Tric iclocarban, T locarban, Tric iclosan, P losan, Polybr - PowerPoint PPT Presentation

Tric iclocarban, T locarban, Tric iclosan, P losan, Polybr lybromina ominated ed Diphenyl Diphenyl Ether Ethers, and 4-nonylphenol in , and 4-nonylphenol in Biosolids and in Soil R Biosolids and in Soil Receiving 33-y eceiving 33-year ear Biosolids Application Biosolids Applica tion Kang Xia ng Xia Associa Associate Pr e Prof ofessor essor De Dept. Cr pt. Crop & Soil En op & Soil Envir viron. Sci. on. Sci. Virginia T Vi Tech kxia@vt.edu 1 540-231-9323

Outline Outline  Wha What ar t are T e Trace Or ace Organic Chemicals (T nic Chemicals (TrOCs)? rOCs)?  Occur Occurrence of ence of T TrOCs OCs in biosolids n biosolids  Fate of te of T TrOCs OCs in biosolids-a n biosolids-applied land pplied land  Futur Future r resear search needs needs 2

 Wha What ar are T e TrOCs? OCs? 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 Antilipidemic, lipid lowering drug bezafibrate Sewer systems Insect repellent DEET Influent Hypertension medication metoprolol TrOCs in wastewater influent of two WWTPs in Beijing, China (Environ. Sci. Technol. 2011, 45:3341–3348) Aug Feb Jan

TrOCs Sewer systems WWTP WWTP Ef Effluent uent Influent Biosolids 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 • Wastewater treated by the WWTPs: R O C C OH H H n (3-20) 0.75 MGD - 0.5 BGD • Annual production • Biosolids produced in the WWTPs: worldwide ~ 500,000 T 0.6 to 100,000 dry ton/ day U.S ~ 200,000 T 9

Case study results 250 16 H H 4-NP Influent R O C C OH 14 [NPnEOs] in Influent (ug L -1 ) H H 200 n (3 ‐ 20) Surfactant 12 10 Weight % 150 8 100 6 4 50 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 Effluent R O C C OH H H 8 n (3 ‐ 20) [NPnEOs] (ug L -1 ) 7 6 5 4 3 2 ND 1 ND 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 effluent of WWTP #13

4-NP and its precursors in biosolids of WWTP #13 Concentration (mg kg-1) 1000 500 10 15 0 5 NP NP1EO R NP2EO NP3EO NP4EO O NP5EO C H H H NP6EO H C OH NP7EO n (3 ‐ 20) NP8EO NP9EO NP10EO NP11EO 0.11 – 1.56 mg kg -1 NP12EO NP13EO biosolids NP14EO NP15EO NP16EO

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

[4 ‐ NP] (mg kg ‐ 1 , d.w.) 1600 Other reported levels 1200 800 400 0 1 2 3 4 5 6 7 8 9 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 2 2 10 1 0 1 1 8 9 10 . 7 2 Concentration (mg kg-1, dry weight) . 1 8 1 . 1 0.1 triclocarban triclosan 0.1 0.01 1000 1 7 0 4 0 5 2 0 6 1 . . 1 7 6 100 5 7 0 3 0 . 10  PBDEs 0.1 4-nonylphenol 1 aerobic anaerobic compost aerobic anaerobic compost (9) (7) (7) (9) (7) (7) Biosolids from 16 WWTPs of 5 states triclocarban, triclosan, PBDEs, 4-NP 4 PPCPs: 300 – 704,000  g kg -1 dry weight 17

 TrOCs OCs in biosolids n biosolids Biosolids from 7 states antiepileptic, antihistamine, antidepressant, fragrance, 25 PPCPs: 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

Concentration reduction (biosolids  compost, %) 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. (million dry tons/year) 9 Biosolids production 8.5 8.2 8 7.6 7.5 7.1 6.9 7 6.5 6 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

23 runoff Effluent uent uptake leaching Ef Biosolids Biosolids WWTP WWTP degradation deposition volatilization TrOCs Influent

 Fate of te of T TrOCs OCs in biosolids-a n biosolids-applied land pplied land A field study: A f eld study: TCC, T TCS, PBDEs PBDEs, and 4-NP in soil after 33 cons and 4-NP in soil after 33 consecutiv ecutive year ears of s of biosolids a biosolids applica plication ion 24

MWRD Experimental design Experimental design • Study site: Study site: esta established in 1973 lished in 1973 Fulton County Fulton County, IL IL • Trea eatments: tments: Fo Four 1. Contr 1. Control: l: 336N-224P k 336N-224P kg/ha-yr /ha-yr 2. 2. Biosolids: Biosolids: 16.8 Mg/ha-yr 16.8 Mg/ha-yr 33-y cumula 33-y cum lativ tive r rates: tes: 3. Biosolids: 3. Biosolids: 33.6 Mg/ha-yr 33.6 Mg/ha-yr 554.5, 1109, 2218 Mg/ha 554.5, 1109, 2218 Mg/ha 4. Biosolids: 4. Biosolids: 67.2 Mg/ha-yr 67.2 Mg/ha-yr *All tr All trea eatments r tments receiv ceived K @ 112 k d K @ 112 kg/ha-yr /ha-yr • Cr Crop: op: Corn ( Corn ( Zea ma Zea mays L. L. ) • Target T et TrOCs: OCs: TC TCC, TC TCS, S, P PBDEs, 4 4-NP 25

Ch Ch Charac Charac aracteristic aracteristic teristics of teristics of s of the compounds inves s of the compounds inves the compounds investigat the compounds investigat igated in t igated in t ed in this ed in this is study is study study study Compo Compo Compound Compound und und Log Log Kow Log Kow Log Kow Kow Use Use Use Use Ch Chemical struc Ch Chemical struc emical structure emical structure ure ure 4-nonylphenol 4-nonylphenol 4.75* 4.75* metabolite of metabolite of (4-NP) (4-NP) nonylphenol nonylphenol CAS # 104-40-5 CAS # 104-40-5 polyethoxylates polyethoxylates OH OH OH OH C 9 H 19 C 9 H 19 C 9 H 19 C 9 H 19 (non-ionic (non-ionic surfactants) surfactants) polybrominated polybrominated log K ow = log K ow = flame retardant flame retardant 5 5 5 5 6 6 6 6 6’ 6’ 6’ 6’ 5’ 5’ 5’ 5’ 0.621(#Br) + 4.12 0.621(#Br) + 4.12 diphenyl ethers diphenyl ethers O O O O 4’ 4’ 4’ 4’ 4 4 4 4 (PBDEs) (PBDEs) 3 3 3 3 2 2 2 2 2’ 2’ 2’ 2’ 3’ 3’ 3’ 3’ Br x Br x Br x Br x Br y Br y Br y Br y Triclosan (TCS) Triclosan (TCS) 4.19* 4.19* OH OH Cl Cl CAS # 3380-34-5 CAS # 3380-34-5 O O Cl Cl Cl Cl bactericides bactericides Triclocarban Triclocarban 4.48* 4.48* O O Cl Cl NH NH (TCC) (TCC) CAS # 101-20-2 CAS # 101-20-2 NH NH Cl Cl Cl Cl 26

• biosolids: biosolids: anaer anaerobic dig bic digestion stion (Metr (Metropolitan W politan Water R ter Reclama amation ion District of District of Gr Grea eater Chica ter Chicago) o) concentration (mg kg -1 , dry weight)  PBDEs TCC TCS 4-NP 24 4.2 0.711 886 • soil w soil was sampled a s sampled at: 0 – 15 , 15 – 0 – 15 , 15 – 30, 30 – 30, 30 – 60, 60 – 60, 60 – 120 cm 20 cm • plant tissue sampled a plant tissue sampled at har harvest: est: leaf leaf, , stalk, stalk, kernel rnel 27

Case study results 800  PBDEs TCC 1400 Concentration (  g kg-1, dry weight) 600 1200 400 1000 200 800 600 0 TCS 4-NP 60 10000 50 8000 40 6000 30 4000 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 28 depths of soil amended with biosolids at four rates