U.
S.
Environmental
Protection
Agency
Draft,
September
9,
2003
Technical
Subgroup
on
Degradation
Test
Methods
for
Telomers
Tentative
Agenda
­
Second
Meeting
(
Teleconference)

Tuesday,
September
9,
2003
10:
00
AM
to
1:
00
PM
Meeting
Location
­
Room
4225
in
EPA
East.
Fifteen
(
15)
teleconference
lines
are
available
for
anticipated
attendees
who
are
unable
to
attend
in
person.

The
call­
in
number
is
202­
275­
0199.
The
access
code
is
3824#.

Please
note
that
the
number
of
conference
lines
available
is
limited,
and
priority
must
be
given
to
anticipated
attendees.
Organizations
with
multiple
remote
attendees
are
requested
to
consolidate
their
participants
to
the
extent
possible,
so
that
multiple
participants
at
the
same
remote
location
could
use
a
single
call­
in
line.

 
Review
of
Action
Items
from
8/
14/
2003
meeting:

TRP:
review
applicability
of
SCAS
test;
consider
degradation
products
for
testing
or
alternative
proposal
to
screen
for
degradants,
measurement
of
rate
constants,
and
consider
extending
the
length
of
the
test
EPA:
comment
on
TRP
proposal,
review
TRP
logic
for
not
testing
water
and
air,
analytical
chemistry
issues,
degradation
products
issues,
and
consider
whether
we
can
consider
drafting
a
soil
testing
proposal
suitable
for
incorporation
into
an
ECA
by
EPA
and
Test
Sponsors
 
Discussion
of
TRP
Action
Items
­
TRP
S
Discussion
of
EPA
Action
Items
­
EPA
S
Next
Steps
U.
S.
Environmental
Protection
Agency
Draft,
September
4,
2003
Anticipated
Attendees
for
September
9,
2003
Telomer
Degradation
Subgroup
Meeting
Rich
Purdy
Treye
Thomas,
CPSC
John
Heinze,
Environmental
Health
Research
Foundation
Volker
Koch,
Clariant
Hiroyuki
Iwai,
Daikin
Satoshi
Komatsu,
Daikin
Ed
Lampert,
Daikin
Yukiko
Nishiyama,
Daikin
Randy
Roussel,
Daikin
Maggie
Martin,
Daikin
Bob
Buck,
DuPont
Bill
Berti,
DuPont
John
Gannon,
DuPont
Steve
Korzeniowski,
DuPont
W.
Michael
McCabe
(
DuPont)
Bill
Hardie,
W.
L.
Gore
Richard
Baillie,
W.
L.
Gore
Erin
Russell,
Clariant
Bill
Beers,
OMNOVA
Solutions
David
Lynch,
EPA/
EETD
Bob
Boethling,
EPA/
EETD
Andy
Mamantov,
EPA/
EETD
Greg
Fritz,
EPA/
EETD
Laurence
Libelo,
EPA/
EETD
Ward
Penberthy,
EPA/
CCD
Eric
Weber,
EPA/
ORD
Tim
Collette.
EPA/
ORD
Ed
Heithmar,
EPA/
ORD
Rich
Leukroth,
EPA/
CCD
Wendy
Hoffman,
EPA/
EETD
Cathy
Fehrenbacher,
EPA/
EETD
Barbara
Leczynski,
EPA/
CCD
Mary
Dominiak,
EPA/
CCD
(
Observer:
Barbara
Smyser,
CPS
[
TRP])
(
Observer:
Katie
Smythe,
RAND
[
TRP])
PFOA
ECA
Telomer
Degradation
Expert
Subgroup
Teleconference
September
9,
2003
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ECA
Telomer
Degradation
Expert
Subgroup
Teleconference
September
9,
2003
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TRP
Telomer
Research
Program
Biodegradation
Technical
Work
Group
Meeting
Telomer­
based
Polymeric
Products
(
TBPP)
Testing
Strategy
9
September
2003
2003­
09­
09
,
page
2
Telomer
Research
Program
Overview

Objective
of
Biodegradation
Studies
for
Telomer­
based
Polymeric
Products

Analytical
Considerations
&
Limitations

Biodegradation
in
Sludge

Biodegradation
in
Soil

Summary
&
Conclusions
2003­
09­
09
,
page
3
Telomer
Research
Program
Study
Objective

Do
Telomer­
based
Polymeric
Products
(
TBPP)
biodegrade
to
PFOA?


TRP
recognizes
that
data
is
needed
to
inform
this
question
and
offers
a
study
approach
where
both
Telomer­
based
Polymeric
Products
and
Telomerbased
Polymers
are
investigated
and
the
desire
for
timely
results.


Proposed
Studies

address
partitioning
and
biotransformation
in
relevant
environmental
compartments

start
with
laboratory
studies
that
are
simple
and
inform
the
question
of
whether
telomer­
based
polymeric
products
and
telomer­
based
polymers
have
the
potential
to
transform
to
PFOA
2003­
09­
09
,
page
4
Telomer
Research
Program
Approach

Focuses
on
relevant
releases
during
the
life­
cycle
of
telomer­
based
products
and
articles

Products
and
treated
articles
were
chosen
using
criteria
such
as
market
end
use,

chemistry
type/
class,
chemical
volume,
article
type,
and
potential
for
human
exposure.


Study
Plans
are
for
Telomer­
based
Polymeric
Products
(
TBPP)
2003­
09­
09
,
page
5
Telomer
Research
Program
80%
Water
20%
Telomer
Polymer
°
Aqueous
Dispersion
of .

°
Polymeric
Particles
100­
200
nm
with...

°
Hydrocarbon
Surfactant(
s)

What
is
a
Typical
Telomer­
Based
Polymeric
Product's
Composition
?


Telomer
Polymeric
Product
Variables

wt.%
active
ingredient
in
product
(~
20%)


wt.%
fluorine

wt.%
Telomer
raw
materials

wt.%
eight­
fluorinated
carbon
chain
C8F17­


PFOA
(
from
product
analysis)


Mol.
Wt.
­
Typically
>
10,000
Daltons

polyacrylates

polyurethanes
2003­
09­
09
,
page
6
Telomer
Research
Program
Release
of
Telomer­
based
polymeric
products

Telomer­
based
polymeric
products
(
TBPP)
enter
the
environment

in
sewage
treatment
plants
(
stp)


in
soil
via
sludge
amendment
to
agricultural
soils

in
surface
water
and
sediment
via
stp
e.
g.
sorbed
to
effluent
particles

in
landfills
from
sludge
or
disposal
of
treated
articles
(
carpets,
textiles,

paper)


TRP
Conclusion
:
Sludge
and
Soil
are
environmental
compartments
where
study
work
should
be
focused
2003­
09­
09
,
page
7
Telomer
Research
Program
Analytical
Methods

First,
establishing
robust
analytical
methods
for
study
matrices
are
mandatory
to
achieve
meaningful
results

Matrices

sludge,
aerobic
and
anaerobic
soil;
appropriate
dispersion
needed

Analytes

Fluoride,
PFOA
and
extractable
Total
Organic
Fluorine
(
TOF)


Extraction
&
Recovery
Demonstration

analyte
recovery
within
test
time
period
must
be
acceptable

sludge
28d
to
84days

soil
4­
6
months

It
is
standard
procedure
to
only
begin
testing
after
having
established
and
demonstrated
the
appropriate
analytical
methods.
2003­
09­
09
,
page
8
Telomer
Research
Program
Demonstrating
Analytical
Feasibility
for
Environmental
Matrices
­
General
Overview
Establish
Dispersion
Method
Establish
Extraction
Method
Establish
Quantification
Method
Quality
Check
Spiking
experiment
Full
Exposure
Period
Quality
Check
START
REAL
TEST
Test
method
not
applicable
yes
yes
no
no
It
has
to
be
proven
 ..

°
that
dispersion,
extraction
and
quantification
is
possible
°
that
the
development
methodology
is
applicable
to
real
test
test
conditions
in
Biodegradation
tests
over
the
full
exposure
period
(
e.
g.
28d,
84d
or
6
months)

Improvement
?
2003­
09­
09
,
page
9
Telomer
Research
Program
Demonstrating
Analytical
Feasibility
for
Application
to
Biodegradation
Studies
Improvement
possible
?

Matrix
Proceed
with
STP
Biodegradability
Study
Overall
Biodegradability
Testing
Flow
Chart
Test
Feasibility
of
Analytical
Procedures
Meets
Quality
Requirements?

NO
Proceed
with
Soil
Biodegradability
Study
YES
YES
2003­
09­
09
,
page
11
Telomer
Research
Program
Sewage
Treatment
Plants
(
STP)

Biodegradability
Testing
Experimental
Design
Discussion
2003­
09­
09
,
page
12
Telomer
Research
Program
Test
Materials
for
STP
Biodegradation
Study
Proposals

Start
with
 .


OECD
302
B
(
Zahn­
Wellens
/
EMPA
Test)
on

Two
(
2)
Telomer­
based
Polymeric
Products
(
TBPP)
&
2
Telomer­
based
polymers
isolated
from
TBPP
Products
will
be
from
the
12
that
are
included
in
the
TRP
LOI

Two
isolated
polymers
from
the
two
Products

to
understand
whether
the
polymer
alone
undergoes
transformation

characterization
of
the
products
and
isolated
polymers
will
be
done

will
enable
method
development
and
demonstration
for
longer­
term
studies

provides
results
in
short
timeframe

Then
 ..
Conduct
302B
on
additional
10
polymeric
products
in
LOI

This
is
a
modification
of
the
TRP
LOI
commitment
2003­
09­
09
,
page
13
Telomer
Research
Program
Test
Materials
for
STP
Biodegradation
Study
Proposals

In
parallel,
we
propose
to
develop
a
study
protocol
to
conduct
 


OPPTS
835.5045
"
Modified
SCAS
Test
For
Insoluble
and
Volatile
Chemicals"


need
to
develop
and
demonstrate
feasible
analytical
methods

on
two
(
2)
Isolated
Polymers
(
from
Telomer
Based
Polymer
Products)


we
want
to
discuss
with
EPA
decision
triggers
for
this
study
Modified
Zahn­
Wellens/
EMPA
test
Telomer­
Based
Polymer
Product
(
TBPP)
Isolated
Polymer
from
TBPP
Does
Polymer
Biodegrade?

Conduct
Modified
SCAS
Test
on
Isolated
Polymer
only*

Does
TBPP
Biodegrade?

Conduct
Modified
SCAS
Test
on
TBPP
*
Residual
telomer­
based
raw
materials
potential
contribution
to
PFOA
is
considered
separately
as
part
of
the
TRP
8­
2
Telomer
B
Alcohol
studies.

Phase
1:
STP
Biodegradability
Testing
Demonstrate
SCAS
Analytical
Feasibility
Decision
points
to
be
discussed
Entry
via
STP
Sludge
Adsorption
or
Sedimentation?

­
HLC?

Effluent?
STOP
Phase
2:
STP
Biodegradability
Testing
Aerobic
Sewage
Treatment
Simulation
Test
Sludge
Adsorption
&
Sedimentation
Tests
Modified
SCAS
Test
for
Insoluble
and
Volatile
Chemicals
OPPTS
835.5045
Significant
Biodegradability?
Significantly
Adsorb
or
Settle
in
Sludge?

Consider
Water
&

Sediment
Compartments
kinetic
study
Decision
points
to
be
discussed
2003­
09­
09
,
page
16
Telomer
Research
Program
Technical
Hurdles
STP
Study
Proposals
2003­
09­
09
,
page
17
Telomer
Research
Program
Activated
Sludge
Adsorption
of
Telomer­
Based
Polymer
STP
Study
Proposals
2003­
09­
09
,
page
18
Telomer
Research
Program
Technical
Hurdles:
Activated
Sludge
Sorption
Guideline

Reliable
Analytical
Methods

Need
methods
with
sufficient
accuracy
to
be
able
to
extract
and
measure
test
substance
in
the
solution
and/
or
the
adsorbed
phase
Issues

Reliable
Analytical
Methods

Total
Organic
Fluorine
is
only
available
tool
but
is
non­
specific

14C­
labeled
polymer
would
be
optimal
to
conduct
this
study,
but
this
would
require
significant
R&
D.
2003­
09­
09
,
page
19
Telomer
Research
Program
Modification
of
OPPTS
835.5045
"
Modified
SCAS
Test
For
Insoluble
and
Volatile
Chemicals"

STP
Study
Proposals
2003­
09­
09
,
page
20
Telomer
Research
Program
Technical
Hurdles:
Modified
SCAS
Test
for
Insoluble
and
Volatile
Chemicals
(
OPPTS
835.5045)

Guideline

Reliable
Analytical
Methods

Requires
use
of
a
chemicalspecific
analytical
technique
or
14C­
labeled
test
chemical

Biodegradability
&
Mass
Balance

Labeled
(
14C)
material
required
for
determining
transformation
pathways,
rates
and
mass
balance.


Mass
balance
established
by
quantifying
parent
chemical
in
settled
effluent
sludge
solids,

effluent
plus
solids,
and
off
gases
Issues

How
to
disperse
Telomer­
based
polymer
and
products
in
SCAS
test
system

Analytical
Methods

Total
Organic
Fluorine
and
Fluoride
ion
are
only
available
tools
but
are
nonspecific

14C­
labeled
polymer
would
be
optimal
,
but
would
require
significant
R&
D.


Biodegradability
&
Mass
Balance

Analyze
for
PFOA
in
water
and
8_
2
Telomer
B
Alcohol
in
air
trap

Need
to
meet
data
quality
standards
for
efficient
Extraction/
Clean­
Up
methods
from
effluent
and
sludge
2003­
09­
09
,
page
21
Telomer
Research
Program
Guideline

Water
solubility
and
Organic
Carbon
content
of
test
chemical
must
be
established.


Exhaust
gases
from
aeration
unit
are
passed
through
a
suitable
trap.
Issues

How
to
determine
water
solubility
and
organic
carbon
content
of
Telomer­

Based
Polymer
&
Products

What
is
a
suitable
trap
for
potential
volatiles
for
Telomer­
Based
polymers
and
products
and
what
are
the
appropriate
extraction
procedures?


Total
Organic
Fluorine
:
a
non­
chemical
specific
endpoint
in
traps

Fluoride
Ion
in
traps

8_
2
Telomer
B
Alcohol
in
traps
if
can
be
demonstrated
to
be
technically
feasible
Technical
Hurdles:
Modified
SCAS
Test
for
Insoluble
and
Volatile
Chemicals
(
OPPTS
835.5045)
2003­
09­
09
,
page
22
Telomer
Research
Program
Proposal
for
Modification
of
Performance
of
Test:

Modified
SCAS
Test
(
OPPTS
835.5045)


Run
study
for
12
weeks

Collect
and
freeze
samples
daily
over
12
weeks

Phase
A:
Analyze
samples
at
Day
0,
Weeks
4,
8,
and
12.
Assess
for:


1)
Total
Organic
Fluorine
and/
or
Fluoride
ion
in
effluent
and
sludge
solids

2)
Presence
of
PFOA
in
effluent
and
sludge
solids

3)
Presence
of
Total
Organic
Fluorine
and/
or
Fluoride
ion
in
Volatility
traps

If
levels
are
significant,
then
look
for
PFOA
and
8_
2
Telomer
B
Alcohol

If
2
&
3
are
negative
or
insignificant
concentrations,
then
stop

If
2
or
3
are
positive
and
significant
concentrations,
then
go
to
Phase
B.


Phase
B:
Further
analysis
of
frozen
sludge
and
water
samples
at
additional
time
points
for
PFOA,
and
if
technically
feasible,
8_
2
Telomer
B
Alcohol
and
measurement
of
rate
constants.
Extraction
of
off­
gases*
from
Volatility
traps
(
e.
g.,
C18)
for:


Total
Organic
Fluorine

Fluoride
[
F­]


8_
2
Telomer
B
Alcohol?

Extraction
from
Settled
Effluent
Sludge
Solids
for:


Total
Organic
Fluorine

Fluoride
[
F­]


PFOA
Extraction
from
Effluent
+
Solids
for:


Total
Organic
Fluorine

Fluoride
[
F­]


PFOA
*
If
TOF
or
Fluoride
concentrations
in
traps
are
significant,
then
evaluate
for
8_
2
Telomer
B
Alcohol
if
"
Quality
Criteria"
for
analytical
feasibility
can
be
met.
2003­
09­
09
,
page
24
Telomer
Research
Program
Modification
of
OECD
307
Aerobic
and
Anaerobic
Transformations
in
Soil
Experimental
Design
Discussion
2003­
09­
09
,
page
25
Telomer
Research
Program
Test
Materials
for
Soil
Biodegradation
Study
Proposals

Start
By
Conducting .


OECD
307
Aerobic
and
Anaerobic
Transformations
in
Soil

Two
(
2)
Telomer­
based
polymers
isolated
from
TBPP
Products
will
be
from
the
12
that
are
included
in
the
TRP
LOI

Two
isolated
polymers
from
the
two
Products

to
understand
whether
the
polymer
alone
undergoes
transformation

characterization
of
the
products
and
isolated
polymers
will
be
done

will
enable
method
development
and
demonstration
2003­
09­
09
,
page
26
Telomer
Research
Program
Biodegradation
Testing
in
Soil
Testing
Strategy
Pilot
Study

Pilot
study
Modified
OECD
307
Test
setting

Establishing
and
Verification
of
the
Analytical
method
for
120
to
180d
Exposure

Testing
two
isolated
polymers

Use
of
the
OECD
307
(
Aerobic
and
anaerobic
transformation
in
soil)
setting

apply
aerobic
and
anaerobic
conditions

Application
of
testing
methodology
to
other
TRP
TBPPs

review
results
from
pilot
study
to
determine
whether
additional
polymers
should
be
investigated

Kinetic
investigations

only
if
PFOA
amount
would
reach
a
certain
level
in
relation
to
the
overall
C8F17­
content
in
TBPPs
2003­
09­
09
,
page
27
Telomer
Research
Program
Technical
Hurdles
Soil
Study
Proposals
2003­
09­
09
,
page
28
Telomer
Research
Program
Technical
Hurdles:

Aerobic
and
Anaerobic
Transformation
in
Soil
Guideline

Analytical
Methods

Applicable
to
all
chemical
substances
which
have
analytical
methods
available
with
sufficient
accuracy
and
sensitivity

Biodegradability
&
Mass
Balance

Labeled
(
14C)
material
required
for
determining
transformation
pathways,
rates
and
mass
balance
Issues

How
to
get
equal
distribution
of
Telomer­
based
polymer
in
soil
matrix

Analytical
Methods

Non­
chemical
Specific
Analytical
limitation
for
cold
studies

14C­
labeled
polymer
would
be
optimal
,
but
would
require
significant
R&
D.


Need
to
meet
data
quality
standards
for
efficient
Extraction/
Clean­
Up
methods

LOD's
&
LOQ's
for
each
endpoint
described
below
needs
to
be
established

Biodegradability
&
Mass
Balance

Analyze
for
PFOA
in
test
system

Total
Organic
Fluorine
in
test
system
and
extract
from
traps

Fluoride
Ion
in
extract
from
traps

if
TOF
or
Fluoride
ion
from
traps
is
significant,

then
evaluate
traps
for
8_
2
Telomer
B
Alcohol
2003­
09­
09
,
page
29
Telomer
Research
Program
Proposal
for
Modification
of
Performance
of
Test:
Aerobic
and
Anaerobic
Transformation
in
Soil
(
OECD
307)


Run
study
for
6
months

Collect
and
freeze
samples
(
frequency:
weekly)
over
6
months

Use
a
Flow
through
System
with
traps
for
volatiles.


Phase
A:
Analyze
samples
at
Day
0,
2
Months,
4
Months
and
6
Months.
Assess
for:


1)
Total
Organic
Fluorine
in
soil
(
aerobic)
&
soil/
water
phases
(
anaerobic)


2)
Presence
of
PFOA
in
soil
(
aerobic)
&
soil/
water
phases
(
anaerobic)


3)
Presence
of
Total
Organic
Fluorine
and/
or
Fluoride
ion
in
Volatility
traps

If
levels
are
significant,
then
look
for
PFOA
and
8_
2
Telomer
B
Alcohol

If
2
&
3
are
negative
or
insignificant
concentrations,
then
stop

If
2
or
3
are
positive
and
significant
concentrations,
then
go
to
Phase
B.


Phase
B:
Further
analysis
of
frozen
samples
for
PFOA,
8_
2
Telomer
B
Alcohol,

and
measurement
of
rate
constants
if
technically
feasible.


Provide
report
at
completion
of
study.
