Evaluating Exposure Risk to Trace Organics Chemicals in Biosolids

Protecting O ur W ater E nvironm ent

Metropolitan Water Reclamation District of Greater Chicago

MM etropolitan etropolitan WW ater ater RR eclam eclam ation ation DD istrict istrict ofof GG reater reater CC hicago hicago Evaluating Exposure Risk To Trace Organics Chemicals in Biosolids

Dr. Lakhwinder Hundal Supervising Environmental Soil Scientist EM&R Department Metropolitan Water Reclamation District of Greater Chicago

MWEA Biosolids Conference, March 11-12, 2014 Holiday Inn — Big Rapids, MI Some Facts About MWRD  Founded in 1889 to protect water quality of Lake Michigan  Services Cook County Illinois including city of Chicago and 125 suburban communities  Service area covers 875 sq. miles and includes 5.5 million people + industry equivalent to 5.7 million people  Operates seven water reclamation plants handling average daily flow of 1.2 billion gallons – Fill 450 acre swimming pool 10 ft. deep daily  Produces ~ 165,000 dry tons biosolids annually – Require ~ 13,750 semis to haul away annual production It’s a Big Pile of Poop!! Projection of Biosolids Use/Disposal in U.S.

Landfill

7070 6666 Other 70 6363 6060 60 Land Application 50 40 2323 23 30 23 2121 2020 Land Application 20 Other 10 1717 % Total of % 1414 1313 1010 Landfill MWRD 0 1998 2000 2005 2010 Year Pelletizer Source: U.S. EPA, 1999 Farmland (20.4%) (69.7%) Final Cover (3.2%) Co-disposal (0.6%)

Golf Courses, Parks, etc. (6.1%) Part 503 Trace Element Limits For Biosolids To Be Land Applied

Part 503 Limits National* Phosphate Trace Element Allowable EQ Average MWRD Fertilizer ------mg/kg------Arsenic* 75 41 7 5 11 Cadmium* 85 39 3 3 65 Copper* 4,300 1,500 570 380 57 Mercury* 57 17 1.3 1.0 NA Molybdenum 75 --- 17 10 NA Nickel* 420 420 53 40 28 Lead* 840 300 80 100 12 Selenium* 100 100 7 5 NA Zinc* 7,500 2,800 1,015 725 240 *Children ingesting biosolids *Plants grown in biosolids-amended soils EQ = Exceptional Quality *Based on USEPA’s 2006 TNSSS NA = Not known

Public Education And Outreach

Perception ≠ Reality

A deformed toad? Research shows that 8% of male sheep exhibit homosexual Cane toad eating a bat? behavior without a whiff of biosolids (New York Times, 1/25/07)

What’s the matter? Dr. Charles Roselli, Oregon Health Bat got your tongue? and Science University Trace Organic Chemicals in Biosolids  Why worry? – some trace organic chemicals may have the ability to alter the functions of Endocrine System and consequently cause adverse health effects in intact organism, its progeny or populations. OH  How may it happen?

HO Universe of Trace Organic (TOrCs) Chemicals

 EPA plans to screen ~87,000 chemicals for endocrine disruption effect

 75,500 industrial chemicals

 3,100 agriculture related chemicals

 >8,000 cosmetics, food additives, and supplements Examples of Common TOrCs Common Sources! Phthalates • Pharmaceuticals PFCs, Musks • Personal care & consumer products TCC, TCS Dioxins • Food additives PBDEs • Waste incineration Steroids • Industrial chemicals Pesticides Flavonoids • Farming, livestock, & forestry • Household sewage Not So Common!

Bisphenol A Surfactants, 4-NP Targeted National Sewage Sludge Survey (TNSSS)

 84 samples at 74 POTWs in 35 states (Aug. 2006 – Mar. 2007)

 Measured 145 analytes, including:

 117 trace organic chemicals

 97 pharmaceuticals, steroids and hormones  72 antibiotics and drugs (Rx and OTC)  25 steroids and hormones  11 polybrominated diphenyl ethers (PBDEs)  4 polycyclic aromatic hydrocarbons (PAHs)  3 inorganic ions  2 semi-volatile organics

 28 metals Concentration of Trace Organic Chemicals in Biosolids –TNSSS 2006

Analyte Use # Detects, (total=84) Conc., µg/kg Flame Retardants BDE-47 (Tetra) Reduces flammability 84 73 – 5,000 BDE-99 (Penta) 84 64 – 4,000 BDE-153 (Hexa) 84 9 – 410 BDE-209 (Deca) 83 150 – 17,000

Pharmaceuticals Azithromycin Antibiotic 80 8 – 5,205

Diphenhydramine Antihistimine 84 37 – 5,730

Caffeine Psychoactive stimulant 39 65 – 1,100

Carbamazepine Anticonvulsant 80 9 – 6,030

Cimetidine Ant-acid 74 4 – 8,330

Ciprofloxacin Antibiotic - strong 84 75 – 40,800

Fluoxetine Antidepressant 79 10 – 3,130

Ibuprofen Anti-inflammatory / Analgesic 54 99 – 11,900

Miconazole Antifungal 80 7 – 9,210

Tetracycline Antibiotic 81 38 – 5,270

Triclocarban Antibacterial 84 187 – 441,000

Triclosan Antibacterial 79 334 – 133,000 *Dry weight basis Concentration of Trace Organic Chemicals in Biosolids –TNSSS 2006

Analyte Use # Detects, (total=84) Conc., µg/kg* Steroids / Hormones Campesterol Plant sterol 84 2,840 – 524,000

Cholestanol Cholesterol derivative 84 3,860 – 4,590,000

Coprostanol Cholesterol derivative 84 7,720 – 43,700,00

Epicoprostanol Pheromone 83 868 – 1,030,000

17 alpha-Estradiol Estrogen replacement 5 16 - 48

17α-Ethynyl Estradiol Synthetic estrogen 0 NA

β-Stigmastanol Plant steroid 83 3,400 – 1,330,000

Stigmasterol Plant steroid 76 455 – 56,500

Testosterone Steroid hormone 17 30 – 2,040

PAHs, Semi-Volatile Organic Compounds

Bis (2-ethylhexyl) phthalate Plasticizer 84 657 – 310,000

4-Chloroaniline Aniline derivative 63 51 – 5,900

Fluoranthene Intermediate 77 45 – 12,000

Pyrene Intermediate 72 44 – 14,000 *Dry weight basis Part 503 Trace Element Limits For Biosolids To Be Land Applied

• 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 Routes of TOrCs Entering The Environment

Farmland Not to scale Source: Boxall, A.B., 2004. EMBO reports. 5:1110-1116 Flame Retardants – PBDEs

 Found in polyurethane foam, furniture, electronics, toys, etc.  Ubiquitous in the environment Common sources of PBDEs 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 Plant Uptake of PBDEs? • Not detected in corn roots • Not detected in corn leaves, stem, and grains

Health risks from exposure to levels of PBDEs in biosolids-amended soils are de minimis

BS Loading Levels in Soil Daily Dose for 15-kg Child Mg/ha ng/g ng/day* 554 118 23.6 1109 300 60.0 2218 658 131.7 Reference Dose for Chronic Oral Exposure (RfD) 10,500 *Based on EPA recommended soil ingestion value of 200 mg/day 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) Plastic bottles and hot  Degrades relatively easily in soil liquids – A bad combo (half-life ranges from 1-10 days) – not mobile in biosolids-amended soil. BPA – Bisphenol A Save your credit card receipts? BPA in credit card receipts = 8-17 g/kg

BPA in biosolids = 0.1–4.6 mg/kg

 How much more concentrated is BPA in credit card receipts than in biosolids? a) Equal b) 400x c) 4,000x 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 Surfactants – Nonylphenol (NP)

 4-NP could be generated in WWTP 4-NP input 4-NP output

61% from influent 6% 39% produced in WWTP

 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 Phthalates – DEHP, DBP, …

 Plasticizer - plastics (PVC, etc.), What’s Up Down There! 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 Phthalates alter boys’ genitals! DBP = 3.9-1310 µg/g Reduce anogenital distance (AGD)

 Degrades relatively easily in soil (half- life ranges from 20-25 days) – not expected to be stable and mobile in AGD = Distance between penile biosolids-amended soil and anal openings DBP in Biosolids How soft is your skin?

 What is the concentration of DBP in body lotions?

a) 1,000 mg/kg b) 5,000 mg/kg c) 10,000 mg/kg 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 TCC 5% by weight  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. TCS – Triclosan

How much biosolids you need to get same amount of TCS as in 1. 4 oz bar of soap?

a) 200 lbs b) 400 lbs c) 600 lbs 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 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 17α-Ethynilestradiol in Biosolids Not ready to start a family? How much biosolids do you have to eat to get 1 low dose birth control pill?

 EE2 in a low dose birth control pill = 50 µg  EE2 in biosolids = 4.6 µg/kg

A B C PFCs – PFOA, PFOS, …  Used in nonstick cookware, stain resistant sofa, carpets, food packaging, 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 easily in soil, degradation of other PFCs produce PFOA and PFOS – may show some mobility in biosolids- amended soils 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 – Coal burning power plant BaP = 1.5-4.0 µg/g; PCBs = 0.6-1.6 µg/g House dust - BaP = 0.4-18 µg/g; PCBs = 0.2-70 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. Dioxins  2,3,7,7-tetrachlorodibenzo-p-dioxin (TCDD) – the most toxic compound ever known to man kind  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 Dioxins disrupt birth ratio: More girls than boys ! do not pose a significant risk to human or environmental health”.  Long-term biosolids land application data collected from the Fulton County site supported EPA’s decision. (Hundal et al., 2008, JEQ) 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  TOrCs (esp. estrogens) were, are, and will always be with us. – phytoestrogens and naturally released estrogens by females (human and animals) – Most of the anthropogenic TOrCs that exhibit estrogenic effect are ~10-106 times less potent than the natural estrogen, 17-estradiol Take Home Messages  Land application of biosolids is a beneficial practice and it does not result in human exposure to TOrCs.  Only less than 1% of nation’s total cropland receives biosolids application.  Diet, ingestion of house dust, and inhalation of air are major sources of human exposure to TOrCs.  Overall, studies to date do not indicate any adverse effects on human health at the low concentrations of TOrCs found in the environment.  However, we can minimize exposure to TOrCs by becoming smart consumers and eliminating indiscriminate use of chemicals in our daily lives. Questions

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Quit treating biosolids like crap