1. Human Pharmaceuticals, Hormones, and Personal Care Products in Water Reuse Processes Joel A. Pedersen 1, Mary Soliman 2, Heesu Park 3, Angelica Castaneda-Jimenez 3 and Mel Suffet 3 1 Environmental Chemistry and Technology Program and Soil Science Department, University of Wisconsin - Madison 2 California Department of Health Services 3 Environmental Science and Engineering Program, UCLA

2. Flow Chart of Water Reuse Plants Influent Flocculation DisinfectionTitle 22 water Lime Barrier water MF RO Sampling points.

3. California Water Recycling Criteria -Title 22 Water - Application to food crops Application to food crops - minimum of secondary treatment + disinfection Irrigation water in contact w/ edible portion Irrigation water in contact w/ edible portion secondary + chemical coagulation + filtration disinfection (“disinfected tertiary recycled water”) Effluent discharged to streams to be pumped out downstream for irrigation purposes Effluent discharged to streams to be pumped out downstream for irrigation purposes secondary treatment secondary treatment===================================== Recharge groundwater to prevent saltwater intrusion - Lime/RO or MF/RO treatment Recharge groundwater to prevent saltwater intrusion - Lime/RO or MF/RO treatment

4. Wastewater Contains Chemicals 1. Inorganic chemicals and NOM found naturally in drinking water. 2. Inorganics & organics from industrial, commercial and other human activities - Target and Non-Target Compounds 3. Chemicals added or byproducts of water and wastewater treatment ============================================================== Measure Target Compounds -HOWEVER - There is a health risk from unidentified chemical(s) at ng to pg/L levels - Non-Target Compounds

5. Objectives Confirm and quantify (19) - PhACs, PCPs, human and synthetic hormones, antioxidants, plasticizers Confirm and quantify (19) target compounds - PhACs, PCPs, human and synthetic hormones, antioxidants, plasticizers Tentative identification of (35) - MS library search - Tentative identification of (35) non-target compounds - MS library search - Evaluate the effects of different water reuse treatment processes on their removal Evaluate the effects of different water reuse treatment processes on their removal - Conventional treatment process (Title 22 water) - Conventional treatment process (Title 22 water) - Lime/RO (Barrier water) - Lime/RO (Barrier water) - MF/RO (Barrier water) - MF/RO (Barrier water) Compare reclaimed water to raw drinking water sources

6. Broad Spectrum Analytical Scheme Sample Metals, Boron TOC, UV Compliance Analysis Acidification (pH3) Na 2 SO 4, Ascorbic Acid, and Surrogate added Continuous Liquid-Liquid Extraction Condensation GC/MS Analysis Identification Quantification Target and Non- Target Analysis

7. Experimental Setting ( 10 L influent/40 L effluent) - Baker et al. 1987 Water Sample Solvent 10 L/hr 1 L/hr Mixture Inlet Water Outlet CLLE Heater Condenser

8. 19 Targeted Analytes (Recovery = 84%, SD = 21%) Human Pharmaceuticals Hormones caffeine 17  -estradiol carbamazepineEstrone, Esterol carisoprodolethinyl estradiol clofibric acidprogesterone diazepamstanolone fenofibratetestosterone gemfibrozilOther compounds ibuprofen BHT (Antioxidant) p-toluenesulfonamide Note: Bold- not seen BHA (Antioxidant) N-butyl benzene- sulfonamide(plasticizer)

9. Targeted Analysis (PTGC - 12 m HP-1, 20 min run time)

10. Carbamazepine – 142-650 ng/L Carbamazepine – 142-650 ng/L Antiepileptic, <3% excreted in urine as parent or epoxide Antiepileptic, <3% excreted in urine as parent or epoxide Inhibits high-frequency neuronal firing by Inhibits high-frequency neuronal firing by reducing Na + currents reducing Na + currents (Drewes et al., 2001; Metcalfe et al., 2001) Pharmaceuticals & Hormones Ethinylestradiol - 43-50 ng/L Ethinylestradiol - 43-50 ng/L Synthetic oral contraceptive Synthetic oral contraceptive (Ternes et al., 1999; Huang and Sedlak, 2001) (Ternes et al., 1999; Huang and Sedlak, 2001) Progesterone - 5*-50 ng/L Progesterone - 5*-50 ng/L (Li et al., 2002) (Li et al., 2002) * < MDL

11. Non-Target Analysis Compound Class35 - Compounds Identified Industrial chemicals & solvents9 Pesticides (methyl parathion, metolachlor) 2 Human pharmaceuticals (Naproxen) 1 Personal care product ingredients3 Plasticizer compounds (Phthalates) 6 Antimicrobials (chloroxylenol, chloropene) PAHs (napthalene and phenanthrene) Fire retardant (tris(2-chloroethyl) phosphate) Steroid related hormones (cholestanol, cholesterol, cholest-4-en-3-one, stigmasterol) 72147214

12. Non-target Analysis (PTGC - 30 m DB-5MS, 75 min run time)

13. Personal Care Product Ingredients Diethyltoluamide (DEET) Diethyltoluamide (DEET) Insect repellent Insect repellent (Snyder et al., 2002) Benzophenone Benzophenone Fragrance fixative Fragrance fixative (Paxéus, 1996) Polycyclic musks Polycyclic musks AHTN (Tonalide) and HHCB (Galaxolide) AHTN (Tonalide) and HHCB (Galaxolide) Synthetic fragrances Synthetic fragrances (Simonich et al., 2000)

14. WATER RECYCLING PLANT

15. Flow Chart of Water Reuse Plants Influent Flocculation DisinfectionTitle 22 water Lime Barrier water MF RO Sampling points.

16. Secondary Effluent Compound Class Plant 1 Plant 2 Plant 3 *Raw DW SPW,CRW,GW Of 19 Target 13 Chemicals (> 95% are ng/L) No Estriol 16 14 4 or Diazepan is observed Of 35 Non-target 16 Chemicals TOTAL 29 ------------------------------------- * Much lower conc. levels BHA, BHT, NBBSA and 18 20 9 34 34 13 than secondary effluent - Caffeine are highest level

17. Plant 1-3 2 o Eff Plant 1 T-22 Plant 2 T-22** Plant 3 T-22 Compoundng/L%R %R%R BHA128-105068888787 ibuprofen50-46979760 carbamazepine142-6504899100 clofibric acid*10-550100053 Ethinyl estradiol20-50010020 stanolonend-162100 na estrone50-22010081100 gemfibrozilnd-480100 na p-Toluene* sulfamide 350-520 656771 ---------------------- All Compounds --------- 5 >100 ng/L ----------- 13 to 8 T 15 to 15 NT 2 new ones ----------- 16 to 9 T 18 to 10NT ----------- 14 to 7 T 18 to 9NT % Removal by Title 22 Waste Treatment 24-hour composite - Plant 1 and 3 - four 6-hr; *** Plant 2 - 24 - 1-hr

19. Remaining after Tertiary Treatments Compound Plant 2 Class T-22 L- RO Plant 3 T-22 L-RO MF- RO Of 19 Target 10 5* Conc. (ng/L) <350 <70* 8 4* 3* <520 <62* <50* Of 35 Non- 10 1* target TOTAL 20 6 Hourly samples for 24 hrs. ------------------------------------- *Much lower levels than BHA, BHT, NBBSA -- Note- GW recharge of 50% 9 2* 2* 17 6 5 6 Hour composite for 24 hrs. secondary effluent - and Caffeine were observed L-RO and MF-RO waters

20. Conclusions 1. STP>Title 22> L-RO> MF-RO ( No. and Conc.) 2.5 Comp’ds > 100 ng/L - 2.5 Comp’ds > 100 ng/L - BHA and BHT, NBBSA, Caffeine and Clofibric acid after Title 22 Treatment. 3.Best treatment alternative was MF/RO. 35% of Target and 15% of non-target compounds are present at > DL for RO and MF/RO treatment. 4. Antioxidants BHA and BHT, plasticizers as NBBSA and Caffeine are observed after MF/RO. Remember BHA and BHT have been shown to leach from polyethylene pipe. 5.Sampling an actual treatment system for correct evaluation of a variable hourly, daily and seasonal influent and effluent and remains a problem.

21. Water Quality Assessment for Indirect Potable Reuse of Water In water reuse, the source is not “pollution free”. Monitoring for a few “target” compounds is meaningless. In water reuse, the source is not “pollution free”. Monitoring for a few “target” compounds is meaningless. Many other compounds are observed by GC or LC/MS and are ignored. “Non - target”compounds are significant. Many other compounds are observed by GC or LC/MS and are ignored. “Non - target”compounds are significant. Idea - Broad Spectrum Analysis and lowering the detection limit of trace organic compounds by large volume of water samples to ng/L to pg/L? level. Idea - Broad Spectrum Analysis and lowering the detection limit of trace organic compounds by large volume of water samples to ng/L to pg/L? level.

22. Broad Spectrum Analysis of Organic Chemicals Screening strategy that uses GC or LC Screening strategy that uses GC or LC profiles to analyze for temporal and spatial changes of both target and non-target compounds Tentative identification of non-target compounds -- MS library search Tentative identification of non-target compounds -- MS library search Confirmation of target compounds and subsequent quantitation Confirmation of target compounds and subsequent quantitation

23. New Strategies for Evaluation of Water Quality for Water Reclamation 1.Present Strategy - MCLs 2.Future Strategies - A. “Treatment Reliability” Standards a. Treatment Redundancy b. Mandate Unit Operations c. Access Treatment Reliability \ B. “Broad Spectrum Chemical Analyses” a. Analyze target and “non-target” compounds present a defined concentration level. Toxicologist- Help. a. Analyze target and “non-target” compounds present above a defined concentration level. Toxicologist- Help. C. “Develop NEW Health and Safety Tests” a. Specify Priority Hazards. e.g. EDCs b. Study Mixtures and Matrices for above.

24. Acknowledgements California DHS (Larry Barrett, DVM) California DHS (Larry Barrett, DVM) Samples from Orange County Water District, West Basin Water District, and Los Angeles Sanitation District. Samples from Orange County Water District, West Basin Water District, and Los Angeles Sanitation District.