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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

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Tric iclocarban, T locarban, Tric iclosan, P losan, Polybr lybromina

  • minated

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 Applica Biosolids Application tion

Kang Xia ng Xia Associa Associate Pr e Prof

  • fessor

essor De

  • Dept. Cr
  • pt. Crop & Soil En
  • p & Soil Envir
  • viron. Sci.
  • n. Sci.

Vi Virginia T Tech

kxia@vt.edu 540-231-9323

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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

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Triclocarban (TCC) Triclosan (TCS) Polybrominated Diphenyl Ethers (PBDEs) 4-nonylphenol (4-NP) Are Trace Organic Chemicals (TrOCs)

  • Wha

What ar are T e TrOCs? OCs?

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  • Therapeutic (disease control)
  • Sub-therapeutic (growth promotion)

Human uses Animal production 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
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Antibiotic for respiratory tract infections Antilipidemic, lipid lowering drug Insect repellent Hypertension medication Feb Jan Aug chloramphenicol bezafibrate metoprolol DEET TrOCs in wastewater influent of two WWTPs in Beijing, China

(Environ. Sci. Technol. 2011, 45:3341–3348)

Sewer systems TrOCs Influent

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Influent WWTP WWTP Biosolids Biosolids Ef Effluent uent TrOCs Sewer systems

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http://www.pbtprofiler.net  Predicted half lives of many TrOCs?

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 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

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 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

  • Annual production

worldwide ~ 500,000 T U.S ~ 200,000 T 4-nonylphenol (4-NP) is a metabolite of nonylphenol polyethoxylates (NPnEOs)

  • NPnEOs are nonionic surfactants

O R C C OH n (3-20) H H H H

Compound of interest

  • 13 secondary WWTPs (GA, SC, KS)
  • Population served by the WWTPs:

5,000 to 0.5 million

  • Wastewater treated by the WWTPs:

0.75 MGD - 0.5 BGD

  • Biosolids produced in the WWTPs:

0.6 to 100,000 dry ton/ day

Study sites

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4-NP and its precursors in WWTP influent of #13

4-NP

50 100 150 200 250 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPnEOs (ethoxylate number) [NPnEOs] in Influent (ug L-1)

Influent 2 4 6 8 10 12 14 16 Weight %

Surfactant

O R C C OH n (3‐20) H H H H

Case study results

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1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPnEOs (ethoxylate number) [NPnEOs] (ug L-1) Effluent

4-NP and its precursors in effluent of WWTP #13

ND ND

O R C C OH n (3‐20) H H H H

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Concentration (mg kg-1)

5 10 15 500 1000 NP13EO NP14EO NP15EO NP NP1EO NP2EO NP3EO NP4EO NP5EO NP6EO NP7EO NP8EO NP9EO NP10EO NP11EO NP12EO NP16EO

4-NP and its precursors in biosolids of WWTP #13

0.11 – 1.56 mg kg-1

biosolids

O R C C OH n (3‐20) H H H H

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4-NP input Daily mass balance for 4-NP in WWTP #13 39% produced in WWTP 61% from influent 4-NP output

6%

degraded? effluent?

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4-NP levels in biosolids and compost from the WWTPs investigated

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[4‐NP] (mg kg‐1, d.w.)

Levels of 4‐NP in biosolids from WWTPs in California. 1600 400 800 1200 Other reported levels 1 2 3 4 5 6 7 8 9 WWT #

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  • WWTPs are ineffective for 4-NP degradation

– there just not enough time!

  • 4-NP is sequestered by biosolids
  • Yes!

However

 Can WWTPs remove 4-NP from influent?  Can biosolids sequester other TrOCs?

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triclocarban, triclosan, PBDEs, 4-NP

1 10 100 1000 0.01 0.1 1 10 100

Concentration (mg kg-1, dry weight)

0.1 1 10 100 0.1 1 1 1 2 2 7 . 2 8 . 9 1 1 . 8 . 6 1 . 5 2 . 3 1 7 6 7 4 5 7 (9) (7) (7) (9) (7) (7)

triclocarban triclosan PBDEs 4-nonylphenol aerobic anaerobic compost aerobic anaerobic compost

Biosolids from 16 WWTPs of 5 states 4 PPCPs: 300 – 704,000 g kg-1 dry weight

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Kinney et al., ES&T, 2006, 40:7207-7215

Biosolids from 7 states 25 PPCPs: 15 – 1,520,000 g kg-1 organic C

antiepileptic, antihistamine, antidepressant, fragrance, disinfectant, detergent metabolites, preservative, fire retardants, plasticizer, fragrance, steroids

  • TrOCs

OCs in biosolids n biosolids

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Water Research, 2010, 44:658

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4-NP levels in biosolids and compost from the WWTPs investigated

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  • Environ. Toxico. Chem. 2010, 29:597–605.

Concentration reduction (biosolids  compost, %)

Concentration reduction of target compounds in biosolids compared with composted biosolids from the same WWTP.

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 Biosolids production, usage, and disposal in U.S.

Benefits:

  • primary nutrients
  • secondary nutrients
  • root growth promoters
  • enhance soil structure
  • C sequestration

(Brown et al., Environ. Sci. Technol., 2011, 45:7451)

1998 2000 2005 2010 Year Biosolids production (million dry tons/year)

6 6.5 7 7.5 8 8.5 9

7.1 7.6 8.2 6.9

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runoff leaching degradation volatilization deposition

Influent WWTP WWTP Biosolids Biosolids Ef Effluent uent TrOCs

uptake

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A f A field study: 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

  • Fate of

te of T TrOCs OCs in biosolids-a n biosolids-applied land pplied land

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  • Study site:

Study site: esta established in 1973 lished in 1973 Fulton County Fulton County, IL IL

  • Trea

eatments: tments: Fo Four 1.

  • 1. Contr

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 3.

  • 3. Biosolids:

Biosolids: 33.6 Mg/ha-yr 33.6 Mg/ha-yr 4.

  • 4. Biosolids:

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

MWRD

33-y cum 33-y cumula lativ tive r rates: tes: 554.5, 1109, 2218 Mg/ha 554.5, 1109, 2218 Mg/ha

Experimental design Experimental design

  • Cr

Crop:

  • p: Corn (

Corn (Zea ma Zea mays L. L.)

  • Target T

et TrOCs: OCs: TC TCC, TC TCS, S, P PBDEs, 4 4-NP

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4.48* Triclocarban (TCC) CAS # 101-20-2 bactericides 4.19* Triclosan (TCS) CAS # 3380-34-5 flame retardant

log Kow = 0.621(#Br) + 4.12

polybrominated diphenyl ethers (PBDEs) metabolite of nonylphenol polyethoxylates (non-ionic surfactants) 4.75* 4-nonylphenol (4-NP) CAS # 104-40-5 Ch Chemical struc emical structure ure Use Use Log Log Kow Kow Compo Compound und Ch Charac aracteristic teristics of s of the compounds inves the compounds investigat igated in t ed in this is study study 4.48* Triclocarban (TCC) CAS # 101-20-2 bactericides 4.19* Triclosan (TCS) CAS # 3380-34-5 flame retardant

log Kow = 0.621(#Br) + 4.12

polybrominated diphenyl ethers (PBDEs) metabolite of nonylphenol polyethoxylates (non-ionic surfactants) 4.75* 4-nonylphenol (4-NP) CAS # 104-40-5 Ch Chemical struc emical structure ure Use Use Log Log Kow Kow Compo Compound und Ch Charac aracteristic teristics of s of the compounds inves the compounds investigat igated in t ed in this is study study

C9H19 OH C9H19 OH

O Brx Bry

6 5 4 3 2 2’ 5’ 6’ 4’ 3’

O Brx Bry

6 5 4 3 2 2’ 5’ 6’ 4’ 3’

Cl Cl O OH Cl

Cl Cl Cl NH O NH

C9H19 OH C9H19 OH

O Brx Bry

6 5 4 3 2 2’ 5’ 6’ 4’ 3’

O Brx Bry

6 5 4 3 2 2’ 5’ 6’ 4’ 3’

Cl Cl O OH Cl

Cl Cl Cl NH O NH

26

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  • 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)

  • )

concentration (mg kg-1, dry weight) TCC TCS PBDEs 4-NP 24 4.2 0.711 886

  • soil w

soil was sampled a s sampled at: 0 – 0 – 15 , 15 – 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

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600 800 1000 1200 1400

33-year cumulative loading (Mg ha-1) Concentration (g kg-1, dry weight)

10 20 30 40 50 60 TCC TCS 554.5 1109 2218 200 400 600 800

33-year cumulative loading (Mg ha-1)

2000 4000 6000 8000 10000 554.5 1109 2218 PBDEs 4-NP

Concentrations of TCC, TCS, PBDEs, and 4-NP in 0 – 15 cm depths of soil amended with biosolids at four rates

Case study results

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Concentrations of TCC, TCS, PBDEs, and 4-NP at different depths in biosolids-amended soil

200 400 600 800 1000 1200 1400

Depth (cm)

0-15 15-30 30-60 60-120

Concentration (g kg-1, dry weight)

10 20 30 40 50 60 TCC TCS

Depth (cm)

0-15 15-30 30-60 60-120 1000 2000 3000 4000 5000 6000 7000 8000 9000 100 200 300 400 500 600 700 554.5 Mg ha-1 1109 Mg ha-1 2218 Mg ha-1 control PBDEs 4-NP

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Percent recovered

20 40 60 80 100 120 1 2 3 4 5 6 7 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Cumulative biosolids loading (Mg ha-1)

1 2 3 4 5 6 7 PBDEs 4-NP TCC TCS 554.5 1109 2218 554.5 1109 2218

Estimated % recoveries of PBDEs, 4-NP, TCC, and TCS, in top 120 cm soil after 33- year of annual application of biosolids.

0 – 15 cm 15 – 30 cm 30 – 60 cm 60 – 120 cm

Mass Balance = Dsoil x Asoil x BDsoil x (Csoil – Csoil)

  • Ybiosolids x Rbiosolids x Cbiosolids

x100% amount detected in soil 33-year cumulative input x100% =

Compound Predicted half life (day) Water Soil TCS 60 120 TCC 60 120 PBDE-47 180 360 4-NP 15 30

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4-NP TCC PBDEs TCS

Concentration ratio

10 20 150 200 Biosolids Soil . 1 7

Σ

Concentration ratio of 4-NP, TCC, PBDEs, and TCS in biosolids and surface soil (0-15 cm) amended with biosolids at accumulative 33-year loading of 2218 Mg ha-1.

210 180 5.7 26 14 1 1

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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

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runoff leaching degradation volatilization deposition

Influent WWTP WWTP Biosolids Biosolids Ef Effluent uent TrOCs

uptake (no) (limited) (varies) ? (limited) (limited)

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  • Long term monitoring of wider range of TrOCs in

biosolids-amended soils and surrounding environment

  • TrOCs transformation in storm water runoff
  • Fast, inexpensive, accurate, multi-compound analytical

methods for detecting TrOCs in environmental samples

  • Evaluation of new wastewater and biosolids treatment

technologies

  • Plant and animal uptake of TrOCs in biosolids-

amended soils

  • Futur

Future r resear search needs needs

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Ac Acknowledg knowledgement: ement:

Dr

  • Drs. Lakhwinde

Lakhwinder Hunda Hundal, Alber , Albert Co Cox, T x, Thomas

  • mas

Granato,

  • , a

and Ku Kuldip Ku Kumar Metr Metropolitan W

  • politan Water R

ter Reclama amation District of ion District of Gr Grea eater Chica ter Chicago Gr Gradua aduate students: te students: Greg Pillar g Pillar Ku Kusum V Verma Rese sear arch tec technic hnician: an: Christina Lusk hristina Lusk