Current Research Initiatives Cyanotoxins, Lead, Etc. · Water Quality and Minimize Costs - 4429 •...

© 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


WRF 101• Research Cooperative

• Governed by utilities

• Over $500M of research

• ~1,000 subscribers



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


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


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


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


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)


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


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



Guidance to Utilities


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


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

15

LOCATION DRINKING WATER RECREATION

REGULATORY LEVELS


OCCURRENCE IN THE U.S.


GENERA & TOXINS

Microcystis Oscillatoria Cylindrospermopsis

Anabaena Planktothorix

Aphanizomenon

Nodularia Lyngbya

MicrocystinAnatoxin

CylindrospermospinSaxitoxin


A Day in the Life of Anabaena

© 2014 Water Research Foundation 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


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


MOLECULAR SIZESInternational Guidance Manual for the Management of Toxic Cyanobacteria-(3148) Dr.

Gayle Newcombe SA Water Corporation


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


Monitoring and Management


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.


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


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


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


28


29


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


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


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


WRA Partnership #4315/#4523

• Optimizing Conventional Treatment for Removal of Cyanobacteria and their Metabolites (#4315)

• Management of Treatment Sludge Impacted by Cyanobacteria (#4523)


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.


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


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.


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.


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


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

http://www.awwa.org/resources-tools/water-knowledge/cyanotoxins.aspx


Advancing the science of water to improve the quality of life

Water Research Foundation

Kim Linton, Regional [email protected]

Waterrf.org

mailto:[email protected]

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Current Research Initiatives Cyanotoxins, Lead, Etc. · Water Quality and Minimize Costs - 4429 •...

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