th June2017 Fluorochemicals - What is the Fuss All About?

Fluorochemicals - What is the Fuss All About?

ROGER A KLEIN1; NIGEL HOLMES21

Cambridge, UK, and Christian Regenhard Center for Emergency Response Studies (RaCERS), John Jay College of Criminal Justice, City University New York (CUNY),

New York NY 20019 USA 2Dept. of Environment & Heritage Protection, Queensland Government

Brisbane 4000 QLD Australia <[email protected]> ; <[email protected]>

ICCE2017 Oslo 19th June2017

Wide Range of End-User Products

© Klein & Holmes June 2017

Slide 2 29-Jun-17

(NIOSH).

What is the Fuss All About?•Waste Streams of Concern• Firewater runoff containing fluorochemicals

• Current operations• Legacy incident and training sites – airports and airbases• Accidental discharge• Old foam stocks

• Landfill leachates• Textiles and fabrics

•Waste water treatment plant (WWTP)• Biosolids – contaminated with short and long chains including PFOA

• Then used for agricultural soil improvement and in domestic compost products

• Effluent – failure to capture short chains

•Manufacturing© Klein & Holmes June 2017

Slide 3 29-Jun-17

Volatiles GWP


What is the Fuss All About?

Tuesday, 09 May 2017 © Klein& Holmes ICCE2017

•PFOS-base products (C8F17SO3H)•Now legacy in most countries but may

occur in waste streams or washouts•Odd and even chain-length, branched chain isomers

(ie PFHxS, PFDS)

• Fluorotelomer products (CnF(2n+1)CH2CH2-)• Widely used in may consumer products• Even chain-length (n=4,6,8……)• Degrade to PFCAs as end-point


What is the Fuss All About?• Indirect Human Exposure

• Drinking water• Food, agriculture, fisheries

• Direct Human Exposure• Domestic products• Impregnated clothing• Respirable air

• Long-term Environmental Contamination• Extreme environmental persistence• Long-range transport

• Scientific Uncertainty• Unknown toxicity and bio-accumulation profiles for end-point degradation products• All extremely environmentally persistent• Long human half lives• Probable links versus proven cause-and-effect

• Legal and Financial Liability• Reputational and brand image damage



PFCAs in Articles of CommerceC8 C8

Food contact paper

Cookware

Home textiles

Apparel

data from Guo et al (2009)


Non-industrial products – uncontrolled use

Direct human exposure by aerosol – liver toxicity Nilsson et al 2016

Professional ski-waxers exposed to 8:2 TOH© Rebecca Renner


Domestic products – in the home

data from Guo et al (2009) USEPA

© Swedish Society for Nature Conservation 2006

© Swedish Society for Nature Conservation 2006

© RAK 2017Human Exposure to PFASSlide 9 29-Jun-17

from UBA 47/2014

Outdoor Jackets

wt%

from UBA 47/2014

Impregnated All-weather Outdoor Clothing

Based on C6 chemistry…………? Really?

© Klein& Holmes ICCE2017Tuesday, 09 May 2017

data from Joensson et al SWEREA (2015)

Extractable PFCs in DWR Jackets


0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

J6%

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

J7%

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

J14%

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

J15%

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

100.00

6:2FTOH

8:2FTOH

10:2FTOH

J6%

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

6:2FTOH

8:2FTOH

10:2FTOH

J7%

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

6:2 FTOH8:2 FTOH10:2 FTOH

J14%

0.00

10.00

20.00

30.00

40.00

50.00

60.00

6:2 FTOH8:2 FTOH10:2 FTOH

J15%

data from UBA (47/2014)

FTOHs

PFCAsµg/kg

Based on C6 chemistry…………? Really?

© Klein& Holmes ICCE2017

data from Joensson et al SWEREA (2015)

Tuesday, 09 May 2017

© RAK 2017Risk ConsiderationsSlide 13 29-Jun-17

TO

Toxi

city

Bio

-acc

um

ula

tio

n

Mo

bili

tyH

2O

so

lub

ility

Vo

lati

lity

C-Chain Length


8:2 Fluorotelomer derivatives PFOA

and other N:2 FT derivatives to N-PFCAs plus other products

+ partial dehydrofluorination products

Precursor chain-length distribution


Firefighting Foam Fluorosurfactantschain-length distribution



Orphan or Legacy Foam Stocks – Total Organic Fluorine (TOF)

AFFF Class B Class ATOF 1.8-0.4%

TOF 0.03% (??)

standardanalysisbeforeTOPA

Perfluoroalkyl substances (PFAS)total detected

after TOPA


CnF2n+1

COOH

CnF2n+1

SO3H

?



µg/L µg/L (x 120)

TOPA X-axis x 120

before

after TOPA

X 120

Perfluorocarboxylic acids (PFCAs)


10

100

1,000

10,000

100,000

1,000,000

10,000,000

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTrDA PFTeA

PFCAs TOPA log-scale

Series1 Series2

10

100

1,000

10,000

100,000

1,000,000

10,000,000

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFTrDA PFTeA

PFCAs before TOPA log-scale

Series1 Series2

Slide 20 29-Jun-17 Perfluoroalkyl substances (PFAS)

before TOPA after TOPA

log10 µg/L log10 µg/L

x ~100+2 log units

© RAK 2017

Scientific UncertaintySlide 21 29-Jun-17


© RAK 2017



PFOS PFOA

© RAK 2017



PFOS PFOA

2000-6000 ng/ml PFOSIn plasma

or5 ng/ml in plasma?

© RAK 2017



© RAK 2017



© RAK 2017

Holistic Risk AssessmentSlide 26 29-Jun-17

© RAK 2017

Holistic Risk AssessmentSlide 27 29-Jun-17

A High Index of Suspicion

© RAK 2017



• Contact details:

• Nigel Holmes

• Department of Environment & Heritage Protection

• Queensland Government

• [email protected]

• [email protected]

• Dr. Roger A. Klein

• Cambridge UK© Klein & Holmes June 2017

Slide 29 29-Jun-17

mailto:[email protected]

mailto:[email protected]

Documents

th June2017 Fluorochemicals - What is the Fuss All About?