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16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Prof. Dr.-Ing. Rita Hilliges
Wasserwirtschaft und Umwelttechnik
University of Applied Science
Hochschule Augsburg
NIVA – Norsk intitutt for vannforskning
Norwegian Institute for Water Research
Organophosphate flame retardants (OPFR)
in municipal wastewater treatment plants
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Flame retarding mechanism of OPFRs
Skoog, 2010
Flame retardants: achieve flammability standard in
furniture, plastics, electronic equipment, textiles
Appr. 200 different types, classified after major constituents
Different mechanisms
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
History of flame retardants
Polychlorinated biphenyls (PCBs)
Banned late 1970ies
Toxic effects: endocrine disruption and neurotoxicity
Persistent: still found in sediment and aquatic foodweb!
1970
1980
1990
2000
2010
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Histroy of flame retardents
Polychlorinated biphenyls (PCBs) 1970
1980
1990
2000
2010
Polybrominated diphenyl ethers (PBDEs)
hormone-disrupting effects, impaired neuro development
Persistent, bioaccumulative, toxic, highly lipophilic
long-range atmospheric transport ubiquitous
Banned 2004/2006: PentaBDE, OctaBDE
2008: DecaBDE
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2
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Histroy of flame retardents
Polychlorinated biphenyls (PCBs) 1970
1980
1990
2000
2010
Polybrominated diphenyl ethers (PBDEs)
Organophosphate flame retardants (OPFRs)
High Production Volume chemicals HPVs
Consumption EU (2006): 91.000 to/a
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Organophosphorus esters
TCEP
TCPP Known for 150 years as nerve gas and plant protective agent
Chlorinated OP: TCEP, TCPP, TDCP…
mainly used as flame retardant
Non-chlorinated OP: TBEP, TEHP, TnBP, TiBP…
mainly used as plasticizer, hydraulic fluids, flame retardant …
TCEP: carinogenic phased out, replaced by TCPP
TCPP and TDCPP: on 4th list of priority substances
EU commission
Suspected: neurotoxic and mutagenic potential
Suspected: persistent (at least chlorinated OP)
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
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OPFRs – Pacific and Indian Ocean air
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
OPFRs – Pacific and Indian Ocean air
global occurence:
marginal seas, open oceans and polar regions
concentrations up to 2 ng/m³
dominated by TCPP
and TCEP (carcirogenous)
1-3 magnitudes higher
than typical PBDE concentrations
heaviliy emitted into surface waters
Suspected sources: WWTPs
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Screening of WWTPs in Norway
Eight municipal WWTPs
in south-east Norway
48.000 – 550.000 p.e.
Four WWTPs with chemical treatment only
Four WWTPs combined chem./bio. treatment
Six WWTPs discharge into marine water
OPFRs and other organic pollutants
Sludge samples
Flow proportional weekly composite samples
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Sludge samples
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Sludge samples Sludge samples (ng/g)
Median Min Max Other studies PNEC
TIBP 102 38.8 356 100a / 27-2,700b 640
TBP 94 26.4 304 39-850b 5,300
TCEP 128 30.4 276 70a / 6.6-110b 0.341 (wet weight)
TCPP 2,580 560 7,200 18,400a / 61-1,900b
1,300-2,200c 0.341 (wet weight)
DBPhP 3.9 0.8 20.8
DPhBP <LoD <LoD <LoD
TDCP 246 8.8 1040 90a / 3.0-260b 330
TBEP 3,660 236 23,600 <5.1-1,900b 810
TPhP 150 26.8 6,000 52-320b 95
EHDPP 2,300 21.2 12,800 320-4,600b
TEHP <LoD <LoD <LoD
ToCP 6 <LoD 20.8
TCP 460 10.8 12,000 8.9
LoD: Limit of Detection a) Bester, 2009 b) Marklund, 2005 c) Bester, 2005
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Effluent samples
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Effluent samples Effluent samples (ng/L)
Median Min Max Other studies
TIBP 168 104 308 29-2800c
TBP 41 <LoD 316 360-6,100a; 19-390c
TCEP 62 3.64 272 350-890a; 19-1800c
Mean: 350, Max: 410b
TCPP 600 14.4 1,160 Mean: 3,000, Max: 6,600b
1,500-24.000a
DBPhP 0.36 <LoD 4
DPhBP <LoD <LoD <LoD
TDCP 104 <LoD 276 130-450a; <8-820c
TBEP 158 <LoD 60,000 Mean: 440, Max: 790b
3,100-30,000a; 240-16,000c
TPhP 16.4 0.68 2,000 41-130a; 15-120c
EHDPP 7.6 1.04 48 9.2-69c
TEHP <LoD <LoD 5.6 <1.4a
ToCP <LoD <LoD 14.4
TCP 1.88 0.48 640
LoD: Limit of Detection a) Marklund, 2005 b) Bester, 2004
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Effluent samples – risk assessment
PNEC PEC PEC/PNEC PEC PEC/PNEC
Marine ng/L effl., max ng/L Max effl., median ng/L median
TIBP 1,100 31 0.03 16.8 0.02
TBP 6,600 32 0.005 4.1 0.001
TCEP 6,500 (fresh water)
27 0.004 6.2 0.001
TCPP 640,000 (fresh water)
116 0.0002 60 0.0001
TDCP 1,300 28 0.02 10.4 0.008
TBEP 1,300 6,000 4.6 15.8 0.01
TPhP 16 200 12.5 16.4 1.03
TCP 3.2 64 20 0.19 0.06
Potential risk to the marine environment!
Calculated OPFR discharge WWPT H (550,000 p.e.): 100 kg/a
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Fate of OPFRs in WWTPs
Mechanical treatment
Chemical treatment
Biological treatment
Removal rate % TBEP TiBP TBP TPhP TCEP TCPP TDCP
Mechanical 30 0 8 31 0 0 22
Mech.+Chemical 40 0 0 40 0 10 20
Mech.+Biological 50 90 60 60 0 0 10
Removal rate % TBEP TiBP TBP TPhP TCEP TCPP TDCP
Mechanical 30 0 8 31 0 0 22
Removal rate % TBEP TiBP TBP TPhP TCEP TCPP TDCP
Mechanical 30 0 8 31 0 0 22
Mech.+Chemical 40 0 0 40 0 10 20
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Fate of OPFRs in WWTPs
Tunnel wash water experiements in Norway (Meland et al., 2011)
Sedimentation and filteration: peat filter / activated carbon filter
activated carbon: median elimination rate 84 %
Removal of chlorinated OPFRs > 70 %
Promising with regard to activated carbon filtration at WWTPs
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Per capita esmissions PBDE
PBDE: brominated flame retardants (banned)
Per capita emissions between 0.01 and 1 µg/day/capita
Evenly distributed by population; independent from size / location
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Per capita esmissions PFCs
PFCs: perflourinated compounds
High surface activity: hydrophobic and oil repelling
Stain resistant fabric protection, water proofing outdoor clothing,
non-stick products (e.g. Teflon)
Per capita emissions < 5 µg/day/capita
Evenly distributed by population; independent from size / location
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Per capita esmissions OPFRs
Per capita emissions up to 245 µg/day/capita
Average ratio: 183
Large site-specific variations
Used in great variety of products
Traffic (road tunnels, airports) / handling of runoff important
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Conclusions
OPFR “new flame retardants”
Concern about ecotoxicological potential
High volume chemicals ubiquitous (Arctic!)
1-2 magnitudes higher concentrations than PBDE
Screening Norway:
TCPP and TBEP dominating in sludge and effluent samples
WWTP effluent: 1 to 250 µg/day/capita
unevenly emitted by population
100 kgOPFRs/a emitted by Norway’s largest WWTP (550.000 p.e.)
Potential risk to marine environment (TBEP, TPhP, TCP)
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Conclusions
Removal of OPFRs in WWTPs:
Very low removal rates for chlorinated OPFRs
Non-chlorinated OPFRs: removal mainly in aeration basins
No significant removal during mechanical treatment
Activated carbon filtration: successful with road runoff
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Acknowledgements
Norwegian climate and pollution agency
Klif - Klima- og Forurensingsdirektoratet: for funding
Full title: “Occurrence of selected organic micropollutants and silver
at wastewater treatment plants in Norway” (report No. TA 2784)
NILU - Norwegian institute for air research: for analysis of samples
You: for your attention!
16th International EWA Symposium “Sustainable Wastewater Management – New solutions for new problems”
Munich, Germany, 8-9 May 2012
Prof. Dr.-Ing. Rita Hilliges
Wasserwirtschaft und Umwelttechnik
University of Applied Science
Hochschule Augsburg
NIVA – Norsk intitutt for vannforskning
Norwegian Institute for Water Research
Organophosphate flame retardants (OPFR)
in municipal wastewater treatment plants