current research initiatives cyanotoxins, lead, etc. · water quality and minimize costs - 4429 •...
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© 2016 Water Research Foundation. ALL RIGHTS RESERVED.© 2016 Water Research Foundation. ALL RIGHTS RESERVED. No part of this presentation may be copied, reproduced, or otherwise utilized without permission.
Current Research InitiativesCyanotoxins, Lead, Etc.
2016 Ohio AWWA Section Conference
Kim LintonRegional Liaison
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Presentation Overview
WRF Background/101
50 Years of Research
Cyanobacteria
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
WRF 101• Research Cooperative
• Governed by utilities
• Over $500M of research
• ~1,000 subscribers
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Regulations
0
20
40
60
80
100
120
NIPDWR
Phase II, LCR
TTHMR
1980
Phase I
SWTR,TCR
Phase II
1990 2000 2010
CCRR,Stage 1 DBPR,
IESWTR
Radionuclides, PNR
Arsenic, SFBR
GWR, LT2ESWTR,
Stage 2 DBPR
ST-LCR RTCR
ICR
Number of Regulated Contaminants
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Value of Disinfection Research(cash funding + in-kind)
$0
$2,000,000
$4,000,000
$6,000,000
$8,000,000
$10,000,000
$12,000,000
$14,000,000
UV Radiation Ozone Chloramines Chlorine Chlorine Dioxide
MDBP Council
Stage 1 DBP RuleStage 2 DBP Rule
WRF is out ahead of regulations to find effective solutions
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Value of Ozone & UV Research(cash funding + in-kind)
$0$500,000
$1,000,000$1,500,000$2,000,000$2,500,000$3,000,000$3,500,000
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010
2012
2014
UV Radiation Ozone
Crypto outbreak
UV inactivates Crypto
WRF helped evaluate solutions to resolving cryptosporidium issues using ozone & UV reducing costs and improving effectiveness
TOTAL UV PROJECTS 51 TOTAL FUNDING Cash: $10,725,345 In-kind: $8,611,083 Total e: $19,336,428
TOTAL OZONE PROJECTS 81TOTAL FUNDING Cash:$14,646,611 In-kind: $22,942,572 Total: $37,589,182
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Value of Ozone & UV Research(cash funding + in-kind)
$0$500,000
$1,000,000$1,500,000$2,000,000$2,500,000$3,000,000$3,500,000
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
2010
2012
2014
UV Radiation Ozone
Crypto outbreak
UV inactivates Crypto
WRF helped evaluate solutions to resolving cryptosporidium issues using ozone & UV reducing costs and improving effectiveness
TOTAL UV PROJECTS 51 TOTAL FUNDING Cash: $10,725,345 In-kind: $8,611,083 Total Value: $19,336,428
TOTAL OZONE PROJECTS 81TOTAL FUNDING Cash:$14,646,611 In-kind: $22,942,572 Total: $37,589,182
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Biological / Biofiltration Research ValueCash + In-kind Dollars
$0
$500,000
$1,000,000
$1,500,000
$2,000,000
$2,500,000
$3,000,000
$3,500,000
1985 1990 1995 2000 2005 2010 2015
Renewed interest –TC Program initially, Focus Area 20091) Strong removal of organics + micro-constituents,
EDCs 2) Cost
TOTAL BIOFILTRATION PROJECTS 51TOTAL FUNDING: Cash: $12,530,127 In-kind: $11,489,194 Total: $24,019,320
2012 – BiofiltrationKnowledge Base (#4459)
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Treatment Projects Published in 2016
• Optimizing Filter Conditions for Improved Manganese Control During Conversion to Biofiltration – 4448
• Full-Scale Engineered Biofiltration Evaluation and Development of a Performance Tracking Tool - 4525
• Chemically Enhanced Biological Filtration to Enhance Water Quality and Minimize Costs - 4429
• Biological Oxidation Filtration for the Removal of Ammonia from Groundwater –4574
• Nitrosamine Occurrence Survey - 4461 • Investigating Coagulant Aid Alternatives to
PolyDADMAC Polymers – 4452• Seasonal Changes in NDMA Formation Potential and its
Removal During Water Treatment - 4444
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Algae Issues
• Seasonal algae blooms present many problems for water utilities— Depleted oxygen— Turbidity— Taste and Odor
• Cyanobacteria— “Blue-green” algae— Not quite algae, not quite bacteria
▪ Photosynthetic but lack well-defined nucleus— Responsible for Taste and Odor compounds— Create and may release toxic compounds
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Guidance to Utilities
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Health Related Guidelines
Cyanotoxin Guidelines
Microcystins USEPA10-day Health AdvisoryTotal microcystins
• 0.3 μg/L for children younger than school age• 1.6 μg/L f or all other age groups
• 1.0 µg/L for MCLR in drinking water (WHO)
Cylindrospermopsin
10-day Health Advisory for cylindrospermopsin
• 0.7 μg/L for children younger than school a• 3.0 μg/L for all oth1er age groups
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WHOMicrocystins: 1.0 ug L-1
Czech Republic, France, Japan, Norway, Poland,
Spain
20-100,000 cells ml-1
20.0 ug L-1
Australia, France, Germany, and the Netherlands
AustraliaMicrocystins:Cylindrospermopsin:PST’s (Saxitoxin):Anatoxin-a
6,500 cell ml-1
1.3 ug L-1
1.0 ug L-1 *
3.0 ug L-1
12.0 ug L-1 *
20,000 cells ml-1
10-20.0 ug L-1*
Australia also has a livestock consumption value
Brazil (MAV)Microcystins:Cylindrospermopsin:PST’s (Saxitoxin):
10,000 cells ml-1
1.0 ug L-1
15.0 ug L-1
3.0 ug L-1
CanadaMicrocystins: 1.5 ug L-1
New Zealand (MAV)Microcystins:Cylindrospermopsin:PST’s (Saxitoxin):Anatoxin-aAnatoxin-a(S)
1.0 ug L-1
1.0 ug L-1
3.0 ug L-1
6.0 ug L-1
1.0 ug L-1
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LOCATION DRINKING WATER RECREATION
REGULATORY LEVELS
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OCCURRENCE IN THE U.S.
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GENERA & TOXINS
Microcystis Oscillatoria Cylindrospermopsis
Anabaena Planktothorix
Aphanizomenon
Nodularia Lyngbya
MicrocystinAnatoxin
CylindrospermospinSaxitoxin
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A Day in the Life of Anabaena
© 2014 Water Research Foundation Foundation. All Rights Reserved.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Ecology of CyanobacteriaWhat is so special?
• Cyanobacteria have gas vesicles— cellular gas-filled hollow protein structures
• Buoyancy can be regulated — A balance of carbohydrate ballast, protein and gas vesicle
volume - determines vertical migration— Allows access light (at surface) and nutrients (at depth)
• Cyanobacteria can dominate in conditions of stratified water— low wind and high solar radiation— low flow in rivers ⇒ stratification
• Buoyancy can provide a competitive advantageover other phytoplankton
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Inside & Out
Intracellular-Toxins are with in the cell.Amenable to physical removal
Extracellular-Toxins are outside the cell.Amenable to chemical oxidation, Absorption, or filtration
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MOLECULAR SIZESInternational Guidance Manual for the Management of Toxic Cyanobacteria-(3148) Dr.
Gayle Newcombe SA Water Corporation
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
2015 WRF WorkshopsTake Home Messages
• Assess your system vulnerability• Identify source water treatment capabilities
Know your system
• Source water monitoring• Early warning program• Analytical capabilities• Treatment capabilities
Be technically prepared
• With the public• With the press
Be ready to communicate
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Monitoring and Management
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Alert Level Framework
Based on Australian work (Du Preez 2006, Newcombe 2011)
Monitoring requirements based upon “Alert Level” 5 levels of Alert Move between levels by exceeding monitoring
thresholds Example (based on historical levels at BJWSA) Note: Trigger levels are “floating” and need to
be adjusted based on site conditions.
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Alert Level Framework Overview
Lower1 Middle2 Upper3
Routine > 50,000 cells/mL algae count, elevate to Action Level 1
Biweekly Algae and
Cyanobacteria
Biweekly Algae and Monthly
Cyanobacteria
Monthly Algae and
Cyanobacteria
Weekly Algae and
Cyanobacteria
Biweekly Algae and
Cyanobacteria
Biweekly Algae and Monthly
Cyanobacteria
Weekly Cyanotoxin and MIB/geosmin at problem location2x/week Algae
and Cyanobacteria
Weekly Algae and
Cyanobacteria
Biweekly Algae Cyanobacteria
2x/week Cyanotoxin and MIB/geosmin in
raw and at problem location
Weekly Cyanotoxin and MIB/geosmin at problem location
Biweekly Cyanotoxin and MIB/geosmin at problem location
Action Level 3
Monitor until: algae count < 200,000 cells/mLCyanotoxins < 1 ppbMIB/geosmin < 10 ppt
Monthly Cyanotoxins at raw and problem location
Action Level 1
> 100,000 cells/mL algae count, elevate to Action Level 2> ? cells/mL Cyanobacteria, elevate to Action Level 2> 0.3 ppb Cyanotoxin, elevate to Action Level 2
Biweekly Cyanotoxin and MIB/geosmin at problem location
> 200,000 cells/mL algae count, elevate to Action Level 3> ? cells/mL Cyanobacteria, elevate to Action Level 3> 1 ppb cyanotoxin, elevate to Action Level 3>10 ppt MIB/geosmin, elevate to Action Level 3
Action Level 2
Sampling RequirementsAction Level
Action Setpoints
Monthly sampling for algae, nutrients, etc
In-town Reservoirs
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Analytical Challenges• Sample collection/characterization
• Representative sampling location & frequency
• Biomass not uniformly distributed in the sample – cell count
• Chlorophyl-a – pigment can be complicated by other pigments
• Phycocyanin fluorescence
• ELISA
• Kits differ by vendor
• Calibration curve not linear
• Interferences from similar compounds
* ADDA compound measures all congeners
• LC/MS/MS• Analytical standards not available for all variants
• No standardized methods currently available
• Round-robin comparison of different methods needed
• Matrix interferences may affect recovery
• Takes longer and is more costly
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27
Post 2004 Bloom - MWRA Improvements to Response
Program • Monitoring
—Purchased FlowCAM to aid with monitoring and enumeration of algae
• Treatment—Purchased new boat and fabricated
improved depth injection system to apply copper sulfate. Boat equipped with GPS
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ELISA versus LC/MS/MS
ELISA LC/MS/MS
Characteristics Measure groups of variants
Measure individual variants
Quantitation Semi-quantitative QuantitativeSample volume <0.5 ml <0.5 ml
MRL 0.15 µg/L 0.1 µg/LTurn-around time Fast Depends
Instrumentation Inexpensive Expensive
Level of expertise Low HighOther(source: Dr. Andy Eaton, Eurofins)
Kits available commercially
EPA Methods 544/545 (Microcystins/ (Cylindrospermopsin)
Screening Confirmatory
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
0
25
50
75
100
Sele
ctiv
ity
Sensitivity
Physico-chemical
Selectivity and Sensitivity Relationships between Analytical Methods for Microcystins
ug ng pg
NMR
TLC
Bioassay
LC/MS
HPLC
ELISAPPIA
Biological andbiochemical
Sensitivity for Microcystin
Methods
MethodSensitivityHPLC 100 ngLC/MS 1 ngLC/MS/MS <10 pgELISA 10 pg
Chart source: Andy Eaton, Eurofins
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
So What’s WRF Doing?
• Performance Evaluation of ELISA Methods for the Analysis of Cyanotoxins (#4647)• identifying all factors that impact results of ELISA
methods• testing whether presence of finished water
byproducts interfere with ELISA results
• CyanoTOX Field Validation (#4672)• wider range of pH conditions and CT
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
WRA Partnership #4315/#4523
• Optimizing Conventional Treatment for Removal of Cyanobacteria and their Metabolites (#4315)
• Management of Treatment Sludge Impacted by Cyanobacteria (#4523)
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Key interim Results of #4523
• Once captured in the sludge, cyanobacteria can remain viable (and possibly multiply) over a period of at least 2-3 weeks
• Toxin release from sludge can be up to 5 times the initial concentration.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Cyanotoxin Utility Action Guide and Research Needs (#4548)
• Phase II: Managing Cyanotoxins in Drinking Water: A Technical Guidance Manual for Drinking Water Practitioners
• publishedSeptember 2016Co-funded w/ AWWA & WRFPI – Hazen & Sawyer
Phase I – Manager’s Guide
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Intracellular Cyanotoxins Removal (Intact Cells)
General Rule:Avoid pre-oxidation that
lyses cells
Removing intact cells is: 1) more cost effective than chemical inactivation2) removes higher fraction of DBP precursors3) removes higher fraction of intracellular T&O
compounds4) easier to monitor removal
Coagulation/Sedimentation/Filtration
Effective for removal of intracellular/particulate toxins.
MembranesMF and UF effective at removing intracellular/particulate toxins. Typically, pretreatment used.
FlotationFlotation processes, like DAF, effective for removal of intracellular cyanotoxins since many of the toxin-forming cyanobacteria are buoyant.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Extracellular Cyanotoxins Removal
MembranesTypically, NF has a molecular weight cut off of 200 to 2000 Daltons; individual membranes must be piloted to verify toxin removal. RO is effective.
Potassium PermanganateEffective for oxidizing microcystins and anatoxins. Not effective for cylindrospermopsin and saxitoxins.
OzoneVery effective for oxidizing microcystin, anatoxin-a and cylindrospermopsin.
Chloramines Not effective.
Chlorine dioxideNot effective at doses typically used for drinking water treatment.
ChlorinationEffective for oxidizing extracellular toxins as long as the pH < 8, ineffective for anatoxin-a.
UV RadiationEffective at degrading extracellular toxins, but at impractically high doses.
Activated Carbon
PAC/GAC: Most types generally effective for removal of microcystin, anatoxin-a, saxitoxins and cylindrospermopsin. Mesoporous carbon for microcystin and cylindrospermopsin.
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Take Home Messages
• Assess your system vulnerability• Identify source water treatment capabilities
Know your system
• Source water monitoring• Early warning program• Analytical capabilities• Treatment capabilities
Be technically prepared
• With the public• With the press
Be ready to communicate
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Spreadsheets and Protocols Developed
• Oxidation—Hazen Adams CyanoTOX – Calculator for
prediction oxidative removal of extracellular toxins
—Protocol for applying CyanoTOX• Sorption
—AWWA PAC Calculator for Cyanotoxin Removal—Protocol for applying PAC Calculator
• All are downloadable for free from http://www.awwa.org/resources-tools/water-knowledge/cyanotoxins.aspx
© 2016 Water Research Foundation. ALL RIGHTS RESERVED.
Advancing the science of water to improve the quality of life
Water Research Foundation
Kim Linton, Regional [email protected]
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