3M
Environmental
Laboratory
Report
No.
E00­
1851
Study
Title
Hydrolysis
Reactions
of
Perfluorooctanoic
Acid
(PFOA)

Data
Requirement:
Based
on
OPPTS:
835.21
10
Author
Thomas
L.
Hatfield,
Ph.
D.

Study
Completion
Date
March
30,2001
Performing
Laboratory
3M
Environmental
Laboratory
Building
2­
3E­
09,935
Bush
Avenue
St.
Paul,
MN
55106
Project
/den
tifica
tion
3M
Laboratory
Report
No:
E00­
1851
Total
Number
of
Pages
99
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~
~~

3M
Environmental
Laboratory
Report
No.
E00­
1851
This
page
has
been
reserved
for
specific
country
requirements.

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3M
Environmental
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E00­
1851
Statement
of
Non­
Compliance
Study
Title:
Hydrolysis
Reactions
of
Perfluorooctanoic
Acid
(PFOA)
Study
Identification
Number:
E00­
1851
This
study
does
not
fully
comply
with
the
requirements
of
the
US
EPA
Good
Laboratory
Practices
(GLP)
Standards
at
40
CFR
Part
792
(TSCA).
However,
many
GLP
standards
were
used
in
the
development
of
the
analytical
method
(Appendix
A),
and
many
of
the
quality
assurance
procedures
followed
in
this
study
were
based
on
the
practices
described
in
the
GLP
documentation.

Sbonsor
Representative
Date
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Inspection
Dates
Quality
Assurance
Statement
Date
Reported
to
Management
I
Study
Director
Phase
Study
Title:
Study
Identification
Number:
E00­
1851
Hydrolysis
Reactions
of
Perfluorooctanoic
Acid
(PFOA)

The
following
table
provides
details
of
the
audits
performed
by
the
3M
Environmental
Laboratory
Quality
Assurance
Unit
(QAU).

I
3/
2/
0
1
I
Data
and
Draft
Report
I
3/
2/
01
I
3/
2/
01
I
I
3/
26­
30/
01
I
Data
and
Draft
Report
I
3/
30/
01
I
3/
30/
01
I
3/
30/
0,
QA
U
Representatid
'
Datd
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~
~~~

3M
Environmental
Laboratory
Report
No
.
E00­
1851
Table
of
Contents
Statement
of
Non­
Compliance
............................................................................................
3
Quality
Assurance
Statement
..............................................................................................
4
List
of
Tables
........................................................................................................................
6
List
of
Figures
.......................................................................................................................
6
Study
Personnel
and
Contributors
.......................................................................................
6
Location
of
Archives
.............................................................................................................
7
Summary
..............................................................................................................................
8
Introduction
..........................................................................................................................
9
Summary
of
Kinetics
Model
...............................................................................................
10
Materials
and
Methods
.......................................................................................................
11
Chemical
Characterizations
..........................................................................................
11
Sample
Analysis
............................................................................................................
12
Deviations
......................................................................................................................
12
Results
and
Discussion
.....................................................................................................
13
Sample
Preparation
......................................................................................................
11
Data
Quality
Objectives
(DQO's)
..................................................................................
13
Anomalous
Analytical
Results
.......................................................................................
13
Statistical
Methods
and
Calculations
............................................................................
14
Data
Summary
and
Discussion
.....................................................................................
14
Conclusions
........................................................................................................................
18
References
.........................................................................................................................
19
Signatures
..........................................................................................................................
20
Appendix
A:
Analytical
Method
..........................................................................................
21
Appendix
B:
Kinetics
Model
...............................................................................................
38
Appendix
C:
Selected
Analytical
and
Kinetics
Results
.....................................................
48
Appendix
D:
Selected
Chromatograms
.............................................................................
71
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List
of
Tables
Table
1.
Summary
of
Results
Based
on
PFOA
Concentrations
........................................
8
Table
2.
Summary
of
Results
Based
on
the
Mean
and
Precision
of
PFOA
Measurements
.....................................................................................................
.8
Table
3.
Characterizations
of
Test
and
Reference
Substances
......................................
1
1
Table
4.
Observed
(50"
C)
Degradation
Rates
of
PFOA
in
Aqueous
Buffered
Solutions
and
at
Various
pH
Levels
....................................................................................
15
Table
5.
Degradation
Rate
and
Half
Life
of
PFOA
in
Aqueous
Buffered
Solutions
Using
Data
Pooled
Over
pH
Levels
5.0,
7.0,
and
9.0
...................................................
15
Table
6.
Degradation
Rate
and
Half
Life
of
PFOA
in
Aqueous
Buffered
Solutions
Based
on
the
Concentration
Mean
and
Standard
Deviation
.........................................
17
List
of
Figures
Figure
1.
Structure
of
the
Ammonium
Salt
of
PFOA
..........................................................
9
Figure
2.
Observed
PFOA
Degradation
for
Various
pH
levels.
.......................................
14
Figure
3.
Pooled
(pH
=
5.0,
7.0,
and
9.0)
PFOA
Data
and
Slope
Regression.
...............
16
Study
Personnel
and
Contributors
Study
Director
Sponsor
Thomas
L.
Hattield,
Ph.
D.
3M
Environmental
Laboratory
Building
2­
3E­
09
935
Bush
Avenue
St.
Paul,
MN
55106
(651)
778­
7863
3M
Corporation
3M
Environmental
Laboratory
and
Professional
Services
Contributing
Personnel
Debra
Wright
Jan
Schultz
Joseph
J.
S.
Tokos,
Ph.
D.
(Pace
Analytical
Services,
Inc.,
1700
Elm
St.,
Minneapolis,
MN
55144)

Jill
Maloney
Karen
Johnson
(Braun
lntertec
Corporation,
6875
Washington
Ave.
South,
Minneapolis,
MN
55439)

Grant
M.
Plummer,
Ph.
D.
(Rho
Squared,
P.
O.
Box
61536,
Durham,
NC
27715)

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Location
of
Archives
The
3M
Environmental
Laboratory
will
retain
the
original
data
documents
and
digital
copies
of
the
original
data
related
to
this
work
for
at
least
10
years
following
the
effective
date
of
any
related
final
ruling.
Information
may
be
obtained
through
written
inquiry
addressed
as
follows:

3M
Environmental
Laboratory
Building
2­
3E­
09
935
Bush
Avenue
St.
Paul,
MN
55106
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Observed
Rate
Constant
at
50"
C
8.1
x
IO­
'
(day­
')
Summary
Calculated
Calculated
(20)
Calculated
Rate
Half
Life
Minimum
Half
Constant
at
25"
C
at
250
Life
at
25"
C
(day''')
(years)
(years)

8.1
x
235
92
We
report
here
the
results
of
our
study
of
the
hydrolysis
of
perfluorooctanoic
acid
(hereafter,
PFOA).
Our
methods
are
described
below
and
in
Appendix
A
to
this
work;
our
results
are
based
on
the
observed
concentrations
of
PFOA
in
buffered
aqueous
solutions
as
a
function
of
time.
3M's
Environmental
Laboratory
staff
developed
the
study
procedures:
they
are
based
on
EPAs
OPPTS
Guideline
Document
835.21
I
O
'
but
do
not
fulfill
all
the
requirements
of
the
guideline.

Our
methods
are
described
below
and
in
Appendix
A
to
this
work;
our
results
are
based
on
the
observed
concentrations
of
PFOA
in
buffered
aqueous
solutions
as
a
function
of
time.
The
chosen
analytical
technique
was
high
performance
liquid
chromatography
with
mass
spectrometry
detection
(HPLC/
MS).
Table
1
summarizes
the
results
of
the
study.

During
this
study,
we
prepared
and
examined
samples
at
six
different
pH
levels
from
1.5
to
1
1
.O
over
a
period
of
109
days,
and
our
results
indicate
no
dependence
of
the
degradation
rate
of
PFOA
on
the
sample
pH
level.
Our
results
based
on
the
PFOA
concentrations,
pooled
over
three
pH
of
the
six
levels
(5.0,
7.0,
and
9.0),
are
presented
in
Tables
1
and
2.

The
mean
value
and
precision
of
PFOA
concentration
measurements
provide
a
second
estimate
of
t,
he
PFOA
half­
life,
presented
in
Table
2.

Table
2.
Summary
of
Results
Based
on
the
Mean
and
Precision
of
PFOA
Measurements
Maximum
Maximum
Calculated
Possible
Rate
at
Calculated
Half
Life
I
50°
C
­4
I
I
1
Rate
at
25"
C
at
25°
C
2.0
x
10
2.0
x
10
2
97
(day")
(day')
(years)

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I
n
t
rod
uct
ion
Three
primary
chemical
routes
of
environmental
degradation
are
hydrolysis,
photolysis,
and
biodegradation.
Studies
of
these
routes
provide
information
on
the
environmental
persistence
of
both
the
"parent"
compounds
and
their
reaction
products,
and
are
ideally
carried
out
over
the
range
of
chemical
conditions
pertinent
to
both
environmental
and
metabolic
processes.

The
hydrolysis
of
PFOA
(or,
more
generally,
its
degradation
in
the
presence
of
bo)
is
addressed
in
this
report.
The
structure
of
the
ammonium
salt
of
the
PFOA
is
illustrated
in
Figure
1.
This
is
the
actual
test
material
used
in
the
study.

Figure
1.
Structure
of
the
Ammonium
Salt
of
PFOA
PFOA
H
H­
A+­
H
I
H
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Summary
of
Kinetics
Model
A
full
mathematical
description
of
the
kinetics
model
employed
in
this
study
is
presented
in
Appendix
6.
The
study
data
allow
two
independent
estimates
of
the
hydrolytic
half­
life
of
PFOA.

The
first
estimate
(see
Table
1)
is
based
on
the
observed
degradation
of
the
"parent"
compound
PFOA
in
dilute,
appropriately
buffered
aqueous
solutions.
Equation
1
describes
the
estimated
half­
life
(?
vi),
in
terms
of
the
estimated
total
parent
hydrolysis
rate
ip
(see
Appendix
8,
Equation
BIO):

Eq.
1
We
determined
the
quantity
cp
from
the
experimental
data
as
described
in
Appendix
B.
To
determine
the
relevant
concentration
ratios
at
each
pH
level
(see
Equations
B8
and
B9),
we
used
either
the
data
corresponding
to
"Day
0"
(t
=
0)
or
the
earliest
available
data
achieving
the
data
quality
objectives
of
the
analytical
method.

A
second
half­
life
estimate
(see
Equation
B37)
is
available
from
the
mean
p
and
standard
deviation
CJ
of
the
observed
PFOA
concentrations,
assuming
that
they
were
essentially
constant
over
the
experimental
portion
of
the
study.
This
estimate
is
Eq.
2
where
A
t
represents
the
sample
incubation
period.

All
the
samples
used
in
this
study
were
maintained
at
a
reaction
temperature
of
50"
(k
3")
C.
The
quoted
results,
valid
for
the
reaction
temperature
25"
C,
were
estimated
from
our
experimental
results
according
to
methods
described
in
Appendix
B
(Eqs.
B38
and
B39).

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Chemical
Lot
Numbe?
Physical
Description
Materials
and
Methods
TCR­
00930­
30,
Lot
332
TCR­
99030­
28,
Lot
101
White
powder
White
powder
Details
of
the
characteristics
of
the
test
materials,
sample
preparation
techniques,
and
analytical
methods
are
presented
in
Appendix
A
(ETS­
8­
212.0,
"Preparation
of
Perfluorooctanoic
Acid
(PFOA)
Hydrolysis
Samples
in
Buffered
Solutions
and
Analysis
by
High
Performance
Liquid
Chromatography
with
Mass
Spectrometry
Detection.")
A
summary
of
these
items
is
provided
below,
as
well
as
a
description
the
known
deviations
from
the
procedures
of
Appendix
A.
3M
prepared
and
analyzed
the
samples
included
in
this
study
between
June
15
and
November
12,2000.

431
Molecular
Weight
(gm
mole­
')
Chemical
Characterizations
Table
3
describes
the
sources
and
properties
of
the
materials
used
in
this
work.
These
materials
were
used
to
prepare
both
the
samples
and
the
quantitative
standards
used
to
quantify
them.
For
this
reason,
and
because
the
related
calculations
involve
only
ratios
of
the
compound
concentrations
(see
Appendix
B,
Equations
88
and
B36),
the
resulting
rate
and
half­
life
estimates
are
largely
independent
of
the
material
purity
levels.

317
Table
3.
Characterizations
of
Test
and
Reference
Substances
I
PFOA
(Ammonium
Salt)
I
PFBS
(Ammonium
salt)
I
P
I
I
Source
I
3M
ICPlPCP
Division
I
3M
Specialty
Chemicals­]

perfluorobutanesulfonate
A
Sample
Preparation
We
prepared
four
5.0­
mL
aqueous
buffer
samples
(a
sample,
a
duplicate,
a
triplicate,
and
a
"matrix
spike")
at
each
of
six
pH
levels
(1.5,
3,
5,
7,
9
and
11)
for
analysis
at
eight
time
intervals
(0,
7,
14,
28,42,
64,
84
and
109
days).
Buffered
solutions
containing
5154
ng/
mL
of
the
analyte
PFOA
formed
the
basis
of
all
these
samples.
The
chosen
buffer
solutions
are
described
fully
in
Appendix
A.

All
the
samples
were
prepared
simultaneously,
and
all
but
the
"Day
0
samples
were
placed
in
an
incubator/
orbital
shaker
maintained
at
50"
(+
3")
C.
One
of
the
"Day
0
samples
and
a
blank
were
spiked
with
the
PFOA
solution,
diluted
7:
l
with
methanol
containing
the
internal
standard
perfluorobutanesulfonate
(PFBS)
and
frozen.
The
resulting
PFBS
concentration
in
all
these
samples
was
158
ng/
ml;
the
resulting
PFOA
concentration
in
the
spiked
samples
was
143
ng/
ml
above
the
original
sample
concentratian.
After
the
appropriate
incubation
times,
subsets
of
the
sample
vials
were
removed
from
the
incubator
and
then
spiked
(as
required),
diluted,
and
frozen
as
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described
immediately
above.
Except
during
the
relatively
short
periods
of
time
required
to
prepare
them,
the
samples
were
shielded
from
light.

Nine
calibration
standards
containing
PFOA
(25
to
999
ng/
ml)
and
PFBS
served
as
the
quantitative
basis
of
the
study.
All
these
standards
were
prepared
in
1.5
mL
of
the
appropriate
pH
buffer
solution
and
8.5
mL
of
methanol.

Sample
Analysis
The
equipment
we
used
for
the
HPLC/
MS
analysis
was
a
Hewlett
Packard
model
1100
equipped
with
a
Dionex
lonPac@
NG­
1
HPLC
column
(aqueous
ammonium
acetate/
methanol
solvent
gradient)
and
an
ALS
Model
G
I
322A
degassing
module.
An
ALS
Model
G1316A
column
heater
maintained
the
column
temperature
at
40°
C,
a
quaternary
pump
supplied
a
column
flow
rate
of
0.3
mumin,
and
an
ALS
Model
G1313A
auto­
sampler
provided
10
pL
sample
injections.
The
detector
was
a
Hewlett
Packard
MSD
mass
spectrometer,
operated
in
negative­
mode
electrospray
ionization
mode;
the
anions
of
PFBS
and
PFOA
were
detected
at
the
mass­
to­
charge
(m/
z)
ratios
299
and
41
3,
respectively.
We
processed
the
resulting
data
using
the
computer
program
Target@
NT
Genie
Integrator.
Further
analytical
details,
including
the
gradient
elution
program,
instrument
and
detector
parameters,
and
performance
specifications,
are
presented
in
Appendix
A.

Deviations
No
deviations
from
the
procedures
defined
in
the
analytical
method
(Appendix
A)
were
noted
during
the
study.
All
calibration
and
sample
results
that
failed
to
meet
the
data
quality
objectives
of
the
method
(and
were
excluded
from
further
analysis)
are
noted
in
the
following
sections.

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Results
and
Discussion
Data
Qualii
Objectives
(DQO's)
We
briefly
describe
the
data
quality
objectives
applied
in
this
study
below.
Appendix
A
describes
them
in
greater
detail.
With
the
exceptions
of
the
anomalous
results
noted
below,
all
the
DQO's
were
met.
Appendix
C
presents
the
results
for
each
sample
set,
organized
by
pH
level.
Calibrations.
The
minimum
acceptable
coefficient
of
determination
(P)
for
linear
fits
to
calibration
data
is
0,990.
The
acceptance
criterion
for
individual
calibration
points
is
that
their
values
fall
within
&
25%
of
the
linear
fit
value;
data
outside
this
range
are
excluded
and
the
linear
fit
is
recalculated.
Data
for
the
high
or
low
calibration
standards
may
be
rejected,
though
this
results
in
a
smaller
effective
calibration
range.
The
average
results
of
calibrations
performed
before
and
after
the
analytical
procedures
are
used
to
calculate
the
analyte
concentrations.
Continuing
Calibration
Verification
(CCV).
Selected
calibration
samples
are
examined
at
the
beginning
of,
during,
and
at
the
end
of
each
analytical
procedure.
The
results
may
not
deviate
by
more
than
k
25%
of
the
known
values.
Sample
Spikes.
The
acceptable
percent
spike
recovery
range
is
70%
to
130%;
recoveries
outside
this
range
%
place
the
analysis
out
of
control,
and
require
intervention
by
the
Team
Leader
or
designee.
Analyte
specificity
is
demonstrated
by
acceptable
analyte
spike
recoveries.
Identically
Prepared
Samples.
Triplicate
sample
results
with
relative
standard
deviations
(RSDs)
greater
than
25%
place
the
analysis
out
of
control,
and
require
intervention
by
the
Team
Leader
or
designee.
Solvent
Blanks.
Concentration
results
for
solvent
blanksmust
exceed
neither
5%
of
the
highest
calibration
standard
nor
25%
of
the
lowest
calibration
level.
System
Suitability.
Suitability
was
demonstrated
by
either
an
abbreviated
mass­
to­
charge
(m/
z)
check­
tune
or
performance
of
a
full
auto­
tune
routine.

Anomalous
Analytical
Results
With
the
following
exceptions,
our
analytical
results
met
or
exceeded
the
data
quality
objectives
of`
Appendix
A.

Spike
Recoveries.
Results
for
five
of
the
eight
sample
triplicates
for
pH
=
3.0
failed
to
meet
`this
data
quality
objective.
Least
squares
determinations
of
a
slope
and
offset
from
the
three
remaining
data
points
at
this
pH
would
be
highly
undetermined,
so
we
have
excluded
all
the
pH
=
3.0
data
from
further
consideration.
Similarly,
results
for
seven
of
the
eight
sample
triplicates
for
pH
=
1
1
.O
failed
to
meet
this
data
quality
objective.
No
least
squares
determinations
of
a
slope
are
possible
in
this
case,
so
we
have
excluded
all
the
pH
=
11
.O
data
from
further
consideration.
Finally,
the
"Day
14"
samples
at
pH
=
1.5
(061500­
PFOA­
075
through
061500­
PFOA­
078)
failed
to
meet
this
spike
recovery
data
quality
objective,
and
we
have
excluded
these
data
from
the
following
rate
and
half­
life
estimates.

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Statistical
Methods
and
Calculations
Using
functions
provided
in
Microsoft@
Excel@
'
software,
we
calculated
means,
standard
deviations,
and
first­
order
rate
constants
(see
Appendix
B,
Equation
88)
for
various
subsets
of
the
acquired
data.
Our
linear
regrdssions
included
the
determination
of
constant
terms,
that
is,
we
did
not
force
the
regression
fits
to
pass
through
the
origin.

As
described
in
Appendix
B
(Equations
838
and
B39),
rates
measured
at
50°
C
were
extrapolated
to
25°
C
by
dividing
by
a
factor
of
10;
this
approximation
is
valid
for
reactions
with
Arrhenius
heats
of
activation
near
18
Kcal/
mole.
2
Data
Summary
and
Discussion
The
LOQ
is
defined
as
the
concentration
of
the
lowest
(accepted)
standard
in
the
calibration
set
for
which
the
known
concentration
exceeds
400%
of
the
indicated
solvent
blank
level
(see
Appendix
A).
During
this
study,
the
LOQ
for
PFOA
was
25
ng/
mL.
Results
for
the
internal
standard
(PFBS)
were
very
consistent
throughout
the
study.
The
percent
relative
standard
deviations
of
the
measured
values,
calculated
for
each
of
the
four
pH
levels
discussed
here
(1.5,
5.0,
7.0,
and
9.0),
ranged
from
1
to
2%.

Figure
2
illustrates
the
concentration
ratios
for
the
four
pH
levels
versus
time.
Table
4
presents
the
results
of
the
50°
C
rate
determinations
based
on
these
data.

Figure
2.
Observed
PFOA
Degradation
for
Various
pH
levels.

­"­­­­
I
0.04
1
*­­
.
I
.­

­._
:
..
.

1
­__
4
f.
­.
­0.12
­0.14
­0.16
­1
1
a
I
I
1
0
20
40
60
80
100
120
Time
(days)

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PH
Observed
Slope
(day­
')
Percent
(20)
Slope
Uncertainty
(day')

1.5
5.0
7.0
9.0
1.7
x
­1.5
x
1
.8
~
­1.1
x
597
76
664
244
I
I
The
slopes
in
Table
4
are
small
in
magnitude,
of
varying
sign,
and
only
poorly
determined;
their
percent
relative
2ts
(95%
confidence)
uncertainties
range
from
76%
to
664%.
The
data
do
not
indicate
degradation
of
PFOA
at
any
of
the
four
pH
levels.

In
the
absence
of
a
clear
trend
relating
the
degradation
rate
to
sample
pH,
it
is
appropriate
to
"pool"
the
data
from
all
pH
levels
and
to
determine
the
degradation
rate
using
the
entire
data
set.
The
mean
concentrations
(ng/
ml)
at
the
pH
levels
1.5,
5.0,
7.0,
and
9.0
are
464,
653,
649,
and
657.
The
pH
=
1.5
data
are
clearly
not
equivalent
to
the
data
at
the
other
three
pH
levels;
this
is
an
effect
of
ion
pairing
at
the
lowest
pH
level.
Under
these
circumstances,
the
only
reliable
data
for
a
pooled
estimate
are
the
data
at
pH
levels
5.0,
7.0,
and
9.0.
Figure
3
illustrates
the
results
of
this
pooled
analysis
according
to
Equation
1,
and
Table
5
summarizes
the
results
of
the
analysis.

Table
5.
Degradation
Rate
and
Half
Life
of
PFOA
in
Aqueous
Buffered
Solutions
Using
Data
Pooled
Over
pH
Levels
5.0,7.0,
and
9.0
I
Observed
Rate
Constant
at
50"
C
8.1
x
IO­"
Percent
(20)
Rate
Constant
Uncertainty
at
50"
C
(day­
')
Calculated
Rate
Constant
at
25"
C
(day1)
8.1
x
Calculated
Half
Life
at
25°
C
235
(years)
Calculated
(20)
Half
Life
Minimum
at
25"
C
(years)
92
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Figure
:3.
Pooled
(pH
=
5.0,
7.0,
and
9.0)
PFOA
Data
and
Slope
Regression.

0.05
CI
0
P
­
0.00
B
C
­
0
Solid
Line:
y
=
­8.08E­
05~
+
1.06E­
03
R2
=
7.49E­
02
0
Dashed
Lines:
20
limits
(slope
and
intercept)

0
20
40
60
80
100
120
time
(days)

The
mean
and
standard
deviation
of
the
PFOA
data
provide
an
alternative
estimate
of
its
half­
life.
Details
of
the
related
calculations
are
presented
below
in
Appendix
B.
The
maximum
degradation
rate
is
given
in
Equation
3
(see
Equation
836):

and
the
miniimum
half­
life
is
given
in
Equation
4
(see
Equation
837):
Eq.
3
Eq.
4
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______~~~
~

3M
Environmental
Laboratory
Report
No.
E00­
1851
A
t
(days)
109
In
both
Equations
3
and
4,
the
mean
PFOS
concentration
(p,)
and
standard
deviation
(
op)
can
be
either
molar
or
mass
quantities.
Table
6
presents
the
results
of
the
calculation.

Maximum
Maximum
Calculated
Observed
Rate
at
Calculated
Half
Life
50"
C
Rate
at
25"
C
at
25"
C
PP
0,

653
7.0
2.0
x
IO'
2.0
x
I
O
+
2
97
(ng/
ml)
(nglml)
(day­
')
(day
­I)
(years)

Page
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Conclusions
We
have
performed
a
study
of
the
aqueous
hydrolysis
of
perfluorooctanoic
acid
(PFOA)
at
50°
C
and
extrapolated
the
results
to
25°
C.
We
included
six
different
pH
levels
in
the
study,
though
data
from
two
of
these
pH
levels
(3.0
and
11)
failed
to
meet
the
data
quality
objective
for
matrix
spike
recovery.
We
also
rejected
the
data
obtained
for
pH
=
1.5
because
ion
pairing
led
to
artificially
low
concentrations
for
all
the
incubation
periods.
Our
results
for
the
remaining
pH
levels
(5.0,
7.0,
and
9.0)
indicate
no
clear
dependence
of
the
degradation
rate
of
PFOA
on
pH.
From
the
data
pooled
over
these
three
pH
levels,
we
estimate
that
the
hydrolytic
half­
life
of
PFOA
at
25°
C
is
greater
than
92
years,
with
the
most
likely
value
of
235
years.
From
the
mean
value
and
precision
of
PFOA
concentrations,
we
estimate
the
hydrolytic
half­
life
of
PFOA
to
be
greater
than
97
years.

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References
"Fate,
Transport
and
Transformation
Test
Guidelines:
835.21
I
O
:
Hydrolysis
as
a
Function
of
pH,"
U.
S.
EPA
Office
of
Prevention,
Pesticides
and
Toxic
Substances,
publication
number
71
2­
C­
98­
057,
January
1998.

p.
131,
1962.
Experimental
Physical
Chemistry",
F.
Daniels,
et
al.,
McGraw
Hill
Book
Co.
(New
York),

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Signatures
William
K.
R.
eagen,
Ph.
D.,
Laboratory
Management
Date
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~
~~

3M
Environmental
Laboratory
Report
No.
E00­
1851
Appendix
A:
Analytical
Method
Method
Number:
ETS­
8­
212.0,
"Preparation
of
Perfluorooctanoic
Acid
(PFOA)
Hydrolysis
Samples
in
Buffered
Solutions
and
Analysis
by
High
Performance
Liquid
Chromatography
with
Mass
Spectrometry
Detection."

This
Appendix
presents
the
analytical
method
employed
in
this
study.

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I
!
I
­"

~MENVIRONM
ENTAL
LABORATORY
METHOD
PREPARATION
OF
PERnUOROOCTANOIC
ACID
(PFOA)
HYDROLYSIS
SAMPLES
IN
BUFFERED
SOLUTIONS
AND
hJAL,
YSIS
BY
HIGH
PERFORMANCE
LIQUID
~OMATOGRAPHY
WITH
MASS
SPECTROlMETRY
DETECTION
Method
Number:
ETS­
8­
212.0
Adoption
Date:
3/
47
1''

Effective
Revision
Date:
.n)

Approved
By:

ETS­
8­
2
12.0
PFOA
Hy&
oIysis
mdAnalysis
by
WLC/
MS
Page
1
of
16
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I
k
1.0
SCOPE
AND
APPLICATION
1.1
This
method
describes
how
to
test
for
possible
hydrolysis
reactions
of
perfluorooctanoic
acid
(PFOA)
in
buffered
solutions
of
pHs
1.5,3.0,5.0,7.0,9.0,
and
11.0.
The
method
is
based
on
EPA
OPPTS:
835.2110
(Reference
18.1).
Hydrolysis
products
are
analyzed
by
high
performance
liquid
chromatography
(HPLC)
with
mass
spectrometry
(MS)
detection
and
quantitation.
PFOA
anion
is
quantified
using
the
anion
of
perfluorobutanesulfonate
(PFBS)
as
an
internal
standard.
Representative
chemical
structures
are
shown
in
Attachment
A.
Compatible
analytes.
PFOA
and
PFBS
samples
may
be
prepared
and
analyzed
by
this
method.
Acceptable
matrices.
Aqueous
buffered
solutions
ranging
from
pH
1.5
to
1
1
.O
are
accqtable.
Method
Performance.
This
method
is
defined
as
performancebased
(see
Section
14).
1.2
1.3
1.4
2.0
SUMMARY
OF
METHOD
2.1
This
method
is
based
on
OPPTS:
835.2110
and
has
been
modified
to
give
additional
infarmation.
Specifically,
multiple
time
points
over
far
longer
periods
of
time
are
used
to
provide
additional
information
regarding
the
hydrolytic
behavior.
Additional
pH's
are
tested
to
provide
insight
into
acidhase
catalysis.
Because
of
the
longer
time
points
used,
(e.
g.
109
days
vs.
7)
and
the
multiple
time
points
(7
or
8
vs.
2)
the
kperature
requirement
o
f
f
0.1
"C
has
been
relaxed
(it
is
impossible
to
hold
this
tight
of
temperature
and
open
the
incubator
to
take
out
samples.)
Oxygen
is
to
be
excluded
(according
to
the
OPPTS
methodology)
to
minimize
bacterial
growth.
However,
the
50°
C
temperature
used
in
the
present
study
is
forbidding
to
most
mesophillic
organisms
and
the
pH
dependence
for
bacterial
growth
is
different
than
that
observed
for
most
chemical
reactions
that
occur
in
water.
Aliquots
of
PFOA
solution
are
added
to
sample
vials
that
contain
5
mL
of
buffered
solution
of
pH
1.5,3.0,5.0,7.0,9.0,
or
11.0,
Appropriate
quality
control
samples
are
prepared.
Sample
vials
are
tightly
capped
and
placed
into
an
orbital
incubator/
shaker
at
50
f
3
"C
and
100
f
50
RPM,
except
for
Day
0
samples,
which
are
immediately
refrigerated
at
4
rt
3
"C
or
frozen
at
­20
f
10
"C.
Sample
vials
are
removed
fiom
the
incubatodshaker
at
designated
intervals
and
refrigerated
or
fkozen.
When
analyzed,
all
samples
are
allowed
to
come
to
room
temperature,
diluted
with
approximately
30
mL
of
methanol
containing
an
internal
standard,
spiked
(for
those
samples
receiving
spikes)
and
mechanically
shaken
for
approximately
15
minutes.
Samples
are
aliquoted
into
separate
autovials.
Calibration
and
quality
control
samples
are
pxpared.
PFOA
is
separated
on
a
reverse­
phase
Dionex
IonPac"
NG­
1
HPLC
column,
using
an
H,
O/
MeOH
solvent
gradient
containing
ammonium
acetate.
Analytes
are
detected
and
quantified
by
electrospray
ionization
mass
spectrometry
in
the
negative­
ion
mode.

ETS­
8­
212.01
PFOA
Hydrolysis
and
Analysis
by
HPLc/
Ms
Page
2
of
16
'

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I
t
.
.
r.__
.­
­
,
­
,­

3.0
DEFINITIONS
3.1
Method
blank.
The
method
blank
determines
if
there
is
contamination
of
the
matrix.
It
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
is
prepared
identically
to
other
samples,
but
it
does
not
contain
analyte
(see
Section
12.1.1).
It
is
used
alone
and
in
conjunction
with
a
method
spike
to
detect
accidental
contamination
(see
Section
14.3).
Method
spike.
A
method
spike
is
a
spiked
method
blank
(see
Section
12.1.1)
used
to
establish
that
the
sample
preparation
method
and
analytical
method
would
quantitatively
detect
target
analyte
in
the
method
blank.
(see
Section
14.6).
Solvent
(methanol)
blank.
To
isolate
instrument
contamination,
pure
methanol
is
analyzed.
If
the
instrument
is
contaminated,
analyte
will
be
detected
in
the
solvent
blank.
(see
section
14.4).
Sample
triplicates.
Samples
are
prepared
in
triplicate
for
each
time
point
and
pH,
and
are
analyzed
identically
(see
Section
12.1.1).
The
averaged
result
represents
the
PFOA
concentration
for
that
time
point
and
pH.
Sample
spike.
A
sample
spike
confim
that
the
method
recovers
analyte
effectively
fiom
the
sample
matrix
(see
Section
14.6).
A
known
amount
of
analyte
is
added
to
a
sample
after
it
is
incubated
(see
Sections
12.1.1).
Internal
standard
(IS).
An
internal
standard
is
used
to
evaluate
and
control
the
precision
(Section
3.7)
and
bias
(Section
3.8)
of
the
analytical
process.
An
analytically
similar
compound
is
added
to
all
samples
and
standards,
creating
a
known,
fixed
concentration
in
all
samples
and
standards
through
the
entire
measurement
process.
Precision.
Precision
is
the
degree
of
agreement
between
individual
sample
results.
It
is
usually
expressed
as
a
standard
deviation.
Bias.
Measurements
are
biased
if
they
are
consistently
high
or
low
(a
systematic
error),
as
compared
to
a
known
value.
Calibration
standard.
A
calibration
standard
is
a
solution
containing
a
known
concentration
of
analyte.
A
series
of
calibration
standards
is
used
to
calibrate
analytical
instrument
response,
producing
a
calibration
curve
to
determine
analyte
concentrations
in
samples.
Continuing
calibration
verification
(CCV)
or
Check
standard.
M
e
r
the
analytical
inslmment
has
been
calibrated,
a
single
calibration
standard
is
analyzed
at
selected
time
intervals
throughout
the
analytical
run.
The
values
are
compared
to
the
calibration
curve
to
ensure
that
the
calibration
curve
is
valid
for
all
samples
over
time,
that
the
instrum
ent
has
not
drifted
out
of
calibration.
Dilution.
A
miscible
solvent
is
added
to
all
samples
to
prepare
them
for
instnunental
analysis.
Laboratory
Water.
Water
with
a
measured
resistivity
of
18.0
MQ­
cm
(or
greater).
Limit
of
quantitation
(LOQ).
The
limit
of
quantitation
&OQ)
is
equal
to
the
concentration
of
the
lowest
standard
in
the
calibration
curve
that
gives
a
response
of
more
than
four
times
the
response
of
the
solvent
blanks
andor
MeOH
blanks.
Use
the
solvent
blanks
andor
MeOH
blanks
that
give
the
highest
analyte
counts.
Residuals.
In
this
method,
a
residual
is
the
absolute
value
of
the
difference
between
the
known,
prepared
concentration
of
a
calibration
standard
and
its
concentration
predicted
by
the
calibration
curve,
divided
by
the
known,
prepared
concentration,
all
multiplied
by
ETS­
8­
2
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Hydrolysis
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HPLUMS
Page
3
of
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24
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3M
Environmental
Laboratory
Report
No.
E00­
1851
I
/
."
~

..
­
*
__

100.
Residuals
for
linear
calibration
curves
can
be
determined
using
Excel.
For
non­
linear
calibration
curves,
the
following
equation
should
be
used
to
determine
a
residual.

4.0
WARNINGS
AND
CAUTIONS
4.1
Health
and
safely
warnings
4.1.1
4.1.2
4.1.3
Wear
the
proper
lab
attire
for
all
parts
of
this
procedure.
Wear
appropriate
gloves
and
proper
eyewear
at
all
times.
For
sample
preparation
and
whenever
possible,
use
solvents
in
the
hood.
For
potential
hazards
of
each
chemical
used,
refer
to
material
safety
data
sheets,
packing
materials,
and
3M
Environmental
Laboratories
Chemical
Hazard
1
Review.
4.2
Cautions
4.2.1
42.2
4.2.3
4.2.4
Rinse
all
glassware
for
standards
preparation
with
MeOH
and
acetone
and
dry,
to
reduce
the
possibility
of
contamination.
Prepare
enough
fresh
HPLC
mobile
phase
to
analyze
all
samples.
Do
not
allow
the
HPLC
pump
to
run
dry.
Ensure
that
there
is
ample
memory
on
the
computer
hard
drive
to
save
all
run
data.
Ensure
that
there
is
enough
nitrogen
in
the
supply
tank
to
analyze
all
samples.

5.0
INTERFERENCES
5.1
Contaminants
in
solvents,
reagents,
glassware,
and
other
sample
preparation
or
analysis
hardware
may
produce
interfiinces.
Routinely
analyze
method
blanks
to
detect
contamination
fiom
these
sources
(see
Section
10.4).
Contaminants
from
columns,
HPLC
tubing,
and
detector
components
may
cause
interference
at
low
detection
levels.
Routinely
analyze
solvent
blanks
(methanol)
to
detect
contamination
from
these
sources
(see
Section
10.5).
5.2
6.0
EQUIPMENT
6.1
6.2
6.3
Analytical
balance
sensitive
to
0.0001
g
Sh;
dcer/
incubator
capable
of
maintaining
a
temperature
of
50
k
3
OC
Hewlett­
Packard
(HP)
1100
HPLC
System,
or
equivalent
6.3.1
Quaternary
pump,
Model
G1311A,
or
equivalent
6.3.2
Solvent
degasser,
Model
G1322A
or
equivalent
,

6.3.3
Autosampler,
ALS
Model
G1313A,
variable
injection
volume
capable,
or
equivalent
6.3.4
Column
heater,
Model
G13
16A
or
equivalent
Dionex
IonPac@
NG­
1
column,
35
mm
x
4.0
mm,
10­
pn
dime&
packing,
or
equivalent
6.4
ETS­
8­
212.0
PFOA
Hydroiysis
and
Analysis
by
HPLUM
Page
4
of
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25
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99
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MAIN
6.5
6.6
6.7
6.8
6.9
6.10
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
3M
Environmental
Laboratory
Report
No.
E00­
1851
~.
I.
"
I
a
.

Mass
spectrometer.
Hewlett­
Packard
LCMSD,
or
equivalent,
capable
of
operating
in
the
selected­
ion­
monitoring
mode
Digital
clock.
The
same
clock
should
be
used
during
any
one
step
of
sample
preparation,
to
emure
that
procedures
are
performed
correctly
and
documented
.accurately.
Corning
Model
308
pH/
Temperature
Meter
with
3­
in­
1
gel­
filled
combination
electrode
(pH/
reference/
temperature),
or
equivalent.
The
pH
meter
must
be
calibrated
with
suitable
buffer
standards
(e.
g.
pH
4.0,7.0
and
9.0
­
Mallinckrodt
or
equivalent)
as
recommended
by
the
manufacturer
for
this
broad
of
a
pH
range.
Refrigerator,
capable
of
maintaining
4
f
3
"C,
or
a
freezer
capable
of
maintaining
­20
f
10
OC
Data
system.
A
PC
computer
capable
of
simultaneously
controlling
the
HPLC
system
and
recording
and
processing
signals
from
the
detector
Data
analysis
sohare.
Hewlett­
Packard­
ChemStation@,
Version
A
6.03
or
higher,
or
Target
Software.

SUPPLIES
AND
MATERIALS
­
Vials,
40­
mL
VOA
(I­
CHEM
or
equivalent)
Crimpcap
autovials,
1
.5
­d
Labels
Graduated
pipets,
glass,
disposable,
1
­mL
to
10­
mL
Pasteur
pipets,
glass,
disposable
Hamilton
Gastight@
syringes
(precision
f
1%
of
total
volume),
lo­@
to
1000­
pL
Volumetric
flasks,
lo­,
2
5
,
loo­,
1
000­,
and
4000­
mL.
Beakers,
glass,
various
sizes
Automatic
pipettor,
capable
of
dispensing
10
to
5000
pL
Miscellaneous
equipment
as
needed
8.0
RE.
4GENTS
AND
SOLUTIONS
8.1
Rewents
8.1..
1
Methanol
(MeOH).
HPLC/
SPEC/
GC
grade
from
EM
Science,
or
equivalent
8.1.2
Laboratory
Water
(LW)
8.1.3
Hydrochloric
acid
(HCl),
reagent
grade
8.1.4
Sodium
hydroxide
(NaOH),
reagent
grade
8.1.5
Sodium
borate
decahydrate
(borax),
reagent
grade
8.1.6
Sodium
bicarbonate
(NaHCO,),
reagent
grade
8.1.7
Potassium
dihydrogen
phosphate
(KHzP04),
reagent
grade
8.1.8
Potassium
acid
phthalate
(KHP),
reagent
grade
8.1.9
Ammonium
acetate
(CH,
COz+
JH,),
reagent
grade
8.1.10
Potassium
salt
of
Perfluorooctanoic
acid
(PFOA)
8.1.11
Potassium
salt
of
Perfluorobutanesulfonate
(PFBS)
8.2
&ick
Solutions
ETS­
8­
212.0
PFOA
Hydrolyssb
and
Analysis
by
HPLUMS
Page
5
of
16
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8.3
8.4
8.5
8.6
8.7
8.8
8.2.1
8.2.2
8.2­
3
8.2.4
8.2.5
8.2.6
82.7
8.2.8
3M
Environmental
Laboratory
Report
No.
E00­
1851
I
,.
.
~

.,
­

Ammonium
acetate
stock
solution.
Dissolve
approximately
3.9
g
CH3C02;
NH,
in
MeOH
to
a
total
volume
of
100
mL
to
give
approximately
500
mM
CH,
C02­
NH4.
PFOA
stock
solution.
Dissolve
approximately
0.1000
g
of
PFOA
in
MeOH
to
a
total
volume
of
10
mL
to
give
approximately
10,000
p
g
/d
PFOA.
PFBS
stock
solution.
Dissolve
approximately
0.0500
g
of
PFBS
in
MeOH
to
a
total
volume
of
25
mL
to
give
approximately
2,000
pg/
mL
PFBS.
Hydrochloric
acid
(HCI)
stock
solution.
Add
approximately
8.6
mL.
of
concentrated
HC1
to
approximately
600
mL
LW,
dilute
to
a
total
volume
of
1
L
to
give
approximately
0.1
M
HC1.
Sodium
hydroxide
(NaOH)
stock
solution.
Dissolve
approximately
4.0
g
of
solid
NaOH
in
LW
to
a
total
volume
of
1
L
to
give
approximately
0.1
M
NaOH.
Potassium
dihydrogen
phosphate
stock
solution.
Dissolve
approximately
13.6
g
of
KH2P0,
in
LW
to
a
total
volume
of
1
L
to
give
approximately
0.1
M
(KH2P04).
Borax
stock
solution.
Dissolve
approximately
9.54
g
of
N~
B40,~
10H20
in
LW
to
a
total
volume
of
1
L
to
give
approximately
0.025
M
N5t2B40,.
Sodium
bicarbonate
stock
solution.
Dissolve
approximately
4.2
g
of
NaHCO,
in
LW
to
a
total
volume
of
1
L
to
give
approximately
0.05
M
NaHCO,.
PFOA
test
analyte
solution.
Dilute
2
mL
of
PFOA
stock
solution
(Section
8.2.2)
with
MeOH
to
a
total
volume
of
10
mL
to
give
approximately
2,000
pg/
mL,
PFOA.
PFOA
spike
solution.
Dilute
0.5
mL
of
PFOA
stock
solution
(Section
8.2.2)
with
MeOH
to
a
total
volume
of
10
mL
to
give
approximately
500
p
g
/d
PFOA.
PFBS
diluting
solution.
Dilute
400
pL
of
PFBS
stock
solution
(Section
8.2.3)
with
MeOH
to
a
total
volume
of
4
L
to
give
approximately
200
ng/
mL
PFBS.
Chromatographic
solvents
8.6.1
Chromatographic
solvent
A.
Dilute
10
mL
of
ammonium
acetate
stock
solution
(Section
8.2.1)
LW
to
a
total
volume
of
1
L
to
give
approximately
5
mM
CH,
CO,*
NH,.
Chromatographic
solvent
B.
Dilute
10
mL
of
ammonium
acetate
stock
solution
(Section
8.2.1)
with
MeOH
to
a
total
volume
of
1
L
to
give
approximately
5
mM
CH,
COyNH,.
8.6.2
Calibration
buffers
for
pH
meter.
Use
commercially
available
pH
meter
calibration
buffers
of
pH
4.0,7.0,
and
10.0
(Mallinckrodt
or
equivalent)
as
recommended
by
the
manufacturer
for
this
broad
of
a
pH
range.
Hydrolysis
buffers.
Buffer
solutions
should
be
made
following
EPA
and
CRC
Handbook
of
Chemistry
and
Physics
guidelines
(References
18.1
and
18.2)
8.8.1
Hydrolysis
buffer
pH
1.5
a)
Add
207
mL
0.1
N
HCl,
250
mL
0.1
M
KC1
to
a
1
L
volumetric
flask.
b)
Adjust
pH
to
1.5
with
HCl
stock
solution
c)
Dilute
to
mark
with
LW
a)
Dissolve
approximately
10.2
g
of
potassium
acid
phthalate
(KHP)
with
approximately
600
mL
of
LW
water
in
a
1
L
volumetric
flask.
b)
Add
approximately
223
mL
of
HC1
stock
solution
(Section
8.2.4).
8.8.2
Hydrolysis
buffer
pH
3.0
ETS­
8­
212.0
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Hydrolysis
and
Analysis
by
HPLC/
uS
Page
6
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3M
Environmental
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Report
No.
E00­
1851
I
I
c)
Adjust
the
pH
to
3.0
with
either
HC1
stock
solution
(Section
8.2.4)
or
NaOH
d)
Bring
to
a
find
volume
of
1
L
with
LW.

a)
Dissolve
approximately
10.2
g
of
potassium
acid
phthalate
(KHP)
with
b)
Add
approximately
226
mL
of
NaOH
stock
solution
(Section
8.2.5).
c)
Adjust
the
pH
to
5.0
with
either
HCl
stock
solution
(Section
8.2.4)
or
NaOH
d)
Bring
to
a
final
volume
of
1
L
with
LW.

a)
Add
approximately
500
mL
of
potassium
&hydrogen
phosphate
stock
b)
Add
approximately
291
mL
ofNaOH
stock
solution
(Section
8.2.5).
c)
Adjust
the
pH
to
7.0
with
either
HC1
stock
solution
(Section
8.2.4)
or
NaOH
d)
Bring
to
a
final
volume
of
1
L
with
LW.

a)
Add
approximately
500
mL
of
borax
stock
solution
(Section
8.2.7)
to
a
1
L
b)
Add
approximately
46
mL
of
HCl
stock
solution
(Section
8.2.4).
c)
Add
LW
to
a
total
volume
of
approximately
950
mL.
d)
Adjust
the
pH
to
9.0
with
either
HCl
stock
solution
(Section
8.2.4)
or
NaOH
stock
solution
(Section
8.2.5).
e)
Bring
to
a
final
volume
of
1
L
with
LW.

a)
Add
approximately
500
mL
of
sodium
bicarbonate
stock
solution
b)
Add
approximately
227
mL
of
NaOH
stock
solution
(Section
8.2.5).
c)
Add
LW
to
a
total
volume
of
approximately
950
mL.
d)
Adjust
the
pH
to
11
.O
with
NaOH
stock
solution
(Section
8.2.5).
e)
Bring
to
a
final
volume
of
1
L
with
LW.
stock
solution
(Section
8.2.5).

8.83
Hydrolysis
buffer
pH
5.0
approximately
600
mL
of
LW
in
a
1
L
volumetric
flask.

stock
solution
(Section
8.2.5).

8.8.4
Hydrolysis
buffer
pH
7.0
solution
(Section
8.2.6)
to
a
1
L
volumetric
flask.

stock
solution
(Section
8.2.5).

8.8.5
Hydrolysis
buffer
pH
9.0
volumetric
flask.

8.8.6
Hydrolysis
buffer
pH
11.0
(Section
8.2.8)
to
a
1
L
volumetric
flask.

9.0
SAMPm
HANDLING
9.1
Retard
the
times
that
samples
were
initially
prepared,
removed
fiom
the
incubator,
placed
in
the
fkeezer
(when
applicable),
removed
from
the
hezer
(when
applicable)
and
subsequently
diluted,
using
the
fluorochemical
degradation
(hydrolysis)
analysis
sample
preparation
sheet
(Attachment
B).
All
samples
for
the
same
pH
group
should
be
analyzed
together.
RefXgerate
or
freeze
them
if
necessary,
and
dilute
them
immediately
preceding
the
analysis.

10.0
QUALITY
CONTROL
10.1
Sa:
Section
12
for
directions
on
preparing
quality
control
samples.

ETS­
8­
2
12.0
PFOA
Hydrolysis
and
Andysis
by
HPLC/
MS
Page
7
of
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102
10.3
10.4
10.5
10.6
10.7
10.8
11.0
3M
Environmental
Laboratory
Report
No.
E00­
1851
Calibration
standards.
Analyze
a
complete
series
of
calibration
standards
before
and
after
each
analytical
run
for
use
as
calibration
curve.
At
the
discretion
of
the
analyst,
t
h
i
s
complete
series
may
be
run
more
often
in
the
d
y
t
i
c
a
l
run.
Continuing
calibration
venfiation
(CCV).
A
CCV
sample
should
be
analyzed
after
no
more
than
20
sample
injections.
A
single
calibration
standard
or
a
complete
series
of
such
standards
(for
use
as
a
calibration
curve)
will
satisfy
this
requirement.
Method
blank.
Analyze
a
minimum
of
one
method
blank
per
time
point
per
pH
(e.
g.,
Day
42,
pH
7.0).
Solvent
blank.
Analyze
one
solvent
blank
before
and
after
every
calibration
curve
as
well
as
before
and
after
every
CCV.
Sample
triplicates.
Prepare
and
analyze
all
hydrolysis
samples
in
triplicate
to
determine
analysis
precision.
Sample
spikes.
Prepare
a
sample
spike
for
each
pH
and
time
point
used
in
the
study.
Final
(diluted)
spike
concentrations
should
approximate
a
mid­
range
calibration
standard.
The
sample
spike
sample
should
be
analyzed
immediately
following
the
sample
triplicates
to
which
it
corresponds.
Internal
standards.
Aliquots
of
PFBS
stock
solution
(Section
8.2.3)
are
added
to
calibration
standards
to
give
a
final
internal
standard
concentration
of
approximately
158
ng/
mL
PFBS.
Samples
should
also
contain
approximately
the
same
concentration
of
PFRS.
CALIBRATION
AND
STANDARDIZATION
11.1
11.2
Standard
preparation.
Prepare
at
least
five
calibration
standards
of
approximately
25
to
1000
ng/
mL
PFOA,
containing
approximately
158
ng/
mL
PFBS
internal
standard.
Standard
curve.
Relate
the
ratio
of
the
analyte
peak
area
of
the
calibration
standards
to
the
internal
standard
peak
area,
using
linear
regression
software.
If
calibration
ratios
are
inconsistent,
external
standard
calibration
may
be
used.
Consult
the
Team
Leader
or
designated
supervisor
for
recommendations
before
using
external
calibration.

12.0
PROCEDURES
ETS8­
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.
1
..
..
~,
...
.....
...
._
.._....._..._.
..
...,_.._I
.....
.
,.
._

Analyte
X
Calibration
standards
12.1
Sample
preparation
and
hydrolysis
12.1.1
The
following
table
summarizes
sample
preparation.

Diluting
solution
Buffer
containing
Spike
internal
standard
X
X
­­
Methanol
only
Incubate
/shake
Methodblanka
I
­­
I
X
I
X
I
­­
Continued
Calibration
verification
(CCV)
X
X
X
­­

Triplicate
I
X
I
X
1
X
I
.
­­
Solvent
blank
Sample
Duplicate
­­
­­
­_
­­
X
X
X
­­
X
X
X
Sample
spikeb
Method
spikeC
­­
I
x
X
X
X
X
­­
X
X
X
­
I
x
­­
­­
I
x
X
12.1.2
Determine
the
number
of
time
points
and
corresponding
samples
to
be
analyzed.
Each
time
point
should
have
six
vials
per
pH:
sample,
duplicate,
triplicate,
sample
spike,
method
spik,
and
method
blank.
12.1.3
Obtain
the
appropriate
number
of
40­
mL
VOA
vials
with
caps,
and
the
partitioned
cardboard
box
they
were
shipped
in.
It
will
be
helpll
to
use
a
separate
box
to
hold
the
vials
for
each
time
point.
12.1.4
Prepare
sample
preparation
worksheets
(Attachment
B),
ahd
label
the
vials
with
the
sample
number,
pH,
time
point,
and
initials
of
the
analyst.
Record
the
pH
and
buffer
ID
of
each
hydrolysis
buffer
solution.
12.1.5
Add
5
mL
of
the
appropriate
buffer
solution
to
all
of
the
labeled
vials.
Always
recap
each
vial
immediately
to
minimize
solvent
evaporation.
12.
l.
6
Using
a
10­
pL
Gastight'
syringe,
add
15
pL
of
PFOA
test
a
d
*
solution
(Section
8.3)
to
the
following
sample
types
for
each
time
point
and
pH:
sample,
duplicate,
triplicate,
and
sample
spike
(see
Section
12.1.1).

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12.1.7
Make
sure
all
vials
are
well­
sealed,
and
place
them
into
a
partitioned
cardbard
case
(with
cover)
to
exclude
light.
It
will
be
helpful
to
use
a
separate
box
to
hold
the
vials
for
each
time
point.
12.1.8
Refrigerate
Day
0
samples
at
4
*
3
OC,
or
freeze
them
at
­20
f
10
"C.
12.1.9
Place
the
remaining
samples
into
a
pre­
warmed
incubator/
shaker
for
the
appropriate
time.
Record
the
time,
temperature,
and
shaking
rate
(RPM).
Continue
to
manually
monitor
the
incubator
temperature
daily
during
the
entire
incubation.
Record
the
temperature
on
the
sample
preparation
sheet
(Attachment
B).
12.1.10
Remove
each
case
fiom
the
incubator
at
the
designated
time.
Refiigmte
them
at
4
f
3
"C,
or
fieeze
them
at
­20
f
10
"C,
until
all
samples
h
m
all
time
points
can
be
analyzed
together.
12.1.11
Before
analysis,
allow
the
incubated
vials
to
come
to
room
temperature.
12.1.12
Add
30
mL
of
PFBS
diluting
solution
(Section
8.5)
to
all
vials.
12.1.13
Using
a
10­
yL
Gastight'
syringe,
add
10
yL
of
PFOA
spike
solution
(Section
8.4)
to
the
method
spike
and
sample
spik
vials
(see
Section
12.1
A).
Recap
the
vials
tightly,
and
invert
them
several
times
to
mix.

autovial.
Cap
the
vials.
12.1.14
Aliquot
approximately
1
mL
of
each
sample
into
the
appropriately
labeled
12.1.15
Transfer
the
vials
to
the
HPLC
autosampler.
HPLC
set­
up
123.1
Review
instrument
method
1
101
PF0A.
M.
Note
that
the
following
instrumentation
set­
up
procedures
apply
to
Hewlett­
PacbdAgilent
HPll
00
equipment
only.
12.2.2
For
each
analysis,
ensure
the
appropriate
HPLC
column
is
in
the
instrument
(Dionex
IonPacdPNG­
l,
35
mm
x
4.0
mm,
10­
pm
diameter
packing,
or
equivalent).
12.23
Ensure
the
correct
type
and
amount
of
eluent
is
loaded
in
the
instrument.
Be
sure
there
is
enough
loaded
to
complete
the
analytical
sequence.
12.2.4
Place
the
samples
in
the
autosampler
tray
and
construct
a
sequence
table
with
calibration
standards,
calibration
check
standards,
and
solvent
blanks.
12.2.5
Verify
that
all
samples
and
standards
are
positioned
correctly.
Enter
sequence
information:
sample
or
standard
ID,
method
name,
and
one
injection
per
sample.
12.2.6
Save
sequence
as
analysis
date
(e.
g.,
on
September
14,2000
save
sequence
as
091400.
s).
Save
data
to
a
subdirectory
labeled
with
analysis
date
(e.
g.,
091400).
12.2.7
Set
the
post­
sequence
command
macro
to
shut
the
system
down
("
STANDBY"
on
HP
systems).
12.2.8
Use
the
following
solvents
(see
Section
8.6),
gradient,
and
instrument
settings
(or
equivalent
­
note
that
the
following
instrumentation
set­
up
procedures
apply
to
Hewlett­
PackardAgilent
Hpl
100
MSD
equipment
only).
12.2.8.1
Chromatographic
solvent
A
(Section
8.6.1).
12.2.8.2
Chromatographic
solvent
B
(Section
8.6.2).
12.2.8.3
Solvent
Gradient
ETS­
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12.2.8.4
Instrument
settings
12.3
Mass
spectrometer
set­
up
123.1
Use
the
following
tables
(or
equivalent)
to­
set
up
the
mass
spectrometer.
(Note
that
the
following
instrumentation
set­
up
procedures
apply
to
Hewlett­
PackardAgilent
HP
1
100
MSD
equipment
only.)

*
M­
I­
I+
is
the
molecular
ion
with
a
loss
of
proton.
For
example,
the
molecular
weight
of
PFBS
is
300,
when
it
loses
a
proton,
it
assumes
a
negative
charge
and
has
a
mass
of
299.

12.4
Autosampler
set­
up
12.#
4.1
Use
the
following
parameters
(or
equivalent)
to
set
up
the
autosampler.

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*
.
­­.
,
.
~

­_
~

.._

12.5
Sample
analysis
12.5.1
After
setting­
up
the
HPLC,
the
mass
spectrometer,
and
the
autosampler,
analyze
a
CCV
after
every
20
sample
injections,
and
the
calibration
standards
at
the
end
of
the
sequence.
To
check
for
analyte
carry­
over,
run
solvent
blanks
after
the
highest
calibration
standard
as
well
as
before
and
after
the
,CCV
(see
Section
10.0).
12.52
Identify
the
electronic
acquisition
files
with
an
appropriate
prefix.
Do
not
exceed
five
characters
if
the
sequence
contains
more
than
99
lines.

13.0
DATA
ANALYSIS
AND
CALCULATIONS
13.1
Peak
evaluation.
Anal@
and
internal
standard
peaks
must
be
symmetrical
­
if
peak
tailing
is
observed,
consult
team
leader
or
designee
for
direction.
They
must
be
identified
by
measuring
their
retention
times
and
by
the
compo'und­
specific
ions.
When
generating
a
calibration
curve,
analyte
peak
heights
must
be
greater
than
four
times
the
baseline
noise
and/
or
solvent
blank
for
that
region
of
the
chromatogram.
Peak
areas
are
integrated
manually
or
automatically
fiom
baseline
to
baseline
through
the
peak.
If
present,
analyte
isomers
appearing
as
either
a
shoulder
or
a
discrete
second
peak
in
the
chromatogram
should
be
integrated
with
the
analyte
peak,
unless
otherwise
indicated.
Quantitation
data
are
calculated
using
PFBS
as
the
internal
standard.
However,
external
standard
calibration
may
be
acceptable.
Consult
the
Team
Leader
or
designated
supervisor
before
using
external
calibration
methodology.
Calculations
involving
analyte
purity.
In
calculations
where
analyte
purity
ratios
cancel
each
other
(e.
g.,
calculation
of
the
hydrolysis
rate
constant,
k
based
on
loss
of
parent
material),
purity
does
not
need
to
be
considered.
Percent
recovery.
Calculate
the
percent
of
PFOA
recovered
from
each
of
the
sample
spikes
using
the
following
equation.
13.2
133
x
100%
[
PFOA]
dcrecred
in
mpie
spike
­
[
PFOA]
detected
in
comspondig
~mnpl.

[
PFOA]
in
SompIe
spike,
added
via
s
p
~e
%
Recovery
=

13.4
Sample
triplicates.
Use
the
following
equation
to
calculate
the
relative
standard
deviation
(RSD)
for
the
triplicate
samples.

x
100%
Standard
Deviation
Mean
Concentration
RSD
=

The
RSD
is
also
known
as
the
coefficient
of
variation,
a
measure
of
the
precision.

13.5
Calculation
of
k.
Calculate
the
PFOA
concentrations
in
each
of
the
pH
matrices
using
the
calibration
and
internal
(or
external)
standard
curves.
Assuming
frrst­
order
kinetics
a
rate
constant
(k)
can
be
determined
by
plotting
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.I.
..
.;
....
.
.
.I
.­
..
._.
,
..
­.
.
..
,
..
.
.
,
,
.
,.
.
,
.
.
.
.

I
Ln
(E;)
versus
negative
elapsed
time
(­
0,

where
the
subscripts
t
and
0
refer
to
analyte
concentrations
at
time
t
and
at
r
=
0,
respectively.
The
slope
of
the
resulting
line
is
k.

14.0
METHOD
PERFORMANCE
14.1
Calibration
curves.
An
acceptable
coefficient
of
determination
(R')
for
linear
curves
is
14.2
14.3
14.4
14.5
14.6
14.7
14.8
14.9
0.9!?
0
or
greater.
Accuracy
should
be
verified,
particularly
at
upper
and
lower
calibration
limits
by
calculating
the
residuals
­residuals
generated
in
curve­
fitting
must
be
between
0
and
25%.
Alternative
methods
of
curve­
fitting
(e.
g.,
quadratic)
require
a
coefficient
of
determination
(9)
of
0.990
or
greater.
Record
the
reason(
s)
for
using
quadratic
curve­
fitting
in
the
raw
data.
If
the
quality
control
parameters
are
not
met,
consult
team
leader
or
designee
for
direction.
Continuing
calibration
verification
(CCV).
Analyte
concentration
must
not
differ
by
more
than
25%
of
its
expected
value,
relative
to
the
initial
calibration
curve.
Accept
only
those
samples
analyzed
before
the
last
accepted
calibration
verification.
Reanalyze
remaining
samples
with
a
new
calibration
curve.
Method
blank.
If
the
contamination
levels
are
greater
than
5%
for
any
particular
target,
consult
the
Team
Leader
or
designated
supervisor
for
recommendations.
For
example,
if
PFOA
were
targeted
at
500
ppb,
contamination
should
be
less
than
25
ppb.
In
those
instances
where
the
5%
level
would
be
below
the
lowest
point
of
the
calibration
curve,
a
25%
value
is
used
rather
than
the
5%
(as
5%
cannot
be
quantified
and
the
25%
level
brings
this
in
line
with
the
LOQ
definition,
see
section
14.8).
Solvent
blanks.
Solvent
blanks
should
show
no
more
than
a
5%
carry­
over
from
a
high
standard
or
CCV.
If
they
do,
two
solvent
blanks
should
be
analyzed
to
rule
out
instrument
contamination.
If
solvent
blanks
are
still
showing
more
than
5%
carry­
over,
or
are
adversely
af3Fecting
the
LOQ
(see
Section
14.8),
the
run
should
be
stopped.
This
indicates
that
the
instrument
is
contaminated
and
should
be
thoroughly
cleaned.
Pay
particular
attention
to
the
electrospray
source.
The
column
and
tubing
may
need
to
be
replaced.
When
the
solvent
blanks
are
improved,
reanalyze
the
sequence
beginning
at
the
last
acceptable
CCV
or
calibration
curve,
starting
with
a
new
calibration
curve.
Sample
triplicates.
If
RSD
precision
values
are
25%
or
greater,
consult
the
Team
Leader
or
designated
supervisor
for
recommendations.
Sample
spikes.
If
sample
spike
recoveries
are
less
than
70%
or
greater
than
130%,
conlsult
the
Team
Leader
or
designated
supervisor
for
recommendations.
Residuals.
The
acceptance
criterion
for
the
residuals
is
less
than
or
equal
to
f
25%.
If
the
residuals
are
higher
than
this,
consult
team
leader
or
designee
for
direction.
No
calibration
curve
will
be
accepted
with
residuals
outside
this
range.
Limit
of
Quantitation.
The
limit
of
quantitation
(LOQ)
is
equal
to
the
lowest
standard
in
the
calibration
curve
that
gives
a
response
of
more
than
four
times
that
of
the
test
anadyte
in
the
solvent
blanks.
Method
Spike.
If
method
spike
recoveries
are
less
than
70%
or
greater
than
130%,
corlsult
the
Team
Leader
or
designated
supervisor
for
recommendations.

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15.0
POILUTION
PREVENTION
AND
WASTE
MANAGEMENT
15.1
Dispose
of
sample
waste
by
placing
it
in
high
or
low
BTU
containers
as
appropriate.
Use
broken
glass
containers
to
dispose
of
glass
pipettes.
15.2
Collect
HPLC
solvent
waste
in
the
satellite
accumulation
can.
When
the
satellite
can
is
full,
empty
it
into
the
flammable
storage
drum
in
the
hazardous
vvaste
collection
area
on
the
second
floor.

16.0
RECORDS
16.1
Print
out
hard
copies
of
all
graphics
and
data
analysis
summaries
for
archiving.
16.2
16.3
16.4
16.5
16.6
16.7
16.8
17.0
Sign
and
date
all
graphics,
and
label
with
the
instrument
ID.
Immediately
fill
out
the
hydrolysis
sample
preparation
worksheet
completely,
including
all
initials
and
dates.
Print
chromatograms
and
internal
standard
reports
for
all
analyses.
Print
calibration
tables
and
curve
information,
and
store
them
in
the
raw
data
file.
Store
hydrolysis
sample
preparation
worksheets
in
the
raw
data
file.
Enter
all
standard
preparation
information
in
the
standards
prepmation
logbook.
Make
a
photocopy
of
the
logbook
page
and
include
the
copy
in
the
raw
data
file.
Archive
electronic
data
to
appropriate
media
when
necessary.

ATTACHMENTS
17.1
17.2
Attachment
A.
Representative
Chemical
Structures
Attachment
B.
Hydrolysis
Sample
Log
sheet
18.0
REFERENCES
18.1
Fate,
Transport
and
Transformation
Test
Guidelines
OPPTS
83.
i.
21
IO:
Hydrolysis
as
a
Function
ofpH;
EPA
712­
C­
98­
057;
U.
S.
Environmental
Protection
Agency,
Office
of
Prevention,
Pesticides
and
Toxic
Substances,
U.
S.
Government
Printhg
Office:
Washington,
DC,
1998.
CRC
Handbook
of
Chemistry
and
Physics,
1
st
Student
Edition;
We&,
R.
C.,
Ed.,
CRC
Press:
Cleveland,
OH,
1988;
p.
D­
87.
18.2
19.0
AFWECTED
DOCUMENTS
None.

20.0
REVISIONS
&ision
Number
Reason
for
Revision
ETS­
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Hydolysis
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.

Attachment
A.
Representative
Chemical
Structures
R'
=
NH,
'
in
this
study,
but
may
also
be
Li',
Na',
K+,
H'.

1.
PFOA
(Perlluorooctanoic
Acid)
h4W
(anion)
=
413
2.
PFBS
(?
erlluorobutanesulfonate)
MW
(anion)
=
299
ETS­
8­
212.0
PFOA
Hydrotysis
anddnalysis
by
HPLC/
US
Page
15
of
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I
/

Attachment
B.
Sample
Preparation
Sheet
Fluorochemlcal
Degradation
(Hydmiysls)
Aniilysb
ETS­
8­
2
12.0
PFOA
Hydrolysis
and
Analysis
by
HPLUMS
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16
of
16
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3M
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Report
No.
E00­
1851
Appendix
B:
Kinetics
Model
This
Appendix
includes
a
mathematical
description
of
the
kinetics
m'odel
employed
in
the
study.

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Kinetics
Model
B1.
Reaction
Components
and
Rates
The
arguments
below
are
based
on
the
following
idealized
set
of
reactions
representing
the
hydrolysis
of
a
parent
compound
P
and
its
hydrolysis
products
A,,
which
number
N.
The
actual
hydrolysis
reactions
that
occur
under
neutral,
acidic,
and
basic
conditions
are
subsumed
in
these
equations,
and
are
assumed
to
proceed
with
pseudo­
first
order
rates
k,,
(for
the
parent)
and
k,,
(for
the
parent's
hydrolysis
products).

(81)
k,
@
n,
A,
+
Yd
P
+
H
2
0
(m
=
1
toN)

(82)
k
h
A,
+H,
O
Ym2
(m=
1
toN)

where
the
general
symbols
Y,,
and
Ym2
represent
all
the
other
hydrolysis
products.

B2.
Parent
Compound
Concentrations
Equation
B
I
indicates
that
the
pseudo­
first
order
differential
change
in
the
parent
concentratioln
P
is
given
by
which
is
equivalent
to
the
separable
differential
equation
dp=($
P
nm
kpm]
dt
Equation
84
may
be
directly
integrated
to
obtain
the
general
solution
With
the
initial
condition
P(
t
=
0)
=
Po,
the
specific
solution
to
Equation
B4
is
P
=
Po
exp
[
­
n,
k,,
t)­
Po
e­
kp
using
the
additional
definition
of
the
total
parent
hydrolysis
rate
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3M
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N
k,
nm
k,,
.

m
1
Equation
BE;
can
be
re­
written
in
a
form
that
allows
a
least­
squares
estimate
of
the
total
parent
hydrolysis
rate:

k,
t
=­
In
[
9)

Using
the
initial
(t
=
0)
measured
value
of
the
parent
concentration
Po
and
later
values
P
measured
at
later
times
t
,
one
can
calculate
and
plot
the
(linear)
quantity
[­
In
(P/
Po
11
versus
time
and
obtain
a
least
­squares
estimate
of
the
slope
of
the
line.

The
resulting
slope
is
the
least­
squares
estimate
f,
of
the
total
parent
hydrolysis
rate.

Equation
B6i
indicates
that
over
a
period
of
time
T1'i
(the
parent
hydrolysis
half­
life)
the
parent
concentration
P
is
reduced
through
hydrolysis
by
a
factor
of
two,
where
2)

=
k,

A
least
squares
estimate
?q;
of
the
parent
hydrolysis
half­
life
is
therefore
available
from
B3.
Product
Compound
Concentrations
The
pseudo,­
first
order
differential
changes
in
the
product
concentrations
4,
(using
Equations
82
and
B6)
are
dA,
=
(
n,
kpmP
­
kAmAm)
dt
=
(
nmkPmPO
e­
kp
­
kAmA,)
dt
(B11)

and
the
(first
order,
non­
separable)
differential
equation
governing
the
product
concentrations
is
%+
k,
Am
=
nmkPmPO
e­
kpt
.
dt
The
"standard
form"
of
Equation
B12
is
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AA+
S(
t)
Arn
=Q(
t)

where
the
"function"
S
(t)
is
actually
a
constant:

s
(`
1
and
Q(
t)
=
nmkPmPO
e­
kpt
.

The
general
solution
A,
to
Equation
61
2
is
contained
in
where
and
IS(
t)
dt
­
IS(
t')
dt'
­
k
h
l
d
t
­
e
k
b
t
e
­e
­e
­

Q(
t)
dS(
t')
dt'
dt
+
C
=
n,
kprnPo~
ekht
e­
kptdt
+
C
I
There
are
two
cases
of
Equation
B18
to
consider.
In
the
circumstance
that
k,,
=
k,
,
which
occurs
only
when
the
hydrolysis
rate
of
the
mth
product
is
identical
to
the
total
parent
hydrolysis
rate,
the
general
solution
to
Equation
B18
is
(for
k,
=
k,)

A,
ekpt
=
nmkPmPO
t
+
C
and,
using
the
initial
condition
A,(
t
=
0)
=
A,
,
the
specific
solution
to
Equation18
is
(for
k,
=
k,)

A,
=(
nmkPmPO
t+
A,
o)
e­
kpt
.

We
note
that
when
k,
=
k,
=
0
(that
is,
when
both
the
parent
and
potential
product
are
hydrolytically
stable),
Equation
B7
requires
(also)
that
k,,
=
0,
so
Equation
820
becomes
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indicating,
as
required,
that
the
product
concentration
does
not
change
with
time.

The
circumstance
k,,
=
kp
is
highly
improbable,
and
is
neglected
in
the
remainder
of
this
discussion.
However,
the
reader
should
bear
in
mind
that
the
expressions
derived
below
do
not
hold
when
the
parent
hydrolysis
rate
kp
and
the
product
hydrolysis
ratek,
approach
each
other.

In
the
more
probable
case,
for
which
k,,
#
kp
(i.
e.
that
the
hydrolysis
rate
of
the
mth
product
is
different
from
the
total
parent
hydrolysis
rate),
the
general
solution
to
Equation
B18
is
and
the
specific
solution
to
Equation
B18
with
the
initial
condition
A,(
t
=
0)=
A,,
is
Of
greatest
interest
here
is
the
case
in
which
the
product
compounds
are
known
to
be
hydrolytically
stable,
that
is,
when
k,
=
0
for
all
m.
In
this
case,
Equation
B23
becomes
(for
hydrolytically
stable
products)

A,
=AmO
+
nrnkF'mPO
(~­~­k
~t
)

k
P
B4.
Relationships
Between
the
Parent
and
Compound
Concentrations
Equations
87
and
824
can
be
combined
to
obtain
(for
hydrolytically
stable
products)

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so
that
(for
hydrolytically
stable
products)

or
(for
hydrolytically
stable
products)

If
the
changes
in
the
product
concentrations
are
all
small
compared
to
the
original
parent
concentration,
that
is,
if
we
may
use
the
expression
(valid
for
­1
I
X
I
1
)

h
(l
+X
)=X
­
­x2
1
+­
1
x3­­
x4+
1
.....
4
L
3
and
Equation
B23
becomes
(for
hydrolytically
stable
products
and
I
m
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or
(for
hydrolytically
stable
products
and
lzflrn
<<
Po
I
m
I
k
t
g
P
m=
l
85.
Parent
Half­
Life
Estimates
Based
on
Limits
of
Quantification
of
the
Products
In
every
experimental
determination
of
k,
,
there
is
some
set
of
values
AfQ
(the
"limits
of
quantitation")
below
which
the
product
concentrations
A,
cannot
be
reliably
measured.
If
during
an
experiment
carried
out
over
the
period
of
timeA
t
all
the
product
concentrations
A,
remain
below
their
limits
of
quantitation,
then
the
maximum
possible
value
of
the
rate
k,
is
obtained
by
assuming
(for
all
the
products)
that
1)
A,,
=
0
and
2)
at
time
t
=:
A
t
,
the
product
concentrations
have
increased
to
the
values
A,
=
AfQ.
With
these
assumptions,
the
experimental
data
indicate
that
the
reaction
rate
k,
is
less
than
some
maximum
value
(kp)­
as
follows:

(for
hydrolytically
stable
products
at
concentrations
below
the
limits
of
quantitation)

Under
the
same
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
T1'i
(see
Equation
B9)
is
greater
than
the
value
(TI/:)
.
as
follows:
min
(for
hydrolytically
stable
products
at
concentrations
below
the
limits
of
quantitation)

The
reader
should
note
that
Equations
B32
and
B33
are
valid
only
when
both
1)
the
products
art?
hydrolytically
stable
and
2)
the
concentrations
of
all
the
potential
products
are
measured.
Otherwise,
the
quantity
(kp)­
in
Equation
832
may
not
actually
represent
the
maximum
possible
value
of
the
rate
constant
k,
,
and
the
related
result
in
Equation
B33
for
(TI/:)
min
.
is
also
questionable.

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B6.
Parent
Half­
Life
Estimates
Based
on
Limits
of
Quantification
and
Experimental
Precision
of
Product
Concentrations
In
certain
ex:
periments,
some
hydrolysis
products
are
present
at
quantifiable
but
essentially
constant
concentrations
over
the
time
(A
t
)
of
the
experiment.
In
this
case,
it
is
the
experimental
precision
of
the
measured
product
concentrations,
rather
than
the
limits
of
quantitation,
which
contribute
to
the
estimate
of
the
maximum
value
of
the
parent
hydrolysis
rate
k,
.
If
the
set
of
concentrations
measured
for
the
mth
product
have
the
mean
value
p,,,
and
standard
deviation
om,
the
data
do
not
exclude
the
possibility
that
the
product
concentration
increased
from
the
initial
value
om
­p,
to
the
value
O,
+
11,
at
time
t
=
A
t
.
Taking
this
possibility
to
be
the
actual
case
for
the
measured
products,
the
maximum
value
of
the
quantity
(A,,,
­
A,,
)
is
20,.
This
reasoning
suggests
that
the
following
estimate
of
the
maximum
parent
hydrolysis
rate
is
appropriate:

(for
hydrolytically
stable
products
at
either
1)
constant
measured
concentrations
with
standard
deviation
Om
or
2)
concentrations
below
the
limits
of
quantitation)

r
1
Under
these
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
TI':
is
greater
than
the
value
(T
.
as
follows:
rnin
(for
hydrolytically
stable
products
at
either
1)
constant
measured
concentrations
with
standard
deviation
om
or
2)
concentrations
below
the
limits
of
quantitation)

r
1­
1
­
A
t
Po
In(
2)
A
r
Q
+
Z2orn]
.
(B35)

Below
LOQ
Cons
tan
t
Tv2
2
=­­
P
(k,
1­

The
reader
Should
note
that
Equations
B34
and
B35
are
valid
only
when
both
1)
the
products
are
hydrolytically
stable
and
2)
the
concentrations
of
all
the
potential
products
are
measured.

B7.
Parent
Half­
Life
Estimates
Based
on
the
Experimental
Precision
of
Parent
­
Concentrations
In
certain
experiments,
the
hydrolytic
parent
remains
at
an
essentially
constant
concentraticin
over
the
time
(A
t
)
of
the
experiment.
In
this
case,
it
is
the
experimental
precision
of
the
measured
parent
concentrations
that
determines
the
maximum
value
of
the
parent
hydrolysis
rate
kp
.
If
the
set
of
concentrations
measured
for
the
parent
have
the
mean
value
pp
and
standard
deviation
op
,
the
data
do
not
exclude
the
possibility
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that
the
product
concentration
increased
from
the
initial
value
pp
­
op
to
the
value
pp
+
op
at
time
t
=
A
t
.
This
reasoning
suggests
that
the
following
estimate
of
the
maximum
parent
hydrolysis
rate
is
appropriate:

(for
esseritially
constant
parent
concentrations
with
mean
value
pp
and
standard
deviation
(5,,
)

2%

CLp
A
t
kp
I
(kp),,
=
­.

Under
these
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
TI';
is
greater
than
the
value
(T
v
i
)
.
as
follows:
rnm
(for
essentially
constant
parent
concentrations
with
mean
value
pp
and
standard
deviation
(5
,,
)

B8.
Temperature
Dependence
of
the
Reaction
Rate
and
Half­
Life
In
order
to
increase
the
speed
of
the
reactions
of
interest,
we
conducted
this
experimental
study
using
samples
maintained
at
the
temperature
50°
C
=
323
K.
Of
greater
interest
are
the
corresponding
results
for
the
environmentally
important
temperature
25°
C
=
298
K.

When
the
Arrhenius
activation
energy
for
a
reaction
is
AHa,
Equation
B38
B'
provides
the
following
relationship
between
the
hydrolysis
rates
(kl
and
k2)
for
that
reaction
at
two
different
absolute
temperatures
(T,
and
T2):

where
R
=
'I
.99
x
AH,=
18
KcaVmole,
the
rate
ratio
k,/
k,
at
the
corresponding
temperatures
TI
=298
K
and
T2=
323
K
is
Kcal
mole­
'
K­
'
is
the
ideal
gas
constant.
Using
the
valueB2
=
exp{
18
[
1­
L]}
=
exp(­
2.35)
=
0.095
:k
1.99~
10"
323
298
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Equation
639
indicates
that
the
hydrolysis
reactions
of
interest
proceed
approximately
ten
times
more
slowly
at
25°
C
than
at
the
chosen
experimental
temperature
of
50°
C.
Accordingly,
the
rate
reactions
reported
here
for
the
temperature
25°
C
are
ten
times
lower
than
those
measured
at
50"
C,
and
the
hydrolysis
half­
life
estimates
reported
here
for
25°
C
sarnples
are
ten
times
longer
than
those
calculated
from
the
50°
C
experimental
data.

References
to
Appendix
B:

B1
I.
N
Levine,
"Physical
Chemistry,"
McGraw­
Hill
(New
York),
pp.
498­
501
(1978).

F.
Daniels,
et
al.,
"Experimental
Physical
Chemistry",
McGraw
Hill
(New
York),
p.
131
(1962).
82
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Appendix
C:
Selected
Analytical
and
Kinetics
Results
This
Appendix
includes
selected
sample
data
and
their
related
kinetics
results.

Page
48
of
99
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BACK
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3M
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No.
E00­
1851
Appendix
D:
Selected
Chromatograms
A
representative
set
of
chromatograms
from
the
present
study
is
included
in
this
Appendix.

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3M
Environmental
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No.
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1851
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1851
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No.
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1851
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