New Insight into Chlorinated Paraffin Pollution

Bo Yuan

Postdoctoral researcher

Department of Environmental Science and Analytical Chemistry (ACES),

Stockholm University, Stockholm, Sweden

Uppsala; Nov 16, 2017

New Insight into

Chlorinated Paraffin Pollution

What are chlorinated paraffins

Chlorinated Paraffins

• Metal-working fluids

• Plasticizers

• Flame retardants

• Sealants

• Paints, etc.

CP

Chlorinated

Paraffins

Chlorinated Paraffins

•

• Congener group (450): CnClm

CnH2n+2 + mCl2 → CnH2n+2-mClm + mHCl

C6 – C38

ParaffinMixture

Moleculechlorine

Chlorinatedparaffinmixture

Category Abbr. chain length range congener group amount

Impurities/byproducts C6 – C9 6 ≤ n ≤ 9 30 CnClm

Short-chain SCCP 10 ≤ n ≤ 13 46 CnClm

Medium-chain MCCP 14 ≤ n ≤ 17 62 CnClm

Long-chain LCCP 18 ≤ n ≤ 38 312 CnClm

Environment Canada (2016)

Annual global production

Glüge et al. / Science of the Total Environment (2016)

CP importation in Sweden

-500

900

2300

3700

5100

1986

1991

1996

2001

2006

2011

2016

N: Flux (ng/g dw)19911986 20161996 2001 2006 2011

200

2500

5000

tons/y

CP import data from KEMI.se

with thanks to Markus Ifverberg (KEMI)

• In Sweden, CPs are only imported.

• The highest importation was 4800

tons in 1991 in Sweden.

• Since the early 1990s, the use of

CPs in Sweden has decreased by

80%.

Why do we study CPs

SCCPs

UNEP (2017)

April, 2017

SCCPs were included

in the Stockholm

Convention on

persistent organic

pollutants (POPs).

Annual global production

Glüge et al. / Science of the Total Environment (2016)

SCCPs

16%

Other CPs

84%

"The other" CPs• MCCPs are persistent in sediments for as

long as 50 – 80 years.

• MCCPs and C18 LCCPs showed

bioaccumulation and biomagnification

potentials.

• SCCPs and MCCPs are on the EU priority

list of substances for further evaluation of

their role in endocrine disruption.

• SCCPs, MCCPs and LCCPs are considered

toxic to aquatic organisms such as

invertebrates.

Darnerud et al. / Archives of Toxicology (1982)

Zeng et al. / Environmental Science & Technology (2017)

Iozza et al. / Environmental Science & Technology (2008)

Zeng et al. / Environmental Pollution (2017)

Glüge et al. / Science of the Total Environment (2016)

Environment Canada (2015)

Thermal degradation products

• Thermal degradation products include polychlorinated benzenes,

toluenes, biphenyls and naphthalenes.

Bergman et al. / Chemosphere (1984)

Xin et al. / Chemosphere (2017)

Recent advances

in techniques for CP analysis

GC-based analytical techniques

Category Abbr. chain length rangecongener group

amount

GC×GC

analysis

Impurities/byproducts C6 – C9 6 ≤ n ≤ 9 30 CnClm 2 CnClm

Short-chain SCCP 10 ≤ n ≤ 13 46 CnClm 24 CnClm

Medium-chain MCCP 14 ≤ n ≤ 17 62 CnClm 24 CnClm

Long-chain LCCP 18 ≤ n ≤ 38 312 CnClm –

Total CP 450 CnClm 50 CnClm

Environment Canada (2016)

Xia et al. / Environmental Science & Technology (2016)

Allows analysis of over 400 CnClm in technical products

or environmental matrices

Few matrix interferences

Recent development of APCI-QTOF-MS

techniques

New insight

- Baltic Sea Coastal Sediment Core

- Indoor dust

- Commercial products

Sweden

Baltic

Sea

Himmerfjärden sewage treatment plant

serves about 340 000 persons of the

southern Stockholm's metropolitan area.

STPs are sinks and

sources of CPs

Sediment core sampling site

Zeng et al. / Environ. Sci. Tech. (2011)

C8

• C8 – C36 CPs were observed in a sediment section representing the year 1967.

• C24 was the dominant alkane-chain-length group, which is consistent with the

reported alkane-chain-length distributions of several LCCP products (Zitko, V.,

Chlorinated paraffins. 1980)

Chlorinated paraffins in

a 50-year-old sediment section

Yuan et al. / Organohalogen Compd. (2017)

Historical profiles of alkane-chain lengths

• The environment and human beings may have been under exposure to CPs of various

ingredients for decades

• SCCPs (10 ± 3%), MCCPs (50 ± 19%), and LCCPs (40 ± 20%)

• Mean percentage of SCCPs in the imported CP products was 10% (KEMI, 1995 – 2010).

2015

2009

2003

1997

1991

1985

1979

1972

1966

1960

12 13 15 16 18 19 21 22109C# 8 11 14 17 20 23 24 26 27 29 3025 28 31 33 34 3632 35

C8-9 SCCPs MCCPs LCCPs

Himmerfjärden, a sewage treatment plant nearby 0 2.3 ng/g d.w.

Ye

ar

of

De

po

sit

ion

Yuan et al. / Environmental Science & Technology (Just accepted)

Australia (5)

China (5)

Canada (6)

The U.K. (4)

Sweden (5)

Wong et al. / Chemosphere (2017)

– 17 halogenated flame retardants (HFRs);

– 17 polybrominated biphenyl ethers (PBDEs);

– 13 organophosphate esters (OPEs);

– chlorinated paraffins (CPs)

Indoor dust

AU

UK

CA

SE

CH

SR

M

AU

UK

CA

SE

CH

SR

M

AU

UK

CA

SE

CH

SR

M

AU

UK

CA

SE

CH

SR

M

0.1

1

10

100

1000

10000

CPsOPEsPBDEs

Dust

concen

tra

tion (

μg

/g)

HFRs

AU = Australia; UK = The United Kingdom; CA = Canada;

SE = Sweden; CH = China; SRM = NIST2585

Wong et al. / Chemosphere (2017)

Total concentrations of HFRs, BDEs, OPEs and CPs in dust

SE5

CH5

AU1

CA5

UK4

3 4 5 6 7 8 910

C10

3 4 5 6 7 8 9103 4 5 6 7 8 910 3 4 5 6 7 8 910 3 4 5 6 7 8 910

C11 C12 C13 C14

3 4 5 6 7 8 910

C15

3 4 5 6 7 8 9103 4 5 6 7 8 910 3 4 5 6 7 8 910 3 4 5 6 7 8 910

C16 C17 C18 C19

3 4 5 6 7 8 910

C20

AustraliaC14

China

Sweden

The U.K.

C18

Canada

Commercial CP products

Glüge et al. / Science of the Total Environment (2016)

CP42

CP52

CP70

CP42

CP52

CP70

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

C14C12 C13 C17C15 C16 C20C18 C19 C21 C22C11C10C9

Cereclor 60L

(SCCP 60 %Cl, ICI, UK)

Cl #

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Hüls52G

(MCCP 52 %Cl, Hüls AG, Germany)

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Uniclor 40

(LCCP 40 %Cl, Neville Chemical, USA)

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Witchlor44

(LCCP 44 %Cl, Dynamit Nobel, Germany)

Det

ecto

r re

spo

nse

CP-52

(?CP 52 %Cl, China)

C24C23 C27C25 C26 C28 C29 C31C30

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

C14C12 C13 C17C15 C16 C20C18 C19 C21 C22C11C10C9

Cereclor 60L

(SCCP 60 %Cl, ICI, UK)

Cl #

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Hüls52G

(MCCP 52 %Cl, Hüls AG, Germany)

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Uniclor 40

(LCCP 40 %Cl, Neville Chemical, USA)

0

50

100

2 5 8 4 7 10 3 6 9 12 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 2 5 8 11 14 4 7 10 13 3 6 9 12 1 4 7 10 13 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 3 6 9 12 15 4 7 10 13 16

Witchlor44

(LCCP 44 %Cl, Dynamit Nobel, Germany)

Det

ecto

r re

spo

nse

CP-52

(?CP 52 %Cl, China)

C24C23 C27C25 C26 C28 C29 C31C30

C9 SCCP MCCP LCCP

Commercial CP products

Highlights

• CPs with chain lengths shorter than 10 and LCCPs are "old"

contaminants that have recently been detected.

• C8 – C36 CPs appear to have persisted in the sediment for c.a.

50 years.

• Dominant flame retardant contaminants in indoor environnent.

• Highly impure commercial CP products.

Perspective

C8

Acknowledgements

SLU och Naturvårdsverket

APCI-QTOF-MS method developement

Christian Bogdal (ETH Zurich), Urs Berger (UFZ), Matthew MacLeod,

Tomas Alsberg, Cynthia A. de Wit

Baltic Sea sediment study

Volker Brüchert (IGV), Anna Sobek, Cynthia A. de Wit

Indoor dust study

Fiona Wong, Go Suzuki (NIES), Cynthia A. de Wit

Commercial product study

Anna Strid, Magnus Breitholtz, Åke Bergman (Swetox)

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