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U.S. Environmental Protection Agency, Office of Research and Development Treatment Options For HABs Impacted Waters Nicholas Dugan, PE Tom Waters, PE Kansas HAB Meeting - Topeka KS January 22, 2020

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  • U.S. Environmental Protection Agency, Office of Research and Development

    Treatment OptionsFor

    HABs Impacted Waters

    Nicholas Dugan, PETom Waters, PE

    Kansas HAB Meeting - Topeka KS January 22, 2020

  • Outline

    A. Background and definitions

    B. Drinking water treatment options:

    i. Permanganate

    ii. Powdered activated carbon (PAC)

    iii. Coagulation/flocculation/sedimentation

    iv. Filtration

    v. Chlorination

    vi. UV/ozone/chlorine dioxide

    C. Analytical methods (if time and interest)

  • Background

    All water bodies contain suspended (planktonic) micro-organisms. They are an essential part of the aquatic food web and include single-cell phototrophic micro-organisms such as:oAlgae (eukaryotic)oCyanobacteria (prokaryotic)

    A harmful algal bloom (HAB) occurs when these micro-organisms multiply to the point that they disturb the baseline ecology of the water body If a bloom is caused by cyanobacteria, why is it called a “harmful algal

    bloom?”oPrior to the use of DNA sequencing, cyanobacteria were

    classified as “blue-green algae”oTerms such as “cyanobacteria” and “blue-green algae” are still

    used interchangeably

  • Background

    Why is a bloom potentially harmful?oUnpleasant appearanceoUnpleasant tastes and/or odorsoCyanobacterial toxinsoNegative impacts on aquatic food webo Increased difficulty in treating drinking water:

    • Maintenance & operation issues• Potential for exceeding health advisory toxin concentration

    values• Potential for loss of confidence in the quality of treated

    drinking water

    Water potentially unsuitable for body-contact recreation by

    humans and animals

  • Background

    Figure adapted from: Kamennaya, N.A., et al; Minerals 2012:2:338-364

    Dissolved CO2

    Complex organic compounds

    Not all cyanobacteria produce toxins In toxin-producing cyanobacteria – timing of toxin production can vary When toxins produced, they are usually contained within the cell membrane Sometimes toxins released from cells into solution

    All cyanobacteria contain light harvesting pigments:• Chlorophyll• Phycocyanin

  • Background

    Microcystin → liverCylindrospermopsin → kidneys & liver

    Anatoxin → central nervous system

  • Background

    IntracellularToxins contained inside the cell

    ExtracellularToxins in solution outside the cell

    CombinedExtracellular + intracellular toxin

    Water sample

  • Federal Finished Drinking Water Toxin Health Advisory Levels

    Toxin Children < 6 yearsChildren ≥ 6 years

    & adults

    Microcystin 0.3 1.6

    Cylindrospermopsin 0.7 3.0

    US EPA 10-day health advisory levels (µg/L)

  • Bloom Response: Iowa

    July 2016 – July 2017: conducted weekly raw water microcystin sampling at all surface water and GWUDI systems → no finished water detects in participating systems

    No ongoing monitoring requirements for surface water or GWUDI systems; a few systems are monitoring as they deem necessary

    2016 – 2017 study report: https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/files/Microcystin_Surveillance_Study_Report_of_Findings_6-2018.pdf

    Flowcharts from 2016 – 2017 study: https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/do

    cs/Microcystin_Flow_Chart.pdf https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/do

    cs/Cylindrospermopsin_Flow_Chart.pdf

    https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/files/Microcystin_Surveillance_Study_Report_of_Findings_6-2018.pdfhttps://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Microcystin_Flow_Chart.pdfhttps://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Cylindrospermopsin_Flow_Chart.pdf

  • Bloom Response: Missouri

    If a bloom is observed in the vicinity of the system intake → contact the state

    Conduct jar test or observe sample using microscope If positive for cyanobacteria → screen raw water using Abraxis test strips If screening test is: Positive, immediately conduct finished water screening, and contact

    the state. Additional treatment guidance will be provided as needed Negative, continue observing bloom

    If finished water screening is: Positive, contact the state, submit sample to state lab for confirmation,

    develop monitoring plan, additional response actions, and public notification in consultation with relevant agencies

    Negative, continue observing bloom, additional screening if warranted

  • Bloom Response: Kansas and Nebraska

    Kansas:o Raw water detect → contact the state → possibly increase

    monitoring frequency and PAC concentrations (if equipped) Nebraska:

    o Only 4 surface water systems in the stateo Proactively sampled raw water at SW and GWUDI systems in

    2018 & 2019o Utilizing 18/19 sampling results and approaches from other

    states to formalize 2020 sampling and response plan

  • Links to R7 State Response Information

    MO: https://dnr.mo.gov/env/esp/wqm/docs/HABDrinkingWaterSamplingProtocol.pdfIA:https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Microcystin_Flow_Chart.pdfIA:https://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Cylindrospermopsin_Flow_Chart.pdfKS: http://www.kdheks.gov/algae-illness/2019_Symposium/Rob_Gavin_2019-01-20_HAB_PWS_Response_Planning_and_Risk_Communication.pdf

    https://dnr.mo.gov/env/esp/wqm/docs/HABDrinkingWaterSamplingProtocol.pdfhttps://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Microcystin_Flow_Chart.pdfhttps://www.iowadnr.gov/Portals/idnr/uploads/water/wso/docs/Cylindrospermopsin_Flow_Chart.pdfhttp://www.kdheks.gov/algae-illness/2019_Symposium/Rob_Gavin_2019-01-20_HAB_PWS_Response_Planning_and_Risk_Communication.pdf

  • Conventional Surface Water Treatment

    Sedimentation

    Source Water

    Chlorine(Cl2)

    Permanganate(MnO4-)

    Powdered activated carbon

    (PAC)

    Coagulant

    Rapidmix Flocculation

    Filtration

    Chloramine(NH2Cl)

    Clearwell

    Distribution systemSludge

  • Permanganate

    Permanganate (MnO4-):oApplied early in the treatment process – often the 1st chemical

    addedoApplied as a sodium or potassium saltoTaste and odor controloDBP precursor controlo Iron and manganese controloControl of zebra mussels in intake structures o Induces oxidative stress in cyanobacterial cells → may lead to

    the release of toxins into solutionoOxidizes toxins released into solution

  • Permanganate – Reaction Rates

    Reaction rate constant (M-1s-1)

    10-1 100 101 102 103 104 105

    Cylindrospermopsin

    Microcystin

    Anatoxin

    Laboratory waterpH 7 - 820 - 22 C

    67 X faster

    1200 X faster

  • Permanganate – Reaction Rates

    • The permanganate/toxin reaction rate depends on the type of toxin: anatoxin >> microcystin >> cylindrospermopsin

    • The permanganate/toxin reaction rate will increase with increasing temperatures

    • Within the pH range of 7 – 9, the permanganate/toxin reaction rate does not change significantly with pH

    • Dissolved natural organic matter (NOM) and inorganic constituents such as iron and manganese can react with permanganate → possibility of competing reactions → potentially slower degradation of toxins

  • Time (minutes)

    0 20 40 60 80 100

    Cel

    ls w

    ith d

    amag

    ed m

    embr

    anes

    (Ct /

    Co)

    0

    2

    4

    6

    8

    10

    0

    2

    4

    6

    8

    10

    Dose = 1 mg/LDose = 2.5 mg/LDose = 5 mg/L

    Impact of KMnO4 on Cyanobacterial Cell Membrane Integrity

    Source: US Environmental Protection Agency

    Permanganate exposure increases the concentration of cells with membrane damage

  • Time (minutes)

    0 20 40 60 80 100

    Chl

    orop

    hyll

    (Ct /

    Co)

    0.5

    0.6

    0.7

    0.8

    0.9

    1.0

    1.1

    0.5

    0.6

    0.7

    0.8

    0.9

    1.0

    1.1

    Dose = 1 mg/LDose = 2.5 mg/LDose = 5 mg/L

    Impact of KMnO4 on Chlorophyll in Cyanobacterial Cells

    Source: US Environmental Protection Agency

    Permanganate exposure decreases chlorophyll concentrations inside cells

  • Time (minutes)

    0 20 40 60 80 100

    Extra

    cellu

    lar m

    icro

    cyst

    ins

    (Ct /

    Co)

    1

    10

    100

    1

    10

    100

    Dose = 1 mg/LDose = 2.5 mg/LDose = 5 mg/L

    Impact of KMnO4 on Toxin Release from Cyanobacterial Cells

    Source: US Environmental Protection Agency

    Permanganate exposure increases extracellular microcystin concentration

  • Operational Considerations for Permanganate Pre-Oxidation

    If possible, monitor for toxins in the treatment plant influent in addition to the source water:o Extracellular toxinso Extra + intracellular toxins (requires freeze/thawing of

    samples) The degree to which toxins exist as extracellular versus

    intracellular may drive treatment decisions

  • Operational Considerations for Permanganate Pre-Oxidation

    If primarily extracellular, continuing permanganate feed will not hurt and increasing the dose may help:o Consider site-specific considerations regarding

    production of colored watero Consider locations of permanganate and powdered

    activated carbon (PAC) application – PAC has the potential to adsorb toxins but also to neutralize permanganate

  • Operational Considerations for Permanganate Pre-Oxidation

    If significant intracellular toxins, have a contingency plan in place for temporarily suspending permanganate application:o Potential for color, taste & odor (T & O), DBP, or

    operational issues if permanganate is used for T & O, iron, DBP precursor, or color control

    o Be prepared to increase PAC dose and modify coagulation conditions to maximize removals of extracellular toxins and toxin-containing cells through coagulation, flocculation, and sedimentation

    o If possible, increase post-filtration chlorine dose

  • Conventional Surface Water Treatment

    Sedimentation

    Source Water

    Chlorine(Cl2)

    Permanganate(MnO4-)

    Powdered activated carbon

    (PAC)

    Coagulant

    Rapidmix Flocculation

    Filtration

    Chloramine(NH2Cl)

    Clearwell

    Distribution systemSludge

  • Background:Powdered Activated Carbon

    Powdered activated carbon (PAC):oTaste and odor controloSeasonal control of trace organics (herbicides, insecticides,

    etc.)oAdsorbs cyanobacterial toxins released into solutionoNeutralizes MnO4-

  • PAC Treatment

    PAC effectiveness depends on:o Type of carbon (wood, coconut,

    coal)o Type of cyanotoxin or other

    compounds to be adsorbedo Dose and contact timeo Natural organic matter (NOM)

    interference

    Micropores: < 2 nmMesopores: 2 - 50 nmMacropores: > 50 nm

    vs. microcystin-LR: 1-3 nm

  • Effectiveness of PAC in Natural Waters

    Toxin

    Toxin concentration

    (µg/L) PAC typePAC dose

    (mg/L)Contact time

    (min) % Removal

    MYC 5 ? 10 60 92

    MYC 22 ? 10 15 41

    MYC 22 Coal 10 60 30 – 60

    MYC 22 Coal 50 60 ≥ 90

    CYL 20 Coal 25 30 60 - > 90

    ANA 73 Coal 30 864* > 80

    * Approximately 14 hours

  • Impact of PAC Addition

    Source: US Environmental Protection Agency

  • Time (minutes)

    0 20 40 60 80 100

    Extra

    cellu

    lar t

    oxin

    con

    cent

    ratio

    n (

    g/L)

    0

    5

    10

    15

    20

    25

    Time (minutes)

    0 20 40 60 80 100

    Extra

    cellu

    lar t

    oxin

    con

    cent

    ratio

    n (

    g/L)

    0

    5

    10

    15

    20

    25

    With PACNo PAC

    – Carbon added after toxin release from cyanobacterial cells

    Impact of PAC Addition

    Source: US Environmental Protection Agency

  • Operational Considerations for PAC

    • Consider sufficient supply, storage space, and safety prior to HAB season

    • Consider operational impacts of adding PAC on sedimentation and filtration processes

    • More frequent sludge removal, higher volumes

    • Potential for filter clogging• Test higher PAC feed rates, if

    needed, prior to HAB season to evaluate potential for line clogging at higher doses

  • Conventional Surface Water Treatment

    Sedimentation

    Source Water

    Chlorine(Cl2)

    Permanganate(MnO4-)

    Powdered activated carbon

    (PAC)

    Coagulant

    Rapidmix Flocculation

    Filtration

    Chloramine(NH2Cl)

    Clearwell

    Distribution systemSludge

  • Background:Coagulation/Flocculation/Sedimentation

    Particulate removal (turbidity) DBP precursor removaloTo some degree when adding coagulant with primary goal of

    optimizing settled water turbidityoTo a greater degree when increasing coagulant dose and

    lowering pH in order to achieve enhanced coagulation Physical removal of Giardia cysts and Cryptosporidium oocysts Coagulant chemical addition destabilizes particles → particles

    remaining after sedimentation are more amenable to filtration Sedimentation basin provides contact time for PAC and

    permanganate Potentially effective barrier to the passage of cyanobacterial cells

  • Cell removal (%)0 10 20 30 40 50 60 70 80 90 100

    Cell Removals through Coagulation and Sedimentation

    Jar test, 65 mg/L alum2

    Pilot-scale, 70 mg/L alum2

    Full-scale, 150-220 mg/LPolyaluminum chloride1

    1Zamyadi et al; Species Dependence of Cyanobacteria Removal Efficiency by Different Drinking Water Treatment Processes; Water Research; 2013:47:2689-27002Drikas et al; Using Coagulation, Flocculation and Settling to Remove Toxic Cyanobacteria; Journal AWWA; 2001:93:2:100-111

  • Bench-Scale Coagulation Experiments with M. aeruginosa

    Water source/pH

    Dose necessary to achieve 80% removal of cells (mg/L)

    Aluminumchlorohydrate

    (ACH) Ferric chloride Aluminum sulfate

    Myponga Reservoir

    pH 7.5 – 7.8 40 40 60

    pH 6.3 20 40 60

    River Murray

    pH 7.2 – 7.6 20 40 80

    pH 6.3 20 20 60

    Myponga turbidity = 1.2 – 8.7 NTU, DOC = 10 – 12 mg/LMurray turbidity = 23 – 101 NTU, DOC = 5.3 - 17Source: Newcombe, G. et al; Optimizing Conventional Treatment for the Removal of Cyanobacteria and Toxins; Water Research Foundation, Denver CO; 2015

  • Toxin Removals through Pilot-Scale Coagulation, Sedimentation, and Filtration

    Microcystin-LR concentration(µg/L)

    Sample point Toxin type Trial 1 Trial 2

    Influent Combined 119 60

    Extracellular 3 2

    Effluent Combined 3 2

    Extracellular 3 2

    Source: Drikas et al; Using Coagulation, Flocculation and Settling to Remove Toxic Cyanobacteria; Journal AWWA; 2001:93:2:100-111

  • Microcystin-LR concentration(µg/L)

    Sample point Toxin type Trial 1 Trial 2

    Influent Combined 119 60

    Extracellular 3 2

    Effluent Combined 3 2

    Extracellular 3 2

    Source: Drikas et al; Using Coagulation, Flocculation and Settling to Remove Toxic Cyanobacteria; Journal AWWA; 2001:93:2:100-111

    Toxin Removals through Pilot-Scale Coagulation, Sedimentation, and Filtration

  • Cell Propagation through a Full-Scale Lake Erie Treatment Facility

    Raw

    Post

    MnO

    4

    Post

    PAC

    Filte

    r inf

    luen

    t

    Filte

    r effl

    uent

    Fini

    shed

    Chl

    orop

    hyll

    a (

    g/L)

    0.001

    0.01

    0.1

    1

    10

    100

    0.001

    0.01

    0.1

    1

    10

    100

    May 19July 1July 21

    Most of the cell removal work is accomplished prior to filtration

  • Physical Removal of Cells through Seven Full-Scale Lake Erie Facilities

    West East150 miles

    Each data point represents the average of 5 – 7 samples collected between May and October

  • Filtration of M. aeruginosaPilot-Scale Seeding Trial Results

    Coagulant

    Baseline filter loading rate

    (m/hr)

    Steady-state removal of

    chlorophyll-a(∆ log)

    Alum+

    cationic polymer

    7 2.8

    10 2.5

    Ferric chloride+

    cationic polymer

    7 2.9

    10 3.8

    • Average influent chlorophyll-a concentration = 26 µg/L (SD = 12 µg/L) • 1 m/hr = 0.41 gal/min•ft2

  • Jar Testing

    Optimizing coagulant and polymer dosing can maximize cell removal through the treatment process. This can be effectively evaluated in most plants using jar testing.

    To evaluate optimal coagulant and polymer dosing for cyanobacteria cell removal, the following parameters can be monitored:o Turbidityo NOMo Pigments (chlorophyll-a, phycocyanin)o Coloro UV254o Particle countso Streaming current or zeta potential

  • Jar Testing Case Study

    Objectives: Understand effect of coagulant on

    cyanobacteria cell removal.

    Understand effect of KMnO4 on coagulation efficacy and cyanotoxin release from cyanobacteria cells.

    Experimental setup: 4 jars stirred at mixing speed

    equivalent to turbulence in raw water main.

    Raw water sample augmented with concentrated cyanobacteria solution obtained with a phytoplankton net.

    Coagulant added at plant’s dose.

    KMnO4 added at plant dose and high dose.

  • Bench-scale Coagulation Experiments with Lake Erie Water and Cyanobacteria

  • Cyanobacterial cells may have different surface chemistry than suspended clay and silt

    Cyanobacterial cells will have lower specific gravity (1.0 – 1.1) than inorganic particles (> 2)

    Some species of cyanobacteria have gas vacuoles → positive buoyancy

    Cyanobacteria can be found as single cells, “clumps” of individual cells, individual filaments, or “mats” of filaments

    For the reasons outlined above, different coagulation chemicals and doses may be required during blooms

    Optimizing coagulation conditions for cyanobacterial cell removal during sedimentation is worth the effort because it will protect the filters

    Operational considerations for Coagulation, Flocculation, Sedimentation and Filtration

  • Optimize coagulation, flocculation and sedimentation process through jar testing

    Filters that regularly achieve turbidity ≤ 0.10 NTU are better suited to remove cyanobacteria in the event of a HAB

    Backwashing filters based on water quality data, such as effluent turbidity, rather than length of time in service can lead to more optimal filter operation

    Trend water quality data regularly to understand baseline operation

    More frequent clarifier sludge removal may be necessary during a HAB

    Operational considerations for Coagulation, Flocculation, Sedimentation and Filtration

  • Conventional Surface Water Treatment

    Sedimentation

    Source Water

    Chlorine(Cl2)

    Permanganate(MnO4-)

    Powdered activated carbon

    (PAC)

    Coagulant

    Rapidmix Flocculation

    Filtration

    Chloramine(NH2Cl)

    Clearwell

    Distribution systemSludge

    44

  • Permanganate and Chlorine – Reaction rates

    10-1 100 101 102 103 104 105

    Cylindrospermopsin

    Microcystin

    Anatoxin

    Apparent rate constant (M-1s-1)

    10-1 100 101 102 103 104 105

    Cylindrospermopsin

    Microcystin

    Anatoxin

    Cl2Laboratory waterpH 4 - 9T = 20 C

    KMnO4Laboratory waterpH 7 - 8T = 20 - 22 C

  • Impact of Chlorination on Microcystin Concentrations

    > 2X increase in

    CT

    > 3X increase in CT

    *Figure based on data from Acero et al, Water Research, 2005:39:1628-1638

    CT for 3-log Giardia inactivation@ 1.0 mg/L Cl2, t = 25° C:• pH 7: 37• pH 8: 54• pH 9: 78

    (CT = 26)

    (CT = 71)

    (CT = 235)

  • Oxidation of Microcystins with Chlorine:Kinetic Study

    Objective: evaluate microcystin oxidation by chlorine in the plant’s raw water at the plant’s typical chlorine dose.

    Augmented a raw water sample with concentrated solution of cyanotoxins obtained from another water body that was experiencing a HAB.

    Cyanobacteria subjected to freeze/thaw and a filtration step to ensure that toxins were extracellular.

    Compared experimental results with AWWA’s CyanoTOX model results: o Calibrated “model” using free chlorine sample results.o Interested in predicted vs. observed microcystins.o Difference is raw water vs. lab water.o Presence of ammonia, other inorganics, and NOM in raw water reduces

    efficacy of chlorine against microcystins.o Understand if a safety factor necessary when predicting chlorine dose

    necessary to oxidize extracellular microcystins in a full-scale wastewater treatment plant (WTP). 47

  • Chlorine and Microcystins Kinetic Study

  • CyanoTOX Inputs

    CALCULATOR INPUT PAGE

    STEP 1. Select the cyanotoxin of interest from the dropdown list Variant MC-LR MC-RR MC-YR MC-LA MC-LY MC-LF MC-MixCyanotoxin Type Microcystin-Mix (MC-Mix) → Percent 5% 20% 50% 10% 5% 10% 100%

    STEP 2. Input the following system parameterspH (between 6-10) 9.2

    Temperature (between 10-30°C) 10

    STEP 3. Input the initial cyanotoxin concentrationCyanotoxin Initial Concentration (µg/L) 3.79(If not known, enter an assumed value for the scenario)

    STEP 4. Select your target option from the dropdown listTarget. Options: 1) Input target cyanotoxin conc. 1) Input target cyanotoxin conc.

    2) No targetTarget cyanotoxin concentration (µg/L) 0.3

    STEP 5. Select the oxidant of interest from the dropdown listOxidant Type Free Chlorine

    STEP 6. Go to your chosen calculator version: CT based or Dose-decay based (tabs in blue)

    STEP 7. Input the following parameters

    Baffling Factor 1Oxidant Dose (mg/L) 7

    Instantaneous oxidant demand (mg/L) 2.95Contact Time (i.e., hydraulic detent. time, min) 300

    Effective Oxidant Half Life (min) 360(Enter a value in minutes OR "ND" for No Decay")

    American Water Works Association 49

  • CyanoTOX Oxidation Calculator

    Dose-decay based results: CT-based results:

  • Operational Considerations for Chlorination

    Consider the toxin:o Chlorine is effective for microcystin and cylindrospermopsino Chlorine is not effective for anatoxin

    Consider pH:o As pH increases, chlorine reaction rate with microcystin

    decreaseso As pH increases, chlorine reaction rate with

    cylindrospermopsin increases and peaks at pH = 7, then begins to decrease

    Consider temperature – all reaction rates increase with temperature

    51

  • Operational Considerations for Chlorination

    Consider competing oxidant demands:o NOMo Iron, manganeseo Ammonia

    Consider the potential for formation of disinfection byproducts Consider contact time:

    o In the treatment planto Between the treatment plant and the first connectiono Other locations in the distribution system (storage tanks)

    Consider where chlorine is dosed and if any competing technologies would limit its effectiveness

    52

  • UV Irradiation

    UV contactors installed toward the end of the treatment process –cells and intracellular toxins have been removed, only extracellular toxin remaining.

    Required UV doses for 2-log disinfection of Cryptosporidium = 5.8 mJ/cm2, Giardia = 5.2 mJ/cm2, virus = 100 mJ/cm2.

    These doses drive full-scale UV contactor design.

    UV doses required for microcystin degradation are significantly higher – existing UV infrastructure not a barrier to toxin passage.

    53

  • Ozone and Chlorine Dioxide

    Chlorine dioxide, at the doses used in drinking water treatment (to limit the formation of chlorite) is not considered effective against microcystins – reaction rate is approximately 3 orders of magnitude lower than permanganate.

    Ozone has been proven effective at degrading microcystins as well as cylindrospermopsins and anatoxin – reaction rate is sufficient to achieve degradation within the confines of ozone contactors used in full-scale drinking water treatment.

    54

  • When optimized, conventional treatment processes (coagulation, flocculation, sedimentation, filtration) are highly effective at removing cyanobacterial cells.

    PAC effectively adsorbs microcystins however, the exact carbon dose will vary depending on the type of cyanotoxin, type of carbon, and the NOM background.

    Conclusions

  • Chlorine effectively degrades microcystins – but the rate of degradation is temperature and pH dependent.

    Ozone effectively degrades microcystins.

    Chlorine dioxide and UV, at the dose levels commonly employed in drinking water treatment, are not effective.

    Permanganate effectively degrades dissolved microcystins –however, the typical location for permanganate addition, early in the treatment process where cyanobacterial cell concentrations are still high, sets up a potential for toxin release – vigilance is recommended.

    Conclusions

  • Disclaimer

    57

    The U.S. Environmental Protection Agency, through its Office of Research and Development, funded and managed, or partially funded and collaborated in, the research described herein. It has been subjected to the Agency’s internal peer and administrative review and has been approved for external publication. Any opinions expressed in this presentation are those of the author(s) and do not necessarily reflect the views of the Agency, therefore, no official endorsement should be inferred. Any mention of trade names or commercial products does not constitute endorsement or recommendation for use. This presentation is for informational purposes only and is not intended as legal advice. You are urged to consult legal counsel concerning any specific situation or legal issues. This presentation does not address all federal, state, and local regulations, and other rules may apply. This presentation does not substitute for any EPA regulation and is not an EPA rule.

  • Analytical Methods

    Enzyme linked immunosorbent assay (ELISA)

    Toxin molecule Antibody (specific to toxin molecule)

    “Immunosorbent”

    +Toxin-antibodycomplex Enzyme

    “Enzyme-linked immunosorbent”

  • Analytical Methods

    Enzyme linked immunosorbent assay (ELISA)

    +Toxin-antibody

    complex Enzyme

    +Reagent

    Enzyme catalyzes reactionthat results in color change

    proportional to toxin concentration

  • Analytical Methods

    Enzyme linked immunosorbent assay (ELISA)

    ELISA plate ready for reading

  • Analytical Methods

    Liquid chromatography with tandem mass spectrometer (LC/MS/MS)

    Sample

    Chromatographycolumn

    Mass spectrometer∆ t

    Separation by mass andfragmentation pattern inthe mass spectrometer

    Separation by timeon the column

  • ELISA versus LCMS(Extracellular Toxin)

  • ELISA vs. LCMS (Extra + Intracellular Toxin)

  • EPA Water Treatment Document

    https://www.epa.gov/sites/production/files/2018-11/documents/water_treatment_optimization_for_cyanotoxins.pdf

  • Bibliography

    65

    Permanganate:o Kim et al, Environmental Science & Technology:2018:52:12:7054-7063o Jeong et al, Water Research:2017:114:189-199o Ding et al, Journal of Environmental Engineering:2010:136:1:2-11o Rodriguez et al, Water Research:2007:41:15:3381-3393o Rodriguez et al, Water Research:2007:41:9:2048-2056o Rodriguez et al, Water Research:2007:41:1:102-110

    Powdered activated carbon:o Park et al, Chemosphere:2017:177:15-23o Vlad, MS Thesis, University of Waterloo, 2015, http://hdl.handle.net/10012/9392o Drogui et al, Environmental Technology:2012:33:4:381-391o Ho et al, Water Research:2011:45:9:2954-2964o Cook & Newcombe, Environmental Technology:2008:29:5:525-534o Cook & Newcombe, Water Science and Technology: Water Supply:2002:2:5-6:201-207

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