hypothesis: reductive dehalogenation of deca and other pbdes in sewage sludge will be extensive

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 HYPOTHESIS: Reductive dehalogenation of Deca and other PBDEs in sewage sludge will be extensive Technical Approach 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: 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. Key Achievements & Future Goals 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 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 ) ( ) ( P m R o k C Ck V C C Q dt dC V C C C k o NET ) ( 842 West Taylor St., M/C 246; 3077 Engineering Research Facility; [email protected]

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Page 1: HYPOTHESIS: Reductive dehalogenation of Deca and other PBDEs in sewage sludge will be extensive

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

HYPOTHESIS: Reductive dehalogenation of Deca and other PBDEs in sewage sludge will be extensive

Technical Approach

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

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

At Steady state:At Steady state:

0.00001

0.0001

0.001

0.01

0.1

Dis Tris Tetra Penta Hexa Hepta Octa Nona

BDE fraction

Nor

mal

ized

To B

DE2

PF-CWRP PD-CWRPSF-CWRP SD-CWRP

0.00001

0.0001

0.001

0.01

0.1

Dis Tris Tetra Penta Hexa Hepta Octa Nona

BDE fraction

Nor

mal

ized

To B

DE20

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.

Key Achievements & Future Goals

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

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

The first report of lower brominated PBDEs being debrominated in the WWTPsBanning Octa and Penta technical product will not eliminate their presence in the environmentContinued use of Deca may still release bioavailable and toxic lower brominated BDEs into the environment

Polybrominated diphenyl ethers (PBDEs)Used as flame retardants in textiles, electronics and furniture industries with up to 10 Br per moleculeConsumer products decompose and end up in wastewater treatment plants (WWTPs)Deca (10 Br atoms) is relatively non-toxic to humansOcta and Penta product more bioavailable and toxic

Banned by the European Union and CaliforniaVoluntary ban by US manufacturers

Deca is still used in electronics and other plasticsHOWEVER: Halogenated compounds CAN BE DEHALOGENATED by anaerobic bacteria

)()( PmRo kCCkVCCQdt

dCV

CCC

k oNET

)(

842 West Taylor St., M/C 246; 3077 Engineering Research Facility; [email protected]

Reductive Drawing

ELECTROOXIDATION OF ORGANIC MATERIALS · dehalogenation and the production of hydrogen peroxide. Reductive dehalogenation of organohalogenatedcompounds is not the most important

METHOD OF DEHALOGENATION USING DIAMONDS …/67531/metadc725527/m2/1/high... · METHOD OF DEHALOGENATION USING DIAMONDS ... The invention together with the above and other objects

Non-reductive GIT and curve countingpeople.maths.ox.ac.uk/berczi/TautologicalIntegrals.pdfNon-reductive GIT and curve counting ... Mumford’s reductive GIT in a nutshell ... ,!Grass(codim