1. 1 Full Scale and Pilot Scale Evaluation of Endocrine Disrupting Compound Removal Through WTP Processes Bob Raczko, P.E. United Water

2. 2 PRESENTATION OUTLINE Background information Research projects: – Water Research Foundation (WRF) – United WERCs WRF project United WERCs project Summary

3. 3 EDCs and PPCPs EDCs - endocrine disrupting chemicals PPCPs - pharmaceuticals and personal care products Includes wide range of daily-use products PharmaceuticalsPersonal care products PesticidesSurfactants PlasticizersPAHs Manmade sources - synthetic chemicals Detected at ug/L and ng/L levels

4. 4 Putting Things in Perspective 1 ppb or 1 ug/L1 ppt or 1 ng/L X 1,000

5. 5 Toxicological Relevance of PPCPs and EDCs DrinkingMax. Water Equiv.Finished LevelWater Level(ug/L) Carbamazepine120.018 Triclosan2,6000.0012 Sulfamethoxazole18,0000.003 Trimethoprim6,700<0.00025 Phenytoin6.80.032 Diclofenac2,300<0.00025 Naproxen20,000<0.0005 Gemfibrozil450.0021 Estradiol0.58<0.0005

6. 6 Research Projects – Endocrine Disrupting Compounds (EDCs) and Pharmaceuticals and Personal Care Products (PPCPs) Water Research Foundation (WRF) – Removal of Unregulated Organic Chemicals in Full-Scale Water Treatment Processes United WERCs – Advanced Pilot Testing of Treatment Processes for Removal of EDCs and PPCPs

7. 7 WaterRF Project Sponsoring Utility:Passaic Valley Water Commission, NJ Principal Investigator:Black & Veatch, consulting engineer Co-PIs:Catherine Spencer, Black & Veatch Dr. Judy Louis, NJDEP Utility Participants:UWNJ, UWRahway, Brick Township Objective: Investigate the effectiveness of full-scale conventional and advanced water treatment processes for removal of endocrine disrupting compounds.

8. 8 WRF Project - Research Approach Sample each treatment plant 4 times – spring/summer/fall/winter Collect samples after each unit treatment process Samples were analyzed by USGS laboratory Analyze for over 100 compounds Pilot testing using Haworth pilot plant - United WERCs project Prepare project report summarizing the findings

9. 9 United WERCs - Research Approach Participants - United Water and NJIT Overall – supplement WRF project by obtaining additional performance data for a variety of conventional and advanced water treatment processes on the removal efficiency of EDCs and PPCPs from drinking water supplies. Specific objectives: – Identify select unregulated compounds to investigate – Spike the Haworth pilot plant influent with the select compounds – Follow these compounds through the pilot plant unit treatment processes – Evaluate their removal and degradation as a function of treatment process – Evaluate potential synergies in treatment processes

10. 10 WaterRF Project Findings Contaminants and levels varied – Round 1 (May 2010) – 23 raw water compounds – Round 2 (August 2010) – 20 raw water compounds but not the same as Round 1 – Round 3 (March 2011) – 30 raw water compounds, many not found prior – Round 4 (July 2011) - 30 raw water compounds, some not found prior Classes of compounds found – Pharmaceuticals, few antibiotics, ingested metabolites – Flame retardants – Fragrance, flavor – Topically applied compounds – PAHs – Pesticides – Solvents/plasticizers – Detergents (nonyl- and octylphenols)

11. 11 Conclusions from the Data Large range in concentration and types of compounds found with precipitation/source volume, seasonal patterns Would be very difficult to regulate using a contaminant-by-contaminant approach Advanced oxidation, especially post-coagulation, effective for oxidation/conversion of many aromatics, alkanes, and cyclic organics GAC adsorption of more non-polar compounds (PAHs, flavor and fragrance compounds, many pharmaceuticals)

12. 12 Nanograms/liter

13. 13 Nanograms/liter

14. 14

15. 15 Category Removal Polycyclic Aromatic Hydrocarbons100% after filtration or GAC Pesticides chloroacetanilide triazine uracil type solvent Variable 66% after GAC Bind weakly to GAC? 100% after GAC Fragrance compound100% after aeration Topically applied - DEET41 – 75% after GAC and chlorine Metabolites caffeine cotinine cholesterol 0 – 65% after GAC <20% in finished water 100% post aeration Pharmaceuticals/Antibiotics100% after GAC Flame retardants – only 1 of 3 removed<10% (2) 100% (1) after GAC Plasticizer100% removed by filtration Volatile88 – 100% after aeration Plant B Process Performance

16. 16 Nanograms/liter

17. 17 Plant D Process Performance

18. 18 United WERCs Project Elements Task 1 - Preliminary InvestigationsMay-December 2010 – Literature Review – Surrogate or indicator parameters – Other treatment processes – Technical Memorandum - deliverableNovember 2010 Task 2 - Pilot TestsApril 2011 – July 2011 – Initial pilot runs – Memorandum - deliverable June 2011 – Additional pilot runs Task 3 - Report PreparationSeptember - December 2011 – Draft report - deliverableNovember 2011 – Final report - deliverableDecember 2011

19. 19 Priority Indicator Compounds (12 Groups, 16 Compounds) ClassesCompounds AnalgesicsAcetaminophen Ibuprofen AntibioticsErythromycin Sulfamethoxazole Trimethoprim AntidepressantsDiazepam AntiepilepticCarbamazepine Beta-BlockersAtenolol Blood Lipid RegulatorsGemfibrozil Fire RetardantTris(2-chloroethyl)phosphate (TCEP) Nicotine MetaboliteCotinine PesticidesAtrizine N,N-Diethyl-meta-toluamide (DEET) Psychomotor StimulantCaffeine Steroids17 β -Estradiol X-ray Contrast AgentIopromide

20. 20 Pilot Plant Flow Diagram Train A – O 2 /VGAC Train B – O 2 /UGAC Train C – UV/H 2 O 2

21. 21 Results of Ozone Tests RemovalPre-OzonePre- Ozone/H 2 O 2 Intermediate Ozone Intermediate Ozone/H 2 O 2 > 90%7356 75 – 90 %1213 75 – 99 %8569 50 – 75 %2220 < 50 %5876 0 – 75 %71096 Note: 1. Number in each box denotes number of compounds removed at given percentage.

22. 22 Results of GAC Tests RemovalVirgin GAC Used GAC > 90%132 75 – 90 %02 75 – 99 %134 50 – 75 %03 < 50 %28 0 – 75 %211 Note: 1. Number in each box denotes number of compounds removed at given percentage.

23. 23 Results of Ozone/GAC Tests RemovalPre-Ozone Virgin GAC Pre-Ozone Used GAC Inter. Ozone Virgin GAC Inter. Ozone Used GAC > 90%13 1 ND - 9 7 ND - 2 15 ND - 13 8 ND - 4 75 – 90 %2102 75 – >99 % 158 10 50 – 75 %0103 < 50 %0602 0 – 75 %0705 Note: 1. Number in each box denotes number of compounds removed at given percentage.

24. 24 Results of UV/H 2 O 2 Tests RemovalUV – 500 H 2 O 2 - 20 UV - 500 H 2 O 2 - 15 UV - 700 H 2 O 2 - 15 UV – 700 H 2 O 2 - 15 > 90%6712 75 – 90 %3211 75 – 99 %9913 50 – 75 %1110 < 50 %5512 0 – 75 %6622 (UV – mJ/Sq cm) (H 2 O 2 – mg/L) Note: 1. Number in each box denotes number of compounds removed at given percentage.

25. 25 Overall Test Results RemovalPre- Ozone Intermediate Ozone/H 2 O 2 Virgin GAC Intermediate Ozone/VGAC UV/H 2 O 2 700/15 > 90%7171 61315 ND - 13 12 ND - 9 75 – 90 % 13001 75 – 99 % 89131513 50 – 75 % 20001 < 50 %56201 0 – 75 %76202 Note: 1. Number in each box denotes number of compounds removed at given percentage.

26. 26 Treatability of Indicator Compounds Acetaminophen Ibuprofen Sulfamethoxazole Trimethoprim Carbamazepine Atenolol Gemfibrozil Atrazine DEET Caffeine 17β-Estradiol Iopromide Erythromycin TCEP Cotinine DEET Caffeine 17β-Estradiol Iopromide Good (75%) to Very Good (>90%)Fair (50%) to Poor (<50%) Indicates removal dependent on treatment process “Good to Very Good” and “Fair to Poor” applies to all treatment processes.

27. 27 Treatment Issues/Concerns Ozone - potential by-products formed GAC - carbon usage rate (or length of run) UV/H 2 O 2 - potential by-products formed

28. 28 Summary Advanced processes (oxidation, AOP, GAC) most effective AOP - UV/H 2 O 2 - may not be practical Future work – Range of effective dosages for ozone – Range of dosages for ozone and H 2 O 2 – GAC contact time and usage rate – By-product formation – Confirm indicator compounds

29. 29 THANK YOU! Any Questions?