Sulforna2ed
Perfluorochemieals
in
the
Environment:
Sources,
Dispersion,
Fate
and
Effects
Prepared
by
3M
March
1,2000
1
Table
of
Contents
.
"
.
I
.

1.0
PREFACE
4
2.0
 XECUTIVE
SUMMARY
5
3.0
INTRODUCTION
TO
FLUOROCHEMICALS
9
4.0
PWYSICALICHEMICAL
PROPERTIES
OF
FLUOROCHEMICALS
5.0
ANALYTICAL
TEST
METHODS
f
OR
FLUORUCHEMICALS
17
6.0
SOURCES
OF
FLUOROCH&
UICALS
19
6.1
Manufaetaring
Waste
Streams
6.1
1
Waste
Stream
Cbmcteriza~
oon
6.12
Air
6.13
Wastcwatcr
6.14
Solid
Waste
20
22
22
22
23
6.2
Supply
Chain
Waste
Streams
24
6.3
Releases
from
Waste
Treatment
and
DhposaI
Methods
24
7.0
ENVIRONMENTAL
TRANSPORT
AND
DISTRIBUTION
.25
8.0
ENVIRONMENTAL`
SAMPLING
FOR
FLUOROCHEMICALS
d.
1
Environmental
Leveb
8.1
1
Historical
Data
8.
f
2
Recent
Analyses
of
Wild
Birds
and
Fish
8.13.
Testing
of
Fishmeal
Used
in
Rat
Studies
8.14
Plant
Site
Analyses
8.15\
 3iosphere
Sampling
27
27
`
27
27
31
3'
1
32
8.2
Human
Expoanre
Levels
8.21
Mdti­
cities
Sampling
8.22
Carpet
Use
Studies
8.23
Paper
and
Packaging
Studies
8.24.
Exposure
ScGnarios
32
.
33.
33
33
33
2
,

9.0
ENVIRONMENTAL
.
T
~
N
S
F
O
~
A
~
~
N
I
D
E
G
~
D
A
T
I
O
N
OF
FLUOROCHEMICALS
34
36
9.1
HydroIyshr
Studies
9.2
Photo ysis
37
9.3
Atmospheric
Studia
,_
37
9.4
Biodmdatioa
Studks
9.41
Microbid
Studies
00
Pdluorochwnicals
9.42
Biological
TrrursformatiOn
9.43
Optimizing
Conditions
for
Biodegradation
38
38
39
39
10.0
ECOTOXiClN
TESTlNG
OF
FLUOROCHEMICALS
.40
11.0
COMPREHENSIVE
PLAN
TO
ASSESS
ENVIRONMENTAL
EXPOSURE
,'
45
11.1
Ptan
Overview
45
11.2
Component
1:
Characterize
Fate
and
Transport
Properties
48
48
11.3
Component
2:
Estimate
Releases
11.4
COUI~
PUCIIL
3:
Chrnslrrkcl:
Dktrlbullun
In
the
Environment
48
11.5
Component
4:
Estimate
exposun!

12.0
ECOTOXJCITY
PETERMJNATIONS
13.0
ECOLOGICAL
RISK
EVALUATION
14.0
REFERENCES
3
49'

49
50
51
1­
0
Preface
\

This
paper
provides
an
overview
of
3M's
c
m
t
knowledge
about
the
sources,
dispersion,
fate
and
effects
of
some
of
its
fluorinated
chemical
products.
It
specifically
addresses
sulfoaated
perfluoronated
chemistry
and
products,
with
the
major
focus
on
those
compounds
with
an
eight
carbon
chain
structure.
There
are
other
fluonhated
chemical
products
but
these
are
not
covered
in
this
white
paper.

The
paper
presents
the
past
testing
nf
these
chemicals
for
environmentally
relevant
properties
aud
assesses
the
quality
and
adequacy
of
past
testing.
It
also
presents
recent
results
of
environmental
sampling,
estimates
of
quantities
of
wastes
generated
at
manufacturing
plantti
and
timom
produd
UJC,
and
XICW
data
011
physical,
chcmicd
and
ecotoxicological
piroperties
of
sulfonated
perfluomhemicals.
It
describes
in
detail
the
comprehensive
exposure
assessment
plan
currently
being
hpkmentted.
This
plan
is
aimed
at
providing
a
better
understanding
of
the
transport,
hte
and
effects
of
these
chemicals
in
the
envirommnt
and
will
helR
the
company
determine
appropriate
@
me
actions.

,­
As
these
studies
return
data,
test
plans
will
be
revised
to
incorporate
new
Wormation.
For
this
reason.
the
results
of
present
testing
should
be
treated
cau~
ously­
Some
data
represent
first
attempts
at
characterization
of
complex
chemicals
in
very
difEcult
and
dynamic
environmental
test
matrices.
The
program
incorporates
new
analytical
technology,
domplex
models
and
many
variables.
Thoso
initid
finding3
aru
subjcct
to
change
as
results
fitom
cunrently
planned
testing
on
degradation,
biological
receptors,
wastes
from
manufacturing
facilities
and
other
exposure
data
are
obtained.

This
paper
shouId
be
read
in
conjmcdon
with
previous
submittals
about
the
health
and
environmental
issues
associated
with
3M's
sulfonated
perfluorochedd
product
line.
In
January
1999,3M
submitted
to
the
Environmental
Protection
Agency
(
 ?
PA)
a
report,
Perfluorooctane
Sulfonate:
Current
Summary
of
Kman
Sera,
Health
d'Toxicology:
­
Datz
that
provided
details
of
analyses
of
pool4
hlfnnd
s
m
samptes
that
demonstrated
the
presence
of
perfluomoctane
sulfonate
(
PFOS)
at
very
low
levels.
Jn
February
1999,3M
provided
a
comprehensive
review,
The
Science
of
Organic
Fluorochemistry,
describing
the
health
effccts
and
backepund
chemistry
atisociated
with
PFOS.
hotha
report
submitted
to
EPA
in
May
1999,
Fluorochemical
Use,
Didbution,
and
Release
Overview,
describes
how
3M
produces
sulfonated
perfluorochemicals,
which
product
iines
incorporate
them,
and
the
uses
for
these
products.
Finally,
various
Section
8(
e)
\

~

submissions
have
been
f
o
d
e
d
to
EPA
relative
to
these
sulfonated
perfIuorochemicals.

.......
!
y!"

!­,,

A!,

...............
____,
.
.
.
.
.
.
.
.
.
4
...
.
.
.
.
.
!
.
.
IIL
.
L
......
.
i
I
2.0
Executive
Summary
3M
produces
sulfonated
perfluorochemicals
by
an
electrochemical
fluorination
process.
This
process
creates
a
complex
and
variable
mix
of
chemicals
in
which
fluorine
atoms
replace
hydrogen
atoms
on
the
organic
feedstock
and
carbon­
carbn
bon&
are
rearranged.
Because
of
the
carborkdluorine
bond
formed
by
this
process,
the
compounds
created
are
considered
to
be
very
stable.
Perfluorochernicals
have
complete
­­
­
.
gf
fluorine
for
hydrogen
Fluomchemicals
can
repel
both
water
and
oils,
reduce
SUrface
tension
dramatically,
act
as
catalystsfor
oligomerization
and
poiymerization,
and
function
under
extreme
conditions.
Major
uses
for
sulfonated
Perfluorochemicals
me
surface
protectors
and
suri8ctanrs.

­
Fluorine's
high
elektrmegativity
confers
a
strong
polarity
to
carbon­
fluorine
bonds,
contributing
tu
the
stability
and
nonreacfive
character
of
perfluorochernick
molecdes.
They
are
unusual
as
that
perfbmalkyl
chains
are
both
oleophobic
and
hydrophobic.
The
addition
of
charged
moieties
to
the
chain
m
y
affect
the
water
solubility
of
the
shorter
Chains.

The
highest
volume
sulfonated
pduorochemical
produced
by
3M
is
perfluorooctanesulfonyf
fluoride
(
POSF).
M
e
r
synthesis,
it
is
used
to
create
several
product
lines.
During
their
me
cycles,
POSF
and
POSF­
based
products
may
degrade.
If
degradation
occurs,
current
research
suggests
peduorooctane
sulfonate,
(
FFOS)
and
a
few
other
perfluorinated
forms
are
degradation
products.
Timchcs
for
&
gradation
am
variable,
with
some
polymeric
products
apparently
stable
for
very
long
periods
of
time.

The
idenMcadon
and
quandfi
cation
of
s"
onased
pertluorochemicals
pose
dLfticult
d
f
i
c
a
l
challenges.
Reliable
methods
for
extraction,
separation
and
identification
of
sulfonated
perfluorochemicals
in
tissues
and
environtnental
matrices
have
evolved
and
have
been
developed
only
h
the
last
few
years.
New
d
f
l
c
a
l
technology
is
providing
capabilities
of
detection
in
wide
Meties
of
matrices
at
parts
per
trillion
(
ppt)
levels
and
identification
of
metabolites
and
breakdown
products.

As
fully
desdbed
throughout
this
p
3M
is
pursUing
an
aggressive
program
to
reduce
releases
to
the
env'konment
while
that
scientific
research
is
being
conducted.
It
is
not
the
purpose
of
this
paper
to
describe
the
n
a
~
r
e
and
extent
of
that
undertaking.
Readers
should
be
made
awm,
however,
that
3M
hw
initiated
a
wide
range
of
activities
to
utilize
available
opportu&
ies
for
rtductions
in
releases.
These
have
included
installation
of
new
controls
to
reduce
waste
streams
in
3M
mufhcming
hilities.
They
have
also
included
product
slewarchhip
efforts
to
comu&
ate
to
customers
and
downstream
users,
information
regarding
fluorochemicals
and
the
need
to
exert
careful
management
over
these
substances.
In
addition.
3M
has
undertaken
major
efforts
to
reinvent
its
products
tbrough
the
use
of
alternative
chemistry
to
reduce
the
volume
of
fluorochemicals
used
in
those
products.
All
of
these
efforts
will
I
4
r,
completion
of
a
comprehensive
exposure
assessment
and
related
scientific
stu
%
f"
'
es
will
q
u
i
r
e
many
years
of
intensive
research.

5
I
.
.
**+
.
.
a
.
.
.
,
..
.
.
.
.
.
I
be
continued
with
htdty
while
the
scientific
research
described
in
this
paper
is
being
carried
out.

3M
i
s
examining
the
M
e
cycle
of
its
sulfonated
perfluorrochemid
prodwts
to
idcntif$
releases
to
the
environment
&
om
manllfacturig
processes,
supply
chains,
product
use
and
disposal.
First
it
is
debmnhhg
waste
streams
generated
throughout
the
life
cycle.
This
informathn
will
be
used
to
csthatc
cllVin0nrm;
nlaI
releases.
This
approach
is
necessary
since
not
all
waste
produced
is
released
to
the
mvironment.
M
a
n
d
i
waste
studies
are
underway
at
the
3M
plant
in
Decatur,
Alabama
on
POSF­
based
processes.
PFOS­
based
waste
streams
generated
Born
these
manufacturing
processes
are
conservatively
estimated
to
be
about
1.1
million
pounds
per
year,
about
90%
as
solid
waste,
most
of
which
i,
s
incinerated
and
destroyed.
Recent
wastewater
controls
have
reduced
amounts
of
PFOS
actually
discharged
to
the
river
by
half
since
1998.

Data
from
business
units
have
identified
key
products
that
contain
the
majority
of
the
fluorochemical
solids
sold
in
the
United
States
in
1997.
Using
this
sales
ioformation,
3M
estimated
customer
and
end
user
waste
stseams.
Motit
of
the
waste
generated
from
these
sources
is
in
the
form
of
solid
w
e
.
Releases
to
the
en*
ment
from
product
disposal
to
landfills,
wastewater
treatment
plants
and
incineration
are
all
being
investigated.

Scvtral
=
xnt
fate
d
tiauspurimtxhdsms
have
been
identified
as
important
to
study.
Initially
models
are
being
used
for
screexing­
level
assessments
of
potential
&
e
mechanisms.
Multi­
media
fugacity
models
are
under
development
to
incorporate
the
unique
properties
of
fluorochemicals.

Sulfonated
perfiuorochcmicals
have
been
detected
at
low
levels
in
some
species
of
eagles
and
wild
birds.
Low
levels
were
detected
in
bird
plasma
and
bird
livers.
3M
believes
that
these
sets
of
data
are
hsuf6Cient
to
draw
conclusions
with
any
statistical
merit.
In
screening
sampling
of
the
river
and
sediments
near
the
Decalxu
manufachving
plant,
PFOS
was
present
in
a
few
samples
collected
near
the
outfall.
All
this
Mixmation
was
used
in
the
design
of
a
more
comprehensive
program
of
biosphere
sampling.
The
goal
of
the
biosphere
samplttg
plan
k
to
SC~
CCIZ
for
PPOS
across
a
range
of
species,
Mbilttls
d
geographic
IOCZA~~
OIB
and
to
identify
mas
on
which
to
focus
scientific
investigation
to
develop
a
better
understanding
of
any
patentiid
environmental
effects.

A
multi­
cities
study
will
determine
envkonmental
distribution
and
potential
sources
of
human
and
ecological
exposure.
The
rnulti­
cities
study
pairs
cities
with
significant
rnanu &
urhg
or
commercial
use
of
fluomchemical
phducts
with
cities
of
the
same
size
without
signiscant
use.
Levels
of
PFOS
and
its
precursors
will
be
measured
in
food,
air,
water,
sedirnen$
and
disposd
facilities.
Additionally,
levels
are
being
measured
arising
from
carpet
use,
product
uses
and
potential
migration
into
food
from
packaging.

The
role
of
hydrolysis,
photolyeis
and
biological
proos~
se~
in
the
degrndation
of
sulfonated
perfluorochemicals
is
being
studied.
Research
suggests
that
the
biodegradation
of
fluorinated
sulfonates
requires
the
presence
of
hydrogen
at
the
alpha
6
.
_
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.
.
..!
..
I
.
.
,
.
.
.
.
.
.
.
.
carbon
on
the
fluorinated
chain
and
that
perfJmrinaterl
malecnles
are
susceptible
to
breakdown
ody
at
non­
ftuorinatd
side
chains.
Degradation
of
&
med
perfluorochemicals
is
not
complete
but
results
in
production
of
other
fluom&~
c&.
Studies
suggest
that
compounds
made
from
POSF,
tl
oommcrcially
important
perfluorochemical
product
and
hWr~~
ediate,
are
bmsfanned
during
metabolism
to
another
sulfonated
perfluomchemical,
PFOS.
PFOS
does
not
appear
to
further
degrade
except
by
incbemtion.
7
Several
sulfonated
p~
uorochedcds
have
been
subjected
to
basic
scmning
tests
for
environmental
toxicity.
Different
species
varied
significantly
in
their
response
t0,
t.
h
same
chemical
even
when
ushg
the
same
hboratory
procedure.
New
testing
is
underway
using
purified
sulfonated
perfluorochemi&
is.
m
d
test
concentratinna,
and
a
wide
variety
of
test
organisms.
Results
of
these
studies
are
reported
in
this
white
paper.

The
research
projects
that
are
yielding
new
infomation
on
sulfonated
perfluomchemicals
are
part
of
a
comprehensive
plan
to
assess
the
potential
pathways
of
emrironmental
exposure
associated
with
the
m8xlllfacture,
use
and
&&
sal
of
sulfonated
perfluomchemical
products.
Figure
1
portrays
the
plan
components.
Work
on
the
plan
is
now
underway
using
a
combination
of
3M
resources
and
outside
expexts.
Recent
analytical
advances
and
this
extensive
research
effort
are
expected
to
contribute
significantly
to
a
better
understanding
of
environmental
fate
and
effects.

The
findings
resulting
&
om
the
comprehensive
pian,
along
with
new
ecotoxicological
test
data,
will
be
used
to
evaluate
ecological
fisk.
W
e
this
evaluation
is
underway,
3M
is
implementing
actions
to
reduce
generation
of
waste
in
m
m
e
g
processes
and
to
reduce
releases
of
sulfonated
perfluorochemicals
into
the
environment
through
process
improvements,
waste
reduction
and
engineering
redesign.

.
.
.
.
.
.
.
.
.
.
,,.,_
._.
.
.
.
.
,
..
~

.
.
.
...
Figure
I.
Diagram
of
Fluorochemicai
Assessment
Plan.

Ecological
Evaluation
Ecotoxicity
ta
etermlnati
ons
.
..
.
.
8
r
­.
...
.
­
.
..
.
:
.
.
""_...
.
.
_
,
".
.
....._
3.0
Introduction
to
Fluorochsmicals
FIuoroehedcaIs
my;
components
of
scvcral
hportaut
3M
product
lines
due
to
their
unique
and
useful
properties.
They
are
stable,
chemically
inert
and
generally
nonreactive.
AS
components
of
products,
they
repel
both
water
and
05
n?&
ce&
tension
much
lower
than
other
su&&
m@,
act
­
85
catalysts
for
oligomerization
and
polymerization,
and
function
where
other
compounds
would
rapidly
degrade.

3M
has
produced
fluomchemicals
commercially
for
over
413
years.
3M
produces
fluorochemicds
by
combining
anhydrous
hydrogen
fluoride
with
hydrocarbon
stock
in
produced
by
3M
is
perfluorooCtandfony1
fluoride
(
POSF).
i
the
presence
of
electrim1
energy.
The
highest
volume
sulfonatc?
d
fluomchemical
1
­
0ctanesulfonyl
fluoride
Perfluoroocmaonyl
fluoride
(
POSF)

The
fluorination
process
o
v
d
yieIds
about
3540%
straight
chain
(
normal)
POSF,
and
a
mjxture
of
byproducts
and
waste
of
ucharacterized
and
variable
composition
conti&&
g:

­
higher
or
lower
straight
chain
homologues,
Q­
CJ?~,
SO,
F,
of
various
chain
lengths
(
7%
of
process
output)

e.
g.
C,
F,,
SO,
F,
C,
FIsSOzF,
C&?,,
SO,
F
­
branched
chain
perfluoroalkyl
products
of
various
chain
lengths
(
18­
200/,
of
CF3CFcF2CF2CFCFzSO$
output)
CF3
CF3
CF3
I
I
I
e.%.
CF,
CF2CF2CF,
CF2CFcF,
SOzF
­
straight
chain,
branched
and
cyclic
perfluoroalkanes
and
ethers
(
20­
25%
of
­'"
tars"
(
high
molecular
weight
fluomchemical
byproducts)
and
other
byproducts,
including
molecular
hydrogen
(
10­
15%
of
output).

Because
of
slight
differences
in
pracess
conditions,
raw
materids,
and
equipment,
the
mixture
produced
by
the
electrochemid
fluorination
process
varies
somewhat
from
lot
to
lot
and
fiom
plant
to
plant.
Numxous
process
steps
are
used
to
convert
the
fluorinated
mixture
into
final
products:
,

9
_.
...
.
..
.
.
.
.
.
1
f
1
.

,
.
.
I
'
fie
largest
production
of
flwrochemicals
occurs
at
the
3M
mmufkctwing
plant
in
Decatur,
Alabama,
and
this
plant
is
the
focus
of
current
studies.
During
productioa,
marry
byproductc
and
wasti?
pmd1xts
are
formed.
The
volatile
waste
products
have
been
vankd
to
the
atmosphere
in
tfie
past
but
hprovemenQ
are
underway
to
capture
and
desmy
releases
by
thennal
oxidation.
The
tars
ate
disposed
at
hazardous
waste
t
a
t
d
i
l
l
s
or
treated
by
incin~
tion,
Thc
byproducts,
many
of
which
arc
inr;
Ompletely
fluorinated
with
hydrogen
atoms
still
present,
are
recycled
back
into
processes
or
partidy
in
stabilization
processes
and
discharged
to
wastewater
treatment
systerqs.
The
'
treatment
sludge
is
landslled.
Some
of
the
non­
POSF­
based
brprdlucts
are
recovered
and
sold
for
secondary
uses.

The
product
of
the.
electrochemical
fluorination
process
is
thus
not
a
pure
chemhl
but
rather
a
mixture
of
isomers
and
homologues.
P
d
u
o
r
o
c
h
~
d
s
have
coplpIete
substitution
of
fluorine
fm
hydrogen.
The
commercialized
POSF
derived
products
are
a
mixture
of
approbtely
70%
hear
POSF
derivatives
and
30%
bianched
POSF
derived
impurities.
POSF
is
used
as
a
product
and
is
also
an
important
intermediate
in
the
synthesis
of
substances
used
in
many
other
3M
products,
To
a
lesser
extent,
homologues
of
POSF,
[
CJ?,,,
SO,
F
where
n=
2­
9,
exclusive
of
81,
are
also
components
used
in
the
formation
of
other
3M
products.

Some
of
the
POSF
derived
products
are
surface
active
materials
and
monomers
of
relatively
low
molecular
weight
(­
500
daItons).
These
monomers
are
used
as
low
molecular
weight
surfactants
or
are
joined
with
other
monomers
to
form
higher
molecular
weight
oligomers
and
polymers
with
a
mix
of
fluorinated
and
unfluorinated
portions.
Fluomchemical
momers
can
also
be
joined
to
phosphates,
to
polymeric
and
oligomeric
urkthane,
or
to
acrylate
hckbones
through
ester
and
other
linkages.
The
majority
of
3M's
sulfonated
perfluomchemicals
produced
are
used
in
polymeric
form
for
treatmmt
of
swfaces
and
materials.
For
example,
fluomchemical
contnining
polymers
(
urethanes,
acrylics
and
esters)
can
provide
soil,
stain,
and
water
resistance
to
persod
apparel
and
home
furnishings.

Some
products
synthesized
from
POSF
and
its
homologues
are
sold
as
raw
materials
to
customers
who
use
them
as
intermediates
or
components
of
their
products.
The
intcmediates
can
be
covalently
bound
to
a
variety
of
polymeric
hydrocarbon
backbones.

The
3M
product
l
i
e
s
that
use
sulfonated
perfluomchemicals
are
summarized
below.
(
product
lines
using
fluorochemicals
that
Contain
no
sulfonyl'groups
8re
not
listed.)

.­.

_
i
....
.
_
..
.
..
.
,
aa*,
c
..
l
.
.
.
.
.
.
.
...,
.,..
,_...,
i
.
_
.,
m:
r;
7ry*.!
yn,,
,
­
.
­­.*

.
,
.
"
1..
___..
..,.
:
.....
.
.
Surface
Treatments
FabricKJphoMery
Protector
(
High
molecular
weight
0
polymers)
Carpet
Proteotor
(
High
M
W
polymers)
Leather
Protector
(
High
MW
polymers)
Paper
and
Packaging
Protector
(
High
MW
phosphate
esters
or
high
MW
PolY=@

Surfactants
(
Low
MW
chemical
substances)
specialty
sufactrmts
Househofd
additives
ElectmpMng
and
etching
bath
surfactants
Coating
and
coating
additives
\

Chemical
intermediates
carpet
spot
cleaners
Fire
Extinguishing
Foam
Concentrates
Mining
and
Oil
Surfactap'.
ts
Other
Uses
Insecticide
Raw
Materials
(
Low
MW
chemical
substances)

Typically
a
fluomchemical
product
contabs
a
small
amount
of
fluorochetnical
residuals:
unreactedor
partially
reacted
starting
materids
or
intermediates.
Residuals
which
are
common
to
formuiations
of
sulfonated
perfluorochmical
products
include:
perfluorooctane
sulfonate
(
PFOS),
N­
ethyl
(
or
N­
methyl)
perfluorooebne
sulfonamide
(
N­
EtFOSA
or
N­
MeFOSA)
,
N­
ethyl
(
or
N­
methyl)
perfluorooctane
sulfonamidoethyl
alcohol
(
N­
Et
FOSE
alcohol
or
N­
MeFOSE
alcohol)
aad
peduorooctanoic
acid
(
PFOA).
Table
1
identifies
some
sulfonated
perfluorochemicals,
their
acronyms,
chemical
name,
and
formulas.

..,.
,
..
.
.
,
I
,.
I*..
­*..­".
I
I
._
.
,
..
_____..__.__
.
.
.­

__..
.
..
I
'

DfSlgUattOD
POSF
PFOS
I
Name
Formula
perfluorooctancsulfmyl
fluoride
W,
7SOP
p
~
u
o
r
~
e
~
~
t
8
.
c;
pltSO3­

PFOSH
perfhiorwctPlesulfonic
acid
\

PFOS.",
salt
C;
F,,
Sqrr
PFOS.
DEA
salt
PF0S.
K
salt
PF0S.
Li
salt
I
12
Perfluorooctancsulfonate
C
$
,
7
~
0
3
W
C
%
C
~
O
~
diethanolamine
sdt
potassium
prrfluorooctanasullbnate
C,
F,,
SO,
K
lithium
pertIuomoct&
subnate
C;;
F,,
SO,
Li
PFDS
(
ethyi)
acetote
perfluom&
canesuIfona.
te
CI$,,
SO3­
4.0
Physical­
Chemical
Properties
of
Fluorachemicalo
Fluorinated
organics
are
less
well
described
in
the
science
literature
than
organic
~
ltu;
ulw
bearing
other
halogens,
i.
e.
bromine
and
chlorine;
whidh
have
been
more
thoroughly
investigated
by
many
researchefs
in
published
reports.
To
understand
the
properties
of
fluorinated
organics,
it
is
necessary
to
describe
the
properties
of
fluorine.
Fluorh~
has
several
characteristics
that
differ
h
m
the
other
halogens
and
c
o
d
b
m
to
the
unusual
properties
of
fluorochemids.

Fluorine
hac
a
van
der
WaaIs
radius
of
1.35
4
more
comparable
to
that
of
oxygen
than
other
halogens,
and
isosterically
similar
to
a
hydroxyl
group.
Fluorine
has
the
highest
electronegativity
(
4.0
­
Pauling
scale)
of
dl
the
halogem,
indccd
&
e
highcst
in
tIrc
periodic
table.
This
coders
a
strong
polarity
to
the
carbon­
fluorine
bond.
The
carbon­
fluorine
bond
is
one
of
the
strongest
in
nature
(­
1
10
kcal/~
l).
This
very
strong,
high
energy
bond
confqibutes
to
the
stability
of
fluorochemicals.

The
high
ionization
potential
of
fluorine
(
401.8
kcal/
mole)
and
its
low
polarkability
leads
to
weak
inter­
and
intramolecular
intemtions.
This
is
demonstrated
by
the
low
boiling
points
of
fluorochemicds
relative
to
molecuIar
weight,
and
their
extremely
low
surfke
tension
and
low
refrzlctive
index.
The
partitioning
behavior
of
perfluoroalkanes
is
unusual.
Some
perfluomalkanes
when
mixed
with
hydrocarbons
and
water
form
three
immiscible
phases,
dimonstrating
that
perfluorjnated
chains
are
both
oleophobic
and
hydrophobic.
A
charged
moiety,
such
as
carboxylio
mid,
sulfonid
mid,
phosphatc
or
a
quaternary
ammonium
group,
when
attached
to
the
perfluorinated
chain,
makes
die
moIecule
more
water
soluble
because
o
f
the
hydrophilic
nature
of
these
charged
moieties.
Therefore,
such
fiu~
ctionalized
fluomchemicals
&
n
have
mfbctht
propertids.
Typically,
the
presence
of
these
charged
groups
on
short
chain
perfluorbated
compouuds
(
cC6)
noticeably
increases
the
solubility
of
the
compound
in
water.

Physical
data
available
on
fluomchemicals
at
3M
have
been
principally
those
parameters
needed
for
quality
contrql
use
and
material
handling.
TabIe
2
summariles
the
physical
data
for
1ow.
molecular
weight,
POSF­
based
fluorochemical
products
that
have
been
developed
for
use
on
Maten4
Safety,
Data
Sheets
(
MSDS).

Some
of
these
perfluorochemical
produtits
am
primarily
used
as
surfactants;
others
&
e
primarily
used
as
intermediates
in
the
formation
of
polymeric
or
oligomeric
products.
Some
of
these'low
molecular
weight
fluomchemicals
are
also
likely
intermediates
in
the
degradation
of
polymeric
compounds.
Some
can
also
result
fiom
environmeftal
transformation
af
other
low
molecular
weight
fluomchemical
products.
It
is
important
to
remember
that
these
data
were
obtained
using
produds
that
were
not
highly
refined,
and
products
may
have
more
than
one
fluorochemical
component.
Some
may
have
nonfluorochdcal
components
that
enter
into
determination
of
the!
valiies.
Beckwe
of
improvements
in
analytical
techniques
and
product
refinement,
these
data
are
in
the
process
of
being
replaced
by
better
quality
dah
13
Table
2.
Physical
Dab
on
Fluorochernical
Products
(
Developed
for
Use
on
MSDS
Sheets)

Product
Principal
boilmg
vapor
vapor
maprate
sotub­
specific
PH
Use
Fluorocbemical
pt@)
pressura
dwsity
BuOAc
in
Grav.
Watepl
meltin$
&
g
d
o
.
­
1
wabr
"
C
@
trU=
A
b
1
pC(
m)
calc.
@
OoC
Interned.
POSF
154b
<
IO
>
1.0
<
1
.
o
neglig
­
1
8
NIA
nCg&
­
1.7
.
NIA
.
Interned.
N­
EtFOSE
alcohol
­
1
18
b*
4
0
s1.0
4.0
*
Surfactant
N­
EtFOSA
­
11oMc
4
0
>
I
NiD
­
1.6
NIA
Interned.
N­
BtFO!
XA
­
150b'
<
IO
.>
LO
<
I
.
Q
nil
­
1.5
N/
A
lntermed
­
N­
EtFOSEMA
­
150b*
4
0
>
1.0
<
LO*
ncglig
­
1.5
NIA
htermed.
N­
McFOSEalcohol
75­
95111
NR)
N/
D
N/
D
neglig
­
1.7
N/
A
­
90m
­

­­
SurfactanrFFOs
r
q
+
salt
­
82b
­
34
­
1.0
c1.0
moderap
­
1.1
­
7
SUI­
Iticranr
PFOS
Drn
salt
­
9Sb
­
31
4.62
4.0
camplete
­
1.1
­
7
.
sutfactant
ClyGinG
derivative
of
­
100b
­
1s
­
0.87
Cl.
0
comglere
­
1.3
­
1
1
Surfactant
PFOS
Li
s
t
­
100
b
N/
D
<
I
complete
­
1.1
6­
8
Surfactant
PFOS
K
salt
NIA
N/
A
NIA
N/
A
slight
­
0.6
7­
8
Surfactant
PerfluoroClO
sulfonic
*
96
b
­
16
­
1.08
4
modem
1.08
8.5­
9.5
acid,

",+

salt
FOSA
ethylene
oxide
adduct
1.34
'
S
&
i
t
N­
FitFOSEd~
ohol,
210b
­
18
0.64
e1
appmc
1.31­
5.5­
8.4
L
Source:
MSDS
Sheers
Abbreviations:
N/
D:
not
determined;
N/
A:
not
applicable;
­:
approximately
*
measured
at
lmm
Hg
#
measured
at
2
mm
Hg
Additional
physical
data
were
developed
in
the
mid­
1970s
and
early
1980s
on
a
few,
high
volume
products.
Typically
these
data
are
related
to
developing
an
understanding
of
environmental
fate,
e.
g.
data
on
soil
mobility
and
partitionins
coefficientc­
They
art?
s
m
d
in
Table
3.
3M
has
evaluated
tbese
data
for
reliability
and
the
reliability
codes
are
included
8s
part
of
the
table.
Pragress
in
analytical
techniques
has
significantly
improved
the
reliability
of
current
dnta
compared
to
the
reliability
of
thcse
historical
data.
Current
physical/
chemid
data
are
found
h
Table
4.

14
,
.
,
a*.
,..
.
......
.
.
­
.

.
.
__
.
,
.
.
.
._.­
I
Product
SoMility
octanol/
watcr
FC
Watet
coefficient
mgn
PrincipIe
m
partition
PFOS
ICsaIt
1080
(
2A)
lO(
2B)

N­
MeFOSE
0.82
56,800
(
2B)

Computer
models
used
in
conjunction
with
empixid
sampling
can
be
used
to
predict
environmental
fate
and
transport
of
these
substances.
Existing
models
can
require
the
following
physicaVchemical
data
for
operation:
molecular
weight;
boiliig/
meIting
point,
pK,
OatanoYwater
partition
coefiicient,
vapor
pressure,
solubility,
Henry's
law
cons&
nt,
density,
evaporation
rate,
heat
of
vaporization,
bioconcentration'
factor,
and
degradation
mechanisms
in
air
and
watcr
(
hydrolysis,
photolysis,
and
biodcgxadation).
Pnxisc
values
for
the
parent
fluorochemid
compound,
its
intermediates,
and
the
end
degradation
product@)
are
essential
for
comprehensive
predictions
about
environmental
fate
and
transport.
logn­
soil
.
Organic
Vapor
OctanoYwater
adsorption
carbon
Pr­
partition
coefficient
adsorption
coefticient
(
K)
coefficient
­
m
1
0.99
66
NID
0
C2B)
(
2B)
ND
77
3,500
N/
D
15
I
alcohol
(
2B)
N­
EtPOSP,
0.03
6,600,000
3.60
~

alcohol
(
2B)
(
4)
.
OB)
N­
EtFOSEA
0.89(
2B)
NID
(
2B)

,
.
.
,
.
.
.
.
.
"
.._­
.
,
.
.
,
..
.
.
,
...
,.­^­­&.­~­­
.
.
.
.
.
...
..
­"_
...
....
..,
..._
­.
111_.­.
I­'
(
2B)
(
2B)
33u
17,
IJOU
1.22
mmHg
(
1B)
(
ZB)
0.
B)
0.
JP@
O0C
(
1A)
N/
D
N/
D
6.0
x
10­
1
Pa
(
1
A)
POSF
lest(
2A)
Nil3
N/
D
NKI
N­
EtFOSA
N
D
N/
D
N/
D
NtD
N/
D
1.6
tor@
20
°
C
(
4)
NLD
0.16
Pa@
O"
C
(
I
N
3M
is
developing
the
missing
physicavchemical
data
on
indivicid
fltiorochemids!
the
assistance
of
several
consultants.
While
labomtory
studies
are
underway
on
physiCaVchemical
properties
of
PFOS,
EtFOSE
alcohol
and
MeFOSE
alcohol,
models
me
being
developed
to
estimate
the
phy&
xd/
cbmioal
propertics
of
other
sulfonated
perfluorochemicals.
The
data
an:
being
determined
using
the
Guidalines
for
the
Testine,
of
Chemicals
developed
by
the
Organization
for
Ecommic
Co­
operation
and
Development
(
OECD)
for
phydcallchemical
testing
(
3)
where
available.
WheE
possible,
melting
points,
boiling
points,
vapor
p~~~
sures,
dissociation
canstants,
water
solubility,
n­
octanol/
water
partition
coefficients,
airhat&
partition
coefficients,
and
soil
adsorptioddesorption
will
be
determined.
This
informtion
is
needed
for
both
environmental
fate,
models
and
mandacturing
emission
models.
Current
modeling
efforts
are
hampered
by
lack
of
data
on
physical/
Chemical
properties.

Data
are
being
colIected
according
to
Good
Labratory
Practice
(
GLP)
standards.
The
&/
water
partition
test
is
non­
standard,
This
test
protocol
was
developed
jointly
by
3M
and
an
outside
expert.
Results
will
be
reviewed
by
several
techaical
experts,
both
within
the
3M
Environmental
Laboratory,
and
outside
&
e
company.
,
'

3M
is
g
e
n
w
'
t
h
e
information
on
soil
sorptioddesorption
charact&
stics
as
non­
GLP,
screening
studies.
These
data
will
&
d
in
the
evaluation
of
the
transport
process
and
parhtioning.
For
example,
,
will
a
fluorochemical
be
retained
by
the
soil
matrix
or
remain
in
the
water
phase?
The
bioconcentration
potential
of
PFOS
and
EtFOSE
alcohol
will
be
examined
through
empirical
testing
that
determines
the
extent
of
the
uptake
of
these
chemicals
by
fish.
Work
on
degradation
including
hydrolysis,
photodegradation
and
biodegradation
is
described
in
mother
section.
(
See
Environmental
Transfonnatioflegradation.)

The
physicdchemical
testing
is
proceeding
in
order
of
PFOS,
EtEOSE
alcohol,
and
MeFOSE
alcohol.
The
results
to
date
are
reported
in
Table
4.
The
inability
to
determine
an
octanoYwater
partition
coefficient
makes
it
difficdt
to
do
predictive
modeling.
\
­

Table
4,
New
PhyslcallChemkat
Testing
Results
on
PFOS,
potassium
s.
att
Parameter
Results
570
m@
Solubility:
pure
water
Solubility:
fresh
water
370
m
a
*
SolubiliQ:
unfiltered
sea
w@
er
4­
5
mg&*
estimated
Solubility:
filtered
sea
water
25
m@*
Vapor
Pressure
3.31
x
104
rn
@
zooc
Melting
Point
>
4OOOC
Boilhg
Point
1
notdculable
OctanoWater
partition
L)

*
Data
developed
in
support
of
other
studies;
not
developed
using
GLP
standards.
­

>

I
not
calculable;
three
phpsoo
AirfWatter
Partition
Coefficient
1
o(
a
x
io4)

16
'
I
,

The
methods
used
in
these
cwrent
pbysicdchemical
tests
will
provide
mIues
reposed
in
consistqnt
formats
that
are
intemationslly
fiuniliar
and
accepted.
This
statdardization
WiIl
aid
in
the
review
and
comparison
of
data
on
iadividual
fluomchemic&
and
in
model
operation
and
prediction.
The
data
Will
oontribute
to
d
y
t
i
c
a
l
mcthod
devclopmwt
4
overall
improvements
in
sample
handling,
sbiming
and
storage
as
well
as
manuf8cturing.

5.0
Analytical
Test
Methods
for
Fluorochemieats
Procedures
for
detecting
and
identifyins
fluomchemicals
in
the
environment
require
a
very
high
level
oftechnieal
expertise,
Most
genBral
analytical
methods
do
not
pmvidc
enough
sensitivityor
selectivity.
The
complex
mixture
of
possible
compo~
mts
in
a
product,
the
multiple
matrices
in
which
they
could
reside
(
e.
g.
the
atmosphere,
soils,
surface
water,
groundwater,
wastewater,
Werent
animal
tissues,
dif erent
animal
species,
plant
species,
foods,
etc.),
and
trace
level
detection
require
selective
extraction
and
diverse
analytical
W
h
k
p
s
.

Each
fluorochemicd
requires
a
unique
analytical
methodology.
Separate
methods
may
be
needed
for
every
matrix.
Validation
of
each
method
is
time
intensive.
Often.
standards
are
not
available.
Reliable
qwtitative
methods
for
extraction,
separation
and
identification
have
been
developed
only
within
the
last
few
years.
Prior
to
that,
relaiively
'
wen
used.
insensitive
find
non­
specific
m.
dyticd
methods,
such
as
"
total
organic
fluoride
(
TOF+),''

The
analytical
technology
ysed
in
extraction,
separation,
identification
and
quantitation
includes
combinations
of:

­
High
Performance
Liquid
Chromatography
(
WLC);
­
High
Pressure
Solvent
Extraction
(
HPSE);

­
Gas
Chromatography
(
GC)
with
a
Flame
Ionization
Detector
(
FID),
a
Mass
Spectrometer
(
MS),
a
Photo
Ionization
Deteotor
(
PID),
or
an
Electron
Capture
Detector
@
CD)
­
ElC&
oSpmy
Tandem
MBS
SPWWOSCOPY
(
ESMSMS);

­
HPLC­
QuadrapoIe­
Time
O
f
Flight­
mass
spectrometer
(
QTOF)

For
example,
analysis
of
PFOS
extracted
from
tissues
requires
ESMSMS
analysis.
This
technique
focuses
quintitation
on
three
secondary
ions
of
one
primtry
ion
at
a
specific
WLC
retention
time.

To
proyide
positive
identification
oftarget
d
y
t
e
s
in
complicated
matrices,
the
3M
Environmentd
Laboratory
uses
a
quadrapole
thne­
of­
flight
mass
spectrom&
er.
The
instrument
provides
hi&
mass
8ccwacy
(
to
0.0005
mu)
and
so
is
useful
in
iden­
L
J
fluomchemical
metabolites
and
intermediates
for
wbich
standards
are
not
available.
Compound
identification
is
bsed
cm
reasonable
HPLC
retention
time
as
compared
to
standard
compounds
of
similar
structure,
reasonable
interpretation
of
fragment
ions
associated
with
the
prime
ion,
hteqmktion
of
the
accurate
ma86
spectnmt,
md
agreement
between
the
experimental
and
theoretical
molecular
weight
(+
O.
OOOS
mu).

The
addition
of
ncw
tCcbl0g.
y
hns
psrmi#
cd
3M
aualysts
lu
intxeise
the
numbers
of
sulfonated
p
e
r
f
l
u
o
r
o
c
~
~
that
can
be
identified,
expand
the
matrices
in
which
theJr
can
be
detected,
and
lower
the
levels
at
which
thiy
are
detected.
The
technology
has
'

expanded
rhe
volwnes
of
analyses
that
can
be
done.
Nonetheless,
capacity
limits
require
analyses
to
be
prioritized.
When
samples
cannot
be
analyzed
soon
after
collection,
w
e
is
taken
to
store
the
samples
appropriately
for
the
matrix
and
the
analytical
method,
both
to
prevent
sample
deterioration
and
contamination.

3M
now
has
in
place
several
methods
for
analysis
of
sulfonated
peduorochemicals
in
several
matrices.
The
methods
produce
data
of
varying
quality.
They
may
be
used
in
combination
to
produce
test
data.
The
method
perfonnance
can
be
categorized
as
follows:

1.

2.

3.

4<
Quantitative
methods
that
have
been
vdidated
by
studies
conducted
according
to
Good
Laboratoiy
Practices
(
OLP).
These
exist
for
analyses
of
samples
of
blood,
liver,
and
several
animal
tissues
of
certain
species,
drinking
water,
and
certain
types
of
fwd.

Quantitative
methods
that
typically
m
based
on
methodologies
that
have
undergone
significant
amdflcd
c
h
a
r
a
e
t
i
o
~
during
development.
These
methods
are
validated
by
extensiW:
quality
conQo1
testing,
but
validation
studies
may
not
have
been
conducted
according
to
GLP
requirements.
These
exist
for
wastewater,
sludge,
and
air,
for
exampie.

Semi­
quantitative
methods
that
Bically
are
based
on
the
quantitative
methods
but
for
WE&
v&
dation
atudics
orc
lacking
or
quality
assurance
m
o
t
be*
demonstrated
because,
for
example,
standards
are
unobtainable
or
sample
matrix
is
extremely
l
i
i
t
e
d
.

Screening
methods
that
typically
are
under
development
or
a
result
of
exploratory
studies.
These
methods
yield
only
qualitative
data,
is.
fhey
reliably
detect
the
presence
or
absence
of
an
analyte.

Method
development
is
conthuhg,
not
only
at
the
3M
En~
mental
Laboratory
but
also
at
independent
laboratories
in
consultation
~
4th
3M
Environmental
Laboratmy
scientists.
For
some
uutrices,
the
detection
l
i
b
sought
are
at
lower
levels.
Method
validation
of
low
level
analyses
may
be
confirmed
at
a
university
or
other
contraot
laboratories,
as
appropriate.
When
samples
are
sent
to
consulting
laboratories,
3M
supplies
the
methodology
or
shares
expertise
to
develop
the
method.
Quality
assutance
is
18
,

required,
along
with
method
validation
and
oversight
at
levels
comparable
to
those
in
the
3M
Environmental
Laboratory.

Continual
improvements
are
sought
in
analyEi0al
methods
as
thc
ability
to
dctcct
traa
quantities
is
essential
for
a
number
of
reasons
such
as:
screening
laboratory
suppiies
and
environments
prior
to
initiating
toxicity
testing,
for
detecting
environmental
exposure,
for
de*
'
g
sources
of
perflwrochemicals,
and
for
u.
n&­
p
d
w
r
o
c
h
d
d
.
metabolism
kinetics,

6.0
Sources
of
Fluorochemicals
A
few
fluorochemicals
occur
natudy
in
the
biosphere,
produced
by
biological
and
geochemical
processes.
Several
green
plants
prodwe
xnonoflwroaceticwid
(
CH,
FCOOrr).
Some
fungi
produce
monofluorinated
organics.
All
flubmhdcals
produced
biolo@
cally
contain
only
one
fluorine
atom.
Vobanoes
and
otber
gedogicd
processes
produce
tetrduomthylene,
sulfur
hexafluoride,
perfluoromethane
and
some
chlorofluorocarbom
in
small
quantities.
.

Most
fluorochemicds
h
the
environment
are
present
as
a
result
of
human
man­
and
use.
Releases
of
fluorochemicals
into
the
mvimmntzut
can
occur
at
each
stage
of
the
fliinrochemksl
product's
life
cycle.
"
hey
can
be
released
when
the
ffuorochemid
is
syntheskzed,
continue
during
incorporation
of
the
ff
uorochemical
into
a
product,
during
the
distribution
of
the
product
to
users,
during
the
use
of
the
product
by
comers,
and
'
during
disposal
practices
at
all
of
these
stages.

3M
is
using
a
two
step
approach
to
estimate
envhmnentd
releases
of
fluorochernicals.
The
initial
efforts
have
focused
on
determining
waste
generated;
the
second
step
will
focus
on
determhing
releases.
This
two
step
approach
is
necessary
since
not
all
waste
produced
will
result
in
a
release
to
the
environment.
Much
of
the
waste
that
is
generated
is
destroyed
through
treatmeat
or
othemise
actively
managed
to
pvmt
release
into
the
environment.
Efforts
are
also
being
made
to
further
tighten
such
controls.

3M
has
estimated
waste
generation
fiom
each
of
the
following
Iife
cycle
stages:
the
manufactcving
processes,
the
supply
and
distribution
chains,'
customer
uses
and
productlwaste
disposal.
r
For
ease
in
comparing
waste
sbream
data,
wastes
are
described
in
term
of"
PF0S
equivalents."
PFOS
equivalents
are
the
weight
of
C&,
SO,
present
in
a
sulfonated
perfluorochemicd
product.
It
is
the
mass
of
PFOS
molecules
that
would
be
formed
in.&
breakdown
of
the
product.
The
assumptions
of
complete
breakdown
to
PFOS
of
each
sulfonated
perfluomchemical
product,
in
the
year
in
which
the
product
was
sold,
are
unlikely
"
worst­
case"
~
ssumptions.
Various
degradation
testing
finds
a
broad
range
of
product
degradation
rates.
Some
polymeric
products
a
p
p
r
to
be
quite
stabie
in
&
g
environment,
with
long
half­
lives;
other
polymers
hydrolyze
quickly.

6.
f
Manufacturing
Waste
Shams
The
assessment
of
the
release
of
sulfonated
perfluorochemicals
into
the
environment
begins
Wiih
manufkturhg
waste
generation.
Some
vask
streams,
such
as
wtistava@
discharge
or
disposal
of
off­
spec
products,
can
be
anticipated
and
controls
provided.
.
Other
waste
can
be
generated
during
any
of
the
steps
required
toproduce
the
fl
uorochemicals
and
manufacture
the
product
The
greatest
production
of
the
parent
fluorochemical
pmdiict,
POSF,
occurs
at
the
Decatur,
Alabamaplant.
Here
POSF
is
created
in
electrocbdical
cells
and
yndergoes
numer0Us"
steps
to
convert
it
into
fin14
products.
Salts
of
PFOS
are
also
xnm­
at
the
facility.
Because
of
its
production
volume,
the
De&
kiIity
has
been
the
focus
of
manufacturing
waste
stteam
studies.
Understanding
waste
generation
and
how
wastes
are
managed
and
disposed
of
pvides'a
better
uoderstanding
of
potential
releases
into
the
environment.
That
undemhnding
will
help
to
identify
opportunities
for
reductions
in
such
releases.
.

The
manufacturing
process
for
donated
perf.
luorochemicaIs
is
complicated.
There
are
more
than
600
intermediate
manufacturing
steps
associated
kith
th~
production
of
POSF
and
POSF­
based
products.
This
translates
into
hundreds
of
process
steps
that
require
venting
or
that
generate
wastewater
or
solid
waste.
AIthough
the
manufixturing
process
attempts
to
capture,
reuse,
and
recycle
most
5uorochemicals
as
desired
product
material,
until
recently,
the
unique
chemisbcies
created
in
each
step
of
the
process
could
not
bg
analyzed
precisely
to
confirm
composition
and
to
quantify
amounts.'
The
rnandacturing
process
is
dynamic,
with
rapidly
changing
matrices
and
many
process
steps.
Ongoing
process
optimization
activities
continuously
change
the
waste
stream
profile.

Progress
has
been
made
inanalytical
techniques.
In
1997,
analytical
laboratory
I
techniques
and
methods
could
quantitatiwdy
identify
the
presence
of
only
one
fluorochemical
analyte
in
awastewater
mattiX,
In
1999,
improved
analytical
techniques
and
methods
were
developed
for
additional
fluorochemical
analytes
in
a
=*
water
matrix.

Advanced
field
monitoxhg
technology
has
been
developed
based
on
Fourier
Transform
Infrared
spectroscopy
(
FTR).
This
field
tool
has
been
used
to
detect
where
emissions
to
air
are
occurribg
during
the
manufacturing
process
and.
to
evaluate
whether
a
process
change
or
a
control
technology
can
decrease
the
release.
As
better
analytical
techniques
become
available,
efforts
are
being
made
to:
­
characterize
the
mjor
manufaclmhg
processes
generating
fiuorochemical
I
evaluate
the
effiveness
of
flwrochemical
xemoval
technologies;
and
­
provide
better
estimates
of
the
amounts
and
kinds
of
flumochdcals
released
to
waste
streams;

~

processes
and
from
waste
treatment
and
the
envhment
from
'
disposal.

Idormation
currently
available
on
waste
streams
generated
during
manufbtwing
processes
at
Deca;
tcu
is
derived
fkom.
calculations,
air
emiSsionS
modeling,
and
limited
testing.
An
overall
site
d
n
a
l
s
bafance
was
developed
in
the
mid­
1990'
s
using
the
amount
of
POSF­
based
solids
initially
created
in
the
electrochemical
cell
and
the
amount
of
POSF
contained
in
ilnal
products
sold.
The
difference
was
an
estimate
of
total
waste
streams
generated
during
processing.
The
emission
factors
derivedfkom
this
balance
are
used
to
calculate
waste
streams
h
m
production
thoughput.
They
are
the
.
basis
for
the
estimates
in
Table
5.
These
eStimates
derived
from
the
material
balance
are
not
precise,
as
this
methodology
can
produce
only
rough
approximations.

The
e
b
$
s
in
Table
5
reflect
the
most
c
m
t
information
available
and
combine
data
derived
from
several
sources:
information
from
the
mid­
90s
site
balance,
wastewater
testing,
waste
disposal
records,
process
models
and
supplemental
information
fiom
1997,
1998
and
1999.
Several
changes
in
waste
disposal
and
processing
have
been
implemented
since
the
mid­
199Os
in
order
to
reduce
potential
releases
to
the
environment.
Wastewater
sludges
that
were
once
land
applied
on
site
are
now
sent
to
a
municipai
landfill
for
disppsd.
Off­
spec
materials
that
were
discharged
to
wasbwater
are
now
shipped
off­
site
to
be
incinerated.

Table
5
helps
to
demonstrate
the
vast
difference
between
volumes
of
wastes
generated
and
volumes
of
releases
to
the
envirOnment,
since
the
vast
majority
of
wastes
sent
to
incineration
are
destroyed
in
the
incineration
process
and
most
material
sent
off­
site
to
Iandfilis
will
be
effectively
managed
to
prevent
release
to
the
environment.

Table
5.
Estirnatied
1998
Wastes
Generated
(
in
PFOS
Equivalents)
at
the
Decatur
Manufacturing
Plant
Waste
Type
.
Estimated
PFOS
Equivalents,
lbs
Air
Emissions
19,000
657,000
Wastes
sent
off­
site
to
Incineration
Wastes
sent
off­
site
to
Laadfills
380,000
Total
Wastes
1,066,000
Note:
The
10,000
lbSryr
of
PFOS
equivdants
in
the
discharge
to
the
river
an:
estimated
releases
to
the
environment
after
wastewater
treatment,
not
the
lbsfyr
generated
prim
to
treatment.
.

Discharge
to
River
after
W
astewater
Treatment
l0,
oOo­
'

21
,
,
.,
.
.
,,,%..,..
..
.
­
.....
..
I
.

_.
.
..
..
.,
_,.
.
I
More
explanation
of
the
estimates
and
efforts
currently
underway
in
air,
wastewater
and
waste
management
follows.

6.11
Waste
Stream
Characterization
Updating
material
balances
forthe
mauufbturhg
process
is
an
ongoing
effort.
Today
process
engineers
use
a
model
of
process
steps
to
calculate
air
emissions.
New
information
is
being
Compiled
to
aid
with
model
operation
and
waste
calculations.
The
effort
to
determine
physidchemical
properties
for
sulfonated
perfluomchemicals
will
improve
model
inputs
and
waste
stream
calculations.
Analytical
technology
is
improving
understanding
of
process
chemistry
Data
from
the
process
engineers'
available
material
balances
h
the
plants
reporting
system
have
been
used
to
supplement
the
e;
arlie?
site
balance
in
esthating
ah
emksions.
Initial
reports
fiom
this
system
indicate
that
most
site
waste
and
air
emissions
result
from
fewer
than
10
key
steps
in
the
early
stages
of
POSF
production.
Process
experts
are
examining
these
steps
for
ways
to
reduce
or
eliminate
the
impurities
and
wastes
generated
intlzesteps.

h
1999,
the
Decatur
plant
installed
a
discotbm
unit
which
heats
the
process
materials,
vaporizing
and
capturing
the
fluorochemicals.
It
will
significantIy
reduce
the
orgmofluorides
in
the
waste'bater.
This
technology
will
operate
tn
rednce
emissions
and
waste
at
the
source.
It
will
make
it
easier
to
segregate
waste
streams
and
recycle
fluorochemical
wastes
back
into
the
process.
*

6.12
Air
3M
engineers
have
reviewed
specific
process
steps
to
determine
what
air
emissions
testing
is
feasible
and
appropriate.
Testing
of
complex
batch­
processing
system
is
difficult
due
to
quickly
changbg
process
conditions,
venting
pressures,
and
difficulty
in
isolating
processes;
however,
characterization
testing
m
y
be
possible.
The
technical
feasibility
of
performing
this
testing
for
two
major
processes
is
now
under
evaluation.
Any
emissions
testing
will
require
modIficatons
to
process
venta
and
mitigation
of
potential
safety
hazards.
About
80
separate
venting
points
are
associated
with
the
equipment
used
to
make
sulfonated
perfluoroc;
hemicals.
\

.
.
~
.
6.13
Waslewaltr
Anatytical
methods
have
been
developed
during
the
past
year
to
better
characterize
the
wastewater
discharge
from
the
site.
The
firse
testing
of
wastewater
before
and
&
er
treatment
for
specific
flmrochdcals
occurred
at
Decatur
early
in
1998.
The
testing
was
22
.
.
.
.
I
.
.
I
~"
limited
and
reflectd
aperating
condition0
for
a
relatively
short
period
of
time
(
24
how
composite!
samples
of
influent
and
effluent
for
one
week)
Some
ofthe
campom&
that
were
identified
in
the
wastewater
were:
a
diester
of
EtFOSE
alcohol,
EtFOSE
alcohol,
MeFOSE
alcohol,
PFOS,
FOSA,
PFOSAA,
PFOA
PPHS.
­
l
In
1998
an
interim
carbon
adsorption
treatment
system
was
installed
as
part
of
wastewater
treatment.
Data
for
the
efnuent
estimate
in
Table
5
reflects
this
change.
This
treatment
system
treats
the
lagat
single
source
of
fluorochemical­
contahbg
wastewafer
in
order
to
remove
PFOS
and
other
sltlfonatRd
~
uorochemicals
fiorn
the
wastewater.
Comparison
of
the
results
from
sampling
done
in
February
1998
with
sampling
done
in
the
end
of
1998
indicates
the
quantity
of
PFOS
discharged
to
the
Tennessee
River
declined
by
about
half.
Tn
additinn
to
the
wbon
adsorption
system,
in­
proesss
operational
changes
were
made
inoff­
spec
product
discharge
procedures
that
also
contributed
to
the
reduction
in
PFOS
content
of
the
discharge
to
the
river.

The
carbon
system
has
been
incorporated
85
a
permanent.
upgrade
of
the
wtemter
treatment
system.
Monitoring
indicates
k
t
with
proper
operation,
carbon
adsorption
removes
better
than
990%
of
PFOS.
Removal
efficiency
of
other
sulfonated
perfluorochemicds
varies,
but
the
treatment
appears
to
provide
a
high
degree
of
removal
for
most,
A
number
of
w85tewBteT
stre'ams
currently
going
to
sewers
are
in
the
process
of
being
diverted
to
t
h
e
d
treatment
facilities
for
disposal.
This
will
r
e
d
t
in
a
reduction
in
the
values
listed
in
Table
5.
3M
has
conducted
an
extensive
review
of
state­
of­
the­
art
technology
for
wastewater
treatment.
Varims
nppdes
are
cmrently
be­
evaluated.
The
long
term
goal
of
wastewater
treatment
at
the
plant
is
to
utili
source
control
and
end­
of­
pipe
treatment
to
remove
nearly
all
sulfonated
perfluorochemicals
from
wastewater
prior
to
discharge
to
the
river.

6.14
Solid
Waste
An
effort
to
identify
all
waste
streams
and
their
disposal
methods
is
undemy.
Existing
waste
tracking
is
done
on
a
site
basis,
so
it
is
difficult
to
distinguish
the
particula
streams
with
PdSF
chemistry.
The
mid­
1990s
emission
estimates
did
not
distinguish
fTinal
disposal
of
the
material
lost
%
om
proddon,
so
s
i
b
records
were
used
in
combination
with
the
existing
emission
estimates
to
create
the
current
picture
af
potential
releases
resuIting
fiom
disposal.

A
review
of
plant
records
for
1998
has
been
completed
to
determine
primary
waste
disposal
locations
for
the
site.
According
to
Decatur
plant
records,
63%
of
the
thlorochemicai
containing
wastes
are
sent
to
incinerators,
33%
of
the
wastes
are
disposed
in
hazardous
waste
landfills
and
4%
in
non­
hazardous
waste
landfills.

'
j
23
.
I
.
.
,.>.
1.
,
,

1
Waste
Stream
I
SuppIyChain
.,,
.
r
Use
1
Disposal
6.2
Supply
Chain
Was&
Stt??
ams
Air
Wastewater
.
Solid
Waste
Using
sales
data,
3M
i
d
w
e
d
key
products
that
Contain
a
majority
of
the
fluor&&^
solids
uscd
in
products.
Thcsc
products
rcpment
39%
O
f
PPOS­
equivalents
sold
by
3~
in
1997
in
the
United
States.
Most
comonly,
these
products
were
sold
to
commercial
users
who
applied
them
or
incorporated
them
into
their
products.

Using
the
information
developed
from
sales,
3M
estimated
customez
and
end
user
waste
streams
(
Table
6).
These
estimates
are
hnprecise
and
based
on
several
assumptions,
but
provide
qualitative
inf'ormation.
Using
the
chemical
formulafor
PFOS,
the
fluorochemical
solids
were
converted
to
"
PFOS
equivalents"
for
ease
in
estimating
and
cornpariug
total
losses
of
&
onat&
l
perflunrochemieals
and
in
comparing
Iossea.
The
assumptions
of
complete
breakdown
to
PFOS
of
each
suEonated
perfluorochemical
produck
in
the
year
in
which
the
product
was
sold,
are
unlikely
"
worst
case"
assumptions.
Product
waste
stream
estimates
axe
based
on
conservative,
worst
case
asgumPtions
about
the
generation
of
waste
streams
at
supply
chain
facilities.
These
are
often
based
on
,
operator
experience
or
engiueering
estimates
rather
than
laboratory
tests
and
c8n
redt
in
wi&
raugtls
in
waste
stream
calculations.
In
estimating
wastes,
these
data
do
not
include
loss
of
product
residuals
in
the
waste
streams
because
information
on
the
properties
of
residuals
and
processes
at
suppiy
chain
kiIities
and
end
user
locations
is
inadequate
to
estimate
this
loss.
_
­
_

2,600
3,300
0
112,000
181,000
.
0
59,000
.
,377,000
1,262,000
Initial
estimates
~
ssociate
waste
streams
generated
fiom
ws
and
disposal
of
the
products
by
customers
of
each
business
Unit.
These
estimates
are
helping
to
focus
efforts
in
improving
customer
stewardship
practices
and
3M
product
reengheering.
As
is
evident,
most
ofthe
waste
generated
is
in
the
form
of
solid
waste.

Table
6.
Customer
and
End
User
Waste
Stm"
n
Estimates,
PFOS
equivalents,
ibs
in
1997
6.3
Releases
fmm
Wesfe
Treatment
and
Disp&
al
Methods
3M
and
its
consultant
a
r
~
gathwhg
Mhsnati~
n
on
trebat
and
waste
handling
at
several
landfills
and
wastewater
treatment
plants
which
receive
wastes
containing
sulfonated
pduomchemicds
k
m
the
supply
chain
facilities
and
3M
manufblmhg
24
*

.
.
facilities.
Information
is
also
being
compiled
on
some
of
the
largest
wastewater
treatment
facilities
and
landfills
in
the
United
States
in
order
to
bstimate
the
potential
perfluomchemical
releases
to
the
environment
from
municipal
disposal
facilties
not
associated
with
the
si~
pply
chin
or
manufhtr;
rin&.

Incineration
is
a
hvored
disposal
method
because
of
its
high
rates
of
destruction
of
sulfonated
compounds.
3M
and
ita
cdnsultant
arc
f&
Gr
evaluating
the
effecdveness
of
incineration
for
this
purpose.
The
basic
bond
breaking
chemistry
of
thermal
destruction
of
POSF­
based
fluorochemcals,
the
destruction
efficiencies
of
various
technologies/
sitmtions
such
as
municipal
incineratorS,
and
the
products
that
could
result
from
incomplete
combustion
are
elements
of
the
study.
The
study
invoives
a
review
of
3M
and
external
litt­
dure
to
compile
infomation
on
tbr:
formation
and
properties
of
thermal
traosfonnation
products
of
sulfiinated
perfluomchemicals.

Modeling
will
be
used
to
determhe
to
th@
ebnt
practical,
the
releases
to
the
environment
from
the
amount
of
material
sent
to
incineration,
mewater
treatment
plants,
and
landfills.

The
goals
of
the
life
cycle
release
studies
are:

­
to
identify
importaut
fluor&
mids
based
on
volume
of
release,
mode
of
­
to
provide
d
u
e
s
for
use
in
modeling
the
distribution
of
fluorochemicals
in
the
­
to
determine
sampkg
sites
and
substantiate
sampling
results;
­
to
predict
which
fluorochemical
releases
may
result
in
exposure
to
humans
and
­
to
identify
fluorochemicals
that
require
M
e
r
study
as
to
their
transport,
f&
e
release
and
chemistry;

environment;

the
enviromenf;
and
and
exposure
potentid.

7.0
Environmental
Transport
and
Distribution
The
transport
and
fate
of
ckxnkals
in
the
environment
depends
on
many
factors
but
principally
on
the
interaction
between
environmental
conditions
(
e.
g.
water,
temperature,
winlight),
and
chemical
p
r
o
a
e
s
(
e+
partitioning
and
reactivity).
In
the
environmental
area,
eleven
important
fate
and
transport
mechanisms
for
sulfonated
perfluomchemicals
have
been
identified
for
further
sbdy.
These
are:

1.
Partitioning
between
air
and
prodwt,
i.
e.
volatilization
from.
product
to
air,
2.
Indoor
air
deposition;
..­
3.
Accumulation
on
airbyme
particulates;
4.
Fate
and
transport
to
the
stratosphere;

25
I
.
.
.
..
a,.,.
L_.
..
..
.
.
.
.
5.
Accumulation
at
the
surface
water
microlayer;
6.
Degradation
(
includes
hydrolysis,
photolysis
and
biodegradation);
7.
Dissociation
in
water;
8­
Uptake
in
plantq;
9.
Uptakeinfish;
10.
Uptakeinbirds;
1
1.
Effi&
ncy
of
wastewatcr
trcatmmt
system.
I
­
­
­

All
of
these
fate
and
transport
mechanisms
have
been
linked
to
models.
Modeling
w
s
mathematical
equations
to
simulate
and
predict
rqil
events
and
processes.
Many
types
of
modets
will
be
considered
for
use
in
this
effort
to
evaluate
sulfonated
perfluorochemicals.
Simple
models
of
ecosystems,
indoor
air,
and
treatment
systems
(
wastewater,
IandiUs)
.

are
being
used
to
screen
fbr
possible
fate
mechanisms,
possible
exposures,
and
possible
sample
detection
limits.
For
example,
one
preliminffly
screening
model
suggests
that
top
trophic
lwei
species
such
as
fish
eating
bids
and
sea
mammals
should
be
examined.
This
finding
was
incorporated
into
the
design
of
the
biosphere
sampling
plaa
Chemicals
differ
greatly
in
their
behavior.
The
major
diffenenaes
in
behavior
of
organic
chemicals
in
the
enviroment
are
due
to
physicaf­
chemical
properties,
AILthoulfh
laboratory
studies
are
underway
on
physicaVchemical
properties
of
PFOS,
EtFOSE
alcohol
and
MeFOSE
alcohol,
models
are
being
developed
to
estimate
the
physicaVchemical
properties
of
other
sulfonated
peffluorochemicals.
This
will
reduce
the
time
and
testing
required
to
gather
these
data
for
use
in
environmental
fate
models.

Fugacity
is
a
concept
that
is
used
to
describe
%
tendency
of
a
compound
to
migrate
in
and
between
one
environmental
medium
and
another.
Different
media
inclpde
air,
water,
soil,
sediment,
and
biota,
all
of
which
together
compose
a
dynamic,
interactive
system­
an
ecosystem.
Predictions
about
movement
of
a
chemical
must
incorporate
both
its
physicaychemid
properties
and
the
environment
the
chemical
is
h.
For
example,
a
low
vapor
pressure
does
not
mean
a
chemical
is
not
present
in
air.
It
may
evaporate
appreciably
from
water
despite
a
low
vapor
pressure
if
it
has
low
sohbility
in
water.
By.
cntcring
thc
physicd­
chuid
propaty
&
kt
on
LZ
r;
hemid
into
a
fugacity
model
of
a
generic
or
specific
environment,
it
is
possible
to
estimate
general
features
of
a
chemical's
likely
behavior
and
fate.
The
output
of
these
calculations
can
be
presented
numerically
and
pictorially.
(
6)

Fugacity
models
Will
be
used
to
predict
fate
and
transprt
of
sulfonated
perfluorochemicds.
Existing
fugacity
models
typically
are
based
on
experience
with
chlorinated
organics.
An
internationally
recognized
modeling
expert
is
developingl
adapting
models
to
consider
the
d
q
u
e
properties
of
fluomchemicals.
The
goal
of
this
modeling
effort
is
to
have
a
multimedia
model
or
models
to
predict
the
fate
of
sullbnated
perfluorochemical
produrn
and
associated
byproducts
in
a
variety
of
ecosystems.

26
8.0
Environmental
Sampling
for
Fluorochemicals
8.9
Envimnmental
Levels
8.11
Historhl
Data
In
the
late
f970sy
3M
conducted
a
very
limited
number
of
studies
to
assess
the
distribution
of
fluorochernical
constituentS
in
the
environment.
Several
kshwater
fish
species
were
tested
for
a
numb
of
fluomchemical
compounds.
In
reviewing
the
data
obtained
from
these
studies
in
context
of
the
current
knowledge
of
the
behavior
of
these
&
rials,
3M
has
coneluded­
that
these
historical
data
are
highly
qucstionabic
and
may
be
misleading.
ThmTore,
they
are
nQt
included
in
this
paper.
The
sections
following
present
more
reliable
data
a
d
i&
omtion
collected
using
validated
sampling
and
analytical
methodologies.
.
.

\

8.12
Recent
Analyses
of
Wild
Birds
and
Fish
In
analysis
in
1999
of
the
plasma
often
fish
eating
birds,
albatross
nestlings
at
Midway
Island
in
the
Pacific
Ocean
and
eagle
nestlings
in
Minnesota
and
Michigan,
PFOS
was
detected
in
each
of
the
samples
h
m
eagles.
The
samples
were
collected
in
1989,
!
92,
and
93
by
Dr.
John
Giesy
of
Michigan
State
University
as
part
of
other
surveys.
Three
of&
e
albatross
adults
show$
no
detectable
levels
of
PFOS
(<
1
ppb
detectian
level).
Detectable,
but
not
quantifiable
levels
of
PFOS
were
f
o
u
l
in
the
remaining
albatross
samples,
bo&
wlhttd
b
m
birds
less
thau
a
year
old.
AU
albamss
samples
were
collected
in
1992­
93.
See
Table
7.
These
data
am
semiqwtihtivey
screeninif
quality.
As
only
a
small
amount
(
e
1
mL)
ofplasma
'
bas
available
to
conduct
the
analyses,
no
matrix
spikes
were
possible
to
estimate
the
method's
recovery
efficiency,
but
the
methods
used
have
been
characterized
in
othery
similar
ktrices.

AAer
the
initial.
screening
results
on
wild
bird
plasma,
the
plasma
fkom
a
second
set
of
wild
birds
was
examined
for
the
presence
of
PFOS.
(
See
Table
7.)
The
some
of
the,
plasma
was
three
sea
eagles
collected
from.
the
Baltic
Sea
and
seven
bald
eagles
caIIected
from
North
America
The
samples
were
collected
in
1992­
93
and
again
by
Dr.
John
Giesy.
PFOS
was
detected
in
all
of
the
eagle
plasma
screened.
These
data
are
semi­
quantitative,
screeniug
qualily.
Twu
matrix
spikes
(
250
ppb)
prepared
from
eagle
plasma
were
extracted
and
analyzed.
Both
showed
>
80%
recovery.
'

27
.
.
'
,
~
­­...
­
".
.....
,
..
,,
..
..
ti
.....
,
.
.
.
.
.
.
­
.............
::
r
.,.,
*.
rmm­''
.
'
'
­
'.
"­­­
.
.
a
,
,
/
,
I
*

Table
7.
Levels
of
PFOS
In
the
Plasma
of
Wild
Birds
BLQ=
Below
Limit
of
Qtmtk&
on
(
10
ppb)
B
L
P
Below
Limit
of
Detaction
(
approximateIy
1
ppb)

Foilowing
the
bird
plasma
studies,
sixty
liver
samples
collected'by
the
US.
Fish
&
Wildlife
Servicti
from
various
species
of
birds
were
d
y
k
d
.
The
dead
birds
were
collected
at
a
variety
of
sites
across
the
United
States.
They
were
not
part
of
a
controlled
research
study,
but
were
selected
for
their
location
and
diet.
AI1
but
sandhill
cranes
are
fish
eating
species.
The
sandhill
cranes
are
an
insect
eating
Species.
The
purpose
of
the
analyses
was
to
detennine
if
the
presence­
of
PFOS
could
be
detected
in
these
sample
matrices.
3M
believes
that
these
sets
of
data
twe
insufficient
to
draw
conclusions
wi&
any
statistical
merit.
The
PFOS
data
in
Table
8
are
semi­
quantitative,
screening
quality,
with
a
margin
of
error
estimated
at
If:
30%.
The
lirnit
of
quantitation
for
PFOS
is
6
ppb.

28
I
.
I
.
_.
,
~
;
;
r.
.­
..
.
.
.
.
.
.
,
._
,
..
.
.
.
I
a
:
,
....
I........

,
.
.
.
c
Table
8.
Analysis
of
Wild
Bird
Livers.

BLQ­
Below
limit
of
quantitation(
6
ppb)
'

29
,
*
.
;
.
.
.
Sample
No.
Species
Locatlon
46
Great
Blue
Heron
St.
Martiaville,
LA
47
Great
Blue
Heron
5t.
Martrtvlllville,
LA
48
areat
Blue
Heron
St.
Martiavillc,
LA
49
Great
Blue
Heron
St.
Martinville,
LA
50
Great
Blue
Heron
St.
Marthville,
LA
51
white
Potieml
~
allcm,
?
iv
52
w
t
e
Pelican
Fallon,
NV
53
White
Pelican
FalIon,
NV
54
White
Pelican
Fallon,
NV
55
White
Pelican
FaIloI&
NV
56
Brow­
Pelican
FLLauderdaleiFL
58
Brown
Pelican
Ft
L;
iUderdale,
FL
­

57
Brown
Pelican
Ft.
Laudardalt.
FL
59
Brown
Pelican
Ft.
Lauded&,
I%
60
Brown
Pelican
Ft
LaUdadaIc,
FL
In
addition
to
wild
birds.
some
fish
&
om
the
wild
were
tested
for
the
presence
of
PFOS.
The
fish
were
collected
in
1997­
98
fiom
sites
h
Michigan
as
part
of
surveys
conducted
by
Dr.
John
Giesy,
They
were
stared
frozen
aud
d
y
z
e
d
in
1999.
Six
species
were
tested.
Low
levels
of
PFOS
were
detected
in
four
of
the
twelve
samples.
Since
no
sample
matrices
were
available
for
btrix
spike
studies,
these
data
are
of
screening
qualify
only.
No
clear
meaning
can
be
drawn
from
the
dah.
They
are
being
used
to
dcvclop
sampling
prugrams.
Table
9
reports
the
findings.
.
PFOS
ppb
188
59
1061
261
173
141
.
­
­
.
362
927
133
291
194
75
71
31
91
Table
9.
PFOS
Screening
in
Fish.

BLD­
Below
Limit
of
Detection
(
apprOXimat01y
7ppb)
BLQ=
Below
Limit
of
Qumtitation
{
approXimately
70
ppb)

No.
1
2
3
4
5
Pine
River,
MI
whole
body
BLD
Lake
Trout
Siskiwit
Lake,
Isle
RoyaIe,
MI
whole
body
BLD
Lake
Trout
Siskiwit
W
e
,
Isle
Rode,
MI
whole
body
BLD
Lake
Trout
Pine
River,
MI
wholebody
BLQ
Laice
*
mut
Lake
Superior
wholebody
BLD
30
6
Walleye
,
,
.
r..
...
:..
..>.
a
1
,
17r"":"
Detroit
River,
MI
wholebody
BLD
r
.
.......
...
.
,,
.
/
I
7
ciscowet
Lake
Superior,
FAarcp*
MI
9
Brown
Trout
Rouge
River,
MI
10
Channel
Catfish
Lake
St.
CtaiFe,
MI
8
Brown
Trout
Detroit
River,
MI
­
ei
C
a
w
1
Lake
S+
Clniip,
W
­
I1
I
.
.
muscle
BLD
muscle
BLD
IiVW
BLQ
muscle
BLD
I
BLQ
12
Channel
Caffish
1
Lake
St.
Claire,
MI
i
I
BLQ
,",
...
8.13
T
d
g
o
f
Fishmeal
Used
in
Rat
Studies
While
performing
human
health
toxicity
studies
(
see
Perfluoroactane
SuIfonate:
Current
SUmmary
of
IIumm
Scra,
Health
and
Toxiwlugy
Data,
Jan~
ary
1999),
3M
found
"
endogenous"
levels
of
PFOS
in
some
of
the
d
v
e
rats
used
in
the
studies.
The
levels
found
in
the
rat
livers
ranged
fiom
29
ppb
to
300
ppb.
Livers
of
rats
from
one
supplier
showed
no
PFOS
above
the
detection
limit
of
15
ppb.
Further
investigation
revealed
fishmeal
to
be
an
ingredient
in
the
rat
chow
fed
to
the
rats
in
which
PFOS
was
detected.
Fishmeal
was
not
a
dietary
component
of
the
mki
that
bad
no
detectable
levels
of,
PFOS.
3M
developed
a
complex
analytical
method
to
analyze
fishmeal
samples
collected
h
m
different
fish
stock.
At
a
detection
limit
of
2
ppm,
PFOS
was
detected
in
three
samples
of
fishmeal
and
not
detected
in
three
samples.
At
this
t
h
e
,
these
data
are
not
con~
lwive.

8.14
Plant
Site
Analyses
In
March
of
1998,3M
conducted
screening
level
sampling
for
PFOS
around
the
Decatw:
plant.
The
outEd1
of
the
Decatur
wastewater
treatment
plant
is
at
a
bay
near
the
mouth
of
Baker's
Creek.
Baker's
Creek
flows
into
the
Tennessee
River,
a
large
river
that
supports
barge
traffic.
About
25
miles
downstream
is
Wheeler
Dam.
The
samples
tested
were
of
water
surface
hlm,
subsurface
water
and
sediment.
A
god
of
the
sampling
was
to
experiment
with
sampling
techniques
and
analytical
methods.
Therefore,
the
anaiytical
data
are
of
screening
quality
only.
Data
on
PFOS
from
the
samplh­
8re
in
Table
10.

Table
I
O
.
Sampling
Near
the
Decatur
Wastewater
Discharge
\

Sample
Locations:
UP1
&
UP2:
Tennessee
River,
upstream
of
discharge
BC
1
:
Baker's
Creek
below
outfall
Q
1
C
42:
Baker's
Creek,
downstream
of
discharge,
in
quiet
waters
near
Tennessee
River
WDl
&
WD2:
Tennessee
River
beiow
Wheeler
Dam
N/
C
=
not
collected
sur~
ace
film
samples
were
skimmexi
fr~
m
tht;
top
ofthe
water,
at
the
air/
water
i
n
~
c
e
.
Sediment
samples
were
collected
from
tho
river
bed
Using
M
Ekman
Ihdgc.
Samph
wcrc
taktn
at
the
water
collection
point
or,
if
sediment
was
lacking
there,
89
close
as
possible
to
it.
'

31
,
,
I
.
._
a_.­_
.,
,
.
._
_...
C.
L_..__.._.__­.
..
..
.
.
,,­....­
.
.
..
.
I
,
..
,.,*.,.,
I­­..,.
I
._
I_.
Based
on
this
initial
sampling.
a
more
extensive
sampling
was
conducted.
Sampling
locations
extended
from
about
10
dies
trps`
trean!
of
the
facility
to
25
mites
below
the
facility.
As
a
result
of
analytical.
te~
hiques
behg
developed
to
lower
detection
limits,
mdyses
of
these
samples
is
pen%
g.

8.15
Biosphere
Sampling
3M
is
building
on
recent
information
with
advances
in
technology
to
design
a
p
r
o
m
that
could
detect
traces
of
sulfonaied
perfluomchemicals
across
a
range
of
species,
envirornental
habitats
and
geographic
locations,
including
soil,
water
and
organisms.
3M's
approach
is
to
use
existing,
scientifically
recognjzed.
sampling
and
data
collection
programs
in
order
to
minimize
the
t
h
e
needed
to
obtain
information.
The
goal
is
to
set
some
bounds
on
the
geographic
regions
where
sulfonated
perfluorochemicals
are
currently
found,
identi@
areas
that
shouId
receive
more
investigation,
and
eliminate
some
general
environments
b
m
further
samplii
in
the
immediate
future.
Key
ecosystem
and
species
of
concern
swrounding
rnanufiictming
plants
are
being
tested
as
well
as
ecosystems
remote
from
rnmufhcturing
and
use
locations.

Where
possible,
synoptic
samples
of
soil,
sediment,
ah
or
water
are
also
being
taken,
but
the
primary;
focus
of
initial
studies
is
tissue
samples
from
biological
reqeptors,
especially
those
in
upper
trophic
levels.
The
i&
ormation
obtained
in
the
initial
studies,
will
be
used
to
determrne
*
appropriate
studies
for
ascertainiqo
critical
pathways.

8.2
Human
Eirposure
Levels
I
Studies
to
investigate
human
exposures
take
several
approwhes:

1.

2.

3.
Environmentid
exposure
of
the
general
U.
S.
population
will
be
assessed
in
1
phases
through
a
"
Multi­
Cities
Study."
This
involves
field
investigation
of
.
paired
cities,
one
with
significant
manufWuring
or
commercial
fluomchemical
use,
matched
with
a
city
without
known
significant
use.
The
study
will
involve
direct
sampling
for
dietary
and
environmental
presence.

Residential
exposure
will
be
assessed
through
a
product's
use
and
controlled
measurements
of
the
product's
releases.
This
study
will
measure
releases
of
fluomchemical
residuals
and
total
PFOS
k
m
carpets.

The
migation
of
sulfonated
perfluomchemicals
used
in
food
packagii
to
the
food
is
being
quantified
for
several
foods.

1.
­
­
.
.
a
.
I
,
.
,
.
,.
/.
.....
..
.
.
..
.
.
..
IF
I
8.21
Muiti­
cities
Sampling
The
mdti­
cities
study
pairs
a
city
having
significant
manufactwing
or
coxmereid
use
of
fluomohemid
products
baaed
on
customer
d
c
s
with
a
city
h
t
docs
uoi.
IniWy
six
cities,
(
three
pairs)
are
being
examined.
This
may
be
expanded,
depending
on
initid
results,
The
multi­
cities
sampling
will
yield
environmental
disbiution
data
as
well
as
data
onpotendal
sources
of
human
exposure.
The
cities
were
selected
to
represent
urba,~~
1ocations
with
various
levels
of
fluorochemical
releases
and
various
types
of
municipal
water
supplies.
The
samples
to
be
obtained,
where
possible,
are:
urban
air,
surface
water
column
and
surfke
microlayer,
sedimm4
river
fish,
drinkhg
water
W
e
,
treated
drinking
water,
tap
water,
the
influent
and
effluent
to
publicly
owned
waste
tmatnient
works,
sludge.
and
municipal
landfill
leachate.
Additionally
a
"
market
basket"
of
several
food
products
will­
be
sampled.
These
include:
beef,
pork,
chicken,
hot
dogs,
catfish,
eggs,
milk,
bread,
green
beans,
apples
h
m
three
grocery
stores
and,
ifpossible,
produce
k
r
n
local
farmer'
markets.

8.22
Carpet
Use
Studies
The
carpet
study
will
estimate
any
loss
of
fluomhemid
from
normal
use
of
carpets.
Lf
a
pilot
study
of
cargets
finds
significant
releases,
then
the
study
will
assess
human
exposure
that.
may
occur
via
Mdatkn,
dermal
and
ingestion
mutes.

8.23
Paper
and
Packaging
Studies
Results
of
past
studies
on
the
migration
of
fluomchemicals
from
packaging
into
food
have
been
submitted
to
the
FDA,
and
FDA
has
cleared
the
use
of
paper
and
packaging
proteclors
fur
h
d
as
indirect
food
additives.
Current
work
focuses
on
the
development
of
new
methodologies
to
extract
various
fluomchemicals
&
om
paper
and
several
foods,
then
perform
quantitative,
low
level
analyses
(<
1
ppb).

834
Exposure
Scenarios
These
scenarios
will
be
developed
wing
data
fiom
release,
fate
and
distribution
studies.
Their
purpose
is
to
priontke
exposure
PR&
WE~
YS
for
fiather
study
by
developing
quantitative
estimates
of
specific
exposures
under
known
conditions
in
a
specific
location.

33
,
..
.
.,..
­...
..­.
.­­..
.
._
.....­..
..
.
".
.
..
.
a
.
.,.,
"­.~
~...
..
.
..
.
.
.
.
.
...
I
8
,
I
_
i.
.
..
....
i­
r.,..
"..
7":""
p­:'
I
­
'
..
,
0
,
I
.

.­
I
­­.
­
9.0
Environmental
TransformationlDerg~
datlon
of
Fluorochemlcals
There
are
many
physical,
chemicsl
and
biol~
gical
mechanisms
that
operate
in
the
environment
to
tran&
om
or
degrade
molecules.
They
include
abiotic
mechanisms,
e.
g.
hydrolysis
an&
photolysis,
and
biotic
mechanisms,
especially
microbial
metabofism.
Because
the
carbon­
fluorine
bond
is
one
of
the
strongest
in
nature,
witb
high
bond
­

energies,
its
cleavage
t.
equireS
large
amounts
of
energy.
Most
chemical
and
physical
processes
naturally
occurring
in
the
biosphere
lack
the
required
energy.
In
the
laboratory,
perfluoroaxkyl
chains
are
not
degded
in
the
chemical
oxygen
demand
(
COD)
test,
nor
in
total
organic
carbon
(
TOC)
analyzers
that
use
very
reactive
chemical
and
ultraviolet
degradation
msc­.
Combustion
docs
dcstroy
orgdc
fluorochcmicals
and
degradation
is
fourid
in
high
temperature
TOC
analyzers.

In
perfluorhated
molecules,
the
fluorines
surround
the
carbon
chain
completely,
shielding
the
carbon­
carbon
bonds
&
om
m
k
.
The
fluorine
atoms
confer
a
"
rigidity"
to
the
conformation
of
the
molecule.
This
rigidity
could
make
it
difficult
for
the
molecule
to
join
with
enzymes,
thereby
blocking
biological
attack
of
the
carbon­
carbon
bond.
As
a
molecule
becomes
more
fluorinated,
carbon­
carbon
bonds,
carbon­
hydrogen
and
carbon­
fluorine
bonds
all
typically
increase
in
strength.

Early
work
with
perfiuorochemical
products
using
standardized
screening
tests
for
degradation
found
little
susceptibility
to
degdati'on.
(
See
Table
1
1
.)
Fluomchomcals
lacking
nonfluorinated
organic
portions
produced
esmtidy
no
biochemical
oxygen
d
e
h
d
(
BOD).
Those
with
ionically
bonded
organics
showed
BODS
near
those
cxptcttd
&
om
thck
non­
fluorinated
portion
alone.
Fluorochemical
swfktants
with­
covalently
bonded
organic
portions
produced
mixed
results.

The
early
data
on
these
degradabi ity
studies
has
been
given
a
reliability
code
that
follows
the
test
results.

I
34
!
.
.
....,_
.
,
.
\

sulfonic
acid,
NH4
salt
K
salt
of
carboxylic
acid
analogue
of
N­
Table
I
I
.
Historical
Results
of
Standard
Degradation
Tesb
on
Fluotoc
hemicSls
(
24)
(
zA>
(
2A)
(
2A)

(
1)
(
W
04
(
U)
(
W
.
462.000
09.
SOq
172.000
179,000
2119,
MQ
Product
PrincipIe
COD
BOD
BOD
BOD
BOD
FIuorochemical
m
m
5asy
10­
2lMay
28­
dsy
N/
l3
N/
D
nil
.

(
4)
merrcg
m
m
z
mg/
Kg
mg/
Kg
POSF
500­
720
(
4)
d
(
4
)
nil(
4)
nii(
4)
N/
D
nil(
1)
NiD
N­
MeFOSEalcohol
163,000
(
1)
N
D
N/
D
N­
EtFOSE
alcohol
260,000
(
4)
nil(
4)
NID
NID
NiD
Nrn­

N
D
nodegradation
in
Warburg
3
hr
stady
or
2.5
montb
shake
flask
study
N­
EtF'OSA
1,800(
4)
d
(
4
)
nil(
4)
Nl(
4)
N/
R
N­
EtFOSEA
2
4
0
,
~
(
1
)
1&
000
19,000
23,000
N/
D
N­
EtFOSEMA
I
80,000
(
1)
800
2,000
1
11,000
N/
D
(
2A)
(
2
4
(
2A)
I
EtFOSE
alcohol
PFOS
Lr"
salt
(
4)
PFOS
K
salt
54,000
N/
D
N/
D
Nn,
N/
D
4,000
nil
nil
nil
Nn,

I
I
I
I
I
PFOS
DEA
salt
I
78,000
j44,
ooo
1
I
82,000
INK)
t
(
ZA)
I@)
I
I
o
I
N­
EtFOSEaIcohol
I
1,070,000
I
0
1
N/
D
I
107,000
I
NiD
Photo
w/
D
cm(
l)
nil
(
1)

1
3%
of
noq
No
deg
m
6
month
shRLe
flask
studies
or
7
day
activated
sludge
studies
40%
removal
BAS
(
3A)

1
I
­
b
COD
means
Chemical
Oxygen
Danand.
It
is
a
measure
of
the
oxygen
e@
valent
of
the
organic
matter
content
of
a
sample
that
is
susccptiilc
to
oxidation
by
a
strong
chemical
oxidant
such
as
potassium
dichromate.

BOD
means
Biochemlcat
oxygw
Demand.
It
i
s
the
amount
of
oxygen
consuxned
by
microbial
processes
while
breaking
down
a
horn
amount
of
a
test
substance.

35
.,
.
.
.
.­..
.
.
.
.
.
.
.
.
__
­
..
.
..
.
.
.
.
.
.
.
.
~
O
D
m­
nwretical
OxYrJcn
Demand.
It
iS
the
t
h
d
d
quantity
of
oxygen
used
when
the
test
compound
is
fully
rnineralhd.
This
value
calculated
usmg
the
structura
of
tho
test
chemical.

BiAS
meam
Bismuth
Active
Substances.
These
are
materials,
such
as
water
soluble
polyethoxylatw
that
prccipitatc
with
bariuru
iewdudubismutbate.

N/
D
means
Not
Determined.

Code
meanings
are:
(
2)
Study
used
publiied
test
guidetines
or
well­
documented
procedures.

(
2)
Study
meets
all
&
e
Criteria
for
quality
tasting
but
has
a
deficiency
(
3)
Study
doeg
NOT
mea
criteria
far
quality
testing;
data
have
one
or
more
fiaws.
Concentrations
wera
measured,
and
all
quality
control
data
were
acceptable.

A.
Concentnitions
NOT
measured.
B.
Analytical
methodology
questionable.

A.
Demondated
waakness
in
experimental
procedures.
B.
Insufiicient
description
of
method
C.
Unacceptable
perfonnana
of
controls.
(
4)
Data
are
available
only
as
summaries;
orighal
reports
not
found.

9.
I
Hydrolysis
Studies
Hydrolysis
is
a
major
mechanism
contributing
to
abiotic
degradation
of
organic
molecules,
although
it
iarely
is
responsible
for
complete
degradatioa
The
hydrolysis
of
sulfonated
compounds
is
described
below.

0
0
II
I
I
R­
S­
X
+
H20
R­
S­
OH
+
HX
1:
.­
8.

X
­
halogen,
OR,
NR
.
­.

3M
is
evduating
the
potential
for
hydrolysis
of
ffuorochemicals
using
EPA
guidance
pate,
Transport
and
Transformation
Test
Guidelines,
Hydi.
02ysi.
s
us
a
Function
of
pH
and
Temperature
](
2),
and
is
conducting
pH
dependent
studies
of
PFOS
and
MeFOSE
alcohol,
as
we11
as
on
fluorwhemical
monomers,
to
estimate
half­
lives.
Selected
fluorochemid
products
are
being
subjected
to
a
single
temperature
(
SOOC),
variable
pH
screening
process.
For
those
that
demonstrate
hydrolysis
or
a
deviation
form
first
order
kinetics,
multiple
pH,
multiple
temjperanrte
studies
are
planned.
Hydrolysis
test
dara
are
being
reviewed
by
an
outside
expert.
,

36
,..*.
..
­
.
,
.
.
..
/*:
,
Like
hydrolysis,
photodegradation
is
a
major
abiotic
mechanism
contributing
to
the
transformation
of
orgdc
molecules,
but
rarely
responsible
fbr
complete
degradation.
Photodegradation
occurs
primarily
in
air,
in
shallow
water,
on
soil
and
vegetative
surfaces.
It
is
likely
an
important
factor
in
the
hte
of
soluble
and
volatile
compounds,
less
so
for
insoluble
and
sorbed
compounds.
Products
and
intermediates
most
SuSceptibIe
to
photodegradation
are
those
most
likely
to
be
used
outdoors
in
sunlight.

Initially,
the
degradation
that
might
occur
in
products
dissolved
or
suspended
in
water
is
under
investigation.
The
first
studies
are
Using
the
PFOS
precursors
such
as
EtFOSE
alcoMl,
MdOSE
"
alcohol,
MeFOSA,
EtFOSA,
andFOSh
Later
Studies
will
WG
POSF­
based
polymers.
If
simple
methods
can
be
found,
gas
phase
photolysis
of
volatile
and
semi­
volatile
fluodemicd
degradation'htmnediates
will
IX
investigated.

The
preliminary
results
suggest
that
PFOS
is
unchanged
as
a
result
of
light
exposure.
However,
EtFOSE
alcohol,
MeFOSE
alcohol,
EtFOSA
and
MeFOSA
as
well
as
a
surfhctmt
and
foamer
product
all
appeared
to
undergo
photolysis
to
FOSA,
PFOA,
a
hydride,
and
olefins.
PFOS
was
not
detected.
One
product,
an
aromatic
perfluorooctane
sulfonate,
did
photodegrade
to
form
PFOS.

9.3
Afmospherle
Studies
Although
PFOS
has
a
low
volatility,
several
PFOS
precursors
me
volatile.
These
include:
EtFOSE
alcohol,
MeFOSE
alcohol,
MeFOSA,
EtFOSA,
and
FOSA.
When
present
as
residuals
in
products,
these
precursors
could
evaporate
into
the
atmosphere
when
the
product
is
sprayed
and
then
dried
Once
in
the
atmosphere,
the
compounds
can
remain
in
the
gas
phase,
condense
on
particulates
present
in
the
atmosphere
and
be
carried
or
settle
out
with
them,
or
be
washed
out
with
rain.
The
measured
vapor
pressure
of
Et­
FOSE
alcohol
is
sufliciently
bigh
that
essentially
all
of
it
is
likely
to
be
in
the
gaF;
phaF;
e
and
not
condensed
on
particulate
matter.
Gas
chromatic
data
suggest
that
other
precuxsors
are
even
more
volatile.
The
low
water
solubility
of
these
compounds
makes
it
unlikely
they
washout
from
the
atmosphere
in
rainwater.

Thus
the
rate
of
removal
of
these
precursbrs
firom
the
atmosphere
will
lik~
ly
depend
on
their
photochemical,
reactivity,
e.
g.
their
reaction
with
hydroxyl
ions
in
the­
atmosphere.
How
widely
distributed
they
are
locally,
regionally
or
globally
depends
on
the
rate
of
photochemical
transf'omation
to
more
soluble
or
less
volatile
products.

3M
is
examining
atmospheric
Metimes
of
these
PFOS
precursors.
Initially
EtFOSE
alcohol
and
MeFOSE
alcohol
will
be
tested
for
reactivity
with
the
OH
mdicsl
in
the
gas
phase.
Modeling
wiI1
determine
their
atmospheric
lifetimes
and
analytical
work
will
'

determine
their
gas­
phase
degradation
products.
Then
those
propetties
of
the
degradation
37
products
that
affect
removal
rates
&
om
the
atmosphere,
e.
g.
solubility
and
vapor
p
m
,
will
be
determined.
This
information
will
be
used
to
predict
distribution
of
these
compounds
r
e
s
d
~
~
f
i
o
m
atmospheric
mechanisms.

9.4
Blodegmdation
Studies
Biodegradation
is
essential
to
the
functioning
of
living
systems.
Natutal
system
rely
on
living
organisms,
especially
microbes,
to
break
down
complex
organic
molecules
to
simple
inorganic
molecuIes
that
can
be
recycled
back
into
the
ecosystem.
Some
microbial
communities
have
demo­
the
ability
to
degrade
some
xenobiotic
compounds.
During
biologically
catalyzed
degradation
of
these
compouuds,
the
degradation
intermediates
produced
are
fkqumtlypf
a
molecular
structure
that
nahually
OCCZVS.
Particularly
importaut
envir0ntnmt.
s
for
biological
breakdown
are:
sewage
treatment
systems,
soils/
sediments,
estuaries
and
wetlands.
Both
aerobic
and
anaerobic
organisms
play
important
roles
in
degradation.
3M
is
studying
biodegradation
uskg
several
approaches.

9.41
Microbial
Studies
an
Perflnorochemicils
Work
at
Michigan
State
Universiv
by
Blake
Key
(
4,7)
under
the
direction
of
Dr.
Craig
Cridde
used
a
laboratory
isolate
of
a
bacterium,
a
Pseudomum
species,
to
investigate
I
the
potential
for
biodegradation
of
fluorhatted
sulfonates.
The
researchers
used
model
fluorinated
sulfonate
compounds:
&
fluoromethane
sulfonate
@
FMS),
trifluoromethane
suIfonate
(
TFMS),
2,2,2­
trifliiomethanesulfanate
(
TES),
PFOS
and
H­
PFOS
.
(
lH,
1
H,
2H,
2H­
pe~
uorooctme
sulfonate).

Criddle
et
al.
demonstratcd
th&
t
thc
microorganism
degraded
thosc
fluomclianical
compounds
containing
hydrogen
and
used
them
as
sulfur
sources
for
growth
under
sulfur­
limiting,
aerobic
conditions.
They
later
found
that
such
degradation
occurred
in
soil
even
when
sulfur
was
not
limiting.
The
organism
completely
defluorinated
DFMS.
It
used
DFMS
as
the
sole
source
of
sulfur,
but­
not
as
a
source
of
carbon
or
energy.
TES
and
H­
PFOS
were
partially
defluohted.
Six
volatile
products
were
detected
for
H­
PFOS,
all
containing
oxygen
and
fluorine
but
not
sulfur.
Where
the
carbons
were
fully
fluorinated,
i.
e.
TFMS
and
PFOS,
no
degradation
was
found.
Cridde
et
al;
concluded
that
the
transformation
of
fluorinated
sulfonates
required
the
presence
of
hydrogen
at
the
alpha­
carbon
on
the
fluorinated
alkyl
chain.
They
theorized
that
when
hydrogen
is
present
at
the
alpha
carbon,
a
site
for
attack
is
provided
and
the
carbon­
sulfur
bond
becomes
more
accessible.
Perfluorinated
compounds
have
a
rigidity
confetred
by
the
fluorine
substitution
and
no
structures
that
are
susceptible
to
electrophilic
or
nucleophiSic
attack
,
._
.
,
­
.
.
.
.
.
..
,
.
38
,
.
"*_
.
,
.
.
.
.
....
..
..
.
.
.
.
.
.

9.42
Biological
Transformation
When
perfluorinated
organic
molecules
do
biodegrade,
it
is
not
the
fluorinated
portion
Lhdt
is
affected.
Enzymes
attack
at
non­
fluorinated
side
chains.
Rather
than
compiete
degradatioa
Le.
degradation
to
inorganic
compounds,
another
fluorinated
molecule
results
from
biodegradation
processes.
'
Existing
studies
of
metabolism
appear
to
indicate
that
for
POSF­
based
compounds;
the
biological
degradation
halts
when
PFOS
is
formed.

POSF
PFOS
.
POSF
derivative
PFOS
Once
formed,
PFOS
has
not
been
shown
to
degrade
any
further
under
any
~
turoll
conditions
except
combustioa
Because
PFOS
is
resistant
to
physical,
chemical
and
biological
degradation,
it
persists
in
the
environment,
but
the
mechanism
of
accumulation
IS
under
study.

9.43
Optimizing
Conditions
for
Biodegradation
Past
studies
on
flwrochemicals
with
hydrocarbon
portions
have
demonstrated
resistance
to
biodegradation
under
sim&
ud
test
conditions,
i.
e.
aerobic
microbial
degradation
using
a
wastewater
inoculum.
These
studies
did
not
examine
all
combinations
of
conditions
that
could
be
opthized
to
favor
the
degradation
of
pa+
lIy
fluorinated
chemicals.

3M
is
conducting
new
screening
studies
for
biodegradation.
These
will'determine
if
aerobic
ador
anaerobic
degradation
of
key
fluorochcmieals
occurs
using
activated
sludge,
anaerobic
sludge,
aquatic
sediments
and
soil.
f
degradation
occurs,
the
studies
will
determine
to
what
extent
it
ocqm
and
the
nature
of
degradation
products.
It
will
also
provide
information
on
the
degree
of
fluomchemical
sorption
onto
microbial
sludges
and
toxicity
to
microbes.
New
studies
are
being
designed
to
promote
degradation.
They
will
use
enriched
environments
that
support
biodegradation,
e.
g.
sewage,
soil,
s6djmmts,
and
cultures
of
microbes
selected
for
biodegradation
capabilities.

'
39
­
­
.
.­
.
,.
.
,
.
..
­­­,_
.
.
.
..
.
._
....
.
7
0.0
Ecotoxiclty
Testing
of
Fluorochemicab
Ecotoxicology
is
the
extension
of
tozdcology
to
the
ecological
effects
of
chemicals.
Ecotoxicological
studies
measure
the
effircts
of
a
chemical
substance
in
the
mviromea
on
indigenous
populations
of
organisms.
They
provide
amwhanism
to
estimate
M.
Ecotoxicologicd
data
are
appropriately
interpreted
with
knowledge
of
the
ecosym
where
the
organisms
he.
Tn
aquatic
ecntnx
studies,
what
may
be
toxic
under
co&
tiom
created
m
the
laboratory,
may
be
more
or
less
toxic
in
the
aquatic
environment
due
to
h
t
o
r
s
present
in
the
aquatic
ecosystem
which
affect
bioavailability.
Also
the
chemid
itself
may
be
transfonncd
89
o
rcsult
of
physical
and
biological
mechanisms,
including
metabolism.
An
gkarate
evaluation
of
the
toxicity
of
a
chemical
requires
knowledge
of
these
factors.

Sulfonated
perfluorochemcals
appear
to
produce
a
variety
of
responses
in
single
species
tests
of
aquatic
org&.
DBercnt
species
have
varied
significantly
in
their
response
to
the
same
chemical
even
when
using
the
same
laboratory
procedure.
In
ecotoxicology,
environmental
concentration
often
substitutes
for
knowing
the
actual
amount
or
dose
of
a
chemical
entering
an
organism,
but
concentration
and
dose
may
not
be
directly
related
and
their
relationship
varies
fkom
species
to
species.

Basic
environmental
todcity
m
a
k
g
data
IUD
av&
lablo
for
mnny
sulfonated
perflwrochemicals
(
see
Table
12),
although
their
quali6
is
variable.
In
considerjng
the
toxicity
test
results,
it
is
important
to
note
the
year
of
the
test.
Test
protocoIs
typically
were
developed
considering
water
soluble,
stable
and
well­
dispersed
compounds.
Compounds
such
as
sulfonated
pe\
rfluorochemicals
challenge
test
protocols
due
to
their
insolubility,
polymeric,
or
s
h
e
active
nature.
The
older
data
may
reflect
these
test
limitations.
Older
test
protocols
are
not
comparable
to
recent
and
current
bioassays
that
follow
accepted,
standardized
test
methods
(
OECDKJSEPA).

Almost
all
previous
testing
used
products
which
are
complex
mixtures
and
not
purified
perfluorochemicals.
In
old
tests,
the
suIfonatd
perfluorochernical
product
us8cz
was
liiely
mom
variablc,
with
mom
i.
mpuritks
bccau~
t
m*
cturing
proccsscs
and
product
purity
have
significantly
improved
over
time.
Several
tests
were
hampered
by
the
insoIubility
of
the
perfluomchemical
and
results
are
expressed
as
greater
than
the
measured
solubility.

Two
sulfonated
pduomchemicals
have
more
toxicity
test
data
than
others
because
of
their
use
as
insecticides
in
ant
and
roach
bait
stations.
These
pduorochemicals
are
N­
EtFOSA
and
PFOS
Li
salt.
Toxicity
data
on
these
compounds
may
be
found
in
the
disclosures
filed
by
other
regis­
ts
under
the
Federal
Insecticide,
Fungicide
and
Rodenticide
Control
Act
(
FIFRA).

40
.
.
.
.
.
..
.
.

Twt
Orgaolsm
.,
.
1
.
.

StudyType
Year
3M
has
evaluated
the
reliability
of
its
aquatic
toxicity
test
data
base.
The
numaid
descriptor
is
model&
after
the
reliability
coding
used
by
EPA's
Office
of
Toxic
Substances
for
the
AQUIRE
(
Aquatic
Idormation
Retrieval)
toxicology
data
base.

Pirn&
alts
promelas
Daphniamagna
Table
12.
Ecotoxicity
Testing
on
Sulfonated
Perfluorochemicai
Products
30
day
hatch,
.020
78
W
histopathol~
kY
,
2D
growth,
SUNiVal
2D
NUEC
.
mo
7s
2D
LOEC
>.(
I20
48
hr
EL50
14.5
98
2
w
48hrELIO
7.3
98
2A,
c
­­
.
.
.
.
.
.
.
.
.

Daphnia
magna
Pimephales
pornelm
Reliability
Cdw.
1.
Study
USMI
published
ftsl
@
eu3Hts
or
well­
doeurnenred
procedures.
C­
01
pe­
ce
~
a
9
satisfactory.
Toxicant
i;
onceOtration
was
meBsumd
Test
water
temperature,
pH
and
dissolved
oxygen
were
measured.
2.
Study
meets
all
the
criteria
far
quality
testing
but
has
one
or
more
ofthe
following
dafichcieacies:
A.
Nominal
test
substance
concentnation;
actual
conecntration
n@

measut6d.

C.
A
water
accommodated
fkaction
(
WAF)
WBS
used.
D.
An8lyticaI
methodology
WBS
questionable.

A.
Demonstrated
weaknesses
in
expcrimentalprocedures.
B,
A
statfc
tesf
with
uome8suTed
concentrations
was
conducted
ia
the
pnsencc
of
precipitate
or
some
undissolved
chemical
C.
insufficient
description
of
methods.
D.
Uns&&
Wory
oontrol
mortality,
B.
Test
water
quality
Mpiabtes
not
Feportctd
or
incomplete.

3.
Study
does
not
meet
the
u
i
t
d
for
@
ity
testing.
Chmctedzed
by
one
o
f
the
following:

3
2
34
Product%
Principal
Fluorochelhical
WSF
N­
MeFOSE
alcohol
N­
EtFQSA
I
I
Pinrephales
promelm
96
hr
LQO
I
>
LO00
,
/
84
2A
3B
48
k
NOEL
%
hrWO
%
hrNOm,
48
hr
EL50
48
kELl0
48
hrNOEL
MhrLLia
5.8
206
115
130
328
184
216
98
'

98
98
98
98
98
98
84
84
41
..,_
.
.
.
.
.
.
.
.
~
­
.
~
.............
.
.
.
.
.
.
.
.
.
.
.
.
.
~

.
.
.
.
,
...
,.,..
,.&
....
,.
............
­
.
.
.
.
.
.
.
.
_
*
..,__
.
..,
­
~.~

.,:

I
.
.
.
.
.
.
'­
.
.
.
..
r..,.
,

82
2A
I
78
2D
7s
2D
77
2A
78
2A
79
2A
74
2A
73
2A
179.
2A
1
92
2A
I
78
2A
179
'
2A
hurdUCt'
8
hindpal
Flnorochcmical
Pim&
altspromeh
­
macrochina
Dophnfa
magna
Pimephula
prom&
h!
limm
PimevMa
llromelm
PFOS
Li
salt
96
hr
LCSO
96
hr
LCSO
96
hr
NOEL
48
hr
ECSO
96
hr
LCSO
30
min
ECSO
96
br
LCSO
PFOS
K
salt:

97
97
$
7
97
97
97
PFOS
DEA
,
Salt
peffluoroCl0
sulfonic
skid,
N)
4+
salt
K
salt
of
csrbo~
fic
acid
analogue
of
N­
Et­
FOSE
alcohol
24
2A
2A
.
2A
2A
2A
N­
EtFOSE
&&
Ol
ethylene
oxide
adduct
I
Code
P
~
w
a
~
n
t
e
&
s
96
br
LCSO
~
1OOO
84
3B
\
Pim&
huItwpromeim
96
hr
LCSD
=+
1000
~

84
3B
Pimephalarprmercls
96
hr
LCSO
85
74
3
A
P
h
~
~
p
r
o
~
96
hr
E50
Micrptox
P.
phatporeum
30
min
EC50
Lkaphniamagnil
48
hr
EC50
48
hr
NOEC
Ptmephulespomelus
I
96
hr
LCSO
Microtox
I
30
min
EClO
30
min
EC50
48hrEC50
28
day
NOEC
4
day
ECSO
cellcount
'
14
day
EC50
cell
count
30
day
NOEC
30
day
LOEC
96
hr
LC50
96
hr
LCSO
96
hr
LC50
48
hr
ECSO
96
hr
LC50
Lepomis
macrochkur
"

Daphnia
mrgna
96
br
NOEC
96
hr
Ed50
96
hr
NOEC
48
hrEC50
48
hrNOEC
30
min
IC50
96
hr
Le0
100
>
lo00
'
210
100
19
~

45
>
280
27
7
82.

95
1
1.9
38
68
11
50
29
32
31
18
44
4.8
330
97
54
600
216
­

9.
L
3
9
270
518
15
285
1.5
78
2A
Table
Key
EC5o.
L
Median
Effective
Concentration.
It
is
the
mucentration
of
a
test
substance
that
causes
a
50%
ef%
tct
on
a
specific
charactars
tic
of
the
test
ocganim
(
e.
g.
immobilization
of
SO?
k
afthe
Daphnia,
redudion
in
algat
ceu
gwwE
by
50%
xs
compared
lo
endpoint
in
a
toxicity
test
with
DapW
and
other
small
ogatlhs
where
death
is
hard
tu
determb
or
in
tests
where
growth
is
measured.
Contds)
after
a
specified
exposure
period.
It
is
the
usual
42
,
,
.
.
I
,
.
.
_
.
..:
.
.
.
.
.
.
.
.
.
­
..
.
,
.
,
.
.
.?
._.
.
.
.
.
.
.
~
,
~
~
...,
.
I
.
.
.
.
~.

I­
_._
.
_
I­.­
L
a
p
Median
Mal
C
o
n
c
~
t
i
o
n
.
It
b
the
caneentretion
of
a
substance
that
kilk
SO?!
of
the
test
organisms
exposed
to
it
in
a
specified
time.
It
is
the
usu81
dndjpomt
in
an
acute
vlxicity
test
with
fish.

1
~
5
0
­
~
f
i
;
~
i
a
o
Inhibitory
Couaocratiua
It
is
the
concentnitton
or
a
tesf
substance
maf
intaibfts
a
biological
process
of
a
test
organism
by
50%
(
e.
g.
I
i
i
t
production,
respiration)
after
a
qmified
exposure
period
NOEL=
Nn
Chewed
Effect
Level
NOEC­
No
Observed
Effect
CrmcentratiOn
.­
_
_
­
.
.

ELPiEffectve
M
g
,
WL­
LedLal
loading.
Thac
are
used
whera
the
test
substance
is
not
completely
water
soluble.
A
water
accomodated
fradon
(
WAF)
is
prepan?
d
The
test
substance
is
loaded
into
water
at
different
loadings
to
prepare
each
test
concentmion.
The
solution^
are
mixed
and
the
liquid
W
o
n
is
decanw
to
usc
as
the
.
fcst
Wata.

Additid
studies
are
unde~
way
on
ecotoxicity
Using
established
OECDIEPA
methods.
Initially
purified
PFOS
and
EtFOSE
alcohol
B
T
~
being
tested
to
determine
acute
and
chronic
toxicity
to
a
wide
range
of
species.
The
results
to
date
ah
found
in
Table
13.

43
Y
r
a
.
.
a,.
.
,
.
'
I
'?.'
.
''
Table
13.
New
Ecotox
Studies
on
PFOS,
potassium
salt
.
I
e
.

Parameter
Wastewatef
Bacteria
(
OECD
209)

Senenasmun
capicconnrhc
(
green
algae)

DapWmagna
(
freshwater
flea)

~
s
&
p
s
f
s
bahta
(
marine
shrimp)

Freshwater
mussel
I
PimnepMespromelmr
(
ffiaad
Illiuuow)

water
Shell
Depositian
Aviad
Dietary
ToXicW
Testing
.
.
Study
Type
Results,

36rNOEc
1.0
mg/
L
3
hr.
EC50
.1080mgn
mgn)
3956
­
­
Inhibition
(
r3
highest
con~
(
1000
96
hr
NOEC
(
growth
rate)
96
hr
ErClO
96
hr.
ErC50
Acute
48
hr
NOEC
.
Acute
48
hr
EClO
Acute
48
hr
K50
Acute
48
hr
EC90
21
day
stmi­
statiC
life
cycie
NOEC
21
day
Semi­
static
lifecycleNOEC
Acuta96hrNOEC
1.2
m
a
Acuas
96
hr
EC50
4.00.3­
5.0)
mgfL
35
day
flow
thru
life
cycle
NOEC
0.28
mg/
L
35
day
flow
thm
life
cycle
NOEC
0.6
mrJr.
Acute
96
ht
NOEC
Acute
96
hr
LC50
65m&
­
48
m
a
65
69­
69]
mgA.

36
mg/
L
57
(
42­>
99)
mg/
L
69
(­
42399)
m@
L
13
m&
26
m@
L
138
(
125­
149)
mg/
L
66
(
36­
99)
mgn,

22
m&

Acute
96
hr.
NOEC
AGUW
96
IIr
LCSO
47
day
eaciy
lifP.
stage
toxicii
NOEC
47
day
early
lifissrage
toxicity
LOEC
Acute
96
hr
NOEC
Acute
96
hr
ECM
(
Solubility
l
i
i
t
s
precluded
ECSO)
Inhibition
@
highest
conc
(
3.3
m@)
3.6
m
a
0.33
mgiL
0.65
mglL
2.1
mgL
~
3
.
3
m'fl
IO
(
8.812)
m&

28%
Acute
Maliant
Duck
LCSO
730
(
532­
IUS9J
mg'kg
AcuteNalIardDuck,
IWmortality
160
m&

All
of
the
results
shown
in
Tabie
12
suffer
from
limitations
in
the
reliability
of
the
data,
and
thoro
is
n
olwr
ncod
for
high
q
d
t
y
Ccoto~
city
dab
using
Cstablishca
OECDlEPA
methods.
Testing
on
purified
PFOS
and
EtFOSE
alcohol
is
in
propss.
However,
the
available
new
&
a
(
Table
13)
and
the
historic
data
are
conSistent
h
that
almost
all
toxicity
values
for
PFOS
and
related
suIfomted
gerfIuorochemicals
are
greater
than
1
mg/
L
and
most
are
greater
tltEm
10
m&.
An
excqtion
is
the
fatliead
minnow
msults
reported
on
Table
12
for
N­
EtFOSE
alcohol
where
apparently
there
is
no
acute
toxicity
at
44
(,

Acute
MaIlard
Duck
NOEC
A~
UaBabwhit~
QUailLC50
­

AcutG
Dobnhibc
Quail,
no
mortality
Acute
Bobwhite
Quail
NOEC
.
.
.
40
m
e
214
(
163­
260)
m&
BO
fk&

80
m&
4
l
or
above
the
water
solubility
level.
The
available
nwdata
on
PFOS
itself
suggest
that
it
has
SMEW
aquatic
toxicity
to
that
of
other
anionic
surfactants
(
9).
Few
other
concIusiox1s
can
be
reliably
drawn
at
this
tiale.
Fbr
instan=,
ecological
risk
assessment
typically
concIusioDs.
.
­
dies
on
chronic
toxicity
V
~
W
S
,
but
th­
too
few
data
on
this
to
draw
any
­.
.­
.
1
I
.
O
Comprehenshr
Plan
to
Assess
Environmental
Exposure
The
ongoiug
activities
described
in
the
previous
sections
of
this
paper
are
being
carried
out
8s
part
of
a
3M
developed
comprehensive
plan
using
B
combination
of
3M
resoyrces
ami
outside
experts.
This
plan,
summwwd
in
Figure
1,
is
designed
to
assess
the
potential
pathwaysof
envhnmerttal
qosure
associated
with
the
man­,
use
and
disposal
of
its
sulfonated
perfluorochemical
products.

The
plan
structure
consists
of
four
components:

1.
Characterize
the
properties
critical
to
understrurding
the
fit6
and
transport
of
sulfonated
perfluorochemicals.

2.
Estimate
the
releases
of
suifonatedperfluorochernieais.

3.
Characterize
the
distiiiution
of
sulfonated
perfluorochemicals
in
the
environment.

4.
Estimate
human
and
ecological
expos&
to
sulfonated
perfluorochemicals.

Several
individual
research
projects
feed
information
into
each
cumponent.
The
mIy
.
components
provide
information
needed
to
mmpleb
the
later
ones.
Thus
the
Wormation
base
expands
when
one
goes
hrnwmpomt
I
to
cornponmt
4.

This
section
provides
80.
overview
of
the
plan
and
its
research
projects.
Specific
descriptions
of
how
and
why
the
research
projects
are
being
conducted
can
be
found
in
the
preceding
sections
of
this
document.
The
results
generated
by
this
plan
wilI
be
combined
with
the
ecotoxicological
studies
to
develop
an
assessment
of
risk.
A
tentative
,
initiation
c4xte
for
each
of
the
research
projects
is
found
in
Figure
2.
It
is
ewcted
that
the
studies
will
continue
over
several
years.

45
E
Figure
I
Diagram
of
Fluorochemicaf
Assessment
Plan.

.
."

46
.
/
Figure
2­
Schedule
for
FC
Exposure
Plan
Components.

lQ­
First
Quarter,
2Q=
Second
Quartet,
3QcThird
Quarter,
4Q=
Fourtb.
Quarter
Characterke
Fate
&
Tmnspart
Pmpertl*
PFOS
PhyolChem
Pppertiqct
EtFOSE
alcohol
PhyaFChern
Pkpertl&
­
MeFOSE
alcohol
PhydChem
Properties
Hydrolysis
Photodegradation
and
AtmospheiicTransport
Biodegradation
(
aerobic
and
anaerobic)
Sorption.
Processes
EtFOSE
alcohol
Bimcentradlon
J
c
.
PFQS
Bioconcentration
Initlation
Dates
Complete
lQ2000
?
Q
2000
?
Q
1999
IQ
1999
IQ
1999
2Q
1999
2Q
2000
4Q
2000
Estimate
Release8
3M
Plant
Effluent
81
Process
Waste
Analyses
I
Q
1999
Estimate
Mfg,
Supply
Chain,
&
Use
Waste
Streams
Estimate'
Waste
Releases
IQ
1999
FC
Thermal
Destructability
2Q
1999
Complete
Characterize
Dlstrlbution
ln
Envimnment
Bird
8,
Fish
Analyses
U.
S.
Bird
Livers
Analyses
Biosphere
Sampling
Pan
Multimedia
Modeling
Muiti­
cities
study.
Complete
Complete
iQ
4999
la
2000
i
Q
1999
Estimate
Exposure
Carpetstudy
Paper
and
P@
caging
Studios
Ekposure
Scenarios
2Q
1999
IC?
1099
24
1999
Ecotoxicity
Daterminations
PFOS
Acute
Eootoxicity
PFOS
Chronic
Ecobxicity
EtFOSE
alcohol
Acute
Emtoxicity
EifOSE
alcohol
Chroniq
Ecotoxicity
FOSA
Acute
Ecotoxicity
FOSA
Chronic
Ecotoxicity
1Q
1999
2Q
1999
29
2000
.3Q
2000
1Q2000
2Q
2000
'
47
1'
.
.
'
'
'
"
.
..
.(
.
.
.
.
,
'
T­
n"
pT'.,".""*
......
..
.....
...
.
.
.
,
:
.
I
.
,
.
.
.
.
_
_
_
.
,.,
..
,
WY.
­>
am
.
1.
1
..
,
11.2
Component
I:
Chamcterize
Feb
and
T'nbparL
Pmperi;
fes
This
component
was
developed
in
three
steps.
First,
the
important
fate
and'transpo;
m
c
c
W
m
wcm
identifid.
Next,
priorides
were
set
for
tesdng,
with
the
likely
degradation
products
having
the
highest
priority
for
tesfipg.
Finally,
methods
and
laboratories
were
selected
to
do
the
testing.
For
sulfonated
perfluorochedds
not
tested,
models
are
being
developed
that
wiU
predict
physical
and
chemical
properties.
The
specific
research
projects
underway
are:
.
_

1.
Physical
and
chemical
properties
testing.
2.
Hydrolysis
testing.
3.
Photodegradation
and
atmospheric
transport
teding.
4.
Anaerobic
and
aerobic
biodegradation
testing.
5.
Soil
and
sediment
sorption
testing.
6.
Bioconcmtxatioon
testing.

77.3
Component
2:
Estimate
Releases
This
component
was
also
developed
in
s
e
v
d
stages.
First
product
sales
data
h
r
n
1997
were
used
to
identify
a
study
set
of
products.
The
study
set
was
based
on
volume
of
use
and
wqste
streams,
mqde
of
release
and
product
chemistry.
Next,
evaluation
efforts
of
the
waste
streams
generated
focused
OB
those
study
set
products
sold
by
3M
in
the
gremst
quantities
in
the
United
States.
Commercial
and
residential
uses
of
these
prcdu~,
including
transportation,
handling
and
appiication
during
the
supply
chains
that
lead
to
product
use,
were
examined.
Additionally,
the
releases
likely
to
result
h
m
disposal
during
these
portions
of
the
products'
life
cycles
weze
also
estixnated.
The
estimates
included
disposal
via
incineration,
landfilling
and
wastewater
treatmest.

Waste
streams
genqtexi
at
the
start
of
the
products'
life
cycles,
i.
e.
the
manufiicmhg
process,
were
also
examined.
Better
estimates
are
contintiiug
to
be
developed
of
waste
streams
occurring
during
the
Illan­
process.

f7A
Component
3:
Characfenize
Didbution
in
the
Environment
This
component
is
distinguished
by
iterative
interaction
between
modeling
and
field
sampling.
Models
are
being
used
to
suggest
sampling
locations
and
detection
limits.
Field
sampiing
is
planned
to
obtain
empirical
data
to
validate
mode1
output
and
hprove
predictions.
As
new
data
become
available,
research
projects
become
more
refined
and
focused.
The
research
projects
completed
or
planned
to
characterize
environmental
distribution
include:
,
r
48
.__
c_
­.
.
.
.
..
..
..
.
.
.
.
.
...
._.&..
I
..
......
I.
1.
Field
samphg
of
environmental
media
near
the
Decatur
manufacaning
plant.
2.
Screening
of
eagle
and
albatross
plasma
and
fish
tissue
from
archived
samples.
3.
Analysis
of
wild
bird
livers.
4.
Biosphcrc
sampling
plan
to
dctaminc
lcvclj
in
biota
of
diff'nt
geographic
locations.
5.
Development
of
a
mdtimda
model
for
predicting
distribution.
6.
Multi­
cities
studies
in
which
cities
of
a
similar
SiZR
are
paired,
one
demonsbating
sigdficant
manufhctmhg
or
commercial
uses
of
sulfonated
perfluorochdcals,
the
other
having
no
identifed
use
of
sulfonated
perfluorochemicals.
_
.

f1.5
Cqmponent
4:
Estimate
 ?
rposunr
When
data
from
the
release
and
Wbution
cpmponents
are
avrtilabb,
hypotheses
will
be
developed
about
important
exposure
pathways.
Iterqtive
sclmpling
and
modeling
will
be
used
to
test
these
hypotheges
and
to
detenrrine
the
important
exposure
pathways
to
be
used
in
risk
assessment.
The
research
projects
planned
to
estimate
exposures
are:

1.
carpet
releases
and
links
to
ingestion,
inhalation
and
dennal
exposure.
2.
Paper
and
packaging
studies
and
ingestion
exposure.
3.
Exposure
scenarios
m
c
h
combine
information
from
the
release,
f&
te,
and
sampling
studies.

12.0
Ecotoxicity.
Determinations
In
conjunction
with
the
studies
described
in
the
four
component
plan
described
above,
3M
is
conducting
ecotoxicological
studies.
Ecotoxicological
studies
arellsed
to
estimate
hazard.
Initial
ecotox
testing
is
focusing
on
PFOS,
EtFOSE
alcohol.
and
FOSA.
The
results
of
the
release,
distribution
and
expome
assessments
may
provide
reasons
to
test
more
substances.

The
following
research
projects
on
ecotoxicity
m
planned
or
underway:

1.
Aquatic
acute
UIXIclty
studies:
sewage
microorganisms,
freshwater
and
marine
algae,
duckweed,
daphnia,
mysid
shrimp,
kshwater
mussels,
fathead
minnows.
_
_
2.
Terrestrial
acute
toxicity
studies:
mallard
duck
and
bobwhite
quail
dietary
exposure
studies,
earthworm
toxicity
studies,
and
green
plant
growth
and
uptake
studies.
3.
Aquatic
chronic
toxicity
studies:
oyster
shell
deposition,
daphnia,
mysid
shrimp,
frog
embryo
development
and
fish
early
life
stage
studies.

49
I
.

4.
Terrestrial
chronic
toxicity
studies:
mallard
duck
and
bobwhite
quail
reproduction.

13.0
Ecological
Risk
Evaluation
Evaluating
ecologkd
risk
is
mom
complex
anclrnore
u
n
d
than
assessment
of
human
heal*
risks
whme
a
clearer
connection
can
be
dram
between
dose
and
response.

L
As
this
comprehensive
science
and
exposure
assessment
pmgram
progresses,
a
framework
in
which
ecological
d9k
catl
be
evaluated
wiU
be
developed.
The
evaluation
of
ecological
risks
and
human
risks
will
both
use
information
about
distribution
in
the
envjronmenf
and
exposure^
gemrated
by
this
comprehensive
exposure
plan,
Because
of
­.
the
scope
and
magnitude
of
the
overall
program,
aspects
of
the
knowledge
gained
will
be
compartmentalized
into
discneet
elements
to
create
this
Wework.
For
example,
as
data
on
ecotoxicologid
prope'rties,
fate
and
ttmsport
mechanisms,
and
environmental
clisuibution
art:
devdoped,
they
will
be
used
to
evaluate
ecolo@
cd
risk
within
a
certain
geographic
area
or
localiry.
The
science
data
and
environmental
sampling
results
will
be
applied
to
a
very
speciiic
area
and
set
of
species
to
evaluate
relative
risks
in
that
area.
Building
a
number
of
these
compartmental
evaluations
will
fesult
in
a
much
more
complete
picture
of
ecological
risk.
This
evaluation
will
identi@
additional
actions
3M
could
talc@
to
minimiZe
themleases
of
sulfonatedperfluorachemicats.

50
14.0
References
i
1.
Coben,
J.
J.
and
Covello,
V.
T.
Risk
M
y
s
i
8
:
A
Guide
to
Principfes
and
Metho&
for
Analyzm
*
g
Health
and
EavimnmentalRisks,
U.
S.
Council
on
Environmental
Quality,
ExecutEve
Office
of
the
President,
1989
­..
­
.
­

2.
Fate,
Transport
and
Tdormation
Test
Guidelines.
Office
of
Preventiow
Pesticides
and
Toxic
Substances
(
OPPTS)
835.21
10,
Hydrolysis
as
a
Function
of
pH
and
Temperature,
EPA
7124­
98­
057,
Jauuary
1998.

3.
Flynr~
RL.
in
``
Mustrial
Applications
of
Organochlorine
Compounds,"
P
r
o
c
~
s
of
the
Symposium
on
Electrochemistry
in
the
Preparation
of
FIuorine
a
d
Its
Compounds,
Childs
and
F~
Bgami,
EMS,
The
Electrochemical
Society,
Inc.:
Pennington,
NJ,
1997;
97­
IS
51.

4.
Guidelines
for
the
Testing
of
Chemicals,
vol.
1,
Section
1,
"
Physical
Chemical
Properties,"
Organisation
for
Economic
Co­
operation
and
Development
(
OECD),
Paris,
France.

5.
Guidelines
for
the
Testing
of
Chemicalsz
vol.
1,
Section
2,
`
Zffects
on
Biotic
syitems,"
Organisation
for
Econorm
`
c
Cwperation
and
Development
(
OECD),
Paris,

6.
Key,
B.
L.;
Howell,
RD.;
Criddle,
C.
S.
"
FluoFinated
Organics
in
the
Biosphere,)'
Emiron.
Sei.
Tecbol,
1997,31:
244­
2454"

7.
Key,
B.
L.;
Howell,
Rb.;
Griddle,
C.
S.
"
Defluorination
of
Organofluorine
Sulfur
Compounds
by
Pseudomonas
Sp.
Strain
D2,"'
Emiron
Sci.
Techno!,
1998,32:
2283­
2287.

8,
Mackay,
D.
SKU,
W.
Y.,
and
Ma,
K.
C.,
lllustrarted
Handbook
of
Physical­
Chemical
Properties
and
Envitonmental
,
Fate
for
Or~
anic
Chemicals.
Volume
I:
Monoaromafic
Hydrocarbons,
Chlorobenzcnes
and
PCBs.
Lewis
Publishers,
Chelsea,
MI.
1992.

9.
Scholz,
N.,
"
Ecotoxiwlogy
of
surf8ctants,"
Tenside
Swfactmts
and
Detergents,
1997,
34~
229­
32.
.
.
.

51
.
I
.
*.
"?­
.
.­:
..
.
..
_.
_.
.
.
..
,
.
.
.
..
..
.
...
,
.
.
..
.
.
.
.
.
..
.
.
~­'­
..
.
L
Cro
,
i
..­
7..
.
.­..
7.
ITII.
T
,­''.,_..
.
.
...
.
.
.
6
.
1..
I
I
­
.
.
.
.
..
.
­
