© 2014 Water Research Foundation. ALL RIGHTS RESERVED. © 2014 Water Research Foundation. ALL RIGHTS RESERVED. No part of this presentation may be copied, reproduced, or otherwise utilized without permission.

WRF Webcast

Managing and Mitigating Cyanotoxins

in Water Supplies

August 28, 2014

© 2014 Water Research Foundation. ALL RIGHTS RESERVED. 2

WRF Reports

• International Guidance Manual for the Management of Toxic Cyanobacteria

• Cyanobacterial (Blue-Green Algal) Toxins: A Resource Guide

• Determination and Significance of Emerging Algal Toxins

• Assessment of Blue-Green Algal Toxins in Raw and Finished Drinking Water

• Development of Molecular Reporters for Monitoring Microcystis Activity and Toxicity

• Early Detection of Cyanobacterial Toxins Using Genetic Methods

• Rapid Concentration and Detection of Microcystin and Other Cyanobacterial By-

Products in Drinking Water

• Methods for Measuring Toxins in Finished Water

• Treatability of Algal Toxins Using Oxidation, Adsorption, and Membrane Technologies

(Reservoir Management Strategies for the Control and Degradation of Algal Toxins

• Removal of Algal Toxins from Drinking Water Using Ozone and GAC

• Evaluation of Integrated Membranes for Taste and Odor and Algal Toxin Control

• Release of Intracellular Metabolites from Cyanobacteria During Oxidation Processes

© 2014 Water Research Foundation. ALL RIGHTS RESERVED. 3

On-Going WRF Projects

• Optimizing Conventional Treatment for Removal of

Cyanobacteria and Toxins (Project 4315)

• Management of Treatment Sludge Impacted by

Cyanobacteria (Project 4523)

• Treatment of Algal Toxins in Rivers and River-Influenced

Groundwater (Project 4526)

© 2014 Water Research Foundation. ALL RIGHTS RESERVED. 4

Cyanotoxin Utility Action Guides and

Research Needs

• AWWA /WITAF Project #270 (Adam Carpenter)

• Water Research Foundation Project #4548 (Djanette Khiari)

• Research team

• The Cadmus Group (K. Sklenar, lead)

• Tamarack Environmental Laboratories (J. Westrick, lead)

• PAC members: Ric De Leon (MWDSC), Keith Cartnick (United

Water), and Joe Nattress (CH2M)

• Project period is March - November 2014

© 2014 Water Research Foundation. ALL RIGHTS RESERVED. 5

Cyanotoxin Utility Action Guides and

Research Needs - Products

1) Guide for water utility managers to determine • if cyanotoxins may be an issue for their systems

• what are the initial steps to consider

2) More detailed actionable literature synopsis for

utility personnel and consultants

3) Identify data gaps important for cyanotoxin risk

management in drinking water supplies

© 2014 Water Research Foundation. ALL RIGHTS RESERVED. 6

WRF State of Science:

Managing Cyanotoxins

waterrf.org/sos

Engage in the Twitter Conversation

#cyanotoxins

Cyanotoxins and Drinking Water

Karen S. Sklenar, Ph.D., The Cadmus Group Judy Westrick, Ph.D., Wayne State University David Szlag, Ph.D., Oakland University

Cyanotoxins and Drinking Water

1. Understand the Problem

2. Know What Tools are Available

3. Plan How to Manage a Cyanotoxin Event

1. Understand the Problem

• Occurrence

• Toxicology

• Guidelines and Regulations

Microcystin Occurrence

1. Understand the Problem

Anatoxin Occurrence

Cylindrospermopsin Occurrence

Cyanotoxin Occurrence Recreational waters v. Potable water supplies

From WHO document Toxic Cyanobacteria in Water: A guide to their public health consequences, monitoring and management.

The World Health Organization (WHO) drinking water guideline for Microcystin LR is 1 µg/L (in finished water).

How was the guideline developed?

Tolerant Daily Intake (TDI, WHO) and Reference Dose (RfD, USEPA) uses the No Observed Adverse Effect Level (NOAEL).

Safety Factors = interspecies, intraspecies, and others (usually 1000x) Regional Difference = average body weight, how much people drink For detailed information, see Ch. 4 of the WHO document Toxic Cyanobacteria in

Water: A guide to their public health consequences, monitoring and management.

LD50

RfD = (NOAEL) safety factors

Guideline Value = (TDI or RfD)(body weight)(portion) L

Are cyanotoxins regulated in drinking water? What levels of toxins are of concern?

• No federal standards for cyanobacteria/cyanotoxins in drinking water • Safe Drinking Water Act (SDWA) requires EPA to publish list of unregulated

contaminants present or expected to be detected in public water systems • Contaminant Candidate List (CCL) • EPA uses CCL to prioritize research to determine if contaminant has

sufficient data to meet regulatory determination criteria specified in SDWA

• As of 2012, three cyanotoxins are listed on the CCL 3: • anatoxin-a • microcystin-LR • cylindrospermopsin

2014 Association of State Drinking Water Administrators (ASDWA) Survey - Preliminary

Results

• 34 states, Navajo Nation and Quebec responded. Of the 34 states, 5 states have drinking water advisory thresholds for microcystin 2 states have drinking water advisory thresholds for other cyanotoxins 6 states have harmful algal bloom response programs/policies addressing

impacts to public drinking water supplies 4 additional states have draft policies 8 more are discussing drafting policies

Information about individual state programs can be found at the following web link: http://www.asdwa.org/index.cfm?fuseaction=Page.viewPage&pageId=646&grandparentID=473&parentID=523&nodeID=1 .

State Microcystin Anatoxin A Cylindrospermopsin Saxitoxin

Florida 10 µg/L, based on Microcystin-

LR only

None None None

Ohio 1 µg/L, based on Microcystin-LR

but meant to include all

microcystin congeners

20 µg/L 1 µg/L 0.2 µg/L

Oklahoma 1 µg/L with a goal of non-detect,

based on all microcystin

congeners

None None None

Oregon Microcystin should be below 1

µg/L in finished water,

otherwise a DO NOT

DRINK public notice will be

posted. Based on all microcystin

congeners

3 µg/L 1 µg/L 3 µg/L

Minnesota 0.04 µg/L, based on Microcystin-

LR but meant to include all

microcystin congeners

None None None

Quebec 1.5 µg/L expressed as

Microcystin-LR toxic equivalents

including congeners LA, RR, YR,

and YM

3.7 µg/L1 None None

Cyanotoxin Drinking Water Advisory Thresholds

1 Canadian drinking water advisory threshold Source: Survey of state drinking water administrators conducted by the Association of State Drinking Water Administrators (ASDWA), D. Mason correspondence

2. Know What Tools are Available

• Analytical

• Source Water Management

• Treatment

• Public Outreach and Risk Communication

0

25

50

75

100

Sele

cti

vit

y

Sensitivity

Physico-chemical

Selectivity and Sensitivity Relationships between Analytical Methods for Microcystins

u g ng pg

NMR

TLC

Bioassay

LC/MS

HPLC

ELISA

PPIA

Biological and

biochemical

l

2. Know Tools Available

ELISA – A Screening Tool

• Why are ELISA

assays only a

screening tool?

– Nonlinear standard

curve

– Cross reactivity

– Not measuring the

cyanotoxin directly

2. Know Tools Available

Separation of the Cyanotoxins by HPLC-PDA

AU

5.00 15.0 25.0 35.0 45.0 55.0

Minutes

CY

C -

6.1

95

MC

Y-L

R –

17

.46

4

MC

Y-L

A –

23

.68

8

MC

Y-L

W –

28

.73

9

MC

Y-L

F –

29

.52

8

MC

Y-R

R –

14

.56

5

AN

A -

9.9

79

Gradient

0.12

0.08

0.04

0.20

0.16

0.24

0.00

Toxic cyanobacteria in water 1999

2. Know Tools Available

Time 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50

%

0

100

8.52

m/z 200 300 400 500 600 700 800 900 1000 1100

%

0

100

%

0

100 2: Scan ES+

2.49e6 995.50

126.98 861.44 213.13

996.47

997.54

LR_8201b 1567 (23.689) Cm (1565:1571-1585:1610) 1: Scan ES+ 2.50e6 482.43

135.06

265.15

995.53

861.45 498.47 862.37 996.45

M+H+

1=Cylindrospermopsin, 2=Anatoxin-a, 3=Cyclo (Arg-Ala-Asp-D-Phe-Val) (IStd), 4=[Leu5]-

Enkephalin (IStd), 5= Microcystin RR, 6=Nodularin, 7=Microcystin YR, 8=Microcystin LR,

9=Microcystin LA, 10=Microcystin LY, 11=Microcystin LW, and 12=Microcystin LF

UPLC/MS/MS Chromatograph

2. Know Tools Available

Nutrient Load Water Temperature Flow Thermal Stratification Rainfall

Monitoring Type Parameters/Variables Demands on equipment Who

Basic Minimal

Site inspection for

indicators of toxic

cyanobacteria in

waterbody

Transparency, discoloration,

scum formation, detached mat

accumulation

Secchi disc, regular site inspection by trained

staff; basic skill requirement, training easily

provided

Operators

Practitioners

Surrogates Low to moderate

Potential for

cyanotoxin problems

in waterbody

Total phosphorus, nitrate and

ammonia, flow regime, thermal

stratification, transparency,

cholorphyll

Photometer, boat, depth sampler, Secchi

disc, submersible temperature/oxygen

probe; basic skills but requires specific

training and supervision

Limnologist

Cyanobacteria Low to moderate

In waterbody and

drinking water

Dominant taxa (quantity):

determination to genus level

only is often sufficient;

quantification only as precise as

needed for management

Microscope, photometer is useful; specific

training and supervision is required, but

quite easily achieved

Phycologist -

trained by

phycologist

Cyanotoxins Moderate to High

In waterbody and

drinking water

microcystis, anatoxin-a,

cylindrospermopin, saxitoxin

ELISA kits (moderate); LC/PDA (moderately

high); LC/MS (high)

Chemist

Source Water Monitoring Approaches

Control Nutrient Input Mix It Up!

Keep It Moving!

U.S. FWS Photo

Copper Sulfate Application

Does it make an algal toxin problem better or worse?

Good Monitoring Program + Different Intake Depths/Locations = Good Reservoir Management

Conventional Filtration

Treatment Process

Relative Effectiveness

Intracellular Cyanotoxins Removal (Intact Cells)

Pretreatment oxidation

Avoid pre-oxidation that lyses cells; removing intact cells is: 1) more cost effective than

chemical inactivation/degradation; 2) removes a higher fraction of DBP precursors; 3)

removes a higher fraction of intracellular taste and odor compounds; and 4) it is easier to

monitor removal.

Coagulation/Sedimentation/Filtration Effective for the removal of intracellular/particulate toxins.

Membranes Microfiltration and ultrafiltration are effective at removing intracellular/particulate toxins.

Typically, pretreatment is used.

Flotation Flotation processes, such as Dissolved Air Flotation (DAF), are effective for removal of

intracellular cyanotoxins since many of the toxin-forming cyanobacteria are buoyant.

Treatment Process

Relative Effectiveness

Extracellular Cyanotoxins Removal

Membranes

Typically, nanofiltration has a molecular weight cut off of 200 to 2000 Daltons;

individual membranes must be piloted to verify toxin removal. Anatoxin-a has a

molecular weight of 165 Daltons. Reverse osmosis is effective.

Potassium Permanganate Effective for oxidizing microcystins and anatoxins. Not effective for

cylindrospermopsin and saxitoxins.

Ozone Very effective for oxidizing extracellular microcystin, anatoxin-a and

cylindrospermopsin.

Chloramines Not effective.

Chlorine dioxide Not effective with doses typically used for drinking water treatment.

Chlorination Effective for oxidizing extracellular cyanotoxins as long as the pH is below 8,

ineffective for anatoxin-a.

UV Radiation Effective at degrading toxins but at impractically high doses.

Activated Carbon

PAC/GAC: Most types are generally effective for removal of microcystin, anatoxin-

a, saxitoxins and cylindrospermopsin. Because adsorption varies by carbon type

and source water chemistry, each application is unique; activated carbons must

be tested to determine effectiveness. Mesoporous carbon for microcystin and

cylindrospermopsin. Microporous carbon for anatoxin-a.

Public Outreach and Communication Before Event – Preparing for an Advisory • Consider timing, audience(s), channels, messages, approval procedures • Collaborate with Partners • Develop Message • Conduct Exercises During Event – Issuing an Advisory Implement established procedures for • Initiating an Advisory • Distributing an Advisory • Ending an Advisory After Event – Evaluating an Advisory • Reporting Requirements • Debrief Event • Conduct an Evaluation • Modify SOPs • Update Public Outreach Procedure

State Webpage Title Web Link

California Blue-Green Algae (Cyanobacteria)

Blooms

http://www.cdph.ca.gov/healthinfo/enviro

nhealth/water/pages/bluegreenalgae.aspx

Illinois Harmful Algal Blooms (HABs) and

Algal Toxins

http://www.epa.state.il.us/water/algal-

bloom/index.html

Indiana Addressing Concerns About Blue-

Green Algae http://www.in.gov/idem/algae/

Maryland Harmful Algae Blooms in Maryland http://www.dnr.state.md.us/bay/hab/index

.html

Massachusetts

Algae Information http://www.mass.gov/eohhs/gov/departm

ents/dph/programs/environmental-

health/exposure-topics/beaches-

algae/algae-information.html

Nebraska 2013 Toxic Blue-green Algae and

Bacteria Sampling Results

http://www.deq.state.ne.us/Beaches.nsf/La

keSampling13

New Hampshire Recreational Exposure to

Cyanobacteria (Blue-Green Algae)

http://des.nh.gov/organization/divisions/

water/wmb/beaches/cyano_bacteria.htm

Ohio Harmful Algal Blooms: Information

for Public Water Systems

http://epa.ohio.gov/ddagw/HAB.aspx

Oregon

Algae Resources for Drinking Water http://public.health.oregon.gov/HealthyEn

vironments/DrinkingWater/Operations/Tr

eatment/Pages/algae.aspx

Vermont Cyanobacteria: Blue Green Algae http://healthvermont.gov/enviro/bg_algae/

bgalgae.aspx

Washington

Blue-Green Algae http://www.doh.wa.gov/CommunityandE

nvironment/Contaminants/BlueGreenAlga

e.aspx

www.asdwa.org/habs

Quick Self-Assessment Step 1: How Vulnerable is Your Water Utility to a

Cyanotoxin Problem?

• Utilities can ask themselves questions to gauge whether they should be preparing for possible cyanotoxin problems.

• This brief assessment considers three categories: o source water monitoring o source water quality o cyanobacteria present during the treatment process.

• If utility answers at least one question in each category in the “high” or “medium” column, they are encouraged to be proactive.

High Medium Low None

Source Water Monitoring

Do you have a source water

monitoring program in place?

Don’t monitor our

source water before

treatment

Test our water some

(e.g., turbidity, total

organic carbon) as it

enters treatment

plant

Monitor source water

monthly (e.g.,

chlorophyll a, algae

counts) at different

depths and locations

Have a comprehensive

source water

monitoring program,

sampling at least

weekly at different

depths, locations

Does your source water quality

monitoring program evaluate

changes over the year?

No No Yes, tracks monthly

water quality trends

(e.g. to help us decide

which source(s) to

use)

Yes, tracks trends at

least weekly of all

monitored parameters

Do you track changes by

comparing water quality data

from year to year?

No No Yes, seasonal or

annual averages are

tracked and

compared

Yes, charts are created

with monthly data for

at least the last five

years

Quick Self-Assessment Step 1: How Vulnerable is Your Water Utility to a Cyanotoxin Problem?

Quick Self-Assessment Step 1: How Vulnerable is Your Water Utility to a Cyanotoxin Problem?

High Medium Low None

Source Water Quality and Aesthetics

Do you have algae growth in

your source water?

Yes, we have blooms

and add copper sulfate

regularly

Yes but we don’t have

to adjust treatment in

response

We have minor algae

growth but no

visually obvious

blooms

Very minimal, if any,

growth

Does your source water stratify

thermally in the summer?

Yes, strong thermocline

and turnover in late

summer/fall with

noticeable water quality

changes

Stratifies but no

noticeable changes in

water quality with

turnover

Stratifies some during

the day but mixes at

night

No

Is your surface water source

affected by drought?

Yes water level drops,

water is warmer due to

drought conditions

Water level drops a

small amount, no

water temperature

increases

No No

Does your water look green or

blue-green?

Yes, the color of our

reservoir changes

noticeably

Slightly No No

Quick Self-Assessment Step 1: How Vulnerable is Your Water Utility to a Cyanotoxin Problem?

High Medium Low None

Cyanobacteria in the Treatment Process

Do you have treatment

processes that are exposed to

sunlight?

Yes, most of our unit

processes are outdoors

and uncovered

Yes at least one of

our unit processes is

exposed to sunlight

No No

Is your filter backwash green?

Yes, frequently Yes, periodically No No

Do you have taste and odor

problems?

Yes we frequently get

complaints during the

summer

Yes we periodically

get complaints

Once every few years No

Are your basins regularly

cleaned?

No, never Maybe once every

few years

At least once a year More than once a year

Quick Self-Assessment Step 2:

How Many Tools Are In Your Toolbox?

Helps utilities determine if they have effective measures

in place to

1. Control cyanobacteria growth and/or treat water for

cyanobacteria and cyanotoxins

2. Reliably use an alternative supply

3. Communicate effectively with consumers and the

public health community

Yes

No

If yes, has the measure been

evaluated for addressing cyanotoxins?

Water Quality Management/Treatment Algae reduction tools for source (e.g. raw) water supply, including

Enhanced circulation/mixing

Chemical addition (e.g. copper sulfate, chlorine)

Ultrasound

Other

Ability to select from different intakes, both in terms of depths/locations and time

(i.e. being able to switch intakes without delay or much effort)

Intake Inline Chemical Addition

Permanganate

Chlorine

Chlorine dioxide

Other

Conventional Treatment

Membrane Filtration

Oxidative Processes (being used for DBP precursor removal, taste and odor control,

or other chemical contaminant removal)

Ozone

Peroxide

Other

Disinfection Processes

Activated Carbon (powdered or granular) or other adsorptive media

Biological Activity

Quick Self-Assessment Step 2:

How Many Tools Are In Your Toolbox?

Yes No If yes, has the measure been

evaluated for addressing

cyanotoxins?

Supplying Water

Can provide enough treated water to all consumers with surface water

supply out of service for a week. If yes, would not feel restricted by the

cost of using or treating the alternative supply at least once a year.

Communicating with the Public

Well-organized, exercised public notification program

Established communication network with the local public health and

medical community

Quick Self-Assessment Step 2:

How Many Tools Are In Your Toolbox?

3. Plan How to Manage a Cyanotoxin Event

Be technically prepared • Catch the bloom as early as possible • Know how to manage source and adjust

treatment Be ready to communicate • With the public • With the press

Catch the bloom as early as possible • Identify early indicators (e.g. pH, water temperature,

Secchi disk depth, location/extent of thermocline) • Define monitoring trigger levels • Identify action thresholds that tie source water

monitoring to operational decisions

3. Plan How to Manage

Species Action Level

Microcystis spp. 2,000 cells/mL

Combination of all potentially toxic cyanobacteria spp. Present

15,000 cells/mL

WHO Cyanobacteria Cell Count Action Levels that Trigger Toxin Sampling for Drinking Water

Early Warning Systems

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

Alg

al

Un

its

/mL

Date

Taste and Odor

Toxin

Filter Cloggers

PollutionIndicators

Total Algae

Courtesy of Ric DeLeon, Metropolitan Water District of Southern California

Intake Avoidance/Management Strategies: • Multiple sources • Different depths • Blending sources

Pretreatment Strategy: • Do not lyse cells • PAC adsorbs dissolved

cyanotoxins • Oxidants can lyse or make

cells leaky

Coagulation/Sedimentation Strategy: • Remove intact cells if you can • Low pH (< 6.3) can increase release of cyanotoxins • < 100 cell/mL onto filters • Sweep coagulation may be a consideration to remove

floating colonies • Optimize treatment using a cyanobacteria surrogate

(phycocyanin, cell counts, chlorophyll, particle counts, streaming current)

Filtration Removal Strategy: • Standard sand, anthracite, multimedia that meet state standards are

effective at removing cyanobacteria cells • GAC may be biologically active; media becomes spent within weeks • If possible, do not recycle filter backwash, sludge supernatant, etc. during

a cyanobacterial bloom

Clearwell Disinfection Strategy:

Ozone Very effective for oxidizing extracellular microcystin, anatoxin-a

and cylindrospermopsin.

Chloramines Not effective.

Chlorine dioxide Not effective with doses typically used for drinking water

treatment.

Chlorine

Effective for oxidizing extracellular microcystin and

cylindrospermopsin, however it is highly pH and temperature

dependent, ineffective for anatoxin-a.

UV Radiation Not effective at doses typically used for disinfection.

Chlorine CT values for reducing 90% of the microcystin concentration (1 log removal)

(compiled from information presented in Acero et al. 2005)

1. Determine how the

microcystin is distributed.

2. Dissolved microcystin. 3. Particulate microcystin over 2 log removal.

4. Monitor cyanobacteria

surrogate

5. 100 cells/ml

6. Biological Active

7. Dissolved microcystin:

Chlorine - variables

Be Ready to Communicate

DO NOT DRINK WATER ADVISORY

IMPORTANT INFORMATION ABOUT YOUR DRINKING WATER

[System] Has Levels of Algae toxin Above Drinking Water acute toxicity values

(Water System Name) routinely monitors for the presence of contaminants in our finished drinking

water that is provided through our treatment and distribution system. Our water system recently

exceeded the Oregon Health Authority’s acute toxicity value for a cyanotoxin[ toxin detected, date

sampled and value detected] which is a by-product of certain algae species that naturally grow in

water. Although this is not currently a regulated contaminant, as our customers, you have a right to

know this acute toxicity value was exceeded, what you should do, and what we are doing to correct

this situation.

What should I do?

• Drinking water above the acute toxicity value of [x] ug/L of [toxin] is not advised. You may want to use an alternative (e.g., bottled) water supply. If you have specific health concerns, consult your doctor.

What does this mean?

Human health effects from cyanotoxins are diverse and may include skin rashes and lesions,

vomiting, gastroenteritis, conjunctivitis, headaches, eye, ear and throat irritations, abdominal cramps,

nausea, diarrhea, fever, sore throat or hay fever-like symptoms. [Long-term exposure to microcystin

can lead to damage to the liver, including cancer].

What is being done?

[Water system name] continues to work with [Insert Water Body Manager] to monitor and test the

algal bloom for harmful toxins. In addition [water system name] is adjusting their treatment process to

more successfully mitigate for the presence of cyanotoxins. Weekly testing will continue until toxin

levels are below the acute toxicity values.

For more information, please contact [name of contact] at [phone number] or [mailing address].

Please share this information with all the other people who drink this water, especially those who

may not have received this notice directly (for example, people in apartments, nursing homes,

schools, and businesses). You can do this by posting this notice in a public place or distributing

copies by hand or mail.

This notice is being sent to you by [system]. State Water System ID#: ___________. Date

distributed: ______

Emergency response plans should include communication strategies so authorized personnel can make quick decisions when needed.

Thank You - Questions?

A man of wisdom delights in water. - Confucius