s c perfluorinated organic compounds in the i m european · pdf file · 2015-02-19s...
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Perfluorinated organic compounds in the European environment– Achievements of
the PERFORCE project
Pim de Voogt
Environmental Chemistry, Institute for Biodiversity and Ecosystem Dynamics IBED, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV
Amsterdam, The [email protected]
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• Introduction- Perfluorinated organic compounds (PFCs)- Target analytes
• The PERFORCE project
• Transport and bioaccumulation
• Analysis of PFCs- PFCs in water- PFCs in sediment- Other matrices
Overview
• Conclusions
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Introduction
• Perfluorinated organic compounds (PFCs)
- Produced and applied for more than 50 years!- Development of LC-MS made environmental
trace analysis possible
o ”new/emerging environmental pollutants”
www.wfrfire.com
Properties- non inflammable, surface active
o wetting and levelinge.g., Fire fighting foams, Coatings, Electronics, Herbicides, Metal Finishing, Oil wells, Polymerisation
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Introduction
• Perfluorinated organic compounds (PFCs)Properties
- both hydrophobic and oleophobico Surface treatment: Carpets, clothing,
leather and paper products etc.
Carpet Protection Paper
Textile ProtectionExcerpt of 3M commercial www.swisspack.ch
ATOFINA commercial
o Fluoropolymer productiono Speciality chemicals
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Target analytesF2C
CF2
F3C
F2C
CF2
F2C
CF2
F2C
SO3-PFOS
PFOA
6:2 FTS
F2C
CF2
F3C
F2C
CF2
F2C
CF2
COO-
8:2 FTOHF2C
CF2
F3C
F2C
CF2
F2C
CH2
H2C
OHCF2
F2C
F2C
CF2
F3C
F2C
CF2
F2C
CF2
F2C
SNH
O O
2PFOSA
Abbreviations:PF..: perfluoro...FT..: fluorotelomer......S: ...sulfonate...A: ...acid/carboxylate...SA: …sulfonamide...SE: sulfonamidoethanol..OH: ..alcohol..X.:
B butyl (C4)Hx hexyl (C6)O octyl (C8)N nonyl (C9)D decyl (C10)a.s.o.
F2C
CF2
F3C
F2C
CF2
F2C
CH2
H2C
SO3-
19 June 2006 Norman workshop Stresa Italy 6
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0
1000
2000
3000
4000
5000
1985-1989
1990-1994
1997 2000 2001 2002
tonn
es
Production of perfluorooctane sulfonyl fluoride (PFOSF)DT = ~11 yrs (Smithwick et al. 2006)
• similar to observed increase of PFOS in polar bears
PFOA emissionshistorical trend of PFOA emissions from all sources from 1999-2006 (Prevedouros et al. 2006) • trends for other PFCAs?
0
50
100
150
200
250
1999 2000 2001 2002 2003 2004 2006
other emissionsAPFO MfgFluoroPolymer Mfg
tonn
es
PFC Production Trends (taken from C.Butt, SETAC E 2006)
0
2
4
6
8
10
12
14
2000 2004
Year
FTO
H p
rodu
ctio
n (x
106 k
g)
FTOH Production (2000-2004)(US EPA docket AR226-1914)
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0
5
10
15
20
25
30
35
40
PFNA PFDA PFUnA PFDoA PFOS
Con
cent
ratio
n (n
g/g
ww
)
19721993200020042005
Resolute Bay Ringed Seals(taken from C.Butt, SETAC E 2006)
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University of Amsterdam (coordinator)
University of Antwerp
Norwegian Institute for Air Research
Netherlands Institute for Fisheries Research
Stockholm University
Du Pont de Nemours (Belgium) BVBA
The PERFORCE projectFunded by the European Union (NEST-508967)
2004-2006; budget ~ 800 k¼Consortium
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The PERFORCE project
Objectives
• Physico-chemical parameters• Evaluation of sources and routes in Europe • New chemical and biological techniques• Quality assurance, interlaboratory studies• European monitoring
o Exposure assessment in Europe
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The PERFORCE project
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Workpackage 1Analytical method development
• Analytical challenges
- Most target PFCs are ionic (not volatile) and- do not possess a chromophore groupo require LC-MS for trace analysis
- Pure and well characterised standards lacking- Blank problems: e.g. PTFE contains PFOA- Most PFCs are poorly soluble in water or hexane - Several PFCs are surface active- Matrix effects in MS ionisation
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PFCs in water samples
Filtration of 500 mL water sample
Water phaseFilter with particles
Solid phase extraction (SPE)
Concentration
HPLC/ESI-MS(MS)
HPLC/ESI(-)-TOF-MS
PLE (ASE)
Concentration and filtration
HPLC/ESI-MS(MS)
HPLC/ESI(-)-TOF-MS
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Particle/water phase distribution
Bound to particles [%]
Dissolved in water [%]
712152872
297995981398
PFDcSPFOSPFHxSPFBSPFOSA6:2 FTS
Bound to particles [%]
Dissolved in water [%]
PFDcAPFNAPFOAPFHpAPFHxA
301023
70909897
39
61
78
22
PFDoA
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Sample chromatogram
0
100
%
0
100
%
4 5 6 7 8 9 10 11 12 13 14 t [min]
0
100
%
0
100
%
PFBS
PFHxAPFHpA
PFOA
PFNAPFDcAm/z 462.96 + 512.96
m/z 312.97 + 362.97 + 412.97
2E2
4E3
PFHxS PFOSm/z 298.94 + 398.94 + 498.93 3E3
6:2 FTSm/z 426.97 + 526.96 8E28:2 FTS
Landfill effluent (water phase)
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PFCs in water: qualitative resultsIsomers of PFOS
Reference standard
Landfill effluent(water phase)
Sea water
Landfill effluent(particle phase)
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PFCs in water: quantitative resultsNordic samples; Dutch samples (sum of particle and water phases)
Carboxylates (mean values); PFCA and PFS
02468
101214161820
Rainwater
Lakewater
Seawater
Sewageeffluent
ng/L
PFHxAPFHpAPFOAPFNAPFDcA
0
100
200
300
400
500
600
700
800
Landfill eff.(mean)
Landfill eff.(max.)
ng/L
0
10
20
30
40
50
60
70
80
Meu
se 1
Meu
se 2
Meu
se 3
Meu
se 4
Meu
se 5
Rhin
e 1
Rhin
e 2
Rhin
e 3
Oth
erSc
held
t 1Sc
held
t 2G
W1
GW
2G
W3
GW
4G
W5
l.o.d
.
location
PFOA
PFNA
PFOS
PFHxS
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PFCs in sediment samples
Freeze-drying andhomogenisation of sample
Extraction with methanol
Centrifugation(Concentration)
Clean up with ENVI-Carb
HPLC/MS
Centrifugation
C.R. Powley et al. (2005)Anal. Chem. 77, 6353-6358
NaOH treatment
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Monitoring the Environment
05
101520253035404550
Haringv
liet
Holland
sche
IJss
el IJIJs
sel
Ketelm
eer
IJsse
lmee
r
Kanaa
l G na
ar T
Maas (
Eijsde
n)
Maas K
eizers
veer)
Nieuwe w
aterweg
Oude M
aas RijnSch
elde
Eems-D
ollard
Noordze
ekus
t 1
Noordze
ekus
t 2
Noordze
ekus
t 3
Noordze
ekus
t 4
location
ng/g
dry
wei
ght
PFOSPFOA
PFOS and PFOA in suspended matter from fresh waters and marine waters in the Netherlands (De Voogt et al. , 2004)
freshwater marine
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Nordic EnvironmentKallenborn R, Berger U, Järnberg U, 2004
Nordic Council http://www.sft.no/nyheter/dokumenter/pfas_nmr2004.pdf
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PFCs in sediment: results
• PFOS is the dominating PFC, followed by PFOA and PFOSA
• Typical levels for freshwater1 and marine1,2
sediments < 10 ng/g dry weight
1 Nordic Council of Ministers (NMR, 2004): Perfluorinated Alkylated Substances (PFAS)in the Nordic Environment, Copenhagen, ISBN 92-893-1051-0, ISSN 0908-6692
2 Higgins et al. (2005) Environ. Sci. Technol. 39, 3946-3956
• Exception: sedimentation areas; sediments from the North Sea close to oil platforms, impact of fire-fighting foams: PFOS 2-30 ng/g dry weight(unpublished results NILU)
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PFCs in biota samples• Most frequently used method: ion pair extraction (Hansen)• Active C (Powley) method (similar to sediment) has
advantages
2.0 2.5 3.0 3.5 4.0
12
510
2050
100
200
Trophic level
PFO
S c
once
ntra
tion
[ng/
g w
et w
eigh
t]
2.0 2.5 3.0 3.5 4.0
12
510
2050
100
200
12
510
2050
100
200
Trophic level
PFO
S c
once
ntra
tion
[ng/
g w
et w
eigh
t]
Ice amphipodsPolar codBlack guillemotGlaucous gull
PFOS bioaccumulation in an Arctic marine food web
PFsulfonates tC6 and PFcarboxylates tC8 bioaccumulate
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PFOS:Concentration ranges in aquatic biota ng.g-1 ww
Van de Vijver et al. (UA) ETC 2003
Scheldt estuary
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s PFCA Pr o file in H u m a n s v s . Ar ct ic b io t a
(t a k en fr o m S.M a b u r y , Un iv .To r o n t o ; SETAC E, 2 0 0 6 )
60 65 70 75 80 85 Time (min)
PFOA
PFNA
PFDAPFUnA
PFDoA PFTrA
X Data
60 65 70 75 80 85 90
PFOA
PFNA
PFDA PFUnA
atmospheric degradation of FTOHsbioaccumulation of long chain PFCAs
19 June 2006 Norman workshop Stresa Italy 24
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Conclusions (analysis)
• Analysis of PFCs poses new challenges compared to”classical” POPs
• Analytical methods are now available for many different PFCs in all kind of samples
• However, uncertainties are still substantial (see first international intercalibration study 2005)
Satisfactory: 5/20Questionable: 6/20Unsatisfactory: 9/20
RSD*= 76%Van Leeuwen et al. 2005RIVO
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Conclusions (general)• Many data are still lacking to complete an accurate
environmental exposure or risk assessment
• PFCs are widely distributed in the environment at levels sometimes exceeding PCBs
• PFOA and longer alkanoic acids (C10-C14) are found inbiota from remote Arctic
• PFOS is a PBT chemical and is globally distributed, but concentrations seem to decline since production ban
• Oceanic route needs further study
• FTOHs can be transformed into PFCAs andFOSAs/FOSEs to PFOS/PFCA
• Most PFCs are still in use, political evaluation and action must be taken
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Acknowledgments
Thanks to Urs Berger (ItM Stockholm), many colleagues at IBED and the following institutions for project collaboration or financial support:
European Union (PERFORCE project NEST-508967)DuPont de Nemours...and the PERFORCE project team...