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]

19 June 2006 Norman workshop Stresa Italy 2

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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-


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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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(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


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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...

s c perfluorinated organic compounds in the i m european · pdf file · 2015-02-19s...

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