subject: environmental chemistry and technology topic: … · subject: environmental chemistry and...
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Andreja Žgajnar Gotvajn
University of Ljubljana, Slovenia
Faculty of Chemistry and Chemical Technology
Chemical, Biochemical and Environmental Engineering
Subject: Environmental Chemistry and
Technology
Topic: PERSISTANT POLLUTANTS
PRESENTATION OUTLINE
Persistent/resistant organics
Problems?
Legislation: EU REACH
Biodegradability testing
Ecotoxicity testing
DEFINITION
Persistent organic pollutants (POPs) are organic compounds that are resistant to environmental degradation:
chemical
biological
photolytic
Their characteristics:
Persist in the environment
Long-range transport (atmosphere, hydrosphere),
Bioaccumulate in human and animal tissue,
Biomagnify in food chains,
Significant impacts on human health
Significant impact on the environment.
PERSISTENCY/RESISTANCY ?
Biodegradation of XENOBIOTICS:
MO with different metabolic/cometabolic pathways
Induction of enzymes in MO
Mutation
Evolution
Other possibilities:
Physico-chemical processes
Biodegradation
DDT
dichloro-diphenyl-trichloro-ethane
For ever or for a long time ?
http://www.planet-lepote.com/forum/viewtopic.php?t=6122&start=30/?registracija=nov_uporabnik, 24. 8. 2012
DAILY USE OF CHEMICALS?
ZERO WASTE MANAGEMENT,GREEN CHEMISTRY ?
(Pichtel, 2005).
http://www.cas.org/cgi-bin/cas/regreport.pl
All registred organic and inorganic substances
Commercially available substances.
% of commercially available substances
2000 2001 2003 2004 2005 2006 2007 2008 2009 2010
17.108.155 18.766.082 22.176.046 24.267.905 26.752.587 30.009.658 32.687.772 37.966.182 50.269.830 55,501,670
960.312
6 %
2.872.816
15 %
6.299.284
28 %
8.143.833
34 %
8.974.433
34 %
11.509.742
38 %
15.965.596
56 %
24.033.991
63 %
35.479.919
71 %
48.807.771
78 %
83,546,456
70,516,747
85%
2014
No. of regulated: 309,061 —> 0,4% !
DAILY USE OF CHEMICALS?
THE IMPACT OF SUBSTANCES ?
RISK ASSESSMENT OF SUBSTANCES?
Hazard
Identification
Dose/Response
Assessment
Actual
Concentrations ?
Risk Assessment
Risk Management
DIRECTIVE 93/21/EEC:
new+existing substances
When ? production, transport, removal
For ? chemicals/mixtures/products
Why ? producers/users/importers
Labeling/regulation:
- physico-chemical properties (explosive…)
- toxicological properties (toxic, harmfull…)
- imapct on human (cancerogenic…)
- environmental impact:
* water
* terrestial (soil, plants…)
New European REACH legislation ?REACH:
Registration
Evaluation,
Authorisation and
Restriction of
CHemical substances
REACH is a new European Community Regulation on chemicals and their safe use (EC
1907/2006).
The new law entered into the force on 1st of June, 2007.
The aim of REACH is to improve the protection of human health and the environment
through the better and earlier identification of the properties of chemical substances.
At the same time, innovative capability and competitiveness of the EU chemicals industry
should be enhanced.
The benefits of the REACH system will come gradually, as more and more substances are
phased into REACH – 11 Years.
The need to fill the data gaps would result in an increased use of laboratory animals for the
next 10 years. To minimise the number of animal tests, the REACH Regulation provides a
number of possibilities to adapt the testing requirements and use existing data and
alternative assessment approaches instead.
New European REACH legislation ?Covers all substances (Minor exceptions).
Manufacturers and importers are required to obtain relevant
information - preregistration.
Data from toxicity testing should be shared.
Information on hazards and risks will be passed down by supply
chain.
According to their quantities:
- 1 to 10 tonnes
- 10 to 100 tonnes
- more than 100 tonnes
CMRs: Carcinogenic, mutagenic or
toxic to reproductionhttp://www.google.si/search?sourceid=navclient&aq=0h&oq=REACH&ie=UTF-
8&rlz=1T4ADFA_enSI411SI413&q=reach+legislation
New European REACH legislation ?
Source: European Chemicals Agency, http://echa.europa.eu/
SUBSTANCES OF VERY HIGH CONCERN - 46
(banned in the next few years?)
Trichloroethylene Carcinogenic
Boric acid Toxic for reproduction
Disodium tetraborate Toxic for reproduction
Tetraboron disodium heptaoxide Toxic for reproduction
Potassium dichromate Carcinogenic, mutagenic, reproduction
Ammonium dichromate Carcinogenic, mutagenic, reproduction
Potassium chromate Carcinogenic and mutagenic
Sodium chromate Carcinogenic, mutagenic, reproduction
2,4-Dinitrotoluene Carcinogenic
Acrylamide Carcinogenic and mutagenic
.....
New European REACH legislation ?Source: European Chemicals Agency, http://echa.europa.eu/
CRITERIA FOR THE IDENTIFICATION OF PERSISTENT, BIOACCUMULATIVE AND
TOXIC SUBSTANCES
Substance fulfils the persistence criterion when:
the half-life in marine water is higher than 60 days,
the half-life in fresh- or estuarine water is higher than 40 days,
the half-life in soil is higher than 120 days.
Substance fulfils the bioaccumulation criterion when:
the bioconcentration factor (BCF) is higher than 2 000.
Substance fulfils the toxicity criterion when:
the long-term no-observed effect concentration (NOEC) for marine or freshwater
organisms is less than 0,01 mg/l,
the substance is classified as carcinogenic (category 1 or 2), mutagenic (category 1
or 2), or toxic for reproduction (category 1, 2, or 3), according to other directives
there is other evidence of chronic toxicity, as identified by the classifications:
T, R48, or Xn, R48 according to Directive 67/548/EEC
New European REACH legislation ?Source: European Chemicals Agency, http://echa.europa.eu/
DESCRIPTION FOR THE SUBSTANCE
Hexachloroethane
CAS No 67-72-1
EINECS No 200-6664
Shall not be used in the
manufacturing or
processing of non-ferrous metals.
Azocolourants
1. Azodyes which, by reductive cleavage of one or more azo groups, may release one or
more of the aromatic amines listed in Appendix 8, in detectable concentrations,
i.e. above 30 ppm in the finished articles or in the dyed parts thereof, according to the
testing methods listed in Appendix 10, shall not be used in textile and leather articles
which may come into direct and prolonged contact with the human skin or oral cavity,
such as:
– clothing, bedding, towels,hairpieces, wigs, hats, nappies and other sanitary items,
sleeping bags,
– footwear, gloves, wristwatch straps, handbags, purses/wallets, briefcases, chair
covers, purses worn round the neck,
– textile or leather toys and toys which include textile or leather garments,
– yarn and fabrics intended for use by the final consumer.
2. Furthermore, the textile and leather articles referred to in paragraph 1 above shall not
be placed on the market unless they conform to the requirements set out in ...
CHARACTERISTICS OF
PERSISTENT ORGANICS
Low water solubility
High lipid solubility
High molecular masses
Low volatility
Biologically active?
Soil, sediments.
Uptake till equilibrium is reached, possible leaching.
Possible consequence: A rise in soil and sediment toxicity.
BIOLOGICAL ACTIVITY
http://www.elsevierimages.com/image/33239.htm, 29. 10. 2010
TRANSPORT PATHWAYS
(EDCs)
CHARACTERSTICS OF
SUBSTANCES ?Structure
Physico-chemical properties: volatility, solubility, miscibility, etc.
Transport pathways
Environmental concentrations
Environmental impact
HOW TO ASSESS RESISTANCY ?
Biodegradability studies.
Chemicals, wastewaters.
Biodegradability is dependent upon:Structure and concentration of the substance
Source and type of MO
Physico-chemical conditions: pH, T, oxygen, etc.
Nutrients: N, P, etc.
A A*CO2 + H2O + Inorganic components
+ E
+ biomass
MO
BIODEGRADABILITY
EXPERIMENTAL SETUP ?
Standardised and non-standardised tests
How ?
Change of parameter vs. time
Basic idea:
Directly: concentration of chemicals biodegradation
Non-directly: non-specific parameters:- O2 consumption- CO2 production- TOC, TC, IC...
Sample
Nutrients
Buffer Water
MO
Xv/t
-
X B /t
=Nutrients
Buffer
MO
Water
Sample
BIODEGRADABILITY TESTING IN EU
Multilevel protocol
Not only quantity, but also other environmental characteristics
(toxicity, mutagenicity, bioaccumulation potential, etc.)
OECD = EU ISO
Level
of testing Test name Annual production (t) Production in 5 years (t)
0 Ready biodegradability 1 5
1 Potential biodegradability:
- on demand: 10 - 100 50
- regulatory: 100 – 1000 500
2 Simulation tests 1000 /
EVALUATION OF
BIODEGRADABILITY
EVALUATION OF
BIODEGRADABILITY
EVALUATION OF
BIODEGRADABILITY
Different aquatic environments: WWTP, rivers, lakes, sediments….
Test
design
Real
processes:
-evaporation
-adsorption
-dillution
-transport
pathways
-...
Possibilities:
-knowledge
-tehnical
-price
-...
? In situ ?
Ecotoxicology – science describing the toxic effectof various agents on living organisms, especially onpopulations and communities within ecosystems.
ECOTOXICITY
Response of tested organisms during the exposition of toxic compound depend on dose of this compound as well as time of the exposure.
Paracelsus (15th century) "All things are poison and nothing is without poison,
only the dose permits something not to be poisonous."
Aquatic ecosystem
TOXICITY TEST
TOXICITY TEST
Physico-chemical analyses
and/or?
Biotests
LC (lethal concentration)
Concentration, causing death of certain amount of tested organisms
48h LC50 = 0.1 mg/l
EC (effective concentration)
Concentration, causing specific response of tested organisms
96h EC50= 0.2 mg/l
RESULTS OF TOXICITY TEST
Most often
found
parameters
BACTERIA Activated sludge
Vibrio fischeri (Photobacterium phosphoreum)
Pseudomonas putida
ALGEA Scenedesmus subspicatus
Selenastrum capricornutum
WATER FLEAS Daphnia magna
Daphnia pulex
Ceriodaphnia dubia
FISH Oncorhynchus mykiss
Brachydanio rerio
Cyprinus carpio
Pimephales promelas
Salvenius fontinalis
TEST ORGANISMS
FUTURE OF POPs?
Synthesis/development.
Increased use over large areas.
Restricted use.
Reduced emissions, as well as bans and controls.
SOME REFERENCES USED/FUTURE READING
Vesilind, P. A., Morgan, S. M.: Introduction to Environmental Engineering, 2nd
Ed., Thomson Brooks/Cole, London, 2004.
Davis, M. L, Masten, S. J.: Principles of Environmental Engineering and
Science, McGraw-Hill, 2004.
Masters G.M., Wendel E: Introduction to Environmental Engineering and
Science. 3rd Ed., Prentice-Hall International, London, 2008.
Baird,C., Cann, M.: Environmental Chemistry, 4th Ed., W.H. Freeman and
Company, New York, 2008.
Sawyer C.N., McCarty P.L., Parkin G.F.: Chemistry for Environmental
Engineering, 5th Ed. McGraw-Hill, New York, 2003.
Society of Environmental Toxicology and Chemistry (SETAC), Ecological Risk
Assessment, Technical Issue Paper, Pensacola, Florida, 1997.
Struijs, J., Van der Berg, R.: Standardized biodegradability tests: Extrapolation
to aerobic environments, Water Research, 29, 1995, 255-262.
Rand, G.M., Fundamentals of Aquatic Toxicology, Effects, Environmental Fate,
and Risk Assessment, 2nd Edition, Taylor and Francis Publishers, London, 1995.
REACH: Regulation (EC) No 1907/2006 of the European Parliament and of the
Council of 18 December 2006 concerning the Registration, Evaluation,
Authorisation and Restriction of Chemicals (REACH).
.....