determination of selected organophosphorus flame ... · tep tcep tcpp tphp tdcpp tbp tbep tkp tehp...
TRANSCRIPT
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
28.11.2006 | Folie 4
Use of OPFR
Flame retardantUpholstererPaints, varnishes(Polyurethane) foamsElectronic devicesgarment
lubricantplasticizer
3
28.11.2006 | Folie 5
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
28.11.2006 | Folie 10
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
28.11.2006 | Folie 11
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
28.11.2006 | Folie 12
Influence of STP in the aquatic environment
STP of Linz
7
28.11.2006 | Folie 13
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
28.11.2006 | Folie 14
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
9
28.11.2006 | Folie 17
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
28.11.2006 | Folie 19
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
28.11.2006 | Folie 20
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
28.11.2006 | Folie 22
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