Algae Algal Toxins and Treatment A Cure for

Algae, Algal Toxins, and Treatment: A Cure for Bad HABits! Scott M. Alpert, Ph. D, PE NC AWWA‐WEA 2015 Annual Conference Raleigh Convention Center, Raleigh, NC, November 15 – 18, 2015

Outline • Introduction • Algae Issues • Water Quality Variability: Turbidity, p. H, DO • HABs, Algal Toxins, and Taste and Odor • Latest Driver: Algal events in Ohio • USEPA Response • June 17 th – Health Advisories released for Microcystins and Cylindrospermopsin • Understanding the “non-regulations” • A Holistic Approach to Cyanotoxin Management • Monitoring, Management, Treatment

Introduction

What is Algae? • Found in the fossil record dating back to approximately 3 billion years ago • Large and diverse group that can occur in most habitats • Photosynthetic • Eukaryotic • Vary from small, single-celled forms to complex http: //www. qualitas-health. com/about-us/media-2/ multicellular forms • Diatoms, Stoneworts, Green Algae, Golden Algae, Dinoflagellates, Brown Algae, Red Algae

Algae Issues • Seasonal algae blooms present many problems for water utilities • Dissolved Oxygen • p. H, 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 toxins = Harmful Algal Bloom (HAB)

0 0, 05208333333 0, 1041666667 0, 15625 0, 2083333334 0, 26041666667 0, 3125 0, 36458333334 0, 416666667 0, 46875 0, 5208333334 0, 57291666667 0, 625 0, 67708333334 0, 7291666667 0, 78125 0, 833333334 0, 88541666667 0, 9375 0, 98958333334 1, 041666667 1, 09375 1, 1458333334 1, 1979166667 1, 25 1, 3020833334 1, 3541666667 1, 40625 1, 458333334 1, 5104166667 1, 5625 1, 6145833334 1, 66666667 1, 71875 1, 7708333334 1, 8229166667 1, 875 1, 9270833334 1, 9791666668 1, 03125 1, 083333334 1, 1354166667 1, 1875 1, 2395833334 1, 291666667 1, 34375 1, 3958333334 1, 4479166667 1, 5520833334 1, 6041666667 1, 65625 1, 708333334 1, 7604166667 1, 8125 1, 8645833334 1, 916666667 1, 96875 p. H Signature in an Algal Bloom 3 -Day Diurnal Variability in p. H (May, June, July, August, September) 9, 5 9 8, 5 8 7, 5 7 6, 5 6 5, 5 5 5/1 - 5/3 6/1 - 6/3 7/1 - 7/3 8/1 - 8/3 9/1 - 9/3

0 0, 05208333333 0, 1041666667 0, 15625 0, 2083333334 0, 26041666667 0, 3125 0, 36458333334 0, 416666667 0, 46875 0, 5208333334 0, 57291666667 0, 625 0, 67708333334 0, 7291666667 0, 78125 0, 833333334 0, 88541666667 0, 9375 0, 98958333334 1, 041666667 1, 09375 1, 1458333334 1, 1979166667 1, 25 1, 3020833334 1, 3541666667 1, 40625 1, 458333334 1, 5104166667 1, 5625 1, 6145833334 1, 66666667 1, 71875 1, 7708333334 1, 8229166667 1, 875 1, 9270833334 1, 9791666668 1, 03125 1, 083333334 1, 1354166667 1, 1875 1, 2395833334 1, 291666667 1, 34375 1, 3958333334 1, 4479166667 1, 5520833334 1, 6041666667 1, 65625 1, 708333334 1, 7604166667 1, 8125 1, 8645833334 1, 916666667 1, 96875 DO (mg/L) DO Variability in a Bloom 3 -Day Diurnal Variability in DO (May, June, July, August, September) 12 10 8 6 4 2 0 5/1 - 5/3 6/1 - 6/3 7/1 - 7/3 8/1 - 8/3 9/1 - 9/3

0 0, 05208333333 0, 1041666667 0, 15625 0, 2083333334 0, 26041666667 0, 3125 0, 36458333334 0, 416666667 0, 46875 0, 5208333334 0, 57291666667 0, 625 0, 67708333334 0, 7291666667 0, 78125 0, 833333334 0, 88541666667 0, 9375 0, 98958333334 1, 041666667 1, 09375 1, 1458333334 1, 1979166667 1, 25 1, 3020833334 1, 3541666667 1, 40625 1, 458333334 1, 5104166667 1, 5625 1, 6145833334 1, 66666667 1, 71875 1, 7708333334 1, 8229166667 1, 875 1, 9270833334 1, 9791666668 1, 03125 1, 083333334 1, 1354166667 1, 1875 1, 2395833334 1, 291666667 1, 34375 1, 3958333334 1, 4479166667 1, 5520833334 1, 6041666667 1, 65625 1, 708333334 1, 7604166667 1, 8125 1, 8645833334 1, 916666667 1, 96875 Chorophyll (mg/L) Chlorophyll (proving it’s a bloom) 3 -Day Diurnal Variability in Chlorophyll (May, June, July, August, September 25 Max = 85. 4 mg/L 20 15 10 5 0 5/1 - 5/3 6/1 - 6/3 7/1 - 7/3 8/1 - 8/3 9/1 - 9/3

Cyanotoxins (Algal Toxins) • Some blue-green can produce one or more toxins • • Do not produce toxins at all times Toxins can affect: • Fish and other aquatic life • Livestock • Pets • Humans Exposure routes in humans • Dermal • Oral (water or food) • Inhalation • Dialysis World Health Organization (WHO) has set a chronic exposure guideline of 1 mg/L.

Main Cyanotoxins of Concern 1. 2. 3. 4. Microcystins Cylindrospermopsin Anatoxin-A Saxitoxin

Cyanotoxins & T&O From Multiple Sources Species Dermatoxin (Irritant) Aphanacapsa spp. Hepatoxin (Liver) Neurotoxin (Nervous) microcystins Microcystis spp. microcystins, nodularin Snowella spp. microcystins Synechococcus spp. microcystins Woronichinia spp. microcystins Lyngbya spp. Lyngbyatoxins Oscillatoria spp. Aplysiatoxins Planktothrix agardhii Aplysiatoxins anatoxins MIB, Geosmin saxitoxins MIB microcystins anatoxins, saxitoxins MIB, Geosmin microcystins saxitoxins MIB, Geosmin Pseudoanabaena spp. Anabaena spp. MIB, Geosmin microcystins, cylindrospermopsin anatoxins, saxitoxins MIB, Geosmin Anabaenopsis elenkii microcystins Aphanizomenon spp. microcystins, cylindrospermopsin anatoxins, saxitoxins Cylindrospermopsis raciborskii cylindrospermopsin saxitoxins Nordularia spp. Taste/Odor Compound microcystins, nodularin Tedesco et al, 2011

State/ Agency US EPA (2015) Children < 6 years old US EPA (2015) All other age groups Ohio Oregon Minnesota Quebec Health Canada World Health Organization (WHO) Microcystin-LR (ug/L) Anatoxin-A (ug/L) Cylindrospermopsin (ug/L) Saxitoxin (ug/L) 0. 3 None 0. 7 None 1. 6 None 3. 0 None 1 20 1 0. 2 1 3 0. 04* None 1. 5 3. 7 None 1. 5 None 1 None * To protect short-term exposure for bottle-fed infants Regulations EPA has determined cyanotoxin levels in tap water that are “protective of human health” and recently issued Health Advisories Levels for public drinking water supplies

Potential Link Between Cyanotoxins and Taste and Odor • USGS 2010 study (ES&T 44, 7361 – 7368) • Sampled 23 Midwest lakes • Multiple toxin classes cooccurred in 48% • Toxins and T&O co-occurred in 91% But T&O presence does not necessarily equate to cyanotoxin presence, and vice-versa!

EPA Reaction to Toledo, 2014 Health Advisories and Guidance

10 Microcystin in Toledo's System – Summer of 2014 20 Raw Microcystin ~ 20 ppb 9 15 Raw Microcystin 5 -10 ppb 8 10 Finished Water Microcystin (mg/L) 7 5 6 5 4 3 0 Finished Water Results -5 Raw Water Microcystin -10 Plant shutdown for multiple days! 2 -15 1 0 4. 8. 2014 5. 28. 2014 7. 17. 2014 9. 5. 2014 10. 25. 2014 12. 14. 2014 -20 2. 2. 2015 Raw Water Microcystin (mg/L) Toledo: 2014

June 17 th, 2015 • EPA publically releases “Health Advisory Levels” and “Potential Preparation and Response” Actions • http: //www 2. epa. gov/nutrient-policydata/guidelines-and-recommendations#more 16

Health Advisory (HA) Levels • EPA underwent rigorous process to evaluate and determine Health Advisory Levels for Microcystins and Cylindrospermopsin • Health Advisories = Informal non-regulatory guidance for unregulated drinking water contaminants to assist federal, state and local officials, and public water systems in protecting public health

10 -day HAs for Microcystin and Cylindrospermopsin: Concentration in drinking water at or below which no adverse noncarcinogenic effects are expected for a ten-day exposure Microcystin 18

Holistic Approach to Algae Concerns: Monitoring, Management, Treatment

Cyanotoxins Add a New Wrinkle to an Old Issue • Many utilities already possess a strong understanding of algae issues in their system • However, given the uncertainty of the EPA Health Advisories and Guidance, many are now concerned about cyanotoxins • Monitoring, Management, Treatment • Do I need to sample for cyanotoxins? • How do I sample for them? • When and where do I sample? • What do I need to do if I detect cyanotoxins?

Algae is a whole system issue, with opportunities for success 2) Cyanobacteria Blooms 1) Nutrients and Algae Promoting Conditions 3) Cyanotoxins/T&O in the Water Treatment Plant B) Limit Extent of Cyanobacteria Blooms A) Reduce Algae Promoting Conditions C) Treatment of toxins and T&O 4) Health Advisories, T&O complaints

System Specific Evaluation Is your source water vulnerable? If so, when (seasonal, year-round)? What is the status of your algae monitoring and management program? Summary of Factors Leading to Algal Blooms Guidelines for Understanding Potential for Algal Growth Key to Step 1 is to understand if you are likely to see algae in your source Tables from Hazen Algae White Paper (Summer, 2015)

Monitoring EPA Advice: • Monitor for cyanotoxins in raw water and be prepared to make treatment changes • If found in raw, monitor in finished as well A Few Questions: • How to monitor? • p. H, DO, chlorophyll, phycocyanin, MIB, geosmin, FPA, microcystins, ELISA, HPLC/MS/MS • Where/when to monitor? • How to confirm results? • What do detections mean / communication of results?

Preparation for Monitoring and Management • Develop SOPs for when and where to monitor • Will I sample in raw only? If I detect in raw, will I sample in plant? Finished? • Base on historical algae information where available (T&O, algae management protocols) • Identify laboratories for algae enumeration and cyanotoxin detection (or self-perform) • Develop “Confirmation” and “Communication” plans, i. e. , • Confirm a positive ELISA kit with an LC/MS/MS analysis • Assess when to alert state primacy agency, public

Monitoring Options Graham et al, 2010

http: //www. hazenandsawyer. com/publications/algae-and-cyanotoxins-

When and Where to Monitor: Tiered and Triggered Approach

Management and Treatment • Algae Management is not new! • Keep the old strategies, tweak with some new information • What is the goal of management and/or treatment? http: //www. qualitas-health. com/about-us/media-2/

Algae Management • A whole system approach is best • Reduce nutrients in reservoir, improve water quality, reduce algae issues Hazen and Sawyer White Paper, 2015

Treatment Strategies Table 6 and Table 7 from Hazen Algae White Paper (Summer, 2015)

Treatment Strategies • • • Oxidative treatment effective for extracellular toxins Oxidative treatments can also lyse cells to release toxins Need to ensure either cells removed before oxidation -or- oxidize long enough to release toxins and oxidize toxins. Table 6 and Table 7 from Hazen Algae White Paper (Summer, 2015)

How Flexible/Capable is Your Existing Treatment Process? Available for download at AWWA. org

How the Model Works 1. Select Cyanotoxin of interest from drop down list: Anatoxin-A, Microcystin-LR, Cylindrospermopsin, Microcystin-Mix 2. Input system parameters 3. Input initial cyanotoxin concentration 4. Select final target endpoint

Model Outputs Results are based on oxidant decay model and CT or oxidant dose and demand information

Communication • Communication plans need to be set up in the case of finished water “hits”: • Alerting appropriate utility staff • Alerting state primacy agency • Alerting public (if required) • The cyanotoxin issue is out in the public view, so being prepared has merit. • EPA document focuses on how to communicate levels above HA

Summary • • • HABs and cyanotoxins have been big news in recent years, even though they are an old issue Delay won’t make go away – EPA instructed to develop plan by November!!! (and UCMR 4 is on horizon!) The issue is a solvable one with a holistic, measured, and proactive approach for Monitoring, Management, and Treatment Understand Your Source (Is algae even an issue? ) Understand Your Treatment Process for Water Quality, Algae, and Cyanotoxin Management Public Communication

Useful Resources • EPA website for algal toxins http: //www 2. epa. gov/nutrient-policy-data/cyanohabs • EPA Cyanotoxin Management Document http: //www 2. epa. gov/sites/production/files/2015 -06/documents/cyanotoxin-managementdrinking-water. pdf • Ohio EPA White Paper http: //epa. ohio. gov/portals/28/documents/HAB/Algal. Toxin. Treatment. White. Paper. pdf • Water. RF Utility Manager’s Guide http: //www. waterrf. org/Public. Report. Library/4548 a. pdf • Hazen-Adams Cyanotoxin Oxidation Calculator http: //www. awwa. org/

Questions? ? ? Scott M. Alpert, Ph. D, PE salpert@hazenandsawyer. com Acknowledgements: Hazen and Sawyer’s Bret Casey, P. E. ; Erik Rosenfeldt, Ph. D. , P. E. ; and Ben Stanford, Ph. D