POLYBROMINATED DIPHENYL ETHER FATE IN WASTEWATER DIGESTERS

Transcription

1 PLYBRMINATED DIPHENYL ETHER FATE IN WASTEWATER DIGESTERS BY Karl Rockne 1, PhD, PE Jayashree Jayaraj 1, PhD, and An Li 2, PhD 1 Department of Civil and Materials Engineering and 2 School of Public Health University of Illinois at Chicago, Chicago, IL Illinois Sustainable Technology Center Research Symposium September 9,

2 PBDEs Polybrominated Diphenyl Ethers Used as FLAME RETARDENT additives Release. radicals Combine with high energy H and H Thus quenching chain reactions 10 homologs 209 congeners, same as PCBs rtho, meta, and para y x C 12 H 10-n n (n = X + Y = 1 to 10) Doubly flanked, flanked and unflanked Not planar, two rings are perpendicular 3 major commercial mixtures Penta DE-71 cta DE-79 Deca Saytex 102E 2

3 What we know: nly ~12 congeners comprise most of the technical products in the technosphere HWEVER: Many more are found in the environment (e.g. Song et al., Li et al ) What accounts for this? UV irradiation? ther chemical breakdown processes? Biodegradation? C- bond 276 kj mol -1, weaker than C-Cl 338 kj mol -1 3

4 How do PBDEs biodegrade? Most likely through Dehalorespiration The sweet spot <0.3 nm H 2 Between sulfate reduction and Fe 3+ reduction Possible players? Dehalococcoides Chloroflexi spp. Desulfomonile spp. thers 4

5 Why are we concerned about debromination? Due to toxicity and bioconcentration concerns, Penta and cta have been banned EU, some states, voluntary ban by manufacturers Industry argues that BDE 209 is non-toxic So it is still used extensively HWEVER: IF BDE 209 is debrominated Safe BDE 209 may produce toxic and/or bioavailable byproducts 5

6 Where might these processes occur? WWTPs A key interface between the technosphere and the environment 6

7 Do conditions in WWTPs allow debromination? PSSIBLY In the sludge digester But, not clear where in multistage systems 7

8 Research Hypotheses H1: PBDE reductive dehalogenation in sewage sludge will be extensive, substantial, and potentially more rapid than for PCBs C- bond is weaker than C-Cl bond H2: Different degradation pathways for PBDEs than PCBs due to the existence of the oxygen atom in PBDEs Possibility of ortho dehalogenation with BDEs 8

9 Research bjectives To address H1 Method development: PBDEs in digester sludge FIELD: Sampling and characterization of WWTP digester sludge Primary and secondary digesters, biosolid product Municipal only and mixed industrial treatment plants LAB: PBDE debromination potential and kinetics With and without dehaloprimers, EDs and bioaugmentation To address H2 Model possible PBDE debromination pathways and kinetics in anaerobic digesters 9

10 PBDE congener standards: Quantification of 43/49; DL ~10 ng/g Mono through Tetra BDE congeners Penta through Deca BDE congeners Standard Congener Formula Standard (Cont.) Congener Formula BDE ,2,3,4,4 -BDE BDE ,2,4,4,5-BDE BDE ,2,4,4,6 -BDE 4 7 2, 4-BDE ,3,4,5,6-BDE 5 8 2, 4 -BDE ,3,4,4,5-BDE ,6-BDE ,3,4,4 6-BDE ,3 -BDE ,3,4,4,5-BDE ,6-BDE ,2,3,4,4,5 -BDE ,4 -BDE a,b 2,2,4,4,5,5 -BDE ,4 -BDE ,2,4,4,5,6 -BDE ,2,4-BDE ,2,4,4,6,6 -BDE , 3,4-BDE ,3,4,4,5,6-BDE ,4,4 -BDE ,2,3,4,5,6-BDE ,4, 6-BDE ,2,3,4,4,5,6-BDE ,4 6-BDE ,3,3,4,4,5,6-BDE ,3,4-BDE ,2,3,3,4,4,5,6-BDE ,3,4-BDE ,2,3,3,4,4,6,6 -BDE , 4,4 -BDE ,2',3,3',4,5,5',6-BDE 19 47a 2,2,4,4 -BDE ,2',3,3',5,5',6,6'-BDE ,2,4,5-BDE ,2',3,4,4',5,6,6'-BDE ,3,4,4 -BDE ,3,3',4,4',5,5',6-BDE , 3,4,6-BDE ,2,3,3,4,4,5,5,6-BDE ,4,4,6-BDE b,c 2,2,3,3,4,4,5,6,6 -BDE ,3,4,4 -BDE ,2,3,3,4,5,5,6,6 -BDE ,2,3,3,4,4,5,5,6,6 -BDE a -Congeners in bold represent main congeners in Penta commercial product DE-71 /omkal 70-DE. b -Congeners in bold italics represent main congeners in cta commercial product DE-79. c -Congeners in bold underline represent main congeners in Deca commercial product DE-83R /SAYTEX 102E. Note that congeners 153 and 154 occur in both Penta and cta and congeners 207 and 208 occur in both cta and Deca. 10

11 WGV -12 MGD (48 MLD) -Almost exclusively residential WW -Two feeds: WGV and KWD -Double stage process: Mesophilic acidogenic Thermophilic methanogenic 10 d HRT Study locations CWRP -Large plant, 400 MGD (1.5 BLD) -Mix of industrial and residential WW -Double stage standard rate process: Acidogenic methanogenic 11

12 WGV Sample Points Influent (Screening) Nitrification Towers Secondary Clarifiers Aeration Tanks RAS Grit Removal Tanks Tertiary Filtration Sludge Handling & Thickening Chlorine Contact Chambers 1 Primary Digester (1.5 d) 2 Secondary Digester (10 d) 3 Filtrate Holding Tank Secondary Dewatering Secondary Holding Tank 4 Disposal 12

13 CWRP Sample Points 13

14 Sampling & analysis Plants sampled seasonally: winter, spring, summer & fall Plants sampled every other day for 9 days Always including 1 weekend 8 or 24 h composites Analyzed for: Solids, M, C, BC, porosity, density (ρ b, ρ p ) Heavy metals, PAHs & PBDEs

15 15 BDE-209 BDE-206 BDE-208 BDE-207 BDE-196 BDE-204 BDE-198 BDE-202 BDE-205 BDE-181 BDE-183 BDE-190 BDE-166 BDE-153 BDE-154 BDE-155 BDE-85 BDE-99 BDE-100 BDE-119 BDE-126 BDE-47 BDE-49 BDE-66 BDE-71 BDE-75 BDE-17 BDE-25 BDE-28 BDE-33 BDE-35 BDE-37 BDE-7 BDE-13 BDE-15 BDE-138 BDE-197 BDE-203 PF-WGV MANY congeners that are not in any technical product

16 PF-CWRP BDE-209 BDE-206 BDE-207 BDE-208 BDE-196 BDE-197 BDE-204 BDE-198 BDE-203 BDE-202 BDE-181 BDE-183 BDE-190 BDE-138 BDE-166 BDE-153 BDE-154 BDE-155 MANY congeners that are not in any technical product BDE-85 BDE-99 BDE-100 BDE-116 BDE-119 BDE-126 BDE-47 BDE-49 BDE-66 BDE-71 BDE-77 BDE-17 BDE-25 BDE-28 BDE-33 BDE-30 BDE-32 BDE-35 BDE-7 16

17 Fate of PBDEs in WWTP digesters 17

18 2000 PBDES by homolog PF CWRP SD CWRP PF WGV PF KWD SD WGV 1200 PF CWRP SD CWRP PF WGV PF KWD SD WGV PF CWRP SD CWRP PF WGV PF KWD SD WGV PF CW RP SD CWRP PF WGV PF KWD SD WGV PBDE Concentration (ng -1 l ) A) -1 PBDE Concentration (ng l ) D) PBDE Concentration (ng -1 l ) G) PBDE Concentration (ng g -1 ) Di BDE_10 Di BDE_7 Di BDE_8/11 Di BDE_12 Di BDE_13 Di BDE_ Penta BDE_ Penta BDE_119 Di-BDEs Penta BDE_99 Penta-BDEs Penta BDE_116 Penta BDE_118 Penta BDE_85 cta BDE_202 cta BDE_197/204 cta BDE_198/203 cta BDE_196 cta BDE_205 cta-bdes PBDE Concentration (ng g -1 ) PBDE Concentration (ng l ) B) -1 PBDE Concentration (ng l ) PBDE Concentration (ng g -1 ) E) Tri BDE_30 Tri BDE_32 Tri BDE_17 Tri BDE_25 Tri BDE_28 Tri BDE_33 Tri BDE_35 Tri BDE_37 Penta BDE_126/ Hexa BDE Penta BDE_126/ Hexa BDE_155/Penta BDE_126 Tri-BDEs Hexa BDE_154 Hexa BDE_153 Hexa BDE_138/ Penta BDE_100 Penta BDE_119 Penta BDE_99 Penta BDE_116 Penta BDE_118 Penta BDE_ PBDE Concentration (ng -1 l ) H) PBDE Concentration (ng g -1 ) Hexa BDE Penta-BDEs Hexa-BDEs PBDE Concentration (ng l -1 ) C) PBDE Concentration (ng l -1 ) Tetra BDE_75 Tetra BDE_49 Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Tetra-BDEs Tetra BDE_75 Tetra BDE_ Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Hexa BDE_155/Penta BDE_126 Nona BDE_208 Nona BDE_207 Nona BDE_206 Nona-BDEs F) Hepta BDE_183 Hepta BDE_181 Hepta BDE_190 Hepta-BDEs Hexa BDE_ Hexa BDE_153 Hexa BDE_138/166 Hexa-BDEs PBDE Concentration (ng l -1 ) I) Tetra-BDEs BDE_209 BDE_209 Deca-BDE Deca-BDE 18

19 BDEs in CWRP, WGV & KWD sludge compared to technical products 0.6 PF CWRP SD CWRP PF WGV PF KWD SD WGV DE-71 PBDE concentration as a fraction PBDE of concentration total BDEs as a fraction of total BDEs PBDE concentration as a fraction of total BDEs Tetra BDE_47 Penta BDE_100 Penta BDE_99 Penta BDE_85 Hexa BDE_154 Hexa BDE_153 Hexa BDE_154 Hexa BDE_153 Hepta BDE_183 cta BDE_197/204 PF CWRP SD CWRP PF WGV PF KWD SD WGV DE-79 PF CWRP SD CWRP PF WGV PF KWD SD WGV Saytex 102-E cta BDE_198/203 cta BDE_196 Nona BDE_208 Nona BDE_207 Nona BDE_206 BDE_209 Nona BDE_207 19

20 Summary: PBDEs in sludge PBDEs present at much higher levels (2x) in WGV Total PBDEs are high in WWTP influent compared to total PAHs and total heavy metals PBDEs in all sludge influents suggest a weathered mixture of Penta DE-71 and Deca SAYTEX 102E commercial mixes BDE-209 is debrominated in the thermophilic WGV digester BDEs do not appear to be extensively debrominated in standard rate digesters at CWRP 20

21 WGV thermophilic digester sludge incubation conditions Amendments Abbreviation 1 WGV methanogenic digester sludge effluent with no amendments ME 2 ME/DM plus haloprimer mix biostimulation ME/DM+HP 3 ME/DM plus Dehalococcoides ethenogenes bioaugmentation ME/DM+DC 4 ME/DM plus lactate, yeast extract, and starch biostimulation ME/DM+LYS 5 ME/DM plus with HP and DC biostimulation and bioaugmentation ME/DM+HP+DC Concentration Concentration Haloprimer (nm) (µg l -1 ) 6 ME/DM plus with HP and LYS biostimulation 2,6-dibromophenol 250 ME/DM+HP+LYS ,6-dibromobiphenyl ME/DM plus with DC and LYS biostimulation and bioaugmentation ME/DM+DC+LYS 1,2,4,5-tetrabromobenzene ME/DM+HP+DC+LYS killed control: 4-bromobenzoic autoclave acid and formalin 500 Kill

22 Cumulative gas production in WGV ME sludge batch incubations Cumulative gas volume (ml) Time (d) ME ME/DM+HP ME/DM+DC ME/DM+LYS ME/DM+HP+DC ME/DM+HP+LYS ME/DM+DC+LYS 22

23 PBDEs Lab incubations ME Day 1 Day 28 PBDE Concentration (ng l -1 ) PBDE Concentration (ng l -1 ) Di BDE_10 Di BDE_ Di BDE_10 Di BDE_7 Di BDE_8/11 Di BDE_12 Di BDE_13 Di BDE_15 Tri BDE_30 Tri BDE_32 Tri BDE_17 Tri BDE_25 Tri BDE_28/Tri BDE_33 Tri BDE_33/Tri BDE_28 Tri BDE_35 Tri BDE_37 Tetra BDE_75 Tetra BDE_49 Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Penta BDE_100 Di BDE_8/11 Di BDE_12 Di BDE_13 Di BDE_15 Tri BDE_30 Tri BDE_32 Tri BDE_17 Tri BDE_25 Tri BDE_28/Tri BDE_33 Tri BDE_33/Tri BDE_28 Tri BDE_35 Tri BDE_37 Tetra BDE_75 Tetra BDE_49 Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Penta BDE_100 Penta BDE_119 Penta BDE_99 Penta BDE_116 Penta BDE_118 Penta BDE_85 Penta BDE_126/ Hexa BDE155 ME/DM+HP+DC Hexa BDE_155/Penta BDE_126 Penta BDE_119 Penta BDE_99 Penta BDE_116 Penta BDE_118 Penta BDE_85 Penta BDE_126/ Hexa BDE155 Hexa BDE_155/Penta BDE_126 Hexa BDE_154 Hexa BDE_153 Hexa BDE_138/166 Hepta BDE_183 Hepta BDE_181 Hepta BDE_190 cta BDE_202 cta BDE_197/204 cta BDE_198/203 cta BDE_196 cta BDE_205 Nona BDE_208 Nona BDE_207 Hexa BDE_154 Hexa BDE_153 Nona BDE_206 BDE_209 Day 1 Day 28 Hexa BDE_138/166 Hepta BDE_183 Hepta BDE_181 Hepta BDE_190 cta BDE_202 cta BDE_197/204 cta BDE_198/203 cta BDE_196 cta BDE_205 Nona BDE_208 Nona BDE_207 Nona BDE_206 BDE_209 23

24 Are there any patterns to the debromination? Compare PSSIBLE pathways based on: Debromination 1 at a time grouped by homolog Compare debromination based on substitution pattern of the parent (o, m, p and df, f) Significantly produced (P) and Completely removal (CR) CMPARE T KNWN PCB/PBDE pathways Caveats: Speculative Possible multi-debromination Production/Debromination balance impossible to predict

25 25 PSSIBLE Debromination Pathways: WGV field BDE-209 BDE-206 BDE-207 BDE-196 BDE-204 BDE-198 BDE-202 BDE-205 BDE-183 BDE-190 BDE-153 BDE-154 BDE-99 BDE-47 BDE-49 BDE-17 BDE-28 BDE-33 BDE-197 BDE-203 BDE-71 BDE-119 p BDE-206 p BDE-181 BDE-138 BDE-166 BDE-85 BDE-100 BDE-66 BDE-15 CR Mono-BDEs?

26 PSSIBLE Debromination Pathways: WGV lab BDE-209 BDE-206 BDE-207 p BDE-208p BDE-196p BDE-197 p BDE-204 p BDE-198 p BDE-203 p BDE-202 p BDE-205 p BDE-181 p BDE-183 BDE-190 BDE-138 p BDE-166 p BDE-153 BDE-154 BDE-155 p BDE-85 BDE-99 p BDE-100 BDE-119 p BDE-126 p BDE-47 p BDE-49 CR BDE-71 CR BDE-75 BDE-17 BDE-25 BDE-28 CR BDE-33 CR 26

27 PSSIBLE Debromination Pathways: WGV ME/DM+HP+DC lab BDE-209 BDE-206 BDE-207 BDE-208 BDE-196 p BDE-197 p BDE-204 p BDE-198 p BDE-203 p BDE-202 p BDE-181 BDE-183 p BDE-190 BDE-138 BDE-166 BDE-153 BDE-154 BDE-155 BDE-85 BDE-99 BDE-100 BDE-116 BDE-119 p BDE-126 BDE-47 BDE-49 BDE-66 p BDE-71 BDE-75 p BDE-17 BDE-25 BDE-28 BDE-33 BDE-32 p BDE-37 p 27 BDE-12 p BDE-13 p

28 Summary of possible debromination pathways WGV Field WGV Lab Biostimulation and Bioaugmentation Pathway Possible Type* Possible Type Possible Type # # # Deca->Nona 3 f-o, df-m df-p 3 df-m, df-p f-o 3 f-o, df-m, dfp (equal) Nona->cta 7 df-m, df-p f-o 7 df-m, df-p, f-o (equal) 7 df-m, df-p, f- o (equal) cta->hepta 5 o, f-m 3 f-o 2 d f-m, o df-m df-m, m Hepta->Hexa 4 o, df-m, f-m 3 o, df-m 3 o Hexa->Penta 4 f-m, o 5 f-m 2 o, f-m o, df-m Penta->Tetra 7 f-m, df-m, f- p, f-o, o, p 4 df-m p, m, f-m 5 o, p, f-m df-m Tetra->Tri 5 f-m, o, p 3 m,p, o 4 o, f-m, p Tri->Di 1 o 3 o, m, p 3 o, p *-Abbreviations o, m, and p represent bromine in the ortho, meta, and para positions respectively; If preceded by df- or f-, the respective bromine is doubly flanked and singly flanked, respectively, by additional bromine(s). Most likely pathways are shown in the upper line in bold. 28

29 Summary-Lab incubation study Gas production DECREASED with HP addition in the absence of LYS -Possibly due to shift in ED to stimulated dehalogenating bacteria ME incubation significant removal of BDE-209; accumulation of toxic tetra BDE-47 & penta BDE-99 ME/DM+HP+DC significant removal of BDE-209; no accumulation of toxic tetra BDE-47 & tetra BDE-99 ME/DM with: LYS or LYS+HP or LYS+DC: Debromination similar to ME only incubation ->NT ED limited Possible pathways->prevalence of meta & ortho debromination In contrast with dehalogenation patterns reported to date 29

30 Modeling PBDE debromination kinetics WGV digester (field) Reactor configuration at WGV is CMFR At SS, w/assumptions regarding X and C +1 ->pseudo 1 st order reaction: 10 d residence time r NET, PF 1 ( C = θ o C) C 30

31 Debromination kinetics - WGV field -1 PBDE debromination/production kinetics rate (d ) PBDE debromination/removal kinetics rate (d -1 ) Decrease in levels! Di BDE_7 Tri BDE_32 Tri BDE_17 Tri BDE_28 Tri BDE_33 Tetra BDE_49 Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Penta BDE_100 Penta BDE_99 Penta BDE_85 Penta BDE_126/ Hexa BDE155 Hexa BDE_155/Penta BDE_126 Increase in levels! Hexa BDE_154 Hexa BDE_153 Hexa BDE_138/166 Hepta BDE_183 Hepta BDE_181 Hepta BDE_190 cta BDE_202 cta BDE_197/204 cta BDE_198/203 cta BDE_196 cta BDE_205 Nona BDE_208 Nona BDE_207 BDE_209 Di BDE_13 Tri BDE_25 Tri BDE_35 Tetra BDE_75 Penta BDE_119 Nona BDE_206 31

32 Modeling PBDE debromination kinetics Batch incubations with ME-WGV sludge Pseudo-first order kinetics in batch reactor dc dt = r NET,PF C Upon integration: ln C o C = r NET, PF t 32

33 Debromination kinetics Lab incubations PBDE debromination kinetics rate (d -1 ) Tetra BDE_75 Tetra BDE_49 Tetra BDE_71 Tetra BDE_47 Tetra BDE_66 Tetra BDE_77 Penta BDE_100 Penta BDE_119 Penta BDE_99 Penta BDE_116 Penta BDE_118 Penta BDE_85 Penta BDE_126/ Hexa BDE155 Hexa BDE_155/Penta BDE_126 Hexa BDE_154 Hexa BDE_153 Hexa BDE_138/166 Hepta BDE_183 Hepta BDE_181 Hepta BDE_190 cta BDE_202 cta BDE_197/204 cta BDE_198/203 cta BDE_196 cta BDE_205 Nona BDE_208 Nona BDE_207 Nona BDE_206 BDE_ ME ME/DM+HP ME/DM+DC ME/DM+LYS ME/DM+HP+DC ME/DM+HP+LYS ME/DM+DC+LYS 33

34 WGV: CMFR with 10 d HRT Summary pseudo 1 st order reaction rate r NET,PF Debromination of ~20 BDE congeners r NET,PF ~0.05 to ~0.5 d -1 6 congeners produced r NET,PF to d -1 BDE 209 debromination rate highest reported (0.26 d -1 ) Batch incubations: 1 st order batch kinetics ME incubation: BDE-209 removal at 0.04 d -1 BUT accumulation of BDE-47 (0.18 d -1 ) & BDE-99 (0.02 d -1 ) ME/DM+HP+DC most effective incubation case 34

35 verall Conclusions PBDE extraction & analysis methods were developed and verified for routine analysis 43 PBDE congeners analyzed in sludge/sludge cake Total PBDEs HIGHER in domestic WGV compared to industrial/domestic CWRP Significant DEBRMINATIN of BDE-209 in thermophilic digester at WGV, whereas no significant removal at CWRP BDE-209 debromination rate at WGV highest ever reported ME only debromination (28 d, batch system) leads to accumulation of toxic intermediates Different from WGV field ME/DM+HP+DC most effective removal, no toxic accumulation Possible pathways->prevalence of meta & ortho debromination In contrast with dehalogenation patterns reported to date 35

36 Acknowledgements Research funding from ISTC Students: Dr. Ke Yin, Dr. Xiuhong Zhao and Kelly Granberg Dr. Wayne Whipple, USEPA Region-5 Managers & perators at CWRP & WGV WWTPs 36