Microconstituents – Emerging Contaminants

1. Microconstituents – Emerging Contaminants Joint Water Resources Symposium New York Water Environment Associations New York Section American Water Works Association In Honor or Edwin C. Tifft, Jr. Syracuse, NY November 14, 2007 Joseph G. Cleary, P.E., BCEE Principal HydroQual, Inc. Mahwah, NJ

2. Presentation Outline • WEF’s Community of Practice Activities • Microconstituents - What’s Included? • Terminology / Name Changes / Key Messages • Treatment Technologies • Approach to Develop Best Solution • Case Studies • Summary

3. WEF Community of Practice Activities

4. Why are Microconstituents a Concern? • Better analytical methods and more monitoring are finding them in numerous receiving waters • Feminized fish discovered in Europe in mid 1990s • Steroids are implicated in Europe in late 1990s • Treatment studies on POTWs (2002-2003) show POTWs are a collection point and one source to receiving waters • USGS study of 139 streams in 2002 detected pharmaceuticals in 80% of samples • More media coverage & public awareness and concerns.

5. WEF Community of Practice (CoP) • Began at WEFTEC 2005 in Washington DC • Deals with hot topics • Broad, diverse membership – a benefit and challenge • 150 Members and growing

6. WEF Key Messages • Committed to sharing clear, factual information • Advancing understanding • Pursuing sound, sustainable solutions • Focusing on source control

7. Two Fundamental Challenges • Technical challenges due to scientific uncertainties • Communication challenges related to public fears and perceptions.

8. WEF Community of Practice (CoP) • Identified work products • Technical Practice Updates • Public & Press Communications • Glossary of Terms • Name for the issue

9. WEFs Public Communication’s Role Staff Products include: • Key Messages • Fact Sheets • Illustrations • Finding Expert Spokespersons • Building Consensus

10. Varying Communication Challenges Include: What to call the compounds without negatively branding them as a “worry” or “concern”? Media accounts and technical publications already using a multiplicity of terms

11. Varying Communication Challenges Include: Scientists wanting to communicate with precision to scientists WEF needs also to communicate with the scientific community, its membership and the general public The required vernacular must vary to suit the audience – so the language must be tailored

12. Communication Challenge • Second challenge - Technical and communications experts • Different audiences • Different vocabulary • Different approaches

13. Microconstituents - What’s Included?

14. Micro Constituents in Water: Where Do They Come From? Courtesy of CH2M Hill

15. Reference: Kobylinski, Hunter and Scruggs, 2005

16. New Emerging Compounds benzene, naphthalenesulfonates HYDROPHILIC surfactants pharmaceuticalsbetablockers, antibiotics, contrast media, analgesics, antiepileptics, parasiticides, babiturates, opioides perfluorinatedcompounds (PFOA) corrosion inhibitorse.g. benzotriazole POLARITY NDMA phosphoric ester flame retardants estrogenes MTBE UV filter from Walter Giger, in Ternes und Joss, IWA Publishing, 2006 musk fragrances Volatility NON VOLATILE LIPOPHILIC VOLATILE

17. 6.0 diclofenac 5.0 March May betablocker musk frag. contrast media antibiotics 4.0 carbamazepine September 3.0 2.0 1.0 0,0 Sotalol Iomeprol Atenolol Tonalide Ibuprofen Iopamidol Diclofenac Galaxolide Diatrizoate Metoprolol Propranolol Clofibric acid Trimethoprim Roxithromycin Carbamazepine Sulfamethoxazole New Emerging Compounds conc. in µg/L 360‘000 Pop. Equiv. Nitrification/Denitrification Ternes et al., Chemosphere 2007

18. Diversity of Endocrine Disruptor Compounds (Falconer (2003) and Wren (2001))

19. Why are Microconstituents a Concern? • A review by the World Health Organization has concluded that low-level environmental exposure to Endocrine Disruptors has not yet been demonstrated to cause harm to human health (Damstra et al., 2002). • Uptake of Endocrine Disruptors by humans from treated drinking water is relatively low in comparison to other sources such as food (GWRC, 2003).

21. Terminology / Name Changes / Key Messages

22. WEF Terminology Challenges • Nov 2005 • Endocrine Disrupting Compounds (EDC) • (goal was communicating with WEF membership) • Feb 2006 • Compounds of Emerging Concern (CEC) • (because not just about endocrine issues) • Oct 2006 • Compounds of Potential Concern • (how to respond to the public – diligence in studying the issue)

23. Terminology Challenge May 2007 More discussion about alarming the public – when we don’t have a basis to ring the alarm bells Micro-constituents No, not little voters but really small things in the water environment that we can now detect (at ppb and ppt) and we don’t know enough about.

24. WEF Key Messages These compounds are referred to in a multiplicity of ways including micro-constituents, trace constituents compounds of emerging concern, etc.   WEF is calling them micro-constituents. We continue to study them as a prudent, conservative course of action reflecting our commitment to continue to assess the potential impact on human health and the environment.

25. WEF Key Messages Low levels of compounds remain but in concentrations that we believe are safe to return to the environment There are differing levels of Wastewater Treatment and Water Treatment We are studying the issue of even the trace amounts of these chemicals that remain after wastewater treatment

26. WEF Key Messages • Treated wastewater is not the only pathway for these substances to enter the environment • Many items we can detect have beneficial effects (i.e. medicines and pest control) • Some improvement quality & longevity of life

27. WEF Key Messages • Effects depend on: • - Nature of compound • - Type of exposure • - Concentration • - Quantity/duration of exposure

28. Some Facts to Keep in Mind • Some compounds are naturally occurring • Society chooses to ingest, bathe in and apply constituents at much higher concentrations than ever found in the environment

29. Treatment Technologies

30. Physical/Chemical Properties – Keys to Treatment • Water Solubility (mg/L) • Henry’s Constant (atm m3/mole) • Octonal Water Coefficient Log Kow (Partitioning to Solids) • Vapor Pressure, Vp • Distribution Coefficient, Kd • Biotransformation Ratio (K bio in soil, water, sludge and sediment) • Biodegradability • Photolysis Rate • Oxidation Rate • Reduction Rate Reference: Williams, 2006

31. Applicable Treatment Technologies for EDCs • Aerobic Biological Treatment Processes including Nitrogen Removal (e.g. Activated Sludge, Membrane Bioreactors) • Chlorination (e.g. bleach, alkaline chlorination) • Advanced Oxidation (UV/Peroxide, Ozone/Peroxide, UV/Ozone • Carbon Adsorption • Membrane Filtration and Reverse Osmosis • Thermal Oxidizers • Anaerobic Biological Treatment

32. Summary of Poseidon Project in Europe (Thomas Ternes) • Membranes & Ozonation in combination with Activated Sludge & Biofilters were evaluated • PPCPs and Estrogens removal focus in Europe • Sludge treatment and urine separation was evaluated • Sorption is an important mechanism for hydrophobic and positively charged compounds • Biodegradation is a key mechanism • Stripping was not effective • Chemical oxidation was an effective polishing step for some PPCPs • Some PPCPs are degraded in anaerobic sludge digestion • Available process models can be used using rate coefficients developed

33. Process Wastewater EQ Tank Jet Aeration Aeration Tank #1 Clarifier Denitrification Selector Effluent Aeration Tank #2 Waste Activated Sludge Jet Aeration Return Activated Sludge Filter Press Activated Sludge

34. Membrane Bioreactor Process

35. Fixed Film Technology

36. Other Treatment Studies • MLE Plant in San Diego (WERF Study, Oppenheimer, 2005) • Six full-scale WWTPs in the U.S. and two pilot scale MBRs (WERF Study, Oppenheimer, 2006) • Half of the 20 PPCPs were removed to greater than 80% at SRT <5 days • No additional removal was attributed to MBR, media filters or longer HRTs • Removal of musk fragrances required SRTs of at least 25 days

37. Results from Two-Stage MBR & Ozone Treatment in Pilot Study • APIs concentrations are listed in g/L • DL: Detection limit • ND: Not detected • Reference: Helmig, Edward et al., WEFTEC 2005

38. Diclofenac Sulfamethoxazole Roxithromycin 17 a-Ethinylestradiol Ozone Treatment Carbamazepine Huber et al., 2003, Env.Sci.Technol.

39. WEF Technical Practice Update on Treatment • EDC Committee Formed @ WEFTEC October 2005 • List of TPUs was developed ( 13 topics) • Treatment was done first • Draft for comment in January 2006 • Review meeting in February 2006 • Committee name changed to “Contaminants of Emerging Concern” now “Microconstituents” • Comments received in March 2006 on Treatment White Paper – Change to Technical Practice Update • Final draft April 2007 • Final version now on WEF website along with others

40. What Has Been Done and What Do We Know • Many studies have demonstrated that activated sludge processes have the potential to remove a large fraction of several suspected EDCs, often to below detection limits (Ying, 2002). • Johnson and Darton (2003) state that the EDCs generally implicated in endocrine disruption in fish – the estrogens E1, E2, EE2, and NP – are all “inherently biodegradable”

41. What Has Been Done and What Do We Know(continued) • Siegrist estimates that about a 10 to 15 day SRT would be required for appreciable EDC removal (Siegrist et al., 2005). • Estrogens can be eliminated in WWTPs by applying a nitrification/denitrification step (SRTs 15 days), or by effluent ozonation, nanofiltraton, or activated carbon. • Anaerobic sludge digestion leads to a degradation of some PPCPs.

42. What Has Been Done and What Do We Know(continued) • Substances that are difficult to biodegrade may be oxidized by AOPs, and the oxidized byproducts may be more amenable to biodegradation (Ried and Mielcke, 2003). • Advanced oxidation process (AOP) are combinations of UV plus hydrogen peroxide, ozone plus hydrogen peroxide, and UV plus ozone, that are specifically designed to increase the formation of powerful hydroxyl radicals to oxidize EDCs and provide disinfection. Ozone shows similar potential to the AOPs for EDC removal.

43. What Has Been Done and What Do We Know(continued) • 100% removal of EDCs from WWTP effluent will not be possible, so the goal should be reduction to levels with no adverse environmental effects. • Source control (e.g., ecolabelling) and source separation (e.g., urine or rain water segregation) are important measures for reducing the PPCP load entering the environment.

44. What is Needed or Not Known? • Toxicological and other environmental impacts are not known for most EDCs. • Risk assessment studies are needed to develop appropriate regulatory actions (Schoenberg, Helmig et al., 2005). • Fate studies are needed describing removals of compounds and pathways: biodegradation/biotransformation, partitioning to solids, volatilization.

45. What is Needed or Not Known?(continued) • Analytical procedures are needed to detect lower levels of estrogens and to distinguish between various forms. • Research to better understand the performance of engineered and natural treatment systems for reduction of these compounds (Oppenheimer et al., 2005). • The hazard potential of the byproducts formed through treatment with advanced oxidation requires additional investigation.

46. Integrated / Holistic Approach to Develop Best Solution

47. Industry Irrigation (soil/aquifer) Water/Sediment “Run off“ infiltration groundwater bank filtrate Waterworks Drinking water Urban Water Cycle STP

48. End of Pipe Approach Production Secondary Wastewater Treatment To POTW Tertiary Wastewater Treatment Raw Water Supply Sludge Utilities Brine Disposal Water Reuse Well Water Supply Integrated vs. End-of-Pipe Approach

49. Collaborative TeamApproach is Best • Mobilize a Team – Include People Closest to Problems and Stakeholders • Include Production, Water and Wastewater Operations, Environmental Compliance Managers • Outside Consultant • Commitment of Management and Team • Frequent Communications and Meetings

50. ApproachSequence of Tasks • Flow Balance & Wastewater Characteristics • Design Basis (flow & wasteloads) • Screen Technologies • Develop Initial Alternatives • Alternative Comparison (cost & non-costs criteria) • Narrow List of Alternatives • Treatability Studies & Process Modeling • Refine Comparison • Select Best Solution