DRAFT
 
For
EPA
Review
and
Comment
TRP
(
9­
May­
03)

Biodegradation
Analysis
of
Telomer­
based
Polymeric
Products:
A
Draft
Proposal
Background
&
Overview
The
following
draft
approach,
rationale
and
attached
protocol
are
proposed
to
gather
information
about
whether
telomer­
based
polymeric
products
might
transform
to
perfluorooctanoic
acid
(
PFOA)
or
its
salts
under
environmentally
relevant
laboratory
study
conditions.
This
proposal
fulfills
the
Telomer
Research
Program
(
TRP)
commitment
described
in
Appendix
4,
Item
5
of
the
TRP
Letter
of
Intent
(
LOI)
dated
March
14,
2003
and
submitted
to
US
EPA
(
Docket
#
OPPT­
2003­
0012).

The
telomer­
based
polymeric
products
are
generally
20%
aqueous
dispersions
of
telomer­
containing
polymeric
particles.
The
telomer
functionality
F(
CF2
CF2
)
n
CH2
CH2
­
is
covalently
bound
to
the
polymer
backbone.

This
proposal
considers
both
biotic
and
abiotic
transformation
processes
that
may
be
relevant.
It
is
expected
that
results
from
ongoing
TRP
studies
on
8­
2
Telomer
B
Alcohol
(
C8
F17
CH2
CH2
OH)
will
provide
helpful
information
to
enable
this
work
to
be
accomplished
­­
specifically,
sampling
and
analysis
methods.
However,
as
the
polymeric
products
are
substantially
more
complex,
it
is
possible
that
difficulties
may
be
encountered
in
developing
and
validating
an
analytical
method
or
methods
to
sufficiently
recover
and
thereby
quantitatively
determine
PFOA
in
these
complex
matrices.

Biotic
Degradation
The
TRP
proposes
to
conduct
initial
biodegradation
screening
studies
on
the
12
telomer­
based
polymeric
products,
which
are
part
of
the
Product
and
Article
Analysis
studies
(
LOI
Item
1)
previously
submitted
to
EPA.
The
selected
polymeric
products
represent
the
majority
of
global
product
types
used
for
textile,
carpet
and
paper
treatment.
The
TRP
proposes
to
conduct
studies
on
these
substances
following
a
modified
OECD
302
28­
day
Inherent
Biodegradation
protocol
(
a
draft
outline
of
the
protocol
is
included
with
this
document).
The
quantitative
determination
of
PFOA
is
the
key
study
endpoint.
Additional
proposed
endpoints
to
be
monitored
include
measurement
of
dissolved
organic
carbon
(
DOC)
or
carbon
dioxide
(
CO2
)
evolution
and
fluoride
(
F­
).
The
OECD
302
inherent
studies
are
proposed
because
the
study
design
would
represent
the
"
most
favorable"
conditions
under
which
biotransformation
may
occur.
The
innoculum
to
be
used
for
the
study
will
be
municipal
sludge.

The
polymers
(
acrylates
and
urethanes),
which
are
the
major
component
of
the
sales
products,
have
molecular
weights
above
1000
ranging
to
well
above
100,000
daltons,
are
non­
polar
and
of
no
 
low
water
solubility.
It
is
widely
reported
in
the
literature
that
polymers
of
this
type
are
not
bioavailable
to
microorganisms
and
would
not
be
expected
to
undergo
transformation.
Should
a
significant
amount
of
PFOA
be
generated
as
a
result
of
biotransformation
in
these
initial
studies
on
the
product
in
its
entirely,
TRP
will
consider
disaggregating
the
polymeric
product
formulation
to
explore
and
identify
specific
components
from
which
PFOA
may
originate
Abiotic
Degradation
Three
predominant
abiotic
degradation
pathways
are
expected
for
telomer­
based
polymeric
products:
(
1)
photolytic,
(
2)
thermal
and
(
3)
incineration.
Studies
to
explore
these
potential
pathways
are
already
included
in
the
TRP
Letter
of
Intent.
Photolytic
and
thermal
degradation
of
polymeric
products
and
articles
treated
with
them
is
described
in
LOI
Appendix
4,
Item
2.
Incineration
is
described
in
Appendix
4,
Item
6.
These
studies
will
provide
information
relevant
to
these
abiotic
transformation
processes.
Pending
the
results
of
these
studies,
additional
work
may
be
planned
to
explore
these
pathways
by
other
study
methodologies.

Telomer
Research
Program
Page
1
of
2
05/
09/
03
DRAFT
 
For
EPA
Review
and
Comment
TRP
(
9­
May­
03)

Telomer
Research
Program
Page
2
of
2
05/
09/
03
Schedule
May
2003
 
Finalize
study
protocols
June
2003
 
Review
study
rationale
and
protocols
with
EPA
June­
Sept
2003
 
Conduct
studies
Submit
study
reports
as
they
become
available.

References
Alexander
M.,
Biodegradation
and
Bioremediation,
Academic
Press,
,
New
York,
1994
Boethling
R.
S.,
Mackay
D.,
Handbook
of
Property
Estimation
Methods
for
Chemicals
Lewis
Publisher,
New
York,
2000,
ISBN1­
56670­
456­
1
Freelove
A.
C.
J.,
Bolam
D.
N.,
White
P.,
Hazlewood,
G.
P.,
Gilbert,
H.
J.,
A
Novel
Carbo­
hydrate­
binding
Protein
Is
a
Component
of
the
Plant
Cell
Wall­
degrading
Complex
of
Piromyces
equi,
J.
Biol.
Chem.
2001,
276
(
46),
43010­
43017
Hilborn
J.,
Coullerez
G.,
Lowe
C.,
Pechy
P.,
Kausch
H.,
Synthesis
of
acrylate
functional
telechelic
poly(
lactic
acid)
oligomer
by
transesterification,
J.
Mat.
Science:
Materials
in
Medicine,
2000,
11,
505­
510
Matsamura
S.
(
Editor),
Biopolymers
Vol.
9,
Miscellanous
Biopolymers
and
Biodegradation
of
Synthetic
Polymers,
Wiley,
New
York,
2002,
ISBN
3­
527­
30228­
X
Scott
G.,
Polymers
and
the
Environment,
RCS
Paperback,
London,
1999,
ISBN
0­
85404­
578­
3
