Document ID: EPA-HQ-OPPT-2002-0051-0012
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2006-03-07T05:00Z

Voluntary
UEIP,
Ammonium
Perfluorooctanoate
Voluntary
Use
and
Exposure
Information
Profile
Ammonium
Perfluorooctanoate
(APFO)

I.
CHEMICAL
IDENTIFICATION
Chemical
Name:
Ammonium
Peffluorooctanoate
CAS
Number:
3825­
26­
l
II.
COMPANY
IDENTIFICATION
Company
Name:
E.
I.
du
Pont
de
Nemours
and
Company
Site
Locations:

Site
where
APFO
is
used
as
a
reaction
aid:

Washington
Works
Route
892
Washington,
WV
26
18
1
Sites
where
APFO
containing
products
made
at
Washington
Works
are
processed:

Parlin
Plant
Cheesequake
Road
Parlin,
NJ
08859
Spruance
Plant
5401
Jefferson
Davis
Hwy.
Richmond,
VA
23234
Site
which
disposes
of
waste
containing
APFO:

Chambers
Works
Rte.
130
Deepwater,
NJ
08023
Technical
Contact:
Robert
F.
Pinchot
(302)
999­
4074
DuPont
Fluoroproducts
Chestnut
Run
Plaza
Bldg.
71
l/
2210
Centre
Boulevard
Wilmington,
DE
1980507
11
2
3
,­­
­
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
,
.

III.
DUPONT
AND
CUSTOMER
ACTIVITIES
Narrative
Description
of
APFO
Use
The
block
diagram
on
the
back
page
titled
"DuPont
US
APFO
Balance"
describes
the
processes
discussed
below.

DuPont
uses
APFO
as
a
reaction
aid
in
the
production
of
polytetrafluoroethylene
(PTFE)
and
tetrafluoroethylene
(TFE)
co­
polymers.
The
process
utilized
at
DuPont's
Washington
Works
for
making
PTFE
and
co­
polymers
consists
of
polymerizing
TFE
(and
other
co­
monomers
if
desired)
in
an
aqueous
media
with
a
small
amount
of
APFO
to
aid
in
the
reaction.

Following
the
polymerization
step,
the
polymer
dispersion
is
either
dried
to
remove
water
and
APFO
or
concentrated
(removing
some
of
the
APFO),
stabilized
and
sold
as
an
aqueous
dispersion.
The
dried
polymer
contains
very
little,
if
any,
APFO.

The
APFO
removed
from
the
polymer
is
recovered
for
recycle,
captured
and
destroyed
off
site
in
an
incinerator,
captured
and
sent
to
an
offsite
industrial
landfill,
and/
or
emitted
to
air
or
water
at
the
Washington
Works.

The
stabilized
polymer
dispersions
are
sold
by
DuPont
to
industrial
customers
(both
in
the
US
and
outside
the
US)
for
a
variety
of
uses,
internally
transferred
to
the
DuPont
Spruance
Plant
for
the
production
of
Teflon@
fibers
and
PTFE
coated
synthetic
fibers,
or
internally
transferred
to
the
DuPont
Parlin
Plant
for
the
production
of
Teflon@
Finishes.

A
small
amount
of
non­
hazardous
waste
polymer,
water,
APFO
and
other
additives
generated
at
Washington
Works
is
treated
in
a
wastewater
treatment
facility
at
DuPont's
Chambers
Works.
This
material
is
either
emitted
in
the
Chambers
Works
water
discharge
or
captured
on
carbon
and
landfilled
in
a
secure
landfill.

The
internal
process
at
the
DuPont
Spurance
Plant
to
produce
Teflon@
fibers
involves,
for
most
of
the
product,
a
"sintering"
step
in
which
the
APFO
contained
in
the
product
is
destroyed
by
the
following
reaction:
'

CFa(
CF&
COO­
NH4+
+
CF~(
CF&
CFZH
+
CO2
+NHs
This
reaction
goes
to
completion
at
350°
C
and
0.2s
residence
time.
A
small
amount
of
product
processed
at
DuPont's
Spruance
plant
does
not
get
sintered
and
thus
contains
a
small
amount
of
residual
APFO.
These
products
are
used
for
industrial
pump,
valve
and
compressor
packing
materials.

'
P.
J.
Krusic,
D.
C.
Roe,
"Thermal
decomposition
of
C8
fluorinated
surfactants
and
related
materials
studied
by
high
temperature
gas­
phase
"F
NMR.
A
new
Alternative
to
thermal
gravimetric
analysis,
DuPont
Internal
Report.
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
The
process
for
making
Teflon@
finishes
at
the
DuPont
Parlin
Plant
involves
a
blending
operation
of
fluoropolymer
dispersions
with
other
additives
including
solvents,
binders,
and
pigments.
The
small
amount
of
APFO
emissions
to
water
from
this
facility
is
due
to
waste
generated
during
product
changeovers.
Some
of
the
fluoropolymer
dispersion
is
processed
at
contract
facilities
where
the
material
is
dried
at
temperatures
~350°
C
thus
destroying
the
APFO
according
to
the
reaction
above.
This
dried
material
is
then
incorporated
into
finishes
products.

The
final
product
produced
is
then
sold
to
applicators
that
apply
the
product
to
a
substrate
(such
as
cookware)
via
automated
spraying
or
rollercoating.
Emissions
of
APFO
from
these
operations
consist
of
overspray
that
is
either
captured
on
filters
and
landfilled
or
absorbed
into
water
resulting
in
a
water
emission.
Product
that
is
applied
to
the
substrate
is
then
typically
"sintered"
at
temperatures
approaching
800°
F
resulting
in
the
removal
of
the
APFO
from
the
substrate
and
subsequent
destruction
according
to
the
reaction
above.

Customers
of
dispersion
products
use
the
material
for
a
variety
of
applications.
However,
most
applications
involve
a
"sintering"
step
where
the
APFO
is
destroyed.
There
are
a
small
number
of
applications
where
the
customer
heats
the
dispersion
products
to
temperatures
that
allow
the
APFO
to
sublime
resulting
in
air
emissions.
There
are
also
a
small
number
of
applications
where
the
customer's
product
is
not
heated
resulting
in
the
APFO
staying
with
the
product.
These
applications
include
industrial
packings,
and
industrial
filter
fabrics.

IV.
SITE
RELEASE
AND
TRANSFER
INFORMATION
FOR
TRI
CHEMICALS
Not
applicable­
APFO
is
not
listed
on
the
TRI
V.
SITE
RELEASE
AND
TRANSFER
INFORMATION
FOR
NON­
TRI
CHEMICALS
A.
On­
site
Air
Releases
Estimated
Total
Annual
Releases
(
lbs.
1999)
Washington
Works
Parlin
Spruance
Chambers
Works
Fugitive
Negligible
0
0
0
Stack
(Point
Source)
24000
0
0
0
Comments
Air
emissions
are
estimated
using
engineering
calculations
and
judgements
and
limited
measurements
of
specific
point
sources
conducted
in
the
past.

4
5
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
B.
On­
site
Water
Releases
Point
Source
Estimated
Total
Annual
Releases
(
Ibs.
1999)
Washington
Works
Parlin
Smuance
Chambers
Works
5.5000
300
150
9500
Comments
Water
emissions
are
estimated
using
engineering
calculations
and
judgements
and
limited
measurements
of
specific
sources
conducted
in
the
past.

Washington
Works
emissions
occur
for
approximately
350
days/
yr
while
the
other
sites'
emissions
occur
for
lo­
100
days/
yr.
Releases
of
APFO
to
the
Ohio
River
from
the
DuPont
Washington
Works
Plant
were
modeled
using
the
Probabilistic
Dilution
Model
(PDM
Beta
Version
4.0
Beta
June
11,
1999,
US
EPA
Office
of
Pollution
Prevention
and
Toxics)
and
a
constructed
Microsoft@
Excel
spreadsheet
model.
APFO
release
data
for
1996
were
used
in
both
modeling
exercises.
2
The
PDM
indicated
that
APFO
concentrations
of
1
.O
ug
C8
L
would
be
exceeded
about
50%
of
the
time
during
the
year.
APFO
concentrations
of
in
the
river
would
exceed
0.1
pg
APFO/
L
90%
of
the
time
during
the
year
and
10
p,
g
APFO/
L
about
2.2%
of
the
time
during
the
year.

Average
annual
APFO
concentrations
in
the
Ohio
River
calculated
by
using
a
Microsoft@
Excel
spreadsheet
was
0.423
pg
APFO/
L.
Modeled
AFPO
concentrations
in
the
river
ranged
from
a
low
of
0.199
pg
APFO/
L
in
March
to
a
high
of
0.965
pg
APFOC­
8/
L
in
September,
which
correspond
to
high
and
low
river
flows,
respectively.
Average
Ohio
River
flows
and
volume
data
calculated
from
the
US
Geological
Survey
was
collected
at
the
Belleville
Dam
and
used
in
the
spreadsheet
model.
The
Belleville
Dam
is
on
the
Ohio
River
13
miles
downstream
of
the
Washington
Works
Plant.
This
river
flow
data
is
the
closest
location
downstream
from
the
plant
where
this
type
of
information
is
available.

In
1999
a
drinking
water
sample
obtained
from
GE
plastics,
Washington
WV,
immediately
downstream
on
the
Ohio
River
from
DuPont
Washington
Works
showed
0.552pg/
l
APFO.

In
addition
samples
obtained
in
January
2000
from
three
different
wells
at
the
Lubeck
Public
Service
District,
downstream
of
Washington
Works
on
the
Ohio
River,
showed
0.8yg/
l,
0.44pg/
l
and
0.3
13
pg/
l.
APFO.

'
W.
R.
Berti,
Modeling
releases
of
ammonium
perfluorooctanoate
into
the
Ohio
River,
DuPont
Internal
Report
EMSE­
054­
00.

5
6
Voluntary
UEIP,
Ammonium
Peffluorooctanoate
C.
On­
Site
Land
Releases
Chambers
Works
treats
APFO
containing
waste
in
a
wastewater
treatment
system.
Engineering
calculations
and
measurements
indicate
that
approximately
30%
of
the
APFO
in
the
wastewater
treated
is
absorbed
on
to
a
carbon
media
that
is
landfilled
on
site.
These
land
releases
are
estimated
to
be
39001b
in
1999.

Prior
operations
have
resulted
in
measurable
APFO
concentrations
in
three
landfills
operated
by
the
Washington
Works
in
West
Virginia.
At
Letart"
landfill
surface
water
measurements
in
1999
and
2000ytd
range
from
2.23p,
g/
l
to
324Op.
g/
l
with
an
average
of
1392ugll.
Groundwater
measurements
taken
during
the
same
time
period
at
Letart
landfill
range
from
60.3pg/
l
to
174OOpg/
l
with
an
average
of
2537pg/
l.
At
the
"local
landfill"
the
groundwater
concentrations
range
from
O.
O46pg/
l
to
39pg/
l
with
an
average
of
8.83pg/
l.
Surface
water
samples
at
the
"local
landfill"
range
from
0.54pg/
l
to
87p,
g/
l
with
an
average
of
18.5pg/
l.
At
Dry
Run
landfill
there
are
limited
measurements
of
groundwater
and
surface
water
with
maximum
concentrations
in
groundwater
of
15pg/
l
and
the
maximum
concentration
in
the
permitted
outfall
has
been
33kg/
l.

In
1999
a
RCRA
Facility
Investigation
was
completed
for
Washington
Works
and
was
submitted
to
EPA
Region
III
in
June
19994.
The
report
contains
data
on
groundwater
concentrations
of
APFO
at
Washington
Works.

D.
Transfers
to
Off­
site
Locations
Washington
Works:

Incineration
Wastewater
treatment
Underground
Injection
Hazardous
Waste
Landfill
Other
landfill
Recycle
or
recovery
Estimated
Total
Annual
Releases
or
Transfers
(lb.
1999)
16000
13400"
0
2600
0
IV.
ON­
SITE
WORKPLACE
EXPOSURE
A.
Information
on
the
Number
of
Employees
Potentially
Exposed
3
Maps
of
the
landfill
locations
and
specific
monitoring
locations
and
results
are
available
upon
request.
4
Report
was
submitted
to
Martin.
T.
Kotsch,
Remedial
Program
Manager,
EPA
Region
III,
Philadelphia.
'
This
is
the
same
material
that
was
described
above
in
paragraph
1
of
section
V.
D.

6
7
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
The
tables
below
describe
the
number
of
workers
that
may
be
exposed
to
APFO
during
their
normal
work
activities
for
each
of
the
three
sites
where
APFO
is
used
or
APFO
containing
product
is
processed.

Hours/
Day
co.
25
0.25
1
l­
8
>8
<lO
Washington
Works
Days/
yr
10­
100
100­
250
242
>250
Routine
worker
activities
that
have
potential
for
exposure:

9
Handling
raw
material
APFO
9
Handling
raw
dispersions
containing
APFO
9
Maintenance
of
polymerization
reaction
systems
9
Polymer
dryer
operation
and
maintenance
9
Packout
of
PTFE
and
co­
polymer
dispersion
products
.9
Operation
and
maintenance
of
APFO
recovery
systems
7
27
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
Parlin
Plant
Hours/
Day
<0.25
0.25­
l
l­
8
>8
<lO
10­
100
Days/
yr
100­
250
1
8
>250
Routine
worker
activities
that
have
potential
for
exposure:

>
Handling
of
PTFE
and
Co­
polymer
dispersion
products
>
Operation
and
maintenance
of
blending
facilities
&
Packout
of
finished
product
Note
that
at
no
time
is
the
material
handled
at
the
Parlin
Plant
at
an
elevated
temperature
where
the
APFO
could
sublime.
Therefore
there
is
little
potential
for
exposure
to
airborne
APFO
at
this
facility.
All
exposure
potential
is
through
skin
contact
during
handling
of
the
polymer
dispersion
materials
all
of
which
contain
<I%
APFO
with
most
containing
~0.25%
APFO.

Hours/
Day
co.
25
0.25­
1
1
­8
>a
cl0
Spruance
Plant
Dayslyr
10­
100
loo­
250
<IO
>250
Routine
worker
activities
that
have
potential
for
exposure:

>
Handling
of
PTFE
and
Co­
polymer
dispersion
products
>
Operation
and
maintenance
of
fiber
coating
facilities
k
Operation
and
maintenance
of
sintering
rolls
p
Packaging
of
non­
sintered
product.

Note
that
the
PTFE
and
co­
polymer
dispersion
products
used
at
the
Spruance
site
contain
<0.9%
APFO
with
most
containing
approximately
0.3%
APFO.

B.
Information
on
the
Exposure
Levels
of
Washington
Works
Employees
Since
most
of
the
processing
done
in
the
US
with
APFO
and
APFO
containing
intermediates
and
products
is
done
at
Washington
Works,
DuPont's
airborne
industrial
hygiene
data
is
concentrated
at
that
site.
The
limited
measurements
of
airborne
APFO
concentrations
at
the
other
sites
where
APFO
containing
products
are
used
have
shown
much
lower
levels
(mostly
non­
detectable)
levels
of
APFO.
The
data
in
the
table
below
8
9
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
reflect
monitoring
done
over
the
last
5
years
at
Washington
Works.
The
sample
results
are
a
combination
of
chemical
operator
and
maintenance
worker
personal
samples.

Year
Sample
#
of
Minimum
Maximum
Mean
Standard
Type
Samples
Concentration
(wb6>
Concentration
(mpb)
Deviation
(mph)
1999
Partial
100
<O.
Ol
0.58
0.06
1
0.151
1998
Shift
83
.OOl
0.78
0.103
0.145
1997
(mostly
100
<O.
Ol
2.4
0.146
0.378
1996
6­
8
7
3
N/
D
0.29
0.055
0.069
1995
hours)
3
2
N/
D
0.16
0.067
0.063
Partial
shift
air
samples
are
taken
at
the
rate
of
200
mL/
min
using
a
Tenax
collection
tube
that
has
been
pretreated
with
sodium
hydroxide/
ethylene
glycol/
methanol.
The
APFO
is
desorbed
from
the
tubes
using
methanolic
hydrogen
chloride,
which
also
serves
as
a
derivatizing
reagent,
converting
the
APFO
to
its
methyl
ester.
After
workup,
the
methyl
ester
is
quantified
using
a
gas
chromatograph
equipped
with
an
electron
capture
detector.
The
methyl
ester
of
perfluorodecanoic
acid
is
used
as
an
internal
standard,
and
at
least
three
calibration
samples
are
prepared
to
cover
the
concentration
range
of
interest.
Precision
is
estimated
to
be
+/­
10%
relative.

The
data
above
show
averages
consistently
below
the
AGCHI
TLV
of
0.01
mg/
m"
with
only
a
very
few
samples
above
the
TLV.
Where
results
are
above
or
near
to
the
TLV,
the
event
is
investigated
and
corrective
action
(additional
personal
protective
equipment
or
engineering
controls)
to
reduce
the
exposure
levels
is
undertaken.
Older
data
from
the
1980's
show
higher
levels
of
exposure.
In
the
early
1990's
Washington
Works
switched
from
receiving
the
APFO
as
a
powder
to
receiving
it
as
an
aqueous
solution.
This
change
was
done
to
reduce
the
potential
for
exposure
during
handling
of
the
dry
powder.
It
should
be
noted
that
in
the
1997
time
period,
the
site
was
starting
up
new
APFO
recovery
facilities.
Operating
and
maintenance
difficulties
associated
with
the
start­
up
of
these
facilities
may
have
contributed
to
the
higher
levels
of
APFO
in
the
personal
samples
during
that
year.

Task
specific
monitoring
data
and
wipe
monitoring
data
exist.
However
these
data
are
not
indicative
of
employee
exposure
and
are
not
presented
here.
These
samples
are
taken
to
identify
areas
where
additional
exposure
controls
may
be
necessary.

Engineering
controls
to
reduce
exposure
consist
of
the
following:

p
Reaction
systems
are
closed
systems
with
continuous
ambient
monitoring
for
monomer
concentrations
>
Ventilation
systems
are
installed
where
airborne
concentrations
are
significant
>
The
polymer
dryers
operate
under
negative
pressure
to
contain
APFO
and
other
materials.

6
mph=
moles
per
billion.
0.56mpb
is
equivalent
to
the
ACGIH
TLV
of
O.
Olmg/
m"

­~._
­
.._­­­­
Voluntary
UEIP,
Ammonium
Perfluorooctanoate
p
Recovery
systems
are
in
place
to
reduce
airborne
emissions,

Personal
protective
equipment
that
workers
regularly
wear
consist
of
the
following:

>
Safety
shoes
and
side­
shield
safety
glasses
in
all
areas.
g
Impervious
gloves
when
handling
APFO
solutions
or
aqueous
dispersion
products.
k
Chemical
protective
coveralls
and
goggles
or
face
shields
when
the
possibility
of
splashes
of
APFO
containing
solutions
is
present.
9
Airline
respirators
or
cartridge
respirators
where
monitoring
has
shown
to
have
high
exposure
potential.

At
Washington
Works,
blood
serum
levels
of
APFO
have
been
measured
since
198
1.
Prior
measurements
of
blood
fluoride
levels
have
been
taken
prior
to
198
1
but
are
of
limited
value
in
assessing
exposure
to
APFO.
A
summary
of
results
of
employees
with
identified
APFO
exposure
potential
the
1995,
1989­
90,
1985,
and
1984
volunteer
sampling
events
is
in
the
table
below.
Due
to
significant
job
assignment
movement
during
this
period
of
time,
analysis
of
trends
of
data
are
difficult.
The
data
in
the
table
below
prior
to
1995
are
for
employees
included
in
the
1995
sampling
data
so
that
comparisons
of
relative
levels
of
APFO
in
blood
serum
can
be
compared.
The
entire
data
set
of
blood
concentrations
is
available
upon
request.

Concentration
Concentration
'
This
individual
was
working
in
a
job
that
has
APFO
exposure
potential
at
the
time
of
the
sample.
*
This
individual
consistently
has
had
the
highest
blood
concentration
of
APFO
since
APFO
specific
samples
were
taken.
This
employee
left
an
APFO
exposure
potential
assignment
in
1991.
In
1995
this
employee's
blood
serum
level
was
4.4ppm.
.c
L
.___.______
­­
_._................
2.
'

.______....__...._..........­.­.....
.i
.'

>

..
q
:..
.._____....__
~~
.,­....
_
.­..­.......
.­