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Human Pharmaceuticals, Hormones, and Personal Care Products in Water Reuse Processes

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

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Human Pharmaceuticals, Hormones, and Personal Care Products in Water Reuse Processes

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  1. Human Pharmaceuticals, Hormones, and Personal Care Products in Water Reuse Processes Joel A. Pedersen1, Mary Soliman2, Heesu Park3,Angelica Castaneda-Jimenez3 and Mel Suffet3 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. Flocculation Disinfection Title 22 water Influent RO Barrier water Lime MF Sampling points Flow Chart of Water Reuse Plants .

  3. California Water Recycling Criteria -Title 22 Water - • Application to food crops - minimum of secondary treatment + disinfection • 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 secondary treatment ===================================== • Recharge groundwater to prevent saltwater intrusion - Lime/RO or MF/RO treatment

  4. Wastewater Contains Chemicals • Inorganic chemicals and NOM found naturally in drinking water. • Inorganics & organics from industrial, commercial and other human activities - Target and Non-Target Compounds • 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) target compounds - PhACs, PCPs, human and synthetic hormones, antioxidants, plasticizers • Tentative identification of (35) non-target compounds - MS library search - • Evaluate the effects of different water reuse treatment processes on their removal - Conventional treatment process (Title 22 water) - Lime/RO (Barrier water) - MF/RO (Barrier water) Compare reclaimed water to raw drinking water sources

  6. Broad Spectrum Analytical Scheme Acidification (pH3) Na2SO4, Ascorbic Acid, and Surrogate added Target and Non- Target Analysis Sample Continuous Liquid-Liquid Extraction • Identification • Quantification Metals, Boron TOC, UV Compliance Analysis GC/MS Analysis Condensation

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

  8. 19 Targeted Analytes (Recovery = 84%, SD = 21%)

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

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

  11. Non-Target Analysis

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

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

  14. WATER RECYCLING PLANT

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

  16. Secondary Effluent

  17. % Removal by Title 22 Waste Treatment 24-hour composite - Plant 1 and 3 - four 6-hr; *** Plant 2 - 24 - 1-hr

  18. Remaining after Tertiary Treatments

  19. Conclusions STP>Title 22> L-RO> MF-RO ( No. and Conc.) 2. 5 Comp’ds > 100 ng/L - BHA and BHT, NBBSA, Caffeine and Clofibric acid after Title 22 Treatment. 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.

  20. 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. • 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.

  21. Broad Spectrum Analysis of Organic Chemicals • 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 • Confirmation of target compounds and subsequent quantitation

  22. New Strategies for Evaluation of Water Quality for Water Reclamation Present Strategy - MCLs 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 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.

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

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