“Chemical Personality of Fluorinated Organics or Why Chemical Architecture

Matters!"

Scott Mabury et alDepartment of Chemistry

University of TorontoFluoros August, 2005

F F

F F

F F

F F

F F

F F

FF

FS

FF

C

F F

F F

F F

F F

F F

F F

FF

F

PFOA

O

O-

PFOS

O

O O-

CO

OF3C

Cl

CH3

FF

FFTefluthrin

Items in Talk ~Items in Talk ~

•• ““NaturalNatural”” OrganofluorinesOrganofluorines

•• Pesticides, Pharmaceuticals, Consumer, Industrial materialsPesticides, Pharmaceuticals, Consumer, Industrial materials

•• Fluorine and the CFluorine and the C--F bondF bond

•• Reactivity ~ oxidation, photolysis, hydrolysis, elimination, meReactivity ~ oxidation, photolysis, hydrolysis, elimination, metabolismtabolism

•• Physical PropertiesPhysical Properties……water solubility, partitioning, volatilitywater solubility, partitioning, volatility

•• Summary with Summary with ‘‘big picturebig picture’’ on PFOS and PFOAon PFOS and PFOA

C CO

OHH

FH

"Fluoroacetate"

OHO

F

Oleic, stearic, palmitic, mystic, etc

Organofluorines =~30; Cl=2,400; Br=2,050

Most Common

F- F2 + 2e (E0 = -3.06V)H2O2 + 2H+ 2e 2H2O (E0 = +1.71V)

[Cl- E0=-1.36V; Br- E0=-1.07]

C CO

SCoA HOOC COOH

OFH H

'Fluorocitrate'inhibit s cit rate t ransport

Highly Toxic

Haloperoxidase?

Natural Organic Fluorines?

C CO

OH

HF

H"Fluoroacetate"

OS+

HO OH

H3CN

N

N

N

NH2-OO

+H3N

S-adenosylmethionine

F- O

HO OH

N

N

N

N

NH2

F

Fluorinase

5'-FDA

C CO

H

HF

HFluoroacetaldehyde

?

O'Hagan et al, 2002, Nature, 416, p279.

Biosynthesis of Fluoroacetate

Aluminum Production: CF4 (82), CF3CF3 (3) [0.75 and 0.11 kg/ton of Al]Freons: CFCl3 (267), CF2Cl2 (535), CF2ClCFCl2 (85)HCFC: CF3CFH2 (12), CHF2Cl (145), CH3CF2Cl (15)HFCs: CF3CHFCF3, CF3CHFCHFCF2CF3, CH2FCF2CHF2

Note: numbers in (x) reflect atmospheric concentration pptv;

IPCC Climate Change 2001: The Scientific Basis

CF4, CF2Cl2, CFCl3, CF3Cl, CHF3, CF2=CF2 (fluorite)1....CFCl3, CF2Cl2, CF2=CF2, CHF2Cl, CHFCl2, CCl2FCClF2 (volcanoes)2...CF3COOH ....estimate of 268 million tons in the world's oceans3; (ocean vents4) 1) Harnisch & Eisenhauer, 1998; Harnischs et al, 2000.

2) Isidorov et al 1990; Isidorov, 1990.3) Frank et al, 20024) Scott et al, 2005

Anthropogenic 'small organofluorines'

Natural Sources as well?

“Small Polyfluorinated Organics”

CF3

NO2O2NN(CH2CH2CH3)2

F3C

HNC

NO

CH3H3C

F3C

O NCH3

HH Cl-+

CF3NO2

OH

CF

F

O

NCO

N

Cl

H H

CO

OF3C

Cl

CH3

FF

FFN

FOH

O O

NN

H3CO

CH3

N

F

OHO

O

O

O

Pesticides and Pharmaceuticals…

CO

H2CCH2

O

Urethane

H2C

H2CCH2

OHN

OCH2

H2C

C O

Ester

CH2CH2OHR

R=CF2CF2CF2CF2CF2CF2CF2CF3

N(CH3)SO2CF2CF2CF2CF2CF2CF2CF2CF3

Ether

R RR

CH2H2C

R

OCH2

H2CR

P ORxOOH

SO OO

Sulfonates (via sulfide) Phosphates

CH2C

R

OHO

Carboxylates

Some Linkages...

in Polymers

Polyfluorinated long alkyl chain materials…

Major Routes to Perfluoro Chains

C8F17SO3-

C8F17SO2F

C8F17SO2N

C8H17SH

C8H17SO2F

PFOSF(CF2CF2)nCH2CH2OH

F(CF2CF2)nCH2CH2I

Sales Products

+

IF5, 2I2; SbF3

Catalysts

TelogenTaxogen

Hydrolysis

CF3CF2(CF2CF2)nI

[adapted from Kissa]

CF2=CF2 CF3CF2I

CF2=CF2

CH2CH2

CH2CH2OH

CH3

Electrochemical

Sales Products

C7F15COO-

PFOA

TelomerizationElectrochemical Fluorination

22,000 liters of AFFF; ~300 kg of PFOS!

“Airport Foam Seeps into Creek”Toronto Star, June 10, 2000

PTFE Leaching of PFOA

Direct releases of Perfluorinated Acids?

PTFE Thermolysis Products

Ellis, D.A., S.A. Mabury, J. Martin, and D.C.G. Muir. 2001. Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment. Nature. 412:321-324; Ellis, DA, JW Martin, DCG Muir, and SA Mabury. 2003. The Use of 19F NMR and Mass Spectrometry for the Elucidation of Novel Fluorinated Acid and Atmospheric Fluoroacid

Precursors Evolved in the Thermolysis of Fluoropolymers. Analyst. 128:756 – 764.

Nomenclature for Fluorinated Polymers

n

FF

FF

FF

FF

FF

FF

FF

F

free-radicalpolymerization

S

"Fluoro- Monomer"

F

"Fluorinated Polymer"

+

F

Esterification

CCH

H

C

H3C

O

HO

OCO

C CH

HH3C

OCO

CCH3

CH2 C

"Monomer"

H2CCH2

H2CO

COC C

H

HH3C

(CH2)xH3C

C

CH3

OO

CH2

m

"Residual Fluoro-alcohol"OO

NH3C CH2

H2COH

"MethyFose Alcohol"

FF

FF

FF

FF

FF

FF

FF

F

S

FF OO

NH3C CH2

H2C

FF

FF

FF

FF

FF

FF

F

FF

S

FF

O

O

NH3C

CH2H2COH F

F

FF

FF

FF

FF

FF

FF

F

S

FF OO

NH3C CH2

H2CH2C

CH2

H2C(CH2)x

H2CCH3

Fluoro alcohols ~ Fugitive Emissions from Residual Material OR Does the Linkage Chemistry Break?

*Dupont Presentation toUSEPA OPPT. Jan 31, 2005US Public Docket AR226-1914

11 to 14 x106 kg/yr (2004)40% in North America80% are in polymers*

Carpet Treatment

Polymer

Potential Sources?

Degradation

N C

FF

FF

FF

FF

FF

FF

FF

F

CH2H2C

OH

FF

F F

F F

F F

F F

F F

F F

FF

FC

F FC

OHH H

H H

FF

FF

FF

FF

FF

FF

FF

F

CH2H2C

FF

OO

OO

FF

FF

FF

FF

FF

FF

FF

F

CH2H2C

FF

O

FF

FF

FF

FF

FF

FF

FF

F

Urethane EtherEster

CH2H2C

FF

Residual

Posters: ENV004, 018, 023Posters: ENV004, 018, 023

Fluorinated Material Dry Weight % Residual

Polyfox-L-DiolTeflonTM AdvanceZonylTM FSO 100ZonylTM FSE8:2 Methacrylate MonomerMotomasterTM Windshield Washer Fluid w/ Teflon

ScotchgardTM Rug and Carpet Protector*

0.11 (0.03)0.34 (0.20)1.03 (0.61)3.80 (1.09)0.04 (0.01)0.36 (0.01)

0.39 (0.06)

C

C

FF

F

CO

HF

HH

HH

FF

F x = 2 to 10FTOH

n=3 or 6 DinglasanDinglasan, MJA and SA Mabury. 2005. , MJA and SA Mabury. 2005. Environ. Sci. Technol. In review

Residuals could be important source of Residuals could be important source of fluoroalcoholsfluoroalcohols……to the atmosphereto the atmosphere

CC

F F F F F FF F F F F FF F F F F F F F F F F F

FF F F F F F F F F FF F F F F F F F F FF

F

FOH

H H

H H 24:2 FTOH"49 Fluorines"

Tentatively identified in a telomer phosphate mixture via GC/MS;Tentatively identified in a telomer phosphate mixture via GC/MS; see see Poster ANA044Poster ANA044

bond length C-X (A)

1.09

1.39

1.78

1.93

EN

2.2

4.0

3.0

2.8

Bond Strength C-X (kcal/mol)

99

110

85

71

H

F

Cl

Br

Van der Waal's radius (A)

1.20

1.35

1.80

1.95

Hydradation X-

(kcal/mol)

-

117

84

78

C Fδ−δ+

Anything Interesting about the CAnything Interesting about the C--F bond?F bond?

f(x)

0.094

0.38

0.28

0.071

3.4

F

Cl

Br

CF3

OH

X

H2C Xδ−δ+

H •O H

H2C Fδ−δ+

H

H2C CH2

FH

C C OHH H

HHCF

FR

Rxn

What does the Fluorine atom do to reactivity What does the Fluorine atom do to reactivity towards Oxidation?towards Oxidation?

Slows it way down!Slows it way down!

NoteNote: Similar story for ring: Similar story for ringoxidations.oxidations.

Kwok & Atkinson; 1995; Kwok & Atkinson; 1995; AtmoAtmo EnvEnv. 29:1685. 29:1685--1695.1695.

•O H

C FF

FH

Lifetime = 260 years!

C FF

FF

Lifetime =>50,000 years!

Slow!

•O HNo Reaction

HFCsHFCs are sloware slow……PFCsPFCs are like diamonds!are like diamonds!

C FF

FF

Lifetime =>50,000 years! Ultimate Fate? Photolysis in upperatmosphere (highly energertic photons)

C•F

FF + F•

Does F• cause O3 destruction like Cl or Br? NO! [104 less than Cl]

F + O2 FO2 (eq far to the right)M

FO2 + O3 FO + 2O2 (very slow)

F + CH4 HF + CH3 (very fast)

F + H2O HF + OH (very fast; exothermic!)

hν

(<210 nm)

Why?

Only option is photolysisOnly option is photolysis……but where?but where?

way up high!way up high!

Wavenumber (cm-1)

800 1000 1200 1400

Rad

ianc

e (1

0-3W

m-2

(cm

-1)-1

)

0

20

40

60

80

100

O3

CO2

CH4H2O

Atmospheric Window

F3C CF3

Lifetime = 10,000 yrsRadiative Efficiency = 0.26 W m-2 ppb-1 GWP (100 yr) = 11,900 (where CO2 = 1)Year 2000 concentration: 3 pptv

IR Transm

ittanceIR

Transmittance

Any problems percolating way up there?Any problems percolating way up there?

Wavenumber (cm-1)

800 1000 1200 1400

σ (1

0-17 cm

2 mol

ecul

e-1)

0.0

0.2

0.4

0.6

0.8

1.0

Rad

ianc

e (1

0-3W

m-2

(cm

-1)-1

)*

0

20

40

60

80

Gal70 H-Gal 1040xAtmospheric Window*

* Calculated for mid-altitude during winter using calculator found on http://geosci.uchicago.edu/~archer/cgimodels/radiation.html

σσ(10(10

-- 1717cmcm33m

oleculem

olecule-- 11

Posters: ENV025 & ANA030Posters: ENV025 & ANA030

F3C O CF

CF3

CF2 OCF2 OCF3

F5S CF3

Lifetime = >1,000 yrsRadiative Efficiency = 0.59 W m-2 ppb-1 GWP (100 yr) = >17,500 (where CO2 = 1)Year 2000 concentration: 4 pptv(Sturges et al, 2000, Science 289:611-613)

R(N, O etc)

CF3

R(N, O etc)

CO

F

R(N, O etc)

CO

OH

-2 F- F-

hν

Photolysis in Natural Waters

H2O

F3C

O NCH3

HH Cl-+

HOOC

O NCH3

HH Cl-+

+ 3 F-

hν

Prozac

R(N, O etc)

F

R(N, O etc)

OH

hν

F-

Br>Cl>F

Can you break a CCan you break a C--F bond? F bond? Only in special cases or conditionsOnly in special cases or conditions

Overall Atmospheric Chemistry of FTOHs

C

C

FF

F

CO

HF

HH

HH

FTOH

FF

F

C

C

FF

F

CO

FH

H

FF

F

H

C

C

FF

F

OF

FF

F

H

C

C

FF

F

OF

FF

F

O O•

C

O

FF

FF

FF

F

O•

C

C

FF

F

+OH/-H2O

xPerfluoroAldehyde

F

+O2/-HO2

FF

F

x

FT-Aldehyde

x

x

CO

n

•

FFn

CO2

+OH/-H2O +O2

+NO/-NO 2 +O2

+NO/-NO 2

Lifetime = 20 d Lifetime = 20 d Lifetime = 30 d

"Unzipping"

C

C

FF

F

OF

FF

F

OH

C

OH

FF

FF

FF

FC

CO

FF

F

FF

FC

CO

FF

x

n n

HO

FF

F n

PFNA (x=6)

PFOA (x=6)

+HOO/-O3

+ROO/-R'CHO-HF+H2O/-HF

"Novel" atmospheric chemistry

Do the Do the SulfamidoethanolsSulfamidoethanols Degrade to Acids in the Atmosphere?Degrade to Acids in the Atmosphere?

Alternative source of PFCAs?Alternative source of PFCAs?

F F

F F

F FS

FF FO

ON

CH3

CH2CH2OH F F

F F

F FS

FF FO

ON

CH3

CH2 CO

H

F F

F F

F FS

FF FO

ON

CH3

H

F F

F F

F FS

FF FO

ON

H

CH2CH2OH

F F

F F

F FS

FF FO

ON

CH2CH3

CH2CH2OHOH

C

F F

F F

F F

FF F

F F

F F

F F

ORS

•

•FF F

MethylFBSE

O

O

Alcohol Oxidation

N-Dealkylation

OH

Addition

OR

PFCAs!!! ....experiments ongoing.

F F

F F

F FS

FF FO

O

•

+

•OH

•OH•OH

SO2

PFBS

Posters: ENV017 & 021Posters: ENV017 & 021

Hydrolysis? Hydrolysis?

R CF

HH

Why?• F- is a VERY poor leaving group;• Thus SN1 and SN2 only go slowly; • polyfluorination increases 'steric' issues;

O:H

F-Only Slowly

half-life (pH 7)

~30 yrs

50 daysHClH3PO4

HFBenzoic acidTFAPFOSPFOA

Low2.123.144.200.5Extremely Low~2

CH3F

(CH3)3CFCH3Br

(CH3)3CCl 23 sec

1 yrpKa

F F

F F

F FS

F FO

OO-

F

F

F

F

F

F

F

FF

CF F

F F

F FO-

F

F

F

F

F

F

F

FF

O

In the environment?

Likely as salts

Except in special casesExcept in special cases……where Fwhere F-- is pushed!is pushed!

C

O•

FFF

F

FF

F

CO

FFCC

FFF

FF

CC C

FFF

F

F

F

CC C

FFF

F

OHF

F

CC C

FFF

F

OHF

F

O CC C

FFF

OHF

FO

F•

•

•+

•

CC

FFF O

F

H2O CC

FFF O

HO

+ F-

HCO3- + 2F-

C

OH

FF

F

F

FF

F

C

CO

FF

F

FF

F

C

CO

FF

n

n

HO

FF

F n

C

C•

FF

F

F

FF

F n

C

C

FF

F

F

FF

F n

O O•O2

R-CH-O-O•

-HF

+H2O/-HF

C

C

FF

F

F

FF

F

R1 R2Atmospheric Reagents

{Reactive?

C

C

F

FF

F

F

FF n

O•

NO/NO2

CO

FF

Fate of Perfluorocarbon Radicals

MajorMajor low %low %

OH

CF3

O

CFF

C

C

FF

FF

FF

F

C

HH

O

OH

C

CC

FFF

FF

CF

OHO

H

F-

+ HF

Eliminat ion

H2O

Stable

α,β unsaturated acids

C

C

FF

FF

FF

F

C

HH

O

H

C

CC

FFF

FF

CF

OH

H + HFH2O

α,β unsaturated aldehydes

abiotic; x=6, pH 7, T=23C ~35 days

biotic (bacteria); x=6, pH 7, T=23C ~14 days

biotic (rats); x=6, pH 7.2, T=23C ~very fast

Biotic & Abiotic are much Faster

Telomer Acids

Telomer Aldehyde

x

x

β-Eliminat ionAcidic "H"

Acidic "H"

If the right ‘architecture’ then ELIMINATE?

*SEE Poster TOX008; is HF the cause of the high toxicity of 10:2*SEE Poster TOX008; is HF the cause of the high toxicity of 10:2 FTCA?FTCA?

**

FF

F F

F F

F F

F F

FF

FC

F F

CO

HF

F

HH

H

H

FF

F F

F F

F F

F F

FF

FC

F F

C

HH

FF

H

FF

F F

F F

F F

F F

FF

FC

F F

CO

HH

FF

OH

FF

F F

F F

F F

F F

FF

FC

F F

CO

OH

F

H

FF

F F

F F

F F

F F

FF

F C

F F

O

OH

-HF

8:2 FTOH

PFOA

8:2 FTOH Acid

8:2 FTOH α,β Acid [major product]

8:2 FTOH Aldehyde

β oxid

atio

n

Microbes

FF

F F

F F

F F

F F

FF

FC

F F

CO

H

α,β 8:2 FTOH Aldehyde

F

H

O

slow

Microbial Metabolism Pathway ~

Posters: ENV011 & 022Posters: ENV011 & 022

Rat Liver Metabolism Pathway ~

NoteNote: important that PFNA (odd PFCA) : important that PFNA (odd PFCA) is, at most, a minor component.is, at most, a minor component.

FF

F F

F F

F F

F F

FF

FC

F F

COHF

F

HH

H

H

FF

F F

F F

F F

F F

FF

FC

F F

C

HH

FF

H

FF

F F

F F

F F

F F

FF

FC

F F

CO

HH

FF

OH

FF

F F

F F

F F

F F

FF

FC

F F

CO

OH

F

HFF

F F

F F

F F

F F

FF

F C

F F

O

OH

O

FF

F F

F F

F F

F F

FF

FC

F F

FF

8:2 FTOH

PFOA

Conjugates...8:2 FTOH Acid

8:2 FTOH α,β Acid

8:2 FTOH Aldehyde

O

OH

Liver cells

α,β 8:2 FTOH Aldehyde

PFNA (minor)

β oxidation

α oxidation

FF

F F

F F

F F

F F

FF

FC

F F

CO

H

F

H

slow

Major

-HF

-HF

GST

GSTGlutathione Adducts

Glutathione Adducts

Hagen, Belisle, et al, 1981. Anal Biochem. 118:336-343; Martin, JW, SA Mabury,and PJ O’Brien. 2005. Metabolic Products and Pathways of FluorotelomerAlcohols in Isolated Rat Hepatocytes. Chemico-Biological Inter. In press .Posters: TOX010Posters: TOX010

FF

F F

F F

F F

F F

FF

FC

F F

CO

OH

F

H

FF

F F

F F

F F

F F

FF

F C

F F

O

OH

PFOA

slow

Why is this reaction so slow?

• OH or FeO+ are strong electrophiles but...

...the β carbon is relatively electron deficient!

Thus is it surprising the β carbon is reactive towards nucleophiles?

FF

F F

F F

F F

F F

FF

FC

F F

CO

H

F

HFAST

G-S-H• •• •

FF

F F

F F

F F

F F

FF

FC

F F

CO

H

S

H

CH2

CHCOOH

NH C CH3O

"Mercapturate"

NO! One hopes it is GSH and not one of the nucelophilic centres on a protein or in DNA.

Where does this go?

FF

F F

F F

F F

F F

FF

FS

F F

FF Conjugates...

O

ON

CH2CH3

CH2CH2OH

FF

F F

F F

F F

F F

FF

FS

F F

FF

O

ON

CH2CH3

CH2COOH

FF

F F

F F

F F

F F

FF

FS

F F

FF

O

ON

H

CH2CH2OH

FF

F F

F F

F F

F F

FF

FS

F F

FF

O

ONH2

FF

F F

F F

F F

F F

FF

FS

F F

FF

O

OO-

PFOS

FF

F F

F F

F F

F F

FF

FS

F F

FF

O

ON

H

CH2COOH

Conjugates...

Conjugates...

Human & Rat Biotransformation of EthylFose

XuXu et al, 2004. Chem. Res. et al, 2004. Chem. Res. ToxicolToxicol. 17: 767. 17: 767--775; 775; TomyTomy et al. 2004. ES&T (Fish Livers)et al. 2004. ES&T (Fish Livers) Posters: ENV006, 014, 015, Posters: ENV006, 014, 015,

No Reactions @ EnvironmentallyRelevant Conditions....even examplesunder 'extreme conditions' are rare orhard to decipher.

F F

F F

F FS

F FO

OO-

F

F

F

F

F

F

F

FF

C

F F

F F

F FO-

F

F

F

F

F

F

F

FF

O

F3C CO

O–

Engineered "bioreactor"

over 90 days

Measured evolution of F-

Kim et al, 2000. Env Eng Sci. 17:

One persuasive example:

Okay but what about those perfluorinated acids Okay but what about those perfluorinated acids that are all the rage?that are all the rage?

YesYes……pretty boring indeed with respect to Reactions!pretty boring indeed with respect to Reactions!

fX fθ

X-F -0.38

0.06

0.20

0.59

-1.11

-5.19

-1.64

0.37

0.94

1.09

1.35

-0.03

-4.13

-0.44

X-Cl

X-Br

X-I

X-COOH

X-COO-

Kow Fragments

Hansch & Leo; EOC 1st Edition

X-OH

Kow Correction Factors "electronic effects"

Nearby Polyhalogenation

2 on same C3 on same C2 on adjacent single-bonded C3 on adjacent single-bonded Cand so forth...

0.601.590.280.56

F

CH2 FCF2F3C

Water SolubilityKow

1∝

C

F F

F F

F FO-

F

F

F

F

F

F

F

FF

O

Water Solubility and PartitioningWater Solubility and Partitioning

CarboxylatesPFC8 PFC10 PFC11 PFC12 PFC14 PFS8 PFS6

BCF

1e+0

1e+1

1e+2

1e+3

1e+4

1e+5

Sulfonates

CarcassLiverBlood

Martin, J., S.A. Mabury, K.S. Solomon, D.C.G. Muir. 2003 Bioconcentration and Tissue Distribution of Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss Environ. Tox. Chem. 22: 189-195.

Martin, J., S.A. Mabury, K.S. Solomon, D.C.G. Muir. 2003 Dietary Accumulation of Perfluorinated Acids in Rainbow Trout (Oncorhynchus mykiss. Environ. Tox. Chem. 22:196-204.

BCF=ku/kd

Additional CF2 results in a ~7x increase in the BCF.

BCF/BAF of PFCAs

fX fθ

X-F 0.07

-0.79

-1.18

-0.20

-1.89

-3.47

-3.67

0.21

-0.53

-0.84

0.32

-2.63

na

-4.69

X-Cl

X-Br

X-CF3

X-CBr3

X-CCl3

X-COOH

V.P. Fragments

Simmons; 1999. JAFC; 47:1711-1716

Henry's Law Fragments

Hine & Mookerjee 1975 in EOC 1st Edition

fX fθ

C-F +0.50

-0.30

-0.87

-3.21

-3.10

+0.14

-0.21

-1.83

C-Cl

C-Br

C-NO2

C-OH

Fluoros Flying?

FF

FF

FF

FF

FF

8:2 FTOH

Cl8-Dioxin

PCB 153

Di-(2-ethylhexyl) pthalate

n-Decane

CBr3H

1,2 Dichlorobenzene

Ethoxybenzene

CH2CH2OH

FF

F

FFF

F

M.W.

464 460

360

390

142

252

147

122

V.P. (Pa)

212* 0.0000000001

0.0001

0.0019

173

724

200

204

Data from "EOC" Schwarzenbach et al ; *Data from Lei, Mabury, et al, unpublished data.

8:2 FTOH by V.P. and M.W.

So are Fluorocarbons very Polarizable? NO!

FF

F F

F F

F F

F F

FF

F

F

F F

F

M.W. R.I.1 Density1 M2 V.P. α5

438 1.282 1.766 155 46773 15.2

(cm3/mole)

α = polarizabilityR.I. = Refractive IndexM = Molar Volume

1Aldrich; 2McGowan et al; 3CRC Online;4Schwarzenbach5Calculated with Gaussian by M. Staikova; *for C10Cl6H16

(Pa)

HH

H H

H H

H H

H H

HH

H

H

H H

H

114 1.398 0.703 124 18194 15.8

ClCl

Cl Cl

Cl Cl

Cl Cl

Cl Cl

ClCl

Cl

Cl

Cl Cl

Cl

"make believe molecule"

Per...Octanes

890 ????? ????? ? 10-3 * 47.1

H

F

Cl

A30

FluoroAlcohol Physical Properties

]]RR22=0.99=0.99

P (Pa) Log Kaw Log Koa Csat Log Kow

4:2 FTOH6:2 FTOH8:2 FTOH10:2 FTOHNEtFosaNMeFoseNEtFose

1670; 992; 489(a) 876; 713; 107(a) 227; 254; 2;4(b) 53; 144; 0.7(a) 7; 0.240.7;0.00040.35; 0.0017; 0.79

1.8 1.7 1.3

3.33.64.24.85.96.87.1

148

w

2.03.34.92.74.1

?

Stock et al 2004. ES&T. 38:1693-1699; Lei et al, 2004. J Chem Eng Data 49:1013-1022; 25CKrusic et al, J Phys Chem A; 2005; 109:6232-6241; (a) calculated at 35C; (b) calculated at 21C; Schoeib et al, 3M Values OPPT DocsBonin, Lau, Ellis, & Mabury, unpublished data.

SummarySummary……major points:major points:

•• OrganofluorinesOrganofluorines are intriguing ~ lots to learn and interesting science to do;are intriguing ~ lots to learn and interesting science to do;

•• They are generally highly persistent because of inductive effecThey are generally highly persistent because of inductive effects of Fts of Fand the and the ‘‘poor leaving grouppoor leaving group’’ ability of Fability of F--; Perfluorinated acids ; Perfluorinated acids could could ‘‘redefine persistenceredefine persistence’’;;

•• Breakage of CBreakage of C--F bonds requires specific conditions;F bonds requires specific conditions;

•• Polyfluorinated compound are highly volatile with respect to maPolyfluorinated compound are highly volatile with respect to mass;ss;

•• Longer chain Perfluorinated compounds are moderately Longer chain Perfluorinated compounds are moderately bioaccumulativebioaccumulative;;

•• Appropriate to treat acids such as PFOS, PFOA, etc as degradatiAppropriate to treat acids such as PFOS, PFOA, etc as degradation products;on products;

•• Intermediates in the conversion of Intermediates in the conversion of FluoroalcoholFluoroalcohol to to PFAcidsPFAcids are are worth worth invesigationinvesigation;;

•• As a first step in solving As a first step in solving ““the problemthe problem”” address address ‘‘residualresidual’’ materials;materials;

•• Chemical Architecture mattersChemical Architecture matters……watch out for large, perfluorinated watch out for large, perfluorinated chemicals that do not react with OH in the atmosphere ~ GWP issuchemicals that do not react with OH in the atmosphere ~ GWP issues.es.

n

FF

FF

FF

FF

FF

FF

FF

F

S

"Fluoro- Monomer"

F

"Fluorinated Polymer"

F

OCO

C CH

HH3C

OCO

CCH3

CH2 CC

CH3

OO

CH2

m

OON

H3C CH2H2C

OH

"MethyFose Alcohol"

FF

FF

FF

FF

FF

FF

FF

F

S

FF OO

NH3C CH2

H2C

FF

FF

FF

FF

FF

FF

F

FF

S

FF

O

O

NH3C

CH2H2COH

FF

FF

FF

FF

FF

FF

FF

F

S

FF OO

NH3C CH2

H2CH2C

CH2

H2C(CH2)x

H2CCH3

FF

FF

FF

FF

FF

FF

FF

F

S

FF OO

O-

PFOS

Atmosphere

"Residual" 1-3 % OH Rxns

Biological Rxns

Human Exposure?

"Intermediates"

PolyFluoroPolyFluoro SulfamidoethanolsSulfamidoethanols…….Big Picture.Big Picture

n

FF

FF

FF

FF

FF

FF

FF

F

CH2

"Fluoro- Monomer"

F

"Fluorinated Polymer"

F

COC C

H

HH3C

COCCH3

CH2 CC

CH3

OO

CH2

m

CH2

8:2 FTOH(and relateds)

H2CCH2

H2C(CH2)x

H2CCH3

FF

FF

FF

FF

FF

FF

FF

F

FF

PFOA, PFNA, etc (Atmo) PFOA (bio)

Atmosphere

"Residual" 1-3 % OH Rxns

Biological Rxns

Human Exposure?

"Intermediates"

HO

FF

FF

FF

FF

FF

FF

FF

F

CH2

FF

CH2O

FF

FF

FF

FF

FF

FF

FF

F

CH2

FF

H2CO

FF

FF F

F

FF F

F

FF

F

FF

CH2

FF

CH2HO

CO OH

C

FF

FF

FF

FF

FF

FF

FF

F

OOH

Differences? More is known (published); potential for longer chain PFCAs from larger FTOHs.

FinaleFinale……the FTOH Fatethe FTOH Fate

Grad Students: Tim Boudreau, Naomi Stock, Wai Chi Kwan, Kiet Chau, Yun Ye, Marla Smithwick, Hans Sanderson, Amila DeSilva,Suzanne Gauthier, Joyce Dinglasan,Craig Butt, Jessica Currie, CoraYoung, Michelle MacDonald, Robert Dumoulin

Post-Docs: Cheryl Moody, David Ellis, Jon Martin, Sean Richards,Charles Wong, Stella Mello, Vasile Furdui

Undergraduate Students: Ryan Sullivan, Stacy Economou, Lisa Deeleebeck, Julia Bonin, Sandy Williams, Erin Marchington

Research Staff: Ying Lei, Dan Mathers

Funding: NSERC operating, strategic (3 yrs), equipment; 3M; Telomer Research Program (1 yr), Omnova Foundation (2 yrs)

Collaborators:Derek Muir; Elizabeth Edwards; Brian Scott, Peter O’Brien, Keith Solomon, & Paul Sibley; Kim Strong; Frank Wania;

Tim Wallington, Mike Hurley, & Mads Sulbaek Andersen et alFord Motor Company

Co-authors, Collaborators, & Funding