Document ID: EPA-HQ-OPPT-2002-0051-0022
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2006-03-07T05:00Z

PHOTODEGRADATION
TEST
SUBSTANCE
­Identity:
Petiuorooctanoic
acid,
ammonium
salt;
may
also
be
referred
to
as
PFOA
ammonium
salt,
Ammonium
perfluorooctanoate,
PFO,
FC116
FC­
126,
FC­
169,
or
FC­
143.
(Octanoic
acid,
pentadecafluoro
ammonium
salt,
CAS
#
3825­
26­
l)

Remarks:
The
test
substance
used
was
14C
labeled
(358
dpm/
pg).
It's
purity
.
was
not
sufficiently
characterized,
though
current
information
indicates
it
is
a
mixture
of
96.5
­
100%
test
substance
and
0
3.5
CS,
CT,
and
Cg
pefluoro
analogue
compounds.
This
testing
is
currently
being
repeated
using
current
procedures
and
best
available
practices.

METH6D:

Method/
guideline
followed
:
Procedure
as
described
in
the
Federal
Register
(Volume
43,
No.
132­
Monday,
July
IO,
1978)
by
the
U.
S.
Environmental
Protection
Agency.
Type
(test
type):
Sirr&
lated
sunlight
GLP
(Y/
N):
No
Year
completed:
1
979
Light
Source:
General
Electric
F­
40BL
fluorescent
black
light
Light
Spectrum
(nm):
Max
output
at
­360
nm
and
essentially
no
output
below
300
nm.
Spectral
energy
characterized
from
290­
600
nm.
Intensity:

Wavelength
Watts
Radiated
290
­
300
0.090
310
­
320
0.235
400­
500
*
I
2.300
I
I
500
­
600
0.340
I
Spectrum
of
substance
(max
lambda,
max
epsilon
and
epsilon
295):
Not
determined.
.

The
test
solution
was
created
by
dissolving
140.0
mg
of
the
test
substance
in
2.8
liters
of
distilled
water.
The
resulting
solution
had
a
specific
activity
of
17,320
dpm/
mL
(0.0078
pC/
mL).

I­
­.­
.
.
_.
­
_­.__
Remarks:

­
Test
medium:
Distilled
water
­
Duration:
30
days
­
Positive
Controls:
None
­
Negative
Controls:
None
Photolyzate
samples
were
collected
after
irradiation
intervals
of
0,
1,
3,
7,
15,
and
30
days.
Samples
were
analyzed
using
a
Liquid
Scintillation
Counter
(LSC),
TLC­
Autoradiograph
and
Gas
Chromatography.

RESULTS
Concentration
of
Substance:
50
mg/
L
Temperature
"C:
2252°
C
`Degradation
%:
0%
after
30
days
Remarks
field:
No
photodegradation
of
the
test
substance
was
detected
in
this
study.
Essentially
the
same
analysis
results
were
obtained
for
the
30­
day
photolyzate
sample
(no
photoproducts
formed)
as
the
O­
day
sample.

Radiocarbon
assays
at
0
and
30
days
also
indicate
no
significant
amount
of
product
was
volatilized
during
the
study.

CONCLUSIONS
No
photodegradation
products
were
detected
in
this
study
using
simulated
sunlight,
indicating
the
test
substance
does
not
undergo
photolysis.

Submitter:
3M
Company,
Environmental
Laboratory,
P.
O.
Box
33331,
St.
Paul,
Minnesota,
55133
DATA
QUALITY
.Reliabillty:
Klimisch
ranking
2.
Testing
meets
the
criteria
for
quality
testing
at
the
time
it
was
conducted.
However,
sample
purity
was
not
properly
characterized.

REFERENCES
3M
Technical
Report
"FC­
143
PHOTOLYSIS
STUDY
USING
SIMULATED
SUNLIGHT."
J.
W.
Todd,
Project
9776750202,
Report
number
002,
February
2,
1979
OTHER
Last
changed:
5/
24/
00
IOlO
1
2­
2­
79
!31[
1
.
.
.

.
For&
674FtGA
.'
TECHNlCAi
REPORT
SlJMRdikY
To:
&NW
CWMUNlCNlWE
CENTER
­
20%
2CN
OlviJon
'Commercial
Chemicals
Division
­
Agrichemical
Project
moo+
Numbor
3068
rroillct
Service
to
TOSCA
F­
N
&

R@
Port
two
9r77&?
0202
Rafmrt
Numbor
FC­
143
PHOTOLYSIS
STUDY
USING
SIMULATED
SUNLIGHT
002
:
T
o
R.
A.
PROKOP
a.
.
.

AUttWW
3.
W.
TODD
E~
PIOY~
NumWW
kotobook
m
43953
Agrichemical
Request
994
No.
ol'w
~~­
k
­N
13
SECURlW)
n
KEYWORWI
&Wct
twnu
from
3M
Tbeaurw.
su&
jat
otbr
wPk8bl4tumr)

uto/
Radiography
ecomposition
nvironment
as­
Chromatography
ayer/
Chromatogrwhy
hotolysis
adiotracer
cintillation
Information
Liriron
I*­=
Investigate
the
photolyic`
stability
of
FC­
143
as
a
function,
of
irradiation
time
and
identify
any
majbr
photoproducts.

WOW
A8SlRAC'T:
(206260
words)
Thir
abstract
informtion
is
distributed
by
tf~
fir
Twhnical
Communications
&ntu
o
hrt
3wm
to
CQmplrnV
R&
D.

Irradiation
of
a
50
ppm
aqueous
solution
of
FC­
143
for
30
days
resulted
in
no
detected
photoproducts
on
analysis
by
thin­
layer­
chromatograpy/
radioautography,
and
by
gas
chromatography
of
derivatized
samples.
The
irradiation
source
produced
300
nm
and
longer
wavelength
ultraviolet
light
to
simulate
natural
sunlight.
.
.
.
.

G034;
54
.
.
­.
.
.

FC­
143/
pHOTOLYSIS
STUDY
USING
SIMULATED
SUNLIGHT
INTRODUCTION
It
is
generally
acknowledged
that
manufactured
chemicals
may­
find
their
way
into
the
environment
in
various
degrees
and
by.
various
means.
Once
in
the
environment
they
may
be
destroyed
or
chemically
altered
by
the
action
of
sunlight
(Crosby
and
Li,
1969).
This
study
investigated
the,
'possible
photodegradation
of
FC­
143
in
distilled
.water
on
exposure
to
simulated
sunlight
(Kohler,
1965).
This
study
was
conducted
essentially
as
recommended
by
the
Environmental
Proeckion
Agency
(Federal
Register).

EXPERIMENTAL
1.
Sample
Materials
FC­
143
is
the
ammonium
salt
of
perfluorooctanoic
acid.

C7F15COONH4
The
major
component
is
the
straight­
chain
C7
but
some
branched
chain
isomers
and
other
homologs
also
are
present.

FC­
143
Water
Solution.

A
50
ppm
solution
of
FC­
143­
14
C
(358
dpm/
pg)
was
prepared
by
dissolving
140.0
mg
of
FC­
143
in
2.8
liters'of
distilled
water.
The
resulting
solution
had
a
specific.
activity
of
17,320
dpm/
ml
(O.
O078./~
C/
ml).

2.
Analysis
Instruments/
Materials
Liquid
Scintillation
Counter
(LSC)
Nuclear­
Chicago
Mark
I
Rotary
Evaporator
B'u'chi
Rotovapor
R
Kuderna­
Danish
Concentrator
10
ml
concentrator
tube
­
Kontes
NO.
K­
570050
Reflux
column
­
Kontes
No.
K­
569251
Heated
water
bath
GO3655
.
.
.
.
II
­2­

Thin
Layer
Chromatography
(TLC)
plates
MERCK
Silica
Gel
60
F­
254;
0.25
mm
thickness
and
20
x
20
cm
size
'
1st
developing
solvent­
ethyl
acetate/
methanol/
water,
75/
15/
10
2nd
developing
solvent­
methyl
ethyl
ketone/
chloroform/
acetic
acid,

55/
30/
15
X­
Ray
Film
KODAK
NS­
2T,
8
x
10
inch
size
Gas
Chromatography
System
(GC)
.
Gas
Chromatograph
­
Hewlett­
Packard
Model
5840
Column
­
6
ft
l/
8
in
od
stainless
steel
packed
with
20%
DC
200
silicone/
lO%
BENTONE
34
on
Carrier
gas
ANAKROM
ABS
(lOO/
llO
mesh)
­
Argon/
methane,
9515
Column
temperature
­
8O*
C
for
4
minute
programed
to
180
at
SOC/
min.
Injection
part
­
on
column,
18O*
C
Detector
­
electron
capture,
300"
C
Sample
injection
­
1~~
1
via
10
cl1
microsyringe
­.
'

D
I
A
Z
A
L
D
DIAZALD
is
Aldrich
Chemical
Company's
trade
name
for
N­
methyl­
N­
nitroso
p­
toluenesulfonamide,
It
is
used
to
prepare
diazomethane,
an
analytical
reactant
chemical.

Diazomethane
solution
­
Alcohol
Free.

Diazomethane
(DAM)
was
used
to
convert
acidified
FC­
143
into
its
corresponding
methyl
ester
just
prior
to
gas
chromatographic
analysis.

C7F15COOH
+
CH2N2
­
C7F15COOCH3.
+
N2
(FC­
143
acid)
(DAM)
(FC­
143
methyl
ester)

The
DAM
reagent
used
must
be
free
of
alcohols
or
the
desired
reaction
product
will
not
form
or
will
degrade
after
it
has
formed.
T
h
e
alcohol­
free
DAM
was
prepared
essentially
.as
recommended
by
Aldrich:

A
solvent
mixture
consisting
of
35
ml
of
2­(
2­
ethoxyethoxy)­
ethanol
and
20
ml
of
diethyl
ether
was
added
to
a
solution
of
6
grams
of
potassium
hydrozide
dissolved
in
10
ml
of
water.
This
mixture
was
c4x3656
.
placed
in
a
100
ml
long­
necked
distilling
flask
fitted
with
a
dropping
funnel,
an
efficient
condenser
and
a
water
bath
at
7OOC.
As
the
distillation
of
the
ether
started
a
solution
of
21.5
g
of
DIAZALD
in
about
200
ml
of
ether
was
added
through
the
dropping
funnel
over
about
20
minutes.
The
etheral
DAM
solution
was
collected
in
a
250­
ml
Erlenmeyer
flask
cooled
in
an
ice
bath.
The
flask
contents
were
transferred
into
a
bottle,
a
bottle,

sealed
with
a
TEFLON­
lined
cap
and
stored
in
a
freezer.
'

3.
Irradiation
The
preparative
photoreactor
used
(Crosby
and
Tang,
1969)
is
.
illustrated
in
Figure
1.
The
lamp
employed
was
a
General
Electric
F­
40BL
fluorescent
black
light
with
maximum
output
at
about
360
nm
and
essentially
no
output
below
300
nm
(.
Table
I,
General
Electric
Co.).
The
temperature
was
controlled
at
22
2
2OC
by
circulating
tap
water
through
flexible
plastic
tubing
wrapped
around
the
reaction
chamber.
Air
was
passed
through
the
photolysis
solution
at
10
q
l/
rein
for
oxygenation
and
mixing.
The
exit
port
was
connected
to
a
vapor
trap.
The
trap
consisted
of
a
6
x
3/
4
in.
glass
tube
containing
first
XAD­
2
resin
and
then
charcoal.
The
photolyzate
was
sampled
after
irradiation
intervals
of
0,
1,
3,
7,
15
and
30
days.
The
samples
were
removed
through
the
reactor
drain
port
and
were
refrigerated
until
analyzed.

4.
Radiocarbon
Recovery
The
photolyzate
samples
were
assayed
for
radiocarbon
by
LSC
to
determine
radiocarbon
recovery
as
a
function
of
irradiation
time.

Similar
results
were
obtained
for
all
samples.
Results
for
the
30
and
O­
day
samples
are
presented
in
Tables
II
and
III,
respectively.

5.
Investigation
for
Photoproducts
by
TLC­
Autoradiography
Aliquots
of
the
30
and
O­
day
photolyzates
were
reduced
in
volume
loo­
fold
before
TLC
analysis.
First
a
loo­
ml
aliquot
of
each
sample
was
'
concentrated
to
about
5
ml
using
a
rotary
vacuum
evaporator
with
with
a
4OGO*
C
water
bath,
50
ml
of
acetonitrile
was
added
and
the
rotovac'ing
continued
to
just
dryness
(Acetonitrile
was
added
to
expeditiously
remove
remaining
water
as
an
azeotrope
and
thereby
minimize
possible
lo&
s
of
radiocarbon).
The
sample
solids
were
dissolved
in
3
ml
of
methanol
and
c4mx57
­4­

I.
.

quantitatively
transferred
into
a
Kuderna­
Danish
concentrator
tube
with
two
additional
3­
ml
washings.
Peflux
tubes
were
attached
and
the
concentrator
tubes
were
immersed
in
a
65­
74'C
water
bath.
The
tube
contents
were
concentrated:
to
exactly
1
ml.

A
10.0
t\
l
aliquot
of
each
sample
concentrate
(equivalent
to
1.0
ml
of
the
original
photolyzate
solution)
was
transferred
onto
a
TLC
plate
using
a
10
pl
microsyringe.
Each
plate
was
developed
two­
dimensionally,
first
with
ethyl
acetate/
methanol/
water
(75/
15/
10)
and
then
with
methyl
ethyl
ketone/
chloroform/
acetic
acid
(55/
30/
15).
The
air­
dried
TLC
plates
were
then
radioautographed.
Figures
2
and
3
are
pictures
of
the
30
and
0­
day:
radioautographs,
respectively.

Various
component
spots
and
areas
on
each
TLC
plate
were
quantitated
for
radiocarbon
by
carefully
scraping
the
silica
gel
from
the
plates
and
LSC.
The
results
are
presented
in
Tables
II
and
III.

6.
Investigation
for
Photoproducts
by
Gas
Chromatography
Perfluorocarboxylic
salts
as
FC­
143
are
not
directly
analyzable
by
gas
chromatography
but
can
be
analyzed
if
acidified
and
methylated
with
DAM.
The
30
and
O­
day
photolyzate
samples
were
analyzed
by
this
method
(3M
Central
Research
Laboratory).
The
procedure
used
is
summarized
below:

Four
ml
of
photolyzate
solution
was
pipetted
into
a
4­
dram
vial
and
acidified
with
0.4
ml
of
concentrated
hydrochloric
acid.
The
resulting
samples
acids
were
quantitatively
extracted
with
two
2­
ml
portions
of
diethyl
ether.
The
ether
extracts
were
combined
in
a
calibrated
lo­
ml
centrifuge
tube.
One
ml
of
DAM
solution
was
added
and
the
sample
allowed.
to
react
for
15
minutes.
Excess
DAM
was
then
removed
by
purging
the
tube
contents
with
a
nitrogen
jet
until
the
yellow
DAM
color
was
almost
gone.
The
sample
solution
was
then
diluted
to
exactly
5
ml
with
diethyl
ether,
and
analyzed
immediately
to
minimize
possible
degradation
due
to
any
instability
of
the
sample
derivative.

The
chromatograms
for
the
30
and
O­
day
photolyzate
samples
are
presented
in
Figure
4.
­5­
(

*
`.

However
several
less
obvious
parameters
are
important:
The
DAM
soultion
should
be
freshly.
prepared,
preferably
the
same
day
it
is
used.
Several
injections
of
sample
may
be
necessary
to
passivate
the
column
before
accurate'and
repeatable
results
are
obtained.

RESULTS
No
photodegradation
of
FC­
143
was
detected
in
this
study.
Essentially
the
same
analysis
results
were
obtained
for
the
300day
photolyzate
sample
(no
photoproducts
formed)
as
the
O­
day
sample,.

The
30
and
O­
day
photolyzates
had
similar
radiocarbon
assays
(Tables
II
and
III)
so
no
significant
amount
of
radiocarbon
was
volatilized
during
the
photolysis
and
so
the
contents
of
the
vapor
trap
were
not
analyzed..
Radiocarbon
recoveries
after
sample
concentration
were
good
.for
the
3b­
day
photolyzate
(99%).
but
l'ess
desirable
for
the
O­
day
sample
dure
to
physical
loss
(86%).
A
repeat
concentration
of
the
O­
day
sample
was
not
done
since
it
is
important
only
as
a
TLC
reference.

Similar
TLC­
radioautographs
were
obtained
indicating
no
change
in
composition
of
the
30­
day
sample
compared
to
the
O­
day
sample
(Figures
2
and
3).
Quantitative
measurement
of
radiocarbon
in
various
TLC
spots
and
background
areas
show
similar
radiocarbon
distribution
and
good'recovery
for
the
30­
day
sample
(Tables
II
and
III).

Similar
gas
­chromatograms
were
obtained
further
confirming
the
same
composition
of
the
30
and
O­
day
samples
(Figure
4).

J.
W.
Todd
i
­6­

.

REFERENCES
Crosby,
D.
G.
and
Li,
M.
1969.
Herbicide
Photodecomposition,
Chapter
12:
321­
363
in
Degradation
of
Herbicides,
Kearney,
P.
C.
and
Kaufman,
D.
D.
Ied),
Marcel
Dekker
Inc.
New
York,
394
p.

Crosby,
D.
G.
and
Tang,
C.
S.,
3.
Agric.
Food
Chem.,
17,
1041,
(196g).,
'

Federal
Register,
Volume
43.
No.
1320Monday,
July
10,
1978.

:

General
Electric
Company,
Lamp
Division,
Cleveland,
OH
.44112.

Keller,
L.
R.
1965.
Ultraviolet
Radiation,
2nd
Ed.
Wiley,
New
York.

312
p.

3M
Central
Research
Laboratory,
Analytical
Request
A­
70732.
.
­
.

Figure
1
­
Photoreactor
.
­7­
.

bulb
GO3661
T
a
b
l
e
I
­
spcctr.
rl,
Eneqy
Dibtribution
f
o
r
a
G
E
FGOBL
B
l
a
c
k
Lignt
hlb
290
­
300
380
­
400
400
­
500
500
­
6
0
0
Watts
Radiated
0.090
0.235
I
.410
)19&
O
4miiuR
tntenaity
<
2.310
Lt
Lt
about
360
nR
I
1.680
2,300
i
0.340
­90
r
Table
II
­
Radiocarbon
recovered
in
300Day
Photolyzate
Solution
and
TLC
Plate
Scrapings
'FIGURE
2)

Sample
Solution
R
e
l
a
t
i
v
e
%
DPM/
ml
17,320
10
Cd
TLC
Plate
Scrapings
Area
Description
DPM(
per
ml)*
%
Recovery
1
FC­
143
16,643
>
97
2
Origin.
66
0.4
I
3
Vackgrounda
288
1.7
Total
16,997
99.1
*
The
amount
of
14C
rad'ibactlvity
on
the.
plate
is
equivalent
to
1
ml
of
the
original
photolyzate
solutfon.
_

Table
III
­
Radiocarbon
recovered
in
O­
Day
Photoyzate
Solution
and
TLC
Plate
Scrapings
`FIGURE
3)

Sample
Solution
TLC
Plate
Scrapings
DPM/
ml
Relative
96
Area
Description
DPM(
per
ml)*
%
Recovery
16,643
10
Cd
1
FC­
143
14,493
84.

2
Origin.
43
0.2
3
llBackgroundtV
222
1.3
Total
14,758
85.5
*
The
amount
.of
14C
radioactivity
on
the
plate
is
equivalent
to
1
ml
of
the
original
photolyzate
solution.

­­
"­
.
­
.
.

loFigure
2­
Photograph
of
TLC
Radioautograph
30
Day
FC­
143
Photolyzate
Reference
Sam
les
50
fig
FC­
143­
P
4C
3
ot
photolyze
FC­
143
0
2
Origin
0
3
Background
(All
areas
less
spots
1
and
2)

DS­
1
=
Developing
Solver,
t
I'll,
75/
15/
10
ethyl
acetate/
methanol
/water,

DS­
2
=
Developing
Solvent
02,
methyl
e.
thyl
ketone/
chloroform/
acetic
acid,
55/
30/
15
.

I
1

ll
.*

Fgiure
3­
Photograph
of
TLC
Radioautograph
O­
Day
FC­
143
Photolyzate
DS­
2
­/

1
I
7
Re
50
17
GL
0
.ference
Sample
pg
FC­
143­
14C
'C­
143
s
0
2
Origin
0
3
Background
(All
area
less
spots
1
and
2)

D&
l
=
Developing
Solver,
t
81,
ethyl
acetate/
methanol/
water,
75/
15/
10
DS­
2
=
Developing
Solvent
62,
methyl
ethyl
ketone/
chloroform/
acetic
acid,
55/
30/
15
b
&
s
l
’
*
.
Figure
4
­
Gas
Chromatogram
of
Derivatized
Photolyzate,
Samples.,

30­
Day
Sample
O­
Day
Sample
43
0
w
63
cn
m
I
/.

Retention
Time
in
Minutes
,­
Retention
Time
in
Minutes
­w