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

Outline Introduction USEPA Response Algae Issues Water Quality Variability: Turbidity, pH, DO HABs, Algal Toxins, and Taste and Odor Latest Driver: Algal events in Ohio USEPA Response June 17th – 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 multicellular forms Diatoms, Stoneworts, Green Algae, Golden Algae, Dinoflagellates, Brown Algae, Red Algae http://www.qualitas-health.com/about-us/media-2/

Algae Issues Seasonal algae blooms present many problems for water utilities Dissolved Oxygen pH, 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)

pH Signature in an Algal Bloom

DO Variability in a Bloom

Chlorophyll (proving it’s a bloom)

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. Produce toxins during genetic strain, growth phase, competition, environmental conditions

Main Cyanotoxins of Concern Microcystins Cylindrospermopsin Anatoxin-A Saxitoxin

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

Microcystin-LR (ug/L) Cylindrospermopsin (ug/L) State/ Agency Microcystin-LR (ug/L) Anatoxin-A (ug/L) Cylindrospermopsin (ug/L) Saxitoxin (ug/L) US EPA (2015) Children < 6 years old 0.3 None 0.7 US EPA (2015) All other age groups 1.6 3.0 Ohio 1 20 0.2 Oregon 3 Minnesota 0.04* Quebec 1.5 3.7 Health Canada World Health Organization (WHO) 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 * To protect short-term exposure for bottle-fed infants

Potential Link Between Cyanotoxins and Taste and Odor USGS 2010 study (ES&T 44, 7361 – 7368) Sampled 23 Midwest lakes Multiple toxin classes co- occurred 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

Plant shutdown for multiple days! Toledo: 2014 Raw Microcystin ~ 20ppb Raw Microcystin 5-10ppb Plant shutdown for multiple days!

June 17th, 2015 EPA publically releases “Health Advisory Levels” and “Potential Preparation and Response” Actions http://www2.epa.gov/nutrient-policy- data/guidelines-and-recommendations#more

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 non-carcinogenic effects are expected for a ten-day exposure Microcystin

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 4) Health Advisories, T&O complaints B) Limit Extent of Cyanobacteria Blooms C) Treatment of toxins and T&O A) Reduce Algae Promoting Conditions

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? pH, 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 http://www.hazenandsawyer.com/publications/algae-and-cyanotoxins-resources/

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 Select Cyanotoxin of interest from drop down list: Anatoxin-A, Microcystin- LR, Cylindrospermopsin, Microcystin-Mix Input system parameters Input initial cyanotoxin concentration Select final target endpoint Select oxidant of use Free chlorine, ozone, permanganate, monochloramine, chlorine dioxide Select model type

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 UCMR4 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

EPA website for algal toxins EPA Cyanotoxin Management Document Useful Resources EPA website for algal toxins http://www2.epa.gov/nutrient-policy-data/cyanohabs EPA Cyanotoxin Management Document http://www2.epa.gov/sites/production/files/2015-06/documents/cyanotoxin-management- drinking-water.pdf Ohio EPA White Paper http://epa.ohio.gov/portals/28/documents/HAB/AlgalToxinTreatmentWhitePaper.pdf WaterRF Utility Manager’s Guide http://www.waterrf.org/PublicReportLibrary/4548a.pdf Hazen-Adams Cyanotoxin Oxidation Calculator http://www.awwa.org/

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