Triclocarban, Triclosan, Polybrominated Diphenyl Ethers, and 4-nonylphenol in Biosolids and in Soil Receiving 33-year Biosolids Application Kang Xia Associate Professor Dept. Crop & Soil Environ. Sci. Virginia Tech [email protected] 1 540-231-9323 Outline What are Trace Organic Chemicals (TrOCs)? Occurrence of TrOCs in biosolids Fate of TrOCs in biosolids-applied land Future research needs 2 What are TrOCs? Triclocarban (TCC) Triclosan (TCS) Polybrominated Diphenyl Ethers (PBDEs) 4-nonylphenol (4-NP) Are Trace Organic Chemicals (TrOCs) 3 Human uses • Prescription drugs • over-the counter drugs • Therapeutic drugs • Veterinary drugs • Fragrances •Cosmetics • Sun-screen products • Diagnostic agents • Nutraceuticals (e.g., vitamins) • Illegal drugs • Flame retardants • Additives in consumer products Animal production uses • Therapeutic (disease control) • Sub-therapeutic (growth promotion) 4 chloramphenicol Antibiotic for respiratory tract infections TrOCs bezafibrate Antilipidemic, lipid lowering drug Sewer systems DEET Insect repellent Influent metoprolol Hypertension medication TrOCs in wastewater influent of two WWTPs in Beijing, China (Environ. Sci. Technol. 2011, 45:3341–3348) Feb Jan Aug TrOCs Sewer systems WWTP Influent Effluent Biosolids Predicted half lives of many TrOCs? http://www.pbtprofiler.net Characteristics of wastewater treatment plants large volume of influent and effluent short detention time (hours to few days) treatment guidelines are pathogen and heavy metal driven Compound Predicted half life (day) Water Soil TCS 60 120 TCC 60 120 PBDE-47 180 360 4-NP 15 30 8 If there is not enough time to degrade TrOCs in WWTPs, where do they go? A case study: Fate of 4-NP in secondary WWTPs Compound of interest Study sites 4-nonylphenol (4-NP) is a metabolite of • 13 secondary WWTPs (GA, SC, KS) nonylphenol polyethoxylates (NPnEOs) • Population served by the WWTPs: • NPnEOs are nonionic surfactants 5,000 to 0.5 million H H R O C COH • Wastewater treated by the WWTPs: H H n (3-20) 0.75 MGD - 0.5 BGD • Annual production • Biosolids produced in the WWTPs: worldwide ~ 500,000 T U.S ~ 200,000 T 0.6 to 100,000 dry ton/day 9 Case study results 250 16 H H 4-NP ) Influent R O C COH 14 -1 H H 200 Surfactant n (3‐20) 12 10 Weight % 150 8 100 6 4 50 [NPnEOs] in Influent (ug L 2 0 0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPnEOs (ethoxylate number) 4-NP and its precursors in WWTP influent of #13 10 H H 9 R O C COH Effluent 8 H H n (3‐20) ) -1 7 6 5 4 3 [NPnEOs] (ug L (ug [NPnEOs] 2 ND 1 ND 0 012345678910111213141516 NPnEOs (ethoxylate number) 4-NP and its precursors in effluent of WWTP #13 1000 H H biosolids R O C COH H H n (3‐20) 500 ) -1 15 10 Concentration (mg kg 5 0.11 – 1.56 mg kg-1 0 NP NP1EO NP2EO NP3EO NP4EO NP5EO NP6EO NP7EO NP8EO NP9EO NP10EO NP11EO NP12EO NP13EO NP14EO NP15EO NP16EO 4-NP and its precursors in biosolids of WWTP #13 4-NP input 4-NP output 61% from influent degraded? 6% effluent? 39% produced in WWTP Daily mass balance for 4-NP in WWTP #13 4-NP levels in biosolids and compost from the WWTPs investigated 1600 d.w.) , 1 ‐ 1200 Other reported levels kg 800 (mg 400 NP] ‐ 0 [4 123456789 WWT # Levels of 4‐NP in biosolids from WWTPs in California. 15 Can WWTPs remove 4-NP from influent? Yes! However WWTPs are ineffective for 4-NP degradation – there just not enough time! 4-NP is sequestered by biosolids Can biosolids sequester other TrOCs? 100 100 22 10 11 10 8. 9 10 7. 2 1. 8 1 1 0.1 , dry weight), dry -1 triclocarban triclosan 0.1 0.01 1 1000 704 0. 61 0. 52 176 100 57 0. 30 Concentration (mg kg 10 0.1 PBDEs 4-nonylphenol 1 aerobic anaerobic compost aerobic anaerobic compost (9) (7) (7) (9) (7) (7) Biosolids from 16 WWTPs of 5 states 4 PPCPs: triclocarban, triclosan, PBDEs, 4-NP -1 300 – 704,000 g kg dry weight 17 TrOCs in biosolids Biosolids from 7 states 25 PPCPs: antiepileptic, antihistamine, antidepressant, fragrance, disinfectant, detergent metabolites, preservative, fire retardants, plasticizer, fragrance, steroids 15 – 1,520,000 g kg-1 organic C 18 Kinney et al., ES&T, 2006, 40:7207-7215 Water Research, 2010, 44:658 4-NP levels in biosolids and compost from the WWTPs investigated compost, %) Concentration reduction (biosolids Concentration reduction of target compounds in biosolids compared with composted biosolids from the same WWTP. Environ. Toxico. Chem. 2010, 29:597–605. Biosolids production, usage, and disposal in U.S. 9 8.5 8.2 8 7.6 7.5 7.1 7 6.9 6.5 Biosolids production 6 (million dry (million dry tons/year) 1998 2000 2005 2010 Year Benefits: • primary nutrients • secondary nutrients • root growth promoters • enhance soil structure • C sequestration (Brown et al., Environ. Sci. Technol., 2011, 45:7451) 22 TrOCs WWTP Influent Effluent deposition Biosolids runoff volatilization uptake degradation leaching 23 Fate of TrOCs in biosolids-applied land A field study: TCC, TCS, PBDEs, and 4-NP in soil after 33 consecutive years of biosolids application 24 MWRD Experimental design • Study site: established in 1973 Fulton County, IL • Treatments: Four 1. Control: 336N-224P kg/ha-yr 2. Biosolids: 16.8 Mg/ha-yr 33-y cumulative rates: 3. Biosolids: 33.6 Mg/ha-yr 554.5, 1109, 2218 Mg/ha 4. Biosolids: 67.2 Mg/ha-yr *All treatments received K @ 112 kg/ha-yr • Crop: Corn (Zea mays L.) • Target TrOCs: TCC, TCS, PBDEs, 4-NP 25 Characteristics of the compounds investigated in this study Compound Log Kow Use Chemical structure 4-nonylphenol 4.75* metabolite of (4-NP) nonylphenol CAS # 104-40-5 polyethoxylates C9H19 OH (non-ionic surfactants) 5 6 6’ 5’ polybrominated log Kow = flame retardant diphenyl ethers 0.621(#Br) + 4.12 4 O 4’ (PBDEs) 32 2’3’ Brx Bry Triclosan (TCS) 4.19* Cl OH CAS # 3380-34-5 O Cl Cl bactericides Triclocarban 4.48* Cl NH O (TCC) NH CAS # 101-20-2 Cl 26 Cl • biosolids: anaerobic digestion (Metropolitan Water Reclamation District of Greater Chicago) concentration (mg kg-1, dry weight) TCC TCS PBDEs 4-NP 24 4.2 0.711 886 • soil was sampled at: 0 – 15 , 15 – 30, 30 – 60, 60 – 120 cm • plant tissue sampled at harvest: leaf, stalk, kernel 27 Case study results 800 TCC PBDEs 1400 600 1200 400 1000 , dry weight) , dry -1 800 200 g kg 600 0 TCS 60 10000 4-NP 50 8000 40 6000 30 4000 Concentration ( 20 2000 10 0 554.5 1109 2218 0 554.5 1109 2218 33-year cumulative loading (Mg ha-1) 33-year cumulative loading (Mg ha-1) Concentrations of TCC, TCS, PBDEs, and 4-NP in 0 – 15 cm depths of soil amended with biosolids at four rates 28 1400 700 TCC PBDEs 1200 600 -1 1000 500 554.5 Mg ha 1109 Mg ha-1 800 400 2218 Mg ha-1 600 300 control , dry weight) , dry 400 200 -1 200 100 g kg 0 0 60 TCS 9000 4-NP 8000 50 7000 40 6000 5000 30 4000 Concentration ( 20 3000 2000 10 1000 0 0 0-15 15-30 30-60 60-120 0-15 15-30 30-60 60-120 Depth (cm) Depth (cm) Concentrations of TCC, TCS, PBDEs, and 4-NP at different depths in biosolids-amended soil 29 120 1.6 PBDEs 4-NP 1.4 0 – 15 cm 100 1.2 15 – 30 cm 80 1.0 30 – 60 cm 60 0.8 0.6 60 – 120 cm 40 0.4 20 0.2 Mass Balance = 0 0.0 7 TCC7 TCS amount detected in soil 6 6 x100% = 33-year cumulative input 5 5 Percent recovered Percent 4 4 o Dsoil x Asoil x BDsoil x (Csoil –Csoil) 3 3 x100% 2 2 Ybiosolids x Rbiosolids x Cbiosolids 1 1 0 0 554.5 1109 2218 554.5 1109 2218 Compound Predicted half life (day) Cumulative biosolids loading (Mg ha-1) Water Soil TCS 60 120 Estimated % recoveries of PBDEs, 4-NP, TCC 60 120 TCC, and TCS, in top 120 cm soil after 33- PBDE-47 180 360 year of annual application of biosolids. 4-NP 15 30 30 210 Biosolids 200 Soil 180 150 26 20 14 Concentration ratio 10 5.7 1 1 0 0.17 4-NP TCCΣ PBDEs TCS Concentration ratio of 4-NP, TCC, PBDEs, and TCS in biosolids and surface soil (0-15 cm) amended with -1 biosolids at accumulative 33-year loading of 2218 Mg ha . 31 Field case study result summary: Target compounds Results Levels in soil increase with biosolids loading Levels in soil sharp decrease with soil depth PBDEs persistent TCC, TCS, 4-NP less persistent Concentrations in soil 4-NP > TCC > PBDEs >TCS (180:26:14:1) PBDEs, 4-NP immobile TCC, TCS limited mobility Plant (corn) uptake No 32 TrOCs WWTP Influent Effluent deposition (limited) Biosolids runoff ? volatilization (limited) uptake (no) degradation (varies) leaching (limited) 33 Future research needs • Fast, inexpensive, accurate, multi-compound analytical methods for detecting TrOCs in environmental samples • Evaluation of new wastewater and biosolids treatment technologies • Long term monitoring of wider range of TrOCs in biosolids-amended soils and surrounding environment • TrOCs transformation in storm water runoff • Plant and animal uptake of TrOCs in biosolids- amended soils 34 Acknowledgement: Drs. Lakhwinder Hundal, Albert Cox, Thomas Granato, and Kuldip Kumar Metropolitan Water Reclamation District of Greater Chicago Graduate students: Greg Pillar Kusum Verma Research technician: Christina Lusk 35.