Ke Yin, Jayashree Jayaraj , Kelly Granberg and Karl Rockne

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Problem Statement and Motivation Key Achievements and Future Goals Technical Approach Rapid and Extensive Debromination of Brominated Flame Retardants in Thermophilic Municipal Wastewater Digesters Ke Yin, Jayashree Jayaraj , Kelly Granberg and Karl Rockne Department of Civil and Materials Engineering, University of Illinois at Chicago Polybrominated diphenyl ethers (PBDEs) Used as flame retardants in textiles, electronics and furniture industries with up to 10 Br per molecule Consumer products decompose and end up in wastewater treatment plants (WWTPs) Deca (10 Br atoms) is relatively non-toxic to humans Octa and Penta product more bioavailable and toxic Banned by the European Union and California Voluntary ban by US manufacturers Deca is still used in electronics and other plastics HOWEVER: Halogenated compounds CAN BE DEHALOGENATED by anaerobic bacteria PBDEs are much higher in domestic wastewater! Deca BDE-209 is rapidly debrominated Kinetic rate of 0.34 day-1 at WGV Highest rate ever reported (100x higher!) Extensive removal in only 10 d The first report of lower brominated PBDEs being debrominated in the WWTPs Banning Octa and Penta technical product will not eliminate their presence in the environment Continued use of Deca may still release bioavailable and toxic lower brominated BDEs into the environment Anaerobic digester sludge sampled from two WWTPs: Calumet (CWRP)– Heavy industrial + domestic waste Woodridge Green Valley (WGV)– Domestic waste only Analyzed 49 PBDEs by mass spectrometry-NCI Debromination rate in continuously mixed flow reactor: ) ( ) ( P m R o k C Ck V C C Q dt dC V C C C k o NET ) ( At Steady state: 0.00001 0.0001 0.001 0.01 0.1 1 Dis Tris Tetra Penta Hexa Hepta Octa N ona BD E fraction NormalizedToBDE209 PF-CWRP PD-CWRP SF-CWRP SD-CWRP 0.00001 0.0001 0.001 0.01 0.1 1 Dis Tris Tetra Penta Hexa Hepta Octa N ona BD E fraction NormalizedToBDE209 PF-WGV MF-WGV SF-WGV SC-WGV Figure 1. Total BDE homolog concentrations normalized to deca BDE in the CWRP (left) and WGV (right) digesters at different locations in the plant. Shown are groupings of dibromo diphenyl ethers through nonabromo diphenyl ethers in primary digester feed (PF), primary digester draw (PD, CWRP only), secondary (methanogenic) digester feed (SF), secondary (methanogenic) digester effluent (SD) and sludge cake (SC, WGV only) samples. Note log scale on the y axis. HYPOTHESIS: Reductive dehalogenation of Deca and other PBDEs in sewage sludge will be extensive

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Rapid and Extensive Debromination of Brominated Flame Retardants in Thermophilic Municipal Wastewater Digesters. Ke Yin, Jayashree Jayaraj , Kelly Granberg and Karl Rockne Department of Civil and Materials Engineering, University of Illinois at Chicago. - PowerPoint PPT Presentation

Transcript of Ke Yin, Jayashree Jayaraj , Kelly Granberg and Karl Rockne

Page 1: Ke  Yin,  Jayashree Jayaraj  , Kelly  Granberg  and Karl Rockne

Problem Statement and Motivation

Key Achievements and Future GoalsTechnical Approach

Rapid and Extensive Debromination of Brominated Flame Retardants in Thermophilic Municipal Wastewater Digesters

Ke Yin, Jayashree Jayaraj , Kelly Granberg and Karl RockneDepartment of Civil and Materials Engineering, University of Illinois at Chicago

Polybrominated diphenyl ethers (PBDEs)

• Used as flame retardants in textiles, electronics and furniture industries with up to 10 Br per molecule

• Consumer products decompose and end up in wastewater treatment plants (WWTPs)

• Deca (10 Br atoms) is relatively non-toxic to humans• Octa and Penta product more bioavailable and toxic

• Banned by the European Union and California• Voluntary ban by US manufacturers

• Deca is still used in electronics and other plastics• HOWEVER: Halogenated compounds CAN BE DEHALOGENATED by

anaerobic bacteria

• PBDEs are much higher in domestic wastewater!• Deca BDE-209 is rapidly debrominated

• Kinetic rate of 0.34 day-1 at WGV• Highest rate ever reported (100x higher!)• Extensive removal in only 10 d

• The first report of lower brominated PBDEs being debrominated in the WWTPs

• Banning Octa and Penta technical product will not eliminate their presence in the environment

• Continued use of Deca may still release bioavailable and toxic lower brominated BDEs into the environment

• Anaerobic digester sludge sampled from two WWTPs:• Calumet (CWRP)– Heavy industrial + domestic waste• Woodridge Green Valley (WGV)– Domestic waste only

• Analyzed 49 PBDEs by mass spectrometry-NCI• Debromination rate in continuously mixed flow reactor:

)()( PmRo kCCkVCCQdtdCV

CCCk o

NET)(

At Steady state:

0.00001

0.0001

0.001

0.01

0.1

1

Dis Tris Tetra Penta Hexa Hepta Octa Nona

BDE fraction

Nor

mal

ized

To

BD

E20

9

PF-CWRP PD-CWRPSF-CWRP SD-CWRP

0.00001

0.0001

0.001

0.01

0.1

1

Dis Tris Tetra Penta Hexa Hepta Octa Nona

BDE fraction

Nor

mal

ized

To

BD

E20

9

PF-WGV MF-WGVSF-WGV SC-WGV

Figure 1. Total BDE homolog concentrations normalized to deca BDE in the CWRP (left) and WGV (right) digesters at different locations in the plant. Shown are groupings of dibromo diphenyl ethers through nonabromo diphenyl ethers in primary digester feed (PF), primary digester draw (PD, CWRP only), secondary (methanogenic) digester feed (SF), secondary (methanogenic) digester effluent (SD) and sludge cake (SC, WGV only) samples. Note log scale on the y axis. HYPOTHESIS: Reductive dehalogenation of Deca and other

PBDEs in sewage sludge will be extensive