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Occurrence And Fate Of EDCs In Biosolids And Biosolids–Amended Soils – An Overview

Metropolitan Water Reclamation District of Greater Chicago. Occurrence And Fate Of EDCs In Biosolids And Biosolids–Amended Soils – An Overview. Dr. Lakhwinder Hundal Sr. Environmental Soil Scientist EM&R Department Metropolitan Water Reclamation District of Greater Chicago. HO.

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Occurrence And Fate Of EDCs In Biosolids And Biosolids–Amended Soils – An Overview

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  1. Metropolitan Water Reclamation District of Greater Chicago Occurrence And Fate Of EDCs In Biosolids And Biosolids–Amended Soils – An Overview Dr. Lakhwinder Hundal Sr. Environmental Soil Scientist EM&R Department Metropolitan Water Reclamation District of Greater Chicago

  2. HO Endocrine Disrupting Compounds • What are they? – Compounds that alter the functions of Endocrine System and consequently cause adversehealth effects in intact organism, its progeny or populations. • How may it happen? OH 17b-Estradiol HO 4-Nonylphenol 4-NP isomer HO

  3. Recent Concerns! Concerns raised regarding the presence of “emerging organic contaminants” or “endocrine disrupting compounds” in biosolids.  Majority of these so called endocrine disrupting compounds (EDCs) are basically “everyday domestic use chemicals”.  These compounds enter the environment mainly via regular or everyday domestic use and routine activities.

  4. Universe of EDCs • EPA plans to screen ~87,000 chemicals for EDC effect • 75,500 industrial chemicals • 3,100 agriculture related chemicals • 8,000 cosmetics, food additives, and supplements Examples of Common EDCs • Steroids – estrogens (17-estradiol, 17α-ethynilestradiol), testosterone • Surfactants – nonylphenol and its ethoxylates • Pesticides – DDT, atrazine, methoxychlor, dieldrin, etc. • Dioxins, PAHs, PCBs, PBDEs, PFCs, etc. • Bisphenol A, phthalates, musks, etc.

  5. Not So Common! EDCs, Where Do They Come From? • Pharmaceuticals • Personal care products • Consumer products • Food • Waste incineration • Industrial chemicals • Farming, livestock, & forestry • Household sewage Common Sources! Phthalates PFCs, Musks TCC, TCS PBDEs Dioxins Steroids Pesticides Flavonoids Bisphenol A Surfactants, 4-NP

  6. Worldwide Sales Market Share 17% USA 9% 43% Europe US $ (Billion) Japan 31% Other 2004 2006 2008 2002 Year Pharmaceutical Production and Use Source: Statistics 2008, VFA VFA is the trade organization of research-based pharmaceutical companies in Germany

  7. Power of Advertising • Direct-to-consumer advertising (DTCA) • Only legal in US and New Zealand • $2.20 earnings for every $1 spent on DTCA Annual Spending (millions of US $) 2006 1996 2000 2002 2004 1998 Year Source: Donohue et al., 2007. The New England Journal of Medicine

  8. “The red are for the illness, the blues are for the side effects of the red and the greens are for the side effects of the blue.”

  9. Why Now? • Recent advances in analytical chemistry have enabled study of chemicals that were previously undetected in the environment. • The advent of LC-MS, especially LC-tandem MS has revolutionized the environmental analysis with ppt (ng/L) level detection of polar compounds in water samples. • Recent studies are largely focused on survey or monitoring (chemical occurrence/exposure effects) with majority of data on occurrence and effects based on aquatic systems. • These publications are attracting growing attention from regulatory agencies, environmental advocates, news media and the public. Trillions >Billions >Millions (ppt) (ppb) (ppm)

  10. Land Application of Biosolids Not to scale

  11. 2010 State-Of-The-Science Review – (Funded by WERF) • BFRs –PBDEs, TBBPA, etc. • Plasticizers –Bisphenol A (BPA) • PPCPs –Antibiotics(tetracyclines, ciprofloxacin, etc.) • –Antimicrobials(TCS and TCC) • –Musks and fragrances(AHTN and galaxolide) • Steroids –Hormones(17α-ethynilestradiol, 17β-estradiol, etc.) • PFCs –PFOA and PFOS

  12. Pesticides – DDT (1874 – 1972) • One of the most effective pesticides • Saved lives • Increased food production • Ubiquitous in the environment • House dust = 0.3-9.6 µg/g • Trace concentrations in biosolids, <0.01 µg/g • Not an issue in land applied biosolids

  13. PAHs (BaP) and PCBs PCBs banned in 1977 • PCBs used as coolants and insulating fluids; were used in plastics, carbonless copy paper, wood floor finishes, etc. • PAHs produced by incomplete burning of C-containing materials • Ubiquitous in the environment • Concentrations in biosolids – BaP = 1.5-4.0 µg/g; PCBs = 0.6-1.6 µg/g House dust, PCBs = 0.2-70 µg/g BaP = 0.4-18 µg/g • Degradation is slow in soil (half-life of PAHs = ~24-570 days; PCBs = 940 days) – not expected to be mobile in biosolids-amended soil. Coal burning power plant

  14. Dioxins • 2,3,7,7-tetrachlorodibenzo-p-dioxin (TCDD) – the most toxic compound ever known • Ubiquitous in the environment • Trace levels in biosolids – declining trend • After 5 years of study,Screening Ecological Risk Analysis, and outside peer review,EPA concluded that“dioxins in land applied biosolids do not pose a significant risk to human or environmental health”. • Long-term biosolids land application data collected from the Fulton County supported EPA’s decision. (Hundal et al., 2008, JEQ) Dioxins disrupt birth ratio: More girls than boys !

  15. Flame Retardants – PBDEs • Found in polyurethane foam, furniture, electronics, toys, etc. • Ubiquitous in the environment House dust, 0.3-36 µg/g (ppm) • Concentrations in biosolids, 0.1-2 µg/g – below levels of concern for human health • LogKOW = 6.53-6.71 • Degradation is slow in soil (half-life ~10 years) – not expected to be mobile in biosolids-amended soil Common sources of PBDEs

  16. 0.8 24-48" 12-24" 0.6 6-12" 0-6" 0.4 0.2 0.0 Fate of PBDEs in Biosolids-Amended Soil Levels of total PBDEs in soil profile after 33 years of continuous biosolids application PBDEs Conc., µg/g 0 554 1109 2218 Cumulative Biosolids Loading, Mg/ha

  17. Bisphenol A (BPA) • Polycarbonates, epoxy resins, polystyrene cups, baby bottles, yogurt containers, etc. • Ubiquitous in the environment • Estrogenic effect known since 1936 • Levels in biosolids – 0.03-36 µg/g;House dust– 0.2-17 µg/g (Rudel et al., 2003, ES&T 37:4583-4553) • Degrades relatively easily in soil (half-life ranges from 1-10 days) –not mobile in biosolids-amended soil. Plastic bottles and hot liquids – A bad combo

  18. Surfactants – Nonylphenol (NP) • Alkylphenol ethoxylates used in detergents, spermicidal lubricant; as emulsifiers in pesticides, paints; etc. • Degradation product 4-NP has estrogenic effect • Estrogenic effect of NP is known since 1938 • Estrogenicity of NP is 106 times lower than 17-estradiol, a natural female hormone • NP is 10 times less potent than genistein, an isofalavonoid found in soybeans – 3 mg/kg • EU banned production and use • NP partitions into biosolids during the wastewater treatment process

  19. 4-NP input 4-NP output 61% from influent 94% in biosolids 6% Degraded? 39% produced in WWTP Effluent? WWTP May Generate 4-NP • Mass balance for 4-NP in a WWTP

  20. WWTP May Generate 4-NP H NPnEOs H R O C C OH H H n (4-20) anaerobic aerobic H H H H OH O O R C O C C R CH2 COOH C H H H H n (1, 2) n (0, 1) NP1EC, NP2EC NP1EO, NP2EO anaerobic R O H 4-Nonylphenol (4-NP)

  21. 12.0 24-48" 10.0 12-24" 6-12" 8.0 0-6" 6.0 4.0 4-NP Conc., µg/g 2.0 0.0 0 554 1109 2218 Cumulative Biosolids Loading, Mg/ha Surfactants – 4-NP • Concentration in biosolids, 600-800 µg/g; House dust = 0.02-85 µg/g • Degrades rapidly in soil, half-life = 3-30 days • Not stable or mobile in biosolids-amended soil Levels of 4-NP in soil profile after 33 years of continuous biosolids application

  22. Phthalates – DEHP, DBP, … • Plasticizer - plastics (PVC, etc.), cosmetics, medical products (bags, tubing, etc.) • Ubiquitous in the environment • Levels in biosolids – 0.1-200 µg/g House dust, DEHP = 16-7700 µg/g DBP = 3.9-1310 µg/g • Degrades relatively easily in soil (half-life ranges from 20-25 days) – not expected to be stable and mobile in biosolids-amended soil What’s Up Down There! Phthalates alter boys’ genitals! Reduce anogenital distance (AGD) AGD = Distance between penile and anal openings

  23. Antimicrobials – TCC, TCS • Used in toothpastes, mouthwash, hand soaps, creams, detergents, etc. • Introduced TCC in 1957, TCS in 1964 • No benefits from use to consumer • Preferably partition into biosolids, LogKow = 4.8 • Detected in biosolids TCC = 20-50 µg/g; TCS = 5-30 µg/g • Half-life in soil, TCS = ~18-30 days, TCC = 108-540 days – TCS is not expected to be mobile in biosolids-amended soil but TCC may persist longer. TCC 5% by weight

  24. TCC and TCS Concentration in Soil after 33 Years of Biosolids Application TCS TCC TCS Conc., µg/kg TCC Conc., µg/kg Cumulative Biosolids Loading, Mg/ha Cumulative Biosolids Loading, Mg/ha

  25. Steroids • Natural – testosterone, 17-estradiol • Degrade rapidly during activated sludge process • Synthetic – 17-ethinylestradiol • Degrades slowly during activated sludge process and partitions into biosolids • Traces could be found in biosolids • Degrades rapidly in agricultural soil (half-life ranges from 1-10 days) • Mobility is not a serious concern

  26. Musks – AHTN, HHCB, … • Synthetic musks and fragrances are used in formulations of body-care products, soaps, detergents, and cleaners • Ubiquitous in the environment • Levels in biosolids – AHTN = ND-51 µg/g HHCB = ND-86 µg/g Levels in house dust – AHTN = 0.1-16 µg/g HHCB = 1.9-81 µg/g • HHCB degrades in soil quite rapidly but AHTN degrades slowly but it is not expected to be highly mobile in biosolids-amended soils

  27. PFCs – PFOA, PFOS, … • Used in nonstick cookware, stain resistant sofa, carpets, food packaging (candy wrappers, pizza boxes, etc.), personal care and cleaning products, electrical goods, etc. • Ubiquitous in the environment • Levels in biosolids – PFOA = ND-4,780 ng/g PFOS = ND-5,383 ng/g Levels in house dust – PFOA = 10.2-1,960 ng/g PFOS = 8.9-12,100 ng/g • PFOA and PFOS do not seem to degrade in soil, degradation of other PFCs produce PFOA and PFOS – mobile in biosolids-amended soils

  28. What can you do! Act, don’t react • Reduce indiscriminate use of chemicals – Prevent release of toxic pollutants in the environment – Prevention is easier and lot cheaper Reality • EDCs (esp. estrogens)were, are, and willalways be with us – phytoestrogens and naturally released estrogens by females (human and animals) – Most of the anthropogenic contaminants that exhibit estrogenic effect are~10-106 times lesspotentthan thenatural estrogen, 17-estradiol

  29. Peeking At The Future New Generation Drugs • Antisense Drug • Cholesterol lowering drug – Mipomersen • Designed to target mRNA that controls disease causing protein • Based on single stranded oligonucleotides resembling DNA & RNA • Incretin Mimetics • Type 2 diabetes drug – Exenatide • Mimics incretin hormone GL-1 produced by endocrine cells

  30. Questions hundall@mwrd.org (708) 588-4201

  31. What Does It Mean?

  32. Something Public Can Relate To

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