1

28.11.2006 | Folie 1

Determination of selected organophosphorus flame retardants (OPFR) in the Aquatic Environment

by LC-MS/MS

28.11.2006

Oliver Gans

28.11.2006 | Folie 2

Analysis of Emerging Pollutants

PharmaceuticalsHuman, Veterinary

SurfactantsAnionic – LAS, Nonionic – NPEOs, Cationic – QACsFluorinated – PFOS, PFOA, etc.

Naphthalene sulphonic acidNatural and synthetic hormones

Estrone, estradiol, 17-α-ethinylestradiol, estriol

Organotin compounds

2

28.11.2006 | Folie 3

Analysis of Emerging Pollutants

PhthalatesPesticides (e.g. Pyrethroides)BenzotriazolesFragances (e.g. nitro and polycyclic musks)Flame retartands

PBDEPFASOPFRs

Publications to results are available on ourhomepage www.umweltbundesamt.at

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Use of OPFR

Flame retardantUpholstererPaints, varnishes(Polyurethane) foamsElectronic devicesgarment

lubricantplasticizer

3

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OPFR - characteristics

Consumption: >40.000 t/year TCPP worldwide>5.000 t/year TCEP, TCPP, TDCPP in the EU

Persistent and stableRelatively low capability for bioaccumulation/biomagnificationmoderate acute toxicity (dependant on the single compound)

but acute aquatic toxicity

Some of them probably carcinogenic to men (especially the chlorinated ones)

28.11.2006 | Folie 6

Examples: OPFR

O P O

O

OOCH3

O

CH3

O CH3

O P O

O

OCl

Cl

Cl

Tris-(2-chloroethyl) phosphate (TCEP)CAS: 115-96-8

Tris (2-butoxyethyl)-phosphat (TBEP) CAS: 78-51-3

4

28.11.2006 | Folie 7

Analysis of OPFR

Water SamplesAddition of surrogate standard (TBP-d27)Liquid-Liquid Extraction with dichloromethaneSolvent change to acetonitrile

Sediment SamplesAddition of surrogate standard (TBP-d27)US extractionSolvent change to acetonitrile

Determination by LC-MS/MS

28.11.2006 | Folie 8

Sediment spiked with 50 ng/g

Sediment with spike of 50 ng/g selected compounds

TCEP

TPhP TBP-d27

TBPTEHP

TCPP

TCEP

TEP

TCPP

TPhP

TBP-d27

TBP

TBP

TKP

TDCPP

TEHP

5

28.11.2006 | Folie 9

Wastewater Samples in Austria

16 municipial STPs16 biological treatment16 nitrogen removal by nitrification13 nitrogen removal by nitrification/denitrification14 phosphorus removalP.e.: 460 – 950.000

Grab samples of the effluentsTo prove occurence in the aquatic environment

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Mean, Max. and Min. in Austrian effluents

0

400

800

1200

1600

2000

TEP TCEP TCPP TPhP TDCPP TBP TBEP TKP TEHP

ng/l

5400

6

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Conclusions – Wastewater

TCEP, TCPP and TBEP are the most abundantConcentration levels are in the low µg/lComparison to other international studies:

Austria (n=16) W. Europe (n=8) Germany (n=2)mean mean mean

TCEP 0,19 0,2 0,36TCPP 0,68 0,6 1,9TBEP 0,91 0,42

Reemtsma et al. 2006 Meyer et al. 2004

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Influence of STP in the aquatic environment

STP of Linz

7

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Results Effluent – Sediments Danube

Effluent Linz Asten right Asten leftng/l [µg/kg TM] [µg/kg TM]

TEP 120 5,7 <3,3TCEP 140 13 n.n.TCPP 1400 110 7TPhP 27 29 <1.3

TDCPP 1400 n.n. n.n.TBP 420 <11 <11

TBEP 57 3,4 2,9TCP n.n. 8,1 <1.5

TEHP n.n. 1,7 3,3

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River and sediment monitoring

DanubeTwo sample points2nd largest river in Europe1900 m3/s (Vienna)

SchwechatInfluenced by industry and high density populationnearby Vienna7.9 m3/s

LiesingInfluenced by industry and high density populationnearby Vienna0.38 m3/s

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Danube, Schwechat and Liesing

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Liesing

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Results – Danube, Schwechat, Liesing

0

100

200

300

400

500

600

TEP TCEP TCPP TPhP TDCPP TBP TBEP

ng/l

Danube1Danube2SchwechatLiesing

28.11.2006 | Folie 18

Conclusions

Max. up to 500 ng/l Especially small rivers are contaminatedContamination pattern of the river danube isdifferent – small influence from the STPsTCEP, TCPP and TBEP – Liesing, SchwechatTBP, TBEP and TCEP – Danubeno TCP and TEHP

10

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Results - sediment

0

20

40

60

80

100

120

140

160

180

200

TEP TCEP TCPP TPhP TDCPP TBP TBEP TCP TEHP

µg/k

g TM

Danube1Danube2SchwechatLiesing

1300

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Conclusions

Max. up to low mg/kg rangeOnly in sediment samples significantdifferences between the Danube sample pointsEspecially small rivers are contaminatedTCPP, TCEP, TPhP, TBEP and TEHP are themost important onesTCP and TEHP in relevant concentrationApparently strong adsorptionSewage sludge might be heavily contaminated

11

28.11.2006 | Folie 21

Schwechat – comparison sedimentto the water phase

Schwechat

0

100

200

300

400

500

600

TEP TCEP TCPP TPhP TDCPP TBP TBEP TKP TEHP

riversediment

1300

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Conclusions

Due different Kd values, different contamination pattern of aqueous and sediment phasemight be important for the fate in STPsTCPP, TCP, TEHP and TPhP more in thesedimentTDCPP, TBP and TBEP more in the water phaseTCEP and TEP in both phases

12

28.11.2006 | Folie 23

Elena Martinez Carballo,Carmen González BarreiroStefan Weiß, Andrea Sitka

Acknowledgement

for your attention