Treating Cyanotoxins with Granular Activated...

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Slide 1

Treating Cyanotoxins with Granular Activated Carbon

Kendra RyanCalgon Carbon Corporation

Municipal Applications Engineer

Ralph Franco PECalgon Carbon Corporation

Director – Municipal Products

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• Background – Algae: Cyanotoxin Compounds‒ Formation Conditions‒ Most Common Cyanotoxins‒ Treatment Approaches

• Activated Carbon‒ Adsorption & Starting Material Basics‒ Activated Carbon in Water Treatment - PAC & GAC‒ Performance Studies

Presentation Overview

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Algae & Cyanotoxins

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• Naturally occurring organisms• Thrive under certain conditions:‒ Sunlight‒ Warm temperatures‒ Slow Moving Water (i.e. Lakes/Reservoirs)‒ Excess nutrients Nitrogen Phosphorous Potassium

• Harmful Algal Blooms (HABs) ‒ Typical season duration = 3 months‒ Promote growth of cyanobacteria

Algae Formation

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Satellite Image of Blue-Green Algal Outbreak on Lake Erie, 2011

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• By-product of cyanobacteria life cycle‒ Over 3,000 known species

• 2 primary classes:‒ Hepatotoxin – affecting the liver‒ Neurotoxin – affecting nerves & nervous system

• 4 primary toxins of interest:‒ Anatoxin-A‒ Cylindrospermopsin‒ Microcystin-LR‒ Saxitoxin

Cyanotoxins

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• Shut-off intake‒ Sufficient Warning‒ Multiple source water options

• Treatment Approaches‒ Adsorption via Powder Activated Carbon‒ Adjustment of Pretreatment chemistry‒ Ozone Oxidation‒ Adsorption via Granular Activated Carbon‒ Reverse Osmosis (RO)‒ UV Advanced Oxidation (UV/AOP)‒ Adjustment of oxidant levels

Operational Options

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Introduction to Activated Carbon

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Structure of Activated Carbon

• Carbon is the base element of graphite

AC is 99%

graphite

• Imperfections result in porosity and greater surface area

AC is a crude

form of graphite

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Bituminous CoalCoconut Shell

Sub-BituminousLignitePeatWood

Starting Materials

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Starting Materials

• Ash impurities• Density• Hardness• Transport pore structure• Adsorption kinetics

Raw material dictates all of the product possibilities

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Manufacturing Processes

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Direct Reagglomerated

Over activation in the outer Part of the granule

Low Activation Even Activation

Granular Activated CarbonProduct differences: Re-agglomeration versus Direct Activation

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Granular Activated Carbon

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Where is it Used?

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Where is it Used?

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Where is it Used?

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Disinfection Byproducts (DBPs)•Trihalomethanes

(THMs)•Haloacetic Acids

(HAA5s)

Carcinogenic VOCs•TCE•PCE

Perfluorinated Compounds (PFCs)•PFOA•PFOS

Algal Toxins•Microcystin•Cylindros-

permopsin•Anatoxin A

Pesticides•1,2,3 –

Trichloropropane (1,2,3-TCP)

•Dieldrin•Glyphosate

EDCs & PCPPs•Medicine•Pharmaceuticals

Defense Barrier•Chemical Spills

Simultaneous Contaminant RemovalUSEPA considers GAC to be an effective treatment technology for:

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Economic Benefit of GAC

The average family of 4 consumes 65,700 gallons of water annually

Tap water filtered by GAC costs a family of 4 roughly $2.00/Month (per

AWWA)

The average 2015 price for bottled water is $1.22/gallon

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Performance Testing

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Importance of Testing•Many factors influence the effective service life of GAC

•Temperature•pH•EBCT•Concentration•Competitive Adsorption

•Extremely difficult to quantify without testing

Why

• Feasibility• Product Comparison• Service Life Estimation• Treatment Technology Comparison

Goals

•Bench Scale•TACTIC•Isotherm •ACT/RSSCT

•In-Process•Pilot Column

Types

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Equilibrium batch carbon adsorption tests‒Series of carbon dosages allowed to equilibrate

INCREASING DOSE OF CARBON

Isotherm

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Accelerated Column Test (ACT)

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•fluctuations in influent•flow rate•pH•bio activity•temperature•TSS•physical filtration•backwashable

Incorporates

Pilot Column

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Removal Case Studies

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Ohio EPA Monitoring Website

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• Surface Water Upstream of GAC contactors

• NOM/TOC present Average feed = 2.1 mg/L

• Spiked with cyanotoxins Anatoxin-A feed = 86 µg/L Cylindrospermopsin feed = 45 µg/L Microcystin-LR feed = 55 µg/L

• Contact Time (EBCT) 7 minutes

Cyanotoxin Case Study #1

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• Filtrasorb 300‒ Reagglomerated bituminous coal‒ 8x30 mesh‒ 900 mg/g Iodine Number‒ Virgin

Cyanotoxin Case Study #1

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Cyanotoxin Case Study #1 – Anatoxin-A

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TOC

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Bed Volumes Treated (BV)

TOC and Microcystin-LR vs Bed Volumes Treated

TOC TOC Feed MC-LR MC-LR Feed

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Cyanotoxin Case Study #1 – Cylindrospermopsin

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Cylin

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tratio

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pb)

TOC

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Bed Volumes Treated (BV)

TOC and Cylindrospermopsin vs Bed Volumes Treated

TOC TOC Feed CYN CYN Feed

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Cyanotoxin Case Study #1 – Microcystin-LR

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TOC

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Bed Volumes Treated (BV)

TOC and Anatoxin-a vs Bed Volumes Treated

TOC TOC Feed ANTX-a ANTX-a Feed

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• 676 days simulated‒ ~245 million gallons water

• Cyanotoxin breakthrough ‒ Initial breakthrough = 52 days‒ 50-70% breakthrough at conclusion

• TOC breakthrough‒ ~60% breakthrough at first cyanotoxin detection

Cyanotoxin Case Study #1

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• Surface Water Upstream of GAC contactors

• NOM/TOC present Average feed = 2.1 mg/L

• Spiked with cyanotoxins Anatoxin-A feed = 86 µg/L Cylindrospermopsin feed = 45 µg/L Microcystin-LR feed = 55 µg/L

• Contact Time (EBCT) 15 minutes

Cyanotoxin Case Study #2

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• Filtrasorb 400‒ Reagglomerated bituminous coal‒ 12x40 mesh‒ 1,000 mg/g Iodine Number‒ Virgin and reactivated GAC

Cyanotoxin Case Study #2

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Cyanotoxin Case Study #2 – Anatoxin-A

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TOC

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Simulated Days of Operation

TOC and Anatoxin-a vs Simulated Days

F-400 TOC CMR F-400 TOC F-400 Feed ANTX-a F-400 ANTX-a CMR F-400 ANTX-a

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Cyanotoxin Case Study #2 – Cylindrospermopsin

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Simulated Days of Operation

TOC and Cylindrospermopsin vs Simulated Days

F-400 TOC CMR F-400 TOC Feed TOC Feed Cyn F-400 Cyn CMR F-400 Cyn

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Cyanotoxin Case Study #2 – Microcystin-LR

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Simulated Days of Operation

TOC and Microcystin-LR vs Simulated Days

CMR F-400 TOC F-400 TOC Feed TOC Feed MC-LR F-400 MC-LR CMR F-400 MC-LR

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Cyanotoxin Case Study #2 – THM Formation

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THMFP vs Simulated Days

F-400 THMFP CMR F-400 THMFP

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• 230 days simulated‒ ~53 million gallons water

• No Cyanotoxin breakthrough ‒ Virgin & reactivated GACs‒ Anatoxin-A detection limit = 0.6 µg/L ‒ Cylindrospermopsin detection limit = 0.03 µg/L ‒ Microcystin-LR detection limit = 0.15 µg/L

• TOC breakthrough‒ Virgin = 74% of influent‒ React = 82% of influent

Cyanotoxin Case Study #2

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• Reagglomerated bituminous coal GAC can be an effective barrier against Anatoxin-A, Cylindrospermopsin, and Microcystin-LR.‒ Both virgin and reactivated‒ Non-detect longer than HAB season‒ Still effective near end of GAC service life for TOC removal/DBP

prevention

Conclusion

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Summary

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• Activated Carbon can be an effective tool for the treatment of Cyanotoxins

• Its important to properly maintain your GAC filters to assure that proper treatment can be obtained during a Harmful Algal Bloom

• Not all Carbons are the same; there are benefits to pilot testing with your specific water to determine the best carbon for your application

Final Takeaways

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Thank you for your time.

Questions?

Ralph Franco PEDirector – Municipal ProductsP: 412-787-6620E: rfranco@calgoncarbon.com