method for the simultaneous analysis of anionic and non-ionic surfactants and their carboxylated metabolites in environmental samples by mixed-mode liquid chromatography-mass spectrometry, J.Chromatogr.A (2006), 1137, 188-197. Perez-Carrera, E. Distribution and reactivity of regulated and emerging organic pollutants in surface and groundwater systems, PhD., University of Cadiz (2009).

153 Poster sessions



Geographical distribution of pesticides in waters of the river Júcar, Spain

Juan Antonio Pascual Aguilar1,2, Vicente Andreu1, Ana Masiá3 and Yolanda Picó3

1 Environmental forensic and Landscape Chemistry Group, Centro de Investigaciones sobre Desertificación-CIDE

(CSIC-UV-GV), Moncada, Spain 2 Centro para el Conocimiento del Paisaje, Matet, Spain

3 Food and Environmental Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

Among emerging contaminants the group of pesticides is associated to farming activities (Richardson, 2012). Research to large basin scale is needed to understand surface waters transport and hydrological connectivity of contaminants. The working hypothesis of this research is that at large geographical scale pesticides and herbicides are related to major landscape land use-cover types.

The methodological framework developed consisted on the application of environmental forensic criteria (Taylor, 2004) combining laboratory analytical water samples and cartographic analysis using Geographical Information Systems (GIS). For the first case, the sampling strategy consisted in the collection of 15 water samples distributed alongside the River Júcar and its two main tributaries (River Cabriel and Magro), located in the River Júcar drainage Basin. After selective sample extraction, 50 pesticides were identified and quantified by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) (Masiá et al., 2013). Geographical analysis were performed after geo-location of sampling points analytical results and integration in the GIS environment using CORINE land use-cover layers for the year 2006.

Out of 50 pesticides 20 were identified and 18 presented concentrations higher than the Limits of Quantification. Values ranged from 0.04 ng·L-1 (Terbuthylazine-2 Hydroxy) to 79.39 ng·L-1 (Carbendazim), 150.75 ng·L-1 (Thiabenzadole) and 222.45 ng·L-1 (Imazalil). Contaminants identified more frequently were Chlorpyriphos, Ethion, Chlorfenvinphos and Imazalil, found in 15, 13, 12 and 10 sites respectively. There is a clear geographical trend in the number of pesticides found and their concentrations. Three main land use-cover areas where stablished, according to the dominant vegetation cover: natural surfaces, rainfed agriculture and intensive irrigation farming. The number of pesticides incrise from natural areas (28 incidencies in 6 sites) to rainfed (37 detections in 5 sites) and irrigation agriculture (50 incidencies in 4 sampling points). Higher levels of concentrations area also found in the sector with intensive irrigation agriculture. Acknowledgements

This work was supported by the Spanish Ministry of Science and Innovation through the project CONSOLIDER-INGENIO 2010 (CSD2009) and by the Ministry and the European Regional Development Fund (ERDF) (projects CGL2011-29703-C02-00, CGL2011-29703-C02-01, CGL2011-29703-C02-02).

References

Masiá, A., Ibáñez, M., Blasco, C., Sancho, J.V., Picó, Y. and Hernández, F. Combined use of liquid chromatography triple quadrupole mass spectrometry and liquid chromatography quadrupole time-of-flight mass spectrometry in systematic screening of pesticides and other contaminants in water samples. Analytica Chimica Acta (2013), 761, 117-127.

Richardson, S.D. Environmental mass spectrometry: emerging contaminants and current issues. Analytical Chemistry (2012), 84, 747–778.

Taylor, D.A. Environmental forensic files. Environmental Health Perspectives (2004), 112, a88–a88.

154 Poster sessions


Study of the occurrence, spatial and temporal distribution of pesticides in water, sediment and biota from Llobregat River Basin

Ana Masiá, Julián Campo, Cristina Blasco and Yolanda Picó

Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

The Llobregat River emerges in the Eastern Pyrenees in North West of Catalonia (Spain), at 1400 m of altitude and flows during approximately 160 km coming into the Mediterranean Sea. It is one of the main water source of the metropolitan area of Barcelona and its surroundings, and it receives the effluent discharges from more than 30 WWTPs. Moreover, it is influenced by industrial and agricultural activities (vineyards) at lower-medium course. Thus, a broad range of organic pollutants have been detected along the river [1,2]. This work presents the results of 43 currently used pesticides monitoring that was carried out from the end of September to the middle of October 2010 and 2011 in water, sediments and biota from Llobregat River Basin. Water samples were taken into amber glass bottles of 2.5 L. Sediment samples were taken using a Van Veen grab sampler and transferred to an aluminum box. Finally, fish samples were collected using electro-fishing to stun them before they are caught with a net and after died stored in a clean plastic bag. Once at laboratory, pesticides were extracted from water by solid-phase extraction (SPE) and from sediment and fish by QuEchERS. The resulted extract was then analyzed by LC-ESI-MS/MS in positive mode. Separation was carried out on a Luna C18 column (150 × 2.0 mm, 3 µm) using a gradient elution profile with mobile phase consisting of water-methanol both, 10 mM ammonium formate. The two most intense precursor ion → product ion transitions were monitored to obtain unambiguous confirmation of the compound identity.

The levels of total pesticides in all matrices were compared in both sampling periods. In water samples, the most frequent pesticides were imazalil, chlorpyriphos and diazinon which appeared in 93 % of the samples during 2010 campaing; and the highest concentration was for malathion (320,3 ng/L). Nevertheless, in 2011 campaign, chlorpyriphos (80 %) and terbuthylazine-2-hydroxy (70 %) were the most ubiquitous, and the maximum concentrations were detected for carbendazim (up to 697 ng/L) and diuron (up to 160 ng/L). Regarding the spatial distribution, the highest concentration in 2010 was found near of the source in LLO1. On the contrary in 2011, there was a concentration gradient of pesticides through the mouth that is particulary marked in the Anoia tributary. In sediments, metolachlor, chlorpyriphos, diazinon and diuron were found in 2010 at low ng/g d.w. level. Differently, in the 2011, carbendazim, thiabendazole, chlorpyriphos, diazinon, dichlofenthion, terbumeton, terbuthylazine-2-hydroxy, terbuthryn and tebuconazole were detected. Some of these compounds were not analyzed in the previos campaign. The concentrations of pesticides were also higher this year. The highest concentration was for chlorpyriphos (130 ng/g d.w.) at the CAR4 (where the Cardener River flows into the Ebro). Finally, pesticides were not detected in fish samples. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects Consolider-Ingenio 2010 CSD2009, and CGL2011-29703-C02-02. We would also like to thank the persons of the research group from IDAEA for taking the samples.

References

Gonzalez, S., López-Roldán, R. and Cortina, J.L. Presence and biological effects of emerging contaminants in Llobregat River Basin: a Review, Environ. Pollut. (2012), 161, 83-92.

Kuser, M., López de Alda, M.J., Hernando, M.D., Petrovic, M., Martín-Alonso, J. and Barceló, D. Analysis and occurrence of pharmaceuticals, estrogens, progestrogens and polar pesticides in sewage treatment plant effluent, river water and drinking water in the Llobregat river basin (Barcelona, Spain), J. Hydrol. (2008), 358, 112-123.

155 Poster sessions



Occurrence of siloxanes in fish samples from the Júcar River

Josep Sanchís1, Francisca Pérez1, Marinella Farré1 and Damià Barceló1,2



Cyclic and linear volatile dimethylsiloxanes (cVMS and lVMS respectively) are low molecular weight organosilicon compounds with intensive use in domestic (personal care products, coatings, paints...) and industrial products. Their emission to the environment has been observed in several recent publications reporting their occurrence in wastewater [1, 2], river environments [1-3], soils [4, 5] and atmosphere [6, 7]. Moreover, cVMS are endocrine disruptors [8, 9] and bioaccumulate in aquatic organisms [10, 11]. Because of all these threats, although they are still not considered in any environmental legislation, volatile dimethylsiloxanes are currently under revision by statal agencies in North America and by the European Comission. Analysis of cVMS and lVMS is challenging because of their high volatility and because of the many sources of contamination in laboratory indoor environment and analytical instrumentation. We have developed and validated an analytical method based on ultrasounds assisted extraction followed by GC-MS/MS. Quantification trustness is ensured by statistically assessing the contamination of a significant number of procedural blanks (minimum 1 blank per sample), which are analyzed in parallel with the real samples, and substracting the background signal. A total of sixteen fish, sampled from the Júcar River in the frame of the SCARCE project, have been analyzed. cVMS have been detected in all but one sample at concentrations between 50 pg/g and the 9.4 ng/g while lVMS have been detected in 75% of the samples at concentrations 6.17 and 69.0 pg/g. As far as our knowledge goes, this is the first study of the occurrence of these compounds in river fish from the Iberian Peninsula. The observed concentrations are consistant with the physico-chemical properties of these compounds (solubility in the low μg/L order, extremely high KOW and high Henry’s constant) in a water environment: cVMS and lVMS will rapidly partition (1) to the atmosphere, where they will distribute globally, (2) to the lipidic content of biota and (3) to the river sediments. Siloxanes concentrations are in the same range than perches analyzed in Scandinavian lakes [11]. On the other hand, their profiles are similar than those observed in sea fish from Barcelona markets while the concentrations here presented are about one order of magnitude lower. This can be explained by the exposure of market fish to indoor environments, were cVMS concentrations have been reported to reach the μg/m3 order, after their capture. Acknowledgements

This work has been supported by the Spanish Ministry of Science and Innovation through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and Nano-Trojan (CTM-2011-24051).

References

[1] Sanchís J., Martínez E., Ginebreda A., Farré M. and Barceló D., Occurrence of linear and cyclic volatile methylsiloxanes in wastewater, surface water and sediments from Catalonia. Science of The Total Environment (2013), 443, 530-538.

[2] Sparham C., Van Egmond R., O’Connor S., Hastie C., Whelan M., Kanda R. and Franklin O., Determination of decamethylcyclopentasiloxane in river water and final effluent by headspace gas chromatography/mass spectrometry. Journal of Chromatography A (2008), 1212, 124-129.

[3] Sparham C., van Egmond R., Hastie C., O’Connor S., Gore D. and Chowdhury N., Determination of decamethylcyclopentasiloxane in river and estuarine sediments in the UK. Journal of Chromatography A (2011), 1218, 817-823.

[4] Sánchez-Brunete C., Miguel E., Albero B. and Tadeo J.L., Determination of cyclic and linear siloxanes in soil samples by ultrasonic-assisted extraction and gas chromatography–mass spectrometry. Journal of Chromatography A (2010), 1217, 7024-7030.

[5] Companioni-Damas E.Y., Santos F.J. and Galceran M.T., Analysis of linear and cyclic methylsiloxanes in sewage sludges and urban soils by concurrent solvent recondensation - large volume injection - gas chromatography-mass spectrometry. Journal of Chromatography A (2012), 1268, 150-156.

156 Poster sessions


[6] Lu Y., Yuan T., Yun S.H., Wang W., Wu Q. and Kannan K., Occurrence of Cyclic and Linear Siloxanes in Indoor Dust from China, and Implications for Human Exposures. Environmental Science & Technology (2010), 44, 6081-6087.

[7] Genualdi S., Harner T., Cheng Y., MacLeod M., Hansen K.M., van Egmond R., Shoeib M. and Lee S.C., Global Distribution of Linear and Cyclic Volatile Methyl Siloxanes in Air. Environmental Science & Technology (2011), 45, 3349-3354.

[8] He B., Rhodes-Brower S., Miller M.R., Munson A.E., Germolec D.R., Walker V.R., Korach K.S. and Meade B.J., Octamethylcyclotetrasiloxane exhibits estrogenic activity in mice via ERα. Toxicology and Applied Pharmacology (2003), 192, 254-261.

[9] Sousa J.V., McNamara P.C., Putt A.E., Machado M.W., Surprenant D.C., Hamelink J.L., Kent D.J., Silberhorn E.M. and Hobson J.F., Effects of octamethylcyclotetrasiloxane (OMCTS) on freshwater and marine organisms. Environmental Toxicology and Chemistry (1995), 14, 1639-1647.

[10] Kierkegaard A., van Egmond R. and McLachlan M.S., Cyclic Volatile Methylsiloxane Bioaccumulation in Flounder and Ragworm in the Humber Estuary, Environmental Science & Technology (2011), 45, 5936-5942.

[11] Kierkegaard A., Bignert A. and McLachlan M.S., Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish lakes. Chemosphere (2012), 93, 789-793.

157 Poster sessions



Study of Silver Nanoparticles in aqueous solutions by Capillary Reversed-Phase Liquid Chromatography, Transmission Electron

Microscopy and UV-Vis techniques

Rodrigo A. Gonzalez-Fuenzalida, Yolanda Moliner-Martínez, Jorge Verdú-Andrés and Pilar Campíns-Falcó

Department of Analytical Chemistry, University of Valencia, Burjassot, Spain

Silver is known for its antimicrobial action and relative low toxicity in humans. Therefore, silver nanoparticles combine silver’s and NP’s properties enhancing the interest of understanding its behaviour and developing methods for its identification and determination. They are used in consumer products, food technology, textiles/fabrics, medical products and devices. This will increase silver exposure to the general population [1] and the impact in the environment in terms of toxicity. Consequently, AgNPs may be considered as a potential emerging contaminant in different matrix such as water.

The objective of this work is to study the response and behaviour of AgNPs which differ in synthesis methods, colours, sizes in aqueous solutions by using multiple techniques in order to establish a reliable analytical method of quantification. At the same time stability of these particles were tested in terms of degradation, organic environment exposure, photochemical radiation, reagents of synthesis functions. TEM was used to estimate AgNPs concentrations by means of particle size diameters; UV-Vis measures allowed to study surface plasmon properties and its variation under the various conditions previously mentioned; Capillary Reversed-Phase Liquid Chromatography provided a highly sensitive (LODs 10-2 nM with 2 μL sample volume injection), concentration responding (linear, R2>0.99) and yet, AgNPs stability dependent signals.

TEM image of AgNPs and AgNP Chromatogram (0.62 nM, at 400 nm)

Acknowledgements

The authors are grateful to the Spanish MICINN (MAT2007-51584 and CSD2007-00010), MINECO (project CTQ2011-26760) and to the GV (Prometeo Program)

References

[1] Wijnhoven, S., Peijnenburg, W., Herberts, C., Nanotoxicology 2009, 3, 109-138

158 Poster sessions


Cost effective methodology as analytics tools for DEHP and their degradation products in waters

Neus Jornet-Martinez, María Muñoz-Ortuño, Yolanda Moliner-Martínez, Rosa Herráez-

Hernández, A. Argente-García and Pilar Campíns-Falcó

Department of Analytical Chemistry, University of Valencia, Burjassot, Spain

Di-(2-ethylhexyl) phthalate (DEHP) is widely used as plasticizer as well as in a broad range of industrial and consumer products. Due to its extensive use and possible migration -phthalates are not chemically bonded to the plastic polymer- is nowadays considered as ubiquitous environmental pollutant [1]. Numerous studies indicated that DEHP can be degraded by bacteria and fungi under different environment conditions [2].

We proposed a new cost-effective method for the separation and quantification of the main DEHP degradation products: (2-ethylhexyl) phthalate (MEHP), diethyl phthalate (DEP) and dibutyl phthalate (DBP). The method combines in-tube solid-phase micro extraction (IT-SPME) with capillary liquid chromatography and UV diode array [3]. Aliquots of 4 mL of acidified water samples were on-line processed into the IT-SPME extractive capillary, which was used in in-valve configuration. After sample loading, the analytes were desorbed with the mobile-phase and transferred to a monolithic capillary column for separation and detection. No pre-treatment is needed. Therefore, the risk of background contamination by phthalates during sample treatment is drastically reduced. The reliability of the proposed method has been tested by analysing several water samples with different matrix. Figure 1 shows the chromatogram given by a positive sample.

Figure 1: Photograph of the IT-SPME – capillary LC system used and chromatogram corresponding to a

washing water. Acknowledgements

The authors are grateful to the Spanish Ministerio de Economía y Competitividad (project CTQ2011-26760) and to The Government of the Generalitat Valenciana (projects ACOMP/2013/155 and PROMETEO 2012/045).

References

[1] Liang D-W. Zhang T. and H. P. Fang. Phathalates biodegradation in the environment. Appl. Microbiol Biotechnol (2008) 80, 183-198.

[2] Barnabé, S,. Beauchesne, I., Cooper, D.G., Nicell, J. A., Phosphate removal by mineral-based sorbents used in filters for small-scale wastewater treatment. Water Res. (2008) 42, 153-162.

[3] Moliner-Martínez, Y., Molins-Legua, C., Verdú-Andrés, J., Herráez-Hernández, R., Campíns-Falcó, P. Advantages of monolithic over particulate columns for multiresidue analysis of organic pollutants by in-tube solid-phase microextraction coupled to capillary liquid chromatography. J. Chromatogr. A (2011) 1218, 6256-6262.

159 Poster sessions



Incidence and distribution of heavy metals in sediments of the Turia River basin

Vicente Andreu1, Eduardo Gimeno2 and Juan A. Pascual1

1 Centro de Investigaciones sobre Desertificación-CIDE (CSIC-UV-GV), Moncada, Spain.

2 Fundación Universidad de Valencia. CIDE, Moncada, Spain

Rivers are one of the mainsources of freshwater to population but, in the same way, receive both point source and difuse pollution, usually frorm wastewaters and agriculture. However, rivers are not independent bodies but they influence different associated ecosystems that compound the catchment. In this sense the fluvial sedimentary phase can act as a sink of pollutants Sediments can act as resevoirs that accumulate contaminants fixing them or allowing their decomposition or metabolization. However, environmental changes oor human induced ones, shuch as variations in water pH, increases in the turbulence or intensity of the water flow, etc.could favour their release to the environment.

In this work, the incidence and distribution of seven heavy metals was monitored in the sediments of the Turia River. Along the river course, 22 zones were selected for sampling according different lithologies, land uses, size of populations and the proximity to waste waters treatment plants (WWTPs), from the headwaters to the mouth. The selected metals (Cd, Co, Cr, Cu, Pb, Ni and Zn) were analysed to determine its total and extractable contents in the sediments. Total content of metals was extracted by microwave acid digestion and the extractable fraction by treatment with EDTA. Atomic Absorption Spectrometry, using graphite furnace when necessary, was used for the determination of all metals.

Highest values were mainly observed in zones 10 and 22, close to urban areas, reaching values of 172.86 mg/kg for Pb, or 58.34 mg/kg for Cr. However, zone 2 near in the headwaters of the Alfambra River and supposedly of reference for the River authorities shows the highest values of zinc with 96.96 mg/kg. Regarding the available/extractable fraction of the metals, Cd, Co and Cr were under the detection limitswith maximum values in zone 22 too, reching in the case of Pb 59.60 mg/kg. The percentage of available metal in the sediments of the studied zones vary between 15 and 40% for Cu, Pb and Zn, being the higher than 60% for Pb and Zn in zone 8 near the city of Teruel.

The organic matter content of the sediments is the parameter most strongly related with all the forms of metals, mainly for Cu, Ni, Pb and Zn, and is a key factor in the availability of them. It has to be noted that the textural distribution of the sediments, particularly the clay content, also influences this last factor in the case of Ni.

A strong tendency towards enrichment of the sediments in heavy metals is observed in the Turia River from North to South, from the headwater to the stuary, with the exception of the possible existence of a contamination source in zone 2. Acknowledgements

This work has been supported by the Spanish Ministry of Science and Innovation and the European Regional Development Funds (ERDF) through the coordinating project MEFTURIA (CGL2011-29703-C02-00), and its subprojects EFAMED and EMEFOR (CGL2011-29703-C02-02), and the project CONSOLIDER-INGENIO 2010 (CSD2009).

160 Poster sessions


Levels of free and combined chlorine found in indoor swimming pools, both in bathing water and air

Javier Pla-Tolós1, Carmen Molins-Legua1, Jorge Verdú-Andres1, Yolanda Moliner-Martínez1,

Rosa Herráez-Hernández1, Pilar Campins-Falcó1 and Salvador Llana2

1Department of Analytical Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain 2 Dpto. de Educación Física y Deportiva, Universidad de Valencia

Swimming activity is a source of exposure to disinfection by- products (DBP), which are potentially toxic. The disinfection in bathing water is mainly carried out by chlorination. Thus, the aim of this study was to analyse the levels of free chlorine and combined chlorine (monochloramine: NH2Cl, dichloramine: NHCl2 and trichloramine: NCl3) in water and air samples in indoor swimming pools as function of the disinfection treatment and the characteristic of the installation (chlorination and UV). The analytical procedure for the determination of combined chlorine in water samples was the DPB (N,N- diethyl-1,4- phenylendiamine) method. The analysis of total chlorine (free and combined chlorine) in air samples was based on the spectrophotometric determination of iodine after the reaction with the chlorine oxidable species in air [1].

The results showed that chlorination leads to the formation of chloramines in bathing water samples, mainly mono- and dichloramine. However, UV-treated swimming pool free chlorine was the predominate specie owing to the absence of organic matter. The level of total chlorine increased as function of the swimming activity in swimming pools with chlorination treatment. In the case of UV-treatment, this content was constant and any significative variation was found with the swimming activity. Similar results were found in air samples, with an increase of the total chlorine as function of the swimming activity in the case of chlorinated swimming pools. In addition, the quality of the installation has been proved an important variable in the exposure of the swimmers to chlorine species. The lower quality of the installation resulted in a higher content of total chlorine, especially in air samples and therefore a higher exposure of the swimmer to DBP.

Figure 1. Comparison of the level of total chlorine in air (mg/m3) and water samples (mg/l) in three swimming pools

with chlorinated disinfection procedure (A and B) and with UV-vis treatment C

Acknowledgements The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045) and MINECO: DEP2011-15805-E)

References

[1] Santa Marins, L, Ibarluzea, J., Basterrechea, M., Goñi, F., Ulibarrena, E., Artieeda, J., Orruño, I. Contaminación del aire interior y del agua de baño en piscinas cubiertas de Guipúzcoa. Gac.Sanit (2009) 23, 115-120.

161 Poster sessions



Development of new supports for in situ estimation of nitrogen containing compounds in atmospheres of wastewater treatment plants

Neus Jornet-Martinez, Yolanda Moliner-Martínez, Jorge Verdú Andrés, Carmen Molins-Legua,

Rosa Herráez Hernández and Pilar Campíns-Falcó

Departmento de Química Analítica, Facultad de Química, Universidad de Valencia, Burjassot, Spain

Reduced nitrogen-containing compounds such as volatile aliphatic amines are important atmospheric pollutants due to their odorous and toxic characteristics. Malodorous emissions from wastewater treatments plants affect negatively quality of life and are a significant contribution to the degradation of ecosystems. However, the determination of nitrogen-containing compounds in such kind of atmospheres has received a limited attention, and to date, most analytical procedures proposed to establish time and space patterns emissions from wastewater treatment plants are focused in sulphur, chlorinated and aromatic hydrocarbons. Therefore, the development of reliable methods for the determination of ammonia and volatile aliphatic amines in atmospheres of wastewater treatment plants is of clear interest [1].

The main aim of the present study was to develop an in-situ sensor for sampling and detection of reduced nitrogen-containing compounds in atmospheres of wastewater treatment plants to estimate both, inmission and emission concentrations. We present a passive dispositive for in situ analysis of treatment plant atmospheres Primary and secondary volatile amines presented different color (figure 1). The dispositive was obtained through easy and direct synthesis by the derivatization reagent 1,2-naphotquinone-4-sulphonate (NQS) embedded in polydimethylsiloxane (PDMS) [2]. The sensor did not need any external source for amine detection, the energy cost is zero, is stable and not toxic. In conclusion, we report a cost-effective amine sensor, being respectful to environment. The detection limit achieved was 3 mg m-3 for dimethylamine, which is in the list of prioriotary pollutants in Europe, being the legislated value for working atmospheres of 3.8 - 9.4 mg m-3 [3].

Figure 1: NQS embedded PDMS a) before vaporous amine exposure and b-e) after amine exposure (50 mg m-3 in 8h): b) diethylamine, c) dimethylamine, d) ethylamine and e) methylamine.

Acknowledgements

The authors are grateful to Generalitat Valenciana (PROMETEO program project 2012/045); N. J-M and Y. M-M expresses their grateful for a PROMETEO grant and a JdC research contract (Ministerio de Ciencia e Innovación of Spain), respectively.

References

[1] Ge, X., Wexler,S.A. and Clegg, S. L. Atmospheric amines. Atmos. Environ., (2011), 45, 524-546.

[2] Patent P201300436. P. Campíns-Falcó, Y. Moliner-Martínez,R., R. Herráez-Hernández, C. Molins-Legua, J. Verdú-Andrés, N. Jornet-Martinez.

[3] European Directive 2000/39/CE, Brussels, 6/8/2000.

162 Poster sessions


Fat determination in effluents of dairy industries by preconcentration in nylon membranes and ATR-IR

María Muñoz-Ortuño, Yolanda Moliner-Martinez, Rosa Herráez-Hernández and Pilar Campíns-

Falcó

Department of Analytical Chemistry, Chemistry Faculty, University of València, Burjassot, Spain

At the present, there is an increasing demand for rapid and cost-effective methods for characterizing industrial effluent, not only for environmental purposes but also for reducing the production and maintenance costs. In this study, a method by attenuated total reflectance infrared spectroscopy (ATR-IR) mode has been developed for the detection and quantification of fat in effluents generated by the dairy industry, because the fat content has been extensively used in the evaluation of the environmental impact of the effluents produced by company of milky [1]. 1 mL of samples or stock solutions, which were manually filtered using a luer-lock glass syringe of 10 mL connected to a 13 mm diameter stainless steel filter holder, was processed. Filtration was performed by passage through the nylon membranes (13 mm of diameter and 0.45 µm of pore diameter) mounted in the filter holder. After extraction, the nylon membranes were then removed from the holder, and placed on the spectrometer so that the upper side of the membrane was in contact with the ATR crystal. The fat content is then determined by measuring the absorbance of the band at 1745cm-1.

The proposed method can be directly applied to quantify fat in effluents within the 2- 12 mg/L range with adequate reproducibility. The intraday precision (CVs) were ≤ 11%, whereas the interday were ≤ 20%. The limit of detection was 0.5 mg/L. The most relevant features of this process are simplicity and speed as the samples can be characterized in a few minutes. Furthermore, in this study an in-situ assay with Sudan III was also developed for detecting visually the fat.

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Acknowledgements

The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045, ACOMP/2013/155) and to Spanish MINECO (project CTQ2011-26760).

References

[1] Brião, V.B. and Granhen-Tavares, C.R. Effluent generation by the dairy industry: preventive attitudes and opportunities. Braz J Chem Eng. (2007), 24, 487-497.

163 Poster sessions



Determination of lactose in effluents of dairy industries

María Muñoz-Ortuño1, Yolanda Moliner-Martinez1, Rosa Herráez-Hernández1, M.T. Picher2 and Pilar Campíns-Falcó1

1Department of Analytical Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain

2 Department of Organic Chemistry, Chemistry Faculty, University of Valencia, Burjassot, Spain

The dairy industry, like most other agro-factories, generates strong wastewaters, moreover, this kind of factory is one of the largest sources of industrial effluents in Europe. The main contributors to the dairy waste effluents are carbohydrates, fats, minerals and proteins from the milk. Also, the decomposition of these contaminants caused discomfort to the surrounding population due to the bad smell released. The aim of research presented in this work was to estimate the concentration of lactose in dairy wastewaters because it is a major component of milk and milk whey. In the case of whey, the contain is about 77-80% of carbohydrates, mainly lactose (1).

A colorimetric method was proposed for in-situ estimation of the quantity of lactose in effluents of dairy industries. Also the response can be measured by a UV-Vis spectrophotometer equipped with a remote diffuse reflection accesory. 20 drops of samples or stock solutions were deposited in silica gel layer. After, the silica gel layer was sopping with a solution of thymol (0.05 g Thymol in 95 mL of EtOH and 5mL H2SO4) and after, the silica gel layer was heated with a hand dryer for 1.5 min in order to develop de color. Finally, the difusse reflectances of samples and stock solutions were also measured. Figure 1 shows the results obtained in function of the concentration. The achieved limit of detection was 5 mg/L. This value was much lower than the usual concentration of lactose in samples of wastewaters (0.5-5.3 g/L in assayed samples provided by several dairy factories).

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gel Acknowledgements

The authors are grateful to the Generalitat Valenciana (Prometeo Program 2012/045, ACOMP/2013/155) and to Spanish MINECO (project CTQ2011-26760).

References

Muangrat, R., Onwudili, J.A. and Williams, P.T. Alkaline subcritical water gasification of dairy industry waste. Bioresource Technology (2011), 102, 6331-6335.

164 Poster sessions


Greenhouse gas emissions in two coastal systems in Cadiz Bay (SW Spain): relationship with organic matter inputs

Macarena Burgos, A. Sierra, Teodora Ortega and Jesús Forja

CACYTMAR, Dep. Química-Física, Puerto Real, Spain

Coastal areas are subject to a great anthropogenic pressure because more than half of the world’s population lives in its vicinity, causing organic matter inputs, which intensifies greenhouse gas emissions into the atmosphere. Greenhouse gas concentrations (CO2, CH4 and N2O) have been estimated in two aquatic systems of Cadiz Bay Natural Park: Rio San Pedro Creek and Sancti Petri Channel.

Water renewal in Rio San Pedro Creek is tidally controlled. Due to its little freshwater input, the Creek is essentially a marine system. Several fish farms are distributed on its banks discharging effluents without previous treatment. Nine sampling stations are distributed along this system 12 Km length. Sancti Petri Channel is a flow channel-ebb tides extending from the inner Cadiz Bay to the Atlantic Ocean along 17 Km. Organic matter pollution sources in this enviroment are straggly. There exist anthropogenic inputs such as aquaculture’s effluents and sewage discharges coming through Iro River, which flows into the Channel central part. In addition there are natural organic matter inputs from surrounding marshes. It has been established 11 sampling stations crossing this system.

Sampling was conducted seasonally during 2013. Partial pressure of CO2 was obtained through total alkalinity and pH measurements. CH4 and N2O concentrations were acquired using a gas chromatograph connected to an equilibration system.

Greenhouse gas values vary between 410.5 and 1272.3 µatm, 24.0 and 295.5 nM and 16.1 and 27.8 nM for pCO2, CH4 and N2O, respectively. Gas concentrations increase close to the fish farm effluent in Rio San Pedro Creek, and next to Iro River in Sancti Petri tidal Channel. Both environments act as greenhouse gas sources into the atmosphere, showing seasonal variations. It has been estimated mean fluxes of 6.8 mmol m-2 d-1 of CO2, 75.3 μmol m-2 d-1 of CH4 and 31.9 μmol m-2 d-1 of N2O.

165 Poster sessions



Anthropogenic effects on greenhouse gas emissions in the Guadalete River Estuary

Macarena Burgos, A. Sierra, Teodora Ortega and Jesús Forja

CACYTMAR, Dpto. Química-Física, Puerto Real, Spain

CO2, CH4 and N2O are responsible for 88% of the atmospheric radiation absorption and they affect (directly and indirectly) the planet climate. Currently, there exist a social concern and an important scientific effort of quantifying the human activities impact on carbon, nitrogen and phosphorus natural cycles. Eutrophization and the increased greenhouse gas atmospheric emissions from coastal areas are evidences of a continuous contamination process, which is able to alter ecosystem functions, and element fluxes to other Earth compartments.

Guadalete River empties into the Cadiz Bay, located in the southwestern Spanish coast. The River has been intensely contaminated since 1970. Currently it receives wastewater effluents from cities and direct discharges from nearby agriculture crop. Eight sampling stations have been established along 18 Km of the Estuary.

Water surface concentrations of CO2, CH4 and N2O were estimated seasonally during 2013. Partial pressure of CO2 was obtained through total alkalinity and pH measurements, while CH4 and N2O concentrations were acquired using a gas chromatograph connected to an equilibration system. Additional parameters such as organic matter, dissolved oxygen, nutrients and chlorophyll were determinate as well, in order to understand the relationship between physicochemical and biological processes. Gas concentrations increase from the River mouth toward the inner part, closer to the anthropogenic pollution inputs, with values varing widely within 193.1 and 3778.3 µatm for pCO2, 14.8 and 1859.0 nM for CH4, 17.4 and 134.6 nM for N2O. Greenhouse gas emissions into the atmosphere show seasonal variability; however, the Guadatete River Estuary acts as greenhouse gas source during the whole year with mean fluxes of 12.3 mmol m-2 d-1, 91.2 μmol m-2 d-1 and 40.8 μmol m-2 d-1 for CO2, CH4 and N2O, respectively.

166 Poster sessions


Hourly variations in the occurrence of several pharmaceuticals and surfactants in urban and industrial wastewater

Dolores Camacho-Muñoz, Julia Martín, Juan L. Santos, Irene Aparicio and Eduardo Alonso


The presence of a broad spectrum of organic pollutants in the environment has been widely recognized as a potential environmental threat (Santos et al., 2010). After their use or application they usually end up in the sewer system reaching wastewater treatment plants, being its source industrial and urban activities. Concentrations of these organic pollutants in influent wastewater can exhibit seasonal, weekly and diurnal variations (Plósz et al., 2010). However, only a few studies have paid attention to spatial temporal evolution of these compounds in the influent loads.

In this work twenty one pharmaceutically active compounds belonging to different therapeutic classes including six non-steroidal antiinflammatory drugs (acetaminophen, diclofenac, ibuprofen, ketoprofen, naproxen and salicylic acid), five antibiotics (ciprofloxacin, norfloxacin, ofloxacin, sulfamethoxazole and trimethoprim), a β-blocker (propranolol), three lipid regulators (bezafibrate, clofibric acid, and gemfibrozil), an antiepileptic drug (carbamazepine), four estrogens (17α-ethinylestradiol, 17β-estradiol, estriol and estrone) and a nervous stimulant (caffeine); and seven surfactants including four linear alkylbenzene sulfonates (LAS C10-C13) and a nonylphenol (NP) and its mono- and diethoxylate derivatives (NP1EO and NP2EO) were analyzed in urban and industrial wastewater collected every hour during 24 h periods. Temporal evolution of the studied compounds, their different sources (domestic and industrial) and their seasonal variations were evaluated.

The highest concentrations of pharmaceutically active compounds were found in urban wastewater, especially in the case of the anti-inflammatory drugs (up to 220 µg L-1) and caffeine (up to 72.4 µg L-1), although the highest concentractions of salicylic acid were quantified in industrial wastewater (3295 µg L-

1). Concentrations of LAS ranged from 12.1 µg L-1 to 2981µg L-1, and from below limit of detection to 171 µg L-1 in urban and industrial wastewater respectively, whereas the concentrations of nonylphenol ethoxylates were significantly lower.

Pharmaceutically active compound were seasonal-dependent whereas LAS and nonylphenol ethoxylates showed a similar pattern in both seasons. Pharmaceutically active compounds showed a distribution in corcondance with the consumption and excretion pattern in the case of urban wastewater and with the schedule of greater industrial activity in the case of industrial wastewater. Temporal evolution of LAS showed peak of concentrations in urban wastewater whereas in industrial wastewater concentrations held steady during all day. Acknowledgements

This work has been carried out in collaboration with Empresa Metropolitana de Abastecimiento y Saneamiento de Aguas de Sevilla (EMASESA), financed by Corporación Tecnológica de Andalucía (CTA) and Agencia de Innovación de Andalucía (IDEA) and supported by the ERDF.

References

Santos, L.H.M.L.M., Araújo, A., Fachini, A., Pena, A., Deleure-Matos, C. and Montenegro, M.C.B.S.D.M. Ecotoxicological aspects related to the presence of pharmaceuticals in the aquatic environment. Journal of Hazardous Materials (2010), 175, 45-95.

Plósz, B.G., Leknes, H., Liltved, H., Thomas, K.V. Diurnal variations in the occurrence and the fate of hormones and antibiotics in activated sludge wastewater treatment in Oslo, Norway. Science of the Total Environment (2010), 408, 1915-1924.

167 Poster sessions



Multi-residue analysis of pharmaceutically active compounds (PhACs) in aqueous matrices by liquid chromatography -quadrupole - time-of-

flight - mass spectrometry

Rosa M. Baena-Nogueras1, Gabriela Aguirre-Martínez1, L. Alves-Maranho1, María Laura Martín-Díaz1, Eduardo González-Mazo1 and Pablo A. Lara-Martín1

1Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz, Puerto Real,

Spain

This work presents the optimization of a method for the simultaneous determination of 97 pharmaceuticals including antibiotics and biocides (62), and other groups of different PhACs (35) such as anti-inflammatories, antihypertensives, lipid regulators, histamine receptor antagonists and psychiatric drugs in aqueous matrices. Target compounds were extracted from water by solid-phase extraction (SPE) using HLB cartridges. SPE was optimized testing the influence of pH, different elution solvents and modifiers (such as formic acid, ammonium formiate and EDTA). Once optimized, we decided to use methanol with 1% of formic acid as extraction solvent, lowering the pH of the samples to 2 and also adding 1 g of EDTA before SPE. The optimized protocol showed acceptable recovery percentages (51-100%) for most of the analytes. Identification and quantification of target (and also non-targey) compounds was performed by liquid chromatography –quadrupole - time-of-flight - mass spectrometry (LC-Q-ToF-MS). The method was used to measure concentrations of PhACs in surface water samples collected from Rio San Pedro and Guadalete River (SW Spain) during both summer and winter seasons. High concentrations were detected for some drugs such as acetaminophen (650 ppt) and caffeine (14 ppb). Those antibiotics detected at highest concentrations were azithromycin (30 ppt), a macrolide, and enrofloxacin (49 ppt), a quinolone. Moreover, several non-target chemicals, mostly surfactants such as linear alkylbenzene sulfonates (LAS) and polyethoxylated alcohols (AEOs), and other personal care products (PCPs) (e.g., polyethylene glycols) were also identified within the same samples. Acknowledgements

This study was carried out within the two projects funded by the Consejería de Innovación, Ciencia y Empresa de la Junta de Andalucía (RNM 5417 and RNM 6613)

168 Poster sessions


Sorption of 3 pharmaceuticals in agricultural soils: hydrochlorothiazide, metoprolol and clarithromycin

Nivis Torres-Fuentes1, Carmen Corada-Fernández1, Eduardo González-Mazo1

Pablo A. Lara-Martín1 and Diana Álvarez-Muñoz1,2

1 Department of Physical-Chemistry, Faculty of Marine and Environmental Sciences, University of Cadiz, Campus of

International Excellence (CEI•MAR), Puerto Real, Spain 2 Catalan Institute for Water Research (ICRA), Parc Científic i Tecnològic de la Universitat de Girona, Girona, Spain

Nowadays, a wide range of contaminants have been identified in the environment. In the case of pharmaceuticals and personal care products (PPCPs) their presence in surface waters is mainly due to treated and untreated discharges from sewage treatment plants. The use of digested sewage sludge or biosolids as sources of nutrients in agricultural soils jeopardizes not only surface waters but also groundwater and soils. Thus, there is a significant risk that amended soils may be contaminated and, later, pollutants are transported to surface waters by runoff and to groundwater through leaching. This is especially important when we consider persistent contaminants that may last many years after their application (e.g., DDT), or biologically active substances such as pharmaceuticals. The present study deals with the sorption of three pharmaceuticals that have been previously found by our research group in soils from the Cadiz area: hydrochlorothiazide (HCTZ), metoprolol (MTP), and clarithromycin (CLTM). Soil samples were collected from the soils over the aquifer of Jerez de la Frontera (code 062.009). Physico-chemical properties of these soils were determined in the laboratory: pH, organic carbon content, water holding capacity and texture. Sorption was determined using the batch equilibrium method according to OECD guideline 106. Briefly, 80 mL tubes were filled with HPLC water (50 mL), agricultural soils (0.5 – 1 g) and several concentrations of the target compounds (0.1 to 500 ng/L). After agitation (48 h), both phases were separated by centrifugation and determination of the concentration of the analytes was carried out by liquid chromatography - time-of-flight - mass spectrometry (LC-ToF-MS) after solid phase and pressurized liquid extractions, respectively. Data for each pharmaceutical were fitted to a Freundlich isotherm model, calculating their respective sorption coefficients. Freundlich constants (Kf) for the selected compounds were: 45.4 L/kg (HCTZ), 43.4 L/kg (MTP) and 3043 L/kg (CLTM), respectively. The correlation factors (r2) obtained were 0.9574 (HCTZ), 09767 (MTP) and 0.7565 (CLTM). In spite of showing relatively low octanol-water partition coefficients (log Kow < 3), all target compounds showed moderate to high sorption capacities onto soils due the presence of positively charged groups in their molecular structures, which enhance their interaction with clays in soils. Acknowledgements

This study was carried out within the project PERCOLA (ref. CGL2011-27349), funded by the Ministerio de Economía y Competitividad

169 Poster sessions



Evaluation of a simple method for the analysis of pharmaceuticals in seafood

Diana Álvarez-Muñoz1, Belinda Huerta1, Sara Rodríguez-Mozaz1 and Damià Barceló1,2



Seafood has traditionally been a popular part of the diet in many parts of the world and in some countries constituted the main supply of animal protein. Its quality is of major concern to general public and health authorities and seafood safety, like any other food type, has become an important issue. Priority contaminats in seafood as a result of environmental contamination need to be assessed and for this purpose a simple and accessible analytical method is required.

Pharmaceutically active compounds (PhACs) are among the contaminats that need to be monitored. They are often detected in aqueous compartments and one of the main concerns is their potential to biaccumulate in biota. Even very low concentrations (ng/l or pg/l) can be toxicologically relevant and may provoke long-term toxic effects not only to wild life but also to human health.

Due to their high consume and commercial valor an oyster (Crassostea gigas) has been chosen as target specie for the method evaluation. Bivalves are natural filters feeders and any dissolved or suspended contaminants present in the water can be easily incorporated into the organism. Besides, this mollusk can be eaten raw requiring an exhaustive quality control. A simple and routinary extraction method was implemented based on pressurized liquid extraction (PLE) and solid phase extraction (SPE) clean-up. For the method evaluation the oysters were spiked at 10 and 100 ng/g of dry weight with a mixture of selected PhACs containing analgesics, anti-inflamatories, lípido regulators, psychiatric drugs, β-blockers and antibiotics between others. The samples were analysed using PLE with methanol: water (1:2) as extraction solvent, followed by a SPE on oasis HLB cartridges, and finally identified and quantified by Ultra Performance Liquid Chromatography - tandem Mass Spectrometry. The method has been critically compared with one previously published (Huerta et. al. 2013) and the advantages and disvantages have been pinpointed.

Acknowledgements

This study has been co-financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065) the EU Project ECSafeSEAFOOD [FP7-KBBE 311820] and by the European Union through the European Regional Development Fund (FEDER). This work was partly supported by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965)

References

Huerta, B., Jakimska, A., Gros, M., Rodríguez-Mozaz, S., Barceló, D. Analysis of multi-class pharmaceuticals in fish tissues by ultra-high-perfomance liquid chromatography tandem mass spectrometry. Journal of Chromatography A (2013), 1288, 63-72.

170 Poster sessions


High-resolution mass spectrometry applications in the identification and detection of transformation products in the aquatic environment

Bozo Zonja1, Sandra Pérez1 and Damià Barceló1,2

1 Water and Soil Research Group, Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute of Water Research (ICRA), Girona, Spain

Platforms with high-resolution MS analyzers such as Orbitrap, are the mostly and widely used analyzers in the structural elucidation of TPs of emerging organic pollutants using LC-MS tecniques. It is now generally recognized that high-resolution instruments afford the most straightforward route towards the reliable characterization of TPs because they allow for the determination of elemental formulae based on the measurement of exact masses with accuracies better than 1-2 ppm in relative mass errors. The high resolving power of the MS- on some instruments now exceeding even 100,000- enables the determination of accurate masses even in complex samples containing potentially interfering compounds with identical nominal masses. Apart from hardware performance, (semi)automated data analysis and interpretation are becoming increasingly important to assist in the elucidation process. Software developments in the field of peak finding, construction of fragmentation trees and prediction of fragmentation patterns assist the analytical chemist to streamline the identification of TPs (Zonja et al. in press).

Classical approach for transformation products (TPs) structure elucidation would be to simulate a certain environmental process in lab scale, determine its transformation products, synthetize the standards or even isolate them from the degradated samples with semipreparative LC and later on searching them in the real environment. This procedure was applied for the identification of photoTPs of the antiviral zanamivir. Structural identification of the TPs was done on LTQ-Orbitrap Velos using different software Sieve (Thermo Scientific) in order to ease the elucidation part. Finally four mayor TPs were identified and its formation mechanistically explained.

A bit different approach and more usefull is the application of suspect analysis for detection of TPs which implies a fast checking of real environmental samples and evaluating if some TPs occure or not. This approach was applied for the detection and structural characterisation of Iodinated contrast media’s (ICMs) photolysis products.. Five ICM – iomeprol, iohexol, iopamidol, iodixanol and diatrizoate were degraded in river water samples at lab-scale conditions using Suntest (simulated sunlight apparatus). Masses of the newly found transformation products were determined and they were tentatively identified. The determination of parent compounds and their TPs in real water samples was performed with data dependant screening with LTQ-Orbitrap-Velos using a different approach to the one used for the work of zanamivir presented previously.This methodology allowed us to have several identification points to the targeted mass (accurate mass, fragmentation pathway and isotope composition – if applicable). The TPs were separated form their parent compounds on a HPLC-semipreparative column. After purification, the compounds were analyzed in NMR in order to additionaly confirm their structure. Purified compounds served as analytical standards allowing us to quantify the presence of these compounds in the aquatic environment. Acknowledgements

BZ acknowledges the Marie Curie Actions ITN CSI:Environment PITN-GA-2010-264329 for the Early Stage Researcher contract and funding. SP acknowledges the contract from the Ramón y Cajal Program. This work was partly supported by Spanish Ministry of Economy and Competitiveness [64551/HID and Consolider-Ingenio 2010 Scarce CSD2009-00065] and the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965).

References

Zonja et al., Transformation Products of Emerging Contaminants: Analytical challenges and Future needs, Wiley books, in press

171 Poster sessions



Pharmaceutical compounds in sludge from different sludge stabilization processes: occurrence and environmental risk assessment

after sludge application onto soils

Juan L. Santos, Julia Martín, Dolores Camacho-Muñoz, A. Santos, Irene Aparicio and Esteban Alonso


The production of sewage sludge generated as a by-product in wastewater treatment plants (WWTPs) is continuously increasing. Agricultural use is the most popular disposal route of this sludge, since it not only represents the cheapest option for sludge disposal, but also constitutes a useful fertilizer and soil conditioner material (Kelessidis and Stasinakis et al., 2012).

The possible threats, for the environment and human health, of the presence of pharmaceutical compounds in sludge used in agricultural lands have also been reported (Sabourin et al., 2012). These compounds are toxic for aquatic and terrestrial organisms and some of them (diclofenac, 17α-ethinylestradiol and 17β-estradiol) have been proposed as priority substances in the field of water policy (Annex 1 of the proposal for a Directive) (EC, 2011). However, no regulation about their presence in sewage sludge is found in the European Union.

The aims of this work were to evaluate the occurrence of twenty-two pharmaceutically active compounds belonging to different therapeutic groups in different sludge stabilization technologies and estimate the environmental risks of the application of the final product of these technologies onto soils due to the presence of pharmaceutical compounds. The types of sludge evaluated were primary, secondary, mixed, aerobically-digested and dehydrated, anaerobically-digested and dehydrated, compost and lagoon sludge.

Nineteen of the twenty-two pharmaceuticals monitored were detected in sewage sludge. The most contaminated samples were primary, secondary and mixed sludge (average sum of pharmaceuticals: 179 µg/kg dry matter (dm), 310 µg/kg dm and 142 µg/kg dm, respectively). Average concentration, in the other types of sewage sludge, were: 8 µg/kg dm in anaerobically-digested sludge, 70 µg/kg dm in aerobically-digested sludge, 63 µg/kg dm in lagoon sludge and 12 µg/kg dm in compost. The antibiotics ciprofloxacin and norfloxacin were the pharmaceuticals at the highest concentration levels in most of the samples (mean values 1.9 and 3.5 mg/kg, respectively). Anaerobic-digestion treatment reduced the concentration of most of the pharmaceutical compounds more significant than aerobic-digestion (especially in the case of bezafibrate and fluoroquinolones) and anaerobic stabilization ponds (in the case of acetaminophen, atenolol, bezafibrate, carbamazepine, 17α-ethinylestradiol, naproxen and salicylic acid).

Risk quotients, expressed as the ratio between the predicted environmental concentration and the predicted non-effect concentration, were lower than 1 for all the pharmaceuticals so no significant risk is expected to occur due to the application of sewage sludge onto soils, except for 17α-ethinylestradiol when chronic toxicity data were used. References

Kelessidis, A., Stasinakis, A.S. Comparative study of the methods used for treatment and final disposal of sewage sludge in European countries. Waste Management (2012), 32, 1186-95.

Sabourin, L., Duenk, P., Bonte-Gelok, S., Payne, M., Lapen, D.R., Topp, E. Uptake of pharmaceuticals, hormones and parabens into vegetables grown in soil fertilized with municipal biosolids. Scince of the Total Environment (2012) 431, 233-236.

EC, 2011. European Commission, COM(2011) 876. Proposal for a Directive of the European Parliament and of the Council amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy.

172 Poster sessions


Green and cheap alternative for the determination of 5-nitroimidazoles in river and well waters based on Cation Selective

Exhaustive Inyection and Sweeping Micellar Electrokinetic Chromatography (CSEI-sweeping-MEKC)

Diego Airado-Rodríguez, Maykel Hernández-Mesa, Carmen Cruces-Blanco and Ana M. García-

Campaña

Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain

The presence of antibiotics in environmental waters is a concerning issue and the development of sensitive and selective methods to control it is a must. 5-Nitroimidazole derivatives (5-NDZs) are human antibiotics mainly employed for treating illness due to anaerobia microbes. 5-NDZs are characterized by their high polarity and low biodegradability, which increases their bioaccumulation in waters.

A novel capillary electrophoresis (CE) method has been developed for 5-NDZ determination in water samples based in the combination of cation-selective exhaustive injection with sweeping micellar electrokinetic chromatography (CSEI-sweep-MEKC). This methodology combines two on-line preconcentration techniques, namely field-enhanced sample injection and sweeping, which implies high sensitivity. On the other hand, the use of electrokinetic injection involves an enhancement of selectivity associated to the injection step.

Dispersive liquid liquid microextraction (DLLME) has been proposed for sample treatment prior to CSEI-sweep-MEKC. This is a novel microextraction technique, initially developed by Rezaee et al [1]. Basically it consists in the rapid injection of an appropriate mixture of an extractive solvent plus a disperser agent, into an aqueous sample, resulting in the formation of a cloudy solution. Analytes of interest are extracted into the extractive solvent droplets. As far as we know this is the first time that this novel microextraction technique has been coupled with CSEI-sweeping-MEKC. In this case, dibromomethane and 2-butanol were employed as extraction solvent and dispersive agent, respectively. The extraction was assisted by salting out effect through by the addition of 16% (w/v) NaCl to water samples. After DLLME performance and evaporation to dryness of the obtained organic extracts, those were redissolved in a low conductivity solvent (5mM phosphoric acid with 5% of methanol) and it was electrokinetically injected at 9.8 KV for 632 s in a bare fused-silica capillary (57.2 cm, 50 µm I.D.). Prior to the injection, the capillary was rinsed with 50 mM phosphate buffer pH 2.5, followed by a plug of a higher conductivity buffer (100 mM phosphate pH 2.5, 50 mbar, 264 s) and a plug of water (50 mbar, 2 s). Separation was carried out applying -30 KV at 20 ºC in 44 mM phosphate buffer pH 2.5, containing 8 % tetrahydrofurane and 123 mM SDS. Analytical signals were monitored at 276 nm.

Validation was performed in river and well waters, obtaining satisfactory results in terms of linearity, precision and trueness. LODs ranged from 0.57 to 4.26 µg/L. The combination of DLLME with the proposed CE methodology constitutes a simple, sensitive and cheap alternative for 5-NDZ determination, in accordance with the aims of green chemistry. Acknowledgements

This work was supported by the Project P08-AGR-4268 (Excellence Project, Junta de Andalucía). DA-R thanks the Spanish Ministry of Science and Innovation for a “Juan de la Cierva” contract. MHM thanks the Plan Propio of the University of Granada for a predoctoral grant.

References

1- Rezaee, M., Assadi, Y., Milani Hosseini, M.R., Aghaee, E., Ahmadi, F. and Berijani, S. J. Chromatogr. A (2006), 1116, 1-9

173 Poster sessions



Temporal trends of illicit drugs in WWTPs in Valencia, Spain

María Jesús Andrés-Costa1, Ana Masiá1, Vicente Andreu2 and Yolanda Picó1

1 Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy,

University of Valencia. Burjassot, Spain 2 Reserch Centre of Desertification (CIDE, CSIC-UV-GVA). Moncada, Valencia, Spain

The presence of drugs of abuse in the aquatic environment has been recognized as an important issue for the ecosystem due their possible negative effect on it (Richardson, 2011). Incomplete removal of these substances during wastewater treatment could be one of the causes of their release in the environment (Zuccato and Castiglioni, 2009). Pollution by illicit drug residues at very low concentrations is generalized in populated areas, with potential risks for human health and the environment (Zuccato, 2008; Castiglioni et al 2007). In addition, back-calculation from the concentration of illicit drug in the influents of wastewater treatment plants (WWTPs) provides an important tool for estimating its local consumption (Daughton 2001).Samples were collected at the WWTPs of Quart-Benager and Pinedo I and II. These plants treat most of the residual water from Valencia city sampling campaigns were in three years, 2011, 2012 and 2013. In March 2011 were collected influent samples for seven consecutive days. In April 2012 were collected influent and effluent samples for fifteen consecutive days and in March 2013 were collected influent and effluent samples for seven consecutive days.

Illicit drugs were extracted using solid phase extraction (SPE) and determined by liquid chromatography tandem mass spectrometry (LC-MS/MS) in positive ionization with an electrospray ionization source (ESI). Compounds were quantified in wastewater and surface water as parent drugs were cocaine (COC), amphetamine (AMP), methamphetamine (MAMP), ecstasy (MDMA) and ketamine (KET). Benzoylecgonine (BE), 6-acethylmorphine (6-MAM), and 11-nor-9-carboxy-delta9-tetrahydrocannabinol (THC-COOH) were the main urinary metabolites for cocaine, heroin and cannabis respectivelyThe determination of illicit drugs in the influent of the selected WWTP shows that cocaine is the drug present at highest concentrations in the wastewater followed by cannabis and amphetamine in 2011, 2012 and 2013. The temporal variation of the illicit drugs shows little variation from one year to other showing a quite stable consumption in Valencia city, even through there is a clear increase in the cannabis consumption during this last sampling without any clear explanation. The results from the concentration levels quantifying in the influent and the effluent demonstrated that the treatment plants eliminate these compounds in a high percentage, fully comparable to other studies on removal efficiency carried out in other European countries as Belgium, United Kindown, Italy or France. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness trough the project SCARCE-CDS 2009-0065, CGL 2011-29703-C02-01 and GCL CGL 2011-29703-C02-02. MJ Andrés Costa also acknowledges to this Ministry the FPI grant to perform her PhD.

References

Castiglioni S, Zuccato E. Chiabrando C., Faneli R., Bagnati R. Detecting illicit drugs and metabolites in wastewater usin high performance liquid chromatography-tandem mass spectrometry. Spectroscopy Europe (2007), 19, 7-9

Daughton CG In: Daughton CG., Jones-Lepp TL., editors Pharmaceuticals and personal care products in the environment. Scientific and regulatory issues. Washington: Americal Chemical Society (2001), 348-164.

Richardson SD. Environmental Mass Spectrometry: Emerging Contaminants and Current Issues. Anal Chem (2011), 84, 747-778.

Zuccato E., Castiglioni S., Illicit drugs in the environment. Philos Trans R Soc A (2009), 367, 3965-3978.

Zuccato E., Castiglioni S., Bagnati, R., Chiabrando C., Grassi P., Fanelli R. Illicit drugs a novel group of environmental contaminats. Water Res (2008), 42, 961-968.

174 Poster sessions


Emerging illicit drugs in waste and surface waters in the Turia River Basin

María Jesús Andrés-Costa1, Ana Masiá1, Cristina Blasco1, Vicente Andreu2 and Yolanda Picó1

1 Environmental and Food Safety Research Group, Department of Medicine Preventive, Faculty of Pharmacy,

University of Valencia. Burjassot, Spain 2 Reserch Centre of Desertification (CIDE, CSIC-UV-GVA). Moncada, Valencia, Spain

The phenomenon of new psychoactive substances is dynamic. A total of 24 new psychoactive substances were officially notified for the first time in the EU in 2009 through the EWS (Early Warning System), up from 41 in 2010, 49 in 2011 and 73 in 2012 (EMCDDA, 2013). Narcotics substances may be excreted through urine or faeces, as parent compound or as secondary metabolites. Then, they can arrive to sewage plants and subsequently to environmental compartments (Boles and Wells, 2010). The aim of this study is to supply a pattern of emerging illicit drugs consumed by analyzing these compounds at the influent and effluent of sewage treatment plants and to estimate their environmental contamination possibly by analyzing samples of surface water in the Turia River Basin.

Samples were collected at 25 sites through the Turia River Basin and wastewater samples were collected from the influent and effluent of three wastewater treatment plants (WWTPs) in Valencia. The 8 emerging illicit drugs selected for this study were α- pyrrolidinopropiophenone (PVP), α- pyrrolidino-pentiophenone (PPP), 4’-methyl- α-pyrrolidinohexanophenone (MPHP), 4’-methyl- α- pyrro-lidinobutiophenone (MPBP), belong to pyrrolidinophenone group, Mephedrone (4MMC), Dibutylone (bk-MMBDB), 4-Methoxyphencyclidine (4-MeO-PCP) and Bufotenine (BUF).

Illicit drugs were extracted from 250 ml of water by solid phase extraction (SPE) and determined by liquid chromatography triple quadruple mass spectrometry (LC-QqQ-MS/MS) using an electrospray ionization source (ESI) in positive ionization mode. The method detection limits ranged from 0.01 to 1.54 ng L-1 and the recoveries from 57 to 127 % with relative standard deviations ≤ 20 % The feasibility of this method was demonstrated by analyzing spiked water samples.

Their application to determine new illicit drugs in the influent of the selected WWTP shows the presence of BUF in all samples (at concentrations up to 325.3 ng L-1) and 4-MeO-PCP in 23.8 % (at concentration up to 240.3 ng L-1). However, BUF and 4MEO-PCP were not detected in the effluent of these WWTPs. Also, these illicit drugs were detected at 7 sampling points of the Turia River Basin at concentrations ranging from 3.8 to 66.8 ng L-1 for BUF and 37.6 ng L-1 for 4-MeO-PCP. The others illicit drugs analyzed, αPVP, MPHP, MPBP, PPP, 4MMC and bk-MMBDB, were not detected in the analyzed samples. To our knowledge, this is the first time that these drugs were detected and monitored in River Basins. This study also highlights the need of future research regarding these drug’s transformation pathways and their ecotoxicological effects. Acknowledgements

This work has been supported by the Spanish Ministry of Economy and Competitiveness trough the project SCARCE-CDS 2009-0065, CGL 2011-29703-C02-01 and CGL 2011-29703-C02-02. MJ Andrés Costa also acknowledges to this Ministry the FPI grant to perform her PhD.

References

Boles TH, Wells MJM. Analysis of amphetamine and methamphetamine as emerging pollutants in wastewater and wastewater-impacted streams. Journal of Chromatography A (2010), 1217, 2561-2568.

European Monitoring Centre for Drugs and Drug Addiction (EMCDDA). EU drug markets report: a strategic analysis. EMCDDA, Lisbon, January 2013.

175 Poster sessions



Occurrence and environmental risk assessment of drugs of abuse in four Spanish river basins

Nicola Mastroianni1, Miren López de Alda1 and Damià Barceló1,2



Based on the last World Drug Report recently published by the United Nation Office on Drugs and Crime (UNODC), around 230 million people (5% of the world’s adult population, aged from 15 to 64 years) has used an illicit drug at least once in 2010 [1].

After consumption, pharmaceutical and drugs of abuse are metabolized and different proportions of the parent compound and/or the metabolic products are excreted into the sewage system. Incomplete removal of these compounds during wastewater treatment results in their release in the aquatic environment where they have been detected at ng/L levels [2]. Occurrence of illicit/abused drugs in surface waters is a well-established issue worldwide, but their potential ecotoxicological effects have been hardly investigated and are basically still unknown. Additionally, these effects may be more significant in those aquatic ecosystems that suffer from severe and variable climate conditions and anthropogenic pressures in terms of water demand and water pollution, such as those existing in Mediterranean river basins.

Direct estimation of effects caused by environmental pollutants on ecosystems is not a straightforward task, and in the case of illicit drugs the lack of experimental toxicological data makes this approach even more difficult.

Ecological risk can be estimated numerically using the Hazard Quotients (HQ) approach, where the HQ is defined as the ratio between the compound measured environmental concentration (PEC) and its chronic toxicity, usually expressed as the no observed effect concentration (NOEC) or the predicted non-effect concentration (PNEC). When NOEC values are not available, EC50 or LC50 (50% effect concentration or 50% lethal concentration, respectively) values from standard ecotoxicological tests can be used eventually after correction by an assessment factor (AF) [3]. If a Hazard Quotient is calculated to be equal or greater than one harmful effects cannot be ruled out, while HQ<1 indicate no risk.

In this context, the main objective of the present work was to study the occurrence of 22 illicit drugs and metabolites in surface water collected along four different Mediterranean river basins of the Iberian Peninsula (Ebro, Llobregat, Jucar and Guadalquivir river basin) and to estimate their potential ecotoxicological risk to the aquatic environment. In the considered basins, a total of 77 samples were collected as grab sample during two consecutive years. The compounds analysed belong to five different chemical groups, namely cocainics, amphetamine like compounds, opiates and opioids, benzodiazepines, lysergic acid diethylamide (LSD) and cannabinoids.

Based on the results collected during the monitoring periods, both spatial and temporal differences were assessed, the locations with the largest loads of drugs were identified, and the HQ corresponding to three different trophic levels (algae, cladocerans and fish) were calculated. When no experimental toxicity data was available, predicted toxicity values from (Quantitative) Structure-Activity Relationship ((Q)SAR) models were selected from the available literature or estimated with the U.S. EPA Ecological Structure Activity Relationships (ECOSAR) Class Program (v1.11). Acknowledgments

This work has been financially supported by the Spanish Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065), by the European Commission through the project SOLUTIONS (contract no. 603437), and by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965). It reflects only the author's views. The Community is not liable for any use that may be made of the information contained therein.

176 Poster sessions


Investigation of drugs of abuse in river water from the Granada Province by means of UHPLC-MS/MS in combination with dispersive liquid-liquid microextraction (DLLME) as environmentally-friendly

sample treatment

Diego Airado-Rodríguez, Manuel Lombardo-Agüí, Ana M. García-Campaña and Carmen Cruces-Blanco1

Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain

In this work, an ultra high performance liquid chromatography - electrospray ionization - tandem mass spectrometry (UHPLC-ESI-MS/MS) method is presented for the detection, identification and quantitation of 20 representative multiclass drugs of abuse, including opiates, cannabinoids, amphetamines, and hallucinogenic compounds. The separation has been achieved in 10 min, using a Kinetex XB-C18 column (100 x 2.1 mm and 1.7 µm particle size), in gradient mode with a mobile phase of 0.013 % aqueous formic acid and acetonitrile with 0.013 % formic acid. Parameters affecting the MS/MS detection by using triple quadrupole were optimized and the corresponding product ions for quantification and confirmation were selected.

The proposed UHPLC-ESI-MS/MS method has been validated in terms of linearity, sensitivity (limits of detection and quantification), trueness (through recovery assays) and precision (repeatability and intermediate precision), and successfully applied to water samples from Riofrío river (Granada).

Dispersive liquid-liquid microextraction (DLLME) is a novel microextraction technique, initially developed by Rezaee et al [1], and based on ternary solvents. Basically it consists in the rapid injection of an appropriate mixture of extractive solvent plus a disperser agent, into an aqueous sample, resulting in the formation of a cloudy solution. Analytes of interest are extracted into the extractive solvent droplets. The compatibility of the proposed UHPLC-ESI-MS/MS methodology with DLLME has been demonstrated for water samples. Experimental design and response surface methodology have been employed for the optimization of critical variables related to DLLME.

Thus, the proposed methodology combines the advantages of DLLME as microextraction technique (cheap, simple and environmentally friendly) with the high sensitivity, selectivity, rapidness and identification capability of UHPLC-MS/MS, showing its usefulness for the simultaneous monitoring of a great variety of abused drugs in environmental water samples, which could be very useful for routine analysis. Acknowledgements

DA-R thanks the Spanish Ministry of Science and Innovation for a “Juan de la Cierva” contract.

References

1- Rezaee, M., Assadi, Y., Milani Hosseini, M.R., Aghaee, E., Ahmadi, F. and Berijani, S. J. Chromatogr. A (2006), 1116, 1-9

177 Poster sessions



Assessment of pharmaceutical Diclofenac occurrence in the Llobregat river via Monte Carlo sensitivity analysis of several parameters using

GREAT-ER model

Zoran Banjac1, Laurie Boithias2, Antoni Ginebreda1, Rafa Marce2, Victoria Osorio1, Sandra Pérez1, Damià Barceló1,2, Sergi Sabater2 and Vicenç Acuña2

1 Water and Soil Quality Research Group, Department of Analytical Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain

Llobregat River basin is heavily exploited by human activities, including urban, industrial and agricultural uses that transfer into both point and diffuse pollution. The biggest contamination comes from 59 WWTPs located throughout the Llobregat river basin.This river manifests typical Mediterranean hydrological pattern, characterized by acute flow fluctuations (between 1 and more than 100 m3 /s).During drought periods WWTP effluents may represent major part of the river flow which is one of the reasons contaminants show in bigger concentration due to less dilution which makes their effects on ecosystem uncertain.

The objective of the ongoing research is to model the environmental occurrence of pharmaceuticals in the Llobregat basin [1] using the GREAT-ER (Geo-referenced Regional environmental Exposure Assessment Tool for European Rivers) [2-3] steady-state model and to assess its sensitivity respect to some of the parameters used. The sensitivity analysis will be performed using Monte Carlo simulation in the statistical software of choice [4] coupled with the GREAT-ER. The anti-inflammatory Diclofenac is selected as a representative and relevant case study, since it has been recently included in the “watch list” set by the new Directive 2013/39/EU (“daughter” of the Water Framework Directive). The first testing exercise will be done for 3 parameters: annual consumption, removal in the WWTP and removal in river. The sensitivity analysis is based on previously assessed uncertainty ranges of these parameters [5]. The uncertainty is captured in statistical frequency distributions. In each Monte Carlo ‘shot’, discrete samples are taken from these distributions, and used as input for the deterministic fate models. The simulation outputs are statistical distributions of predicted environmental concentrations (PECs) for each river stretch. This study will provide (1) the sensitivity of each involved parameters and (2) a reliable assessment of the parameter set, by comparing the outputs of each model iteration with the observed concentrations of Diclofenac at 14 sampling sites throughout the Llobregat river and its tributaries. Such a calibrated model may be potentially extended to assess the environmental occurrence of other pharmaceuticals under a wide range of hydrological flow conditions and WWTP treatment processes. References

1 The Handbook of Environmental Chemistry. Volume 21, (2012). The Llobregat: The Story of a Polluted Mediterranean River, Eds. S. Sabater, A. Ginebreda and D. Barceló, Springer-Verlag, Heidelberg Berlin

2 Boeije, G., Vanrolleghem, P. & Matthies, M. (1997). A geo-referenced aquatic exposure prediction methodology for ‘down-the-drain’ chemicals. Water Science and Technology, 36(5), 251-258.

3 Boeije, G. & Schowanek, D. (1997). Prediction and visualization of the environmental

concentration of consumer chemicals: the GREAT-ER project. Study Day on Global Environmental

Impact, IAWQ - Belgian Committee, Brussels, June 6, 1997

4. Guiding principles for the Monte Carlo analysis,Risk Assessment Forum,U.S. Environmental Protection Agency,Washington, DC 20460, EPA/630/R-97/001,1997

5. BOITHIAS L, MARCÉ R, ACUÑA V, ALDEKOA J, OSORIO V, PETROVIĆ M, FRANCES F, GINEBREDA A, SABATER S, 2013, Assessment of the water purification ecosystem service regarding in-stream pharmaceutical residues: exploring the GREAT-ER model parameters based on data uncertainty, In preparation.

178 Poster sessions


Application of ArcGIS software to display the occurrence and risk of chemical pollutants

Maja Kuzmanović1, Antoni Ginebreda1, Mira Petrović2,3 and Damià Barceló1,2

1 Water and Soil Quality Research Group, Department of Analytical Chemistry, IDAEA-CSIC, Barcelona, Spain 2 Catalan Institute for Water Research (ICRA), Girona, Spain


The increasing contamination of aquatic systems with numerous man-made and natural chemicals is one of the key environmental problems. Although most of these chemicals are present at low concentrations, many of them may pose ecotoxicological concerns especially when occurring as components of chemical mixtures. In the EU there are more than 100000 registered chemicals listed by EINECS of which many are in daily use. One approach for identifying potentially dangerous compounds is screening of the environment for a large set of chemicals together ith an assessment of the potential toxicity of the observed concentrations, which can be done by use of measured or predicted effect concentrations for standard test species. Moreover, combined biological and chemical-analytical approaches provide an important progress in identification of those toxicants that are relevant for site-specific risk and towards an estimation of the portion of an effect that can be explained by analysed chemicals.

The main objective of this work was to display the data of occurrence and risk of chemical pollutants in specific geospatial frame of four river basins (Llobregat, Ebro, Jucar and Guadalquivir).

In this study we used ArcMap Software which is the main component of Esri's ArcGIS suite of geospatial processing programs, and it is used primarily to view, edit, create, and analyze geospatial data. ArcMap allows exploration of data within a data set, symbolize features accordingly and create maps.

We used ArcMap to display the distribution of occurrence of 81 pharmaceuticals 42 pesticides 31 endocrine disrupting compounds(EDCs) 21 perfluorinated compounds(PFCs) and 21 illicit drugs along 77 sites located in 4 Iberian river basins (Llobregat, Ebro, Jucar and Guadalquivir) measured on SCARCE project. We have identified the “hot spots” of pollution in each of 4 rivers. The occurrence of chemical pollutants was put in context of potential sources as agriculture, urbanization, wastewater discharges etc.

Furthermore, according to frequency of detection and total content of chemical we have identified the most important pollutants in terms of occurrence.

Moreover, we have assessed the ecological risk for the same chemicals by calculating toxic units (TU) for algae, Daphnia sp. and fish for each of measured chemicals. Pesticides were the group of compounds with highest risk to ecosystem. Finally, the risk maps were created by adding the risk data to maps and the risk “hot spots” were identified mostly around big cities along the rivers where besides pesticides, pharmaceuticals, EDC’s and PFC’s risk was increased.

Acknowledgements

The authors wish to acknowledge the financial support provided by the Spanish Ministry of Science and Innovation through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and CEMAGUA (CGL2007-64551/HID) HID), and the Generalitat de Catalunya (Grup Consolidat de Recerca: Unitat de Qualitat de l'Aigua i Sòls, 2009SGR965.). Maja Kuzmanovic acknowledges AGAUR fellowship

179 Poster sessions



Improving the WFD purposes by the incorporation of ecotoxicity tests

Neus Roig1,2, Jordi Sierra1,3, Martí Nadal2, Ignacio Moreno4, Elena Nieto4, Miriam Hampel4, Julián Blasco , Marta Schuhmacher1,2 and Jose Luis Domingo2

1 Environmental Engineering Laboratory, Departament d'Enginyeria Quimica, Universitat Rovira i Virgili, Tarragona,

Spain 2 Laboratory of Toxicology and Environmental Health, School of Medicine, IISPV, Universitat Rovira i Virgili, Reus,

Spain 3 Laboratori d’Edafologia, Facultat de Farmàcia, Universitat de Barcelona, Barcelona, Spain

4 Departamento Ecología y Gestión Costera, Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Cadiz, Spain

The approval of the European Water Framework Directive (WFD) supposed a big step regarding aquatic ecosystems protection. According to this Directive, assessment of ecological status is based on three quality elements: biological, physicochemical and hydromorphological, but ecotoxicological status is still not included. Some studies have observed that biological status is not always in coherence with physicochemical status, maybe due to the adaptation mechanisms of aquatic organisms under chronic chemical exposure. In these situations, ecotoxicity tests could be useful to obtain a better characterisation of these specific ecosystems.

The general aim of this work is to add a battery of ecotoxicity tests to the current analyses defined by WFD in order to obtain a better ecological characterization of freshwater systems. The specific aims of this work are: (1) to compare the effectiveness and viability of different ecotoxicity tests performed with freshwater sediments (directly and with pore water) taking as target organisms different aquatic species, and (2) to evaluate the relationship between stream pollutants concentrations (organic pollutants and metals), biological and hydromorphological status and sediments ecotoxicity. For this purpose, thirteen sampling sites within the Ebro river watershed were selected. Data about priority pollutants in water, sediment and fish as well as biological and hydromorphological status of each sampling point will be achieved. Moreover, in each sampling reach, composite samples of sediment were collected by using a Van Veen grab. Sediment samples were stored at 4ºC prior to the ecotoxicity analyses.

The ecotoxicity of pore water was evaluated by different bioassays (Vibrio fischeri, Pseudokirshneriella subcapitata and Daphnia magna) while the ecotoxicity of whole sediment was evaluated in Vibrio fischeri, Nitzschia palea and Chironomus ripariusIn addition, the concentration of total heavy metals and metal bioavailability was calculated by a sequential extraction according to the Community Bureau of Reference (BCR) method. To distinguish the potentially toxic fraction associated to heavy metals burden of sediments, an analysis of acid-volatile sulphide (AVS) and simultaneously extracted metals (SEM) was performed. Complementary sediment variables as humidity, porosity, percentages of fines (<63 µm) organic carbon and organic matter were determined.

This study expect to demonstrate that the integration of chemical, biological and ecotoxicological analyses could be crucial to understand the hazard of pollutants in aquatic ecosystems, especially, in freshwater sediments. Future research in this area is needed in order to obtain more data and be able to establish a tree decision of freshwater analyses evaluation. The poster will present the methodology purposed for this study as well as the first preliminary results obtained from ecotoxicity tests. Acknowledgements

Authors would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065). Moreover, authors would like to thank especially Confederación Hidrográfica del Ebro as well as United Research Services, S.L.U. for their collaboration with the sediment sampling campaign.

180 Poster sessions


A chemical determination of the sediment fluxes at the Barasona Reservoir

José A. López-Tarazón1,2, Pilar López3, Damià Vericat2,4,5 Isabel Muñoz3 and Ramon J.

Batalla2,4,6

1 School of Natural Sciences and Psychology, Liverpool John Moores University, Liverpool, UK 2 Departament de Medi Ambient i Ciències del Sòl (DMACS), Universitat de Lleida, Lleida, Spain

3 Departament d’Ecologia, Universitat de Barcelona, Barcelona, Spain 4 Centre Tecnològic Forestal de Catalunya, Solsona (Lleida), Spain

5 Institute of Geography and Earth Sciences, Aberystwyth University, Ceredigion, UK 6 Catalan Institute for Water Research (ICRA), Girona, Spain

Reservoir siltation compounds problems and negative impacts on both environmental and socio-economical issues. The first is focused mainly on macrophyte communities, invertebrate biodiversity, fish habitat and contamination by pollutants accumulation, whilst the latter refers especially to reservoir sedimentation, causing water quality issues and, specially, a progressive reduction in dam impoundment capacity, which creates serious problems for water management. Thus, Water Authorities and managers should paid special attention to this question. The Barasona Reservoir (i.e., responsible of the irrigation of more than 70,000 ha in Aragon and Catalunya) experiences acute siltation problems threatening its long-term impoundment capacity. Sediment load mainly come from Eocene marls located in the middle part of its draining basin (i.e., Ésera and Isábena rivers). Within this context a study is being carried out within SCARCE with the aim of studying the transfer of sediments and its chemical characteristics through the Barasona Reservoir to accomplish two main objectives: i) establishing the basic chemical characteristics of the fine sediment that is deposited in the reservoir and flows out through the dam and, ii) studying the retention of C, N and P associated to fine particle sedimentation. In the present work we present the results obtained after the first chemical analyses (C and N) of the sediment inputs (i.e., Ésera and Isábena rivers) and outputs (i.e., sediment sluiced down through the dam) to evaluate the effects of the hydrology on the transport of these elements and to quantify the total sediment load (together with C and N) that enters and goes out the reservoir. For this, we established an integrated sediment monitoring strategy to control the sediment input to the reservoir, by means of sampling (by using an ISCO 3700 automatic sampler) at the outlet of the Rivers Ésera and Isábena, and the output from the reservoir itself. To observe the effects of the hydrology over sediment (and elements) transport, sampling was set up with the objective of obtaining water samples at 3 different discharge ranges (i.e., low, medium and high flows) established according the long-term discharge registers of the sampling sites. This way, we had samples for all the discharge classes, obtaining integrated averaged samples at each sampling point at a given flow strength. Total C, and N were determined through dry material using an elemental CN auto-analyzer, whereas organic C was determined after acid treatment of bulk sample and further analysis for total carbon. Finally, to help in the interpretation of the results, grain size distribution for all samples were also determined, with a Beckman-Couter LS 230 particle analyzer in two aliquots, one aliquot was analysed directly after dispersion with pyrophosphate and ultrasound, and the other was treated for organic matter elimination by adding H2O2. Main results show that, for absolute values, the highest concentrations of both C (total and organic) and N are always transported by the medium-high flows, a fact that could be considered as obvious if we take into account that is during these flows when the highest suspended sediment loads are transported. However, it is remarkable that when we analyse the relative values of dry weight, this pattern turns around being the low flows which, in proportion to the total load, transport the highest concentrations of both total and organic C (not so clear for N), Finally, the highest C/N ratios (up to 130) are observed during low-flows again, pointing out that sediments transported during low-flows are mainly organic; on the other hand, small-very small ratios are observed during medium-high flows, probably influenced by the huge amounts of inorganics sediments that are transported during flood events.

181 Poster sessions



Exposure to human pharmaceuticals produces differential transcriptome expression fingerprints in the brain of the seabream,

Sparus aurata

Miriam Hampel1,2, Massimo Milan1, Julián Blasco1, Serena Ferraresso1 and Luca Bargelloni3

1 Instituto de Ciencias Marinas de Andalucía (ICMAN-CSIC), Puerto Real, Spain 2 Department of Comparative Biomedicine and Food Science, University of Padova, Legnaro, Italy

Abstract

Pharmaceuticals are pseudo persistent aquatic pollutants with unknown effects at environmentally relevant concentrations. Gilthead seabream (Sparus aurata) were exposed to Acetaminophen (APAP): 31.90 ± 11.07; Atenolol (AT): 0.95 ± 0.38 and Carbamazepine (CBZ): 6.95 ± 0.13 µg•L-1 for 28 days to (1) determine whether exposure to environmentally relevant concentrations of the pharmaceuticals alters the brain transcripome; and (2) identify different expression profiles and treatment specific modes of action and pathways. After APAP, AT and CBZ treatment, 411, 7 and 612 differently expressed transcripts were identified, respectively. Out of these, 248 features were common between APAP and CBZ and one between CBZ and AT. Two features were common across all treatments.

Figure 1. Venn diagram representation of differentially expressed genes in the brain of APAP, AT and CBZ -treated seabream. Venn diagram shows the overlaps of differentially expressed genes based on at least a 1.5-fold filter change with a p≤0.05.

Gene set enrichment analysis revealed effects on several biological process-, cellular compartment- and molecular function-related GO terms indicating towards known mechanisms from human and rodent exposures. Lysosome pathway, and androgen and estrogen metabolism were altered by APAP and CBZ, respectively. These data suggest (1) that exposure to environmentally relevant concentrations of the pharmaceuticals alters the brain’s gene expression profile of the seabream; (2) the existence of treatment specific processes that may be useful for biomarker development; and (3) that many responses observed in seabream are similar to humans.

Acknowledgements

This study was funded by a Marie Curie European Reintegration Grant (Proposal N° 239325-ERA4PHARM, FP7-PEOPLE-ERG-2008), the project SCARCE, funded by the Spanish Ministry for Sciences and Innovation (Consolider-Ingenio 2010 CSD2009-00065) and the project I2TEP for Cross Border Research and Technology Transfer between Spain and Portugal funded by the European Community (Interreg EU). The stay of M. Hampel at the University of Padua was funded by a mobility aid from the Spanish National Council for Scientific Research (CSIC).

182 Poster sessions


Environmentally relevant concentrations of three human pharmaceuticals alter the liver transcriptome of the Atlantic salmon,

Salmo salar

Miriam Hampel1, Esteban Alonso2, Irene Aparicio2, James Bron2, Juan Luis Santos2, John Taggart1 and Michael Leaver1

1 Institute of Aquaculture, University of Stirling, Stirling, UK

2 Department of Analytical Chemistry, University of Seville, Seville, Spain

Abstract

The combination of increasing consumption rates and limited elimination under conventional waste water treatment practices of many pharmaceutical compounds has now led to their detection in aquatic environments. Three of the most frequently detected pharmaceuticals in the environment are Acetaminophen (APAP), Atenolol (AT) and Carbamazepine (CBZ). Atlantic salmon (parr) was exposed to environmentally relevant levels of APAP (54.77 ± 34.67 µg•L-1), AT (11.08 ± 7.98 µg•L-1) and CBZ (7.85 ± 0.13 µg•L-1). Gene expression was analyzed in liver tissues using a 16K GRASP (University of Victoria, Canada) cDNA microarray revealing a significant (p<0.05) up- or down-regulation of 938, 548 and 497 features after APAP, AT and CBZ treatment, respectively. Candidate gene lists for each treatment were submitted to Blast2Go and Kegg for functional annotation and to analyze for induced pathways, respectively. Both analyses revealed several common features but also identified treatment specific processes which in many cases were similar to those observed in humans or rodents. The ontologic analysis indicated that different pathways were changed; suggesting that salmon may be affected by environmentally relevant doses of the selected pharmaceutical compounds. Acknowledgements

This work was supported by a Marie Curie Fellowship to MH (Proposal N° EIF-039691-SALMONPHARM, FP6-2005-Mobility-5).

183 Poster sessions



Temperature forcing and pharmaceuticals occurrence as proxy of global change. Subtlethal effects (osmoregulatory capacity, ingestion

and respiration rates) in the freshwater crustacean, A. desmarestii

Elena Nieto, Miriam Hampel, Enrique González-Ortegón, Pilar Drake and Julián Blasco

Institute for Marine Science of Andalusia, Department of Ecology and Coastal Management, Puerto Real, Spain

Many studies have been published on the occurrence and fate of pharmaceutical compounds in different matrices such as ground water (Daughton and Ternes, 1999; Kolpin et al., 2002), surface water (Ternes, 1998; Kolpin et al., 2002) and sediment (Silva et al., 2011). However, there is a lack of information about climate change effects on toxicity of chemical compounds. In order to improve the knowledge about this subject, we performed a series of toxicity tests on the freshwater shrimp Atyaephyra desmarestii as model organism. A. desmarestii is widely distributed in clean freshwater bodies and has been successfully employed in pharmaceuticals ecotoxicity tests (Nieto et al., 2013). Selected sublethal endpoints were osmoregulatory capacity and ingestion- and respiration rate as indicators of physiological changes. The shrimps were exposed to three pharmaceutical compounds with high comsumption rates worldwide: Diclofenac (DF) and Ibuprofen (IB) which belong to the group of non-steroidal anti-inflammatory drugs (NSAIDs) and Carbamazepine (CBZ), an anticonvulsant at two different temperatures (20 and 25ºC). Sublethal responses were monitored at environmental relevant concentrations, ranging between 10-70µg·L-1 for the three selected compounds. No significant differences were found between controls and treatment (Dunnett´s test p<0.05) in organisms exposed at 20º C and only for DF there was a decrease in respiration rate close to statistical significance under conditions of severe anoxia (1 mg O2·L-1). Similar results were found in the organisms exposed at 25º C where no significant differences were found between control and treatment for osmoregulatory capacity and ingestion rate. In the case of respiration rate, a significant difference with respect to the control (Dunnett´s test p>0.05) was found in CBZ exposed organisms under conditions of moderate hypoxia (3 mg O2·L-1) and well oxygenated water (5 mg O2·L-1). These results indicate that the presence of CBZ even at relatively low concentrations may produce respiratory defiencies in exposed organisms in well oxygenated water under increasing temperature conditions. This fact underlines the possibility to use the presence of contaminants and the increase of temperature as proxy for ecological risk assessment in the context of global change. Acknowledgements

This study was sponsored by the Consolider-Ingenio 2010 project SCARCE (Consolider-Ingenio 2010 CSD2009-00065) from the Spanish Ministry of Sciences and Innovation. We would like to thank the support of the Intramural CSIC project 201230E034.

References

Daughton, C.G., Ternes, T.A. 1999. Pharmaceuticals and Personal Care Products in the Environment: Agents of Subtle Change?. Environmental Health Perspectives. 6, 907-938.

Kolpin, D.W, Furlong, E.T, Meyer, M.T, Thurman, E.M, Zaugg, S.D, Barber, L.B, Buxton, H.T, 2002, Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. Streams, 1999-2000: a national reconnaissance, Environ Sci Technol. 36, 1202-1211.

Nieto, E., Blasco, J., González-Ortegón, E., Drake, P., Hampel, M., 2013. Is Atyaephyra desmarestii a useful candidate for lethal and sublethal toxicity test on pharmaceutical compounds?, Journal of Hazardous Materials, in press.

Silva, B.F.d.. Jelic, A., López-Serna, R., Mozeto, A.A., Petrovic, M., Barceló, D. 2011, Occurrence and distribution of pharmaceuticals in surface water, suspended solids and sediments of the Ebro river basin, Spain, Chemosphere. 85, 1331-1339.

Ternes, T.A., 1998. Ocurrence of pharmaceuticals in German sewage treatment plants and rivers. Water Res. 32, 3245-3260.

184 Poster sessions


A comparative study of recirculation and continuous mode for pollutant ions exchange from pretreated olive mill wastewater

M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2 and A. Martínez-Férez1

1 Chemical Engineering Department, University of Granada, Granada, Spain

2 Molecular Biology & Biochemical Engineering Department, University Pablo de Olavide, Seville

In this research work, a comparative study of recirculation and continuous mode was carried out to evaluate the performance of ion exchange (IE) process for the removal of main pollutant ions present in olive mill wastewater (OMW). This industrial effluent, which is highly contaminant, was previously treated by means of chemical oxidation based on Fenton's reagent, flocculation-sedimentation and filtration through olive stones [1]. Sodium, iron, chloride and phenolic compounds are the main pollutants in this wastewater [2]. The aim of this study was to reduce as much as possible concentration of the mentioned ions in pretreated OMW for its reuse in the olive oil production process. In this sense, the Drinking Water Directive, Council Directive 98/83/EC sets the maximum concentration in drinking water at 200 µg L-1 for iron, 200 mg L-1 for sodium and 250 mg L-1 for chloride [3]. Although phenols level is not established by any directive, it is important to avoid it as much as possible due to its toxicity. IE process using Dowex Marathon C and Amberlite IRA-67 resins was investigated at laboratory scale for these ions removal. Recirculation and continuous mode experimental studies were conducted to evaluate the effect of resins disposition and temperature.The relative position of both IE resins was firstly studied and it was found that the optimum arrangement consisted on the cation exchange resin (Dowex Marathon C) followed by the anion exchange one (Amberlite IRA-67). Moreover, concentrations of the assayed pollutants were below the maximum levels established by the legislation, both in recirculation and in continuous mode, under the optimized conditions. Finally, it was probed that both IE resins have good application potential for the removal of iron, sodium, chloride and phenolic compounds from pretreated OMW.

A) B)

Figure 1: Flow diagrams of Ion exchange process for purification of pretreated OMW: A) Recirculation mode experiments; B) Continuous mode experiments.

Acknowledgements

Spanish Ministry of Science and Innovation is acknowledged for funding the project CTQ2010-21411: Depuration of wastewater from olive oil industry for reuse in the process.

References

[1] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A. and Ochando, J. Degradation of organic matter in olive oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journa (2011), 173 (2), 503-510.

[2] Garrido Hoyos, S.E., Martínez Nieto, L., Camacho Rubio, F., Ramos Cormenzana, A. Kinetics of aerobic treatment of olive mill wastewater (OMW) with Aspergillus terreus, Process Biochem., 37 (10) (2002) 1169–1176.

[3] European Commission. 1998. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption.

185 Poster sessions



Effect of ions concentration on the remediation of sodium and iron from olive mill effluent by ion exchange technique

M. D. Victor-Ortega1, J.M. Ochando-Pulido1, G. Hodaifa2, L. Martínez-Nieto1 and A. Martínez-

Férez1



The sorption of sodium and total iron from synthetic pretreated olive mill wastewater (OMW) was investigated by using a gel strong acid cation exchange resin, which is based on a styrene-divinyl benzene copolymer matrix with sulfonate functional groups (Dowex Marathon C). OMW has very high chemical oxygen demand (COD) and elevated concentration of organic matter [1]. Furthermore, inorganic compounds such as several salts of potassium, calcium, iron, magnesium, sodium and copper are presents in OMW [2]. In this research study, a semibatch Ion Exchange (IE) system is proposed as an efficient alternative for purification of OMW pretreated by means of chemical oxidation based on Fenton's reagent, followed by a coagulation–flocculation step and a filtration in series through three different kinds of adsorbent materials [3].

Batch sorption experiments were carried out to evaluate the removal of sodium and iron, which are principal metal cations in this effluent, from synthetic water simulating pretreated OMW at varying these pollutant ions initial concentrations and contact time. Initial concentrations of 250, 500, 750 and 1000 mg/L, and 0.400, 1.00, 2.50 and 5.00 mg/L were fixed for sodium and iron ions respectively, since these are typical ranges in real olive mill effluents. The results show that concentrations of sodium and total iron were considerably reduced with increasing contact time. In addition, the equilibrium was obtained in about 45 min for theses ions and from this point forward concentrations were lower than the maximum levels established by the Drinking Water Directive (DWD) [4]. The uptake of sodium and total iron ions by the assayed resin was reversible and so it has good potential for the removal of the mentioned ions from pretreated OMW.

Properties Type Matrix Ionic form

as shipped Particle size

Effective pH range

Total exchangecapacity

Shipping weight

Dowex Marathon C

Strong-acid cation

Styrene-DVB, gel

H+ 0.55-0.65 nm 0-14 1.80 eq/L 800 g/L

Figure 1: Physicochemical properties of Dowex Marathon C resin.

Acknowledgements


References


[2] Rozzi, A., Limoni, N., Menegatti, S., Boari, G., Liberti, L. and Passino, R. Influence of Na and Ca alkalinity on UASB treatment of olive mill effluents. Part 1. Preliminary results. Process Chem. (1988), 23, 86-90.

[3] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Flocculation-sedimentation combined with chemical oxidation process, Clean – Soil, air and water, 39 (10) (2011) 949-955.

[4] European Commission. 1998. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption.

186 Poster sessions


Comparing different nanofiltration and reverse osmosis membranes for final remediation of olive mill wastewater

J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2, L. Martínez-Nieto1 and A. Martínez-

Férez1



The present study focuses on the management of OMW in order to achieve the quality to recirculate the final effluent to the manufacture process or at least to the olives washing machines to finally close the loop. With this goal, membrane processes were conducted on laboratory scale on real fresh OMW samples. To preserve the membranes from deleterious fouling phenomena commonly encountered in all membrane facilities, OMW was conducted to a pretreatment comprising Fenton-like advanced oxidation, flocculation-sedimentation and filtration through olive stones in series. One nanofiltration (NF) and two rather different reverse osmosis (RO) polymeric membranes were tested for the ulterior OMW purification. Membranes performances in terms of productivity and permeate quality were confronted and discussed, and the suitability of the Fenton-like process as pretreatment step regarding OMW depuration by membranes was evaluated [1, 2].

An average-sized olive oil factory produces 10-15 m3/day of olive mill wastewater (OMW). Low pH, extremely high concentration of suspended and dissolved solids, as well as heavy organic load is characteristic of OMW. Among the latter, the high concentration of phenols and tannins commonly present in this effluent confers OMW phytotoxic and antimicrobial properties and low biodegradability that hinder conventional biological treatments. Inorganic compounds including chloride, sulfate and phosphoric salts of potassium, calcium, iron, magnesium, sodium, copper and traces of other elements are also present in OMW [3].

Membrane technologies have been demonstrated to be an effective vehicle for removing most organic and inorganic compounds and microorganisms in regard to wastewater reclamation in the last years. Nevertheless, membranes fouling inhibition and control are currently ones of the main challenges of membrane technology. Membrane fouling depends on hydrodynamics as well as solute concentration and nature in the feedstock, among other factors [4]. Pretreatment of the feedstock has been underlined as key regarding fouling inhibition strategies [5]. Acknowledgements


References


[2] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Degradation of organic matter in olive oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journal, 173 (2) (2011) 503-510.


[4] Stoller, M. On the effect of flocculation as pretreatment process and particle size distribution for membrane fouling reduction, Desalination. 240 (2009) 209-217.

[5] Stoller, M., Chianese, A. Optimization of membrane batch processes by means of the critical flux theory, Desalination, 191 (2006) 62-70.

187 Poster sessions



Steady-state performance enhancement of a diafiltration reverse osmosis system for final salinity rejection of olive mill wastewater

J.M. Ochando-Pulido1, M. D. Victor-Ortega1, G. Hodaifa2 and A. Martínez-Férez1



This work aims to modeling the impacts on concentration polarization and fouling resistances driven by recirculating a fraction of the permeate stream on a thin-film composite reverse osmosis (RO) membrane (polyamide/polysulfone) for the final purification of OMW previously pretreated by means of chemical oxidation based on Fenton's reagent, flocculation-sedimentation and filtration through olive stones [1, 2].

In this regard, optimum operating pressure and cross-flow velocity were found in our former experiments to be equal to 25 bar and 5.1 m/s respectively, whereas operating temperature of 15 °C was chosen to simulate the temperature conditions close to the ones experienced on average during the olive oil production campaign, when OMW is derived and should be managed [3]. Upon those fixed operating conditions, influence of permeate recirculation fraction (0 - 30%) on membrane performance was studied in diafiltration (semicontinuous) mode. Results were analyzed by the resistances-in-series and critical flux models to check for the influence of the permeate recirculation ratio on concentration polarization and fouling build-up on the membrane.

Olive mill wastewater (OMW) is a heavy polluted liquid stream characterized by an acid pH value, black color, very high chemical oxygen demand (COD) and a high concentration of microbial growth inhibiting compounds, such as phenolic compounds and tannins. Also inorganic compounds such as chloride, sulfate and phosphoric salts of potassium, calcium, iron, magnesium, sodium, copper and traces of other elements are present in OMW [4].

Still scarce are the studies addressing the depuration of (OMW) by means of membrane technology, and there are still some unresolved problems related to membrane fouling that slow down large-scale applications. Membrane fouling reduces the performances of membranes over time and depends on hydrodynamics and solute concentration in the feedstock, among other factors. Proper feedstock pretreatment and operating conditions are essential in fouling inhibition strategies [5, 6]. Acknowledgements


References

1] Martínez Nieto, L. Hodaifa, G., Rodríguez Vives, S., Giménez Casares, J.A., Ochando, J. Degradation of organic matter in olive oil mill wastewater through homogeneous Fenton-like reaction, Chem. Eng. Journal, 173 (2) (2011) 503-510.


[3] Ochando-Pulido, J.M., Rodriguez-Vives, S., Martinez-Ferez, A. The effect of permeate recirculation on the depuration of pretreated olive mill wastewater through reverse osmosis membranes, Desalination, 286 (2012) 145-154.


[5] Stoller, M. On the effect of flocculation as pretreatment process and particle size distribution for membrane fouling reduction, Desalination. 240 (2009) 209-217.

[6] Stoller, M., Chianese, A. Optimization of membrane batch processes by means of the critical flux theory, Desalination, 191 (2006) 62-70.

188 Poster sessions


Freshwater scarcity effects on the different components of a European estuary from Mediterranean-climate zone

Enrique González-Ortegón1, Alberto Arias1, Francisco Baldó2, José Antonio Cuesta1, Carlos

Fernández-Delgado3, César Vilas4 and Pilar Drake1

1 Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Spain 2 Instituto Español de Oceanografía, Cádiz, Spain

3 Departamento Biología Animal, Universidad de Córdoba, Córdoba, Spain 4 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

In the Mediterranean-climate zone, the recurrent drought events and the increasing water demand are usually leading to a decreased freshwater input to estuaries that threat their proper function as nursery areas. In this study, all the published results of the Guadalquivir estuary related to this topic were analysed to provide integrated and valuable insights on the effects of water scarcity on the different components of the estuaries from this climate zone.

During drought events, the estuary is totally flood-dominated, with the consequent alteration of its environmental conditions: decreasing the suspended particulate matter (SPM) and nutrients inputs and thus the turbidity, but increasing their residence time and the salinity intrusion. As the estuarine primary production (PP) is usually light-limited, the water scarcity (lower turbidity) is usually linked to an increase of the autochthonous primary production; conversely, the low river inflow causes a reduction of the allochthonous input of Chl a to the estuary. Among species using the estuary as a nursery area, marine species tend to hold a more steady position within the salinity gradient (limited osmoregulatory capacity); thus, the extended seawater intrusion during drought events favours the entrance of straggler marine species and increase the abundance of marine migrants. However, high dam discharge water after drought may lead to a persistent increase in the SPM and turbidity. Such unusual situation seems to cause: low autochthonous PP and low densities of some key species, as the common prey Mesopodopsis slabberi and the predators Engraulis encrasicolus and Pomadasys incisus; and a shift in the distribution of the most euryhaline prey Neomysis integer and the predators species Dicentrarchus punctatus and Crangon crangon, towards more saline waters, causing an increase in the inter-specific competition (for food/habitat) within the estuarine nursery area.

The estuarine flushing generates: a turbidity plume, which acts as an estuarine cue for some species, as glass eels; and a net nutrient input to adjacent sea water, causing an enrichment of its PP and favouring its role as spawning and nursery grounds for marine species (fish and decapod crustaceans). However, under a scenario of freshwater scarcity, there is a reduction of the estuarine plume extend (decreased recruitment of some marine species) and of the fertilization of the adjacent coast (loss of its function as spawning and nursery grounds).

In conclusion, freshwater scarcity is causing currently transitory changes in the estuarine communities, but a quick reestablishment (strong resilience) is observed together with the recovery of environmental conditions. However, if the decreasing trend in freshwater input persists, more extreme and persistent unhealthy physical conditions can be expected and, beyond a certain threshold, the estuarine communities may become less resilient (more persistent or even permanent community changes). Simirlarly, the adjacent sea water area could loss its function as spawning and nursery grounds for marine species. Acknowledgements

The study was co-funded by the Spanish Ministry of Economy and Competitiveness, and the EU Fishery Grant through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065).

189 Poster sessions



Effects of stream habitat complexity and biodiversity on leaf litter decomposition

Lorea Flores1, R. A. Bailey2,3, Arturo Elosegi1, Aitor Larrañaga1, B. R. Rall4 and J. Reiss5

1 Fac. of Science and Technology; University of the Basque Country, Leioa, Spain

2 Mathematical Sciences Institute, Queen Mary University, London, UK 3 School of Mathematics and Statistics, University of St Andrews, St Andrews, UK

4 J. F. Blumenbach, Institute of Zoology and Anthropology, University of Goettingen, Goettingen, Germany 5 Dept. of Life Sciences, Whitelands College, Roehampton University, London, UK

Biodiversity affects ecosystem functioning, especially when multiple processes are considered simultaneously. Most of the information on the relationship between biodiversity and ecosystem functioning is derived from field or laboratory experiments which typically neglect that the performance of organisms can be modulated by abiotic factors that may influence interactions of organisms, and by the horizontal and vertical linkages among organisms, for example within a food web. Therefore the objectives of this study were to test 1) the effects of biodiversity on leaf decomposition with the combinations of three crustacean species; 2) if habitat complexity influenced the interactions of these three species and leaf decomposition; and 3) if the functional response of a predator changed with habitat complexity.

To test these objectives we performed two laboratory experiments. To simulate habitat complexity we added structures made of artificial plastic plants and we constructed a total of 4 levels of habitat complexity using different numbers and arrangements of rings. In the first experiment, three invertebrate detritivore species were used: the amphipod Gammarus pulex (L.), the isopod Asellus aquaticus (L.) and the copepod Cyclops viridis (Jurine, 1820). Species were assembled in mono-, di- and tricultures and leaf mass loss and generation of fine organic matter were measured after 29 days. In the second experiment, the predator Ischnura elegans (Vander Linden, 1820; Zygoptera, Odonata) was exposed to prey densities (Asellus aquaticus) ranging from 1 to 120. Prey consumption was measured after 24 h and predation values were fitted to functional response curves to elucidate if habitat complexity affected the shape of the functional response.

Preliminary results showed that different assemblages of consumers performed similarly when they had the same biomass, i.e. we observed no biodiversity effects. However, habitat complexity had an effect on the response with leaf consumption being lower at higher habitat complexity. In addition, although habitat complexity seemed not to affect the shape of the functional response of the predator, predation rates tended to be lower with higher habitat complexity. So far, these results showed that habitat complexity is an important factor modulating organism interactions and ecosystem functioning. Acknowledgements

This project was funded by the Spanish Ministry of Economy and Competitiveness (Consolider-Ingenio CSD2009-00065). L. Flores also acknowledges a predoctoral grant from the Spanish Ministry of Education, Culture and Sports. We also want to thank Nigel Reeve, the head of Ecology of the Richmond park (London) and John Arbon and Richard Bullock from the London Wetland Centre for giving the permission to sample organisms.

190 Poster sessions


The effects of a mixture of pharmaceuticals compounds at environmental concentrations on epilithic biofilms: constant flow vs

water intermittency conditions

Natàlia Corcoll1, Maria Casellas1, Belinda Huerta1, Helena Guasch2, Sara Rodríguez-Mozaz1, Albert Serra2, Damià Barceló1,3 and Sergi Sabater1,2

1 Catalan Institute for Water Research (ICRA), Girona Spain

2 Institue of Aquatic Ecology, University of Girona, Girona, Spain 3 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDEA-CSIC, Barcelona, Spain

The occurrence of complex mixtures of pharmaceutical compounds in river ecosystems (from ng/L to few µg/L) has increased in the last decades, but their potential toxicity on non-target organisms, such as algae and bacteria composing epilithic biofilms, still remain poorly studied. In Mediterranean basins, temporary rivers are abundant (Larned et al. 2010). Climate change-runoff models predict an increase in the occurrence and frequence of water intermittency periods (Kundzewicz et al. 2008). This physical factor alters the functioning and biomass of biofilm communities (Timoner et al. 2012), and in consequence may alter their sensitivity to toxicants (Proia et al. 2013). This study aims to evaluate the effects of a chronic exposure of a mixture of pharmaceutical compounds at environmental concentrations on the structure and metabolic processes of biofilms. Biofilm communities exposed to a strong dry period (one week without flow) may have, or may have not, a different sensitivity to pharmaceuticals exposure in comparison to those under constant flows. In order to address these issues, an experiment was performed in facility of artificial streams (ESF, ICRA) consisting of 12 channels. The experimental design had four treatments with 3 replicates (channels) for treatment, resulting in a bifactorial design: i) Flow continuous_Non pharmaceuticals exposure, ii) Flow continuous_Pharmaceuticals exposure, iii) Flow intermittency_Non pharmaceuticals exposure and iv) Flow intermittency_Pharmaceuticals exposure. Treatments including the pharmaceuticals exposure were reached by exposing biofilm communities for six weeks to a mixture of 9 pharmaceuticals (from 6 different therapeutic families), selected from those more commonly found in polluted sites of Mediterranean rivers at environmental concentrations (Osorio et al. 2012). In treatments including a flow intermittency period, when biofilm was 3 weeks old, the water flow was stopped for 1 week to simulate a dry period, and was restablished during 2 weeks more, named the rewetting period. Biofilms of all treatmens were sampled during the rewetting period. Biofilm responses to stressors (pharmaceuticals exposure and water intermittency) were determined based on their structure, metabolic processes, sensitivity to pharmaceuticals (short-term dose-response tests) and pharmaceuticals accumulation capacity. The obtained results showed that a chronic exposure of a mixture of pharmaceuticals at environmental concentrations inhibits slightly algal biomass, cyanobacteria abundance, alters the structure of bacterial community (based on DGGE analyses) and enhances metabolic process (such as primary production and community respiration). Bacteria community showed a lower EC50 to a short-term pharmaceuticals exposure than the algal community, suggesting a higher sensitivity to pharmacetuticals exposure in bacteria than in algae. In addition, it was observed that the effects of pharmaceuticals on biofilms were stronger in those communities exposed to water intermittency. Metabolic processes markedly increased in those communities exposed both to pharmaceuticals and water intermiitency. Algal community exposed to water intemittency became more sensitive to short-term exposure of pharmaceuticals (lower EC50 value) than those growing under constant flow. These results support the hypothesis that the observed decrease in algal biomass and biofilm thickness due to flow intermittency enhances the diffusion of chemicals from the water column and increase their potential toxicity on algae (Ivorra et al. 2000; Guasch et al. 2003). In contrast, the bacteria community previously exposed to water intermittency became more tolerant to short-term exposure of pharmaceuticals (higher EC50) tha those under constant flow. This finding confirms the hypothesis that bacterial species tolerant to water intermittency may result also more tolerant to pharmaceutical exposure

191 Poster sessions



than those dominating under constant flow conditions (co-tolerance phenomena). Our results may contribute to better predict the potential effects of mixtures of pharmaceutical compounds on biofilms in natural conditions, and also to better understand the role of water intermittency periods on pharmaceuticals toxicity on algae and bacteria communities composing biofilms. Acknowledgements

The authors thank Dr. Carles Borrego for his advice during bacterial molecular analyses. This study was financed by Spanish Ministry of Economy and Competitiveness through the project SCARCE (Consolider-Ingenio 2010 CSD2009-00065), by the European Union through the European Regional Development Fund (FEDER) and by the Generalitat de Catalunya (Consolidated Research Group: Water and Soil Quality Unit 2009-SGR-965).

References

Guasch, H., Admiraal, W., Sabater, S. 2003. Contrasting effects of organic and inorganic toxicants on freshwater periphyton. Aquatic Toxicology 64, 165–175.

Kundzewicz, Z. W., Mata, L.J., Arnell, N.W., Döll, P., Jimenez, B., Miller, K., Oki, T., Sen, Z., Shiklomanov, I. 2008. The implications of projected climate change for freshwater resources and their management. Hydrological Sciences Journal 53, 3-10.

Larned, S. T., Datry, T., Arscott, D. B., Tockner, K. 2010. Emerging concepts in temporary-river ecology Freshwater Biology 55, 717–738.

Ivorra, N., Bremer, S., Guasch, H., Kraak, M.H.S., Admiraal, W. 2000. Differences in the Sensitivity of Benthic Microalgae To Zn and Cd Regarding Biofilm Development and Exposure History. Environmental Toxicology and Chemistry 19, 1332.

Osorio, V., Marcé, R., Pérez, S., Ginebreda, A., Cortina, J.L., Barceló, D. 2012. Occurrence and modeling of pharmaceuticals on a sewage-impacted Mediterranean river and their dynamics under different hydrological conditions. The Science of the total environment 440, 3–13.

Proia, L., Vilches, C., Boninneau, C., Kantiani, L., Farré, M., Romaní, A. M., Sabater, S., Guasch, H. 2013. Drought episode modulates the response of river biofilms to triclosan. Aquatic toxicology 127, 36–45.

Timoner, X., Acuña, V., Von Schiller, D., Sabater, S. 2012. Functional responses of stream biofilms to flow cessation, desiccation and rewetting. Freshwater Biology 57, 1565–1578.

192 Poster sessions


Invertebrate community response to water and sediment chemical composition in Mediterranean rivers

Núria de Castro-Català1, Damià Barceló2,3, Sandra Pérez2, Mira Petrovic3, Yolanda Picó4 and

Isabel Muñoz1

1 Department of Ecology, University of Barcelona, Barcelona, Spain 2 Water and Soil Quality Research Group, Department of Environmental Chemistry, IDEA-CSIC, Barcelona, Spain

3 Catalan Institute for Water Research (ICRA), Girona, Spain 4 Environmental and Food Safety Research Group, Faculty of Pharmacy, University of Valencia, Burjassot, Spain

River water is used for agricultural, industrial and domestic purposes that lead to water contamination with numerous natural and synthetic compounds. Emerging pollutants are a large and previously unknown group of compounds that are not totally removed by wastewater treatment plants (WWTPs) and can be found ubiquitously in natural waters. Although most of these compounds are present at low concentrations, many of them raise considerable ecotoxicological concerns, particularly when present as components of complex mixture (Loos et al., 2009). However, there is little information on their effects in freshwater communities.

The objective of this study was to check the relationships between invertebrate communities and the presence of different groups of emerging pollutants in the water and in the sediment of 4 Iberian basins (Llobregat, Júcar, Guadalquivir, and Ebro).

Four to six sites were sampled in each river during two consecutive years (2010, 2011) in early autumn. Five sediment samples (10–15 cm in depth) were collected randomly with a core in each sampling site to study the invertebrate community in the sediment. More than 800 pollutants, including pharmaceuticals, pesticides, metals, illicit drugs, perfluorinated compounds and endocrine disrupting compounds were measured in water and sediment matrix.. Physicochemical parameters were also measured in each site.

A preliminary analysis based on Spearman’s rank correlations was performed to check the relationship between pollutants, physicochemical data and invertebrate community composition.

Negative significant relationships were found between the abundances of invertebrate taxa and chemical concentrations. Pharmaceuticals and pesticides were the two families of pollutants which were repeatedly correlated with different genera, both in the water and in the sediment matrix. For pesticides the response of invertebrates was similar in the water and in the sediment, specifically for those which have endocrine disrupting effects (e.g. Tolytriazole). Significant relationships were also found for some flame retardants and alkylphenols. The invertebrates which defined these correlations were some Chironomidae (midges, e.g. Polypedilum spp.) and some Oligochaeta (worms, e.g. Lumbriculus spp.). The response pattern of pharmaceuticals was different depending on the matrix (water vs. sediment). Analgesics and anti-inflammatory, histamine receptor antagonists and lipid regulators showed significant relationships with most of the invertebrate taxa only in the water. However, in the sediment matrix the response was more variable depending on the species and the group of compounds. Nutrients (PO4

- and NO3-) were also

negatively correlated with most of the taxa, showing the general effect of nutrient enrichment in the studied basins. Additional statistical analyses are in process in order to detect particular patterns for each basin. References

Loos, R., Gawlik, B.M., Locoro, G., Rimaviciute, E., Contini, S., Bidoglio, G.. EU-wide survey of polar organic persistent pollutants in European river waters. Environ. Poll. (2009), 157, 561-568.

193 Poster sessions



Effects of water abstraction on large river ecosystem metabolism

Maite Arroita, Ibon Aristi and Arturo Elosegi

Faculty of Science and Technology, the University of the Basque Country, Bilbao, Spain

Water abstraction is increasing worldwide to satisfy the rising demand of energy and water, what dramatically affects the hydrology of streams and rivers. Being discharge one of the major factors controlling river ecosystems, these changes caused by water abstraction can have important consequences for whole-system metabolism (production and respiration), which are fundamental indicators of ecosystem functioning. Still, the impacts of water abstraction on ecosystem metabolism have been little studied. Besides, most studies are limited to low-order streams, being measurements in large rivers very rare. Therefore, the aim of this study was to assess the effects of water abstraction on large river ecosystem metabolism.

The experiment was performed in three sections of the Aragon River (tributary of River Ebro) affected by hydropower schemes: Santacara, Mélida and Caparroso (Navarre). All three hydropower schemes have a maximum diversion capacity of 70 m3·s-1, slightly higher than the annual mean flow (68.6 m3·s-1). Two reaches were selected at each section: a Control reach not affected by diversion, and an Impact reach in the short-circuited reach. At the top and the bottom stations of each river reach dissolved oxygen, water temperature, water level and conductivity were measured continuously for 24 hours. Gross primary production (GPP) and ecosystem respiration (ER) were calculated following the two-station open-channel method. Nominal travel time and water velocity were determined using a slug addition of Bromide as KBr.

More than the 50 % of the discharge was abstracted during the study period, what led to narrower and shallower river reaches, as well as slower water velocities. These alterations caused an increase in the amplitude of the diurnal changes in dissolved oxygen in Santacara and Mélida. At these two sites GPP and ER were higher in Impact reaches, leading to a higher ecosystem flux. The opposite happened in Caparroso, where the amplitude, GPP, ER and ecosystem flux were lower in river reaches affected by water abstraction. In spite of these differences, all reaches were autotrophic.

Overall, our results suggest that water abstraction affects river ecosystem metabolism, although the direction of change can depend on site-specific features. Acknowledgements

This work has been supported by the Spanish Ministry of Science and Innovation through the project Consolider-Ingenio CSD2009-00065 and the project ABSTRACT CGL2012-35848.

194 Poster sessions


Effects of restoring stream dead wood on reach-scale storage and decomposition of organic matter

Aitor Larrañaga1, Lorea Flores1, Ibon Aristi1, Inmaculada Arostegui1, Maite Arroita1, Joserra

Díez2 and Arturo Elosegi1

1 Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain 2 University college of Teacher Training, University of the Basque Country, Vitoria-Gasteiz, Spain

Stream channel complexity affects physical structure, biotic communities, and functioning of stream ecosystems. Large wood is a key element in the creation and maintenance of physically complex stream channels in forested areas, but human activities often reduce the loading of instream wood reducing its ecological contribution. In an attempt to enhance stream habitat and ecosystem functioning, large wood was experimentally introduced into 4 mountain streams in the Basque Country (northern Spain) (Flores et al., 2011). The restoration modified the area covered by the three main benthic habitats: whereas gravel and organic matter jams incremented their cover, cobble decreased it. To increment the accuracy of the estimates we stratified the sampling and measured the storage and breakdown rate of organic matter in each of the three habitats. We tested for the effect of our intervention at the reach level with a novel approach based on a combination of permutation and bootstrap. We estimated total benthic organic matter and decomposition at the stream reach level from the samples taken in the different habitats and published processing rates of different materials (Arroita et al., 2012). In the biggest stream the effect of restoration on organic matter storage and decomposition revealed to be non-significant. Nevertheless, considering all four streams together, the experimental reaches displayed significantly higher values of organic matter storage and decomposition than control stream reaches after the restoration (between 36 and 400 % higher, Fig. 1). These relative increments seemed to be explained by the amount of wood added. Similarly, total decomposition was between 10 and 300% higher in the experimental than in the control reaches. Therefore, restoring wood loading is related to a tendency to increase the capacity to store and decompose organic inputs at the reach level.

Figure 1: distribution of the estimates of the total benthic organic matter at the control and the experimental reaches after the restoration. Vertical line represents median of each distribution.

Acknowledgements

This project was funded by the EU (project LIFE NAT/E/000067) and by the Spanish Ministry of Economy and Competitiveness (projects CGL2007-65176/HID and Consolider-Ingenio CSD2009-00065) and also benefited by support from the Basque Government (Project IT-422-07), the University of the Basque Country (project GIU0538), the Province Government of Guipuscoa and the Municipalities of Oiartzun and Renteria.

References

Arroita, M., Aristi, I., Flores, L., Larrañaga, A., Díez, J., Mora, J., Romaní, A.M. and Elosegi, A. The use of wooden sticks to assess stream ecosystem functioning: Comparison with leaf breakdown rates, Science of the Total Environment, 440, 115-122.

Flores, L., Larrañaga, A., Díez, J. and Elosegi, A. Experimental wood addition in streams: effects on organic matter storage and breakdown, Freshwater Biology, 56, 2156-2167.

195 Poster sessions



Effects of WWTP effluent on the metabolism of a Mediterranean river

Ibon Aristi1, Maite Arroita1, Lydia Ponsati2, Sergi Sabater2,3, Daniel von Schiller2, Arturo Elosegi1 and Vicenç Acuña2

1Faculty of Science and Technology, University of the Basque Country, Bilbao, Spain

2 Catalan Institute for Water Research (ICRA), Girona, Spain 3 Institute of Aquatic Ecology, University of Girona, Girona, Spain

Humans are largely increasing the number of pollutants in the environment, and the contamination of both surface and subsurface waters has become a serious problem (Schwarenbach et al., 2006). This led legislators to establish new protection goals and regulatory approaches for environmental management such as the water framework directive (WFD, EC 2000), and managers to build and operate many waste water treatment plants (WWTP). Nowadays, over 13,000 WWTP have been constructed in Spain. Sewage waters are generally a mixture of domestic and industrial wastewater, and often include rainwater run-off from roads and other paved areas, and although the efficiency of WWTP has improved thanks to technological advances, they are unable to eliminate all the pollutants they receive. Thus, effluents from WWTP are a source of nutrients and pollutants that can affect ecosystem processes in the receiving river reaches. Nutrients from WWTP can produce eutrophication, affecting primary producers (algae, macrophytes) and microbial heterotrophs (bacteria, fungi), as they can use dissolved nutrients (e.g. Stelzer et al 2003). On the other hand, WWTP effluents include pollutants such as pharmaceuticals, pesticides, etc., which can impact aquatic ecosystems (Brunberg & Blomqvist, 2001). Nowadays there is little information on how WWTP effluents affect ecosystem functioning and the self-purification capacity of receiving river reaches. To assess this issue, we studied the impact of the effluents from Puigcerdà WWTP on the carbon components and ecosystem metabolism of the receiving Segre River. We established a control (C) reach upstream, and an impact (I) reach downstream the effluent with 4 consecutive sites starting at 500 m distance. In all of them, nutrient and pollutant concentrations were measured, at midday and midnight, and suspended particulate organic matter (SPOM) and benthic organic matter (BOM) analysed. Finally, ecosystem metabolism was measured for each site using the double-station open-channel method. Ecosystem respiration (ER), gross primary production (GPP), net ecosystem metabolism (NEM), ecosystem flux (EF) and production vs. respiration ratio (P/R) were calculated. Nutrient and pollutant concentrations decreased downstream as a consequence of both dilution and self-purification. SPOM also decreased downstream, but BOM did not. Ecosystem metabolism increased below the WWTP, but there were no clear spatial trends downstream, suggesting that ecosystem functioning did not recover natural values in the studied reach. References

Brunberg, AK. & Bromqvist, P. Quantification of anthropogenic threats to lakes in a lowland country of Central Sweden. Ambio (2001), 30, 127-134.

Stelzer, RS., Heffernan, J. & Likens, GE. The influence of dissolved nutrients and particulate organic matter quality on microbial respiration and biomass in a forest stream. Freshwater Biol. (2003), 48, 1925-37.

Schwarenbach, R., Escher, BJ., Fenner, K., Hoffstetter, TB., Johnson, CA., von Gunten, U. & Wehrli, B. The challenge of micropollutants in aquatic systems. Science (2006), 313, 1072-1077.

196 Poster sessions


An assessment of environmental factors influencing species distribution in a temperate estuary: a binomial approach

Enrique González-Ortegón1, César Vilas4, Alberto Arias1, Francisco Baldó2, José Antonio

Cuesta1, Carlos Fernández-Delgado3 and Pilar Drake1

1 Instituto de Ciencias Marinas de Andalucía (CSIC), Puerto Real, Spain 2 Instituto Español de Oceanografía, Cádiz, Spain

3 Dpto Biología Animal, Universidad de Córdoba, Córdoba, Spain 4 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

The analysis of species–environment relationship has always been a central issue in ecology. Presence and absence data allow us to estimate the probability of occurrence of the species and the optimum and tolerance range (the realized niche) for the environmental variable of interest. Under a scenario of water scarcity, freshwater discharges (FSW) to estuaries and, accordingly, estuarine salinity are expected to be remarkably altered (González-Ortegón and Drake 2013). The aim of this study was to identify which environmental variables influences the choices of nursery grounds for the marine species and reduce the presence of estuarine species in the Guadalquivir estuary. Data used in this study were the presence and absence of a subset of 40 species (among fish and crustaceans) in the Guadalquivir estuary (SW Spain). Because of the presence-absence nature of the response variables and non-linear effect of some explanatory variables, the most appropriate technique for these analyses was GAM using a binomial model (Zuur et al., 2009). Salinity and mysids were the main factors explained the presence of marine species in the Guadalquivir estuary. 75% of these models included salinity as a main factor to explain the occurrence of species. FSW from the dam to the estuary during 4 days decreased the presence of marine species and increased the presence of estuarine invertebrates and diadrom species. By contrast FSW during 15 days triggered the absence in all studied species.These relationships between presence-absence and environmental factors were in the most of cases linear, especially for temperature and salinity; but in other cases, especially freshwater discharges, the responses show a bell-shaped curve which indicated an optimal threshold for the prevalence of the target species. In spite of all these species inhabit the same ecosystem, each binomial model is specific and temporal-dependent: none species share an identical model. Similar behaviour at different seasons could explain the elevated number of species (200) collected in this estuary by now. Methodologicaly, this study confirm that presence–absence models are affected systematically by the prevalence (i.e. the frequency of occurrence) of the target organism (Manel et al 2001). With the exception of some estuarine species, presence-absence models are not useful for species with a low prevalence (<20%; common for occasional species e.g. Parapleustes asimilis) or with a high prevalence (>90%; common for estuarine species e.g. Pomatoschistus minutus). Conversely, just in a 23% of studied species, the binomial models explained a 50% or more of their variances. Most of these species were marine species with a presence ranging from 50 to 80% in the Guadalquivir estuary. This could reveal the importance of this kind of model in marine species which enter estuaries seasonally from open sea. Acknowledgements

The study was co-funded by the Spanish Ministry of Economy and Competitiveness, and the EU Fishery Grant through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065).

References

González-Ortegón, E.and Drake P. Effects of freshwater inputs on the lower trophic levels of a temperate estuary: physical, physiological or trophic forcing? Aquat Sci (2012), 74, 455–69.

Manel, S., Williams, H. C. and Ormerod, S.J. Evaluating presence–absence models in ecology: the need to account for prevalence, Journal of Applied Ecology (2001), 38, 921–931.

Zuur, A.F., E.N. Ieno, N.J. Walker, A.A. Saveliev, and G.M. Smith..Mixed effects models and extensions in ecology with R. (2009), New York: Springer.

197 Poster sessions



Effect of black poplar plantations in the base river flow in a Mediterranean stream

Núria Ferrer and Albert Folch

Hydrogeology Group, Dept. of Geotechnical Engineering and Geo-Sciences, Universitat Politècnica de Catalunya-

BarcelonaTech, Barcelona, Spain

This study aims to assess the effect of poplar plantations in the base river flow of Santa Coloma River basin (290 km2) located at the N of Barcelona city. To do it a numerical flow model (Visual Moflow 4.5) has been constructed to simulate the shallow aquifers in the area (Folch et al. 2010) and the stream-aquifer interaction for several years.

As in other areas around the world, in this basin the poplar roots tend to reach the water table of shallow aquifers increasing evapotranspiration (ET) mainly during the summer months. This direct ET from de aquifer has been included in to the model mass balance based in the study of Meiresonne et al. (1999) for the period between June and September. Then, a direct ET of the aquifer of 4 mm/day has been added for the dry days while a value of 2 mm/day has been included for days with precipitation and the day after.

The mass balance shows that poplar extracts an average of 2.66 hm3, a 20% of the total recharge of the modeled area. This effect reduces the groundwater flow to the stream and in other areas increase infiltration from the stream to the aquifer. As a result, there is a reduction in the stream flow by 47 % on average compared a model without poplar plantations.

This reduction in flow occurs mainly in the summer months when the river is more sensitive drying the river more often than it would happen with other land uses. References

FOLCH, A., CASADELLÀ, L., ASTUI, MENCIÓ, A., O., MASSANA, J., VIDAL-GAVILAN, G., PÉREZ-PARICIO, A. i MAS-PLA, J. (2010). Verifying conceptual flow models ina river-connected alluvial aquifer for management purposes using numerical modeling. En: XVIII International Conference on Water Resources (CMWR 2010), Barcelona, Spain.

MEIRESONNE, L., NADEZHDIN, N., i CERMAK, J. (1999). Measured sap flow and simulated transpiration from a poplar stand in Flanders ( Belgium ). Agricultural and Forest Metereology, 96, 165–173.

198 Poster sessions


Water management in a restored wetland influences trophic links and species composition in the aquatic macroinvertebrate community

Enrique González-Ortegón1, M.E.M. Walton1, Bushra Moghaddam1, Cesar Vilas2, Ana Prieto2,

H.A. Kennedy1, J. Pedro Cañavate2 and Lewis Le Vay1

1 School of Ocean Sciences, College of Natural Sciences, Bangor University, Menai Bridge, UK

2 IFAPA Centro El Toruño, El Puerto de Santa María, Spain

Water regulation modifies the natural flood regime, salinity and temperature of aquatic ecosystems, and hence community composition and structure. Invasions by non-indigenous species can also cause significant change in the native populations and habitats. However, little is known about how ecological impacts such as water regulation and invasive species affect food webs and other ecological processes.

This study explores how water management in reconstructed wetlands and introduction of the shrimp Palaemon macrodactylus affects the trophic niche of the native Palaemonetes varians. Reconstructed wetlands of Veta La Palma (VP) (west bank of the Guadalquivir estuary, SW Spain) comprise a total extension of 3000 ha with 70 ha unit ponds dedicated to extensive and semi-extensive aquaculture. Water is managed by different regimes of water exchange (E) with the Guadalquivir estuary, depending on whether extensive (E=1% d-1) or mixed (E=5% d-1) aquaculture is performed. These ponds offer an excellent opportunity to study how water regulation influences species composition in the aquatic community. We estimated density of aquatic fauna, studied stomach contents of the two shrimps species and analysed food web faunal and source samples for stable isotope analysis (SIA).

P. varians was found at similar average density in both the extensive (6.14 g m-2 of dry weight) and mixed (6.77 g m-2) ponds, while P. macrodactylus was found only almost entirely only in mixed ponds (10.20 g m-2). A low dissimilarity (33.2 %) was found for the aquatic community and water management was the main factor contributing to dissimilarity. Mysids and copepods were the most abundant species in mixed ponds, while ostracods and chironomids were more abundant in extensive ponds. Isotopic signatures of potential prey of P. varians and P. macrodactylus were significantly different between winter and summer (R=0.43, p=0.01) and between mixed and extensive ponds (R= 0.3-0.5, p<0.01). This separation by carbon sources might be due to a different origin of primary production and organic matter (allochthonous from the estuary vs. autochthonous).

A combined analysis of stomach contents and isotopic composition of P. macrodactylus and P. varians showed that although there is some dietary overlap, the shrimp species have different trophic niches: P. macrodactylus is more pelagic-carnivorous (main preys are mysids, copepods and exclusively amphipods), while P. varians is mainly benthonic (consuming mainly isopods, ostracods, polychaetes and sediment). Although, native P. varians is able to diversify to pelagic preys (mysids and copepods) in the mixed ponds, where these prey densities are higher, in spite of the presence of the non-native P. macrodactylus. Analysing the isotopic composition of P. varians across ponds and seasons showed a significant effect of water regulation (R=0.7, p<0.01), with 76% of this difference being explained by higher 15N values for P. varians in mixed (15.3 ‰) versus extensive (12.8 ‰) ponds.

In conclusion, the feeding of P. varians appears not to be affected by the presence of P. macrodactylus, remaining benthonic and in fact diversifying to include P. macrodactylus prey items when these prey densities increase, resulting in some dietary overlap. Differences in the trophic ecology identified in stomach contents and isotopic signature of both species are clearly explained by water management. Acknowledgements

The study was Co-funded by the European Union Atlantic Area Transnational Programme (2007 - 2013) through the SEAFARE project. Financial support to E. González-Ortegón was given by Marie Curie fellowship with European funds. Others financial support through SCARCE (Consolider-Ingenio 2010 CSD2009-00065).Merck and Biotage are acknowledged for the gift of LC

199 Poster sessions



columns and SPE cartridges, respectively. Nicola Mastroianni acknowledges the JAE Program (CSIC-European Social Funds).

References

1. UNODC, 2013. World drugs report 2013, United Nation Office on Drugs and Crime. available at http://www.unodc.org/unodc/secured/wdr/wdr2013/World_Drug_Report_2013.pdf, accessed on September 20, 2013.

2. Pal, R., et al., Illicit drugs and the environment — A review. Science of the Total Environment, 2013. 463–464(0): p. 1079-1092.

3. Ginebreda, A., et al., Environmental risk assessment of pharmaceuticals in rivers: Relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain). Environment International, 2010. 36(2): p. 153-162.

200 Poster sessions


Integrated Water Resources Management and related indicators

Andrea Momblanch, Joaquín Andreu and Javier Paredes

Universitat Politècnica de València

Current trends at international level, and specifically at European level, advance towards sustainable and efficient management of natural resources. This current is expressed in the “European Water Framework Directive” (EP, 2000), the strategies “Europe 2020” (EC, 2010) and “EU biodiversity strategy to 2020” (EC, 2011), and in “A Blueprint to safeguard Europe’s Water Resources” (EC, 2012), among other official documents. Moreover, as population grows and other water demanding sectors develop the issue of water allocation has become more complex (Andreu et al., 2012). This is why, simulation models need to be adapted to consider the sustainable management of water resources (Loucks, 2000), inside the broader objective of sustainable development. This has brought about simulation models to evolve towards new approaches like Decision Support Systems, experts systems, collaborative planning and management, and dynamic decision systems, among others (Solera, 2003). In line with the abovementioned concepts, the Integrated Water Resources Management is a process which promotes the coordinated development and management of water, land and related resources in order to maximise the resultant economic and social welfare in an equitable manner without compromising the sustainability of vital ecosystems, as defined by the Global Water Partnership (2000). From this definition, it is clear that in order to cover so many water and ecosystems related aspects the use of integrative models is increasingly necessary. In this work, a methodology comprised of five coordinated modules is used to integrate aspects of water resources evaluation, diffuse pollution evaluation, water allocation, water quality, and habitat suitability for aquatic species. These five modules are part of the AQUATOOL DSS Shell for integrated water planning and management (Andreu et al., 1996) and have been designed for more than 20 years following well established methodologies for water resources systems analysis. AQUATOOL allows analysing the effect of multiple management alternatives and scenarios on the relevant variables in a river basin. Thus, it is easier to conduct tradeoff analysis, risk evaluations, and other useful processes which provide data for informed decision making.

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201 Poster sessions



Figure 1 shows the information flow through the different models. It makes evident that the management of the river basin impacts on the available water resources and the water quality of runoff. Moreover, water resources allocation decisions impact all the basin uses, including the environmental uses and the water quality (Paredes-Arquiola et al., 2013). With this methodology, it is easy to conduct tradeoff analyses that help to balance the different significant issues in a whole river basin. The influence of different environmental flow regimes on water quality and habitat suitability have been analysed in previous studies (Paredes-Arquiola et al., 2013). But, the new methodology presented here also allows relating changes in the land uses of the river basin to, for instance, changes in water quality or habitat suitability, maintaining the same management rules. So, the potential of the effective linkage of these tools is very broad.

In this work, the proposed methodology for Integrated Water Resources Management is applied to the Tormes Water Resources System, in Spain. The period of analysis goes from October 1996 to September 2007, which includes a critical period related to a drought event. The potential of jointly analysing different aspects of a water resources system are exemplified. Some indicators and graphics are proposed to synthesise all the relevant information for decision making, which explicitly show the gains and losses of each objective in diverse scenarios. Based on this, a tradeoff analysis is proposed to present the evolution of water quality, satisfaction of demands and habitat availability, as environmental flows change in several points of the water resources system. The results are analysed through graphics that can be easily understood by decision makers and stakeholders, supporting sound and informed decisions.

Acknowledgements

The autor would like to thank the Spanish Ministry of Economy and Competitiveness for its financial support through the projects SCARCE (Consolider-Ingenio 2010 CSD2009-00065) and NUTEGES (VI Plan Nacional de I+D+I 2008-2011, CGL2012-34978). Besides, I show gratitude to the European Commission for financing the projects SIRIUS (FP7-SPACE-2010-1, 262902), DROUGHT-R&SPI (programa FP7-ENV-2011, 282769) and ENHANCE (FP7-ENV-2012, 308438).

References

Andreu, J., Capilla, J. and Sanchis, E. AquaTool, a generalized decision-support system for water resources planning and operational management. Journal of Hydrology (1996), 177, 269-291.

Andreu, J., Momblanch, A., Paredes, J., Pérez, M.A. and Solera, A. Potential role of standardized water accounting in Spanish basins. In: Godfrey J. and Chalmers K. (eds.) International Water Accounting: Effective Management of a Scarce Resource. Edward Elgar Publishing Inc. (2012), 123-138.

EC, European Commission. Europe 2020. A strategy for smart, sustainable and inclusive growth. European Commission, 3.3.2010 COM (2010) 2020 final.

EC, European Commission. Our life insurance, our natural capital: an EU biodiversity strategy to 2020. European Commission, 5.2011 COM (2011) 244 final.

EC, European Commission. A Blueprint to Safeguard Europe's Water Resources. European Commission, 14.11.2012 COM (2012) 673 final.

EP, European Parliament. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Official Journal L 327, 22-12-2000 (2000).

Global Water Partnership. Integrated Water Resources Management. Global Water Partnership Technical Advisory Committee, Background Paper no.4 (2000).

Loucks, D. Sustainable water resources management. Water international (2000), 25 (1), 3-10.

Paredes-Arquiola, J., Solera, A., Martinez-Capel, F., Momblanch, A. and Andreu, J. Integrating water management, habitat modelling and water quality at basin scale and environmental flow assessment: case study of Tormes River, Spain. Hydrological Science Journal (in press).

Solera, A. Herramientas y métodos para la ayuda a la decisión en la gestión sistemática de recursos hídricos. Aplicación a las cuencas de los ríos Tajo y Júcar. PhD Thesis (2003) – Universitat Politècnica de València.

202 Poster sessions


WaterDiss2.0: Disseminating Water Research across the European Union

Beatriz Medina1, C. Roberts2, T. Simms2, U. Stein3 and G. Nion4

1 Amphos 21, Spain

2 The Chancellor, masters and Scholars of the University of Oxford 3 Ecologic, Germany, UK

4 Office International del L’Eau, France

The outcomes of research into water resource problems funded by the European Union have often been very slow to be taken up by practitioners; typically, almost a decade can pass between the start of a project, and any subsequent impact on policymakers, industry or communities. Moreover, some projects seem never to produce results that are of value to potential users. The WaterDiss2.0 project is a collaboration between partners in France, the UK, Germany, Italy, Spain, Poland and Romania, to review FP6 and FP7 projects, and to consider the most effective ways of promoting dissemination and uptake of research findings.

Over 70 projects, some completed and some still in progress, have been reviewed (through questionnaire, text analysis, interviews) in conjunction with their Principal Investigators, and agreements have encouraged specific forms of dissemination for particular outputs. Projects were grouped into unambiguous water-related themes such as flooding, river restoration, water resources, drought, water treatment processes, and pollution control. The projects’ own intended dissemination methodologies were evaluated, and some new methods of engagement have been suggested for adoption, and then trialled.

Potential dissemination methods include not only traditional conference papers, or publications in peer-refereed journals but workshops, videos, magazine articles, summer schools for young scientists, staff exchanges, one-to-one meetings with policymakers or industry specialists and a variety of other innovative techniques.

The WaterDiss2.0 analysis shows that successful uptake usually occurs when project outcomes are developed in conjunction with practitioners at the start of the research programme, and when specific and early attention is paid to the dissemination process itself. Engagement with key stakeholders needs to be sustained over extended periods. The mutual expectations of funders and the recipients of research funding are crucial when considering dissemination, and must be clarified at the beginning of a programme. Impact is most likely when the potential users of research are personally engaged, enthusiastic and knowledgeable about a specific topic area; multiple presentations of research findings on a broad variety of themes are likely to be ineffective, even if potential audiences are very large. Beyond this, more active styles of engagement, such as interactive workshops rather than conferences, appear most effective at prompting take up and genuine learning for application. This allows trust to develop between all the participants. Failure to observe these elementary priorities can lead to researchers effectively ‘walking away’ from projects at the end of the funded programme, and important outcomes languishing only in unread publications.

On reflection, some of the challenges faced by water researchers are also mirrored in the encounters experienced in participating in the WaterDiss2.0 project itself. Multinational and multilingual working, and the development of cross-disciplinary European understanding can be as equally problematic for this project team, as for broader research communities.



List of participants

205 List of participants



List of participants

A Aceña Sanchez, Jaume Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Acuña, Vicenç Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Aguirre, Gabriela Department of Physical-Chemistry University of Cádiz Poligono Rio San pedro 11510 Cadiz, Spain (+34) 677 32 21 67 [email protected] Airado-Rodríguez, Diego Department of Analytical Chemistry Univesity of Granada Avda Fuentenueva S/N 18071 Granada, Spain (+34) 605183233 [email protected] Alvarez, Diana Chemical Contamination of Water Bodies Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Andrés-Costa, María Jesús Preventive Medicine University of València (UV) Av. Vicent Andrés Estellés, s/n 46100 Burjassot, Spain (+34) 963 54 41 18 [email protected]

Andreu Álvarez, Joaquin Instº Ingeniería del Agua y Medio Ambiente Universidad Politécnica de Valencia Camino de Vera s/n 46022 Valencia, Spain (+34) 96 387 70 00 [email protected] Andreu Perez, Vicente Degradación y Conservación de Suelos Centro de Investigaciones sobre Desertificación-CIDE (CSIC) Ctra. Moncada-Naquera Km 4.5 46113 Moncada, Spain (+34) 963 42 41 62 [email protected] Aparicio, Irene Analytical Chemistry University of Seville Virgen de Africa, 7 41011 Seville, Spain (+34) 655 67 09 35 [email protected] Arias, Alberto M. Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected] Aristi, Ibon Ecology University of the Basque Country (UPV/EHU) PO Box 644 48080 Bilbao, Spain (+34) 615 00 54 14 [email protected] Arroita, Maite Plant Biology and Ecology University of the Basque Country (UPV/EHU) PO Box 644 48080 Bilbao, Spain (+34) 946 01 59 39 [email protected]


B Baena-Nogueras, Rosa María Department of Physical-Chemistry University of Cádiz Av. República Saharaui s/n 11510 Puerto Real, Spain (+34) 956 01 65 31 [email protected] Banjac, Zoran Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Baldó, Francisco Instituto Español de Oceanografía Puerto Pesquero, Muelle de Levante s/n 11006 Cádiz, Spain (+34) 647356608 [email protected] Barceló, Damià Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Biel Maeso, Miriam Dep. Physical-Chemistry University of Cadiz Av. República Saharaui s/n 11510 Puerto Real, Spain (+34) 651426543 [email protected]

Blasco, Julian Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected] Boithias, Laurie Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Brack, Werner Department Effect-Directed Analysis Helmholtz-Zentrum für Umweltforschung GmbH - UFZ Permoserstraße, 15 4318 Leipzig, Germany (+49) 341 235 1531 [email protected] Burgos Martín, Macarena Department of Physical-Chemistry University of Cádiz Av. República Saharaui s/n 11510 Puerto Real, Spain (+34) 617 57 50 35 [email protected] Bautista, Susana Department of Ecology University of Alicante Apdo. 99 03080 Alicante, Spain (+34) 965 90 34 00 ext.3372 [email protected]

C Cabello Villarejo, Violeta Human geography University of Sevilla Maria de Padilla s/n 41004 Sevilla, Spain (+34) 955549526 [email protected]

Calvo, José Luis Instituto Andaluz de Tecnología Leonardo Da Vinci 2. Pct Cartuja 41092 Sevilla, Spain (+34) 954 46 80 10 [email protected]




Camacho Muñoz, María Dolores Analytical Chemistry University of Sevilla Virgen de África, 7 41011 Seville, Spain (+34) 677131036 [email protected] Campo, Julián Food and Environmental Safety Research Group University of València Av. Vicent Andrés Estellés s/n 46100 Burjassot, Spain (+34) 963 54 49 58 [email protected] de Castro, Núria Department of Ecology University of Barcelona Avda. Diagonal, 643 08028 Barcelona, Spain (+34) 93 402 15 07 [email protected] Cifuentes Sánchez, Víctor Juan Confederación Hidrogràfica del Guadalquivir Plaza de España, Sector II y Sector III 41071 Sevilla, Spain (+34) 955 63 75 02 [email protected]

Corada-Fernandez, Carmen Department of Physical-Chemistry University of Cádiz Campus Río San Pedro, s/n 11510 Puerto Real, Spain (+34) 646 70 18 22 [email protected] Corcellas i Carramiñana, Cayo Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Corcoll, Natàlia Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected]

D Diez, Joserra Mathematics and Experimental Sciences Didactics University of the Basque Country (UPV/EHU) Juan Ibáñez de Sto. Domingo, 1 1006 Vitoria-Gasteiz, Spain (+34) 945 01 40 20 [email protected] Drake, Pilar Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected]

Durán Lalaguna, Concha Area de Calidad de Aguas Confederación Hidrográfica del Ebro Paseo Sagasta 24-28 50007 Zaragoza, Spain (34) 976 71 10 00 ext 22321 [email protected]



E Elosegi, Arturo Plant Biology and Ecology University of the Basque Country (UPV/EHU) PO Box 644 48080 Bilbao, Spain (+34) 946 01 55 14 [email protected] Elorza Tenreiro, Francisco Matemática Aplicada y Métodos Informáticos UPM - Escuela Técn. Superios de Ingenieros de Minas CALLE RíOS ROSAS, 21 28003 Madrid, Spain (+34) 913367066 [email protected]

Enjuanes, Antoni Departament d’Agricultura, Alimentació i Acció Rural Generalitat de Catalunya Gran Via de Les Corts Catalanes, 612-614 08007 Barcelona, Spain (+34) 93 304 67 00 ext. 6726 [email protected]

F Farré, Marinel.la Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Feld, Christian K. Department of Aquatic Ecology University of Duisburg-Essen Universitaetsstrasse, 5 45141 Essen. Germany (+49) 201 183 43 90 [email protected] Fernández Delgado, Carlos Zoology University of Córdoba Campus Universitario de Rabanales 14014 Córdoba, Spain (+34) 957 21 86 05 [email protected] Ferrer Matvieychuc, Graciela Economia Aplicada Universitat de València Av. Taronger s/n – Ed. Facultat d Economia, 2a 46022 València, Spain 34963828418 [email protected]

Flores, Lorea Plant Biology and Ecology University of the Basque Country (UPV/EHU) PO Box 644 48080 Bilbao, Spain (+34) 946 01 59 69 [email protected] Folch, Albert Department of Geotechnical Engineering and Geosciences Technical University of Catalonia Jordi Girona, 31 08034 Barcelona (+34) 93 401 180 60 [email protected] Francés, Félix Research Institute of Water and Environmental Engineering (IIAMA) Technical University of València (UPV) Camino de Vera s/n 46022 Valencia, Spain (+34) 963 87 76 12 [email protected]




G Ginebreda, Antoni Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] González Aranda, Juan Miguel Spanish Ministry of Economy and Competitiveness Paseo de la Castellana, 162 28046 Madrid, Spain (+34) 915 836 040 [email protected] Gonzalez-Ortegon, Enrique Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected]

González-Fuenzalida, Rodrigo Analytical Chemistry University of Valencia Dr Moliner, 50, Building E. 2nd floor 46100 Burjassot, Spain (+34) 963 54 43 34 [email protected] Gorga, Marina Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Grimalt Obrador, Joan Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected]

H Hampel, Miriam Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956832612 [email protected] Hansen, Peter D. Ecological Impact Research and Ecotoxicology Berlin Institute of Technology (BIT) Ernst-Reuter-Platz, 1 10587 Berlin, Germany (+49) 314 289 99 [email protected] Hernández García, Marta Alternative Water Resources CETaqua Carretera d'Esplugues, 75 08940 Cornellà de Llobregat, Spain (+34) 93 312 48 00 [email protected]

Hidalgo López, Arturo Matemática Aplicada y Métodos Informáticos Technical University of Madrid (UPM) Ríos Rosas, 21 28003 Madrid, Spain (+34) 91 336 32 33 [email protected] Huerta Buitrago, Belinda Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected]



J Jornet-Martínez, Neus Analytical Chemistry University of Valencia Dr Moliner, 50, Building E. 2nd floor 46100 Burjassot , Spain (+34) 963 54 43 34 [email protected]

Johns, Joseph Babadi Dir. of Policy, Programmes, Research and Development, Masianday Foundation 16th Street, Fajaranjula Golf Course Road 22099 Banjul, Gambia (+220) 790 63 08 [email protected]

K Kaptan, Kubilay Disaster Education, Application and Research Center (AFAM) Istanbul Aydin University Inonu Caddesi, 38, sefakoy 34295 Istanbul, Türkiye (+90) 533 813 29 97 [email protected] Kersting, Teresa Water, Economic and Society CETaqua Carretera d'Esplugues, 75 08940 Cornellà de Llobregat, Spain (+34) 93 312 48 62 [email protected]

Kuzmanovic, Maja Water and Soil Quality Research Group Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected]

L La- Roca, Francesc Economia Aplicada Universitat de Valencia Campus dels Tarongers, Oriental 2F05 46022 Valencia, Spain (+34) 96 382 8418 [email protected] Lara Martin, Pablo Antonio Department of Physical-Chemistry University of Cádiz Campus Río San Pedro, s/n 11510 Puerto Real, Spain (+34) 956 01 61 59 [email protected] Larrañaga, Aitor Department of Plant Biology and Ecology University of the Basque Country (UPV/EHU) PO Box 644 48080 Bilbao, Spain (+34) 946 01 79 54 [email protected]

Lerdo de Tejada, Francisco Confederación Hidrográfica del Guadalquivir Av. República Argentina, 43 acc. 1ª planta 41071 Sevilla, Spain (+34) 95 563 75 31 [email protected] López de Alda, Miren Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] López Benito, Alfredo Matemática Aplicada y Métodos Informáticos Technical University of Madrid (UPM) Ríos Rosas, 21 28003 Madrid, Spain (+34) 913363233 [email protected]




López-Roldán, Ramón Environment and Health CETaqua Carretera d'Esplugues, 75 08940 Cornellà de Llobregat, Spain (+34) 93 312 48 86 [email protected]

Ludwig, Ralf Department of Geography Ludwig-Maximilians-Universitaet München Luisenstrasse 37 80333 Munich, Germany (+49) 89 2180 6677 [email protected]

M Marcé, Rafael Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Jesus Marco de Lucas IFCA-CSIC Juan Jorda, Avda de los Castros s/n 39005 Santander, Spain (+34) 660573808 [email protected] Martín-Díaz, M.Laura Dep. Chemical Physical University Of Cadiz Poligono Rio San Pedr S/N 11510 Puerto Real, Spain (+34) 607 93 32 90 [email protected] Martínez, Elena Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Masia Reyes, Ana Food and Environmental Safety Research Group University of València Av. Vicent Andrés Estellés s/n 46100 Burjassot, Spain (+34) 963 54 49 58 [email protected]

Mastroianni, Nicola Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 652 54 97 65 [email protected] Medina, Beatriz Environmental Communications AMPHOS 21 Passeig garcia i faria, 49-51 08019 Bbarcelona, Spain (+34) 93 583 05 00 [email protected] Momblanch Benavent, Andrea Ingeniería Hidráulica y Medio Ambiente Universidad Politécnica de Valencia Camino de Vera s/n 46022 Valencia, Spain (+34) 96 387 70 00 [email protected] Moreno-Garrido, Ignacio Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected] Muñoz, Isabel Department of Ecology University of Barcelona Avda. Diagonal, 643 08028 Barcelona, Spain (+34) 93 402 15 12 [email protected]



Muñoz Ortuño, María Analytical Chemistry University of València Doctor Moliner, 50 46100 Burjassot, Spain (+34) 963 54 43 34 [email protected]

N Naber, Sawsan Faculty of Agriculture University of Jordan P.O. Box 13042 11942 Amman, Jordan (+962) 777 48 44 60 [email protected] Navarro, Enrique Instituto Pirenaico de Ecología Av. Montañana 1005 50059 Zaragoza, Spain (+34) 636 35 93 58 [email protected]

Navarro-Ortega, Alícia Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Nieto Cristóbal, Elena Dept. of Ecology and Coastal Management Inst. for Marine Science of Andalusia (ICMAN-CSIC) Av. República Saharaui, s/n 11519 Puerto Real, Spain (+34) 956 83 26 12 [email protected]

P Pascual Aguilar, Juan Antonio Degradación y Conservación de Suelos Centro de Investigaciones sobre Desertificación-CIDE (CSIC) Ctra. Moncada-Naquera Km 4.5 46113 Moncada, Spain (+34) 963 42 42 17 [email protected] Pérez, Sandra Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected] Petrovic, Mira Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected]

Pico Garcia, Yolanda Food and Environmental Safety Research Group University of València Av. Vicent Andrés Estellés s/n 46100 Burjassot, Spain (+34) 963 54 30 92 [email protected] Pintado Herrera, Marina Department of Physical-Chemistry University of Cádiz Campus Río San Pedro, s/n 11510 Puerto Real, Spain (+34) 956016531 [email protected] Pla Tolós, Javier Analytical Chemistry University of València Doctor Moliner, 50 46100 Burjassot, Spain (+34) 963 54 43 34 [email protected]




Playán, Enrique The Joint Programming Initiative on water Ministry of Economy and Competitiveness Albacete 5, 2ª planta Este 28027 Madrid (+34)976 71 60 87 [email protected]

Q Quiroga, Angels Department of Environmental Chemistry IDAEA-CSIC Jordi Girona, 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected]

R Roig Montserrat, Neus Department of Chemical Engineering Rovira i Virgili University Paisos Catalans, 26 43007 Tarragona, Spain (+34) 977 55 85 53 [email protected]

Rodríguez Mozaz, Sara Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected]

S Sabater, Sergi Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Saenz, Antonio Instituto Andaluz De Tecnología Leonardo da Vinci 2, PCT Cartuja 41092 Sevilla, Spain (+34) 954 46 80 10 [email protected] Sánchez Canales, María Escuela Técn. Superios de Ingenieros de Minas Technical University of Madrid (UPM) Ríos Rosas, 21 28003 Madrid, Spain (+34) 91 336 70 47 [email protected]

Sànchez-Vila, Xavier Department of Geotechnical Engineering and Geosciences, Technical University of Catalonia Jordi Girona, 31 08034 Barcelona (+34) 93 401 180 60 [email protected] Sanchez Gimeno, Benjamin Secretaria General de Ciencia y Tecnología MINECO C/ Albacete 5 28028 Madrid, Spain (+34) 619 43 34 93 [email protected] Sanchís Sandoval, Josep Àngel Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 649 23 79 76 [email protected]



Santos, Juan Luis Analytical Chemistry University of Seville Virgen de África 41011 Seville, Spain (+34) 954 55 62 50 [email protected] von Schiller, Daniel Resources and Ecosystems Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972183380 [email protected] Schuhmacher, Marta Department of Chemical Engineering Rovira i Virgili University Paisos Catalans, 26 43007 Tarragona, Spain (+34) 977 55 96 53 [email protected]

Shatanawi, Muhammad Land, Water and Environment Univeristy of Jordan P.O. Box 13042 11942 Amman, Jordan (+962) 777 48 44 99 [email protected] Sierra, Jordi Chemical Engineering, ETSQ University Rovira i Virgili (URV) Països Catalans, 26 43007 Tarragona, Spain (+34) 977 55 8553 [email protected] Siirila, Erica Ingeniería del Terreno Technical University of Catalunya. BarcelonaTECH Jordi Girona, 1-3 08034 Barcelona, Spain (+34) 93 401 18 60 [email protected]

T Terrado Casanovas, Marta Catalan Institute for Water Research (ICRA) Emili Grahit, 101 - Edifici H2O - PCiT 17003 Girona, Spain (+34) 972 18 33 80 [email protected] Torres-Fuentes, Nivis Department of Physical-Chemistry University of Cádiz Campus Río San Pedro, s/n 11510 Cadiz, Spain (+34) 691 34 63 10 [email protected]

Traverso Soto, Juan Manuel Department of Physical-Chemistry University of Cádiz Campus Río San Pedro, s/n 11510 Puerto Real, Spain (+34) 956 01 61 59 [email protected]

V Víctor-Ortega, María Dolores Department of Chemical Engineering Univesity of Granada Avda Fuentenueva S/N 18071 Granada, Spain (+34) 655 19 46 25 [email protected]

Villegas, Marina Subdirección General de Proyectos de Investigación Ministry of Economy and Competitiveness Albacete 5, 2ª planta Este 28027 Madrid [email protected]




Z Zampieri, Matteo Climate Services Division Centro Euro Mediterraneo sui Cambiamenti Climatici Viale Aldo Moro, 44 40127 Bologna, Italy (+39) 051 378 26 07 [email protected]

Zonja, Bozo Department of Environmental Chemistry IDAEA-CSIC Jordi Girona 18-26 08034 Barcelona, Spain (+34) 93 400 61 00 [email protected]

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