Telomer
Research
Program
Annual
Report
of
Activities
for
TRP
Grant
to
University
of
Toronto;
Scott
Mabury,
PI
Project
years:
1
September,
2001
to
1
September,
2002.

Students/
PostDocs
currently
active
on
the
FTOH
project:
Postdocs:
Dr.
David
Ellis,
Dr.
Jon
Martin,
Dr.
Stella
Melo,
Grad
students:
Naomi
Stock,
Ella
Ye,
Undergrad
Studens:
Kerry
Pratt,
Fiona
Lau,
Ryan
Sullivan,
and
Lisa
Deeleebeck.
Note:
TRP
funds
support
the
research
of
Dr.
David
Ellis
while
other
funds
support
the
rest
of
the
team.

Academic
Co­
Investigators:
Derek
Muir
(
NWRI),
Keith
Solomon
and
Paul
Sibley
(
UofGuelph),
Kim
Strong
(
Toronto­
Physics),
Tim
Burrow
(
Toronto;
Chemistry;
NMR
Facility),
Ying
Lei
(
Toronto;
Chemistry;
ANALEST).

Project
Coordination:
During
the
initial
year
of
the
project
the
UofT
research
team
hosted
TRP
visits
in
Fall,
2001
(
Libre,
Hoke,
Buck,
Kaiser)
for
a
general
research
progress,
a
priorities
setting
exercise,
Winter,
2002
(
Kaiser
and
Gearhart)
for
familiarization
with
our
analytical
techniques
for
FTOH
air
sampling/
analyses
and
a
late
spring
2002
`
update'
meeting
with
Libre,
Hoke,
and
Buck.
Further
there
were
at
least
2
conference
calls
concerning
air
sampling
and
vapour
pressure
measurements
that
transpired
during
this
period.
A
number
of
visits
prior
to
Sept,
2001
also
occurred
both
in
Toronto
and
Guelph
to
explore
research
interests
and
analytical
techniques.

Status
of
NSERC.
Strategic
Matching
Funds:
A
proposal
was
submitted
in
mid­
April
to
NSERC
to
pursue
additional
funds
for
our
FTOH
work.
This
proposal
has
Mabury
as
PI
and
Muir,
Sibley,
and
Solomon
as
Co­
Investigators.
Notification
of
success
in
this
grant
cycle
will
likely
be
in
November.

Specific
Objectives
for
TRP
funds
for
Year
1
(
from
the
research
agreement
appendix):
Based
on
the
October
26,
2001
meeting
that
included
the
Mabury
(
Toronto),
Muir
(
NWRI)
and
Sibley
(
Guelph)
and
Hoke,
Buck,
and
Kaiser
(
Dupont)
and
Libre
(
Atofina)
the
specific
work
to
be
continued
and
expanded
for
the
TRP
funded
portion
of
this
project
is
to
focus
in
year
1
on
three
specific
areas
and
include
the
following:
1)
analytical
methodologies;
2)
environmental
monitoring
and
3)
environmental
fate
determination.
Analytical
methods
will
directly
focus
on
further
optimizing
our
sampling
and
GC­
based
analysis
techniques
of
fluoro­
telomer
alcohols
primarily
in
air
samples
and
developing
the
basic
methods
utilizing
lc/
ms/
ms
to
determine
our
hypothesized
degradation
products
which
are
the
telomer­
acids.
Environmental
monitoring
will
comprise
air
sampling
at
Toronto
in
an
ongoing
campaign
and
an
intensive
air
sampling
at
selected
locations
across
North
America.
Initial
samples
for
telomer
degradation
products
will
also
be
run
focusing
on
atmospheric
particles
and
municipal
outfalls.
Our
main
objectives
in
the
environmental
fate
area
are
to
determine
degradation
pathways
and
kinetic
rates
for
atmospheric
pathways
and
further
refine
our
physical
property
measurements.

Good
progress
has
been
made
in
each
of
these
areas
and
is
reported
below.
A
large
air
sampling
study
(
FAMAS)
conducted
last
November
and
an
arctic
sampling
expedition
this
July,
smog
chamber
experiments,
initial
experiments
investigating
biodegradation
pathways,
and
further
experiments
focusing
on
physical
property
measurements
of
FTOHs
and
polyfluorinated
alkyl
chains,
have
taken
up
the
bulk
of
effort
during
our
inaugural
year
of
TRP
funding.

Environmental
Monitoring
1.
Fluorinated
Telomer
Alcohols
in
the
North
American
Atmosphere
(
Stock,
Martin,
Lau)
The
presence
of
fluorinated
telomer
alcohols
and
other
fluorinated
compounds
in
the
North
American
atmosphere
was
investigated
using
high­
volume
air
samplers.
In
November
2001,
samples
were
collected
in
six
cities
throughout
North
America,
which
were
chosen
as
remote
locations
or
for
nearby
presence
of
industrial
sources
(
Winnipeg
MB,
Long
Point
ON,
Reno
NV,
Cleves
OH,
Toronto
ON,
and
Griffin
GA).
This
study
was
given
the
acronym
"
FAMAS"
for
fluoroalcohol
monitoring
in
air
samples.
Both
gaseous
and
particulate­
bound
fluoroorganics
were
collected
on
media
consisting
of
XAD­
2,
polyurethane
foam
and
quartz
fiber
filters.
All
samples
were
approximately
1000
m3.
Due
to
the
potential
for
contamination
all
sample
preparations
and
subsequent
extractions
were
conducted
in
Class
100
clean
room
conditions.
Briefly,
these
samples
were
extracted
in
large
custom,
glass
columns
by
soaking
in
methanol
and
five
aliquots
of
ethyl
acetate.
The
aliquots
were
combined
and
an
internal
standard
was
added.
The
samples
were
rotovapped
to
~
5
mL,
filtered
using
a
nylon
0.2
µ
m
filter
and
subsequently
reduced
to
~
200
µ
L
under
pure
nitrogen.
Blank
extraction
samples
were
also
run.
Samples
were
separated
using
gas
chromatography
(
either
30
or
60
m
DB­
35
column
with
5
micron
film)
and
detected
using
chemical
ionization
mass
spectrometry
(
GC/
CI­
MS)
(
quadrupole
instrument).
Several
fluorinated
compounds
­
including
fluorotelomer
alcohols
and
perfluoro­
sulfonamides
­
were
detected
at
pg/
m3
concentrations
in
all
locations
(
Table
1).
Low
concentrations
of
fluoroorganics
were
consistently
detected
in
field
blanks;
however,
this
did
not
prevent
confirmation
or
quantification
of
environmental
concentrations.
As
the
sample
extraction
method
lacked
an
adequate
clean­
up
step,
chromatography
difficulties
were
unavoidable.
This
proved
especially
true
for
the
10:
2
FTOH
where
adequate
chromatography
was
not
achieved
and
thus
no
quantitative
data
are
reported.
Currently,
a
clean­
up
step
is
under
development
and
samples
will
be
cleaned­
up
and
re­
analyzed.
In
addition,
the
samples
will
also
be
analyzed
via
gas
chromatography
coupled
with
tandem
mass
spectrometry
(
GC/
MS/
MS)
(
iontrap
instrumentation).
We
believe
this
will
provide
a
more
robust
analytical
technique
with
the
added
value
of
MS/
MS
spectra
for
enhanced
identification.
Table
1.
Concentration
of
fluorotelomer
alcohols
(
FTOHs)
and
perfluorooctane
sulfonamidoethanols
(
FOSEs)
in
North
American
air
samples.

SAMPLE
LOCATION
6:
2
FTOH
(
µ
g/
m3)
8:
2
FTOH
(
µ
g/
m3)
NEtFOSE
(
µ
g/
m3)
NMeFOSE
(
µ
g/
m3)
Cleves,
OH
72
±
48
79
±
35
11
±
10
18
±
5
Griffin,
GA
 
127
±
71
40
±
7
371
±
309
Long
Point,
ON
16
±
5
21
±
12
6
±
4
10
±
4
Reno,
NV
51
±
9
50
±
7
506
±
217
152
±
48
Toronto,
ON
62
±
28
25
±
22
38
±
46
31
±
4
Winnipeg,
MB
26
±
24
18
±
3
27
±
6
64
±
18
 
chromatography
difficulties
2.
Fluorinated
Telomer
Alcohols
in
the
Lake
Ontario
Ecosystem
(
Stock)
In
June
2002,
Naomi
Stock
(
PhD
student)
participated
in
a
5­
day
research
cruise,
aboard
the
CGCS
Limnos,
of
Lake
Ontario.
At
each
of
three
stations,
water,
sediment,
zooplankton
and
phytoplankton
samples
were
collected.
Air
samples,
using
high
volume
air
samplers
and
polyurethane
foam/
XAD­
2
sampling
media
(
as
previously
described),
were
also
collected
for
the
duration
of
the
cruise.
Currently,
methods
are
being
developed
to
analyze
these
samples
for
a
suite
of
fluorinated
compounds
including
the
fluorinated
telomer
alcohols
and
possible
degradation
products.
Briefly,
air
samples
will
be
extracted
and
analyzed
via
gas
chromatography
coupled
with
mass
spectrometry
as
previously
described.
Water
samples
will
be
concentrated
onto
XAD­
7,
extracted
using
a
method
similar
to
that
employed
for
air
samples
and
analyzed
via
liquid
chromatography
coupled
with
tandem
mass
spectrometry.
Sediment
and
biota
samples
will
be
extracted
using
an
ion­
pairing
agent
and
also
analyzed
via
liquid
chromatography
coupled
with
tandem
mass
spectrometry.

3.
FTOHs
in
the
Arctic?
(
Martin,
Stock)
Using
additional
funding
provided
by
the
Northern
Contaminants
Progam
(
NCP),
Drs.
Martin
and
Mabury
traveled
to
Kuujjuarapik
(
Quebec)
between
the
dates
of
July
11th
and
17th,
2002,
for
collection
of
multiple
environmental
samples.
Kuujjuarapik
is
located
at
the
mouth
of
the
Great
Whale
river
on
the
eastern
shore
of
Hudson
Bay,
just
north
of
James
Bay.
This
location
is
subarctic,
and
was
chosen
primarily
because
it
is
an
intermediate
distance
between
the
high
population
density
of
the
Great
Lakes
region
and
the
Canadian
Arctic.
The
University
of
Laval
also
has
a
research
center
at
this
location
(
Centre
D'Etudes
Nordiques)
which
provided
us
with
boats
and
other
necessary
sampling
equipment.

To
test
the
hypothesis
that
telomer
alcohols
(
and
3M
sulfonamidoethanols)
can
be
transported
to
remote
regions,
an
air
sampler
was
installed
in
Kuujjuarapik
to
collect
air
samples
by
the
same
method
as
Martin
et
al..
To
date
we
have
collected
only
two
samples,
along
with
a
field
blank,
but
the
sampler
is
still
installed
and
we
hope
to
take
continuous
samples
if
any
telomer
alcohols
are
detected
in
the
existing
samples
that
have
yet
to
be
extracted
and
analyzed.
It
is
expected
that
air
sample
data
will
complement
the
smog
chamber
work,
allowing
for
a
better
understanding
of
the
long­
range
transport
potential
for
telomer
alcohols.

Water
and
biota
samples
were
also
collected
for
the
purposes
of
our
NCP
project
(
Table
2)
(
i.
e.
analysis
of
perfluorinated
acids)
but
will
also
be
analyzed
for
fluorinated
neutrals
(
including
telomer
alcohols)
when
appropriate
methods
have
been
developed
for
extraction
and
analysis
of
tissues.
Water
samples
(
40
L)
were
collected
in
Hudson
Bay
and
in
the
Great
Whale
River
by
pumping
water
through
XAD
columns
in
the
field.
Sampled
biota
included
phytoplankton,
zooplankton,
and
fish.
Even
if
air
samples
reveal
no
traces
of
fluorinated
neutrals
(
i.
e.
due
to
detection
limits),
biota
may
reveal
traces
because
of
the
predictably
high
bioaccumulation
potential
for
the
longer
chained
telomer
alcohols.

Table
2.
Biotic
and
abiotic
samples
collected
in
Kuujjuarapik,
Quebec.

Sample
Details
Status
Kuujjuarapik
Air
2
samples,
1
blank
Cold
Storage
Hudson
Bay
Water
3
samples
(
40
L
each)
Cold
storage
Great
Whale
River
Water
1
sample
(
40
L),
1
blank
Cold
storage
Fish
Livers
Pike
(
1),
Whitefish
(
2),
Suckers
(
3),
sculpin
(
2),
Trout
(
1).
Frozen
Hudson
Bay
Phytoplankton
500
grams
frozen
Fresh
Water
Zooplankton
3
locations­
Mixed
Copepods,
chironomids,
cladocera,
diptera,
rotifera,
calanoida.
frozen
Physical
Properties
4.
Vapour
Pressure
by
the
GC
method
(
Le).
The
GC
retention
time
method
by
Bidleman
(
1981)
was
chosen,
because
it
allows
the
relatively
rapid
determination
of
the
temperature
dependent
vapor
pressure
of
a
large
number
of
compounds.
Small
quantities
of
the
substances
are
sufficient,
and
a
very
high
purity
is
not
required.
Based
on
a
comprehensive
review
Delle
Site
(
1997)
concluded
that
this
method
"
can
be
recommended
as
one
of
the
most
suitable
[
methods]
for
the
determination
of
the
vapor
pressure
of
low
volatility
compounds."
Another
recent
study
concluded
that
capillary
GC
is
capable
of
providing
vapor
pressure
data
for
non­
polar
and
slightly
polar
compounds
with
relative
errors
that
"
are
either
comparable
with
or
lower
than
those
resulting
from
more
cumbersome
direct
experimental
techniques"
(
Svoboda
and
Koutek,
2002).
The
method's
success
and
reliability
however
is
dependent
on
the
availability
of
high
quality
vapor
pressure
data
for
some
related
compounds
to
serve
as
standard
reference
and
calibration
compounds.

Isothermal
gas
chromatographic
retention
times
at
six
temperatures
within
the
range
30
to
80
°
C
were
determined.
Super­
cooled
liquid
vapor
pressures
PL
were
obtained
from
these
retention
times
following
the
procedure
described
by
Bidleman
(
1981)
and
Hinckley
et
al.
(
1990).
Specifically,
for
each
analyte
a
vapor
pressure
PGC
at
25
°
C
was
calculated
using:

ln
(
PGC/
Pa)
=
( 
VAPH
/
 
VAPHref)
·
ln
(
PLref/
Pa)
+
C
(
1)

where
PLref
and
 
VAPHref
refer
to
the
well­
established
liquid
phase
vapor
pressure
at
25
°
C
and
the
enthalpy
of
vaporization
of
a
standard
reference
compound.
The
enthalpies
of
vaporization
are
assumed
to
be
constant
over
the
temperature
range
from
25
°
C
to
the
temperatures
of
the
GC
retention
time
measurements.
The
enthalpy
ratio
ratio
 
VAPH
/
 
VAPHre
and
the
constant
C
in
eq
(
1)
were
obtained
by
linearly
regressing
the
logarithm
of
the
ratios
of
the
measured
isothermal
GC
retention
times
tR/
tRref
at
each
temperature
against
the
logarithm
of
the
vapor
pressure
of
the
reference
compound
at
that
temperature
using
the
relation
(
Bidleman,
1981),

ln
(
tR/
tRref)
=
[
1­( 
VAPH
/
 
VAPHref)]
ln
(
PLref/
Pa)
­
C
(
2)

Eq
2
assumes
that
the
infinite
dilution
activity
coefficients
in
the
stationary
phase
are
the
same
for
both
the
analyte
and
the
reference
compound
(
Hinckley
et
al.,
1991).
As
this
is
an
approximation,
PGC
is
not
always
identical
to
the
vapor
pressure
of
the
(
super­
cooled)
liquid
PL,
and
a
calibration
of
the
method
with
closely
related
compounds
is
advisable
(
Bidleman,
1981,
Hinckley
et
al.,
1990).
In
the
current
study,
hexachlorobenzene
served
as
the
standard
reference
compound.
For
the
calibration
we
employed
the
following
compounds
with
well
established
vapor
pressure
at
25
°
C:
1,2­
dichlorobenzene,
1,3­
dichlorobenzene,
1,4­
dichlorobenzene,
1,2,3
trichlorobenzene,
1,2,4­
trichlorobenzene,
1,3,5­
trichlorobenzene,
1,2,3,4
tetrachlorobenzene,
1,2,3,5­
tetrachlorobenzene,
1,2,4,5­
tetrachlorobenzene,
pentachlorobenzene,
Pentafluorotoluene,
Pentafluorophenol,
TCTFB,
Octafluorophthalene,
decafluorobiphenyl,
 ­
HCH,
 ­
HCH,
 ­
HCH,
Aldrin,
Heptachlor,
Dieldrin,
p,
p'­
DDE,
o,
p'­
DDT,
p,
p'­
DDT.

Table
3.
Vapour
pressure
values
for
FTOHs
obtained
using
the
GC
retention
time
method.

Log
PGC
PGC
log
PL
PL
PL
PL
250C
mean
mean
mean
mean
stdev
RSD
4:
2
FTOH
2.401
252
3.18
1514.4
321.4
21%

6:
2
FTOH
2.161
145.2
2.90
801.7
149.0
19%

8:
2
FTOH
1.662
45.90
2.33
212
34
16%

10:
2
FTOH
1.123
13.27
1.70
50
7
13%

5)
Measurement
of
Vapor
Pressure
by
Boiling
Point
Method
(
Deeleebeck,
Ellis)

The
vapor
pressure
(
Vp)
of
the
liquids
4:
2,
6:
2,
8:
2
and
10:
2
telomer
alcohols
were
measured
using
the
boiling
point
method.
This
method
involved
a
25
mL
round
bottom
flask
connected
to
a
miniature
thermometry
adapter
and
condenser;
15
mL
of
the
analyte
was
added
to
the
round
bottom
flask.
In
the
case
of
fluorinated
materials,
they
were
first
de­
gased
by
a
procedure
which
involved
cooling
the
mother
liquor
to
­
198
°
C
Table
4.
Test
Chemicals,
Vp
(
Pa)

(
liquid
N2)
followed
by
warming
to
room
temperature
while
a
vacuum
was
maintained
at
~
15
mmHg.
Following
this
the
pressure
of
the
system
was
reduced
appropriately
and
allowed
to
equilibrate.
The
analyte
was
then
brought
to
its
boiling
point
and
the
temperature
and
pressure
recorded.
This
procedure
was
repeated
for
decreasing
values
of
pressure,
which
were
achieved
by
removing
the
air
from
the
apparatus
with
a
vacuum
pump.
To
determine
the
vapor
pressure
at
25
degrees
centigrade,
the
natural
log
(
ln)
of
pressure
in
Pascal's
was
plotted
against
the
temperature
in
Kelvin.
The
best
linear
fit
to
Compound
Experimental
Literature
difference
Cyclohexane
15720
+/­
3
13370
18%
Toluene
6400
+/­
200
4910
30%
m­
Xylene
2900
+/­
100
2250
29%
the
data
points
was
used
to
extrapolate
the
boiling
point
of
the
chemical
at
298
K,
the
vapor
pressure
at
room
temperature.
The
method
was
first
calibrated
using
cyclohexane,
m­
xylene,
and
toluene
and
the
vapor
pressures
measured
were
compared
with
typical
literature
values
(
n
=
3,
Table
4).
The
same
method
was
then
applied
to
the
telomer
alcohols,
the
results
are
presented
in
Table
5
(
n=
3).
The
telomer
Vp's
were
compared
with
literature
values
for
the
corresponding
hydrogenated
versions,
i.
e.
fluorine
replaced
with
hydrogen.
The
increase
in
Vp
associated
with
the
incorporation
of
fluorine
is
seen
clearly
in
Figure
1.
The
rate
of
decrease
in
Vp
for
the
telomers
as
a
function
of
increase
in
mass
is
much
slower
than
would
normally
be
expected
when
compared
with
their
hydrocarbon
counterparts,
resulting
in
the
vapor
pressure
of
the
8:
2
being
similar
to
that
of
octanol
(
Figure
2).

Table
5.
Telomers,
Vp
(
Pa)

6.
Measurement
of
chain
rigidity
of
perfluorinated
fluorinated
compounds
by
NMR
(
Pratt,
Ellis,
&
Burrow)

The
physical
properties,
such
as
vapor
pressure
or
Kow,
of
fluorinated
molecules
will
be
determined,
to
some
degree,
by
the
internal
molecular
geometry
of
the
molecule.
7
7.5
8
8.5
9
9.5
10
10.5
11
11.5
12
300
400
500
Temperature
(
K)
Ln
pressure
(
Pa)

fluorinated
non­
fluorinated
CX3(
CX2)
NCH2CH2OH
X=
F
X=
H
N=
9
N=
3
Figure
1.
Change
in
vapor
as
a
function
of
temperature
0
2
4
6
8
10
12
­
50
150
350
550
Mass
(
grams/
mol)
Ln
pressure
(
Pa)

Alcohols
Telomers
Figure
2.
Change
in
Vapor
Pressure
a
function
of
mass.
Compound
Run
1
Run
2
Run
3
Average
Std.
Dev.
4:
2
998
1022
956
990
30
6:
2
784
663
692
710
60
8:
2
247.7
247.7
272.1
250
20
10:
2
138.00
138.2
156.8
140
10
Interaction
of
the
fluorine
nuclei
result
in
19F
NMR
coupling
constants.
The
magnitude
of
these
coupling
constants
is
a
function
of
the
torsional
angle
between
adjacent
C
 
F
moieties.
The
amount
of
energy
required
to
allow
free
rotation
between
two
adjacent
C
 
F
units
is
proportional
to
the
"
stiffness"
of
the
alkyl
chain,
which
in
turn
is
related
to
the
Vp
of
the
molecule.
1D
19NMR
is
inadequate
in
the
determination
of
long
range
coupling
constant
in
perfluoroalkyl
chains
due
to
spectral
overlap.
We
have
developed
a
2D
Jresolved
experiment
that
facilitates
these
measurements
for
which
an
example
is
shown
for
perfluorobutanoic
acid
in
Figures
3a
&
b.

Figure
3.
A)
1D
19F
NMR
for
perfluorobutanoic
acid
with
spectral
overlap
and
B)
2D
J­
resolved
NMR
now
showing
coupling
constants
for
all
fluorine
atoms.

This
method
allowed
for
the
assignment
of
all
fluorine
coupling
constants
and
furthermore
indicted
that
at
room
temperature
perfluorobutanoic
and
longer
chain
acids
have
a
rigid
back
bone
structure
between
the
CF2
units,
with
free
rotation
allowed
around
the
CF3
 
CF2
bond.
This
molecular
rigidity
facilitates
interpretation
of
the
underlying
origins
of
the
high
Vp
of
polyfluorinated
materials
seen
our
vapour
pressure
measurements.
The
enthalpy
of
free
rotation
of
the
carbon
backbone
of
the
acid
was
established
using
variable
temperature
NMR.
A
comparison
between
the
effect
of
chain
length
and
the
amount
of
energy
required
for
free
rotation
was
made.
Figure
4
shows
a
temperature
dependent
plot
of
the
1D
NMR
for
the
CF3
group
and
two
identical
CF2
groups
for
the
perfluoro
­
octanoic
and
­
butanoic
acids.
The
coalescence
point
for
butanoic
acid
is
seen
at
60
º
C
while
it
is
90
º
C
for
the
octanoic
acid.
This
indicates
that
a
perfluorochain
becomes
energetically
more
rigid
as
a
function
of
chain
length
and
is
thus
less
easily
distorted.
The
results
assist
in
explaining
the
minimal
change
in
vapor
pressure
as
chain
length
increases.
Hz
­
10
­
5
0
5
10
15
Hz
­
15
­
5
0
5
10
20
Hz
­
4
­
2
0
1
2
3
4
5
ppm
­
118.64
­
118.60
ppm
­
80.33
­
80.30
ppm
­
126.842
­
126.834
CF3
CF3
A)
CF2
CF2
CF2
CF2
B)
Figure
4.
Temperature
dependent
19F
NMR
for
perfluorobutanoic
and
octanoic
acids
7.
Global
Warming
Potentials
of
Fluorinated
Telomer
Alcohols
(
Stock
&
Melo)
In
collaboration
with
Prof.
Kim
Strong
(
Department
of
Physics,
University
of
Toronto),
Dr.
Stella
Melo
(
Postdoctoral
Fellow)
and
David
Barclay
(
undergraduate
student),
our
research
group
is
in
the
process
of
measuring
the
absorption
cross
sections
of
the
4:
2,
6:
2,
8:
2
and
10:
2
FTOHs.
These
cross
section
measurements
are
obtained
in
the
infrared
atmospheric
window
at
a
range
of
temperatures
and
pressures.
Once
the
absorption
cross
section
measurements
are
complete
we
can
calculate
the
radiative
forcing
for
this
polyfluorinated
mateirals,
and
ultimately
calculate
a
global
warming
potential
of
each
fluorinated
telomer
alcohol
once
we
have
the
accurate
lifetime
data
from
our
smog
chamber
studies
(
see
below).
It
is
not
expected
that
the
FTOHs
will
have
high
GWP
but
they
may
have
extremely
high
radiative
forcing
values
due
to
the
large
number
of
C­
F
bonds
(
e.
g.
21
in
10:
2
FTOH).
ppm
­
126.6
­
126.5
­
126.4
­
126.3
­
126.2
­
126.1
ppm
­
118.5
­
118.4
­
118.3
­
118.2
­
118.1
­
118.0
ppm
­
80.25
­
80.20
­
80.15
­
80.10
­
80.05
Temperature
(
º
C)

100
90
80
70
60
50
40
30
ppm
­
125.7
­
125.5
­
125.3
­
125.1
ppm
­
117.5
­
117.4
­
117.3
­
117.2
­
117.1
­
117.0
ppm
­
80.25
­
80.20
­
80.15
­
80.10
­
80.05
Temperature
(
º
C)

100
90
80
70
60
50
40
30
Perfluorooctanoic
Acid
CF
Perfluorobutanoic
Acid
3
CF2
CF2
Analytical
Methodologies
8)
Synthesis
of
isotopically
labeled
internal
standards
(
Ellis
&
Sullivan)

The
synthesis
of
an
isotopically
labeled
6:
2
aldehyde
(
M
+
2
molecular
ion)
has
been
conducted
and
will
be
converted
to
the
6:
2
alcohol
(
M
+
3)
according
the
scheme
outlined
in
Figure
5
for
use
as
internal
standards
in
the
analysis
of
these
and
related
chemicals.

Figure
5.
Synthesis
of
labeled
6:
2
aldehyde
and
alcohols.

9)
Mass
Spectroscopic
Studies
of
Telomer
Alcohols
and
Products
(
Ellis)

A
systematic
mass
spectrometry
study
of
the
telomer
alcohols
along
with
their
oxidized
products,
saturated
and
 ,
  
unsaturated
fluoroacids,
was
conducted
using
negative
and
positive
chemical
ionization
(
NCI
and
PCI).
The
compounds
investigated
are
shown
in
Table
6.

Table
6.
Chemical
I.
D.
and
acronymns
for
the
telomer
based
chemicals
used
in
the
MS
study.
Telomer
Alcohols
Telomer
Acids
Telomer
  ­
Unsaturated
Acids
n
=
2
(
4:
2)*
n
=
2
(
4:
2A)
n
=
2
(
4:
2UA)
n
=
4
(
6:
2)
n
=
4
(
6:
2A)
n
=
4
(
6:
2UA)
n
=
6
(
8:
2)
n
=
6
(
8:
2A)
n
=
6
(
8:
2UA)
n
=
8
(
10:
2)
n
=
8
(
10:
2A)
n
=
8
(
10:
2UA)
*
Acronyms
are
given
for
each
in
parenthesis.
CF3(
CF2)
5I
+
13CH2
13CHOC(
O)
CH3
AIBN
CF3(
CF2)
5
13CH2
13CHIOC(
O)
CH3
CF3(
CF2)
5
13CH2
13CHO
(
6:
2
Aldehyde)
H3O+

NaBD4
CF3(
CF2)
5
13CH2
13CDHOH
(
6:
2
Alcohol)

CF3(
CF2)
nCF2CH2CH2OH
CF3(
CF2)
nCF2CH2C(
O)
OH
CF3(
CF2)
nCFCHC(
O)
OH
In
the
case
of
the
fluoroalcohols,
NCI
resulted
in
the
production
of
more
elaborate
spectra
than
the
other
classes.
Moreover,
it
showed
the
interesting
production
of
HF2
­
and
the
complexation
of
this
species
with
the
parent
molecule
(
Figure
6).

Figure
6.
NCI
mass
spectrum
for
the
6:
2
alcohol
showing
the
production
of
HF2
­

Alteration
of
the
functional
group
attached
to
fluoroalkyl
moiety
had
a
large
impact
upon
the
fragmentation
channels,
which
were
identified
(
see,
for
example,
Figures
12a
and
b)
and
also
on
the
magnitude
of
fragment
produced.

Figure
7.
a)
Hypothesized
fragmentation
pattern
for
the
6:
2
telomer
alcohol
in
NCI
mode
and,
b)
fragmentation
pattern
for
the
6:
2
telomer
acid.
a)
b)

CHCO
O
m/
z
357
­
FCO2
CH
m/
z
294
­
HF
m/
z
274
C
E
Isomer
Z
Isomer
CCO
O
m/
z
318
­
F
CHCO
O
­
HF
m/
z
338
­
CO2
CF3(
CF2)
2CF2CF2CF
CF3(
CF2)
2CFCF2CF
CF3(
CF2)
2CFCF2C
CF3(
CF2)
2CFCF2C
CF3(
CF2)
2CFCF2CF
O
m/
z
377
CF3(
CF2)
2CF2CF2CH2CO
­
HF
O
m/
z
378
CF3(
CF2)
2CF2CF2CH2COH
­
H
m/
z
364
CF3(
CF2)
4CF2CH2CH2OH
.
F
CF3(
CF2)
4CF2CH2CH2OH
.
HF2
m/
z
383
m/
z
403
+
F
­
H
CF3(
CF2)
4CF2CH2CH2O
+
HF2
CF3(
CF2)
4CF2CH2CH2OH
m/
z
363
m/
z
323
­
F
C8F11H2O
C8F10H2O
m/
z
304
­
HF
C8F9HO
m/
z
284
­
HF
Pressure
Dependant
Channel
­
CO
C7F9H
m/
z
256
C8F8O
m/
z
264
­
CO
C7F8
m/
z
236
m/
z
294
­
HF
C7F10H4O
C7F9H3O
m/
z
274
­
CO
C6F9H3
m/
z
246
­
CF3
­
2HF
Although
the
exact
structure
of
these
intermediates
requires
further
investigation,
other
researchers,
in
the
case
of
hydrofluorocarbons,
have
invoked
a
six
membered
back
bonding
transition
state
between
the
hydrocarbon
portion
of
the
chain
and
the
fluorocarbon
portion
to
support
the
sequential
loss
of
HF
in
similar
systems
(
Napoli
et.
al.).
Previous
x­
ray
crystallographic
studies
suggest
that
the
perfluoro­
portion
of
the
molecular
chain
adopts
a
ridged
zigzag
geometry
with
the
end
hydrocarbon
segment
of
the
chain
folding
back
on
top
of
that
fluorinated
portion
(
Wang
and
Ober,
Erkoc
and
Erkoc).
It
has
also
been
shown
that
there
is
evidence
for
the
cleavage
of
the
CF2
 
CH2
bond
within
the
molecule
suggesting
there
is
unusually
high
stability
of
this
bond
which
could
be
explained
by
a
H­­­­
F
bridging
interaction.

Such
intramolecular
interaction
in
the
case
of
telomer
alcohols
in
the
liquid
phase
is
supported
by
the
studies
conducted
by
Von
Werner
and
Wrackmeyer.
They
showed
that
fluorination
in
the
 
position
to
a
CH2OH
group
had
a
marked
effect
on
the
13C
NMR
chemical
shift
while
having
little
effect
upon
the
 
CH2,
an
effect
which
has
been
assigned
to
the
hyperconjugative
interaction
of
the
lone
pair
of
electrons
of
the
fluorine
at
that
carbon.
In
later
studies
Von
Werner
and
Wrackmeyer
also
employed
17O
NMR
and
showed
that
electron
density
at
the
oxygen
is
increased
as
observed
through
the
oxygen
shielding
effect.
This
strongly
suggests
that
the
terminal
ethanolic
group
is
closely
associated
with
the
fluorocarbon
potion
of
the
molecule.
We
believe
it
is
this
association,
and
with
it
changes
in
electron
density
distributions,
that
lead
to
the
favoured
complexations
of
F­
and
HF2
­.
Futhermore,
this
association
would
not
occur
in
the
case
of
CF3CH2CH2OH
and
thus
this
molecule
would
exhibit
differences
in
it
physical
and
reactive
properties
relative
to
the
Telomer
alcohols.

Detailed
analysis
and
comparisons
of
the
mass
spectral
data
obtained
collectively
from
all
analytes
allowed
certain
conclusions
to
be
drawn
concerning
their
thermodynamic
physical
properties
and
from
this
hypotheses
can
be
made
toward
environmental
fate.
For
example,
the
unique
geometries
associated
with
the
compounds
and
the
resultant
effect
this
imparts
upon
the
physical
properties
may
lead
to
novel
and
interesting
chemistries
in
the
atmospheric
gas
phase.
For
example,
these
results
suggest
that
the
telomer
alcohols
may
have
a
close
association,
an
association
that
one
would
not
expect
for
alcohols,
with
tropospheric
charged
species
and/
or
polar
species
as
evidenced
from
their
universal
association
with
F­
and
HF2
­.
Complexation
with
gas
phase
species
such
as
sulphate,
or
even
with
non­
charged
polar
molecules
such
as
water
vapor,
may
effect
their
dissemination.
Atmospheric
lifetimes,
for
example
reaction
rates
with
tropospheric
cleansing
reagents
such
as
hydroxy
radicals
may
also
be
effected
by
such
complexations,
allowing
longer­
range
transport.

It
would
appear
from
the
fragmentation
that
occurs
that
the
lowest
energy
pathway
for
the
degradation
of
the
alcohols,
either
biotically
or
abiotically,
would
result
in
the
production
of
stable
polyflourometabolites,
which
in
turn
might
be
expected
to
be
environmentally
persistent.
From
these
results,
it
can
be
postulated
that
the
electron
density
distribution
associated
with
such
unique
structural
geometries
will
impact
physical
properties
such
as
vapor
pressures,
(
e.
g.
vapor
pressures
will
be
greater
than
expected
from
linear
predictions
based
upon
the
molecules
size
and
functional
groups)
which
is
indeed
experimentally
observed
to
be
the
case.
The
unique
differences
in
geometry
of
these
molecules
is
also
expected
to
influence
physical
properties
of
the
molecules
such
as
Kow
and
hence
bioaccumulation.
This
postulation
is
supported
by
the
recent
observation
that
bioaccumulation
potential
increases
ten
fold
for
every
additional
CF2
unit
within
the
alkyl
chain
for
perfluoroacids
(
Martin
et
al).

Fate
Pathways
10)
Atmospheric
Degradation
Processes
(
Ellis
&
Martin)

The
telomer
alcohols
are
proposed
to
degrade
in
the
atmosphere
following
a
mechanism
outlined
in
Figure
8.

Figure
8.
Proposed
atmospheric
degradation
of
Telomer
alcohols,
6:
2
alcohol
is
used
as
an
illustrative
example.
F
F
F
F
F
F
F
F
F
F
CH2CH2OH
F
F
F
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
C
O
OH
F
F
F
F
F
F
F
F
F
F
CH2CHOH
F
F
F
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
C
O
H
F
F
F
F
F
F
F
F
C
F
F
F
C
O
H
H
F
C°

F
F
F
F
F
F
F
F
C
F
F
F
C
O
H
H
F
OH
C
F
F
F
F
F
F
F
F
C
F
F
F
C
O
H
H
F
OH
O
O°
C
F
F
F
F
F
F
F
F
C
F
F
F
C
O
H
H
F
OH
O°
C
F
F
F
F
F
F
F
F
°
C
F
F
F
C
O
H
H
OH
O
F
C
F
F
F
F
F
F
F
F
F
F
F
O
OH
F
F
F
F
F
F
F
F
F
F
CH2°

F
F
F
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
C°
O
F
F
F
F
F
F
F
F
F
F
CH2OO°

F
F
F
F
F
F
F
F
F
F
F
F
F
CH2O°

F
F
F
F
F
F
F
F
F
F
F
F
F
C
F
F
F
O
H
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
COO°
O
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
CO°
O
C
°
F
F
F
F
F
F
F
F
F
F
OH
O2
NO
NOT
OBSERVED
6:
2
FTOH
Tropospheric
Reactions;
Possibilities
OH
h 
F
F
F
UnZips
6::
2
Ald
PFHxA
OH
O2
H2O/
particles
loss
of
HF
OH
O2
NO
H2O
h 
OH
O2
NO
O2
O2
NO
Note:
?
whether
this
is
an
artifact
pathway.
°

Cavalli
et
al,
2002,
ES&
T
36:
1263­
1270
Mashimi
et
al,
2000.
J.
Phys.
Chem
A,
104:
7255­
7260;
Vesine
et
al,
2000.
J.
Phys.
Chem
A,
104:
8512­
8520.
Vesine
et
al,
2000.
J.
Phys.
Chem
A,
104:
8512­
8520.
This
hypothesis
was
tested
using
a
10m3
artificial
atmospheric
smog
chamber.
The
6:
2
alcohol
was
introduced
to
the
system
along
with
cyclohexane
(
a
reference
compound),
NO
gas,
and
isopropylnitrite
(
an
indirect
source
of
OH).
The
system
was
irradiated
using
black
lights
and
sample
aliquots
were
taken
and
analyzed
as
a
function
of
time.
Real
time
NOx
and
O3
concentrations
were
monitored
in
order
to
eliminate
possible
secondary
loss
reactions.
Samples
were
collected
in
real
time
by
SPME
and
analyzed
using
GC/
MS.
Samples
were
also
taken
using
XAD
and
Na2CO3
denuders,
low
temperature
gas
phase
condensation
bubblers,
and
by
passing
gas
samples
through
DNPH
SPE
cartridges
for
further
analysis.
Continuous
air
flow
from
the
chamber
was
passed
through
nylon
and
XAD
coated
filters
which
were
collected
and
analyzed
for
particulate
formation.
Post
chamber
analyses
were
conducted
using
19F
NMR,
LC/
MS/
MS
and
GC/
MS.
The
telomer
alcohol
does
not
undergo
photolysis
at
the
wavelengths
of
light
used
and
it
does
not
undergo
significant
wall
reactions,
or
with
NOx
and
O3
under
the
conditions
used.
The
gas
phase
condensate
obtained
from
the
smog
chamber
at
low
temperature
(­
78
°
C)
by
bubbling
the
air
through
acetone
was
analyzed
directly
using
19F
NMR.
The
resultant
spectra,
acquired
over
a
24­
hour
period
clearly
indicated
the
presence
of
the
6:
2
alcohol
and
a
second
fluorinated
species
that
we
have
tentatively
assigned
as
fluoride.
No
other
fluorinated
intermediates
were
observed,
possibly
due
to
the
low
concentrations
of
fluorinated
intermediates
coupled
with
the
low
sensitivity
of
the
NMR
experiment.
GC/
MS
analysis
of
samples
acquired
by
passing
smog
chamber
air
through
an
XAD
bed
have
thus
far
only
indicated
the
presence
of
starting
material.
Due
to
the
volatility
of
the
proposed
intermediates
it
was
recognized
this
may
be
result
of
poor
trapping
efficiency.
Larger
volumes
of
air
have
been
passed
icwe
pre­
coated
XAD
denuders
that
have
a
greater
capacity
for
such
materials.
These
samples
are
currently
being
analyzed.

The
pseudo
first
order
kinetics
for
the
reaction
of
the
6:
2
telomer
with
OH
relative
to
cyclohexane
is
shown
in
Figure
9.

Figure
9.
Relative
rates
of
reaction
for
cyclohexane
with
6:
2
telomer
OH
Degradation
of
6:
2
Telomer
y
=
0.
4006x
+
0.0237
R2
=
0.981
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0
0.2
0.4
0.6
0.8
1
ln([
Cyclohex
ane]
t0/[
Cyclohexane]
t)
ln([
Telomer]
t0/[
Telomer]
t)
Using
a
rate
constant
of
7.49
x10­
12
molecule
cm3
s­
1
at
298K
for
the
reaction
of
OH
with
cyclohexane
resulted
in
a
calculated
rate
constant
for
the
6:
2
telomer
alcohol
of
2.8
±
0.1
molecule
cm3
s­
1
(
n=
2).
The
reported
literature
value
for
the
OH
initiated
degradation
of
butanol
is
8.24
±
0.84
x10­
12
molecule
cm3
s­
1
which
is
as
expected
greater
than
the
measured
value
for
the
6:
2
telomer
alcohol
due
to
the
effect
of
fluorination.
However,
this
rate
is
greater
than
would
be
predicted
using
the
Kwok
and
Atkinson
method
of
prediction.
We
believe
that
this
is
a
result
of
secondary,
through
space
interaction
of
the
ethanolic
substituent
with
the
fluorinated
tail
of
the
molecule,
a
hypothesis
that
is
supported
by
MS
data
obtained
(
details
of
which
are
presented
in
above)
and
from
the
literature
dealing
with
similar
compounds.
The
product
perfluorohexanoic
acid
was
positively
identified
(
n=
3)
by
LC/
MS/
MS
(
Figure
10)
and
is
currently
being
quantified
relative
to
the
starting
material
~
it
does
not
appear
to
be
the
major
route
for
degradation.
Overall
we
have
had
significant
difficulties
in
isolating
and
identifying
the
bulk
of
the
FTOH
degradation
products.
For
instance
we've
only
obtained
sporadic
evidence
for
the
initial
aldehyde
via
GC/
MS
and
we
do
observe
fluoride
in
some
samples.
These
results
may
indeed
indicate
that
the
`
unzipping'
route
is
the
dominate
fate
pathway
for
the
FTOHs
(
see
Fig
8).
A
good
deal
of
further
work
must
be
done
obtaining
a
mass
balance
of
products
and
confirming
the
degradation
pathway.

Figure
10.
LC/
MS/
MS
indicating
the
production
of
perfluorohexanoic
Acid
The
proposed
intermediate
aldehyde
and
acids
(
Section
5)
that
potentially
lead
to
the
formation
of
perfluorohexanoic
and
longer
chain
acids
(
Figure
5)
were
synthesized
by
the
methods
outlined
in
Figure
8
for
the
use
as
standards
for
the
identification
of
these
intermediates.
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
2.75
3.00
Time
0
100
%
cmII84k
Sm
(
Mn,
2x3)
MRM
of
15
Channels
ES­
313
>
269
1.07e3
0.82
PFHxA
Figure
11.
Synthesis
of
fluoro
aldehyde
and
acid
standards.

A
further
interesting
observation
is
that
1H,
1H,
2H,
2H
perfluorodecyliodide,
which
is
an
impurity
contained
within
the
manufactured
6:
2
telomer,
is
not
observed
to
degrade
under
these
conditions,
thus
indicating
greatly
reduced
reactivity
with
OH
and
ultimately
a
much
longer
tropospheric
lifetime.

11)
Biodegradation
of
FTOHs
(
Ye
&
Dinglasan)

Range
finding
experiments
have
been
initiated
on
the
suite
of
FTOHs
with
initial
experiments
focused
on
the
fate
of
the
6:
2
FTOH
in
a
mixed
culture
of
microbes.
Mixed
enrichment
aerobic
degrading
cultures
were
obtained
from
a
1,
2
DCA
site
in
LA,
U.
S.
and
subsequently
maintained
on
either
1,2
DCA
or
ethanol.
Two
isolates
have
been
identified
to
date
from
this
mixed
culture
~
a
Ralstonia
sp.
and
a
Xanthobacter
sp..
These
experiments
have
clearly
shown
that
the
6:
2
fluorotelomer
alcohol
is
efficiently
oxidized
to
the
6:
2
telomer
acid
(
see
Fig
12)
which
then
either
hydrolyzes
or
further
metabolizes
to
the
6:
2
 ,
 
acid.
Low
but
clearly
measurable
quantities
of
the
perfluoroacid
PFHxA
are
observed
to
build
up
in
the
reaction
vessels.
Work
currently
is
focused
on
optimizing
analytical
methods
to
monitor
all
compounds
of
interest
during
the
biodegradation
experiment
with
particular
focus
on
observing
the
relevant
intermediates
(
e.
g.
the
6:
2
aldehyde
which
has
been
synthesized).
To
accurately
determine
the
reaction
pathway
subsequent
experiments
will
dose
the
microbial
media
with
the
6:
2
aldehyde,
acid,
alpha­
beta
acid,
and
PFHxA
in
order
to
obtain
rates
and
pathway
information
on
each.
We
will
then
compare
the
relative
suscepbilities
of
the
4:
2
through
10:
2
FTOHs
and
confirm
whether
the
degradation
pathway
is
similar
across
the
varied
chain
length.
CF3(
CF2)
nCH2COH
O
CF3(
CF2)
nCH2CH2OH
(
n
=
3,
5,
7,
9)
CrO3/
H2SO4
CF3(
CF2)
nCH2COH
O
NaOH
(
aq)
THF
(
n
=
3,
5,
7,
9)
CF3(
CF2)
n­
1CF
CHCOH
O
CF3(
CF2)
5CH2CH
O
CF3(
CF2)
5CH2CH2OH
CF3(
CF2)
4CF
CHCH
O
PCC
Dess
Martin
CH2CCl2
CH2CCl2
CF3(
CF2)
5CH2CH2OH
Figure
12.
Proposed
biodegradation
pathway
of
6:
2
FTOH
with
intermediates
so
far
confirmed
by
LC/
MS/
MS.
We
are
unclear
specifically
where
PFHxA
arises
but
it
appears
to
follow
the
build
up
slowly
after
high
concentrations
of
the
6:
2
 ,
 
acid
are
formed.

References
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T.
F.
Estimation
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F
F
F
F
F
F
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CH2CH2OH
F
F
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F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
C
O
H
F
F
F
F
F
F
F
F
F
F
CH2
F
F
F
C
O
OH
C
F
F
F
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F
F
F
F
C
F
F
F
C
O
OH
H
F
C
F
F
F
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F
F
F
F
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F
6:
2
 ,
 
6:
2
FTOH
6:
2
Aldehyde
6:
2
Acid
O
OH
?
others?
observed
observed
observed
Martin,
J.
W.;
Muir,
D.
C.
G.;
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K.
R.;
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Tissue
Distribution
of
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Acids
in
Rainbow
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(
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Chem.
Accepted.

Martin,
J.,
S.
A.
Mabury,
K.
S.
Solomon,
D.
C.
G.
Muir.
2002
Dietary
Accumulation
of
Perfluorinated
Acids
in
Rainbow
Trout
(
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mykiss.
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M,
Krotz
L,
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V.
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vaporization
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18.

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Presentations
S.
A.
Mabury,
"
Environmental
and
Analytical
Chemistry
of
Fluorinated
Surfactants".
DIOXIN
2002,
Barcelona,
Espana,
August,
2002.
Invited
Speaker,
Organizer
of
the
session
on
"
New
POPs".
Published
Short
Paper
in
"
Xenobiotics".

S.
A.
Mabury,
"
Fluorinated
Chemicals
in
the
Environment
~
Redefining
Persistence?"
GLRM.
American
Chemical
Society,
Minneapolis,
MN,
June,
2002.
Invited
platform.

Martin,
J.
W.,
Muir,
D.
C.
G.,
Stock,
N.,
Moody,
C.
A.,
Ellis,
D.
A.,
Kwan,
W.
C.,
Mabury,
S.
A.
"
Detection
of
Fluorinated
Organic
Contaminants
in
Atmospheric
Samples
by
GC/
CI/
MS".
International
Association
of
Great
Lakes
Research
45th
Annual
Conference,
Winnipeg,
May,
2002.
Platform
Presentation.

S.
A.
Mabury,
"
Redefining
Persistence
~
Fluorinated
Chemicals
in
the
Environment".
Environalysis
2002.
Toronto,
ON.
May,
2002.
Invited
Keynote.

S.
A.
Mabury,
"
Flights
of
Fancy
~
Fluorinated
Chemicals
in
the
Environment".
University
of
California­
Davis.
May,
2002.
Invited
Seminar.

S.
A.
Mabury,
"
Perfluorinated
Surfactants
in
Environmental
Samples
~
Analysis
by
LC/
MS/
MS."
223rd
American
Chemical
Society,
Environmental
Chemistry
Division.
April,
2002.
Invited
Platform.

S.
A.
Mabury,
"
19F
NMR
in
Analytical
Chemistry",
Asia­
Pacific
Conference
on
Analytical
Science,
19­
22
Feb,
2002,
Shangri­
La
Hotel,
Manila,
Philippines.
Invited
Keynote
Speaker.
S.
A.
Mabury,
"
Analytical
and
Environmental
Chemistry
of
Fluorinated
Pollutants",
Department
of
Chemistry,
University
of
the
Philippines­
Los
Banos,
Feb,
2002.
Invited
Seminar.

S.
A.
Mabury,
"
Carbonate
Radical
and
the
PhotoFate
Test
System.
Institute
of
Chemistry,
University
of
the
Philippines­
Diliman,
Feb,
2002.
Invited
Seminar.

S.
A.
Mabury,
"
A
New
Class
of
Pollutant
~
Fluorinated
Compounds",
Natural
Science
Research
Institute,
University
of
the
Philippines­
Diliman,
Feb,
2002.
Invited
Seminar.

S.
A.
Mabury,
"
Fluorinated
Chemicals
in
the
Environment:
Analytical
and
Environmental
Chemistry"
Stanford
University,
Nov.
30,
2001.
Invited
Seminar.

S.
A.
Mabury.
"
What
Makes
a
Chemical
a
Pollutant".
Inaugural
speaker
in
the
"
University
of
Toronto
Lecture
Series
in
Markham".
October
3,
2001.
Invited
platform.
