Document ID: EPA-HQ-OPPT-2002-0051-0023
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2006-03-07T05:00Z

a
3M
Environmental
Laboratory
Report
No.
E00­
2192
Study
Tit/
e
Screening
Studies
on
the
Aqueous
Photolytic
Degradation
of
Perfluorooctanoic
Acid
(PFOA)

Data
Requirement
Consistent
With:

OPPTS:
835.5270
"Indirect
Photolysis
Screening
Test"
­and­
OECD
Draft
Document
"Phototransformation
of
Chemicals
in
Water
­
Direct
and
Indirect
Photolysis",
August
2000
Author
Thomas
L.
Hatfield,
Ph.
D.

Study
Completion
Date
April
20th,
2001
Performing
Laboratory
3M
Environmental
Laboratory
Building
2­
3E­
09,
935
Bush
Avenue
St.
Paul,
MN
55106
Project
Identification
3M
Laboratory
Report
No:
E00­
2192
Total
Number
of
Pages
148
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This
page
has
been
reserved
for
specific
country
requirements.

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Non
­
Compliance
Statement
Study
Title:

Study
Identification
Number:
E00­
2192
Screening
Studies
on
the
Aqueous
Photolytic
Degradation
of
Perfluorooctonic
Acid
(PFOA)

By
design,
this
study
does
not
comply
with
the
requirements
of
the
US
EPA
Good
Laboratory
Practices
Standards
at
40
CFR
Part
792
(TSCA).
However,
the
3M
Environmental
Laboratory
Quality
Assurance
Unit
has
performed
audits
of
all
data,
related
documentation
and
final
report.

Test
and
reference
substance
receipt
and
use,
dosing
and
incubation
of
the
test
system,
and
analyses
were
conducted
and
documented
according
to
procedures
developed
by
3M,
based
on
References
1
and
2.

Sponsor
Representative
Date
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03/
30/
01­
03/
3
I
/O
1
04/
18/
0
1
­04/
19/
0
1
Quality
Assurance
Statement
Data
03/
3
1
/O
1
03/
3
1
/O
1
Draft
Report
0411
910
1
04/
19/
01
Study
Title:
Screening
Studies
on
the
Aqueous
Photolytic
Degradation
of
Perfluorooctanoic
Acid
(PFOA)

Study
Identification
Number:
E00­
2192
This
study
has
been
inspected
by
the
3M
Laboratory
Quality
Assurance
Unit
as
indicated
in
the
following
table
Inspection
Dates
Date
Reported
to
Management
I
Study
Director
Phase
Quality
Assurance
Unit
Date
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.
E00­
2192
Table
of
Contents
Non
.
Compliance
Statement
..........................................................
.....
...................................
3
Quality
Assurance
Statement
................................................................................................
4
Study
Personnel
and
Contributors
.........................................................................................
7
Table
of
Contents
...................................................................................................................
5
Summary
................................................................................................................................
8
Introduction
..............................................................................................................................
9
Materials
and
Methods
...........................................................................................................
11
Chemical
Characterization
................................................................................................
11
Method
Summaries
...........................................................................................................
11
Deviations
..........................................................................................................................
13
Results
and
Discussion
.........................................................................................................
14
Data
Quality
Objectives
.....................................................................................................
14
Analytical
Results
..............................................................................................................
14
Data
Summary
and
Discussion
........................................................................................
15
Conclusions
...........................................................................................................................
18
References
.............................................................................................................................
19
Signatures
..............................................................................................................................
20
Appendix
A:
Analytical
Methods
..............................................................................................
21
Appendix
B:
Chemical
Characterization
................................................................................
105
Appendix
C:
Kinetics
Model
and
Kinetics
Calculations
..........................................................
109
Appendix
D:
Representative
Chromatograms
.......................................................................
119
Appendix
E:
Soil
Types
and
Characterizations
......................................................................
138
Appendix
F:
Light
Intensity
Measurements
at
45"
South
Latitude
(Miami
FL)
.......................
140
Appendix
G:
Characteristics
of
the
Spectral
Output
of
the
Suntest
Instruments
..................
142
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List
of
Tables
Table
1
.
Typical
Sample
Preparation
Scheme
Used
in
the
Present
Investigation
...............
12
Table
2
.
Observed
Products
and
Mass
Balance
Determinations
for
pH
7
Buffer.
Synthetic
Humic
Water
and
Iron
Oxide
Containing
Water
.................................................................
16
List
of
Figures
Figure
1
.
Structures
of
the
Compounds
Targeted
by
LC/
MS
Analysis
.................................
9
Figure
2
.
Pooled
concentration
data
from
the
iron
oxide
rich
matrix
....................................
17
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6
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Study
Personnel
and
Contributors
Study
Director
Thomas
L.
Hatfield,
Ph.
D.
3M
Environmental
Laboratory
Building
2­
3E­
09
935
Bush
Avenue
St.
Paul,
MN
55106
(651)
778­
7863
Sponsor
3M
Corporation
3M
Environmental
Laboratory
Contributing
Personnel
Kent
Lindstrom
Anh
Dao
Vo
3M
Environmental
Laboratory
Professional
Services
Contributing
Personnel
Anthony
(Tony)
Scales
Debra
Wright
Jan
Schutz
Rufat
Mischiev
(Pace
Analytical
Services,
Inc.,
1700
Elm
St.,
Minneapolis,
MN
55144)

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

Location
of
Archives
Digital
copies
of
original
data,
and
all
original
paper
data
have
been
archived
and
will
be
retained
in
the
3M
Environmental
Laboratory
archives
for
at
least
I
O
years
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Summary
We
report
here
the
results
of
studies
performed
to
determine
the
aqueous
photolytic
behavior
of
perfluorooctanoic
acid
(PFOA)
and
to
identify
its
primary
degradation
products.
Our
techniques
are
based
on
both
EPA
and
OECD
guidance
documents.
lS2
In
this
study,
both
direct
photolysis
(the
interaction
of
light
with
the
target
molecule
leading
to
a
chemical
change)
and
indirect
photolysis
(the
interaction
of
light
with
the
sample
matrix
to
produce
radical
species
that
subsequently
react
with
the
target
material)
were
studied
using
a
synthetic
light
source.

Neither
direct
nor
indirect
photolytic
decomposition
of
PFOA
were
observed
based
on
loss
of
starting
material,
nor
were
any
of
the
predicted
degradation
products
detected
above
their
limits
of
quantitation.
The
rates
of
photolytic
degradation
are
highly
dependent
on
the
experimental
conditions.
However,
using
an
iron
oxide
(FenOs)
photoinitiator
matrix
model,
we
estimate
the
PFOA
half­
life
to
be
greater
than
349
days.

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Introduction
Photolysis
reactions,
hydrolysis
reactions
and
biodegradation
are
the
primary
routes
of
degradation
of
chemical
compounds
in
the
environment.
Studies
of
photo­
induced
reactions
yield
information
on
the
persistence
of
the
parent
material
as
well
as
information
on
the
identity
and
stability
of
products
formed.
Photolytic
reactions
occur
by
two
types
of
mechanisms.
The
first
mechanism,
direct
photolysis,
can
be
defined
as
the
direct
absorption
of
a
photon
by
the
target
species
that
leads
to
a
chemical
change.
The
second
mechanism,
indirect
photolysis,
can
be
defined
as
a
chemical
or
electronic
excitation
transfer
from
a
light
absorbing
species
to
the
test
substance,
which
then
undergoes
some
type
of
chemical
change.
In
the
present
investigation,
an
artificial
light
source
was
used
to
study
both
the
direct
and
indirect
photolysis
reactions
of
PFOA.

The
test
material,
PFOA,
was
dissolved
in
pH
7
buffered
water
and
then
exposed
to
simulated
sunlight
to
test
for
direct
phot~
lysis?
'~
To
test
for
indirect
photolysis,
PFOA
was
dissolved
into
three
separate
matrices
and
exposed
to
simulated
sunlight
for
periods
of
time
from
69.5
to
164
hours.
These
exposures
tested
how
each
particular
matrix
would
effect
the
photolytic
decomposition
of
PFOA.
The
first
test
matrix
was
a
pH
7
buffered
aqueous
solution
to
which
H202
was
added
as
a
well
characterized
source
of
.OH
radicals?*
6
This
was
used
to
test
for
the
propensity
of
PFOA
to
undergo
indirect
photolytic
decomposition.
The
second
matrix
contained
Fez03
in
water,
as
this
matrix
has
been
shown
to
generate
hydroxyl
radicals
via
a
Fenton­
type
reaction
in
the
presence
of
both
natural
and
artificial
sunlight.
7g8
The
third
matrix
contained
a
standard
humic
material,
diluted
to
levels
that
have
been
shown
to
approximate
an
environmental
environment."
'

To
effectively
determine
photolytic
decomposition,
the
concentration
of
parent
material
must
be
monitored
over
time.
Further,
it
is
also
important
to
understand
what
the
degradation
products
are
and
how
much
of
each
are
formed.
The
present
investigation
quantified
the
parent
material
and
two
predicted
degradation
products
(PFHpA
­
perfluoroheptanoic
acid
and
PFPA
­
perfluoropentanoic
acid)
and
monitored
for
any
change
in
concentration
of
PFHxA
­
perfluoro­
hexanoic
acid
by
LC/
MS.
Structures
of
the
pertinent
compounds
are
illustrated
in
Figure
1.

Figure
I.
Structures
of
the
Compounds
Targeted
by
LClMS
Analysis
PFOA
F
F
F
F
F
F
PFHpA
PFHxA
PFPA
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E00­
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Because
it
was
possible
that
volatile
degradation
products
could
be
produced,
we
decided
to
monitor
for
selected
C2
through
c8
2­
or
3­
substituted
pemuoronated
olefins
(e.
g.
c8F16)
and
1­
or
2­
substituted
hydrides
(e.
g.
C8F17H)
in
both
the
iron­
rich
matrix
and
the
pH
7
buffer
matrix
by
dynamic
purge
and
trap
gas
chromatography/
mass
spectrometry.
The
selected
target
compounds
are
representative
of
the
types
of
volatile
compounds
that
could
be
generated
in
the
photolysis
of
PFOA.

Determination
of
a
maximum
kinetic
rate
constant
(kp)­
was
based
on
the
data
from
the
iron
rich
matrix
(as
the
experimental
error
was
lowest
in
this
matrix)
using
the
following
first
order
kinetics
equation.
(See
Appendix
C
for
a
complete
kinetic
derivation
and
the
exact
mathematical
solution.
This
equation
is
valid
for
essentially
constant
parent
concentrations
with
a
mean
value
p,,
and
a
standard
deviation
of
q,.)

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Materials
and
Methods
Chemical
Characterization
Information
on
the
chemical
characterization
of
both
reference
substances
and
control
substances
is
presented
in
Appendix
B.

Method
Summaries
Copies
of
all
analytical
methods
used
in
this
investigation
are
attached
in
Appendix
A.
Equipment
settings,
conditions
and
complete
quality
control
parameters
are
listed
in
the
pertinent
methods.

UVNisible
analysis
were
performed
following
3M
Environmental
Laboratory
Method
ETS­
9­
46.0
"Operation
and
Maintenance
of
the
Hewlett
Packard
8453
UV­
Visible
Spectrophotometer"
An
aqueous
saturated
solution
of
PFOA
was
prepared
and
an
initial
UVNlS
spectrum
recorded.
No
absorbance
above
baseline
over
the
range
190­
1
I00
nm
was
detected.

Sample
preparation
for
this
analysis
followed
3M
Environmental
Laboratory
Method
ETS­
8­
177.0
"Indirect
Photolysis
Screening
Test
in
Synthetic
Humic
Water"
or
ETS­
8476.0
"Preparation
of
Samples
for
Photolytic
Exposure
Studies
in
Aqueous
Matrices".
A
typical
sample
preparation
table
for
an
indirect
photolysis
screening
test
is
shown
in
Table
1
on
the
following
page­

The
general
method
of
sample
preparation
is
as
follows.
For
each
time
point
under
each
condition
shown
in
Table
1,
ten
40­
mL
sample
screw
cap
VOA
vials
were
prepared:
sample,
duplicate,
triplicate,
sample
spike,
matrix
blank,
matrix
blank
spike
(assured
no
accidental
contamination
of
matrix
by
target
compounds),
direct
photolysis
sample,
direct
photolysis
sample
spike
(assured
that
degradation
observed
was
due
to
indirect
photolysis
and
not
another
process),
control
blank
and
control
blank
spike
(assured
no
accidental
contamination
of
the
blank
had
occurred).
All
vials
contained
5
mL
of
appropriate
matrix:
pH
7
buffer,
Fe+
3
at
a
24X
molar
excess
in
water,
or
HZOZ
at
1:
l
molar
equivalent,
added
every
24
hours.
Aliquots
of
PFOA
were
added
to
the
vials
as
indicated
in
Table
1.
The
initial
time
point
vials
(labeled
as
"Time
Zero"
on
the
sample
preparation
sheets
in
Appendix
B)
were
then
refrigerated
at
4S"
C.
These
samples
served
as
controls
with
which
to
determine
what
change,
if
any,
occurred
during
the
time
the
remaining
vials
were
in
the
photo­
reactor.
Exposed
samples
were
placed
upside
down
in
a
custom
built
holder
in
the
photo­
reactor.
Unexposed
samples
were
wrapped
in
aluminum
foil,
sealed
in
a
plastic
bag
and
placed
under
the
sample
rack
inside
the
photo­
reactor
to
assure
that
any
degradation
or
difference
in
degradation
was
due
to
photolysis
and
not
some
other
process.
During
the
course
of
the
exposure,
a
water
bath
held
the
temperature
of
the
water
surrounding
the
bottom
of
the
vials
(which
contained
the
aqueous
samples)
at
25
f
3°
C.
The
temperature
of
the
chamber
itself
was
allowed
to
drift
to
70
t­
I
0°
C.
After
exposure,
the
samples
were
removed
for
analysis.

Selected
portions
of
the
sample
setup
were
modified
to
accommodate
additional
samples
and
controls,
to
improve
the
quality
control
of
the
analysis
or
out
of
experimental
necessity.
Details
of
these
modifications
are
shown
on
the
individual
sample
data
sheets
shown
in
Appendix
D.
For
example,
the
portion
of
the
study
employing
iron
oxide
as
a
radical
generating
species
was
set
up
with
both
triplicate
samples
and
duplicate
sample
spikes.

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Description
The
artificial
light
chamber
used
in
this
analysis
was
either
a
Suntest
CPS+
or
Suntest
XLS+,
the
operation
of
which
followed
3M
Environmental
Laboratory
Method
ETS­
9­
44.0
"Operation
and
Maintenance
of
the
Sunlight
Exposure
System,
Immersion
Unit,
and
Recirculating
Water
Chiller
System".
The
output
intensity
was
held
at
the
desired
level
(680
w/
m2)
by
a
continuous
feed
back
loop
between
an
internal
radiometer
and
the
variable
light
source.

Test
Matrix
Control
Test
Post
Photolysis
Sample
Type
(e.
g.
Fe203
Matrix
Substance
Target
Analyte
(Conditions)
in
water)
(e.
g.
(PFOA)
spike
Table
1.
Typical
Sample
Preparation
Scheme
Used
in
the
Present
Investigation
I
I
water)
I
Ind.
Photo.
Sample
Rep
1
+
0
+
0
Initial
Ind.
Photo.
Sample
Rep
2
+
0
+
0
Initial
Ind.
Photo.
Sample
Rep
3
+
0
+
0
Initial
Ind.
Photo.
Sample
Spike
+
0
+
+
Initial
Matrix
Blank
+
0
0
0
.
Initial
Matrix
Blank
Spike
+
0
0
+
Initial
Direct
Photo.
Sample
0
+
+
0
Initial
Direct
Photo.
Spike
0
+
+
+
Initial
Control
Blank
0
+
0
0
Initial
Control
Blank
Spike
0
+
0
+
Initial
Ind.
Photo.
Sample
Rep
1
+
0
+
0
Light
Ind.
Photo.
Sample
Rep
2
+
0
+
0
Light.
Ind.
Photo.
Sample
Rep
3
+
0
+
0
Light
Ind.
Photo.
Sample
Spike
+
0
+
+
Light
Mabix
Blank
+
0
0
0
Light
Matrix
Blank
Spike
+
0
0
+
Light
Direct
Photo.
Sample
0
+
+
0
Light
Direct
Photo.
Spike
0
+
+
+
Light
Control
Blank
0
+
0
0
Light
Control
Blank
Spike
0
+
0
+
Light
LC/
MS*
With
W/
out
Y
4
YO2
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Ind.
Photo.
Sample
Rep
1
+
0
+
0
NoLight
11
X
X
Ind.
Photo.
Sample
Rep
2
+
0
+
0
No
Light
Ind.
Photo.
Sample
Rep
3
+
0
+
0
No
Light
Ind.
Photo.
Sample
Spike
+
0
+
+
No
Light
Matrix
Blank
+
0
0
0
No
Light
Matrix
Blank
Spike
+
0
0
+
No
Light
Direct
Photo.
Sample
0
+
+
0
No
Light
Direct
Photo.
Spike
0
+
+
+
No
Light
Control
Blank
0
+
0
0
No
Light
Control
Blank
Spike
0
+
0
+
No
Light
+
=
added
to
test
vial;
0
=
NOT
added
totest
vial;
*Duplicate
sets,
one
with
H202,
one
wit1
material
test
where
H202
was
not
added)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
u
t
(excludes
GC/
MS*
With
W/
out
Y
4
w
2
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
e
Humic
GC/
MS
analysis
followed
3M
Environmental
Laboratory
Method
ETS­
8­
182.0
"Analysis
of
Fluorochemicals
by
Archon
Purge
and
Trap
Autosampler,
Tekmar
Purge
and
Trap
Concentrator
and
Agilent
Gas
Chromatograph/
Mass
Spectrometer".
Equipment
settings,
separation
conditions
and
ions
monitored
are
presented
in
this
method.
Equipment
procedures
for
the
GC/
MS
system
followed
3M
Environmental
Laboratory
SOP
ETS­
9­
49.0
"Routine
Maintenance
Page
12
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of
Archon
Purge
and
Trap
Autosampler,
Tekmar
Purge
and
Trap
Concentrator
and
Agilent
Gas
Chromatograph/
Mass
Spectrometer".

The
HPLC/
MS
analysis
followed
3M
Environmental
Laboratory
Method
ETS­
8­
181.0
"Analysis
of
Photolysis
Samples
for
Fluorochemicals
by
High
Performance
Liquid
Chromatography
With
Mass
Spectrometry
Detection".
Equipment
settings,
separation
conditions
and
ions
monitored
are
presented
in
this
method.

Deviations
Calibration
points
were
deleted
at
both
ends
of
the
PFHpA
and
PFPA
curves.
The
lowest
point
on
the
curve
was
deleted
due
to
poor
integration
and
the
two
highest
points
were
deleted
to
improve
quantitation.
The
resulting
effective
concentration
ranges
were
5.5­
21
9
ppb
for
PFPA
and
5.2­
206
ppb
for
PFHpA.

While
setting
up
additional
studies
on
the
photochemical
behavior
of
other
compounds
in
synthetic
humic
material,
it
was
determined
that
the
commercial
humic
material
(Aldrich)
did
not
contain
the
appropriate
amount
of
dissolved
organic
carbon
when
the
solution
is
prepared
as
recommend
in
reference
I.
The
study
director
believes
that
this
may
have
inhibited
any
possible
photodegradation
of
PFOA
and
that
these
data
should
therefore
be
considered
of
screening
quality
only.
Further,
the
samples
from
this
matrix
showed
high
levels
of
background
ions
with
the
same
charge
to
mass
ratio
as
that
of
the
targeted
materials
and
the
manual
intergration
of
some
peaks
was
therefore
required.

PFHxA
was
identified
as
a
possible
degradation
product.
However,
no
suitable
standard
of
this
material
could
be
obtained
for
the
LC/
MS
portion
of
this
study.
Area
of
the
chromatographic
peak
corresponding
to
the
PFHxA
anion
(m/
z
=
313)
were
monitored.
No
changes
greater
than
10%
relative
were
observed
above
the
small
amounts
of
PFHxA
initially
present
in
the
PFOA
standard.

The
PFOA
samples
numbered
0515­
PFOAfe­
07,
and
30
(LC/
MS)
failed
to
meet
spike
recovery
criteria
in
the
iron
oxide
portion
of
this
investigation
and
0515PFOAfe­
30
and
90
failed
control
sample
recovery.
LC/
MS
method
blanks
051
5­
PFOAfe­
21,3Il45,55
showed
low
recovery.
The
GC/
MS
CCV
R0602046
failed
to
pass
criteria.
The
samples
numbered
0515­
PFOAshw­
04,
14
and
28
failed
to
meet
spike
recovery
criteria
and
control
sample
0515shw­
28
showed
low
recovery
in
the
synthetic
humic
portion
of
this
investigation.
Samples
numbered
051
5­
PFOA­
08,
50,
14
and
48
failed
to
meet
spike
recovery
criteria
in
the
pH
7
buffer
portion
of
this
investigation.
Control
sample
051
5­
PFOA­
48
showed
low
PFOA
recovery
while
four
sample
triplicate
sets
for
PFPA
analysis
had
high
RSD.
The
GC/
MS
samples
numbered
051500­
PFOAfe­
067,077
and
090
failed
to
meet
spike
recovery
criteria
in
the
iron
oxide
portion
of
the
investigation.
Two
samples,
051500­
PFOAshw­
12
and
051
500­
PFOAshw­
17
leaked.
These
failures
represent
only
2%
of
all
samples
and
QC
data
and
therefore
have
no
significant
impact
on
the
results.

During
the
exposure
time
of
the
pH
7
buffered
matrix,
the
lamp
went
out
and
the
temperature
drifted.
However,
this
represents
less
than
3%
of
the
total
time
the
samples
were
exposed.
The
conclusions
are
not
effected
and
the
kinetic
determinations
didn't
rely
on
this
data.

Page
13
of
148
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E00­
2192
~~

Results
and
Discussion
Data
Quality
Objectives
The
following
data
quality
objectives
are
summaries
of
those
found
in
the
methods
from
Appendix
A.

Calibration
curves.
An
acceptable
coefficient
of
determination
(R2)
for
linear
curves
is
0.990
or
greater.
Curve
linearity,
intercept,
and
quantitation
accuracy
should
be
verified,
particularly
at
upper
and
lower
calibration
limits.
Residuals
generated
in
curve­
fitting
must
be
within
k
25%
of
the
known
standard
value.
Alternative
methods
of
curve­
fitting
(e.
g.,
quadratic)
require
a
correlation
coefficient
(r)
of
0.990
or
greater.
Reasons
for
the
use
of
quadratic
curve­
fitting
must
be
documented
in
the
raw
data.

Solvent
blanks,
Matrix
blanks,
Control
blanks.
Blanks
should
show
no
more
than
5%
of
the
level
of
a
high
standard
or
CCV
and
should
show
less
than
25%
of
the
lowest
point
of
the
calibration
curve.
If
solvent
blanks
show
more
than
a
5%
carryover,
it
may
be
necessary
to
rule
out
instrument
contamination
using
duplicate
solvent
blank
injections.
If,
after
duplicate
solvent
blanks,
there
is
still
more
than
5%
carry­
over,
or
the
LOQ
is
adversely
affected,
the
run
should
be
stopped.
This
indicates
that
the
instrument
is
contaminated
and
should
be
thoroughly
cleaned.

Sample
spikes,
Matrix
spikes,
Control
spikes.
Acceptable
spike
recoveries
must
be
between
75
and
125%
for
both
LC/
MS
and
GC/
MS
analysis.
Values
outside
these
ranges
must
be
documented
and
evaluated
by
the
Team
Leader
or
designated
supervisor.

Sample
triplicates.
All
samples
are
prepared
in
triplicate
(unless
otherwise
noted).
Acceptable
RSD
precision
values
are
less
than
or
equal
to
25%.
Values
above
25%
must
be
documented
and
evaluated
by
the
Team
Leader
or
designated
supervisor.

Continuing
calibration
verification
(CCV).
The
analyte
concentrations
must
not
vary
by
more
than
Q5%
of
their
expected
values,
relative
to
the
initial
calibration
curve.
Accept
only
those
samples
analyzed
before
the
most
recently
accepted
calibration
verification.
Reanalyze
remaining
samples
with
a
new
calibration
curve.

Limit
of
Quantitation.
The
limit
of
quantitation
(LOQ)
is
equal
to
the
concentration
of
lowest
standard
in
the
calibration
curve
that
has
an
area
greater
than
or
equal
to
four
times
the
solvent
blanks
and
possessing
a
residual
less
than
25%
of
the
actual
value.

Control
Samples.
Control
samples
must
be
within
=5%
of
the
nominal
concentration.

Analytical
Results
Data
quality
objectives
for
this
study,
outlined
in
the
3M
laboratory
method
for
this
study
(see
Appendix
A),
were
met,
with
the
exceptions
noted
in
the
Deviations
section.

Calibration
curves.
Calibration
curves
were
prepared
according
to
the
particular
target
at
the
required
levels.
For
example,
calibration
curves
for
PFOA
ranged
from
25
to
2000
ppb.
Calibration
curves
for
degradation
products
for
analysis
by
LC/
MS
typically
ranged
from
2­
200
ppb.
Calibration
curves
for
GC/
MS
analysis
ranged
from
1
ppb
to
15
ppb.
Using
these
standards,
calibration
curves
were
run
before
and
after
every
analytical
sequence.
A
correlation
coefficient
(r)
of
0.990
or
greater
was
achieved
for
all
curves.

Page
14
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148
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Report
No.
E00­
2192
Solvent
blanks.
All
solvent
blanks
(MeOH)
were
less
than
25%
of
the
method
LOQ.
In
certain
cases,
as
noted
in
the
Deviations
section,
the
LOQ
was
raised
so
that
the
solvent
blanks
met
this
criteria.

Sample
spikes.
All
spike
recoveries
for
the
LC/
MS
portion
of
the
investigation
were
between
75
and
125%,
except
where
noted
in
the
Deviations
section.
All
spike
recoveries
were
between
75
and
125%
for
the
GUMS
portion
of
the
investigation,
except
were
noted
in
the
Deviations
section.

Sample
triplicates.
All
sample
RSD
values
were
25%
or
less.

Continuing
calibration
verification.
All
CCV
samples
were
within
25%
of
the
expected
value.

Limit
of
Quantitation.
The
LOQ
varied
dependant
upon
target.
In
some
cases,
the
LOQ
was
defined
as
the
lowest
standard
that
was
greater
than
4X
the
solvent
blank
level,
see
deviations
section
for
additional
information.

Method
Blanks.
All
method
blanks
were
below
25%
of
the
LOQ.

Control
Samples.
All
control
samples
were
within
25%.

Data
Summary
and
Discussion
Direct
and
indirect
photolytic
decomposition
of
PFOA
was
tested
in
three
separate
matrices:
a
pH
7
buffered
water,
a
synthetic
humic
water
and
an
iron
rich
water.
The
samples
were
exposed
to
680
w/
m2
over
the
wavelength
range
of
290­
800
nm
and
for
time
periods
of
69.5­
164
hours.
Results
from
the
quantitation
of
the
parent
material
and
the
potential
degradation
products
over
time,
as
well
as
mass
balance
determinations,
are
shown
in
Table
2.

As
observed
in
Table
2a,
direct
photolytic
decomposition
of
PFOA
could
not
be
detected
within
experimental
error.
Indirect
photolysis
was
not
observed
in
any
of
the
three
matrices
(the
H202
rich
pH
7
buffer
­
Table
2a,
the
Fe+
3
containing
matrix
­
Table
2b
and
the
humic
containing
matrix
­
Table
2c).
There
was
a
slight
increase
(4
ppb)
in
the
PFHpA
concentration
in
the
Fe+
3
and
H202
containing
matrix.
However,
because
of
the
small
size
of
the
increase,
it
is
unclear
whether
this
increase
was
due
to
indirect
photolysis
of
PFOA,
to
photodegradation
of
an
unknown
impurity
in
the
PFOA
standard,
or
to
experimental
error.

Page
15
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3M
Environmental
Laboratory
Report
No.
E00­
2192
Dir.
Photo.
Sample'
Initial
Time
Point
ND
Nc
Ind.
Photo.
Sample'
Exp.
to
Light
ND
Nc
Dir.
Photo.
Sample`
Exp.
to
Light
ND
Nc
1
Ind.
Photo.
SamDle'
Not
Exuosed
ND
Nc
Table
2.
Observed
Products
and
Mass
Balance
Determinations
for
pH
7
Buffer,
Synthetic
Humic
Water
and
Iron
Oxide
Containing
Water
2a.
Matrix:
pH
7
Buffer,
With
and
Without
H202
~

Dir.
Photo.
Sample'
Not
Exposed
I
M
)I
Nc
Detection
Limits
I
0.292
I
r4
0.178
Sample
Conditions
I
PFPA
I
PFHxA
164
hour
Exposure
Initial
Time
Point
Ind.
Photo.
Sample'
nanomoles
nanomols
ND
Nc
Sample
Conditions
Fe203
W/
yO;
Initial
Time
Point
Fez03
WO/@
O,`
Initial
Time
Point
F
e
z
0
3
W/
yO:
Exp.
to
Light
F
e
z
0
3
w/
yO:
Not
Exposed
Detection
Limits
69.5
hour
exposure
Fez03
WO/
yO,
'
Exp.
to
Light
Fe203
WO/
yO,
'
Not
Exposed
Mass
PFPA
PFHxA
PFHpA
PFOA
Volatiles
Balance
(percent)
ND
'
Nc
0.846
122
ND
106%
ND
Nc
0.808
121
ND
105%
ND
NC
1.27
105
ND
91.8%
ND
Nc
0.808
116
ND
101%
ND
Nc
0.769
121
ND
105%
ND
NC
0.789
118
.
ND
102%
nanomoles
nanomoles
nanomoles
nanomoles
nanomoles
0.729
f
0.348
0.500
2.03
0.0095`
0.394
99.3%
0.385
97.9%
0.404
55.1
95.8%
0.385
56.8
98.8%
0.356
56.4
ND
97.9%

Sample
Conditions
PFPA
164
hour
exposure
nanomoles
Humic
Water`
Initial
Time
Point
ND
Water*
Initial
Time
Point
ND
Humic
Water`
Exp.
to
Light
ND
Humic
Water`
Not
Exposed
ND
water'
Exp.
to
Light
NA
0.356
I
55.7
1
96.8%
0.2019
I
4.06
I
0.0095*
I
PFHxA
PFHpA
PFOA
Mass
Balance
nanomoles
nanomoles
nanomoles
(percent)
~

Nc
0.433
55.7
96.8%
Nc
0.469
60.2
105%
Nc
0.404
52.0
90.5%
NA
N4
NA
NA
Nc
0.394
59.3
103%
Vials
initially
contained
57.9
nMoles
PFOA.
1.
Indirect
Photloysis
Sample:
These
samples
had
H202
added
as
a
radical
source,
results
are
from
triplicate
samples.
2.
Direct
Photolysis
Sample:
These
samples
did
not
have
H
2
4
added,
results
are
from
triplicate
samples.
*Sum
total
of
all
volatiles.
ND
=
non
detect.
NC
=
No
Change­
Detection
limit
represents
the
change
in
the
initial
concentration
that
could
be
relaiably
determined,
see
deviations
section
for
discussion.

2b.
Matrix:
Fe203
in
Water,
With
and
Without
H202
WaterZ
NotExposed
I
ND
Nc
I
0.391
I
55.0
I
95.6%
Vials
initially
contained
116
nMoles
PFOA.
1.
Samples
had
H202
and
Fe2O3
added
as
a
radical
generating
species,
results
are
from
triplicate
samples.
2.
Samples
contained
just
Fe203
as
a
radical
generating
species,
results
are
from
triplicate
samples.
*Sum
total
of
all
volatiles.
ND
=
non
detect.
NC
=
No
Change­
Detection
limit
represents
the
change
in
the
initial
concentration
that
could
be
relaiably
determined,
see
deviations
section
for
discussion.

Vials
initially
contained
57.9
nMoles
PFOA.
1.
Samples
contained
Humic
Materials,
samples
are
from
triplicate
analysis.
2.
Samples
were
plain
water,
results
are
from
a
single
replicate.
3.
Vial
leaked,
all
data
listed
as
NA
or
not
applicable.
ND
=
non
detect.
NC
=
No
Change­
Detection
limit
represents
the
change
in
the
initial
concentration
that
could
be
relaiably
determined,
see
deviations
section
for
discussion.

Page
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E00­
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Dashed
lines
indicate
the
l
a
limits.
Solid
line
indicates
the
maximum
slope.
0
0
The
Fez03
data
were
used
as
an
environmental
model
to
generate
a
half­
life
estimate
for
the
degradation
of
PFOA.
Because
no
degradation
was
observed,
data
from
Table
2b,
Fe203
with
and
without
H202,
was
pooled
to
determine
the
experimental
error
of
the
analysis.
This
data,
shown
graphically
in
Figure
2,
yielded
an
estimated
environmental
half­
life
of
2
349
days.
The
exact
mathematical
solution
is
shown
in
Appendix
C.

Figure
2.
Pooled
concentration
data
from
the
iron
oxide
rich
matrix.

I
0
0
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Conclusions
A
quantitative
preliminary
investigation
was
undertaken
to
determine
the
photolytic
stability
of
perfluorooctonic
acid
(PFOA)
and
to
identify
the
primary
degradation
products.
The
investigation
included
experimental
conditions
that
addressed
both
direct
and
indirect
photolysis.
To
test
for
direct
photolysis,
samples
of
PFOA
in
pH
7
buffer
were
exposed
to
a
synthetic
light
source
for
selected
periods
of
time.
Direct
photolytic
decomposition
of
PFOA
was
not
observed
based
on
loss
of
starting
material,
nor
were
any
of
the
predicted
degradation
products
detected
above
their
limit
of
quantitation.

To
test
for
indirect
photolysis,
a
synthetic
light
source
was
used
to
initiate
radical
formation
in
three
separate
matrices:
a
synthetic
humic
matrix,
a
hydrogen
peroxide
rich
matrix,
and
an
iron
containing
matrix
(as
Fe203).
Degradation
of
PFOA
was
not
observed
in
any
matrix
outside
of
the
experimental
precision
of
the
analytical
methodology.
Mass
balance
for
the
degradation
study
was
100
k
10%
under
all
experimental
conditions.
A
minimum
half­
life
for
PFOA
based
upon
these
preliminary
studies
was
calculated
to
be
2
349
days.

Page
18
of
148
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References
1.
Fafe,
Transporf
and
Transformation
Test
Guidelines,
OPPTS
835.5270
lndirecf
Phofolysis
Screening
Test;
EPA712­
C­
98­
099;
United
States
Environmental
Protection
Agency,
U.
S.
Government
Printing
Office:
Washington,
DC,
1998,
pp.
1­
22.

2.
Of
CD
Guideline
for
Tesfing
of
Chemicals,
Phofofransformation
of
Chemicals
in
Wafer­
Direct
and
lndirecf
Phofoysis,
(Draft
Document);
OECD,
2000,
pp.
1­
59.

3.
Scrano,
L.;
Bufo,
S.
A.;
Perucci,
P.;
Meallier,
P.;
Mansour,
M.
Photolysis
and
Hydrolysis
of
Rimsulfuron.
fesfic.
Sci.
1999,
Vol.
55,
pp.
955­
961.

4.
Nubbe,
M.
E.;
Adams,
V.
D.;
Moore,
W.
M.
The
Direct
and
Sensitized
Photeoxidation
of
Hexachlorocyclopentadiene.
Waf.
Res.
1995,
Vol.
29,
No.
5,
pp.
1287­
1293.

5.
Ogata,
Y.;
Tomizawa,
K.;
Furuta,
K.
Chemistry
of
Peroxides,
in
S.
Patai
(ed.).
The
Chemistry
of
Peroxides
1983,
p.
720.

6.
Lunak,
S.;
Sedlak,
P.
Photoinitiated
Reactions
of
Hydrogen
Peroxide
in
the
Liquid
Phase.
J.
Phofochem.
Photobiol.
A.:
Chem.
1992,
Vol.
68,
pp.
1­
33.

7.
Kachanova,
Z.
P.;
Kozlov,
J.
N.
Zh.
Fiz.
Khim.
1973,
Vol.
47,
p.
2107.
,

8.
Behar,
B.;
Stein,
G.
Science
1966,
Vol.
154,
p.
1012.

9.
Takahashi,
N.;
Ito,
M.;
Mikami,
N.;
Matsuda,
T.;
Miyamoto,
J.
Identification
of
Reactive
Oxygen
Species
Generated
by
Irradiation
of
Aqueous
Humic
Acid
Solution.
J.
Pesticide
Sci.
1988,
Vol.
13,
pp.
429­
435.

Page
19
of
148
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Signatures
The
final
draft
of
this
report
is
a
true
representation
of
the
data
developed
in
this
study.
It
has
been
issued
by:

09/
2A/
Management
Date
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Appendix
A:
Analytical
Methods
This
appendix
presents
the
analytical
methods
and
Standard
Operating
Procedures
used
in
the
present
study.

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ETS­
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181
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Operation
and
Maintenance
of
the
Hewlett
Packard
8453
UV­
Visible
Spectrophotometer
Operation
and
Maintenance
of
the
Sunlight
Exposure
System,
Immersion
Unit,
and
Recirculating
Water
Chiller
System
Routine
Maintenance
of
Archon
Purge
and
Trap
Autosampler,
Tekmar
Purge
and
Trap
Concentrator
and
Agilent
Gas
Chromatograph/
Mass
Spectrometer
Analysis
of
Fluorochemicals
by
Archon
Purge
and
Trap
Autosampler,
Tekmar
Purge
and
Trap
Concentrator
and
Agilent
Gas
Chromatograph/
Mass
Spectrometer
Indirect
Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Preparation
of
Samples
for
Photolytic
Exposure
Studies
in
Aqueous
Matrices
Analysis
of
Photolysis
Samples
for
Fluorochemicals
by
High
Performance
Liquid
Chromatography
With
Mass
Spectrometry
Detection
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3M
ENVIRONMENTAL
LABORATORY
METEOD
ANAlLYSIS
OF
PHOTOLYSIS
SAMPLES
FOR
FLUOROCHEMICALS
BY
HIGH
PERFORMANCE
LIQUID
CHROMATOGRAPHY
WITH
MASS
SPECTROMETRY
DETECTION
Method
Number:
ETS­
8­
181.0
Adoption
Date:
jd/
L
4
1
Effective
Revision
Date:

Approved
by:

uc/­
aJ
~t
)

Date
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Management
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Comuound
Perfluorooctanoic
acid
Pefluorooctanesul
fonate
Perfluorooctanesul
fonamide
N­
methylpefluorooctanesulfonamide
N­
ethylperfluorooctan~~
ulfonamide
2­(
NmefhylperfluoIooctanesulfonamido)
ethyl
alcohol
~­(
N­
e~
yl~~
uo~
terfluorooctanesulfonamido)

ethyl
alcohol
Acronvm
COfnOOUIId
Acronvm
PFOA
Pduorobutanoic
acid
PFBA
PFOS
Perfluorobutanesutfonate
PFBS
FBSA
FOSA
Pdluorabucanesu!
fanamide
N­
MeFOSA
N­
methylperfluorobutanesulfonamide
N­
MeFBSA
N­
EtFOSA
N­
eth
ylperfluorobutanesul
fonamide
N­
EtFBSA
N­
MeFOSE­
OH
2­(
N­
methylperfluorobutanesulfonamido)
N­
MeFBSE­
OH
ethyl
alcohol
N­
EtFOSE­
OH
2­(
N­
ethylperfluorobutanesulfonamido)
N­
EtFBSE­
OH
ethyl
alcohol
I
I
1.3
Compatible
matrices
for
analysis.
Aqueous
(Millipore
ASTM
Type
I
water),
buffered
water,
lake
water,
sea
water
and
metal
slurries
(TiO2,
Fez03,
etc.)
that
have
been
diluted
with
an
appropriate
analytical
solvent
such
as
acetone
or
methanol.

2.0
SUMMARY
OF
METHOD
2.1
This
method
describes
the
analysis
of
fluorochemicals
in
a
specified
matrix,
using
HPLC
electrospray
mass
spectrometry
for
chemical
separation
and
detectiodquantification.
The
analysis
is
performed
by
separating
target
analytes
on
an
HPLC
analytical
column
such
as
a
Dionex
NGl
(35x
4.6mm,
lOpmpar!
kle),
Betasil
C18
column
(50x2
mm,
5
pm
particle)
or
equivalent
using
an
ammonium
acetateh4eOH
solvent
gradient.
Detection
by
electrospray
ionization
mass
spectrometery
in
either
the
positive
or
negative
mode
is
utilized
to
quantify
data.
The
MSD
may
be
run
in
Selected
Ion
Monitoring
(SIM)
mode,
looking
for
specific,
pre­
selected
and
set
analyte
ions
(ie.
m/
z
499
for
PFOS
(deprotonated)),
or
SCAN
mode
which
collects
and
stores
data
for
all
ions
in
a
specified
mass
range.
Data
quantification
is
then
performed
using
either
HP
ChemStation
or
Target
Sohare.

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AnaIysis
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Photolysis
Samples
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Fluorochemicals
by
HpLC/
MS
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3.0
3.1
­

3.2
3.3
3.4
3.5
3.6
3.7
3.8
,3.9
DEFINITIONS
Calibration
Standard.
A
dilution
of
various
amounts
of
a
stock,
intermediate
or
purchased
standard
to
achieve
standard
solutions
in
a
concentration
range
of
interest.

CaIibration
Curve.
The
graphical
relationship
between
known
values,
such
as
concentration
of
a
series
of
calibration
standards
and
their
instrumental
response.

Internal
Standard
Quantification.
Process
of
establishing
a
relationship
betw;
een
the
ratio
of
the
target
analyte(
s)
response
to
internal
standard
or
surrogate
response
and
a
known
concentration
of
the
target
analyte(
s).
The
ratio
of
analyte
to
internal
standard
response
is
used
to
generate
the
calibration
curve
and
determine
unknown
concentrations.
External
Standard
Quantification.
Process
of
establishing
the
concentration
of
a
target
mdyte
by
plotting
the
theoretical
amount
(in
units
of
ppb
or
ppm,
etc.)
versus
the
response
of
the
target
andyte(
s)
on
column.
The
resultant
curve(
s)
shall
be
used
to
determine
unknown
concentrations
by
comparing
the
area
response
of
target
analyte(
s)
to
the
area
response
and
corresponding
analyte
amount
on
the
appropriate
analyte's
calibration
curve.
Differences
in
sample
masdvolume
analyzed,
if
noted,
must
be
compensated
for
by
a
factor
applied
to
the
value.
Correlation
Coefficient
(r).
A
measure
of
the
degree
of
correlation
between
two
variables.
This
term
is
generally
used
to
evaluate
the
linearity
of
a
Least
Squares
Linear
regression.
An
r
value
of
0.98
is
at
the
lower
bounds
of
what
is
considered
linear.
Values
of
r
may
range
.from
­1
to
+l.
A
value
of
+1
denotes
perfect
direct
functional
relationship
between
two
variables.
A
value
of
­1
also
denotes
a
perfect
inverse
relationship.
When
r
=
0,
there
is
no
effect
of
one
variable
upon
the
other
variable.
Coefficient
of
Determination
(r2).
The
square
of
the
correlation
coefficient.
It
is
the
proportion
of
the
variation
in
the
dependent
variable
that
is
accounted
for
by
the
independent
variable.
Internal
standard.
A
horn
amount
of
a
compound
or
element
similar
in
analytical
behavior
to
the
compound(
s)
or
element@)
of
interest,
added
to
all
samples
and
standards,
and
carried
through
the
entire
measurement
process
(post­
photolysis,
after
solvent
dilution).
It
provides
a
reference
for
evaluating
and
controlling
the
precision
and
bias
of
the
applied
analytical
method.
Samples
are
to
be
quantified
using
the
internal
standard.
Surrogate.
An
organic
compound
similar
to
the
target
analyte(
s)
in
chemical
composition
and
behavior
in
the
analytical
process
but
is
not
normally
found
in
the
sample@).
A
surrogate
may
be
added
to
samples
along
with
the
test
analyte
&re
and/
or
post
photolysis)
to
monitor
the
sample
integrity
(leaks
or
matrix
effects).
The
surrogate
may
be
added
to
the
calibration
standards
to
serve
as
a
qualitative
reference
for
the
samples.
Continuing
Calibration
Verification
(CCV).
Standards
analyzed
during
an
analytical
run
to
verify
the
continued
accuracy
of
the
calibration
curve.
This
solution
may
or
may
not
be
prepared
from
a
different
source
or
lot
number
than
the
calibration
curve
standards.

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Analysis
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3.10
Solvent
Blank.
A
sample
of
analyte­
fiee
medium
(for
example,
methanol,
1:
7
diluted
buffer:
methanol)
that
is
not
taken
through
the
sample
preparation
process.
This
blank
is
used
to
evaluate
instrument
contamination.

Blank.
For
photolysis
studies,
there
are
multiple
blanks
to
adequately
represent
the
variables
of
the
study
exposed,
Unexposed
and
Day
0
samples
WitWwithout
peroxide
addition).
These
blanks
are
carried
through
the
sample
preparation,
photolytic
and
analytical
procedures
to
monitor
for
contamination
during
any
step.
It
is
also
used
to
establish
a
chromatographic
baselinebackground
and
monitor
for
analytical
interference
or
suppression
of
target
analyte(
s)
from
the
matrix.
3.11.1
Matrix
Blank:
An
analyte­
free
matrix
(buffered
water,
lake
water,
etc.)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
It
is
used
to
document
the
test
system
without
test
analyte
present.
3.11.2.
Control
Blank
An
analyte­
free
matrix
(ASTM
Type
II
water)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
It
serves
as
a
control
for
the
test
matrix
to
monitor
background
levels,
interferences
or
suppression
of
target
analyte(
s)
from
the
test
matrix.
3.1
1
3.12
Limit
of
Quantitation
(LOQ).
The
lowest
concentration
that
can
be
reliably
measured
within
specified
limits
of
accuracy
during
routine
laboratory
operating
conditions.
The
LOQ
is
generally
5
to
10
times
the
minimum
concentration
with
a
99%
confidence
limit
that
the
concentration
is
greater
than
zero.
However,
it
may
be
nominally
chosen
within
these
guidelines
to
simplie
data
reporting.
For
many
analytes,
the
LOQ
is
selected
as
the
lowest
non­
zero
standard
in
the
calibration
curve
that
is
greater
than
4
times
the
level
of
the
matrix
blank.
Sample
LOQ
are
highly
matrix­
dependent.
Sample
Triplicates.
Three
samples
taken
from
and
representative
of
the
same
sampIe
some
and
separately
carried
through
aI1
steps
of
the
extraction,
photolysis
and
analytical
procedures
in
an
identical
manner.
There
are
multiple
sets
of
triplicate
samples
to
adequately
represent
the
photolytic
variables
of
the
study
(Exposed,
Unexposed
and
Day
0
WiWwithout
peroxide
addition).
Triplicate
samples
are
used
to
assess
variance
of
the
photolytic
method,
including
sample
preparation,
photolysis,
and
analysis.

Control
Sample.
A
known
matrix
(ASTM
Type
II
water)
containing
the
test
analyte(
s)
carried
throughout
the
entire
sample
preparation,
photolytic
and
analytical
procedure.
There
are
multiple
sets
of
triplicate
samples
to
adequately
represent
the
photolytic
variables
of
the
study
(Exposed,
Unexposed
and
Day
0
witWwithout
peroxide
addition).
This
is
used
to
document
method
performance
and
matrix
effects
by
comparing
recoveries
from
the
different
matrices
and
sample
types.

Relative
Standard
Deviation
(RSD).
A
measure
of
precision
defined
as
the
standard
deviation
of
three
or
more
values
divided
by
the
average
of
the
values
and
multiplied
by
100.
(Also
reported
as
Coefficient
of
Variation
(CV)).
Analytical
Spike
(AS).
Prepared
by
adding
a
known
mass
of
target
analyte(
s)
to
a
specified
amount
of
a
sample
or
control
matrix
prior
to
analysis.
This
assumes
that
an
independent
estimate
of
target
analyte
concentration
is
available.
Analytical
spikes
are
used
to
determine
the
effect
of
the
matrix
on
recovery
efficiency.
There
are
multiple
3.13
3.14
3.15
3.16
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3.17
3.18
3.19
3.20
3.21
3.22
4.0
types
of
spiked
samples
to
adequately
represent
the
photolytic
variables
of
the
study
Gxposed,
Unexposed
and
Day
0
;
withlwithout
peroxide
addition.)
3.16.1
Matrix
Spike.
The
test
matrix
(buffered
water,
lake
water)
sample
containing
the
test
analyte
or
blank
to
which
a
known
mass
of
target
analyte(
s)
is
added
prior
to
analysis.
3.16.2
Control
Spike.
The
control
matrix
(ASTM
Type
II
water)
sample
containing
the
test
analyte
or
blank
to
which
a
known
mass
of
target
analyte(
s)
is
added
prior
to
analysis.

Accuracy.
The
closeness
of
agreement
between
an
experimentally
determined
value
and
an
accepted
reference
value.
When
applied
to
a
set
of
observed
values,
accuracy
is
a
combination
of
a
random
(precision)
and
a
common
systematic
(bias)
component.
For
purposes
of
the
study,
the
acceptance
criterion
is
75%
to
125%
of
the
nominal
value.
Dilution.
A
step
in
the
sample
preparation
procedure
in
which
a
solvent
(Le.
methanol,
acetone)
is
added
to
the
test
analyte/
sample
matrix
(i.
e.
water,
buffer,
etc.)
to
prepare
it
for
instrumental
analysis.
Atmospheric
Pressure
Ionization
(MI):
The
Agilent
Technologies
HPLC
1100MSD
system
allows
for
ionization
of
incoming
liquid
sample
from
the
analytical
column
to
the
mass
spectrometer
interface
by
utilizing
a
source,
probe,
hot
gas,
and
specific
voltages.
Electrospray
Ionization
@S,
ESI):
A
method
of
ionization
performed
at
atmospheric
pressure,
whereby
ions
in
solution
are
transferred
to
the
gas
phase
via
tiny
charge
droplets.
These
charged
droplets
are
produced
by
the
application
of
a
strong
electrical
field.
Mass
Spectrometry,
Mass
Spectrometer
(MS),
Mass
Spectrometer
Detector
(MSD):
The
API
HP1100
MSD
system
equipped
with
a
quadrupole
mass
selective
detector,
Ions
are
selectively
discriminated
by
mass
to
charge
ratio
(dz)
and
subsequently
detected,
Geometric
Mean
of
the
calibration
curve:
The
square
root
of
the
product
of
the
high
standard
concentration
and
the
low
calibration
curve
standard.
When
preparing
calibration
curve
standards,
the
number
of
calibration
standards
below
the
geometric
mean
shall
equal
the
number
of
calibration
standards
above
the
geometric
mean.
Having
equal
distribution
of
calibration
standards
above
and
below
the
geometric
mean
when
analyzing
and
reprocessing
data,
effectively
weights
the
curve
such
that
both
the
high
and
low
ends
of
the
curve
are
given
equivalent
significance.

.
WARNINGS
AND
CAUTIONS
4.1
Health
and
safety
warnings
4.1.1
Wear
the
proper
lab
attire
for
all
parts
of
this
procedure.
Wear
gloves
and
proper
eyewear
when
performing
sample
preparation
in
the
laboratory
at
all
times.
Wear
proper
eyewear
when
working
at
the
instrument
in
the
laboratory.

ETS­
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181
.O
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Analysis
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Photolysis
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4.1.2
Handle
all
solvents
in
a
hood
for
all
parts
of
the
described
sample
preparation
procedure.
Whenever
possible
and
practical,
dilute
samples
with
solvent
in
a
hood.

4.1.3
For
potential
hazards
of
each
chemical
used,
refer
to
material
safety
data
sheets,
packing
materials,
and
the
3M
Environmental
Laboratory
Chemical
Hazard
Review.

4.2
Cautions
4.2.1
All
glassware
in
which
standards
are
prepared
should
be
rinsed
with
acetone
and
methanol
to
reduce
the
possibility
of
contamination.

4.2.2
Ensure
that
the
HPLC
mobile
phases
are
prepared
prior
to
beginning
a
run
sequence,
and
that
there
is
sufficient
quantity
to
complete
the
run.
Do
not
allow
the
pump
to
run
dry.

4.2.3
Ensure
that
before
starting
the
run
sequence
there
is
ample
hard
disk
space
on
the
computer
to
save
all
run
data.

4.2.4
Ensure
that
there
is
enough
nitrogen
in
the
supply
tank
to
complete
sequence
runs.

5.0
INTERFERENCE
5.1
Contaminants
in
solvents,
reagents,
glassware,
and
other
sample
processing
or
analysis
hardware
may
cause
interference.
Use
the
routine
analysis
of
laboratory
method
blanks
to
demonstrate
that
there
is
no
such
interference.
Contamination
fiom
columns,
HPLC
tubing,
and
detector
components
may
cause
interference
at
low
detection
levels.
The
routine
analysis
of
solvent
blanks
must
be
used
to
demonstrate
that
there
is
no
such
interference.
5.2
6.0
EQUIPMENT
6.1
6.2
Analytical
balance
sensitive
to
0.1
mg.
Hewlett­
Packard
(HP)
1100
HPLC
System,
or
equivalent.

6.2.1
Pump,
binary,
Model
G1312;
Quaternary,
Model
G1311
A,
or
equivalent.

6.2.2
Solvent
degasser,
Model
G1322A
or
equivalent.

6.2.3
Autosampler,
ALS
Model
G1313A,
variable
injection
volume
or
equivalent.

6.2.4
Column
heater,
Model
G1316A,
or
equivalent.

Betad*
C18,50
x
2
mrn;
Dionex
IonPac@
NG1
Guard
column,
4
x
35
mm;
or
equivalent.
Mass
spectrometer.
Hewlett­
Packard
MSD
Model
G1946A,
or
equivalent.

Refrigerator
capable
of
maintaining
4
5
3
"C.
Data
system.
A
personal
computer
capable
of
controlling
the
HPLC
system
as
well
as
recording
and
processing
signals
from
the
detector.
6.3
6.4
6.5
6.6
ETS­
8­
181
.O
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Analysis
of
Photolysis
Samples
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Fluorochemicals
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HPLCMS
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6.7
System
control/
data
analysis
software:
Hewlett
Packard
ChemStationQ
Version
A.
6.03
or
later.

6.8
Data
reprocessing
software:
Thru­
Put
Systems
Target
NT,
Revision
4.03,
Build
157
or
later.
Hewlett
Packard
ChemStation@,
Version
A.
6.03
or
later.

7.0
SUPPLIES
AND
MATERIALS
7.1
7.2
7.3
Labels
7.4
7.5
Pasteur
pipets,
gIass,
disposable
7.6
7.7
Volumetric
flasks,
various
sizes
7.8
Beakers,
glass,
various
sizes
7.9
Vials,
40
mL,
VOA
(I­
Chem
or
equivalent)
Crimp
cap
autovials,
1.8
mL
Graduated
pipets,
glass,
disposable,
1
mL
to
IO
mL
Hamilton
Gastight@
syringes
(precision
f
1%
of
total
volume),
10
pL­
1000
pL
Automatic
pipettor,
capable
of
dispensing
10­
5000
pL
8.0
REAGENTS
AND
STANDARDS
8.1
8.2
8.3
8.4
Methanol
(MeOH).
HPLC/
SPEC/
GC
grade
from
EM
Science,
or
equivalent
Acetone.
HPLC/
SPEC/
GC
grade
from
EM
Science,
or
equivalent
ASTM
Type
I1
Water.
Water
with
lower
resistance
must
not
be
used.

Ammonium
acetate,
2
mM
in
water.
This
solution
is
chromatographic
solvent
A
(see
ammonium
acetate
crystals
to
a
l­
L
volumetric
flask
containing
about
500
mL
water,
adding
10
mL
of
methanol,
diluting
to
the
mark
with
18.0
MQ
water
and
mixing.)
Stock,
internal
standard,
surrogate,
post­
photolysis
spike
and
calibration
solutions
All
weights
should
be
recorded
to
the
nearest
0.0001
g
in
a
standards
preparation
log:

85.1
Fluorochemical
or
target
malyte
prepared
in
acetonitrile
(or
suitable
analytical
solvent).
(Example:
A
stock
solution
is
prepared
at
a
concentration
of
approximately
30,000
p
g
/d
by
weighing
0.3
g
of
target
analyte
in
a
10­
mL
volumetric
flask
and
bringing
to
the
mark
with
suitable
analytical
solvent.
This
solution
is
diluted
in
solvent
to
make
additional,
appropriate
standards.
Follow
specified
guidelines
for
documenting
removal
of
test
analyte
and
target
analyte(
s),
use
of
balance,
preparation
of
diluted
solutions
and
calibration
standards
in
the
appropriate
log
books.
Maintain
photocopies
of
the
preparation
pages
and
worksheets
in
a
raw
data
file,
Section
12.2.1).
(Example:
An
acceptable
eluent
solution
is
made
by
adding
0.15
g
8.5
ETS­
8­
1
81.0
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9.0
SAMPLE
HANDLING
9.1
Standards
and
diluted
samples
are
stored
in
capped
autovials
or
capped
40
mL
VOA
vials
until
analysis.
9.2
If
analysis
will
be
delayed,
standards
and
sample
extracts
may
be
stored
at
4
OC
f
3
"C
or
room
temperature,
until
analysis
can
be
performed.
Document
storage
conditions
on
sample
prep
worksheet
with
date
and
initials.

10.0
QUALXTY
CONTROL
10.1
Calibration
Standards.
Calibration
standards
(Section
11)
used
to
.generate
a
calibration
10.2
10.3
10.4
10.5
curve
should
be
prepared
in
the
same
type
of
solvent
or
matrix
as
in
the
study
samples.
The
number
of
calibration
standards
and
the
concentration
levels
should
be
sufficient
to
encompass
the
expected
concentrations
of
the
study
samples.
In
general,
a
minimum
of
five
calibration
standards
is
required
for
fit
of
linear
regression.
Broad
calibration
ranges
(greater
than
three
orders
of
magnitude
between
low
and
high
standards),
may
require
use
of
a
quadratic
fit
of
the
data
and
requires
more
points
to
adequately
represent
the
calibration
range.
Continuing
Calibration
Verification
(CCV).
Analyze
a
mid­
range
calibration
standard
after
a
maximum
of
every
fifteen
samples.
Solvent
blank.
Solvent
blanks
are
run
before
and
after
every
calibration
curve,
CCV,
matrix
and
control
blank
(if
contamination
is
noted),
and
after
batches
of
no
more
than
30
injections.
Acceptable
values
for
the
blanks
are
values
below
25%
of
the
limit
of
quantitation
(LOQ)
of
the
instrument.
If
analyte
carryover
is
a
problem,
use
back­
to­
back
solvent
blanks.
Sample
Triplicates.
Analyze
all
sets
of
triplicate
samples
to
provide
a
measure
of
the
precision
of
analysis.
Study
samples
will
be
analyzed
in
batches
of
no
more
than
30
samples.
Multiple
batches
in
an
analytical
sequence
will
be
bracketed
by
calibration
standards
at
the
beginning
and
end
of
each
study
sample
batch.
AX1
samples
(matrix
and
control
samples,
blanks
and
spikes)
from
a
specified
exposure
type
or
time
may
be
analyzed
within
the
same
analytical
batch.

Analytical
spikes.
Prepare
analytical
spike
sample
for
each
sample
type
as
applicable
to
determine
the
matrix
effect
on
the
recovery
efficiency.
Concentrations
of
the
spike
should
be
approximately
equal
to
a
mid­
range
calibration
standard.
The
matrix
spike
sample
should
be
analyzed
periodically
to
measure
the
precision
associated
with
the
analysis.
The
analyst
shall
accept
percent
spike
recoveries
of
100
k
25%.
Spike
recoveries
outside
of
this
range
should
be
noted
and
used
with
other
criteria
to
evaluate
the
condition
of
the
analytical
run
or
necessity
for
repeat
analysis.
Consult
with
the
Team
Leader
or
designee
for
direction
and
fmal
acceptance
or
rejection
of
the
analytical
run.
Samples
may
be
spiked
at
two
different
concentrations
to
ensure
that
the
resulting
levels
of
target
analyte(
s)
are
within
the
viable
range
of
the
calibration
curve.

ETS­
8­
181
.O
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Analysis
of
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HPLCMS
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11.0
CALIBRATION
AND
STANDARDIZATION
11.1
Analyze
standards
prior
to
and
following
each
set
of
samples.
The
linear
regression
will
be
calculated
from
the
plot
of
all
individual
calibration
points,
including
but
not
forced
through
zero,
using
HP
ChemStation
or
Target
NT
Software.
A
minimum
of
five
calibration
standards
is
required
to
generate
linear
regression
for
target
analyte(
s).
If
the
calibration
curve
residuals
are
greater
than
25%
deviation
fiom
the
theoretical
value,
quadratic
curve
fitting
and/
or
dropping
lowhigh
curve
points
may
be
required
if
data
review
shows
this
to
be
a
consistent
and
more
accurate
representation
of
the
instrument
response.
Document
in
the
raw
data
the
technical
justification
for
any
deviation
and
consult
with
the
team
leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
of
the
data.
11.1.1
Use
the
following
documentatiodfootnotes
maybe
used
to
justify
dropping
highflow
curve
points.

1)
"Higb/
low
calibration
points
(list
points)
were
excluded
to
provide
a
better
fit
over
the
linear
range
appropriate
to
the
measured
data."

2)
"Low
level
calibration
point(
s)
were
not
4x
higher
than
the
extraction
blank;
these
points
were
excluded
&om
the
curve
to
disqualify
a
data
range
that
may
have
been
significantly
affected
by
background
levels
of
the
analyte."
3)
"Hiwow
calibration
point(
s)
(list
points)
were
excluded
as
they
were
not
within
the
4
2
5
%
accuracy
requirements
of
the
method
when
the
curves
were
evaluated
over
a
linear
range
appropriate
to
the
data.
'
11.2
If
the
curve
does
not
meet
requirements
perform
routine
maintenance
or
prepare
a
new
standard
curve
(if
necessary)
and
reanalyze.

12.0
PROCEDURES
12.1
Instrument
set
up.
Within
"Method
and
Run
Control"
in
the
HP
ChemStation
SootWare
window,
turn
the
system
"on"
to:
turn
on
the
drying
gas
flow;
initiate
solvent
flow
through
the
column
and
nebulizing
needle;
equilibrate
the
column
compartment;
and
equilibrate
the
MSD
spray
chamber
temperatures
and
conditions.
The
system
module
displays
should
turn
a
green
color
to
indicate
the
instrument
is
"ready"
for
analysis.
A
yellow
color
indicates
that
the
system
is
not
ready,
but
is
working
to
"get
ready."
A
red
colored
module
icon
indicates
a
type
of
systematic
failure
and
should
be
corrected
prior
to
proceeding.
Check
the
run
log
for
error
messages
and
error
codes
if
the
problem
is
not
apparent.
MSD
set­
up.
Turn
the
MSD
"on"
in
the
software
to
equilibrate
the
system.
12.2.1
Check
the
level
of
nitrogen
in
the
tank
and
ensure
there
is
enough
to
complete
the
12.2
impending
run.

12.2.2
Clean
the
MSD
according
to
the
Equipment
Procedure
ETS­
9­
34.0
Operation
and
Maintenance
of
HP
LCMS
System.

ETS­
8­
181.0
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Polarity
Acquisition
mode
Gain
Fragmentor
Dwell
time
Carillaw
voltaae
12.2.3
Perform
a
Check
Tune
or
Autotune
to
ensure
system
operational
qualification
and
performance
verification
of
the
MSD.
Log
the
Tune
results
and
keep
a
copy
with
the
analytical
raw
data
~~

NegaUve
(or
Positive)

SIM
(or
SCAN)

1
.O
(up
to
7.0)

70
(may
be
set
to
one
voltage,
or
ramped
for
each
ion)

183
msec
(time
is
a
function
of
the
amount
of
ions).

3500.
or
eauivalent
12.2.4
Load
the
method
file
and
ensure
that
the
following
parameters
are
appropriately
set
for
the
target
analyte(
s):
Example
mass
spectrometer
set
up':
I
MSD:
1
Ionization
mode
I
API­
ES
lor
API­
APCI)

Drying
gas
Nebulizer
pressure
Nitrogen,
or
equivalent
30
pig,
or
equivalent
Drying
gas
flow
Drying
gas
temp
~
~.~

8
Umin,
or
equivalent
300'
C,
or
equivalent
12.3
LCCheck
TIME
(MIN)

0.0
1
.o
12.3.1
Check
that
the
appropriate
HPLC
column
is
in
the
instrument
for
analysis.
12.3.2
Check
that
the
correct
eluent
solutions
are
in
bottles
to
be
used
and
that
enough
is
available
to
complete
the
sequence
run.
Adjust
the
solvent
bottle
level
electronically
within
the
method
and
run
control
window.

12.3.3
Ensure
that
the
method
file
has
the
appropriate
LC
pump
parameters
for
solvent
flow/
gradient
program
,
column
LDjtemperature,
injection
volume
and
stop
time.
Solvent
A:
Ammonium
Acetate
2mM
in
water
(with
1%
MeOH)
(or
equivalent).
Solvent
B:
Methanol
(or
equivalent).

Example
Solvent
Gradient:

*%
A
%0
FLOW
RATE
60
40
0.3
mUmin
60
40
0.3
mUmin
4.0
11.0
5
95
0.3
mumin
5
95
0.3
mUmin
Page
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~

AUTO­
SAMPLER
PROORAM:

INJECTION
VOLUME:
increases
to
a
higher
organic
content
over
time
to
separate
the
analytes,
and
elute
them
off
the
column
in
a
timely
fashion.
After
all
analytes
have
eluted,
the
solvent
ratio
is
then
switched
back
to
"initial
conditions"
and
held
until
the
column
pressure
has
stabilized
(
indicating
re­
equilibration
to
initial
conditions)
prior
to
the
next
injection.

12.3.4
Auto­
sampler
setup:

­

None
5.0
vL,
or
equivalent
I
AUTO­
SAMPLER:
I
ALS
Model
GI
31
3A
I
I
12.3.5
Place
the
samples
in
the
autosampler
tray
and
construct
a
sequence
table
with
appropriate
calibration
standards,
calibration
check
standards
and
solvent
blanks.

12.3.5.1
123.5.2
12.3.5.3
12.3.5.4
Verify
that
all
samples
and
standards
are
positioned
correctly.
Enter
the
identification
code
for
each
standard
and
samples.
For
solvent
blanks,
identie
the
solvent
and
the
traceability
number.
Use
one
injection
per
sample.
Ensure
the
method
file
is
correctly
entered
for
all
samples.

12.4
Sequence
and
electronic
storage
of
data
files.

12.4.1
Within
the
sequence
parameters,
enter
sequence
information
(brief
sample
population
description
and
instrument
name).
12.4.2
Set
post­
sequence
command
macro
to
shut
down
system
after
the
run
is
completed
(Example:
"STANDBY"
on
HP1100iMSD
systems).
12.4.3
Save
all
data
to
a
subdirectory
labeled
with
instrument
and
analysis
date
(e.
g.
H100200
for
analysis
on
"Hillary,)`
on
2
October,
2000).
12.4.4
Name
data
within
the
subdirectory
with
instrument
ID
and
injectiodrun
number
(e.
g.
for
samples
acquired
on
"Hillary7',
data
files
shall
be
"HILLOOOl".
.
.
.
"`~
LLOO##"
').
DO
NOT
exceed
five
identification
characters
for
analysis
of
more
than
99
samples
since
eight
characters
total
are
available
for
sample
ID,
and
the
last
three
digits
are
for
sample
numbering
purposes
(leaving
the
first
five
characters
for
data
file
identification).
12.4.5
Save
sequence
as
analysis
date
and
instrument
letter
(e.
g.
For
analysis
on
instrument
"Hillary"
on
October
2,2000
save
sequence
table
as
H100200.
s).

12.5
Sample
analysis
12.5.1
Enter
the
standard,
sample,
blank
identification
into
the
sequence
table.
Analyze
calibration
standards
first,
then
up
to
30
injections,
followed
by
the
calibration
standards
re­
injected.
Multiple
sets
of
samples
can
be
set
up
in
the
sequence
table
with
each
set
bracketed
by
calibration
standards.
Analyze
a
single
continuing
calibration
standard
(CCV)
after
a
maximum
of
15
injections.
Solvent
blanks
shall
be
analyzed
before
and
after
the
CCV
and
before
method
and
control
blanks,
if
Page
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necessary.
Two
solvent
blanks
shall
be
analyzed
at
the
end
of
the
calibration
standards
to
ensure
that
there
is
no
cany
over
from
the
highest
standard
concentration.
Solvent
blanks
may
also
be
used
to
separate
groups
of
samples
and
evaluate
for
carry
over
problems
fiom
actual
samples.
Ensure
standards,
blanks,
samples,
and
matrix
spikes
in
the
auto­
sampler
tray
vials
are
in
same
order
as
listed
in
the
sequence.
12.5.2
Print
a
copy
of
the
tune
results,
method
and
sequence
to
be
stored
with
raw
data.
12.5.3
Start
the
sequence.

12.6
Post
Analysis.
Prepare
a
folder
identified
specifically
to
the
project
and
save
data,
method
and
sequence
files.
This
will
be
considered
the
raw
electronic
data
to
be
archived.

13.0
DATA
ANALYSIS
AND
CALCULATIONS
13.1
Peak
Evaluation.
Peaks
must
be
symmetric
in
shape
and
identified
by
extracting
compound­
specific
ions.
Peaks
considered
for
quantification
must
have
peak
heights
greater
than
4
times
any
baseline
level
for
that
region
of
the
chromatogram.
Peak
area
integration
is
from
baseline
to
baseline
using
automatic
or
manual
integration.
Manual
integration
is
not
acceptable
for
calibration
standards
and
should
only
be
used
in
extreme
cases
as
designated
by
the
Team
Leader.
Samples
and
standards
that
may
need
to
be
manually
integrated
must
be
documented
in
the
raw
data
as
to
why
the
peak
was
manually
integrated.

Integration
Codes.
The
following
integration
codes
may
be
utilized
to
document
what
type
of
manual
integration
was
performed.
13.2
A
Adjust
Left
Anchor
B:
Adjust
Right
Anchor
C:
Delete
Integration
D:
Add
Integration
Additionally,
QAU
encourages
the
data
reviewer
to
write
comments
directly
on
the
chromatogram
if
there
is
anything
unusual.
Date
and
initial
all
documentation.

13.3
Matrix
spikes.
Calculate
the
percent
recovery
for
each
of
the
matrix
spikes.
Calculate
the
matrix
spike
percent
recoveries
using
the
following
equation:

%
Recovery
=
(observed
stiked
samtde
result
­
observed
samule
result)
x
100
Using
the
observed
matrix
spike
recoveries,
calculate
the
average
spike
recovery.
Nominal
amount
spiked
'

13.4
Accuracy,
Calculate
the
accuracy
of
each
calculated
calibration
standard
and
CCV
samples
using
the
following
equation.
Accuracy
=
(Measured
Conc.)
x
100
Nominal
Conc.

Page
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13.5
Sample
Triplicates.
Calculate
the
relative
standard
deviation
(%
RSD)
for
the
triplicate
samples:

RSD
=
Standard
Deviation
of
Samde
Set
x
100
Average
of
Sample
Set
.

14.0
METHOD
PERFORMANCE
14.1
14.2
14.3
14.4
14.5
14.6
Coefficient
of
Determination
(9).
The
coefficient
of
determination
(r')
for
the
calibration
curves
should
be
0.990
or
greater.
The
curves
should
be
examined
closely
for
linearity
and
intercept,
particularly
for
accuracy
of
quantitation
at
the
low
and
hi&
ends
of
the
curve.
The
accuracy
of
all
standards
used
for
calibration
must
be
within
75­
125%.
It
may
be
necessary
to
use
quadratic
fits
of
the
data,
usually
when
broad
range
curves
(greater
than
3
orders
of
magnitude
between
the
low
and
high
concentration
standards)
are
used.
Document
in
the
raw
data
the
technical
justification
for
using
quadratic
equations.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Calibration
Standards.
The
acceptance
criterion
for
the
calibration
standards
is
that
the
accuracy
of
each
standard
is
75%
to
125%
(k
25
%
difference)
of
the
nominal
value.
Calibration
standards
outside
this
range
are
to
be
noted.
Document
in
the
raw
data
the
technical
justification
for
deviations.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Internal
Standard
(IS)
and
Surrogate.
Review
of
the
internal
standard
and
surrogate
performance
is
performed
by
averaging
the
area
response
throughout
the
analytical
run
and
calculating
%RSD.
Inconsistencies
in
the
internal
standard
peak
area
may
indicate
instrumental
changes
over
time.
Inconsistencies
in
the
surrogate
peak
area
may
indicate
instrumental
changes,
injection
error,
or
changes
in
the
test­
system.
Consult
with
the
Team
Leader
or
designee
for
direction
and
final
acceptance
or
rejection
of
the
analytical
run.

Continuing
Calibration
Verification.
If
the
accuracy
for
the
amount
of
measured
analyte
is
greater
than
25%
from
the
nominal
value
relative
to
the
initial
standard
curve,
the
Team
Leader
should
be
consulted.
Only
those
samples
analyzed
before
the
last
acceptable
calibration
check
standard
may
be
used.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Solvent
Blanks.
Solvent
blanks
should
show
no
more
than
a
5%
canyover
from
a
high
standard
or
calibration
check
standard.
If
so,
two
solvent
blanks
may
be
necessary
to
rule
out
instrumental
Contamination.
If
peaks
greater
than
25%
of
the
peak
area
of
the
designated
LOQ
value
are
observed
in
sequential
solvent
blanks,
this
is
indicative
of
instrument
contamination.
The
instrument
shall
be
serviced
by
thoroughly
cleaning
the
electrospray
source,
and
replacingkleaning
c
o
l
m
s
,
tubing,
etc.
(as
designated
in
the
Equipment
Procedure,
ETS­
9­
34.0)
and
the
analysis
restarted.
Consult
with
the
Team
Leader
or
designee
for
direction
and
final
acceptance
or
rejection
of
the
analytical
run.
Matrix
Blanks.
Matrix
blanks
are
the
basis
for
determining
the
LOQ
and
are
monitored
at
various
times
in
the
analytical
run.
Samples
with
greater
than
25%
of
the
peak
area
of
the
designated
LOQ
value
observed
in
matrix
blanks
are
indicative
of
matrix
effect,

ETS­
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14.7
14.8
14.9
sample
contamination
or
instrument
contamination.
Evaluation
of
the
solvent
and
control
bIanks
may
be
necessary
to
determine
these
effects.
Use
of
solvent
blanks
prior
to
the
matrix
blank
may
be
necessary
to
rule
out
instrumental
or
sample
contamination.
Control
Blanks.
Control
blanks
are
the
basis
for
determining
matrix
effect
(interference
or
suppression)
and
also
to
monitor
for
instrumental
or
sample
contamination.
Use
of
solvent
blanks
prior
to
the
matrix
blank
may
be
necessary
to
rule
out
instrumental
or
sample
contamination.
Limit
of
Quantitation
(LOQ).
The
LOQ
is
equal
to
the
lowest
acceptable
standard
(i.
e.
%
accuracy
is
S
25
%
nominal
value)
in
the
calibration
curve
that
is
greater
than
4
times
the
level
of
the
matrix
blanks.
Sample
Triplicates.
The
analyst
shall
accept
%RSD
values
<
25%.
%RSD
values
=­
25%
should
be
noted.
Data
used
in
the
final
report
that
is
deemed
out
of
control
will
be
required
to
have
technical
justification
for
why
the
data
is
used,
documented
in
the
final
report
and
raw
data.
Consult
with
the
Te,
m
Leader
or
designee
for
direction,
and
for
find
acceptance
or
rejection
of
the
data.

14.10
Control
Samples.
The
acceptance
criterion
for
the
control
samples
is
that
the
accuracy
is
75%
to
125%
of
the
nominal
value.
These
will
be
used
as
a
reference
for
matrix
effect
and
overall
method
performance.
Control
samples
outside
this
range
are
to
be
noted.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Data
used
in
final
report
that
is
deemed
out
of
control
will
be
required
to
have
a
technical
justification
for
why
the
data
are
being
used,
documented
in
the
final
report
and
raw
data.

14.11
Analytical
Spikes.
The
analyst
shall
accept
percent
spike
recovery
values
of
100
rt
25%.
Spike
recoveries
outside
of
this
range
should
be
noted.
Consult
with
the
Team
Leader
or
designee
for
direction,
and
for
final
acceptance
or
rejection
of
the
data.
Data
used
in
final
report
that
is
deemed
out
of
control
will
be
required
to
have
a
technical
justification
for
'

why
the
data
are
being
used,
documented
in
the
final
report
and
raw
data.

14.12
System
SuitabWty.
Without
performing
a
method
validation,
system
suitability
can
be
demonstrated
by
acceptable
instnunental
checks
(e.
g.
abbreviated
&z
check­
tune,
or
full
auto­
tune
routines.
Consult
the
appropriate
instrumental
manuals
(Reference
18.2).
Furthermore,
overlaying
calibration
curves
and
implementing
check
standards
(CCV),
the
method
shall
be
self­
validating
if
all
data
quality
objectives
are
satisfied.

15.0
POLLUTION
PREVENTION
AND
WASTE
MANAGEMENT
15.1
15.2
15.3
Dispose
of
sample
waste
by
placing
in
high
or
low
BTU
containers
as
appropriate.
Use
broken
glass
containers
to
dispose
of
glass
pipettes.
Collect
HPLC
solvent
waste
in
the
satellite
accumulation
can.
Empty
into
the
flammable
storage
drum
in
the
hazardous
waste
collection
area
on
the
2nd
floor.
Use
smaller
bore
columns
when
possible
to
minimize
waste
generation.

ETS­
8­
181
.O
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16.0
RECORDS
16.1
16.2
16.3
16.4
16.5
16.6
16.7
16.8
Print
hard
copies
of
all
graphics
and
data
analysis
summaries
for
archiving.

Sign
and
date
all
graphics
and
label
with
instnunent
ID.
Fill
out
appropriate
preparation
worksheets
completely,
making
sure
to
include
all
initids
and
dates,
along
with
the
study
number
and
sample
identification.
Print
out
the
sample
acquisition
sequence
table,
reduce
the
size
with
photocopying
and
tape
the
photocopy
into
the
instrument
log.
Keep
the
original
copy
for
the
raw
data
files.
Print
chromatograms,
reprocessing
sequence
and
batch
reports
for
all
analyses.
Print
calibration
tables
and
curve
information
and
store
in
the
raw
data
file.
Enter
all
standard
preparation
infomation
in
the
standards
preparation
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.

17.0
ATTACHMENTS
17.1
None.

18.0
REFF,
RENCES
18.1
18.2
ETS­
9­
34.0,
Hewlett
Packard
1
1OOiMSD
Equipment
Procedure.
Hewlett
Packard
1100/
MSD
instruction
CD/
ROM.

19.0
AFFECTED
DOCUMENTS
19.1
None.

20.0
REVISIONS
Revision
number
Reason
for
revision
Date
of
Revision
ETS­
8­
18
1.0
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3M
ENVIRONMENTAL
LABORATORY
Method
Preparation
of
Samples
for
Photolytic
Exposure
Studies
in
Aqueous
Matrices
Method
Number:
ETS­
8­
176.0
Adoption
Date:

Approved
By:

Laboratory
Manager
fl
Date
ETS­
8­
176.
OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
1
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Perfiuomoctanoic
acid
Perfluorooctanesulfonate
PcrfYuor
ooctanesulfonamide
1.0
SCOPE
AND
APPLICATION
PFOA
Peffluorobutanoic
acid
PFBA
PFOS
Perfluorobutanesulfonate
PFBS
FOSA
Perfluorobutanesul
fonamide
FBSA
1.1
Purpose.
Chemicals
dissolved
in
aqueous
solutions
are
subject
to
two
types
of
photoreaction.
The
first
type
(direct
photolysis)
occurs
when
the
chemical
of
interest
absorbs
sunlight
directly
and
is
transformed
to
products
when
unstable,
excited
states
of
the
molecule
lead
to
decomposition.
The
second
type
is
indirect
photolysis,
where
degradation
of
the
dissolved
chemical
is
the
result
of
chemical
or
electronic
excitation
transfer
fkom
light­
absorbing
species
in
the
water.
The
simplest
reaction
involves
the
absorption
of
W
energy
by
hydrogen
peroxide
(H202)
to
produce
2
hydroxl
radicals.
These
may
react
with
any
species
in
the
water,
including
solvent,
b
a
e
r
,
dissolved
organic
material
and
target
material.
Use
of
water
and
H202
is
very
controlled
and
predictable.
Other
sources
in
other
matrices
are
not
as
controlled
or
predicable,
but
are
more
environmentally
relevant,
Natural
waters
such
as
lake
and
sea
water
can
be
used
for
the
photolytic
reaction
matrix
because
it
may
,contain
dissolved
organic
material
that
absorbs
sunlight
and
produces
reactive
intermediates
that
include
singlet
oxygen
('
0
2
)
which
may
promote
indirect
photolysis
of
the
test
substance.
Another
transient
species
photochemically
produced
by
the
reaction
of
W
light
and
dissolved
organic
materials
(humic)
is
hydrogen
peroxide
(H202)
which
may
react
further
to
form
the
hydroxyl
radical.
The
addition
of
HzO2
to
test
solutions
may
be
utilized
as
a
free
radical
source
to
initiate
indirect
photolytic
reactions
in
controlled
test
solutions
such
as
MilliQ
water
or
buffers.
Further
studies
involving
the
use
of
either
naturally
occurring
metal
complexes
such
as
Fe(
II1)
which
undergo
photoreduction
to
Fe(
I1)
and
free
radicals
or
addition
of
Ti02
as
a
catalytic
surface
for
indirect
photolysis
may
also
be
evaluated
within
this
method.

CompatibIe
analytes.
Test
substance
and
degradation
products
for
photolytic
exposure
include
but
are
not
limited
to:
1.2
Z­(
N­
methylperfluoro
octanesulfonamido)
ethyl
alcohol
Z­(
N­
ethylperfluorooctanesuIfonamido)
ethyl
alcohol
1
­oeduorooctene
1
Comaound
I
Acronym
I
Compound
I
Acronym
I
N­
MeFOSE­
OH
Z­(
N­
methylperfluorobutancsulfonamido)
ethyl
N­
EtFOSE­
OH
2­(
N­
ethy$
e~
uorobutanesuIfonamido)
ethyl
alcohol
alcohol
­
1­
ueffluombutene
N­
methylperfluorooctanesulfonamide
1
N­
MeFOSA
N­
methylperfluorobutanesulfonamide
I
N­
MeFBSA
~~

N­
ethvluemuomoctanesulfonamide
I
N­
EtFOSA
I
N­
ethvl~
erfiuombutanesulfonamide
1
N­
EtFBSA
I
N­
MeFBSE­
OH
N­
EtFBSE­
OH
4
­~
­
~~

r
.
.
,
and
other
C.,
thru
Cla
homologues.
and
oolymeric
materials
based
on
the
aforementioned
comKunds.
I
ETS­
8­
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of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
2
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Other
possible
degradation
products
include,
but
are
not
limited
to:

C2
lMpcrfluomthanc(
lH­
pE2)
IH­
perfluoroethane
(IH­
pfCz)
1
C,
1
H­
perfluompropane
(IH­
pE3)
LH­
perfluobpmpane
(ZH­
plC3)
pcffluom­
1
­propene
(pE3­
lenc)

C,
perfluom­
l­
buttoe
(pR;
Q­
lene)
Pcrtluom­
2­
butenc
(pE4­
2ene)
2H­
pcfflwmbutane
(2H­
prOr)
1H­
perfluombutane
(1H­
pE4)

C,
2H­
perfluororpcnme
OH­
PES)
perfluom­
1­
pen~
e
@fCS­
lcne)
pcrfluorPZ­
pentcac
@CS­
Zenc)

Cs
perUuom­
2lmene
(pfC6­
2cnc)
lfi­
perfluorohcxaoe
(1H­
pE6)
perfluom­
1­
hcxene
(pE6­
lenc)
IH­
perfluomhcxme
(IHpE6)

C,
2H­
pcrfluorohcptane
(2H­
pE5)
Perfluom­
l­
hcptene
(ptC7­
lene)
IH­
ptrfluoroheptane
(IH­
ptC'?)

Ce
perfluom­
lsctene
(pfC8­
lene)
2H­
perfluomoctane
(2H­
pE8)
Perfluor0­
2­
octene
(pfC8­
2ene)
IH­
perfluomme
(IH­
pE8)
2H­
pcrfluorohexene
(2H­
pE6)

1.3
Acceptable
matrices.
Aqueous
solution
of
test
substance
including
but
not
limited
to
the
following
matrices:
pH
7
phosphate
b
a
e
r
,
18.2
MR
resistivity
water,
seawater
and
metal
solutions.

2.0
SUMMARY
OF
METHOD
2.1
The
objective
of
the
photolytic
exposure
study
is
to
determine
whether
the
test
substance
undergoes
degradation
by
either
direct
or
indirect
photolysis,
and
to
identify
and
quanti@
degradation
products
formed
in
the
test
matrix
under
these
conditions.
Study
samples
(5
mL
aqueous
matrix)
are
prepared
in
40
mL
glass
VOA
vials
equipped
with
screw­
top
caps
with
septa.
Study
sets
are
prepared
in
duplicate
for
separate
analysis
by
LCMS
and
dynamic
purge
and
trap
GC/
MS.
When
required,
the
addition
of
30%
H20z
solution
to
initiate
radical
formation
is
performed
prior
to
the
photolytic
exposure
and
at
specified
intervals
throughout
the
exposure
study.
Vials
are
placed
in
the
photo­
reactor
and
immersed
in
a
water
bath
controlled
at
23­
26
OC.
Samples
are
exposed
to
approximately
261
W/
m2
of
3
10­
800
nm
photo­
irradiance
for
a
specified
number
of
%hour
periods.
An
%hour
period
of
irradiance
is
defined
as
one
day's
worth
of
sunlight.
Other
parameters
are
acceptable,
with
the
time
and
settings
noted
for
each
study.
The
number
of
days
to
expose
samples
is
determined
by
the
Team
Leader.
The
amount
of
irradiation
received
by
the
samples
may
be
monitored
in
one
of
the
following
three
ways:
1)
calculating
the
total
wattage
per
length
of
exposure
2)
use
of
a
radiometer
to
measure
irradiance
output,
a
d
o
r
3)
use
of
a
quinine
monohydrochloride
dihydrate
(QMD)
actinometer
solution
exposed
along
with
the
samples
and
monitored
for
change
UV
absorption
over
time.
The
use
of
the
radiometer
provides
an
accurate
measurement
at
specified
time­
points;
whereas
calculating
the
total
wattage
per
exposure
length
and
use
of
the
QMD
actinometer
provide
time­
averaged
total
integrated
energies.
Suntest
instruments
contain
an
internal
radiometer
for
maintenance
of
constant
irradiance.
A
second
radiometer
may
be
used
as
a
check
for
consistency.
At
the
end
of
the
exposure
time,
samples
are
removed
from
the
photoreactor
and
either
subsequently
analyzed
or
stored
at
1­
5
"C.
Study
samples
to
be
analyzed
by
LCMS
are
prepared
for
analysis
by
diluting
the
5
mL
sample
volume
with
30
mL
of
suitable
analytical
solvent
(e.
g.
methanol)
containing
internal
standard.
The
GCMS
study
samples
are
stored
inverted
prior
to
purge
and
trap
GCMS
anaIysis.

ETS­
8­
176,
OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
3
of
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2.2
An
example
of
samples
to
be
prepared
for
each
study
is
shown
in
the
table
below.
Exact
lists
may
vary,
dependent
upon
the
test
specifics
for
each
study
and
will
be
noted
in
individual
study
reports.
Typically,
there
are
extra
control
samples
for
certain
matrices
such
as
Fe203.

Sample
Rep
2
+
0
+
0
Time
0
Sample
Rep
3
+
0
+
0
Time
0
Sample
Spike
+
0
+
+
Time
0
MatrixBlank
+
0
0
0
Time
0
MatrixBlankSpike
+
0
0
+
Time
0
Control
Sample
0
f
+
0
Time
0
Contml
Spike
0
+
+
+
Time
0
Control
Blank
0
+
0
0
Time
0
Control
Blank
Spike
0
+
0
+
Time
0
kc+
p.,.

7
0
+
0
Exposed
Sample
Rep
2
+
0
+
0
Exposed
Sample
Rep
3
+
0
+
0
fipo=
d
Sample
Spike
+
0
+
+
Exposed
Matrix
Blank
+
0
0
0
Exposed
Matrix
Blank
Spike
+
0
0
+
Expo=
d
Cantml
Sample
0
+
+
0
Exposed
Conhol
Spike
0
+
+
+
Exposed
Control
Blank
Spike
0
+
0
+
Exposed
Control
Blank
0
+
0
0
Exposed
_I___

7
Ssmp
e
Rep
1
+
0
U
m
X
p
i
Z
Sample
Rep
2
Sample
Rep
3
Sample
Spike
Matrix
Blank
Control
Sample
I
Matrix
Blank
Spike
,
CMltrol
Blank
Unexposed
Unexposed
Unexposed
Unexposed
Unexposed
Unexposed
Unexposed
Unexwsed
LCMS
7?%=
mEz
WA
Hi01
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
..

X
X
X
X
­
GCMS
77E­
YEz
HzOr
H20,

X
X
X
X
X
X
X
X
X
X
X
X
._
x
X
X
X
X
X
X
X
w/
H24,
One
set
w/
o
H202
3.0
QUALITY
CONTROL­
DEFINITION/
FREQUENCY/
PERFORMANCE
CRITERIA
3.1
Blanks
3.1.1
Definition:
Matrix
Blank
An
analyte­
free
matrix
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
the
sample
processing.
For
photolysis
studies,
there
are
multiple
matrix
blanks
to
adequately
represent
the
variables
within
the
study
in
reference
to
the
matrix
(e.
g.
Exposed,
Unexposed,
Time
0;
with
peroxide,
without
peroxide).
The
matrix
blanks
are
carried
through
the
complete
sample
preparation,
experimental
treatment
and
analytical
procedure.
The
matrix
blank
is
used
to
document
contamination
resulting
from
the
experimental
treatment
and
analytical
process.
Refer
to
the
table
below
for
an
example
of
matrix
blank
types.
The
matrix
blank
is
used
to
document
the
actual
test
system
without
the
test
substance.
The
control
blank
is
used
to
control
the
test
matrix
and
trace
any
background
levels
of
target'analyte
that
may
be
matrix­
specific.
The
table
below
shows
an
example
of
a
control
blank
ETS­
8­
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OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
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Matrix
ID
Matrix
Blank
Conbpi
Blank
Matrix
descrintian
Freauency
Performance
Criteria
Example:
1
Replicate
per
light
and
backWJmd
level
of
0.0
1
M
Phosphate
Buffer,
pH
7
Example:
ASTM
Type
I1
Water
dark
exposure,
for
each
h
e
point
and
for
each
analytical
methodology.
*e
LOQ.
target
analfie
shall
be
less
than
25%
the
area
Counts
Of
Matrix
Descridion
I
I
I
I
J
Frequencv
of
Use
Performance
Criteria
3.2
Limit
of
Quantitation
(LOQ)
3.2.1
Definition:
The
lowest
concentration
that
can
be
reliably
measured
within
specified
limits
of
accuracy
during
routine
laboratory
operating
conditions.
Sample
LOQs
are
highly
matrix­
dependent.
3.2.2
Qual@
Control
and
Performance
Criteria:
The
LOQ
is
generally
5
to
10
times
the
minimum
concentration
with
a
99%
confidence
limit
that
the
concentration
is
greater
than
zero.
However,
it
may
be
nominally
chosen
within
these
guidelines
to
simplify
data
reporting.
For
many
analytes,
the
LOQ
is
selected
as
the
lowest
non­
zero
standard
in
the
calibration
curve
that
is
greater
than
4
times
the
level
of
the
solvent
blaaks
and
indicates
good
accuracy
(2
25%)
of
the
nominal
calibration
standard
concentration.

3.3.1
Definition:
Three
aliquots
prepared
as
representatives
of
the
same
sample
source
(i.
e.
test
substance)
and
carried
through
all
steps
of
the
photolytic
study
process
and
analytical
procedures
in
an
identical
manner.
The
results
fiom
triplicate
analyses
are
used
to
evaluate
variability
of
the
total
method,
including
sample
preparation,
photolytic
process
and
analysis.
3.3.2
Petformcmce
Criteria:
The
samples
in
the
test
matrix
will
be
prepared
in
triplicate.
Each
replicate
wilI
be
prepared
for
each
treatment
type:
light
and
dark
exposures,
with
and
without
hydrogen
peroxide,
for
EACH
time­
point,
and
for
each
analytical
methodology
(e.
g.
LC/
MS
andor
GCMS).
See
the
following
table:
3.3
Sample
Triplicate
Test
Matrix
containing
test
analyte(
s)

3.4
Control
Sample
3.4.1
Definition:
A
known
matrix
containing
the
test
analyte(
s)
carried
throughout
the
entire
analytical
procedure.
This
is
used
to
document
laboratory
performance
(Le.
precision
of
sample
preparation
by
comparing
spike
recoveries
from
the
different
matrices
and
sample
types).
A
control
sample
consists
of
a
control
matrix
spiked
with
test
analyte(
s).
A
control
sample
should
be
analyzed
with
each
batch
of
samples
processed
to
verify
that
the
precision
and
bias
of
the
analytical
process
ETS­
8­
176.0Preparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
5
of
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with
target
analyte(
s)
just
prior
to
analysis
are
within
control
limits.
The
results
of
control
sample
analyses
are
compared
to
control
limits
established
for
both
precision
and
bias
to
determine
usability
of
the
data.
3.4.2
Performance
Criteria.
One
control
sample
will
be
prepared
per
matrix,
per
treatment
type.
See
the
following
table:

The
analyst
shall
accept
Il)
latrixDescription
Control
Matrix
rmdtest
substance­
spiked
with
target
analyte(
s)
just
prior
to
analysis
Test
Matrix
without
test
substance,
spiked
with
target
analyte(
s)
just
prior
to
anaiysis
Control
Matrix
without
test
substance,
spiked
with
target
analyte(
s)
just
prior
to
analysis
Control
matrix
with
test
anal@(@
added
1
Replicate
per
treatment
type.
of
100
2
25%.
Ifspike
recoveries
are
greater
than
125%
or
less
than
7%
document
that
the
spike
sample
is
out
of
the
specifications
and
justie,
if
possible,
the
reason,
1
Replicate
per
treatment
type.

~

1
Replicate
per
treatment
type.
Freauencv
of
Use
I
Performance
Criteria
1
3.5
Analytical
Spike
(AS)
3.5.1
Deftition:
Prepared
by
adding
a
known
mass
of
target
analyte(
s)
to
a
specified
amount
of
a
diluted
andor
aliquoted
sample.
This
assumes
that
an
independent
estimate
of
target
analyte
concentration
is
available.
Analytical
spikes
are
used
to
evaluate
the
recovery
efficiency
of
the
analyte
and
the
effect
of
the
matrix
on
the
measurements.
3.5.2
Quality
Control
and
Performance
Criteria:
One
sample
spike
will
be
prepared
in
the
actual
test
matrix
sample,
and
one
control
spike
in
the
control
matrix
will
be
prepared.
Each
replicate
will
be
prepared
per
treatment
type:
for
light
and
dark
exposures,
with
and
without
hydrogen
peroxide,
for
each
time­
point,
and
for
each
analytical
methodology
(i.
e.
LCMS
andor
GCMS).
In
addition,
one
matrix
blank
spike
and
one
control
blank
spike
will
be
prepared.
See
the
following
table:

I
Performance
Criteria
1
I
Matrix
Descriotion
I
Freauency
of
Use
E
s
t
Ma&
andtest
substance,
spiked
I
1
Replicate
per
treatment
type.
I
I
ETS­
8­
176.
OPreparafion
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
6
of
18
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Matrix
Description
Sample
diluted
with
30
mL
of
internal
standard
compound
dissolved
in
a
suitable
analytical
solvent
to
be
quantified
using
the
internal
standard
providing
that
the
response
of
the
internal
standard
is
consistent
(k
5%
relative).
Use
of
external
calibration
methodology
requires
written
justification
by
the
Team
Leader.
3.6.2
Surrogaie
DeJinition
(applies
io
L
W
S
and
GWSsampies):
A
known
amount
of
a
compound
similar
in
analytical
behavior
to
the
target
analyt~(
s)
of
interest
may
be
added
to
all
samples
and
standards
(pre­
or
post­
irradiation,
at
the
discretion
of
the
Team
Leader)
and
carried
through
the
nzmaining
sample
preparation
and
analytical
process.
If
added
before
exposure,
it
monitors
the
presence
of
vial
leaks
during
photolysis,
as
well
as
the
performance
of
the
purge
and
trap
auto­
sampler
and
concentrator.
Surrogate
analysis
is
used
to
evaluate
and
control
the
precision
and
bias
of
the
analytical
method.
Surrogates
are
not
used
for
quantitation.

Freauencv
of
Use
Performance
Criteria
Every
LclMS
sample
analyzed
The
Coefficient
of
Variation,
or
%RSD
shall
be
calculated
for
the
area
response
of
all
appropriate
samples
per
analytical
batch.
The
analyst
shall
accept
%RSD
values
of
45%.
The
recovery
and
precision
of
the
surroEates
Note:
Internal
standardr
are
used
in
all
experiments.
The
use
of
surrogate
standards
may
or
may
not
be
used.

with
surrogate
compound
spiked
into
it.
­
should
be
100
%?
S%
and
4
5
%,
respectively.
Unacceptable
values
shall
be
documented
and
Every
sample
analyzed
justified,
if
poss,.
le.

3.7
Other
Definitions.
3.7.1
3.7.2
3.7.3
3.7.4
3.7.5
3.7.6
3.7.7
Test
AnalyteISubstance:
Any
substance
(mixture
or
controlled
compound)
added
or
administered
to
the
test
system
for
the
purpose
of
chemical
analysis.
Degradation
Product(@:
Secondary
d
y
t
e
s
of
interest
produced
as
a
result
of
chemical
reactions
during
the
photolysis
and
monitored
(qualitatively
or
quantitatively)
during
the
sample
analysis
procedure.
Target
Analyte(
s):
The
analyte(
s)
singled
out
in
the
analytical
phase
of
the
study
is
the
target
analyte.
The
target
analyte
may
be
identical
to
the
test
substance
used
in
the
experimental
phase
of
the
study,
a
by­
product
or
degradation
product
that
is
monitored
(qualitatively
or
quantitatively)
during
the
sample
analysis
procedure.
Test
Matrix:
The
physical
matrix
in
which
the
study
will
be
conducted.
Also
referred
to
as
the
test
system.
Control
Matrix:
A
known
physical
matrix
to
be
included
with
the
study
for
comparison
with
the
test
matrix.
Relative
Standard
Deviation
(RSD):
A
measure
of
relative
precision
for
three
or
more
sample
replicates;
defined
as
the
sample
standard
deviation
divided
by
the
sample
average
and
multiplied
by
100.
This
is
expressed
as
percent
(%
RSD).
Accuracy:
The
closeness
of
agreement
between
an
experimentally
determined
value
and
an
accepted
reference
value;
defined
as
the
measured
value
divided
by
the
nominal
value
and
multiplied
by
100.

ETS­
8­
176.
OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
7
of
18
Page
43
of
148
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TO
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3M
Environmental
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Report
No.
E00­
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4.0
HEALTH
AND
SAFETY
WARNINGS
4.1
Safety
4.1.1
Wear
the
proper
lab
attire,
gloves
and
eye
protection
for
all
parts
of
these
procedures.
4.1.2
Handle
all
solvents
in
a
hood
for
all
parts
of
the
described
sample
preparation
procedure.
4.1.3
For
potential
hazards
of
each
chemical
used,
refer
to
material
safety
data
sheets,
packing
materials,
and
3M
Environmental
Laboratory's
Chemical
Hazard
Review.
4.1.4
No
mouth
pipetting
is
allowed.

4.2.1
Glassware
in
which
standards
are
prepared
should
be
rinsed
with
solvent
to
reduce
the
possibility
of
accidental
contamination.
4.2.2
The
photoreactors
are
equipped
with
a
continuous
flow
of
cooling
water,
which
poses
a
threat
of
electrocution
during
the
handling
of
the
photoreactor
during
irradiation
sequences.
To
avoid
possible
injury,
inspect
the
units
frequently
for
water
leakage
and
electrical
outlets
and
wiring
for
wear
and'tear.
Replace
any
worn
parts
immediately.
4.2.3
Wear
dark
protective
eyewear
when
operating
the
reactor.
Do
not
look
directly
at
the
activated
lamp.
Use
caution
when
handling
samples
in
the
reactor;
the
interior
walls
of
the
reactor
and
exposed
glass
vials
become
extremely
hot.
4.2
Cautions
5.0
Interference
5.1
Solvents,
water
and
matrix
components
could
interfere
with
detection
thereby
decreasing
sensitivity
in
the
sample
analysis.
Care
must
be
taken
to
prevent
a11
possible
contaminants
by
using
fresh
reagents,
analytical
grade
solvents
and
clean
glassware
during
the
sample
preparation
processes.

6.0
EQUIPMENT
6.1
6.2
Analytical
balance
sensitive
to
0.1
m
g
Photoreactor:
Suntest
CPS+,
=Si­,
or
equivalent,
equipped
with
a
xenon
arc­
lamp
and
capable
of
producing
integrated
inadiance
values
from
100­
680
W/
m2
over
the
wavelength
range
of
290­
800
nm.
Lamp
output
must
be
filtered
to
allow
only
290­
800
nm
wavelengths.
A
flowing
water
bath
with
circulating
pump
is
required.
Consult
the
appropriate
3M
SOP
for
instructions.
Water
recirculating
cooler
capable
of
maintaining
temperature
at
25
O
C
f
5
OC,
from
Poly
Science,
Model
1
177­
P
or
equivalent.
Agilent
Technologies
W­
visible
Spectrophotometer,
equipped
with
tungsten
and
deuterium
lamps,
Model
8453,
or
equivalent.
Consult
the
appropriate
3M
SOP
for
instructions.
6.4.1
Autosampler
equipped
with
eight
sample
cell
holders:
Agilent
Technologies
Model
GI
1
ZOA,
Thermostatted
Cell
Holder:
Model
0845
1­
601
04,
or
equivalent.
1.0­
cm
path
length
quartz
spectrophotometer
cell
fiom
Hewlett
Packard,
or
equivalent.
6.3
6.4
6.4.1.1
6.4.2
Long
Path­
Length
Cell
Holder,
Hewlett
Packard
(#
89076C)
or
equivalent.

ETS­
8­
176.
OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
8
of
18
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E00­
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6.4.2.1
10­
cm
path
length
quartz
cell
equipped
with
stopcocks,
Hewlett
Packard
Part
#
5061­
3392,
or
equivalent.
6.4.3
Data
acquisition
and
analysis
software,
HP
ChemStation
for
W­
Visible
Spectroscopy,
GI
1
16AA,
Rev.
B.
01.02,
or
later.
6.4.4
PC
Computer
capable
of
d
n
g
appropriate
analysis
software
to
acquire
and
report
data.
Centrifige
capable
of
maintaining
>
2000
rpm
for
10
minutes
at
ambient
temperature.
Radiometer
(optionaI)
capable
of
monitoring
the
energy
from
a
xenon
source
from
290
to
480
ntn
over
time.
Model
PMA2100,
Version
1.16,
Solar
Light
Company,
Inc.,
or
equivalent.
Consult
the
appropriate
3M
SOP
for
instructions.
6.5
6.6
7.0
7.1
7.2
7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
­

7.1
1
SUPPLIES
AND
MATERIALS
40
mL
amber
and
clear
glass
VOA
vials
with
screw
caps
with
septa.
Crimp
cap
autovials­
1.5
mL,
caps,
crimper,
and
decapper.
Adhesive­
backed
labels
(return
address
size)
for
labeling
quartz
vials
and
autovials.
Disposable
glass
graduated
pipettes,
1
mL
to
10
mL.
Disposable
glass
Pasteur
pipettes
and
rubber
bulbs.
Glass
beakers,
various
sizes.
Volumetric
flasks,
from
10
mL
to
1000
mL.
Hamilton
Gastight@
syringes
(precision
f
1%
of
the
total
volume),
5
pL
to
1000
pL.
10
mL
Bottle­
top
dispenser,
Calibrex,
Model
#
5
1
1,
or
equivalent.
Adjustable
repeater
pipette,
Wheaton
Step­
pette
4
1
1,
or
equivalent,
equipped
with
the
appropriate
volumetric
range
pipette
tips.
Ziploc@
plastic
bags,
or
equivalent.

8.0
REAGENTS
AND
STANDARDS
8.1
8.2
8.3
Methanol
(MeOB).
HPLC/
SPEC/
GC
andor
purge
and
trap
grade
(EM
Science,
or
equivalent.
Acetonitrile
(ACN).
HPLC/
SPEC/
GC
and/
or
purge
and
trap
grad
fiom
EM
Science,
or
equivalent.
Aqueous
Matrix,
includes
but
is
not
i
i
t
e
d
to
the
following
matrix
types:
8.3.1
ASTM
Type
I
water.
Milli­
Q@
or
equivalent,
with
a
measured
resistivity
>I
8.0
MR­
cm.
8.3.2
0.01
M
pH
7.0
Phosphate
Buffer.
Example:
Weigh
1.36
g
mzP04
into
a
2
L
volumetric
flask
and
dissolve
into
1
L
of
Type
I
water.
Add
600
mL
of
0.1
%
NaOH.
Adjust
to
pH
7.0
k
0.1%
with
0.1%
NaOH
or
dilute
Hzs04
and
dilute
to
the
mark
with
Type
I
water
for
a
fmal
conc.
of
10
mM.
8.3.3
Lake
Surface
water.
Collected
from
a
known
source,
with
known
specifications
for
Dissolved
Organic
Carbon
(DOC)
and
Total
Organic
Carbon
(TOC).
8.3.4
Sea
water.
Collected
from
a
known
source,
with
known
DOC
and
TOC
specifications.
8.3.5
Aqueous
metal
solutions
and
slurries
(e.
g.
TiOz,
Fe203).
Example:
Dilute
0.015
g
of
Ti02
(Aldrich
Chemical
or
equivalent)
to
500
mL
with
Milli­
Q@
water.
8.3.6
Aqueous
solutions
containing
soil.
Example:
Prepare
samples
containing
0.7g
of
characterized
soil
or
sediment
in
5
mL
of
MilIi­
Q@
water.

ETS­
8­
176.
OPrepuration
ofSumples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
9
of
18
Page
45
of
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TO
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3M
Environmental
Laboratory
Report
No.
E00­
2192
8.4
8.5
8.6
8.7
8.8
Hydrogen
Peroxide
(Hz02).
30%
aqueous
solution
fiom
EM
Science,
or
equivalent.
Potassium
phosphate.
Reagent
grade
fiom
JT
Baker
or
equivalent.
Stock
Solutions
8.6.1
Stock
solutions
for
the
test
analyte,
target
analytes,
internal
standard
are
prepared
in
an
organic
solvent
(e.
g.
methanol,
acetonitrile)
at
concentrations
of
approximately
10,000
pg/
d
by
weighting
approximately
0.
I
g
of
the
appropriate
substance
into
a
lO.­
mL
volumetric
flask
and
diluting
to
the
mark
with
solvent.
This
solution
is
then
diluted
to
make
appropriate
working
solutions.
Test
Analyte
Solution:
8.7.1
Example
for
water
soluble
analvtefs):
Example:
A
1
pg/
mL.
test
substance
solution
in
the
test
matrix
(Section
8.3)
is
prepared
by
diluting
0.050
mL
of
stock
solution
(Section
8.6.1)
to
500
mL
with
test
matrix.
Aliquots
(5
mL)
of
this
solution
will
transferred
to
VOA
vials
for
subsequent
photolysis.
8.7.2
Example
for
poor
water
soluble
analvtefs)
or
those
with
adsorption
difficulties:
Prepare
a
solution
of
the
test
substance
in
acetonitrile
(Example:
A
500
pg/
mL
test
analyte
solution
is
prepared
by
diluting
500
pl
of
stock
solution
(Section
8.6.1)
into
a
10
mL
volumetric
flask
and
diluting
to
mark
with
acetonitrile).
Calculate
the
test
analyte
concentration
such
that
the
organic
content
in
the
test
vial
is
no
more
than
1
%
of
the
total
sample
matrix
volume.
Example:
A
1
pg/
mL
test
analyte
in
the
test
matrix
(Section
8.3)
is
prepared
by
injecting
10
pL
of
a
500
pg/
mL
test
substance
stock
(Section
8.6.1)
into
a
VOA
vial
containing
5
mL
of
the
test
matrix.

*Acetonitrile
is
currently
the
preferred
solvent
to
use
when
introducing
the
test
substance
to
the
test
matrix
because
it
does
not
interfere.
Methanol
is
a
radical
scavenger,
which
can
photooxidize
during
the
exposure
and
decrease
the
indirect
photolysis
of
the
intended
test
substance.
Evidence
of
this
phenomenon
(approximately
10%
decrease
in
the
concentrations
of
the
final
products)
has
been
observed
in
a
study
here
at
3M
(EtFOSE­
OHphotolysis
in
pH
7
buffer,
with
and
without
presence
of
Meow).

Target
Analyte(
s)
Spiking
solution:
Example:
A
spike
solution
of
test
analyte
and
target
analyte(
s)
(e.
g.
projected
degradation
products)
in
methanol
or
acetonitrile
is
prepared
by
diluting
500
pL
of
test
analyte
stock
solution
and
100
pL
of
target
analyte(
s)
stock
solution
(Section
8.6.1)
into
10
mL
with
MeOH.
The
final
concentration
is
approximately
500
p
g
/d
test
substance/
100
pg/
mL
target
analytes.
Addition
of
10
pL
of
this
target
analyte
spiking
solution
into
the
35­
mL
diluted
sample
volume
will
result
in
approximately
140
ng/
ml
and
30
ndnd
concentrations
for
the
test
analyte
and
targ6t
analyte(
s),
respectively.

We­
estimation
of
the
degradation
potential
of
the
test
analyte
and
subsequent
degradation
products
is
not
always
possible.
Ifpossible,
an
analyticalpre­
screening
of
representative
samples
should
be
performed
for
accurate
spiking.
General
rule
of
thumb
has
been
that
the
test
analjte
spike
amount
be
ETS­
8­
176.
QPreporation
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
10
of
18
Page
46
of
148
BACK
TO
MAIN
8.9
8.10
8.1
1
9.0
9.1
­

9.2
9.3
9.4
3M
Environmental
Laboratory
Report
No.
E00­
2192
approximately
25%­
50%
of
the
initial
concentratioR
The
target
analyte(
s)
spike
amount
has
been
10­
I
00
ng/
ml,
depending
on
expected
levels
under
specifc
conditions,
More
than
one
spike
solution
may
be
utilized
to
adequately
represent
the
levels
in
the
samples.
&ample:
A
test
analyte
that
undergoes
significant
degradation
during
photolysis
will
require
a
lower
spike
concentration
in
the
Exposed
sample
set
due
to
less
test
analyte
remaining.
The
Day
0
and
Unexposed
sample
sets,
which
have
not
degraded,
may
require
higher
test
amlyte
spike
concentrations.

Dilution
Solution
containing
Internal
Standard:
The
diluting
solution
shall
contain
internal
standard
at
an
area
response
level
equivalent
to
approximately
half
the
are
response
of
the
test
analyte's
high
standard
in
the
calibration
curve.
Enough
dilution
solution
shall
be
prepared
for
use
in
all
the
study
samples
and
in
preparation
of
the
calibration
curve
samples.
Example:
Internal
standard
solution
is
prepared
by
diluting
100
pL
of
stock
solution
(Section
8.6.1)
to
4.0
L
with
MeOH
to
a
concentration
of
250
ng/
mL.
Quinine
monohydrochloride
dihydrate
(QMD).
90%
from
Aldrich
Chemical.
QMD
solution:
A
2%
(wh)
solution
of
quinine
monohydrochloride
dihydrate
solution
is
prepared
by
weighing
approximately
2.0
g
into
a
weigh
boat,
transferring
to
a
100
mL
.
flask
and
diluting
to
volume
with
Milli­
Q"
water.

SAMPLE
HANDLING
Record
times
of
initial
preparation,
reference
numbers
of
reagents
used
and
the
amounts,
appropriate
dates,
times
and
initials
on
the
photolysis
sample
preparation
worksheet..
Record
photolysis
reactor
used,
radiometer
(
if
applicable),
computer
for
data
collection,
photolysis
start
and
end
on
the
sample
preparation
sheet
and
in
the
photolysis
reactor
log
books.
Record
times,
dates
and
initials
of
sample
treatment
post­
photolysis,
reference
numbers
of
reagents
used,
and
storage
conditions.
Upon
addition
of
the
test
substance
solution,
invert
the
40
mL.
VOA
sample
vials
(cap­
side
down)
to
prevent
loss
of
any
potential
volatile
target
analytes
during
the
rest
of
the
procedure.
This
is
particularly
important
for
the
GCMS
samples.
GCMS
samples
may
only
be
turned
upright
immediately
before
being
loaded
onto
the
purge
and
trap
autosampler.
The
LCMS
samples
may
be
turned
upright
after
the
photolysis
process
has
been
completed.
The
exception
to
this
being
the
need
to
briefly
turn
the
samples
upright
for
H202
injection
through
the
septa
of
the
appropriate
VOA
sample
vials
at
specified
time
intervals
(See
Section
12.6
and
Section
12.
I
l
,
7).
The
completed
photolysis
samples
remain
inverted
and
refrigerated
at
1­
5
'C
prior
to
analysis
by
LC/
MS
or
sample
purge
and
trap
GCMS.
Sample
preparation
prior
to
LCMS
analysis
requires
the
addition
of
30
mL
of
diluting
solvent
containing
internal
standard
to
the
5­
mL
photolysis
samples.
This
is
to
ensure
complete
recovery
of
the
target
analytes
fkom
the
glass
VOA
vial
surface
and
to
dilute
the
samples
into
a
working
analytical
range.
Day
0
study
samples
stored
at
1­
5
OC
during
the
time
of
photolytic
exposure.
are
removed
and
prepared
for
analysis
at
the
same
time
as
the
exposed
and
unexposed
samples.

ETS­
8­
176.
OP~
eparatjon
of
Samplesfor
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
11
of
18
Page
47
of
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TO
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3M
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Report
No.
E00­
2192
10.0
QUALITY
CONTROL
10.1
Refer
to
the
definitions
section
for
the
quality
control
specified
for
each
respective
sample
type.

11.0
CALIBRATION
AND
STANDARDIZATION
11.1
11.2
11.3
The
compounds
of
interest
must
be
characterized
according
to
laboratory
specifications.
All
equipment
used,
such
as
the
analytical
balance,
radiometer,
etc.
should
be
calibrated
prior
to
use
(daily,
weekly,
etc.)
as
specified
in
the
standard
operating
procedure(
s).
All
samples
analyzed
will
be
run
against
a
standard
curve
containing
varying
amounts
of
target
andytes,
and
a
fixed
amount
of
internal
standard
or
surrogate
compound.
Refer
to
the
appropriate
LC/
MS
and
GCIMS
methodologies
for
further
analytical
information.

12.0
PXOCEDURE
12.1
Obtain
the
absorbance
spectra
of
the
test
compound
in
aqueous
solution
using
a
W­
Visible
Spectrophotometer
(ETS­
9­
46.0).
12.1.1
Using
a
10­
cm
quartz
spectrophotometer
cell,
obtain
a
blank
water
absorbance
reading
over
the
range
290­
800
nm
to
determine
a
background
or
baseline
reading.
12.1.2
Aliquot
a
solution
of
water
containing
test
substance,
at
a
concentration
less
than
half
the
solubility
limit,
into
a
10
cm
quartz
spectrophotometer
cell
and
obtain
an
absorbance
reading
over
the
range
290­
800
nm.
A
positive
absorbance
may
indicate
the
potential
of
the
analyte
to
undergo
direct
photolysis.
Non­
absorbing
d
y
t
e
s
would
be
more
likely
to
undergo
indirect
photolysis
as
the
potential
degradation
pathway.
12.2
Obtain
the
appropriate
number
of
clear
and
amber
40­
mL
glass
vials
with
caps
and
cardboard
boxes.
Label
the
vial
caps
using
a
black
permanent
pen
to
distinctly
identify
samples.
Paper
labels
will
be
applied
post­
hydrolysis
as
they
don't
stick
in
water.
Prepare
appropriate
sample
preparation
worksheets
and
create
labels
for
each
sample
to
affix
to
the
40
mL
VOA
vials
and
the
autovials
for
analysis
after
photolysis.
The
labels
should
include
the
study
number,
sample
number,
test
compound,
matrix,
exposure
type
(exposed
unexposed
Day
0),
date
and
initials
of
the
analyst.
Aliquot
5
mL
of
the
following
solutions
into
clear
(for
EXPOSED
samples)
and
amber
(for
UNEXPOSED
and
DAY
0
samples)
40
mL
glass
VOA
vials:
12.4.1
Matrix
with
test
substance
(sample
reps
1,2,3,
and
sample
spike).
12.4.2
Matrix
without
test
substance
(matrix
blank
and
matrix
blank
spike).
12.4.3
Control
matrix
with
test
substance
(control
sample
and
control
spike).
12.4.4
Control
matrix
without
test
substance
(control
blank
and
control
blank
spike).
(When
appropriate,
fest
substance
may
be
added
after
5mL
aliquots
of
matrix
have
been
added
to
the
vials.
See
Section
8.7)
All
exposed,
unexposed,
and
day
0
samples
will
contain
sample
sets
with
and
without
peroxide
and
prepared
for
LCMS
and
GCMS
analyses
according
to
the
following
table:
12.3
12.4
12.5
ETS­
8­
176.
OPreparation
of
Sumpies
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
12
of
18
Page
48
of
148
BACK
TO
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3M
Environmental
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Report
No.
E00­
2192
Sample
Treatmenmype
Matrix
with
test
substance
Matrix
without
test
substance
#
of
Samples
#
of
Spikes
6
+HZ02
(3LC/
MS,
3GC/
MS)

6
­HzOz
(3LCMS
,3GC/
MS)
2
i&
O2
(1LCIMS,
lGCIMS)

2
­HZ02
(1
ILCIMS,
IGCMS)
2
+HzO2
(lLcIMS,
lGCIMS)

2
­HzOz
(lLC/
MS,
lGC/
MS)

2
+HZ02
(lLCIMS,
lGCIMS)

2
­H24
(lLC/
MS,
1GCIMS)

Control
matrix
with
test
substance
Control
matrix
without
test
substance
EXPOSED,
UNEXPOSED,
&
DAY
0
12.6
12.7
12.8
12.9
13.0
2
+HzO2
(lLC/
MS,
IGCiMS)

2
­HzOz
(IlLCIMS,
lGC/
MS)

2
+HzOz
(lLC/
MS,
lGC/
MS)

2
­HzOz
(I
lLCIMS,
IGCIMS)
2
+HZ02
(lLC/
MS,
lGC/
MS)

2
­H24
(1
lLC/
MS,
lGC/
MS)

2
+HzOz
(ILC/
MS,
lGCIMS)

2­
Hz02
(1
lLC/
MS,
lGCMS)

24x
3perexptypes72
16x3=
48
Separate
the
vials
into
three
boxes
labeled
"Day
0,"
"Exposed,"
and
"Unexposed."
Initial
addition
of
peroxide
(Section
8.4)
is
done
at
this
time
by
removing
the
cap
and
injecting
the
appropriate
amount
(e.
g.
10
­
50
pL)
into
the
vial.
(Subsequent
additions
of
peroxide
shall
be
injected
through
the
septa
of
the
VOA
vials.)
For
use
of
quinine
actinometer
(Optional):
Prepare
a
batch
of
quinine
irradiation
control
samples
by
aliquoting
5
mL
of
the
2%
aqueous
solution
(Section
8.8)
into
the
appropriate
number
of
clear
and
amber
40
mL
I­
CHEM
vials.
Prepare
one
clear
and
one
amber
vial
per
reactor,
per
day
ofexposure.
Store
the
vials
at
1­
5
OC
and
protected
from
light
prior
to
use.
Place
one
clear
vial
in
the
reactor
per
day,
while
removing
exposed
quinine
controls.
Exposed
quinine
controls
need
to
be
wrapped
in
foil
upon
removal
to
protect
from
further
exposure.
Store
at
1­
5
"C
prior
to
measuring
the
absorbance
via
W­
Vis
Spectrophotometer.
The
absorbance
measurement
should
be
performed
as
soon
as
possible,
as
the
absorbance
increase
rate
after
light
source
removal
may
be
20%
of
the
rate
of
when
light
is
present.
(Reference
18.5).
Place
all
the
"Day
0"
samples
immediately
in
a
cooler
at
1­
5
OC
or
freeze
at
a
continuos
temperature
of
less
than
0
"C,
inverted
and
protected
from
light.
Place
"Unexposed"
sample
vials
(amber)
into
Ziploc@
bags
separated
and
labeled
as
"with
peroxide"
and
"
without
peroxide",
respectively.
Place
the
bags
in
the
bottom
of
the
water
bath,
under
the
photoreactor
tray
that
holds
the
exposed
samples.
The
"unexposed"
samples
will
remain
immersed
in
the
23­
26
"C
water
bath
under
the
exposed
samples
for
the
duration
of
the
exposure.
Include
one
quinine
control
sample
in
an
amber
vial
with
the
unexposed
sample
set.

1
PHOTOREACTOR
SET
UP
ETS­
8­
176.0Preparation
ofSamp/
es
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
13
of
18
Page
49
of
148
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Report
No.
E00­
2192
Irradiance
Source
Average
Optimum
Natural
Daylight'
13.1
Set
the
irradiation
intensity
at
the
desired
output.
For
most
experimental
conditions,
an
intensity
of
261
W/
m2
is
chosen
because
it
yields
the
equivalent
average
optimum
natural
daylight
d
i
t
i
o
n
for
300­
400
nm
at
known
latitude.
(see
the
table
below):

Approximate
Inteerated
and
Individual
Irradiances
in
W/
mz
250­
300
nm
300­
400
nm
400­
800
nm
340
nm
420
nm
0.0
27.8
259.0
0.30
0.67
Atlas
Photoreactor
with
intepted
irradiance
output
of
261
W/
m
300­
800
nm
using
the
IR
Reflecting
and
290
cut­
on
filters
0.08
­~

27.8
234.36
0.24
0.71
Parameter
ETS­
8­
176.
OPrepurration
of
Samples
for
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
14
of
18
Setting
Page
50
of
148
Flowing
Water
CIFW")

Irradiation
intensity
Duration
of
exposure
ON
Example:
261
watts/
rn*

Example:
Bhours
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
for
the
unexposed
samples,
reactor
tray
holder
for
the
exposed
samples,
or
the
cooler
for
the
Day
0
samples).
Note:
Don't
forget
to
add
peroxide
to
appropriate
Day
0
samples!
Remove
the
exposed
quinine
control
sample
from
the
reactor
tray
and
visually
confm
a
color
change
as
an
indicator
of
photoreactor
performance.
The
solution
should
be
a
grayhrown
color
after
irradiation.
Record
the
total
time
exposure
of
the
sample,
wrap
the
sample
in
foil
to
protect
from
light
and
analyze
the
quinine
sample.
Place
a
new
quinine
solution
vial
into
the
photoreactor
tray
with
the
exposed
samples.
Note:
Quinine
samples
do
NOT
receive
peroxide.
13.10
Record
the
chamber
temperature
daily
on
the
sample
prep
sheets.
13.11
Upon
completion
of
the
photolytic
exposure,
samples
are
removed,
labeled
with
adhesive­
backed
labels
and
the
study
sets
(Exposed,
Unexposed
and
Day
0)
organized
for
LC/
MS
or
GCMS
analysis.
If
subsequent
analysis
can
not
be
performed
immediately,
store
samples
in
a
cooler
at
1­
5
OC.

13.12
Pertinent
information
regarding
start
and
stop
times
of
photoreactor
exposure
study,
water
bath
and
chamber
temperatures,
addition
of
peroxide,
and
an
explanation
of
unexpected
occurrences
shall
be
documented
on
the
sample
preparation
worksheets,
with
appropriate
dates,
times
and
initials,
13.9
14.0
SAMPLE
PREPARATION
FOR
ANALYSIS.
14.1
LC/
MS
sample
extraction
and
prep.
14.1.1
Dilute
all
5
mL
samples
by
a
factor
of
1:
7
v/
v
by
adding
30
mL
of
an
appropriate
analytical
solvent
containing
internal
standard
(Section
8.6.2)
to
all
vials.
14.1.2
Add
spike
solution
(Section
8.6)
containing
the
target
analytes
to
the
appropriate
samples.
14.1.3
Ensure
the
sample
vials
are
inverted
several
times
to
ensure
adequate
mixing.
14.1.4
If
samples
appear
cloudy,
and/
or
the
sample
matrix
appears
unclear,
it
may
be
necessary
to
centrifige
the
samples,
at
an
appropriate
speed
and
duration
(e.
g.
2000
rpm
for
10
minutes),
until
no
noticeable
particulate
matter
is
suspended
in
the
sample.
14.1.5
Aliquot
approximately
1
mL
into
autovials
and
tightly
cap.

14.2.1
Set
up
autosampler
and
concentrator
methods.
If
samples'have
been
kept
in
cold
14.23
Spike
vials
through
the
septa
and
place
in
the
autosampler.
14.2
GCMS
sample
preparation.

storage,
bring
samples
to
room
temperature
(approximately
23­
26
"C).

15.0
DATA
ANALYSIS
AND
CALCULATIONS
15.1
15.2
15.3
The
amount
of
target
analytes
in
the
sample
will
be
quantified
against
a
standard
curve
regression.
Means
will
be
calculated
by
adding
the
individual
entities
and
dividing
the
resultant
sum
by
the
number
of
individual
entities.
Standard
deviations
will
be
calcdated
using
either
Microsoft
Excel@
or
Microsoft
Access@
to
calculate
standard
deviation.
The
built
in
function
contains
the
following
equation
which
is
based
on
the
individual
entities
(n)
being
less
than
30:

nCx2
­
(Cn)
2
J
n(
n­
1)

ETS­
8­
176.0Prepurution
of
Samples
for
Photolysis
Studies
in
Aqueous
Mairices
Method
Page
15
of
18
Page
51
of
148
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Report
No.
E00­
2192
15.4
Sample
precision
will
be
reported
as
%
relative
standard
deviation
(%
RSD).
Sample
%
RSD
will
be
calculated
using
the
following
equation:

A
B
X
100
=Sample
%
RSD
where:
A=
standard
deviation
of
averaged
samples
B=
average
of
samples
16.0
METHOD
PERFORMANCE
16.1
Refer
to
the
definitions
section
for
the
method
performance
specificationshiteria
for
each
respective
sample
type.

17.0
POLLUTION
PREVENTION
AND
WASTE
MANAGEMENT
17.1
Dispose
of
sample
waste
by
placing
in
high
or
low
BTU
containers
as
appropriate.
Use
broken
glass
containers
to
dispose
of
glass
pipettes.

18.0
RECORDS
18.1
­
Fill
out
the
photolysis
sample
preparation
worksheet
documents
completely,
makiig
sure
to
include
all
initials
and
dates.
Store
photolysis
sample
preparation
worksheets
in
the
raw
data
file.
Enter
all
standard,
stock,
solutions,
etc.
preparation
information
in
the
proper
preparation
logbook(
s).
Make
a
photocopy
of
the
logbook
pages
used,
and
include
the
copy
in
the
raw
data
file.
Photocopied
logbook
pages
will
be
included
in
the
final
data
packet.
Archive
electronic
data
to
compact
disc
media.
18.2
18.3
19.0
ATTACHMENTS
~
­~

19.1
Attachment
A:
Example
Photolysis
Prep
sheet.

20.0
REFERENCES
20.1
20.2
20.3
20.4
Crosby,
Helz,
and
Zepp.
Aauatic
Surface
Photochemistrv.
p
480
Interpersonal
conversation
with
Carrie
O'Connor,
Optical
Systems
Engineer,
Atlas
Electric
Devices.
"Suntest
CPS/
CPS+
Spectral
Irradiance
Distribution,"
table
distributed
by
Atlas
Electric
Devices
Company,
sent
via
fax
by
Richard
Sherwin,
Sales
Representative,
26
July,
2000.
"Atlas
Xenon
Filter
Combination
and
Sunlight
Measurements,"
information
generated
by
Atlas
Electric
Devices
Company
sent
via
fax
by
Richard
Sherwin,
Sales
Representative,
26
July,
2000.

ETS­
8­
176.
OPreparation
of
Samplesfor
Photolysis
Studies
in
Aqueous
Matrices
Method
Page
16
of
18
Page
52
of
148
BACK
TO
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3M
Environmental
Laboratory
Report
No.
E00­
2192
20.5
Bergstrom,
David
H.,
Thomas
C.
Kester,
and
Shangdong
Zhan.
"Quinine
Chemical
Actinometry
Studies
Under
Two
Light
Sources
Specified
by
the
ICH
Guideline
on
Photostability
Testing."
21.0
AFFECTED
DOCUMENTS
21.1
None
22.0
REVISIONS
Revision
Number.
­
­
___
~
~

Reason
For
Revision
ETS­
8­
176.
OPreparation
of
Samplesfor
Photolysis
Studies
in
Aqueous
Mutrices
Method
Page
17
of
18
Revision
­
Date
Page
53
of
148
BACK
TO
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Environmental
Laboratory
Report
No.
E00­
2192
Attachment
A
­
Photolysis
Sample
Prep
Sheet
Fluorocbemical
Degradation
(Photolysis)
Analysis
Sample
Prep
Sheet
Tu1
Andyte
P
r
o
j
a
t
h
h
Requat
Number
ExpamreType:
Nomind
Eipor
Annlylir:
*FoNowlng
lnltld
sample
ptvp
all
sumplea
1~
111
ba
placed
caprl&
Lwn
mrdverrlcd.
Fd/
owit@
oto/
pk
Lky
0
smnplrc
wfll
kpulled
mrdeXUUWd
with
Erparrdd
Wnuparedsumplcs
Control
Matrix:

I
I
I
I
I
ETS­
8­
176.
OPreparation
of
Samples
for
Photolysis
Studies
in
Aqueous
Mowices
Method
Page
18
of
18
Page
54
of
148
BACK
TO
MAIN
3M
Environ­
mental
Laboratory
Report
No.
E00­
2192
3M
ENVIRONMENTAL
LABORATORY
EQUIPMENT
PROCEDURE
OPERATION
AND
MAINTENANCE
OF
THE
SUNLIGHT
EXPOSURE
SYSTEM,
IMMERSION
U",
AND
RECIRCULATING
WATER
CHILLER
SYSTEM
Procedure
Number:
ETS­
9­
44.0
Exact
Copy
of
Original
@?
,3­
zy­
4J
Initial
Date
Revision
Effective
Date:

Approved
by:

ETS­
944.0
Page
1
of8
Equipment
Procedure
for
the
Atlm
S
W
E
S
T
Sunlight
Exposure
System
Page
55
of
148
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No.
E00­
2192
1.0
SCOPE
AND
APPLICATION
1.1
This
equipment
procedure
describes
the
regular
operation
and
maintenance
of
the
Atlas
SUNTEST"
Sunlight
Exposure
System
equipped
with
an
immersion
unit
and
recirculating
water
chiller.

2.0
DEFINITIONS
2.1
Photon
energy:
U
=
hv
=
hc/
h
where
h
is
Planck's
constant,
c
is
the
speed
of
light,
and
v
and
h
are
the
frequency
and
wavelength
of
light.
Therefore,
the
energy
of
a
photon,
U,
is
inversely
proportionate
to
the
wavelength.
Irradiance:
The
energy
output
('TJ"
in
the
above
equation
for
energy
of
a
photon)
in
Wattsfm2
specific
to
a
wavelength
or
wavelength
range.
The
irradiance
output
specific
to
the
types
of
Atlas
wavelength
filters
available
(Reference
14.9)
should
be
used
as
a
guide
to
calculating
the
global
irradiance
(in
units
of
W/(
m2nm)
needed
to
give
a
specific
energy
over
a
desired
wavelength
range.
2.2
3.0
DESCRIPTION
3.1
The
Atlas
SUNTEST"
Sunliht
Exposure
System
CPS+
or
XLS+)
produces
visible
and
ultraviolet
light
(250­
765
W/
lm2).
Light
proiuced
is
filtered
with
a
filter
or
combination
of
filters
to
aIIow
specific
wavelength
ranges.
Samples
are
exposed
to
the
light
in
a
reflecting
chamber.
An
immersion
unit
with
water
recirculation
through
a
chiller
provides
a
cooled,
constant
sample
temperature.

4.0
IDENTIFICATION
4.1
4.2
4.3
Atlas
SUNTEST@
XLS+,
equipped
with
a
xenon
arclamp,
lamp
filter(
s)
available
from
Atlas
to
allow
specific
irradiance
ranges,
and
immersion
unit.
Atlas
SUNTEST@
a
s
+,
equipped
with
a
xenon
arclamp,
lamp
filter(@
available
from
Atlas
to
allow
specific
irradiance
ranges,
and
immersion
unit.
Neslab
CFT­
33
Refrigerated
recirculator
or
equivalent
5.0
WARNINGS
AND
CAUTIONS
5.1
Health
and
Safety
Warnings:
5.1.1
5.1.2
Wear
appropriate
laboratory
safety
personal
protective
equipment.
The
xenon
lamp
emits
ultraviolet
light
which
can
cause
burns
to
the
skin
and
permanent
damage
to
the
eyes.
Never
attempt
to
operate
the
unit
with
the
test
chamber
door
open.
When
filling
the
sample
immersion
unit
with
water,
always
shut
off
all
power
to
the
SUNTEST@
device
and
the
immersion
unit
to
prevent
electrical
shock.

Handle
optical
parts
carefully;
fingerprints
on
the
lamp,
filter
or
quartz
dish
can
result
in
altered
spectral
output
or
early
lamp
failure.
The
reflective
coating
of
the
test
chamber
walls
is
sensitive
to
scratches.
Do
not
use
any
abrasives
or
harsh
cleaning
agents
that
may
cause
scratches
and
non­
uniform
illumination
of
the
test
chamber.
5.1.3
5.2
Cautions:
5.2.1
53.2
Page
2
of
8
ETS­
9­
44.0
Equipment
Procedure
for
the
Atlus
SUNTEST
Sunlight
Exposure
System
Page
56
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
Filter1
Atlas
Part
Number
Quartz
Dish
w/
IR
reflective
coating,
PN
56052388
Quartz
Dish,
PN
56052373
W
Special
SupraxQ
Filter,
PN
56052371
5.2.3
5.2.4
5.2.5
Keep
SLJNTES'P
unit
clear
of
obstructions
that
would
block
vents;
overheating
may
cause
blown
fuses,
shortened
lamp
life
or
other
damage.
After
beginning
the
experiment,
always
make
sure
that
the
sample
vials
are
sufficiently
submerged.
Excessive
heat
may
affect
the
results
of
the
experiment.
Manually
drain
the
immersion
tank
on
the
XLS+
models
after
stopping
the
run;
otherwise,
the
water
will
overflow.

ProDerties
IEt
reflective
coating
(supplied
standard
with
unit)
Uncoated
(to
allow
higher
black
standard
temperatures)
Cut­
on
at
290
nm,
simulates
outdoor
solar
6.0
SPECIAL
INSTRUCTIONS
6.1
None.

Window
Glass
Solar
ID
65
Filter,
PN
7.0
RESPONSIBILITY
7.1
The
analytical
group
of
personnel
who
routinely
operates
the
equipment
is
collectively
responsible
for
the
instrument
operation
as
described
in
this
document.
The
person
responsible
for
maintenance
and
calibration
(and
an
alternate)
will
be
identified
in
the
h
n
t
of
the
equipment
logbook.

mm
(0.118
in.)
window
glass.
Cut­
on
at
320
nm,
simulates
exposure
behind
6
8.0
SUPPLIES
AND
MATERIALS
8.1
Xenon
lamp
for
XLS+,
Atlas
PN
56077798
56077769
Solar
Standard
Filter,
PN
56077759
mm
(0.236
in.)
window
glass.
(Must
be
used
with
Window
Glass
Filter
above.)
Cut­
on
at
290
nm,
simulates
outdoor
solar
i
radiation
at
optimal
UV
intensity.
8.2
8.3
Hand­
tools
as
required
8.4
­­
WipesTM
8.5
Xenon
lami
for
CPS+,
Atlas
PN
56001794
Optional
radiation
filter(
s)
for
lamp
available
h
m
Atlas:

1
radiation.
I
Cut­
on
at
3
10
nm,
simulates
exposure
behind
3
Window
Glass
Filter,
PN
56052372
ETS­
9­
44.0
Page
3
of
8
Equipment
Procedure
for
the
Atlas
SUNTEST
Sunlight
Exposure
Systein
Page
57
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
9.0
CLEANING
PROCEDURES
All
routine
and
non­
routine
cleaning
procedures
will
be
performed
by
person(
s)
designated
in
the
front
of
the
instrument
logbook;
see
Section
12).
9.1
Routine
cleaning
9.1.1
Clean
the
inlet
air
filters
at
the
back
of
the
SUNTEST@
unit
every
6
months
with
a
mild
soap
solution.
Rinse
in
clean
water.
When
more
severe
contamination
is
present,
vacuum
the
filters
or
replace
them.
Clean
the
reflector
in
the
test
chamber
when
it
is
dirty,
using
a
soft
cloth
and
mild
soap
solution.
DO
NOT
use
any
abrasive,
cleaning
materials
or
the
reflector
may
be
permanently
damaged
and
irradiance
uniformity
will
be
altered.
Clean
and/
or
flush
the
water
tank
and
water
lines
on
the
immersion
unit
monthly
to
prevent
build
up
of
residue
in
the
circulating
water
system.
9.1.2
9.1.3
10.0
MAINTENANCE
PROCEDURES
10.1
Routine
maintenance
will
be
performed
by
the
person(
s)
designated
in
the
front
of
the
equipment
log
(see
Section
12):
10.1.1
Replace
the
xenon
lamp
after
1500
hours
or
when
the
required
irradiance
level
cannot
be
achieved
(e.
g.
error
message
reads
"E
MAX
Power
reached;
CHANGE
XENON
L
W
")
Refer
to
the
SUNTESP
instruction
manual
for
details
on
how
to
replace
the
lamp.
If
the
temperature
near
the
lamp
becomes
too
high,
the
h
e
blows
to
interrupt
power
and
save
the
lamp
(indicated
by
the
error
message
"DOOR
OPEN
or
TEMPERATURE
FUSE").
Refer
to
the
SUNTEST"
instruction
manual
for
details
on
how
to
replace
the
fuse.
Record
routine
maintenance
in
the
equipment
log
(see
Section
12).
10.1.2
10.1.3
Non­
routine
maintenance
will
be
performed
by
the
person@)
designated
in
the
ftont
of
the
equipment
log
(see
Section
12):
10.2.1
10.2
If
the
equipment
fails
to
operate,
refer
to
the
equipment
manual
for
further
instructions,
if
necessary.
Contact
the
Team
Leader
for
instructions
if
the
equipment
cannot
be
made
operational.
If
an
abnormal
operating
situation
occurs
or
if
calibration
verification
fails,
contact
the
responsible
individual
identified
in
the
equipment
log.
Label
the
equipment
as
"out
of
service"
if
it
cannot
be
immediately
repaired.
Record
non­
routine
maintenance
in
the
equipment
log
(see
Section
12).
10.2.2
10.2.3
11.0
INSTRUMENT
CALIBRATION
11.1
The
photoreactor
is
set
to
maintain
a
specified
integrated
energy
output.
The
amount
of
energy
output
fkom
the
lamp
may
be
monitored
with
the
use
of
a
radiometer.
The
radiometer
system
will
provide
and
record
instantaneous
energy
output.
Refer
to
ETS­
9­
50.0
Operation
and
Maintenance
of
Radiometer
and
Detector.
Calibration
of
SUNTEST"
systems
will
be
performed
two
times
each
year
by
Atlas
Electric
Devices
Company.
11.2
ETS­
9­
44.0
Page
4
of
8
Equipment
Procedure
for
the
Atlas
SUNTEST
Sunlight
EXpOSltre
System
Page
58
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
12.0
OPERATING
PROCEDURES
12.1
12.2
Immersion
Unit
For
more
detailed
operating
instructions
refer
to
the
equipment
operating
manuals.

12.2.1
To
begin
operation,
fill
the
tank
with
water
until
the
level
indicator
is
up
to
the
full
mark.
12.2.2
T
u
the
power
on.

12.3.1
SUNTEST"
XLW
or
SUNTEST@
CPS+
unit
set­
up
12.4.1
12.3
Chiller
Turn
the
power
on.
Set
water
temperature
knob
to
desired
set
point.
Allow
temperature
to
equilibrate
before
igniting
the
SUNTEST"
lamps.

Select
the
desired
wavelength
filter
b
m
the
parts
listed
under
Section
8.4
to
achieve
the
proper
irradiation
specified
in
the
program,
and
program
the
photoreactor
with
the
filter
type
information:
12.4
With
the
photoreactor
menu
in
the
''Program"
mode,
select
the
appropriate
filter
combination
type:

ODtical
filter
System
Designations
A:
Coated
quartz
glass
only
B:
Coated
quartz
glass
with
W
special
glass
C:
Coated
quartz
glass
with
window
glass
D:
Uncoated
quartz
glass
only
E:
Uncoated
quartz
glass
with
W
special
glass
F:
Uncoated
quartz
glass
with
window
glass
I
I
12.4.2
Selectioddetemination
of
energy
output
(W/
m')
12.4.2.1
Irradiance
control
and
display
is
between
250­
765
W/
m2
(nominally
300­
800
nm).
The
irradiance
is
determined
by
the
settings
of
the
test
program
[including
type
of
filter@)
used].
The
selectable
range
is
from
250
W/
m2
to
765
W/
m2
(page
12,
XLS­
t
Instruction
manual).
The
total
(integrated)
energy
output
(300­
800
nm)
is
directly
dependent
on
the
type
of
lamp
filter@)
used.
E.
g.
if
the
filter
has
a
narrow
range
such
as
a
cut­
on
at
400
nm,
all
irradiance
energy
coming
from
wavelengths
c400
nm
will
not
reach
the
samples,
and
the
total
integrated
irradiance
will
be
less
than
if
the
filter's
cut­
on
was
at,
for
example,
290
nm.
Once
the
proper
filter(
s)
idare
designated,
the
photoreactor
will
base
the
energy
output
on
what
type
of
wavelengths
are
being
allowed
to
pass
through
the
filter
system
to
reach
the
samples.
To
calculate
the
energy
output
to
program
into
the
system,
refer
to
References
14.7,
14.8
and
14.9
as
guides
to
calculate
the
desired
spectral
irradiance.
Reference
14.7
may
be
used
to
calculate
the
programmed
global
irradiance
necessary
to
achieve
desired
irradiances
at
specific
wavelengths
or
wavelength
ranges.
Reference
14.8
may
be
used
to
reference
sunlight
measurements
and
to
correlate
natural
sunlight
to
the
Atlas
Suntestm
photoreactors.
Reference
14.9
is
a
useful
reference
for
determining
irradiances
at
a
specific
12.4.2.2
Page
5
of
8
ETS­
9­
44.0
Equipment
Procedure
for
the
Atlas
SUNTESTStmlight
Exposure
System
Page
59
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
wavelength
or
a
wavelength
range
using
specific
filter
combinations
at
specified
global
irradiances
of
250,500,
and
765
W/(
m2nm).
12.5
Photoreactor
M
y
s
i
s
set
up
12.5.1
12.5.2
12.5.3
12.5.4
12.5.5
12.5.6
12.5.7
12.5.8
12.59
Place
VOA
(volatile
organic
analysis)
vials
containing
samples
(see
the
appropriate
analytical
method)
into
the
test
chamber.
Sample
vials
to
be
exposed
must
be
cap
side
down
to
allow
light
to
enter
the
vial.
Tighten
caps
securely
to
prevent
leakage.
Secure
the
vials
in
the
chamber
to
prevent
floating
once
the
water
begins
to
circulate.
Close
the
chamber
door
and
turn
the
power
on.
From
the
initial
LCD
display,
use
the
arrow
keys
to
select
Program.
Press
"Enter".
If
programming
a
new
method
is
necessary,
use
the
arrow
key
to
select
Programming.
Press
"Enter".
Input
program
number,
number
of
phases,
desired
irradiance,
immersion
hction,
phase
time
and
switch
off
criteria.
Each
entry
is
followed
by
the
"Enter"
key.
To
start
the
program,
select
"Program
Start"
and
press
the
"Enter"
key.
Press
"Escape"
for
the
next
screens
if
the
filter
has
not
been
changed
and
no
printout
is
desired.
Input
program
number
and
press
"Start"
Program
will
begin
with
lamp
ignition.
Note:
Due
to
the
modified
sample
chamber
in
the
SUNTEST@
XLS+
models,
the
water
initially
present
in
the
immersion
tank
is
not
sufficient
to
fill
the
sample
chamber
once
a
program
has
started.
Refill
the
immersion
Unit
as
the
water
level
drops
below
the
fill
line.
Once
a
program
has
finished,
drain
the
immersion
tank
so
that
it
does
not
overflow
when
water
from
the
sample
chamber
drains
back
down
into
the
immekion
unit.
Failure
to
do
so
may
result
in
remote
flooding.
To
interrupt
operation
(e.
g.
to
add
peroxide
reagent)
Press
"Stop".
If
it
is
necessary
to
turn
the
power
off
(to
exchange
the
lamp,
for
example)
wait
until
the
fan
turns
off
in
1­
3
minutes
before
turning
power
switch
to
"Off'
and
unplugging
the
power
cod.
When
ready
to
continue
operation,
turn
power
"On".
12.5.10
To
resume
operation,
press
"Start".
The
program
will
continue
at
the
point
of
interruption.
12.5.11
To
read
parameters
during
the
program
run,
scroll
through
the
parameters
of
the
running
program
by
using
the
arrow
keys.
This
is
helpful
to
see
how
many
more
hours
are
remaining
in
the
running
program.

reached.
To
display
the
total
time
and
irradiance,
press
"Enter".
Record
exposure
time
in
instrument
run
log.
Then
turn
power
"Off'.
12.5.13
To
manually
stop
the
program,
press
"Stop".
Wait
until
lamp
is
cooled,
then
press
"Escape".
Power
can
then
be
turned
"Off'.
12.5.12
The
SUNTEST@
will
shut
off
automatically
when
the
switch­
off
criteria
are
ETS­
944.0
Page
6
of
8
Equipment
Procedure
for
the
AtIa
SUNTESTStinlight
Exposure
System
Page
60
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
13.0
RECORDS
13.1
Instrument
logbooks
13.1.1
Equipment
Log:
The
person(
s)
designated
at
the
front
of
the
equipment
log
will
record
all
cleaning
and
maintenance
activities
in
the
appropriate
log
for
each
SUNTEST@
system.
Records
for
routine
maintenance
of
equipment
must
include
the
dates
of
the
operation,
whether
the
operations
followed
the
SOP,
and
the
initials
of
the
person
performing
the
operation.
Records
for
non­
routine
repairs
performed
as
a
result
of
instrument
failure
or
malfunction
must
include
the
nature
of
the
defect,
how
and
when
the
defect
was
discovered,
any
remedial
action
taken
in
response
to
the
defect,
and
the
date
and
initials
of
the
person
performing
the
maintenance.
Maintenance
by
outside
contractors
should
include
their
name
and
company
affiliation.
Run
Log:
Record
each
experiment
in
the
appropriate
instrument
logbook.
Enter
the
operators
initials,
time
and
date
of
exposure,
lamp
intensity
and
water
temperature
as
the
samples
are
placed
in
the
chamber.
When
samples
are
finished,
record
the
time
and
date
when
samples
came
out,
the
ending
chamber
temperature
and
the
actual
hours
of
exposure.
All
entries
made
in
the
run
log
should
be
initialed
and
dated.
SUNTEST"
Data
Output
Log:
XENOVIEW@
2.2
Storage
Sohare
will
receive
and
record
the
measurement
data
transferred
from
the
SUNTEST@
system
to
a
computer
or
printer,
while
a
program
is
in
progress.
The
measurement
data
recorded
includes:
number
of
phases,
phase
time,
chamber
temperature,
radiant
exposure,
irradiance,
running
time,
date
and
time
data
is
recorded.
Refer
to
XENOVDEW"
software
instruction
manual
for
details
on
how
to
operate
software.
Any
printouts
of
program
or
other
data
should
be
initialed
and
dated
prior
to
adding
to
the
study
file.
13.1.2
13.1.3
13.2
1dentification.
records
for
each
system
include
equipment
ID,
manufacturer,
model
number,
and
serial
number
of
each
individual
component.
In
addition,
if
components
are
removed
or
added,
the
above
information
must
be
written
in
the
logbook
including
the
date
the
change
was
made
and
initials
of
the
analyst
completing
the
change.

14.0
REFERENCES
14.1
SUNTEST@
XLS/
XLS+
Instruction
Manual,
Doc.
No.
20­
8036­
00
Rev.
0
12/
98
Atlas
14.2
14.3
14.4
14.5
14.6
14.7
14.8
14.9
Electric
Devices
Company.
SUNTEST@
CPS/
CPS+
Operating
Manual,
6/
97
Atlas
Company.
SUNTEST@
XLS+
Immersion
Device
Operating
Manual,
2/
99
Atlas
Company.
SUNTEST@
CPS+/
XLS+
Software
Documentation
1.4
Atlas
Company.
XENOVmV
2.2
Storage
Software
operating
Instructions.
ETS­
9­
50.0,
Operation
and
Maintenance
of
Radiometer
and
Detector.
*`
SUNTEST%
adiance
in
W/
m2*
nm".
Tables
finished
by
Atlas
Company,
"Atlas
Xenon
Filter
Combination".
Table
furnished
by
Atlas
Company.
"SUNEST"
CPS/
CPS+
Spectral
Irradiance
Distribution".
Table
furnished
by
Atlas
Company.

ETS­
94.0
Page
7
of
8
Equipment
Procedure
for
the
Atlas
SUNTEST
Sunlight
Exposure
Systein
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15.0
AFFECTED
DOCUMENTS
15.1
None.

16.0
REVISIONS
Revision
Revision
Number.
Reason
For
Revision
­
Date
ETS­
944.0
Page
8
of
8
Equipment
Procedure
for
the
Atlas
SUNTEST
Sunlight
Exposure
System
Page
62
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3M
ENVIRONMENTAL
LABORATORY
ANALYSIS
OF
FLUOROCHEMICALS
BY
ARCHON
PURGE
AND
TRAP
AUTOSAMPLER,
TEKMAR
PURGE
AND
TRAP
CONCENTRATOR
AND
AGILENT
GAS
,

CHROMATOGRAPHBV~
ASS
SPECTROMETER
Procedure
Number:
ETS­
3­
1820
Exact
Copy
of
Original
Initial
Date
"r
sizz+
Adoption
Date:
2a
00
11
Revision
Date:

Approved
by:

T
,h/&/
Ud
Laboratoj
Manager
Date
ETS­
8­
182.0
Analysis
of
FCs
by
Purge
&
Trap
Autosampler/
Concentrator/
GC/
MS
Page
63
of
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No.
E00­
2192
1.0
SCOPE
AND
APPLICATION
1.1
Scope.
This
method
is
used
for
the
analysis
of
selected
hydrolysis
and
photolysis
samples
for
the
presence
of
degradation
products
such
as
olefins
and
hydrides
using
gas
chromatographylmass
spectrometry
in
a
full
scan
mode.
An
Archon
autosampler
and
Tekmar
Purge
and
Trap
concentrator
(or
an
equivalent
system)
is
coupled
to
a
GC
for
purging
analytes
from
the
liquid
matrix
and
concentrating
them
on
the
trap
column
before
injecting
on
to
the
GC.
Applicable
compounds.
Compounds
that
may
be
analyzed
by
this
method
are
listed
below.
Other
fluorochemicals
may
be
detected
by
monitoring
mass
spectra
and
running
library
comparison.
Compounds
that
are
detected
but
do
not
have
appropriate
standards,
will
be
quantified
relative
to
structurally
similar
standard
compounds
listed
below.
1.2.1
lH­
perfluoroethane
(1H­
pfC2)
1.2.2
Perfluro­
2­
butene
(pfC4­
2ene)
1.2.3
1H­
perfluropropane
(1H­
pfC3)
1.2.4
IH­
perfluorobutane
(lH­
pC4)
1.2.5
Perfluoro­
2­
heptene
(pfC7­
2ene)
1.2.6
Perfluoro­
l­
heptene
(pfC7­
lene)
1.2.7
1H­
perfluorohexane
(1H­
pE6)
1.2.8
Perfluoro­
2­
octene
(pfC8­
2ene)
1.2.9
1H­
perfluoroheptane
(1H­
pfC7)
1.2.10
2H­
perfluorooctane
(ZH­
pfC8)
1.2.11
1H­
perfluorooctane
(1H­
pfC8)
Instrument
Surrogate
compounds.
Added
at
the
time
of
analysis
and
used
to
monitor
performance
of
purge
and
trap
autosampler
and
concentrator.
1.3.1
Dibromofluoromethane
1.3.2
Toluene­
d8
1.3.3
4­
Bromofluorobenzene
1.3.4
Pentafluorobenzene
1.3.5
1,4­
Difluorobenzene
1.3.6
Chlorobenzene­
d5
13.7
1,4­
Dichlorobenzene­
d4
Sample
Surrogate
compounds.
May
be
added
at
the
time
of
sample
preparation.
1
A.
1
Perfluorocyclohexane
1.2
1.3
1.4
2.0
SUMMARY
OF
METHOD
2.1
A
dynamic
purge
and
trap
system
(autosampler
and
concentrator)
is
coupled
to
a
temperature
programmed
GC
for
analyte
separation
and
subsequent
mass
spectrometer
detection
and
quanitation.
The
liquid
sample
is
purged
for
20
min.
in
the
sample
vial,
and
the
volatile
components
are
swept
onto
a
chemical
trap
in
the
concentrator.
In
the
subsequent
desorption
mode,
gas
flows
in
opposite
direction
and
temperature
of
the
chemical
trap
increases
to
250
"C.
The
trapped
analytes
are
transferred
onto
the
GC
column
for
GCMS
separation,
detection,
and
quanitation.
Through
this
process,
a
high
volume
of
sample
is
injected
and
most
of
the
non­
volatile
matrix
components
stay
in
the
sample
vial,
allowing
low
level
detection
of
fluorochemicals.

ETS­
8­
182.0
Page
2
of
12
Analysis
of
FCs
by
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&
Trap
Autosampler/
Concentrator/
GC/
MS
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3.0
DEFINITIONS
3.1
Calibration
Standard.
A
dilution
of
various
amounts
of
a
stock,
intermediate
or
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
purchased
standard
to
achieve
standard
soIutions
in
a
concentration
range
of
interest,
Calibration
Curve.
The
graphical
relationship
between
known
values,
such
as
concentration
of
a
series
of
calibration
standards
and
their
instrumental
response.
External
Standard
Quantification.
Process
of
establishing
the
concentration
of
a
target
analyte
by
plotting
the
theoretical
amount
(in
units
of
ng/
mL
or
pg/
mL,
etc.)
versus
the
response
of
the
target
analyte(
s)
on
column.
The
resultant
curve(
s)
shall
be
used
to
determine
unknown
concentrations
by
comparing
the
area
response
of
target
analyte(
s)
to
the
area
response
and
corresponding
analyte
amount
on
the
appropriate
analyte's
calibration
curve.
Coefficient
of
Determination
(r").
The
square
of
the
correlation
coefficient,
It
is
the
proportion
of
the
variation
in
the
dependent
variable
that
is
accounted
for
by
the
independent
variable.
Instrument
Surrogate.
An
organic
compound
similar
to
the
target
analyte(
s)
in
behavior
in
the
analytical
process,
but
is
not
normally
found
in
the
sample(
s).
A
surrogate
may
be
added
to
sample
vial
during
instrument
analysis.
Sample
Surrogate.
An
organic
compound
similar
to
the
target
analyte(
s)
in
chemical
composition
and
behavior
in
the
analytical
process,
but
is
not
normally
found
in
the
sample(
s).
A
surrogate
may
be
added
to
sample
triplicates
and
matrix
spike
samples
along
with
the
test
analyte
(pre­
photolysis).
Continuing
Calibration
Verification
(CCV).
Standards
analyzed
during
an
analytical
nm
to
verify
the
continued
accuracy
of
the
calibration
curve.
This
solution
may
or
may
not
be
prepared
from
a
different
source
or
lot
number
than
the
calibration
curve
standards.
Solvent
Blank.
A
sample
of
analyte­
free
medium
that
is
not
taken
through
the
sample
preparation
process.
This
blank
is
used
to
evaluate
instrument
contamination.
Blank,
For
photolysis
studies,
there
are
multiple
blanks
to
adequately
represent
the
variables
of
the
study
(Exposed,
Unexposed
and
Day
0
samples
witldwithout
peroxide
addition).
The
blank
is
canied
through
the
sample
preparation,
photolytic
and
analytical
procedures
to
monitor
for
contamination
during
any
step.
It
is
also
used
to
establish
a
chromatographic
baselinehackground
and
monitor
for
analytical
interference
or
suppression
of
target
andyte(
s)
from
the
matrix.
3.9.1
Matrix
Blank
A
sample
of
analyte­
fkee
matrix
(buffered
water,
lake
water,
etc.)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
It
is
used
to
document
the
test
system
without
test
analyte.
3.9.2
Control
Blank:
A
sample
of
analyte­
flee
matrix
(Milli­
Q
water)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
It
is
used
to
control
the
test
matrix
and
monitor
matrix
specific
ETS­
8­
182.0
Analysk
of
F
a
by
Purge
&
Trap
AutosampIer/
Concentrator/
GC/
MS
Page
3
of
12
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E00­
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3.10
3.11
3.12
3.13
3.14
3.15
4.0
background
levels,
interferences
or
suppression
of
target
analytgs)
from
the
matrix.
Limit
of
Quantitation
(LOQ).
The
lowest
concentration
that
can
be
reliably
measured
within
specified
limits
of
accuracy
during
routine
laboratory
operating
conditions.
The
LOQ
is
generally
5
to
10
times
the
minimum
concentration
with
a
99%
confidence
limit
that
the
concentration
is
greater
than
zero.
However,
it
may
be
nominally
chosen
within
these
guidelines
to
simplify
data
reporting.
For
many
analytes,
the
LOQ
is
selected
as
the
lowest
non­;
BO
standard
in
the
calibration
curve
that
is
greater
than
4
times
the
level
of
the
matrix
blank.
Sample
Triplicates.
Three
samples
taken
from
and
representative
of
the
same
sample
source.
These
are
prepared
separately
and
canied
through
all
steps
of
the
exposure,
extraction
and
analytical
procedures
in
an
identical
manner.
There
are
multiple
sets
of
triplicate
samples
to
adequately
represent
the
photolytic
variables
of
the
study
(Exposed,
Unexposed
and
Day
0
WiWwithout
peroxide
addition).
Triplicate
samples
are
used
to
assess
variance
of
the
photolytic
method,
including
sample
preparation,
photolysis
exposure,
and
analysis.
Relative
Standard
Deviation
(RSD).
A
measure
of
precision
defined
as
the
standard
deviation
of
three
or
more
values
divided
by
the
average
of
the
values
and
multiplied
by
100.
(Also
reported
as
Coefficient
of
Variation
(CV)).
Analytical
Spike.
Prepared
by
adding
a
known
mass
of
target
anaIyte(
s)
to
a
specified
mount
of
a
sample
or
control
matrix
prior
to
analysis.
This
assumes
that
an
independent
estimate
of
target
analyte
concentration
is
available.
Matrix
spikes
are
used
to
determine
the
effect
of
the
matrix
on
method
recovery
efficiency.
Accuracy.
The
closeness
of
agreement
between
an
experimentally
determined
value
and
an
accepted
reference
value.
When
applied
to
a
set
of
observed
values,
accuracy
is
a
combination
of
a
random
(precision)
and
a
common
systematic
(bias)
component.
For
purposes
of
the
study,
the
acceptance
criterion
is
75%
to
125%
of
the
nominal
value,
Geometric
Mean
of
the
calibration
curve:
The
square
root
of
the
product
of
the
high
standard
concentration
and
the
low
calibration
curve
standard.
When
preparing
calibration
curve
standards,
the
number
of
calibration
standards
below
the
geometric
mean
shall
equal
the
number
of
calibration
standards
above
the
geometric
mean.
Having
equal
distribution
of
calibration
standards
above
and
below
the
geometric
mean
when
analyzing
and
reprocessing
data,
effectively
weights
the
curve
such
that
both
the
high
and
low
ends
of
the
curve
are
given
equivalent
significance.

WARNINGS
AND
CAUTIONS
4.1
Health
and
Safety
Warnings:
4.1.1
The
operator
must
be
familiar
with
the
purge
and
trap
autosampler/
concentrator/
GC/
MS
system
and
associated
hazards,
such
as
high
temperature,
effluent
venting,
solvent
use,
and
low­
pressure
vacuum
system.
See
instrument
manuals
ETS­
8­
182.0
Page
4
of
12
Analysis
of
FCs
by
Purge
&
Trap
Autosampler/
Concen#
rator/
GU~
S
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4.1.2
All
exhaust
vents,
including
the
GC
oven
vent,
Tekmar
concentrator
purge
vent,
split
vent
and
mass
spectrometer
pump
exhaust
must
be
connected
to
the
laboratory
vent
system
to
keep
potentially
hazardous
effluent
from
mixing
with
laboratory
air.

It
is
recommended
that
a
grounded
antistatic
Wrist
strap
be
worn
while
disconnecting
al1
wires,
contacts,
or
cables
which
are
connected
to
printed
circuit
boards
within
the
Archon
autosampler,
Tekmar
concentrator
or
MS
analyzer.
4.2.2
To
prevent
the
breakage
of
the
Standard
Vial
on
the
Archon
autosampler,
do
not
use
my
tool
and
do
not
overtighten
the
thumbnut.
4.2
Cautions:
4.2.1
5.0
INTERFERENCE
5.1
Methanol,
water
and
other
co­
extracted
matrix
components
could
interfere
with
detection
decreasing
sensitivity.

6.0
EQUIPMENT
6.1
System:
"Rufus",
or
equivalent:
6.1.1
Autosampler:
Varian,
Archon
6.1.2
Concentrator:
LSC2000,
Tekmar
6.1.3
GC:
6890,
Agilent
6.1.4
MS:
5973N,
AgiIent
6.1.5
Column,
GS­
GASPRO
60m
x
0.23mm,
J&
W
7.0
SUPPLKES
AND
MATERIALS
7.1
Helium,
ultra­
high­
purity
7.2
401111
VOA
vials,
e.
g.
I­
Chem,
S236­
0040
8.0
REAGENTS
AND
STANDARD
8.1
8.2
Methanol,
Purge
and
Trap
grade
or
equivalent
Standards.
Typically
a
minimurn
of
five
calibration
standards,
ranging
fiom
1
ng/
ml
to
20
ng/
ml
are
prepared.
This
concentration
range
should
bracket
the
concentration
of
samples
and
matrix
spikes;
if
the
analyte
concentration
exceeds
this
range,
then
the
calibration
range
should
be
increased,
Instrument
Surrogates.
Used
only
to
monitor
performance
ofpurge
and
trap
autosampler
and
concentrator
and
not
for
quantitation.
Sample
Surrogates.
May
be
used
to
monitor
sample
preparation,
photolytic
exposure
and
analytical
perfonnance.
8.3
8.4
9.0
SAMPLE
HANDLING
9.1
Store
standards
and
samples
in
the
refrigerator
at
4
'
C
5
3
C
until
analysis
time.

Page
5
of
12
ETS­
8­
182.0
Analysis
of
FCS
by
Purge
&
Trap
Autosampler/
Concenhator/
GC/
MS
Page
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9.2
For
the
analysis,
pull
samples
and
standards
out
of
the
freezer
and
bring
them
to
room
temperature.

10.0
QUALITY
CONTROL
10.1
Calibration
Standards.
Calibration
standards
(Section
11)
used
to
generate
a
calibration
curve.
The
number
of
calibration
standards
and
the
concentration
levels
should
be
sufficient
to
encompass
the
expected
concentrations
of
the
study
samples.
In
general,
a
minimum
of
live
calibration
standards
is
required
for
fit
of
linear
regression.

Continuing
Calibration
Verification
(0
.
Analyze
a
mid­
range
calibration
standard
after
a
maximum
of
every
fifteen
samples.

Solvent
blank.
Solvent
blanks
are
run
before
and
after
every
calibration
curve,
CCV,
matrix
and
control
bIank
(see
3.9.2),
and
after
batches
of
no
more
than
30
injections.
Acceptable
values
for
the
bIanks
are
values
below
25%
of
the
limit
of
quantitation
0;
OQ
of
the
instrument.
If
analyte
carryover
is
a
problem,
use
back­
to­
back
solvent
blanks.
Sample
Triplicates.
hepare
and
analyze
all
samples
in
triplicate
to
provide
a
measure
of
the
precision
of
analysis.
Analytical
Spikes.
Prepare
a
matrix
spike
sample
for
each
sample
type
as
applicable
to
determine
the
matrix
effect
on
the
recovery
efficiency.
Concentrations
of
the
spike
should
be
approximately
equal
to
a
mid­
range
calibration
standard.
The
matrix
spike
sample
should
be
analyzed
periodically
to
measure
the
precision
associated
with
the
analysis.
The
analyst
shall
accept
percent
spike
recoveries
of
100
f
25%.
Spike
recoveries
outside
of
this
range
should
be
noted
and
used
with
other
criteria
to
evaluate
the
condition
of
the
analytical
run.
Consult
with
the
Team
Leader
or
designee
for
direction
and
final
acceptance
or
rejection
of
the
anaIytica1
run.
10.2
10.3
10.4
10.5
11.0
CALIBRATION
AND
STANDARDIZATION
113.1
Analyze
standards
prior
to
each
set
of
samples.
The
linear
regression
will
be
calculated
from
the
plot
of
all
individual
calibration
points,
without
including
or
not
forcing
through
zero,
using
Target
NT
Software.
A
minimum
of
five
calibration
standards
is
required
to
generate.
linear
regression
for
target
analyte(
s).
If
the
calibration
curve
residuals
are
greater
than
25%
deviation
from
the
theoretical
value,
quadratic
curve
fitting
andor
dropping
lowhigh
curve
points
may
be
required
if
data
review
shows
this
to
be
a
consistent
and
more
accurate
representation
of
the
instrument
response.
Document
in
the
raw
data
the
technical
justification
for
any
deviation
and
consult
with
the
team
leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
of
the
data.
If
the
curve
does
not
meet
requirements
perform
routine
maintenance
or
prepare
a
new
standard
curve
(if
necessary)
and
reanalyze
11.2
ETS­
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Analysis
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FCs
by
Purge
&
Trap
Autosampler/
Concentrator/
GUMS
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12.0
PROCEDURES
12.1
Set
Archon
autosampler
12.1.1
Archon
System
Settings
US
Probe
Temp
180
Xfer
line
Temp
180
US
Valve
Temp
105
Gripper
Open
750
Standby
Pol
CLOSED
DesDrn
Pol
CLOSED
STOP
Pol.
CLOSED
Gripper
Closed
999
Equilb.
Count
0
Equilb.
Time
0
Needle
Sparge?
YES
Ign.
Vial
Type?
YES
Ignore
No
Vial?
NO
HotWater
Rinse?
NO
Vial
Checks?
YES
Beep
on
Error?
YES
Sample
Type
Soil
First
Vial
1
Last
Vial
up
to
51
Sample
VoIume
10
Standard1
(l
a
)
YES
Standard
2
NO
S.
PreHeat
Stir
NO
Stir
NO
Syring
Flushes
0
PreHeat
YES
PreHeat
Temp
35
PreHeat
Time
1
.o
Purge
Time
20.0
Desorb
Time(
m)
0.5
Oper.
Mode
Remote
Cycle
Timer
0.0
Am.
Timer
0.0
Link
to
Method
0.0
12.1.2
Archon
System
Options
Barcode
Scanner
NO
12.1.3
Archon
Method
Soil
Purge
Flow
40mVmin
Soil
Purge
Pressure
2Opsi
ETS­
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182.0
Analysis
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by
Purge
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Autosumpler/
Concentrarator/
GU!
S
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12.2
Set
Tekmar
options
Standby
Purge
Dry
Purge
Desorb
Preheat
Desorb
Bake
BGB
BGB
Auto
VaIve
Line
Mount
Runs
per
Sample
40°
C
(30°
C
by
purge)
20.0omin
2.0Omin
245°
C
0.5Omin
at
250°
C
1
O.
OOrnin
at
26OOC
OFF
Delay
Osec
Drain
ON
180°
C
180°
C
100°
C
1
Purge
Flow
4OmLlmin
Purge
Pressure
2Opsi
Trap
VOCARB
3000
Containing:
Carbopack
B
Carboxen
1000
Carboxen
1001
12.3
Set
GC
conditions
12.3.1
Oven:
Initial
temp:
40
C
Initial
time:
4.00min
Ramp
at
15.00
C/
min
Final
time:
1O.
Oomin
12.3.2
Front
Inlet:
Mode:
Split
Initial
temp:
180
OC
Pressure:
8.5Opsi
(on)
Split
ratio:
10.7
:
1
Split
flow:
16.1
mYmh
Total
flow:
20.6
mumin
to
28OoC
12.4
Set
MS
conditions
12.4.1
Adjust
conditions
as
needed
to
optimize
system
performance
and
document
operating
conditions
in
the
instrument
run
log.
Acquisition
mode:
Scan
(&
om
10
m/
z
to
650
m/
z)
MS
source
temp:
230
C
MS
quadruple
temp:
150
C
Interface
temp:
260
C
MultipIier
voltage:
adjust
to
give
required
low
standard
sensitivity
ETS­
B­
182.0
Analysis
of
FCs
by
Purge
&
Trap
Autosampler/
Concentrator/
GCLMS
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Reviewcode
M1
12.5
Set
up
the
instrument
acquisition
method.
Name
the
sequence.
The
sequence
includes
a
sample
list
documenting
the
method
used
and
datafiles
created.
The
sequence
should
be
documented
n
the
run
files.

12.6.1
Set
up
autosampler
and
concentrator
methods.
Bring
samples
to
room
12.6
Sample
analysis.

temperature
(­
22
C),
spike
them
and
place
them
on
autosampler.
Generate
a
mass
spectrometer
tune
report
and
review.
Operating
conditions
provided
above
are
recommended
and
may
be
adjusted
to
optimize
system
performance.
Analyze
all
standard,
samples,
and
spiked
samples
using
the
same
analytical
conditions.
Document
the
conditions
in
the
m
Iog.

version
4.0
for
processing.
'
12.6.2
When
data
acquisition
is
complete,
data
files
shouId
be
transferred
to
Target
­Explanation
Peak
was
not
automatically
integrated
by
Target,
therefore,
integrated
manuallv
13.0
DATA
ANALYSIS
AND
CALCULATION
13.1
Each
batch
of
data
should
be
processed
using
Target
Genie
integrator.
Integration
parameters
should
be
set
to
minimize
the
number
of
manual
integratidns
required
yet
still
result
in
uniform
integration
of
peaks
at
all
concentration
levels.
If
manual
integrations
are
required,
a
review
code
should
be
assigned
to
indicate
the
reason.
Review
dodes
are
listed
below.

­
­_

M
2
M3
M
4
M5
___~
_.___

Peak
was
automatically
integrated;
was
reintegrated
manually
to
improve
sample­
to­
sample
integration
consistency.
Incorrect
quantification
ion
peak
was
integrated;
manual
integration
was
done
to
select
the
correct
peak.
Incorrect
monitor
ion
peak
was
integrated;
manual
integration
was
done
to
select
the
correct
peak.
Others
(sDecifvl
13.2
When
data
processing
is
complete,
summarize
the
data
using
an
appropriate
form.
Formula
is
provided
below
for
some
of
the
calculations
that
may
be
required.
13.2.1
Calculate
matrix
spike
percent
recoveries
using
the
following
equation:

(observed
concentration
­
background
concentration)
'
x
100
expected
concentration
%Recovery
=

14.0
METHOD
PERFORMANCE
14.1
Coeficient
of
Determination
(9).
The
coefficient
of
determination
(?)
for
the
initial
calibration
curves
should
be
0.990
or
greater.
The
curves
should
be
examined
closely
for
Page
9
of
12
ETS­
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Analysis
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AutosmpIerlConcentraior/
CC/
MS
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14.2
14.3
14.4
14.5
14.6
14.7
14.8
14.9
linearity
and
intercept,
particularly
for
accuracy
of
quantitation
at
the
low
and
high
ends
of
the
curve.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Calibration
Standards.
The
acceptance
criterion
for
the
calibration
standards
is
that
the
accuracy
of
each
standard
is
75%
to
125%
(A
25
%
difference)
of
the
nominal
value.
Calibration
standards
outside
this
range
are
to
be
noted.
Document
in
the
raw
data
the
technical
justification
for
deviations.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Instrument
Surrogate.
Review
of
the
instrument
surrogate
performance
is
performed
by
monitoring
instrument
surrogate
recoveries
throughout
the
run.
Inconsistencies
in
the
recoveries
may
be
the
result
of
instrumental
changes,
or
injection
error.
Consult
with
the
Team
Leader
or
designee
for
direction
and
final
acceptance
or
rejection
of
the
analytical
run.
Sample
Surrogate.
Sample
surrogate
performance
is
evaluated
by
averaging
the
area
response
throughout
the
analytical
run
and
calculating
%RSD.
Inconsistencies
in
the
surrogate
peak
area
may
indicate
instrumental
changes,
injection
error,
or
changes
in
the
test­
system.
Consult
with
the
Team
Leader
or
designee
for
direction
and
final
acceptance
or
rejection
of
the
analytical
run.
Continuing
Calibration
Verification.
If
the
accuracy
for
the
amount
of
quantified
analyte
is
greater
than
25%
from
the
nominal
value
relative
to
the
initial
standard
curve,
the
Team
Leader
should
be
consulted.
Only
those
samples
analyzed
before
the
last
acceptable
calibration
check
standard
will
be
used.
Consult
with
the
Team
Leader
or
designee
for
direction
and
for
final
acceptance
or
rejection
for
the
data.
Solvent
Blanks.
Solvent
blanks
should
show
no
more
than
a
5%
carryover
from
a
high
standard
or
calibration
check
standard.
If
so,
two
sequential
solvent
blanks
may
be
necessary
to
rule
out
instrumental
contamination
Matrix
Blanks.
Matrix
blanks
are
the
basis
for
determining
the
LOQ.
and
are
monitored
at
various
times
in
the
analytical
run.
Peaks
with
greater
than
25%
of
the
peak
area
of
the
designated
LOQ
value
observed
in
matrix
blanks
are
indicative
of
either
matrix
effect,
sample
contamination
or
instrument
contamination.
Use
of
solvent
blanks
prior
to
the
matrix
blank
may
be
necessary
to
rule
out
instrumental
contamination
or
sample
contamination.
Control
Blanks.
Control
blanks
are
the
basis
for
determining
matrix
effect
(interference
or
suppression).
Peaks
with
greater
than
25%
of
the
peak
area
of
the
designated
LOQ
value
observed
in
control
blanks
are
indicative
of
either
matrix
effect,
sample
contamination
or
instrument
contamination.
Limit
of
Quantitation
(LOQ).
The
LOQ
is
equal
to
the
lowest
acceptable
standard
(i.
e.
%
accuracy
is
f;
25
%
nominal
value)
in
the
calibration
curve
that
is
greater
than
4
times
the
level
of
the
matrix
blanks.

14.10
Sample
Triplicates.
The
analyst
shall
accept
%RSD
values
<
25%.
%RSD
values
>
25%
should
be
noted.
Data
used
in
the
final
report
that
is
deemed
out
of
control
will
be
ETS­
8­
182.0
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GCYMS
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required
to
have
technical
justification
for
why
the
data
is
used,
documented
in
the
final
report
and
raw
data.
Consult
with
the
Team
Leader
or
designee
for
direction,
and
for
final
acceptance
or
rejection
of
the
data.

14.11
Analytical
Spikes.
The
analyst
shall
accept
percent
spike
recovery
values
of
100
f
25%.
Spike
recoveries
outside
of
this
range
should
be
noted.
Consult
with
the
Team
Leader
or
designee
for
direction,
and
for
final
acceptance
or
rejection
of
the
data.
Data
that
are
used
in
final
report
that
is
deemed
out
of
control
will
be
required
to
have
a
technical
justification
for
why
the
data
are
being
used,
documented
in
the
final
report
and
raw
data.

14.12
System
Suitability.

14.12.1
Tuning:
A
mass
spectrometer
tune
report
shall
be
generated
before
starting
each
analytical
sequence.
If
the
tune
parameters
do
not
meet
the
criteria
suggested
by
the
mass
spectrometer
manual,
then
the
mass
spectrometer
should
be
re­
tuned.
If
mass
28
is
present
in
the
tune
report
at
>IO%
relative
to
mass
69
then
an
air
leak
is
present
in
the
system.
The
source
of
the
leak
should
be
isolated
and
fixed
before
the
sequence
is
stated,
however
if
a
slight
air
leak
is
detected,
data
can
be
collected,
analyzed,
and
used
as
long
as
the
data
quality
objectives
are
met.

15.0
POLLUTION
PREVENTION
AND
WASTE
MANAGEMENT
15.1
Dispose
of
sample
vials
in
low
BTU
and
flammable
solvent
in
high
BTU
containers.
Dispose
of
glass
pipette
waste
in
broken
glass
containers
located
in
the
laboratory.

16.0
RECORDS
16.1
Store
chromatograms
in
the
study
folder
that
is
labeled
with
the
study
number.
Include
the
following
information
on
each
chromatogram
either
in
the
header
or
hand
written
on
the
chromatogram:
injection
date,
analyst's
initial,
sample
unique
number,
sample
name,
.preparation
date,
incubation
period,
dilution
factor
(if
applicable),
and
instrument
name.
Store
a
copy
of
the
acquisition
conditions
with
the
chromatogram
packet.
Plot
the
calibration
curve
by
non­
weighted
linear
regression
and
store
in
the
study/
project
folder.
Print
the
sequence
and
MS
tune
report
fiom
HP
Chemstation.
The
sequence
should
be
initialed
and
dated,
and
stored
in
the
run
log
binder.
The
MS
tune
report
should
be
stored
in
the
tune
report
file.
Copy
of
the
sequence
and
MS
tune
report
should
be
placed
in
appropriate
study/
project
folder.
Summarize
data
using
suitable
sohare
and
store
in
the
study/
project
folder.
Back
up
electronic
data
to
appropriate
medium
(primarily
CD).
Record
in
the
study/
project
folder
the
filename
and
location
of
backup
electronic
data.
List
the
documents
and
records
generated
when
performing
this
method
and
where
they
are
to
be
archived.
16.2
16.3
16.4
16.5
16.6
ETS­
8­
182.0
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17.0
ATTACHMENT
17.1
None.

18.0
REFERENCES
18.1
18.2
18.3
18.4
Archon
Purge
and
Trap
Autosampler
System
Operator's
Manual,
1996,
Varian.
Tekmar
LSC200
Instruction
Manual,
1996,
Tekmar.
Agilent
MSD
Hardware
Manual
for
5973N,
1999,
Agilent.
Agilent
6890
Series
Gas
Chromatograph,
volumes
1­
3,
1999,
Agilent
19.0
AFFECTED
DOCUMENTS
19.1
None.

20.0
REVISIONS
Revision
Revision
Number.
Reason
For
Revision
­
Date
ED­
8­
182.0
Analysis
o
f
F
G
by
Purge
&
Trap
Autosampfer/
Concentrator/
GC/
MS
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12
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I
3M
ENVIRONMENTAL,
LABORATORY
Method
Indirect
Photolysis
Screening
Test
in
Synthetic
Humic
Water
Method
Number:
ETS­
8­
177.0
Adoption
Date:
,./..+
e
Revision
Effective
Date:

Approved
By:

ETS­
8­
177.0
Indirect
Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
1
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16
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Comwund
1
.o
SCOPE
AND
APPLICATION
1.1
Purpose.
Chemicals
dissolved
in
natural
waters
are
subject
to
two
types
of
Acronym
Compound
Acronym
1.2
1.3
Peduorooctanesuf
fonate
photoreaction.
In
the
fvst
case,
the
chemical
of
interest
absorbs
sunlight
directly
and
is
transformed
to
products
when
unstable
excited
states
of
the
molecule
lead
to
decomposition.
In
the
second
case,
reaction
of
dissolved
chemical
is
the
result
of
chemical
or
electronic
excitation
transfer
€tom
light­
absorbing
species
in
the
water.
Synthetic
humic
water
(SHW)
is
used
for
the
photolytic
reaction
matrix
because
it
contains
dissolved
organic
material
that
absorbs
sunlight
and
produces
reactive
intermediates
that
include
singlet
oxygen
(`
0,)
that
promotes
indirect
photolysis
of
the
test
substance.
The
method
is
divided
into
two
phases.
Phase
one
includes
the
preparation
of
SHW.
Phase
Two
provides
a
procedure
to
calculate
solar
photolysis
rate
constants
and
half­
lives
of
test
chemicals
in
pure
water
(PW)
and
SHW.
This
phase
also
includes
parallel
solar
irradiation
of
a
radiometer
to
calculate
k,
o
(the
indirect
photolysis
rate
in
the
test
vessel,
e.
g.
40
mL
glass
VOA
vial)
and
kpE
(the
near­
surface
photolysis
rate
constant
in
natural
water
bodies).
Compatible
Analytes.
Chemicals
that
will
be
subjected
to
this
indirect
photolysis
screening
and
testing
method
include
but
are
not
limited
to
the
following
compounds:

PFOS
Perfluorobutanesuifonate
PFBS
N­
methylperfluorooctanesulfonamide
N­
ethylperfluorooctanesulfonamide
N­
MeFOSA
N­
methylperfluorobutanesulfonamide
N­
MeFBSA
N­
EtFOSA
N­
ethylperfluorobutanesul
fonamide
N­
EtFBSA
Z­(
N­
methylperfIuorooctane
sulfonamido)
ethyl
alcohol
su1fonamido)
ethyl
alcohol
I­
perfluorooctene
Z­(
N­
ethyIprrfluorooctanc
­~
­

N­
MeFOSEOH
2­(
N­
methylper€
luorobutanesulfonamido)
ethyl
N­
MeFBSE
alcohol
OH
N­
EtFOSE­
OH
2­(
N­
ethylperfluorobutanesu1fonamido)
ethyl
N­
EtFBSE­
OH
alcohol
­­
I
­perfluorobutene
­­
I
Perfluorooctanehydride
I
IH,
f&
hy,
jrjde
1
Peffluorobutanehydride
I
...
and
other
C4
through
C1o
homologues,
and
polymeric
materials
based
on
the
above
aforementioned
compounds.
I
1.4
Acceptable
matrix.
Synthetic
humic
water
(SHW),
0.005
M
pH
7.0
Phosphate
Buffer.

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Water
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2.0
SUMMARY
OF
METHOD
2.1
Phase
One:
A
solution
of
standardized
synthetic
humic
water
is
prepared
by
water
extraction
of
commercial
humic
material.
The
SHW
is
buffered
at
pH
7
with
0.005
M
Phosphate
buffer
to
maintain
pH
and
pre­
aged
in
the
photoreactor
to
produce
predictable
bleaching
behavior.
It
is
then
diluted
at
the
time
of
use
to
a
W­
visible
absorbance
typical
of
most
surface
fresh
waters
(approximately
0.5
AU
at
370
nm).
Phase
Two:
Study
samples
(5mL
aqueous
matrix)
are,
prepared
in
40
mL
glass
VOA
vials
equipped
with
screw­
top
caps
with
septa.
Test
substance
is
added
to
the
vials
where
indicated.
(See
table
below.)
Vials
are
placed
in
the
photoreactor
and
immersed
in
a
water
bath
controlled
at
25
f
5
OC.
Samples
to
be
exposed
are
photolyzed
in
the
photoreactor
at
261
W/
m2
(300­
800
nm)
for
designated
time
intervals.
A
suggested
set
of
time
intervals
is
listed
below.
Additional
timepoints
may
be
added,
if
necessary,
or
as
assigned
by
the
Team
Leader.
Time
0
samples
will
be
refiigerated
at
1­
5
"C.
until
all
timepoints
have
been
completed.
Dark
controls
(unexposed)
will
also
be
prepared
for
each
timepoint.
Absorbance
controls
will
be
used
to
monitor
photo­
bleaching
of
the
SHW.
Exposed
and
unexposedabsorbance
controls
will
be
prepared
per
timepoint.
2.2
2.2.1
Samples
to
be
prepared
for
each
timepoint
and
for
each
exposure
type:

Control
Mahix(#
l)
blank
0
+
0
0
0
Control
Mabix(#
l)
sample
0
+
0
+
0
Control
Matrix(#
l)
spike
0
+
0
+
+
Contra\
Matrix(%)
blank
0
0
+
0
0
Concml
Matrix(#
Z)
ramplo
0
0
+
i­
0
Control
Maaix(#
Z)
spike
0
0
+
+
+
Absorbance
Control
+
0
0
0
0
Where
"+"
=
addition
of
solution
or
test
substance
and
"0"
=NO
addition,
­
LCWS
Analysis
A
A
A
A
A
A
A
A
A
A
A
A
A
NA
­
GCMS
Analysis
A
A
A
A
A
A
A
A
A
A
A
A
A
NA
at
370
nm
NA
N
A
N
A
N
A
N
A
N
A
NA
NA
N
A
NA
N
A
NA
N
A
A
N
A
N
A
A
analysis
performed,
and
NA
=
no
analysis.
Time
Point
#
of
Exposed
#
of
Unex)
Samples
Samples
Analysis
GUMS
Analysis
UVNis
Analysis
(
Exp
+
Unexp)
(Exp
+
Unexp)
(Exp
+
Unexp)
0
0
30
(Time
0)
13
13
4
8hr
30
30
26
26.
8
16
hr
30
30
26
26
8
32
hr
30
30
26
26
8
64
hr
30
30
26
26
8
128
hr
30
30
26
26
8
150
I80
143
1
43
44
­

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0.01
M
Phosphate
Buffer,
pH
7:
1
Replicate
per
light
and
dark
exposure,
for
each
he
and
for
ea&
analytical
methodology.
ASTM
Typo
II
Watcr
3.0
QUALITY
CONTROL­
DEFlNITION/
FREQUENCY~
ERFORMANCE
CRITERIA
3.1
Blanks
3.1.1
Definitions:
Matrix
Blank.
A
sample
of
analyte­
free
matrix
(e.
g.
SHWhuffer)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
For
photolysis
studies,
there
are
multipte
matrix
blanks
to
adequately
represent
the
variables
of
the
study
with
reference
to
the
matrix
(e.
g.
Exposed,
Unexposed
and
Time
0).
The
matrix
blank
is
carried
through
the
sample
preparation,
photolytic
and
analytical
procedures
to
monitor
for
contamination
during
any
step.
It
is
also
used
to
establish
a
chromatographic
baseline
and
monitor
for
interference
or
suppression
of
target
analyte(
s)
from
the
matrix.
Control
Blank.
A
sample
of
analyte­
free
control
matrix
(such
as
buffer
or
ASTM
Type
11
water)
to
which
all
reagents
are
added
in
the
same
volumes
or
proportions
as
used
in
sample
processing.
The
control
matrix
serves
as
a
monitor
of
the
effect
of
the
matrix
on
the
test
substance,
test
analytes
and
chromatographic
behavior.
For
photolysis
studies,
there
are
multiple
control
blanks
to
adequately
represent
the
v,
piables
of
the
study
with
reference
to
the
matrix
(e.
g.
Exposed,
Unexposed
and
Time
0
samples).
The
control
blank
is
carried
through
the
sample
preparation,
photolytic
and
analytical
procedures
to
monitor
for
contamination
during
any
step.
It
is
also
used
to
establish
a
chromatographic
baseIine
and
monitor
for
interference
or
suppression
of
target
analyte(
s)
from
the
control
matrix.
3.1.2
FreqnencyPerformance
Criteria:
Listed
in
the
following
table:

b
Y
background
level
Of
*get
dp
shall
be
less
than
25%
the
area
counts
Of
the
LOQ.
I
MatrixID
Matrix
Blank
(Buffer/
SHW)

ControlBlank
#1
(BuffedPW)
Frewency
Performance
1
Criteria
Matrix
descriDtion
3.2
Sample
Triplicate
3.2.1
Definition:
Three
aliquots
prepared
as
representatives
of
the
same
sample
source
(e.
g.
test
substance)
and
carried
through
all
steps
of
the
photolytic
study
process
and
analytical
procedures
in
an
identical
manner.
The
results
from
triplicate
analyses
are
used
to
evaluate
variance
of
the
total
method,
including
sample
preparation,
photolytic
process
and
analysis.

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Water
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Matrix
Description
I
Frequency
I
3.2.2
Frequency/
Performance
Criteria:
Listed
in
the
followin&
table:

Performance
Criteria
test
substance
lightand
&k
for
he
pobc
and
for
each
analytical
test
substance
me&
odology
The
analyst
shall
accept
%RSDs
<25%.
Precision
Test
Matrix
and
test
substance
must
be
documented
and
justified
(if
The
analyst
shall
accept
accuracy
of
100
f
25%.
If
accuracy
is
outside
of
this
range,
dowment
and
justify,
if
possible,
the
reason
for
the
deviation.
3.3
Analytical
Spike
(AS)
3.3.1
Defmition:
A
known
mass
of
target
analyte(
s)
in
a
specified
amount
of
a
diluted
andor
aliquotted
sample.
This
assumes
that
an
independent
estimate
of
target
analyte
concentration
is
available.
Analytical
spikes
are
used
to
evaluate
the
recovery
efficiency
of
the
andyte
and
the
matrix
effect.
Frequency/
Performance
Criteria:
Listed
in
the
following
table:
3.3.2
Matrix
Dewriotion
Test
Matrix
and
test
substance,
spiked
with
target
anaIyte(
s)
just
prior
to
analysis
Test
Matrix
with
NO
test
substance,
spiked
with
target
analyte(
s)
just
prior
Control
Matrix
(#
1)
and
test
substance,
spiked
with
target
analyte(
s)
just
priar
to
analysis
Control
Matrix
(#
2)
and
test
substance,
spiked
with
target
analyte(
s)
just
prior
to
analysis
to
analysis
Frequency
I
2
spiked
samples
per
treatment
type
(one
in
lower
half
of
the
calibration
range,
and
one
in
the
upper
half
of
the
calibration
range)

1
Replicate
per
treatment
type
(mid­
range
spike
concentmtian)
Performance
Criteria
The
analyst
shall
accept
accuracy
of
100
f
25%.
If
accuracy
is
outside
of
this
range,
document
and
justify,
if
possible,
the
reason
for
the
deviation..

3.4
Control
Sample
3.4.1
Definition:
Ahown
matrix
containing
the
test
substance
caxried
through
the
entire
sample
preparation,
photolytic
and
analytical
procedure.
This
is
used
to
document
laboratory
perfonname
by
comparing
recoveries
and
matrix
effects
from
the
different
matrices
and
sample
types.
Frequency/
Performance
Criteria:
Listed
in
the
following
table:
3.4.2
I
MoMx
Description
I
Frequency
1
Performance
Criteria
1
Control
Matrix
(#
1)
and
I
1
Replicate
per
I
I
pw
Page
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Control
Matrix
(#
1)
Buffer/
S€
IW
only
3.5
Absorbance
Control
3.5.1
Definition:
An
analyte­
free
matrix
that
is
canied
through
the
sample
processing
procedure
and
analyzed
by
absorption
spectroscopy
at
370
nm.
It
is
used
to
monitor
the
photo­
bleaching
rate
of
the
SHW
during
the
testing
phase.
Frequency/
Performance
Criteria:
Listed
in
the
table
below.
3.5.2
2
Replicates
per
light
and
dark
exposure,
for
each
time
point
pathlength
cell)
Absorbance
measured
at
370
nm
is
between
0.01AU­
0.05
AU
(1
cm
Matrix
Description
I
Frequency
I
Performance
Criteria
I
I
3.6
lntemal
StandardlSurrogate
3.6.1
Internal
Standard
Definition
(applies
to
LC/
MS
samples):
A
known
amount
of
a
compound
similar
in
analytical
behavior
to
the
target
analyte(
s)
of
interest
(e.
g.
3,3,4,4,5,5,6,6,7,7,
8,8,8­
tridecafluorooctane
sulfonic
acid
(THPFOS)
if
perfluorooctane
sulfonate
(PFOS)
were
to
be
the
target
analyte),
added
to
all
samples
and
standards
(post­
irradiation),
and
carried
through
the
entire
analytical
process.
It
provides
a
reference
for
evaluating
and
controlling
the
precision
and
bias
of
the
applied
analytical
method.
Samples
are
to
be
quantified
using
the
internal
standard.
Surrogate
Definition
(applies
to
LC/
MS
and
GCMS
samples):
A
known
amount
of
a
compound
similar
in
analytical
behavior
to
the
target
analyte(
s)
that
may
be
added
to
all
samples
(pre­
or
post­
irradiation,
at
the
discretion
of
the
Team
Leader),
and
carried
through
the
remaining
sample
preparation
and/
or
analytical
process.
If
added
before
exposure,
it
monitors
the
presence
of
vial
leaks
during
photolysis,
as
well
as
the
performance
of
the
purge
and
trap
autosampler
and
concentrator.
Surrogate
analysis
is
used
to
evaluate
the
precision
and
bias
of
the
applied
analytical
method.
Surrogates
are
not
used
for
quantitation.
Frequency/
Performance
Criteria:
Listed
in
the
following
table:
3.6.2
3.6.3
Matrix
DescriDtion
Sample
muted
with
30
mL
of
internal
standard
compound
dissolved
in
a
suitable
analytical
solvent
Sample
with
surrogate
compound
spiked
into
it.
__~
­~

Freauencv
of
Use
I
Performance
Criteria
­

Every
LCMS
sample
analyzed
May
be
added
to
every
L
C
W
and
GCMS
sample
analyzed
The
O/
oRSD
for
internal
standards
shall
be
calculated
for
the
area
response
of
all
appropriate
samples
per
analytical
batch.
The
analyst
shall
accept
%RSD
values
of
45%.
%RSD
values
>15%
shall
be
documented
and
justified,
if
possible.
The
%
recovery
of
internal
standards
should
be
100
k
25%.
.Surrogates
are
examined
for
qualitative
information
only
(Le.,
area
response
should
be
relatively
constant).

ETS­
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Photolysis
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3.7
Other
Definitions.
3.7.1
3.7.2
3.7.3
3.7.4
3.7.5
3.7.6
3.7.7
Test
Substanceflest
Analyte:
Any
substance
(mixture
or
controlled
compound)
added
or
administered
to
the
test
system
for
the
purpose
of
chemical
analysis.
Degradation
Product(
s):
Secondary
analytes
of
interest
produced
as
a
result
of
chemical
reactions
during
the
photolysis
and
monitored
(qualitatively
or
quantitatively)
during
the
sample
analysis
procedure.
Target
Analyte(
s):
The
analyte(
s)
singled
out
in
the
analytical
phase
of
the
study
is
the
target
analyte.
The
target
analyte
may
be
identical
to
the
test
substance
used
in
the
experimental
phase
of
the
study,
a
by­
product
or
degradation
product
that
is
monitored
(qualitatively
or
quantitatively)
during
the
sample
analysis
procedure.
Test
Matrix:
The
physical
matrix
in
which
the
study
will
be
conducted.
Relative
Percent
Difference
(RPD):
A
measure
of
precision
defined
as
the
absolute
value
of
the
&f€
erence
of
the
two
values
divided
by
the
average
of
the
two
values
and
multiplied
by
100.
Relative
Standard
Deviation
(RSD):
A
measure
of
relative
precision
for
three
or
more
sample
replicates;
defined
as
the
sample
standard
deviation
divided
by
the
sample
average
and
multiplied
by
100.
This
is
expressed
as
a
percent
(%
RSD).
Limit
of
Qnantitation
(LOQ):
The
lowest
concentration
that
can
be
reliably
achieved
within
specified
limits
of
precision
and
accuracy
during
routine
laboratory
operating
conditions.
The
LOQ
can
be
estimated
as
10
times
the
background
level
in
the
blank
samples.
However,
it
may
be
nominally
chosen
within
these
guidelines
to
simplify
data
reporting.
For
many
analytes,
the
LOQ
analyte
concentration
is
selected
as
the
lowest
non­
zero
standard
in
the
calibration
curve
that
is
over
four
times
the
background
level
in
the
blanks.
Sample
LOQs
are
highly
matrix­
dependent.

4.0
WARNINGS
AND
CAUTIONS
4.1
Health
and
Safety
Warnings
4.1.1
4.1.2
4.1.3
Wear
the
proper
lab
attire
for
all
parts
of
these
procedures.
Wear
gloves
and
eye
protection
at
all
times,
Handle
all
solvents
in
a
hood
for
all
parts
of
the
described
sample
preparation
procedure.
For
potential
hazards
of
each
chemical
used,
refer
to
material
safety
data
sheets,
packing
materials,
and
3M
Environmental
Laboratory's
Chemical
Hazard
Review.
No
mouth
pipetting
is
allowed.

The
photoreactors
are
equipped
with
a
continuous
flow
of
cooling
water
that
poses
a
threat
of
electrocution
when
handling
the
photoreactor
during
irradiation
sequences.
4.1.4
4.2.1
4.2
Cautions
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4.2.2
Wear
dark
protective
eyewear
when
operating
the
reactor.
Do
not
look
directly
at
the
activated
lamp.
Use
caution
when
handling
samples
in
the
reactor;
the
interior
walls
of
the
reactor
and
exposed
glass
vials
become
extremely
hot.

5.0
INTERFERENCE
5.1
Contaminants
in
solvents,
reagents,
glassware
and
other
sample
processing
or
analysis
hardware
may
cause
interference.
To
reduce
the
possibility
of
interference,
glassware
in
which
standards
are
prepared
should
be
pre­
rinsed
with
methanol
and
allowed
to
dry
before
use.
The
routine
analysis
of
laboratory
method
blanks
must
be
used
to
demonstrate
that
there
is
no
interference
under
the
conditions
of
the
analysis.

6.0
EQUIPMENT
6.1
6.2
Analytical
balance
sensitive
to
0.1
mg
Photoreactor:
Suntest
CPSi­,
XLS+,
or
equivalent,
capable
of
producing
250~
765
Wattdm',
equipped
with
a
xenon
arclamp
(e.
g.
2200
W
Xenon
Lamp)
and
the
appropriate
filters
to
allow
the
desired
wavelength
(e.
g.
W
Special
Suprax"
with
cut­
on
at
290
nm,
and
Quartz
dish
with
IR
reflective
coating),
and
a
flowing
water
bath
circulating
pump
or
Water
cooler/
recircdator
capable
of
maintaining
temperature
at
25
"C
f
5
OC
.
UV­
Visible
Spectrophotometer
(W­
VIS),
equipped
with
tungsten
and
deuterium
lamps,
model
8453,
or
equivalent
6.4.1
equivalent.
6.3
6.4
Autosampler:
Model
G1120A,
or
I­
cm
pathlength
cell
holder:
Model
08451­
60104,
or
equivalent.
1
­cm
pathlength
quartz
spectrophotometer
cell,
or
equivalent.
Long
Path­
Length
Cell
Holder,
Hewlett
Packard
part
number
89076C,
or
equivalent
6.4.1.1
6.4.2
6.4.2.1
10­
crn
path
length
quartz
cell
equipped
with
stopcocks,
Hewlett
Packard
Part
#
5061­
3392,
or
equivalent.
6.4.3
Data
System:
A
PC
capable
of
controlling
the
W­
Visible
Spectrophotometer
system.
Centrifuge
capable
of
maintaining
>2000
rpm
for
10
minutes
at
ambient
temperature
(22­
26
"C).
Radiometer,
capable
of
detecting
and
recording
irradiation
output
of
the
photoreactor
for
the
duration
of
the
study.
Lab
Oven,
capable
of
maintaining
70­
80
"C.
Data
acquisition
and
analysis
software,
HP
ChemStation
for
UV­
Visible
Spectroscopy,
G11
IGAA
Rev.
B.
01.02,
or
later.
6.5
6.6
6.7
6.8
7.0
SUPPLIES
AND
MATERIALS
7.1
7.2
7.3
7.4
40­
mL
amber
and
clear
glass
vials
(VOA)
with
screw
caps.
Crimp
cap
autovials:
1
.S­
mL,
caps,
crimper,
and
decapper.
Adhesive­
backed
labels
(return
address
size)
for
labeling
quartz
vials
and
autovials.
Disposable
glass
graduated
pipettes,
1
mL
to
10
mL.

ETS­
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Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
8
of
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of
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7.5
7.6
Glass
beakers,
various
sizes.
7.7
7.8
7.9
1
0­
mL
Bottle­
top
dispenser.
7.10
7.11
500­
mL
glass
screw­
top
containers.
Disposable
glass
Pasteur
pipettes
and
rubber
bulbs.

Volumetric
flasks,
from
10
mL
to
1000
mL.
Hamilton
Gastight@
syringes
(precision*
1%
of
the
total
volume),
5
pL
to
1000
pL.

Teflon*
filters
filter
holder
apparatus:
0.4
pm
pore­
size
and
0.2
pm
pore­
size
filters
(47
mm
diameter,
Gelmanm
or
equivalent.

8.0
REAGENTS
AND
STANDARDS
8.1
WaterRure
water
(PW),
ASTM
Type
II
water
at
a
minimum
8.2
8.3
8.4
8.5,
8.6
8.7
8.8
8.9
8.10
Methanol
(MeOH),
HPLC/
SPEC/
GC
grade
from
EM
Science
or
equivalent.
Acetone,
HPLC/
SPEC/
GC
grade
from
EM
Science
or
equivalent.
Acetonitrile,
HPLC/
SPEC/
GC
grade
from
EM
Science
or
equivalent.
Humic
acid,
sodium
salt,
fiom
Aldrich
or
equivalent.
NaOH,
reagent
grade
Grom
EM
ScienceTM
or
equivalent.
0.1
YO
NaOH
solution
Example:
Weigh
approximateIy
1
.O
g
sodium
hydroxide
into
a
weigh
boat
and
transfer
quantitatively
to
a
1
L
volumetric
flask
and
dilute
to
the
mark
with
PW
or
equivalent.
Sulfuric
Acid
(H,
SO,),
reagent
grade
from
Fisher
or
equivalent.
Potassium
phosphate,
reagent
grade
from
JT
Baker
or
equivalent.
8.9.1
0.005
M,
pH
7.0
Phosphate
Buffer.
Example:
Weigh
1.36
g
KH,
PO,
into
a
weigh
boat
and
transfer
to
a
1
L
volumetric
flask
using
PW
and
dilute
to
the
mark.
Transfer
the
1
L
of
solution
to
a
2
L
volumetric
flask.
Add
600
mL
of
0.1%
NaOH,
adjust
the
pH
to
7.0
f
0.1
with
0.1%
NaOH
or
dilute
H2S04,
and
dilute
to
the
mark
with
PW.
Method
Blank
Solutions:

Method
Blank
h
e
s
Matrix
ID
Test
Matrix
Buffer/
SHW
Control
Matrix
(#
1)
Buffer/
PW
Matrix
descriRtion
Example:
1:
lO
Solution:
Dilute
50
mL
Synthetic
Humic
Water
with
0.01
M
pH
7.0
Phosphate
Buffer
solution
to
500
mL.

Example:
1:
lO
Solution:
Dilute
50
mL
Pure
Water
(ASTM
Type
n)
with
0.01
M
pH
7.0
Phosphate
Buffer
solution
to
500
mL.

1
Control
Matrix
(#
2)
PW
I
Pure
Water
(ASTM
Type
II)
I
8.11
Stock
Solutions.
Stock
solutions
for
internal
standards
and
spiking
solutions
are
prepared
in
MeOH
at
concentrations
of
approximately
10,000
pg/
mL
by
weighing
approximately
0.1
g
of
the
appropriate
substance
into
a
1
O­
mL
volumetric
flask
and
bringing
to
the
mark
with
MeOH.
Dilute
to
make
appropriate
working
solutions.
8.11.1
Diluting
Solution
with
Internal
Standard:
The
diluting
solution
shall
contain
internal
standard
at
an
area
response
level
equivaht
to
approximately
half
the
ETS­
8­
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Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
9
of
16
Page
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8.12
area
response
of
the
test
substance's
high
standard
in
the
calibration
curve.
Example:
Internal
standard
solution
in
MeOH
is
prepared
by
diluting
50pL
of
internal
standard
stock
solution
(Section
8.1
1)
to
1
L
with
MeOH
to
a
nominal
concentration
of
0.5
AU
pg/
mL,.
Test
SoIutions
8.12.1
Test
Substance:
Prepare
a
solution
of
the
test
substance
in
acetonitrile.
Calculate
the
concentration
so
that
after
the
test
substance
is
added
to
the
test
vial,
no
more
than
1%
of
the
volume
in
the
test
vial
will
be
solvent.
(e.
g.
50pL
added
to
5
mL
of
matrix
=
1%
v/
v)
Then
measure
the
absorbance
of
the
test
substance
solution
diluted
with
bufferlwater
matrix
to
the
desired
concentration,
The
maximum
absorbance
at
any
wavelength
greater
than
29Onm
must
be
e
0.05,
when
measured
in
a
standard
1­
cm
pathlength
cell.
Example:
A
900
pg/
mL
solution
of
test
substance
in
acetonitrile
is
prepared
by
weighing
90
mg
of
test
substance
into
a
100
mL
volUmetric
flask
and
diluting
to
the
mark
with
acetonitrile.

9.0
SAMPLE
HANDLING
9.1
9.2
Record
times
of
initial
preparation
and
dilution
on
the
fluorochemical
degradation
(photolysis)
analysis
sample
prep
sheet
(Attachment
A).
Once
the
test
substance
solution
has
been
added,
the
40
mL
VOA
sample
vials
shall
be
stored
and
handled
cap­
side
down
to
minimize
loss
of
any
potential
volatile
analytes.
After
the
exposure
period,
the
LCMS
samples
may
be
turned
upright
and
stored
in
a
cooler
at
1­
5
"C.
After
the
exposure
period,
GCMS
samples
shall
be
maintained
in
an
inverted
position
in
a
cooler
at
1­
5
"C
until
they
are
loaded
onto
the
autosampler.
Once
the
30­
mL
aliquot
of
diluting
solvent
has
been
added
to
the
LCMS
photolysis
samples,
(see
Section
12.0),
the
samples
should
be
analyzed
as
soon
as
possible.
Alternatively,
the
samples
may
be
stored
at
1­
5
"C.
Day
0
samples
are
to
be
stored
at
1­
5
"C
during
the
time
of
sample
exposure,
and
then
diluted
along
with
the
exposed
and
unexposed
samples
just
prior
to
analysis.
9.3
10.0
QUALITY
CONTROL
10.1
Quality
control
parameters
(and
the
fiequency
of
use)
are
included
in
Section
3.0.

11.0
CALIBRATION
AND
STANDARDIZATION
11.1
11.2
The
analytes
of
interest
must
be
standardized
according
to
laboratory
specifications.
AI1
equipment
used,
such
as
the
analytical
balance,
photoreactors,
etc.
should
be
calibrated
prior
to
use
(daily,
weekly,
etc.)
as
specified
in
its
standard
operating
procedure.
All
samples
analyzed
will
be
run
against
a
standard
curve
containing
varying
amounts
of
test
substance,
and
a
fixed
amount
of
internal
standard
or
surrogate
compound.
11.3
ETS­
8­
177.0
Indirect
Photobsis
Screening
Tests
in
Synthetic
Humic
Wuter
Page
10
of
16
Page
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BACK
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Report
No.
E00­
2192
Irradiance
Source
Average
Optimum
Natural
Daylight`

Atlas
Photoreactor
with
integrated
irradiance
output
of
261
W/
m2
300­
800
nm
using
the
IR
Reflecting
and
290
cut­
on
filters
12.0
PROCEDURES
12.1
Phase
One­
Preparation
and
standardization
of
svnthetic
humic
water.

ADDrOXimate
Inteprated
and
Individual
Irradiances
in
W/
m2
250­
300
nm
300­
400nm
`400­
8OOnm
340m
420nm
o,
o
27.8
259.0
0.30
0.67
0.08
27.8
234.36
0.24
0.71
12.1.1
12.1.2.
12.1.3
12.1.4
12.1.5
12.1.6
12.1.7
12.1.8
Weigh
approximately
2.5
g
humic
acid
kt0
a
tared
250
mL
centrifuge
tube.
Add
0.1%
NaOH
solution
to
250
mL.
Screw­
cap
shut
and
tape
the
tube
and
place
horizontally
on
an
orbital
shaker.
Shake
vigorously
(e.
g.
100­
250
rpm)
at
room
temperature
for
approximately
one
hour.
Centrifuge
the
250
mL
of
solution
at
approximately
2000
rpm
for
10
minutes
or
until
solution
has
cleared,
and
then
filter
the
supernatant
through
a
0.4pm
filter
into
a
clean
500­
mL
glass
screw­
top
container.
Adjust
the
pH
of
the
solution
to
7.0
with
dilute
H2S04
or
0.1
%
NaOH.
Filter­
sterilize
the
solution
through
a
0.2pm
diameter
poresize
filter
into
a
clean
500­
mL
glass
screw­
top
container.
Seal
the
container
and
place
cap­
side
down
in
the
photoreactor
chamber.
Expose
the
SHW
24
hours
at
261
W/
mz
to
pre­
age
the
solution
(equivalent
to
three
day's
worth
of
Miami,
Florida
sunlight).
The
EPA's
definition
of
"1
Day"
of
irradiation
is
"eight
hours,"
The
irradiation
intensity
of
261
W/
m2
was
chosen
because
it
yields
the
equivalent
average
optimum
natural
daylight
radiation
for
300­
400
nm
(see
the
table
below):

12.1.9
Aliquot
the
SHW
into
a
l­
cm
quam
W­
VIS
cuvette
and
analyze
the
absorbance
at
370
nm.
12.1.10
Check
the
pH
of
the
solution
using
pH
paper
or
a
pH
probe.
Adjust
the
pH
if
necessary
to
7.0
f
0.1
using
a
dilute
&SO4
solution
or
0.1%
NaOH
solution.
12.1.11
Calculate
the
dilution
factor
necessary
to
decrease
the
absorbance
to
approximately
0.5
AU
(in
a
I­
cm
pathlength
cell)
in
1
L
of
SHW:

9.5
=
L
,n
J
1L
x
where:
the
measured
absorbance
of
the
SHW
at
370
nm
x
=
the
volume
of
SHW
needed
to
dilute
to
1
L
with
water.

12.1.12
Bring
the
solution
to
the
exact
dilution
calculated
in
12.1.11
with
PW.

Page
11
of
16
ETS­
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Screening
T
e
s
~
in
Synthetic
Humic
Water
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12.1.13
Verify
that
the
absorbance
is
approximately
0.5
AU
by
aliquoting
the
diluted
12.1.14
Transfer
the
SHW
stock
solution
into
an
amber,
or
clear
foil­
wrapped
1
L
glass
SHW
into
a
I­
cm
W­
VIS
cuvette
and
taking
the
absorbance
reading
at
370
nm.

storage
bottle,
tightly
cap
and
refiigerate.
12.2
Phase
Two
12.2.1
12.2.2
12.2.3
12.2.4
12.2.5
Fill
out
the
"Fluorochemical
Degradation
(Photolysis)
Sample
Prep
Sheet"
(Attachment
A)
as
much
as
possible,
assigning
sequential
unique
ID
numbers
to
each
sample
to
be
prepared,
Obtain
the
appropriate
number
of
clear
and
amber
40­
mL
glass
vials
with
caps
and
cardboard
boxes.
Label
the
vial
caps
using
a
black
permanent
marker
to
distinctly
identifl
samples.
Create
labels
for
each
sample
to
be
affixed
to
the
40­
mL
vials
and
the
autosampler
vials
after
photolysis
is
completed.
The
labels
should
include
the
sample
number,
test
substance,
matrix,
exposure
type
(e.
g.
exposedunexposed/
Time
0),
date
and
initials
of
the
analyst.
Aliquot
5.0
mL
of
BuffbdSHW,
BufferPW
and
PW
solutions
into
clear
(for
exposed
samples)
and
amber
(for
unexposed
and
Time
0
samples)
40­
mL
glass
VOA
vials.
Add
test
substance
to
the
appropriate
vials.
See
the
table
below
for
list
of
vials,
replicates,
and
sample
types.
If
pre­
hydrolysis
surrogates
are
to
be
used,
add
them
also
at
this
point.
Create
one
set
of
samples
(listed
below)
per
time
point
andfor
each
analytical
methodology.
(LC/
MS
and
GC/
MS):

J
M
a
t
r
i
x
Description
2
Test
Substance
+
C1earlExpose.
d
sample
Rep
1
+
0
0
Sample
Rep
2
+
Sample
Rep
3
+
0
0
+
Cleafiposcd
Sample
Spike
I
+
Sample
Spike
2
­?.
0
0
+
Clear/
Exposed
1
C
~n
t
d
Mabix(#
I)
blank
0
0
0
Control
Mabix(#
l)
spike
0
0
Clearnzxposed
(Buffer/
SHW)
(Buffer/
PW)
(PW
+
0
0
Clearkposed
0
0
+
Clearkposed
Matrix
Blank
+
0
0
0
ClearExposed
+
+
+
0
0
CleadExposed
Control
Uatrix(#
l)
sample
+
+
+
0
0
0
C!
ear/
Exposcd
Conml
Mabix(#
2)
blank
+
+
Contml
Uabix(#
2)
sample
0
0
Clear/
Exposed
+
Control
Mahix(#
2)
spike
0
0
+
CleadEXposed
`
Matrix
Blank
Spike
+
0
0
0
Clearfixposed
ClearExposed
Sample
Rep
1
Sample
Rep
2
Sample
Rep
3
Sample
Spike
1
Sample
Spike
2
Test
Matrix
Blank
Test
Matrix
Blank
Spike
Control
Matrix(#
l)
blank
Control
Matrix(#
l)
sample
Control
Matrix(#
l)
d
k
e
Control
Matrix(#
2)
blank
Control
hIabix(
32)
sample
+
+
+
+
+
+
+
0
0
0
0
0
0
0
0
0
0
0
0
+
+
+
0
0
0
0
0
0
0
0
0
0
0
0
+
+
+
+
+
+
+
0
0
0
+
+
0
+
AmberAJnexposed
ArnberNnexposed
AmberiUnexposed
AmbcriUnexposed
AmberiUnexposed
AmberNnexposed
AmberiUnexposcd
AmbnNnexposed
AmberNnexposed
AmberNnexposed
AmberNnexposcd
AmbcrAJnexposed
Control
hlatrix(
32)
spike
0
0
+
+.
ArnberNnexposed
ETS­
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Tests
in
Qnthetic
Humic
Wafer
Page
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Control
Matrix(#
l)=
SHwIBuffer
1:
9
v/
v
Control
Matrix(#
2)=
PWBuffer
1
:9
v/
v
Create
one
set
of
samples
(listed
below)
for
each
time
point
for
WMS
analysis:

12.2.6
12.2.7
12.2.8
12.2.9
Store
the
"Time
0"
vials
in
a
labeled
box
at
1­
5
"C.
Place
all
the
vials
that
will
go
into
the
photoreactor
into
an
oven
set
to
70­
80
"C.
for
5­
10
minutes
to
acclimate
the
vials,
liquid
and
headspace
to
photoreactor
conditions.
Upon
removing
the
vials
h
m
the
oven,
immediately
re­
tighten
the
caps
and
proceed
to
load
the
reactor.
Place
the
amber
"unexposed"
vials
in
plastic
bags
and
arrange
on
the
bottom
of
the
photolysis
tray
(make
sure
that
they
don't
float
once
the
tray
is
filled
with
water).
The
"unexposed"
vials
will
remain
submerged
in
the
cooling
water
(25
f
5
"C)
during
the
exposure.
(The
vials
are
exposure­
and
temperature­
controlled.)
Place
the
clear
"exposed"
vials
in
the
rack
in
the
photoreactor
tray
cap­
side
down,
and
install
the
rack
so
that
the
VOA
vial
caps
will
be
submerged
throughout
the
duration
of
exposure.
12.2.10
Prepare
the
radiometer
to
read
intensity
of
irradiance
over
the
duration
of
the
exposure.
See
SOP
ETS­
9­
50.0
for
operation
of
radiometer.
12.2.11
Expose
the
samples
for
the
designated
time
intervals
at
261
W/
m*.
See
SOP
ETS­
9­
44.0
for
operation
of
the
photoreactor.
12.2.12
Following
each
exposure
interval,
remove
vials
from
the
photoreactor
and
store
inverted
in
a
cooler
at
1­
5
"C.
After
all
exposures
have
been
completed,
remove
all
sample
vials
as
well
as
the
"Time
0"
vials
from
the
cooler
and
analyze
as
a
single
batch
for
each
instrument.
12.2.13
W
­V
I
S
absorbance
control
analysis
12.2.13.1
Analyze
the
pH
7.0
SHWhuffer
absorbance
controls
by
WNisible
absorbance
spectroscopy
at
370
nm
by
aliquoting
the
test
solution
directly
into
a
1­
cm
or
greater
pathlength
quartz
cuvette
and
obtaining
the
spectra,

,
See
SOP
ETS­
9­
46.0
for
operation
of
the
WNIS
instrument,
The
resultant
peak
at
370
nm
will
be
analyzed
to
determine
the
change
in
absorbance
between
the
Time
0,
exposed
and
unexposed
samples.
12.2.14
LC/
MS
sample
analysis
12.2.15
Dilute
the
exposed
and
unexposed
samples
for
all
timepoints
with
30
mL
internal
standard
solution
in
methanol
(Section
8.1
1.1).
Add
spiking
solution
to
the
appropriate
vials.
Invert
each
vial
several
times
to
mix.

autosampler
for
analysis
of
the
parent
compound
and
possible
degradation
products.
Analyze
according
to
ETS­
8­
18
1
.O.
12.2.16
Transfer
aliquots
of
LC/
MS
samples
into
autovials
and
then
place
them
in
the
12.2.17
GCMS
sample
analysis
ETS­
8­
177.0
Indirect
Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
13
of
16
Page
87
of
148
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TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
12.2.17.1
Analyze
the
exposed
and
unexposed
samples
for
all
timepoints
as­
is
by
purge
and
trap
GCMS.
Add
spiking
and
surrogate
solutions,
as
required,
to
the
appropriate
vials.
Analyze
according
to
ETS­
8­
182.0.
12.2.17.2
Important:
Maintain
vials
in
the
inverted
position
until
they
can
be
placed
in
the
autosampler.

13.0
DATA
A
N
f
i
Y
S
I
S
AND
CALCULATIONS
13.1
Not
applicable,
as
this
is
a
sample
preparation
and
analysis
method.
Consult
the
appropriate
analytical
protocol
for
guidance
regarding
data
analysis
and
calculations.

14.0
METHOD
PERFORMANCE
14.1
Not
applicable.

15.0
15.1
POLLUTION
PREVENTION
AND
WASTE
MANAGEMENT
Dispose
of
sample
waste'by
placing
in
high
or
low
BTU
(British
Thermal
Unit)
waste
containers
as
appropriate.
Use
broken
glass
containers
to
dispose
of
glass
pipettes.

16.0
RECORDS
16.1
16.2
16.3
16.4
Print
out
hard
copies
of
all
graphics
and
data
analysis
summaries
for
archiving.
Sign
and
date
all
graphics
and
label
with
instrument
ID.
Fill
out
the
sample
preparation
worksheet(
s)
documents
completely,
making
sure
to
includa
all
initials
and
dates.
Archive
electronic
data
to
compact
disc
media.

17.0
ATTACHMENTS
17.1
"Fluorochemical
Degradation
(photolysis)
Sample
Prep
Sheet"

18.0
REFERENCES
18.1
18.2
18.3
Interpersonal
conversation
with
Carrie
O'Connor,
Optical
Systems
Engineer,
Atlas
Electric
Devices.
"Suntest
CPS/
CPS+
Spectral
Irradiance
Distribution,"
table
distributed
by
Atlas
EIectric
Devices
Company,
sent
via
fax
by
Richard
Sherwin,
Sales
Representative,
26
July,
2000.
"Atlas
Xenon
Filter
Combination
and
Sunlight
Measurements,"
information
generated
by
Atlas
Electric
Devices
Company
sent
via
fax
by
Richard
Sherwin,
Sales
Representative,
26
July,
2000.
OPPTS
835.5270,
Indirect
Photolysis
Screening
Test:
Sunlight
photolysis
in
water
containing
dissolved
humic
substances.
18.4
ETS­
8­
177.0
Indirect
Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
14
of
16
Page
88
of
148
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TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
19.0
AFFECTED
DOCUMENTS
19.1
None
20.0
Revisions
Revision
Revision
Number.
Reason
For
Revision
­
Date
ETS­
8­
177.0
Indirect
Photolysis
Screening
Tests
in
Synthetic
Humic
Water
Page
15
of
16
Page
89
of
148
BACK
TO
MAIN
0
0
W
0
Z
03
v
.o
0
a
v­
rc
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
3M
ENVIRONMENTAL
LABORATORY
EQUIPMENT
PROCEDURE
OPERATION
AND
MAINTENANCE
OF
THE
HEWLETT
PACKARD
8453
W­
VISIBLE
SPECTROPHOTOMETER
Procedure
Number:
ETS­
9­
46.0
Adoption
Date:
/o/
zJbr7
Revision
Effective
Date:

Approved
by:

/A/*/"
Laboratory
Management
'
Date
Page
I
of
9
ETS­
9­
46.0
Operation
and
Maintenance
of
the
HP8453
W­
Vis
Spectrophotometer
Page
91
of
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TO
MAIN
3M
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Report
No.
E00­
2192
1.0
SCOPE
AND
APPLICATION
1.1
This
equipment
procedure
describes
the
operation,
cleaning,
and
maintenance
of
the
Hewlett­
Packard
8453
UV­
Visible
Spectroscopy
System.

2.0
DEFINITIONS
2.1
Absorbance:
Measure
of
concentration
of
material
present:
expressed
as
product
of
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
molar
extinction
coefficient
(E),
pathlength
(b),
and
concentration
(c),
wriien
as
A
=
E
b
c
(also
known
as
Beer's
Law).
Cuvette
or
flow
cell:
Transparent
receptacle
in
which
sample
solutions
are
introduced
into
the
light
path
of
spectrometers.
Usually,
two
sides
are
equal
(e.
g.
1
cm
x
1
cm)
while
the
third
dimension
is
elongated,
possibly
as
long
as
15
cm.
For
W
work,
the
material
is
quartz.
Visible
work
permits
the
use
of
glass
or
plastic
cuvettes.
Pathlength:
The
distance
the
light
passes
through
the
sample
in
its
holder.
In
practical
terms,
the
inside
dimension
of
the
cuvette
(usually
1
cm).
Slit
width:
Size
of
opening
through
which
light
from
cuvette
emerges.
Choice
of
slit
width
depends
on
wavelength
range,
separation
ability
of
wavelength
selector,
and
desired
isolation
of
specific
wavelength.
Slit
width
is
often
fixed
or
automatically
programmed.
Solvent
Cutoff:
The
wavelength
at
which
the
solvent
absorbs
a
significant
portion
of
the
light,
causing
a
loss
of
signal.
In
other
words,
the
solvent
becomes
opaque
to
the
wavelengths
being
used.
This
is
common
in
the
ultraviolet,
rare
in
the
visible.
Transmittance:
Ratio
of
the
radiant
power
transmitted
by
a
sample
to
the
radiant
power
transmitted
by
a
blank
in
an
equivalent
cell
or
by
some
other
means
of
compensation
for
solvent
absorption,
reflection
losses,
etc.
Visible:
The
portion
of
the
electromagnetic
spectrum,
from
400
to
800
nm,
detectable
by
human
eyes.
Ultra­
violet
(UV):
The
portion
of
the
invisisble
electromagnetic
spectrum
composed
of
wavelengths
of
10400
nm.
In
UV
spectrometry
we
are
primarily
interested
in
the
near­
W
(quartz)
region
extending
from
200
to
380
nm.
UV
Spectrum:
a
plot
of
wavelength
(or
fiequency)
of
absorption
versus
the
absorption
intensity
(absorbance
or
transmittance).

3.0
DESCRIPTION
3.1
The
HP
8453
spectrophotometer
is
a
single­
beam,
microprocessor­
controlled,
UV­
visible
spectrophotometer
with
collimating
optics.
The
ChemStationB
for
W­
Visible
spectroscopy
software
running
on
a
PC
with
Microsof@
NT
operating
system
provides
instrument
control,
data
acquisition,
and
data
evaluation.

4.0
IDENTIFICATION
4.1
Hewlett
Packard
G1103A
Serial
No.
CN93500458
4.2
Hewlett
Packard
89Q9QA
Serial
No.
DE14300757
5.0
WARNINGS
AND
CAUTlONS
5.1
Health
and
Safety
Warnings:

ETS­
9­
46.0
Page
2
of
9
Operation
and
Maintenance
ofthe
HP8453
UV­
Vis
Spectrophotometer
Page
92
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148
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MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
5.1.1
Eye
damage
may
result
from
directly
viewing
light
produced
by
deuterium
lamps
used
in
detectors
and
spectrophotometers.
Always
turn
off
the
deuterium
lamp
before
opening
the
lamp
door
on
the
instrument.
5.1.2
Some
adjustments
described
in
the
service
manual
are
made
with
power
supplied
to
the
instrument,
and
protective
covers
removed.
Electricity
and
heat
available
at
many
points
may,
if
contacted,
result
in
personal
injury.
5.1.3
Capacitors
inside
the
instrument
may
still
be
charged,
even
though
the
instrument
has
been
disconnected
from
its
source
of
supply.
Dangerous
voltages,
capable
of
causing
serious
personal
injury,
are
present
in
this
instrument.
Use
extreme
caution
when
handling,
testing,
and
adjusting.

5.2.1
Never
touch
the
quartz
envelope
of
the
deuterium
lamp
with
your
fingers.
Fingerprints
absorb
W
light
and
may
be
burnt
in,
thus
reducing
lifetime
of
the
lamp.
5.2.2
Quartz
sample
cells
or
sample
cells
with
quartz
faceplates
are
required
if
you
want
to
use
the
full
190
to
1
100
nm
wavelength
range
of
the
spectrophotometer.
Good
quality
glass
cells
may
be
used
when
working
above
3
50
nm.
Disposable
plastic
sample
cells
are
not
recommended
for
use.
5.2.3
For
high
precision
measurements,
wait
until
the
spectrophotometer
and
the
lamps
have
reached
thermal
equilibrium.
The
time
required
is
a
function
of
environmental
conditions
but
the
instrument
should
be
ready
after
45
minutes.
To
determine
if
the
spectrophotometer
is
in
stable
working
condi.
tion,
the
HP
8453
Self­
test
may
be
performed.
(See
section
13.1)
5.2.4
Ensure
cell
windows
are
free
of
fingerprints
and
other
contamination.
5.2.5
Avoid
the
use
of
alkaline
solutions
(pH
>
9.5)
which
can
attack
quartz
and
thus
impair
the
optical
properties
of
the
flow
cells.
5.2.6
Solution
in
cell
should
be
free
of
floating
particles.
5.2.7
Solution
in
cell
and
cell
walls
should
be
fiee
of
bubbles.
5.2.8
Ensure
that
solution
in
cell
is
homogeneous
by
thoroughly
mixing
before
measurement.
5.2.9
Blank
is
measured
on
the
same
solvent
as
sample.
5.2.10
Blank
measurement
should
show
a
flat
baseline.
5.2.11
Cell
orientation
of
blank
and
sample
measurements
should
be
the
same.
5.2.12
Ideally,
the
cell
is
not
removed
between
sample
measurements,
which
means
the
cell
is
filledrjnsed
using
a
pipette
or
a
flow
cell
is
used.
5.2.13
Time
between
blank
and
sample
measurements
should
be
short.
5.2
Cautions:

6.0
SPECIAL
INSTRUCTIONS
6.1
None.

7.0
RESPONSIBILITY
7.1
The
operator
is
responsible
for
routine
maintenance
and
cleaning.

ETS­
9­
46.0
Page
3
of
9
Operation
and
Maintenance
of
the
HP8453
UV­
Vis
Spectrophotometer
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3M
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Report
No.
E00­
2192
7.2
The
person
responsible
for
the
equipment
(and
an
alternate)
will
be
identified
in
the
front
of
the
equipment
logbook,
and
are
responsible
for
all
routine
and
non­
routine
maintenance
and
associated
documentation.

8.0
SUPPLIES
AND
MATERIALS
8.1
Pozidriv
screwdriver
8.2
Isopropanol,
reagent
grade
8.3
8.4
Surgical
cotton
swabs,
lint­
free.
8.5
Deuterium
lamp
assembly,
Agilent
8453
(Part
No.
2140­
0605).
.
8.6
Canister
of
compressed
oil­
free
air.

Lamp,
Tungsten
G1315A,
Agilent
8453A
(Part
No.
G1103­
60001).

9.0
INSTRUMENT
CLEANING
PROCEDURES
9.1
Cleaning
the
Stray
Light
Filter.
(Recommended
at
one­
yearly
intervals
or
more
frequently
when
operating
the
spectrophotometer
in
a
particularly
dirty
environment.)
9.1.1
9.1.2
9.1.3
9.1.4
9.1.5
9.1.6
9.1.7
9.1.8
9.1.9
Turn
off
the
instr&
en<
and
d&,
connect
the
power
cord.
Take
the
plastic
and
sheet
metal
rear
covers
off,
see
"Removing
and
Replacing
Covers"
on
page
109
of
the
HP
8453
Service
Manual.
Remove
any
accessory
board
or
MI0
board
that
may
be
plugged
in
from
the
rear
side
of
the
instrument.
Remove
the
upper
rear
foam
block.
Disconnect
the
shutter
cable
from
the
SPM
board.
Open
the
screw
that
fixes
the
shutter
assembly
to
the
optical
unit
and
remove
the
shutter
assembly.
Dampen
a
lint­
free,
surgical
cotton
swab
with
reagent
grade
isopropanol
and
gently
swab
the
surface
of
the
stray
light
filter.
Repeat
several
times
with
clean
swabs
and
alcohol
each
time,
Use
a
canister
of
compressed
oil­
free
air
to
further
clean
the
stray
light
filter.
Position
the
shutter
assembly
above
the
source
lens
and
fix
the
screw
that
holds
it
at
the
optical
unit,
see
Figure
39
on
page
124
of
the
Service
manual.
Connect
the
shutter
cable
to
the
SPM
board.
Replace
the
upper
rear
and
upper
fkont
foam
blocks.
If
available,
replace
any
accessory
board
or
MI0
board
(plugged
in
from
the
rear
side
of
the
instrument).
9.1.10
Replace
the
plastic
and
sheet
metal
rear
covers.
Push
the
plastic
rear
cover
down
so
that
it
locates
on
both
sides,
see
"Removing
and
Replacing
Covers"
on
page
109
of
the
HP
8453
Service
Manual.

spectrophotometer
passes
the
self­
test,
this
means
that
the
green
light
on
the
front
panel
comes
on
and
that
you
can
do
a
blank
measurement
from
the
sohare.
9J.
11
Reconnect
the
line
power
and
turn
on
the
instrument.
Check
that
the
9.2
Cleaning
the
Source
Lens
from
the
Sample
Compartment
Side.
(Recommended
at
one­
yearly
intervals
or
more
frequently
when
operating
the
spectrophotometer
in
a
particularly
dirty
environment.)
9.2.1
Turn
off
the
instrument
and
disconnect
the
power
cord.
9.2.2
Remove
any
cuvette
holder
from
the
sample
compartment.

ETS­
9­
46.0
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9
Operation
and
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W­
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Report
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2192
9.2.3
9.2.4
9.2.5
9.2.6
9.2.7
To
have
better
access
you
may
want
to
take
the
plastic
and
sheet
metal
rear
covers
off,
see
"Removing
and
Replacing
Covers"
on
page
109
of
the
HP
8453
Service
Manual.
Dampen
a
lint­
free,
surgical
cotton
swab
with
reagent
grade
isopropanol
and
gently
swab
the
surface
of
the
source
lens.
Repeat
several
times
With
clean
swabs
and
alcohol
each
time.
Use
a
canister
of
compressed
oil­
free
air
to
M
e
r
clean
the
source
lens.
If
you
have
taken
the
covers
off,
replace
them.
Replace
the
cuvette
holder:
Reconnect
line
power
and
turn
on
the
instrument.
Check
that
the
spectrophotometer
passes
the
self­
test,
this
means
that
the
green
Iight
on
the
front
panel
comes
on
and
that
you
can
do
a
blank
measurement
from
the
software.
9.3
Cleaning
the
Spectrograph
Lens.
(Recommended
at
one­
yearly
intervals
or
more
hquently
when
operating
the
spectrophotometer
in
a
particularly
dirty
environment.)
9.3.1
Turn
off
the
instrument
and
disconnect
the
power
cord.
9.3.2
Remove
any
cuvette
holder
from
the
sample
compartment.
9.3.3
To
have
better
access
you
may
want
to
take
the
plastic
and
sheet
metal
rear
covers
off,
see
"Removing
and
Replacing
Covers"
on
page
109
of
the
HP
8453
Service
Manual.
9.3.4
Dampen
a
lint­
free,
surgical
cotton
swab
with
reagent
grade
isopropanol
and
gently
swab
the
surface
of
the
spectrograph
lens.
Repeat
several
times
with
clean
swabs
and
alcohol
each
time.
9.3.5
Use
a
canister
of
compressed
oil­
free
air
to
m
e
r
clean
the
spectrograph
lens,
9.3.6
If
you
have
taken
the
covers
off,
replace
them.
Replace
the
cell
holder
in
the
sample
compartment.
9.3.7
Reconnect
line
power
and
turn
on
the
instrument.
Check
that
the
spectrophotometer
passes
the
self­
test,
this
means
that
the
green
light
on
the
front
panel
comes
on
and
that
you
can
do
a
blank
measurement
from
the
software.

10.0
MAINTENANCE
PROCEDURES
10.1
Routine
maintenance.

10.1.1.1
10.1.1.2
10.1.1.3
10.1.1
Cleaning
the
stray
light
filter.
Indicators
for
a
dirty
stray
light
filter
include:
After
exchanging
the
lamps,
the
intensity
test
executed
by
the
ChemStation
software
still
falls
below
the
specified
level.
One
of
the
stray
light
tests
fails.
The
photometric
accuracy
test
fails.
10.1.2
Cleaning
the
lenses
that
are
accessible
from
the
sample
compartment
side.
An
indication
for
dirty
lenses
is
when,
after
exchanging
the
lamps,
the
intensity
test
executed
by
the
ChemStation
software
still
falls
below
the
specified
level.
10.2
Non­
routine:
Document
any
non­
routine
maintenance.
10.2.1
Exchange
the
deuterium
or
the
tungsten
lamp
when
the
intensity
test,
which
is
executed
through
the
ChemStation
software,
falls
below
the
specified
level
or
when
one
of
the
lamps
no
longer
ignites.
See
HP
8453
Service
Manual
for
lamp
replacement
procedure
(p.
96).

ETS­
9­
46.0
Page
5
of
9
Operation
and
Maintenance
of
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HP8453
UV­
Vis
Spectrophotometer
Page
95
of
148
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TO
MAIN
3M
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Laboratory
Report
No.
E00­
2192
11.0
OPERATING
PROCEDURES
11.1
Powering
Up
the
HP
8453'W­
Visible
Spectrophotometer
and
PC
controller.
11.1.1
Switch
on
the
PC
and
boot
the
PC
operating
system.
11.1.2
Switch
on
the
spectrophotometer
and
wait
until
the
spectrophotometer's
indicator
light
turns
green.
This
process
includes
the
spectrophotometer's
self
test
and
takes
about
one
minute.
11.1.3
Launch
a
measurement
session
by
pressing
the
operating
system's
"Start"
button
and
select
"Programs",
"HP
W­
Visible
ChemStatiom",
"spectrometer
1
onlne"
11.1.4
The
system
is
ready
to
use
if
the
blue
"busy"
status
display
on
the
system's
bottom
message
line
turns
off.
Note:
For
high
precision
measurements
wait
until
the
spectrophotometer
and
the
lamps
have
reached
thermal
equilibrium.
The
time
required
is
a
function
of
environmental
conditions
but
should
be
ready
after
45
minutes.
11.1.5
The
first
measurement
to
perform
is
a
reference
measurement.
After
this
alignment
you
are
ready
to
measure
absorbance
data
and
spectra
11.2
Inserting
a
Cell.
11.2.1
The
HP
8453
is
shipped
with
the
standard
single­
cell
holder
which
accommodates
11.2.2
Move
the
locking
lever
to
its
up
position.
11.2.3
Insert
the
sample
cell,
making
sure
you
orient
it
correctly.
The
frosted
(non­
clear)

11.2.4
Lock
the
sample
cell
in
place
by
pushing
the
locking
lever
back
down.
11.2.5
Small
volume
flow
cells
and
particularly
any
cells
With
less
than
a
2
mm
aperture
standard
cells
or
flow
cells.

sides
of
the
sample
cell
should
not
be
in
the
path
of
the
light
beam.

may
require
use
of
the
optional
adjustable
cell
holder.
This
device
helps
you
ensure
the
cells
are
properly
centered
in
the
light
path.
11.3
Entering
a
Cell's
Path
Length.
11.3.1
Click
"Setup"
on
the
Instrument
Panel.
11.3.2
Type
the
path
length
in
cm
in
the
"Setup
Manual"
dialog
box.
11.3.3
Click
"OK"
to
set
the
specified
path
length.

11.4.1
Start
a
measurement
session
by
selecting
Instrument
I
online
fiom
the
menu.
11.4.2
Perform
a
reference
measurement.
Typically
the
cell
containing
the
solvent
used
11.4
Starting
a
Measurement
Session,

with
your
samples
is
put
in
the
measurement
position
and
a
blank
measurement
performed.
To
start
this
measurement,
click
the
"Blank"
button
on
the
Instrument
Panel
or
press
the
spectrophotometer's
"Blank"
button,
11.4.3
Perform
a
sample
measurement.
To
get
the
most
precise
results,
use
the
same
cell
in
the
same
orientation
to
the
measurement
beam.
Flush
the
cell
about
three
times
with
the
sample
solution
and
start
the
measurement
by
clicking
the
Instnunent
Panel's
"Sample"
button
or
by
pressing
the
spectrophotometer's
"Sample"
button.
11.5
Setting
up
a
Method
for
Single
Component
Analysis.
11.5.1
Choose
the
"Quantification"
task
from
the
data
analysis
panel.
11.5.2
Enter
the
used
wavelength
in
the
input
fields.

ETS­
9­
46.0
Page
6
of
9
Operation
and
Maintenance
of
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HP8453
W­
Vis
Spectrophotometer
Page
96
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148
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MAIN
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Laboratory
Report
No.
E00­
2192
11.53
If
background
correction
is
desired,
select
"Single
Reference
Wavelength",
"Subtract
Average
Over
a
Range"
or
"Three­
point
Drop
Line"
from
the
background
correction
combo
box.
11.5.3.1
11.5.3.2
"Single
Reference
Wavelength"
requires
the
input
of
one
wavelength
in
the
adjacent
wavelength
edit
field
on
the
right
side
of
the
combo
box.
For
"Subtract
Average
Over
a
Range"
or
"Three­
point
Drop
Line"
you
must
define
the
rangehaseline
by
entering
the
start
and
end
wavelengths
in
the
two
adjacent
wavelength
edit
field
on
the
right
side
of
the
combo
box.
11.5.4
Specify
a
name
for
the
analyte.
11.5.5
Choose
"Concentration"
to
enter
the
analyte
concentration
directly
or
"Weight
&
Volume"
to
have
the
ChemStation
calculate
the
concentration.
Enter
the
units
for
the
concentration
or
the
weight
and
volume.

measurement,
select
"Prompt
for
Standard
Information".
In
the
combo
box
you
can
select
whether
the
prompt
asks
you
for
the
concentration,
or
calculates
the
concentration
based
on
volume,
weight
and
purity.

Dilution
Factor"
of
sample.
11.5.6
If
you
want
to
be
prompted
for
the
concentration
of
the
standards
during
11.5.7
If
you
have
diluted
samples
and
want
to
correct
for
dilution,
select
"Prompt
for
11.5.8
Choose
the
desired
calibration
curve
type.
11.5.9
Select
the
desired
data
type
and
display
range
of
the
spectra
in
the
graphical
11.5.10
Choose
"OK"
to
close
the
dialog
box.
11.5.11
Perform
the
following
steps
ifyou
want
to
calibrate
the
method.
window.

11.5.11.1
Measure
a
blank
on
the
solvent
if
necessary
using
the
"Blank"
button
in
the
instrument
panel.
11.5.11.2
Measure
the
standards
using
the
"Standard"
button
in
the
instrument
panel.
If
you
have
selected
one
of
the
prompts,
the
appropriate
values
will
be
requested
in
a
diaIog
box.
The
spectrum
is
displayed
automatically
in
the
"Standard
Spectra"
window
as
they
are
measured.
Note:
There
is
no
fixed
limit
to
the
number
of
calibration
standards
that
can
be
incorporated
into
a
calibration.
However,
each
of
the
calibration
curve
types
requires
a
minimum
number
of
standards
of
different
concentrations,
which
can
be
found
in
Table
7,
page
45
of
the
HP
Manual:
Understanding
Your
UV­
Visible
Spectroscopy
System.
The
ChemStation@
s
o
h
a
r
e
calibrates
automatically
when
at
least
the
minimum
number
of
standards
has
been
measured.
A
table
with
the
used
standards
and
values
as
well
as
calibration
curve
is
displayed.
11.5.11.3
If
the
calibration
is
successfitl,
the
calibration
curve
icon
of
the
data
analysis
panel
changes
from
red
to
green.
11.6
Measuring
and
Displaying
an
Absorbance
Spectrum
11.6.1
Select
the
"Clear"
icon
using
the
Toolbar,
to
delete
any
spectral
data
that
you
do
11.6.2
Select
the
"Spectrum/
Peaks"
task
from
the
Method
menu
or
data
analysis
panel.
11.4.3
Select
the
boxes
€or
"PeaWVdley
Find"
if
necessary.
not
wish
to
keep.

ETS­
9­
46.0
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7
of
9
Operation
and
Maintenance
of
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HP8453
UV­
Vis
Spectrophotometer
Page
97
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
11.6.4
Select
"Absorbance"
as
data
type.
11.6.5
Set
the
display
range
you
want
to
see
in
the
graphical
window.
11.6.6
Choose
"OK"
to
close
the
"Spectrum/
Peaks
Parameters"
dialog
box.
11.6.7
Measure
a
Blank
on
the
solvent
if
necessary
using
the
"Blank"
button
in
the
instrument
panel.
11.6.8
Measure
all
the
samples
using
the
"Sample"
button
in
the
instrument
panel.
The
spectra
are
displayed
automatically
in
the
"Sample
Spectra"
window
as
they
are
measured
and
depending
on
the
selected
parameters
you
will
get
a
table
of
results.
11.7
Loading
Spectra:
11.7.1
Choose
"Load"
from
the
"File"
menu,
then
choose
the
type
of
spectra
that
you
want
to
load
(Samples
or
Standards)
from
the
submenu
to
display
the
"Load
Spectra''
dialog
box.

directory
from
the
"Directories"
list.

close
the
dialog
box.
11.7.2
If
the
spectra
you
wish
to
load
are
not
in
the
"File
Name"
list,
select
a
different
11.73
Select
the
spectra
you
wish
to
load
from
the
File
Name
list
and
choose
OK
to
11.8
Saving
Spectra:
11.8.1
Choose
"Save"
from
the
"File"
menu,
then
choose
the
type
of
spectra
that
you
want
to
save
(Samples,
Standards
or
Selected
Spectra)
fiom
the
submenu
to
display
the
"Save
Spectra
As"
dialog
box.
11.8.2
If
you
wish
to
save
the
spectra
in
a
directory
other
than
the
current
one,
seIect
the
new
directory
from
the
"Directories"
list.
11.8.3
Type
the
name
you
wish
to
save
the
spectra
as
in
the
"File
Name"
field
and
choose
"OK"
to
close
the
dialog
box.
11.8.3.1
A
valid
file
name
consist
of
eight
dphanumeric
characters
and
the
file
extension
.sd
or
.std.
Usually,
the
extension
.std
is
used
for
standards
only.
11.8.4
You
can
also
save
spectra
using
the
ToolBar.

12.0
RECOROS
12.1
Document
all
cleaning
and
maintenance
performed
on
the
instrument
in
the
maintenance
or
dmaintenance
logbook.
Include
a
description
of
the
procedure(
s)
performed,
name
of
person
who
performed
procedure@),
any
unusual
observations,
parts
replaced
or
needing
replacement,
and
whether
the
procedure
was
routine
or
non­
routine.
Logbooks
are
archived
when
complete.

13.0
TESTING,
CALIBRATION
AND/
OR
STANDARDIZATION
PROCEDURES
13.1.1
Make
sure
that
you
are
in
the
"Verification
and
Diagnostics"
mode.
The
mode
is
13.1.2
Select
the
"Self­
Test"
task
in
the
analysis
panel's
selection
box.
13.1.3
Choose
"Self­
Test".
Start
from
the
"Task"
menu
or
click
"Start"
to
start
the
self­

13.1.4
The
self­
test
results
will
be
displayed
in
a
window
with
passlfail
criteria.
Calibrating
for
a
single
component
analysis.
13.1
HP
8453
Self­
Test:

indicated
on
the
tool
bar
of
the
HP
ChemStationa
session.

test.

13.2
ETS­
9­
46.0
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8
of9
Operation
and
Maintenance
of
the
HP8453
UV­
Vis
Spectrophotometer
Page
98
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
.
`C
13.2.1
Calibration
for
single
component
analysis
is
based
on
the
measurement
of
standard
samples
with
known
concentrations.
During
the
calibration
process,
the
software
calculates
the
calibration
coefficients,
which
are
then
used
for
the
quantification
of
unknown
samples.
13.2.2
The
status
for
calibration
can
be
seen
in
the
data
analysis
panel:
13.2.2.1
Uncalibrated:
RED
dashed
calibration
curve
icon.
13.2.2.2
Calibrated:
GREEN
continuous
calibration
curve
icon.

13.23.1
Load
or
set
up
a
method
for
the
"Quantification"
task.
13.2.3.2
If
the
"Standard"
spectra
window
is
not
displayed,
choose
"Show"
standards
in
the
data
analysis
panel.
13.2.33
You
can
either
load
the
standards
from
file
or
measure
them.
13.2.3.4
To
measure
standards:
13.2.3
To
calibrate
for
single
component
anaIysis:

13.2.3.4.1
Measure
a
bank
on
the
solvent
if
necessary
using
the
"Blank"
button
in
13.2.3.4.2
Measure
the
standards
using
the
"Standard"
button
in
the
instrument
the
instrument
panel.

panel.
If
you
have
selected
one
of
the
prompts
in
the
method,
the
appropriate
values
will
be
requested
in
a
dialog
box.
13.2.4
The
spectra
are
displayed
automatically
in
the
"Standard
Spectra"
window
as
the
standards
are
measured.
A
minimum
number
of
standards
is
required,
depending
on
the
selected
calibration
curve.
The
ChemStationm
softwae
calibrates
automatically
when
at
least
the
minimum
number
of
standards
have
been
measured.
A
table
with
the
used
standards
and
values
as
well
as
a
calibration
curve
is
displayed.
13.2.5
If
the
calibration
is
successfil,
the
calibration
curve
icon
of
the
data
analysis
panel
changes
&om
red
to
green.

14.0
REFERENCES
14.1
Defhtions
obtained
from
www.
spectroscopymag.
com.
14.2
HP
Manual:
Understanding
Your
W­
Visible
Spectroscopy
System,
Hewlett­
Packard:
Wilmington,
DE,
1997.
Part
No.
G1115­
90005.
14.3
HI'
8453
W­
Visible
Spectrophotometer
Operator's
Manual,
Hewlett­
Packard:
Wilmington,
DE,
2000.
Part
No.
G1115­
90012.
14.4
HP
8453
W­
Visible
Spectrophotometer
Service
Manual,
Hewlett­
Packard:
Wilmington,
DE,
1998.
PartNo.
G111S­
90003.

15.0
AFFECTED
DOCUMENTS
15.1
None.

16.0
REVISIONS
Revision
Revision
Number.
Reason
For
Revision
­
Date
ETS­
9­
46.0
Page
9
of
9
Operation
and
Maintenance
of
the
HP8453
UV­
Vis
Spectrophotometer
Page
99
of
14%
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
3M
ENVIRONMENTAL
LABORATORY
­­­

EQUIPMENT
PROCEDURE
TEKMAR
PURGE
AND
TRAP
CONCENTRATOR
AND
AGILENT
GAS
CHROMATOGRAPH/
MASS
SPECTROMETER
ROUTINE
MAXBTENANCE
OF
hCHON
PURGE
AND
TRAP
AUTOSAMPLER,

Procedure
Number:
ETS­
9­
49.0
Adoption
Date:
,c/!
z+.

Approved
by:

Laboratory
Manager
Date
ETS­
9­
49.0
Routine
Maintenance
of
the
Purge
&
Trap
Autosantpler/
Concentrutor/
GC/
MS
Page
100
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
1.0
SCOPE
AND
APPLICATION
(VSE
NUMBERED
TIER
I)
This
equipment
procedure
describes
the
maintenance
required
for
optimal
operation
of
the
Archon
Purge
and
Trap
Autosampler,
Telanar
Purge
and
Trap
Concentrator
and
Agilent
gas
chromatograph
/
mass
spectrometer
(GCMS)
system.
Specific
items
requiring
routine
maintenance
include
occasional
tightening
vial
escalator's
nuts
and
refilling
the
Standard
Vial
and
water
bottle
in
the
Archon
autosampler
and
periodic
cleaning
of
the
mass
spectrometer
ion
source.
1.1
2.0
DEFINITIONS
2.1
None.

3.0
DESCRIPTION
3.1
Archon
purge
and
trap
autosampler
equipped
with
Tekmar
purge
and
trap
concentrator
and
Agilent
gas
chromatograph
and
mass
spectrometer.

4.0
IDENTIFICATION
4.1
System
:
"Rufus".
(An
equivalent
system
may
be
used).
4.1.1
Autosampler:
serial
number
13006,
Varian,
Archon
4.1.2
Concentrator:
serial
number
90297002,
LSC2000,
Tekmar
4.1.3
GC:
serial
number
US00034972,6890
G1530A,
Agilent
'

4.1.4
MS:
serial
number
US01180105,5973N
G2589A,
Agilent
4.1.5
PC:
serial
number
US94850812,
D6720T,
HP
Kayak
XA
5.0
WARNINGS
AND
CAUTIONS
5.1
'Health
and
Safety
Warnings:
5.1.1
Cooling
the
Telanar
before
removing
the
side
cover
for
maintenance
prevents
contact
bums.
5.1.2
Turning
off
power
source
for
Tekmar
before
removing
the
side
cover
will
prevent
electric
shock.

5.2.1
It
is
recommended
that
a
grounded
antistatic
wrist
strap
be
worn
while
disconnecting
all
wires,
contacts,
or
cables
which
are
connected
to
printed
circuit
boards
within
Archon
autosampler,
Tekmar
concentrator
or
MS
analyzer.
5.2.2
To
prevent
the
breakage
of
the
Standard
Vial
on
Archon
autosampler,
during
the
refill,
do
not
use
any
tool
and
do
not
overtighten
the
thumbnut.
5.2.3
Never
add
oil
while
the
foreline
pump
is
on.
5.2
Cautions:

6.0
SPECIAL
INSTRUCTIONS
6.1
Not
applicable.

ETS­
9­
49.0
Page
2
of
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Maintenance
of
the
Purge
&
Trap
Autosampler/
Concentrator/
GC/
MS
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7.0
RESPONSIBILITY
7.1
Routine
maintenance
procedures
may
be
performed
by
a
primary
custodian,
and
by
any
analyst
who
has
been
trained
to
perform
these
maintenance
procedures
by
a
primary
custodian.

8.0
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14
8.15
8.16
SUPPLIES
AND
MATERIALS
Graphite
Ferrules,
0.4
mm
I.
D.
for
0.25
mm
columns
Abrasive
paper,
Hewlett­
Packard,
part
no.
5061­
5896
Alumina
abrasive
powder,
Hewlett­
Packard,
part
no.
8660­
079
1
Acetone,
reagent
grade
Dichloromethane,
reagent
grade
Methanol,
purge
and
trap
grade
Gloves
(clean,
lint­
free,
cotton),
Hewlett­
Packard,
part
no.
8650­
0030
(large);
8650­
0029
Cotton
swabs
Chem­
wipes
Glass
beakers
Sonicator
Base
deactivated
2
mm
ID
gooseneck
splitless
injection
port
liners,
Restek
Corporation,
part
#20796­
210.5,
or
equivalent
1
1
mm
diameter
Themogreen
LB2
septa,
Supelco,
part
#23
163,
or
equivalent
Viton
injection
port
O­
rings,
Restek
Corporation,
part
#20377,
or
equivalent
Septum
wrench,
Hewlett­
Packard,
part
#19251­
00100
Tweezers
(small)

9.0
CLEANING
PROCEDURES
NIA
10.0
MAlNTENANCE
PROCEDURES
10.1
Routine:
Tighten
the
elevator`
s
assembly
nuts
when
Archon
autosampler
displays
error
10.2
10.3
message
I'
Elevator
not
homed
position
`I.

10.1.1
Stop
autosampler
run
by
pressing
STOP
button
on
the
front
display
twice.
10.1.2
Open
the
back
cover
of
autosampler
10.1.3
Tighten
top
and
bottom
nuts
on
the
elevator's
assembly,
do
not
over
tighten
them,
10.1.4
Close
the
back
cover
of
autosampler
Routine:
Fill
the
water
bottle,
empty
the
waste
bottle.
Routine:
If
internal
standards
or
surrogates
are
to
be
used,
be
certain
the
Standard
Vial
is
filled
with
the
required
internal
standard
or
surrogate.
10.3.1
Turn
the
helium
gas
"OFF"
with
the
toggle
switch.
10.3.2
Push
"System"
key,
choose
Maintenance,
Standard
Control,
Front
Park.
10.3.3
Grasp
the
vial
and
loosen
the
black
thumbnut.
SIide
the
Vial
down.

ETS­
949.0
Page
3
of5
Routine
Maintenance
of
the
Purge
&
Trap
AutosampIer/
Concenhtor/
GC/
MS
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10.3.4
Clean
the
vial
with
methanol,
dry
it
thoroughly
and
fill
the
vial
with
10.3.5
Slide
the
vial
back
up
into
standard
mount.
Finger­
tighten
thumbnut
until
it
is
10.3.6
Turn
the
helium
gas
into
ON
position.
Prime
Standard
Loop.
Routine:
GCMS
forelhe
pump
maintenance.
10.4.1
Examine
the
oil
level
window
daily.
If
the
oil
level
is
near
or
below
the
lower
10.4.1.1
Vent
the
MSD
according
to
the
MSD
Hardware
Manual.
10.4.1.2
Remove
the
fill
cap.
10.4.1.3
Add
pump
fluid
until
the
oil
level
in
the
window
is
near,
but
not
above,
the
upper
line.
10.4.1.4
Reinstall
the
fill
cap.
10.4.1.5
Pump
down
the
MSD
according
to
the
MSD
Hardware
Manual
approximately
5
ml
of
standard
or
smgate
snug.
Do
not
use
any
tool
and
do
not
overthighten.

10.4
line
then
add
foreline
pump
oil.
Never
add
oil
while
the
foreline
pump
is
on.

10.4.2
Change
foreline
pump
oil
every
6­
12
months
according
to
the
MSD
Hardware
I
Nonroutine:
Document
any
nonroutine
mahtenance
in
the
instrument's
maintenance
logbook.
manual.
10.5
11
.O
OPERATING
PROCEDURES
11.1
For
operating
procedures,
refer
to
an
appropriate
analytical
method,
or
to
the
Archon
Purge
and
Trap
Autosampler
System
Operator's
Manual,
Tekmar
LSCZOO
Instruction
Manual
and
the
Hewlett­
Packard
MSD
Hardware
Manual
for
HP
5973N
&
HP
6890
Series
Mass
Selective
Detectors.
I
12.0
RECORDS
12.1
Document
any
maintenance
performed
on
the
instrument
in
the
maintenance
or
dmaintenance
logbook.
Jnclude.
a
description
of
the
procedure(
s)
performed,
any
unusual
observations,
parts
replaced
or
needing
replacement,
and
whether
the
procedure
was
routine
or
non­
routine.
Be
sure
to
date
and
initial
the
entry.
Logbooks
are
archived
when
complete.

13.0
TESTING,
CALIBRATION
AND/
OR
STANDARDIZATION
PROCEDURES
13.1
After
cleanhg
the
source
and
allowing
sufficient
time
for
the
vacuum
to
pump
down
and
the
mass
spectrometer
to
equilibrate
to
operation
temperature,
run
an
autotune;
check
for
improved
performance
and
for
the
presence
or
absence
of
air
leaks.
A
tune
report
can
also
be
used
to
check
for
leaks
after
performing
injection
port
maintenance.

14.0
REFERENCES
14.1
14.2
Tekmar
LSC200
Instruction
Manual
Archon
Purge
and
Trap
Autosampler
System
Operator's
Manual
ETS­
9­
49.0
Page
4
of
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Routine
Maintenance
of
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Purge
&
Trap
Autosampler/
Concenttor/
GC/
MS
Page
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14.3
HewIett­
Packard
MSD
Hardware
Manual
for
Hp
5973N
&
HP
6890
Series
Mass
Selective
Detectors.

15.0
AFFECTED
DOCUMENTS
15.2
None.

16.0
REVISIONS
Revision
Revision
Number.
Reason
For
Revision
ETS­
949.0
Page
5
of
5
Routine
Maintenance
of
the
Purge
&
Trap
Autosampler/
Concentrator/
GC/
MS
Page
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2192
Appendix
B:
Chemical
Characterization
This
appendix
includes
chemical
characterization
information
for
both
reference
substances
and
control
substances.

Page
105
of
148
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No.
E00­
2192
IUPAC
Name
Chemical
Characterization
I
I
I
Substance
PFOA
PF'HpA
Perfluorooctanoic
acid,
ammonium
salt
Pertluoroheptanoic
acid
Chemical
Formula
CsFisO2NH4
C7F1102H
I
Source
I
3M
Saecialtv
Chemicals
I
Aldrich
Identifier
3825­
26­
1*
375­
85­
9*

Expiration
Date
Storage
Conditions
Chemical
Lot
Number
Substance
~
~

2002
2005
Frozen
Frozen
332
TCR­
9913
1­
25
C,
Hydride
I
C7
Perfluoroheptenes
(90/
10
I
mix)
Physical
Description
Purity
White
wax
or
powder
Clear
Crystals
95%
98%
1
I
i
I
Chemical
Formula
I
C4F&
F=
C7F5.
C,
FIICF=
CF,
I
C,
F
I
10%
2­
Perfluoroheptene,
90%
Perfluoroheptene
IUPAC
Name
I
Identifier
I
355­
63­
5*
I
272
13­
61­
2*
1,1,2,2,3,3,4,4,5,5,6,6,7,7,7
pentadecafluoroheptane
~

I
~~

Source
Lancaster
Synthesis
Expiration
Date
2005
I
Storage
Conditions
I
Frozen
I
Frozen
~~
~~

Lancaster
Synthesis
2005
Chemical
Lot
Number
Physical
Description
Purity
PFPA
I
90004250,
TNA
3025
900591
1,
TNA­
3026
Clear
ambient
liquid
Clear
ambient
liquid
100%
97%
Perfluoropentanoic
acid
2706­
90­
3*
I
Aldrich
Frozen
SD­
043
I
Clear
Liquid
95%
1
I
C6
Hydride
355­
37­
3*
Lancaster
Synthesis
Frozen
I
98%
I
Page
106
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E00­
2192
Reference
Substance
IUPAC
Name
Chemical
Formula
Identifier
Source
Reference
Substances
(continued)

Cs
Hydride/
Olefin
Mix
Cs
Terminal
Hydride
C4
Terminal
Hydride
1,1,1,2,3,3,4,4,4
heptadecafluorooctane
nonafluorobut
ane
1,1,1,2,2,3,3,4,4,5,5,6,6,7,8,8,8
1
1
2
2
3
3
4
6,6
pentadecafluorooctane,
2­
perfluorooctene
'
'
'
'
'
'
'
'
'
'
'
'
'
'
'

C6F
13CFHCF3'
C6F
13CF=
CF2
C8F17H
CP9H
TCR­
99030­
18
335­
65­
9*
375­
17­
7*

3M
Specialtv
Chemicals
Aldrich
Chemical
Crescent
Chemical
~~
~

Storage
Conditions
Chemical
Lot
Number
I
Exairation
Date
I
6/
6/
99
I
2002
I
2002
~

Frozen
Frozen
Frozen
1
04307PN,
TNA­
2983
6A­
46,
TNA­
3997
Physical
Description
Clear
ambient
liquid
Clear
ambient
liquid
Clear
ambient
liquid
Purity
Chemical
Formula
I
85%
Cs
Hydride,
15%
Cs
Olefin
C4FS
C3F7H
99%

Identifier
99%

360­
89­
4*
2252­
84­
4*
I
354­
33­
6*
I
I
I
Reference
Substance
C4
Interior
Olefin
C3
Terminal
Hydride
C2
Terminal
Hydride
Source
1,1,2,2,2
pentafluoroethane
1,1,2,2,3,3,3
hepta
fluoropropane
2­
Perfluorobutene
IUPAC
Name
Lancaster
Synthesis
I
Lancaster
Synthesis
Lancaster
Synthesis
~~
~~

Physical
Description
Purity
Clear
ambient
liquid
Gas
Gas
97%
97%
99%
I
Extiration
Date
I
2002
I
2010
1
2010
~~

I
Storage
Conditions
I
Frozen
I
Flammable
I
Flammable
~~

I
Chemical
Lot
Number
I
G00195.
TNA­
4298
I
G0062B.
TNA­
4294
I
G00492.
TNA­
3021
Page
107
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2192
Control
Substances
PFCH
PFBS
Pentafluorobenzene
structure
Perfluorobutane­
sulfonate,
potassium
salt
C&
FS
C&
IZ
IUPAC
Name
Perfluorocyclo­
hexane
C4FWzK
Pentafluorobenzene
I
Physical
Description
I
Colorless
Moist
Solid
I
White
Powder
I
Methanol
solution
Use
Source
Instrumental
Surrogate
Standard
For
GCIMS
analysis
Surrogate
Standard
For
GC/
MS
Internal
Standard
for
LC/
MS
analysis
analysis
Aldrich
Chemical
3M
Specialtv
Chemicals
Restek
Corn.

I
Control
Substances
I
Chlorobenzene­&
I
Toluene­&
I
Dibromofluoromethane
Expiration
Date
Storage
Conditions
Chemical
Lot
Number
~~

2005
2002
612002
Frozen
Frozen
Frozen
01911AU
TCR­
99030­
028
A013256
Purity
97%
97%<
99%
(2500
p
g
i
d
i0.2%)

I
Chemical
Lot
Number
I
A013256
I
A012973
I
A012973
structure
C&
IDs
I
c7
D8
I
Control
Substances
I
1,4
Difluorobenzene
I
4­
Bromofluoro­
benzene
I
1,4­
Dichlorobenzene­
d.,
CHBrzF
IUPAC
Name
Use
Chlorobenzene­
d5
Toluene­
d8
'
Dibromo
fluoromethane
Use
Source
Expiration
Date
Storage
Conditions
Instrumental
Surrogate
Standard
Instrm
For
GCMS
analysis
Standard
Eor
CIL/
IW~
analysis
analysis
Restek
Corp.
Restek
Corp.
Restek
Corp.
612002
212002
212002
Frozen
Frozen
Frozen
Physical
Description
­
~

Methanol
solution
Methanol
solution
Methanol
solution
*CAS
Number
Purity
Page
108
of
148
99%
(2500
p
g
/d
&
0.2%)
I
99%
(2500
p
g
/d
F
0.2%)
I
99%
(2500
pglmL
0.2%)

Structure
IUPAC
Name
c6
H4FZ
C6HdBrF
C6C12D4
1,4
Difluorobenzene
4­
Bromofluoro­
benzene
1,4­
Dichlorobenzene­
d4
Instrumental
Surrogate
Standard
For
GCIMS
analysis
Instrumental
Surrogate
Standard
For
GCIMS
analv&
Instrumental
Surrogate
Standard
For
GCIMS
analysis
Some
~

Restek
Corp.
Restek
Corp.

Expiration
Date
612002
I
212002
612002
Storage
Conditions
Frozen
Frozen
Frozen
Chemical
Lot
Number
Physical
Description
Purity
A013256
A012973
.
A013256
Methanol
solution
Methanol
solution
Methanol
solution
99%
(2500
pdmL
k
0.2%)
99%
(2500
~g/
rnL
0.2%)
99%
(2500
DglrnL
k
0.2%)
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~

Appendix
C:
Kinetics
Model
and
Kinetics
Calculations
This
appendix
presents
the
mathematical
description
of
the
kinetics
model
employed
in
this
study
and
the
application
of
this
model
in
the
determination
of
the
estimated
half­
lives
presented.

Page
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Kinetics
Model
C1.
Reaction
Components
and
Rates
The
arguments
below
are
based
on
the
following
idealized
set
of
reactions
representing
the
photodegradation
of
a
parent
compound
P
and
its
products
A,,
which
number
N.
The
actual
reactions
that
occur
are
subsumed
in
these
equations,
and
are
assumed
to
proceed
with
pseudo­
first
order
rates
k,,
(for
the
parent)
and
k,,
(for
the
products).

k
Prn
P
+
photon
+n,
A,+
Y,
(m=
ltoN)

k
h
A,
+photon
+
YmZ
(m=
1
toN)

where
"photon
may
either
represent
a
photon
of
light
or
it
may
represent
some
other
species
in
solution
that
reacted
with
a
photon
to
produce
a
new
reactive
species
and
the
general
symbols
Y,,
and
YmZ
represent
all
the
other
hydrolysis
products.

C2.
Parent
Compound
Concentrations
Equation
C1
indicates
that
the
pseudo­
first
order
differential
change
in
the
parent
concentration
P
at
a
constant
flux
of
light
or
a
constant
concentration
of
radicals
is
given
by
which
is
equivalent
to
the
separable
differential
equation
g=­[
z
P
n,
kpm]
dt
Equation
C4
may
be
directly
integrated
to
obtain
the
general
solution
In[
P]=
­c
nm
k,,
t
+C
[
my1
)

With
the
initial
condition
P(
t
=
0)
=
Po,
the
specific
solution
to
Equation
C4
is
using
the
additional
definition
of
the
total
parent
photolysis
rate
Page
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2192
N
k,
­c
n,
k,,
.
m=
l
Equation
C6
can
be
re­
written
in
a
form
that
allows
a
least­
squares
estimate
of
the
total
parent
hydrolysis
rate:

k,
t
=
­In
[
i]

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)]
versus
time
and
obtain
a
least
­squares
estimate
of
the
slope
of
the
line.
The
resulting
slope
is
the
least­
squares
estimate
c,
of
the
total
parent
photolysis
rate.

Equation
C6
indicates
that
over
a
period
of
time
TI':
(the
parent
half­
life)
the
parent
concentration
P
is
reduced
through
hydrolysis
by
a
factor
of
two,
where
A
least
squares
estimate
of
the
parent
photolysis
half­
life
is
therefore
available
from
C3.
Product
Compound
Concentrations
The
pseudo­
first
order
differential
changes
in
the
product
concentrations
&,
(using
Equations
C2
and
C6)
are
dA,
=
(
n,
kpmP
­
k,,
A,)
dt
=
(
n,
k,,
Po
e­
kp
*
­
kAmA,)
dt
(CIV
and
the
(first
order,
non­
separable)
differential
equation
governing
the
product
concentrations
is
%+
k,
A,
=
n,
kp,
Po
e­
kpt
dt
The
"standard
form"
of
Equation
C12
is
Page
11
1
of
148
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MAIN
A:
+
S
(t)
A,
=
Q(
t)

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

(t>
=
kAm
and
Q(
t)
=
n,
kp,
Po
e­
kpt
.

The
general
solution
A,
to
Equation
C12
is
contained
in
where
3M
Environmental
Laboratory
Report
No.
E00­
2192
and
There
are
two
cases
of
Equation
C18
to
consider.
In
the
circumstance
that
kArn
=
k,
,
which
occurs
only
when
the
rate
of
the
mth
product
is
identical
to
the
total
parent
photolysis
rate,
the
general
solution
to
Equation
818
is
(for
k,
=
k,)

A,
ekpt
=
nmkPmPO
t
+C
and,
using
the
initial
condition
A
,(
t
=
0)
=
A,
,
the
specific
solution
to
Equation1
8
is
(for
k,
=
k,
)

A,
=
(n,
k,,
Po
t
+A,
)
e­
kp
.

Page
112
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E00­
2192
We
note
that
when
k,
=
k,
=
0
(that
is,
when
both
the
parent
and
potential
product
are
photolytically
stable),
Equation
C7
requires
(also)
that
kp,
=
0,
so
Equation
C20
becomes
A,
=A,

indicating,
as
required,
that
the
product
concentration
does
not
change
with
time.

The
circumstance
k,,
=
k,
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
photolysis
rate
k,
and
the
product
photolysis
ratek,
approach
each
other.

In
the
more
probable
case,
for
which
k,,
#
k,
(Le.
that
the
rate
of
the
mth
product
is
different
from
the
total
parent
rate),
the
general
solution
to
Equation
C18
is
and
the
specific
solution
to
Equation
C18
with
the
initial
condition
A,(
t
=
0)=
A,,
is
nmkPmPO
kP
­
kAm
1
e­
k,
t
­
nmkPmPO
e­
kp
t
k
P
­
kAm
Of
greatest
interest
here
is
the
case
in
which
the
product
compounds
are
known
to
be
photolytically
stable,
that
is,
when
k,
=
0
for
all
m.
In
this
case,
Equation
C23
becomes
(for
stable
products)

A,
=A,,
+
nmkPmPO
(1­
e­
kp
t
)

k
P
C4.
Relationships
Between
the
Parent
and
Compound
Concentrations
Equations
C7
and
C24
can
be
combined
to
obtain
(for
stable
products)

Page
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so
that
(for
stable
products)

or
(for
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
5
1
)

ln(
l+
X)=
X­
­x2
1
+­
x3
1
­­
x4
1
+.....
3
4
L
and
Equation
B23
becomes
(for
stable
products
and
or
Page
114
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BACK
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Report
No.
E00­
2192
(for
stable
products
and
Am
­Amo
c
m
<<
Po
)

C5.
Parent
Half­
Life
Estimates
Based
on
Limits
of
Quantification
of
the
Products
In
every
experimental
determination
of
k,
,
there
is
some
set
of
values
A;
Q
(the
"limits
of
quantitation")
below
which
the
product
concentrations
A,
cannot
be
reliably
measured.
If
during
an
experiment
carried
out
over
the
period
of
timed
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,
=
A:
Q.
With
these
assumptions,
the
experimental
data
indicate
that
the
reaction
rate
k,
is
less
than
some
maximum
value
(kP),,
as
follows:

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

Under
the
same
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
TI':
(see
Equation
C9)
is
greater
than
the
value
(T
vi)
.
as
follows:
mm
(for
photolytically
stable
products
at
concentrations
below
the
limits
of
quantitation)

The
reader
should
note
that
Equations
C32
and
C33
are
valid
only
when
both
1)
the
products
are
stable
and
2)
the
concentrations
of
all
the
potential
products
are
measured.
Otherwise,
the
quantity
(k,),
in
Equation
C32
may
not
actually
represent
the
maximum
possible
value
of
the
rate
constant
k,
,
and
the
related
result
in
Equation
C33
for
(Tv:)
.
is
also
questionable.
mm
Page
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C6.
Parent
Half­
Life
Estimates
Based
on
Limits
of
Quantification
and
Experimental
Precision
of
Product
Concentrations
In
certain
experiments,
some
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
0,
,
the
data
do
not
exclude
the
possibility
that
the
product
concentration
increased
from
the
initial
value
0,
­pm
to
the
value
(T,
+
p,
at
time
t
=
A
t
.
Taking
this
possibility
to
be
the
actual
case
for
the
measured
products,
the
maximum
value
of
the
quantity
(A,
­
Am,
)
is
2
0
,.
This
reasoning
suggests
that
the
following
estimate
of
the
maximum
parent
photolysis
rate
is
appropriate:

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

r
1
k,
5
(k,)­
=
­1
1
AZQ+
corn].
'0
A
BelowLOQ
Cons
tan
t
Under
these
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
T1'i
is
greater
than
the
value
(T
v
;)
.
as
follows:
mm
(for
stable
products
at
either
1)
constant
measured
concentrations
with
standard
deviation
om
or
2)
concentrations
below
the
limits
of
quantitation)

The
reader
should
note
that
Equations
C34
and
C35
are
valid
only
when
both
1)
the
products
are
photolytically
stable
and
2)
the
concentrations
of
all
the
potential
products
are
measured.

C7.
Parent
Half­
Life
Estimates
Based
on
the
Experimental
Precision
of
Parent
Concentrations
In
certain
experiments,
the
concentration
of
the
parent
remains
essentially
constant
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
k,
.
If
the
set
of
concentrations
measured
for
the
parent
have
the
mean
value
pp
and
standard
deviation
0,
,
the
data
do
not
exclude
the
possibility
that
the
product
concentration
increased
Page
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3M
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E00­
2192
from
the
initial
value
pp
­
CY,
to
the
value
pp
+CY,
at
time
t
=
A
t
.
This
reasoning
suggests
that
the
following
estimate
of
the
maximum
parent
photolysis
rate
is
appropriate:

(for
essentially
constant
parent
concentrations
with
mean
value
p,
and
standard
deviation
0,
)

Under
these
circumstances
and
assumptions,
the
experimental
data
indicate
that
the
parent
half­
life
T1'i
is
greater
than
the
value
(Ty;)
min
as
follows:

(for
essentially
constant
parent
concentrations
with
mean
value
pp
and
standard
deviation
CYp
)

References
to
Appendix
C:

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

c2
F.
Daniels,
et
al.,
"Experimental
Physical
Chemistry",
McGraw
Hill
(New
York),
p.
131
(1962).

Kinetic
Calculations
­
Indirect
Photolysis
Only
two
values
of
the
parent
concentration
were
recorded
(€
',
and
P
)
which
represent
the
values
before
and
after
the
exposure
period
of
length
At.
In
this
case,
no
least
squares
regression
is
possible
to
determine
the
rate
k,
in
Equation
C8:

k,
t
=
­In
[
g]

The
measured
values
of
for
Po
and
P
are
1427
nglml
and
1432
ng/
ml,
respectively.
Equation
C39
is
appropriate:

Page
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2192
The
observed
rate
using
At
=
69.5
hours,
&,
=
1478nglm1,
and
O,,
=
33.2
ng/
ml
is
k,
=
6.46
x
IO4
hours".

The
rate
of
photolysis
in
the
reactor
k,
is
related
to
the
actinic
rate
of
photolysis
kACT
by
kACT
=
kP(
y)

where
I,,
=
261
w/
m2
is
the
actinic
solar
intensity
(at
45"
south
latitude)
and
the
measured
reactor
intensity
is
I,
=
680
w/
m2.
This
gives
k,
=
6
.4
6
~1
0
­~
hr­
'
[
62;;
;;;:
I=
2.48~
10­
4
hr­
'

For
samples
under
constant
illumination,
the
reaction
rate
and
half­
life
are
related
by
Equation
C9:

However,
the
actinic
half­
life
is
three
times
larger,
according
the
standard
eight­
hour
exposure
day.
This
leads
to
3w
2)
k
ACT
(indirect
photolysis)
TA$!=
­
=
349
days,

Page
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~
~

Appendix
D:
Representative
Chromatograms
Chromatograms
from
the
present
study
are
included
in
this
appendix.

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#
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Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOOO2.
D
Sample
Name:
MeOH
blank
E===
E======
III=====
PEP==
I==~===========~=~=~============~~========­­­­­­

Injection
Date
:
5/
18/
00
3:
07:
45
PM
Seq.
Line
:
2
Sample
Name
:
MeOH
blank
Vial
:
99
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M.
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
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Method
:
C:\
HPCHEM\
l\
METHODS\
R0518AX.
M
Last
changed
:
7/
10/
00
9:
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20
AM
by
kej
SIM
Analysis
(ES­)
f
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PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4
~3
5
m
.
(modified
after
loading)
(Results
are
from
a
previously
saved
MSDI
263.
EIC=
2627:
263.7
(RO518LXlBlRUSHooo2.
D)
API­
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Negative
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(RO516OOB~
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D)
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Instrument
17/
10/
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9:
43:
20
AM
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,
..

.
,
.i
.

i
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#
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of
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Data
File
C:\
HPCHEM\
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DATA\
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rushOOO3.
D
Sample
Name:
1:
7
MilliQ/
MeOH
==============
3=======~­====~=­======~==­===~=====­==~====­==~======

Injection
Date
:
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3:
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02
PM
Seq.
Line
:
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Sample
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:
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MeOH
Vial
:
98
Acq.
Operator
:
kej
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:
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Last
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9:
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(ES­)
for
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PFOA
using
Dionex
IonPac
NG1
column,
4x35mm.
(modified
after
loading)

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D
4
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..........................................................
­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­===========

Injection
Date
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Seq.
Line
:
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Sample
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PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
RO518AX.
M
Last
changed
:
7/
10/
00
9:
43:
28
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)
(Results
are
from
a
previously
saved
Instrument
1
7/
10/
00
9:
43:
28
AM
kej
Page
1
of
2
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of
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TO
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Report
No.
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2192
Batch
Run
#
5
of
62
Data
File
C:\
HPCHEM\
1\
DATA\
R051800~\
rush0005.
D
Sample
Name:
00028­
37­
01
.....................................................................

Injection
Date
:
5/
18/
00
4:
02:
35
PM
Seq.
Line
:
5
Sample
Name
:
00028­
37­
01
Vial
:
2
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHoDS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
k
e
j
Analysis
Method
:
C:\
HPCHEM\~\
METHODS\
RO~~~
AX.
M
Last
changed
:
7/
10/
00
9:
43:
32
AM
by
k
e
j
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)

MSDI
363,
EICm382.7383.7
(Rffi18WB\
RUSHM)
05.
D)
API­
ES
NegalNa/

5WW
25Mx)
0
­­­­
I__.­

4
6
8
10
mil
~~~.
0
MSD1
413,
EiC1412.7:
413.7
2
1
,.
(Rffi18008\
RUSHMK15.
D)
.
I
'
API­
ES
NagaIl~
e
­
I
A
Instrument
1
7/
10/
00
9:
43:
32
AM
kej
Page
1
of
2
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123
of
148
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TO
MAIN
3M
Environmental
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Report
No.
E00­
2192
9ooo
BMX)

­
Batch
Run
#
6
of
62
Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOOO6.
D
Calibration
Std
2
­d%­.
JL­&

Z
A
h/­­

I
..""
Sample
Name:
00028­
37­
02
sow0
25wo
1__­­..­­__
5
0
­­

~~
1
0
MSD1
,b,,
413,
EIC.
412
7
413
2
7
(ROSlsoOBRUSHOW6.
D)
4
API­
ES
Negabv~
6
8
10
I
,
,p
mi
......................................................................

Injection
Date
:
5/
18/
00
4:
20:
50
PM
Seq.
Line
:
6
Sample
Name
:
00028­
37­
02
Vial
:
3
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODs\
RO518AX.
M
Last
changed
:
7/
10/
00
9:
43:
36
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)

I
MSDl
263,
EiC1262.7263.7
(RO518WE\
RUSHO~.
D)
API­
ES
Negatii
I
I
Instrument
1
7/
10/
00
9:
43:
36
AM
kej
Page
1
of
2
Page
124
of
148
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TO
MAIN
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Environmental
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Report
No.
E00­
2192
Batch
Run
#
13
of
62
Data
File
C:\
Hi?
CHEM\
1\
DATA\
R0518OOB\
rushOOl3.
D
Sample
Name:
00028­
37­
09
=I==
P=
l==========
r=
s==­=
P
IE=
P====
fl====­
P=====
PI=
I=====
EPS==============
P==

Injection
Date
:
5/
18/
00
6:
28:
34
PM
Seq.
Line
:
13
Sample
Name
:
00028­
37­
09
Vial
:
10
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518AX.
M
Last
changed
:
7/
10/
00
9:
44:
04
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4
x
3
5
~.
(modified
after
loading)

MSDl
263,
ElC=
2627:
263.7
(ROslsOOEWUSHWl3.
D)
API­
ES
Negatlvc
lmm{
8­
Calibration
Std
9
,~"~"'
I
'
'
'
,~~~I
0
2
4
6
8
10
m
MSD13W.
EIC1.352.7363.7
(R051800BWUSHW13
D)
APES
Negative
2oowo
I
"'
I
)..I
'
'
.,

0
2
4
6
8
10
m
MSDl
299,
ElC=
298.7:
299.7
(R051EWBWJSHW13.
D)
API­
ES
NegaWe
I
".I
.'

0
2
4
6
8
10
MSDl
413,
ElC=
412.7:
413.7
(ROslBWBWUSH0013.
D)
APES
Negative
Instrument
1
1/
10/
00
9:
44:
04
AM
kej
Page
1
of
2
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125
of
148
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TO
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Environmental
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Report
No.
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2192
Batch
Run
#
29
of
62
Data
File
C:\
HPCHEM\
l\
DATA\
R0518OOB\
rush0029.
D
Sample
Name:
0515­
PFOAfe­
11
===
19=
1=======
1======
E=
I==
I===~=========­===~~=====~===================~==

Injection
Date
:
5/
18/
00
11:
20:
33
PM
Seq.
Line
:
29
Sample
Name
:
0515­
PFOAfe­
11
Vial
:
21
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
19/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
RO51BAX.
M
Last
changed
:
7/
10/
00
9:
45:
05
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35mm.
(modified
after
loading)

MSDI
263.
EIC+
282.7:
283.7
(RaSl8OOEvlUSHPms.
D)
APCES
Negative
0
2
4
6
IO
mip
t
MSDl
383,
EIC=
362.7:
363.7
(RaSl8WBWUSHomS.
D)
API­
ES
Negative
10
mh
­­­
:I
3m
­­
LA/

0
2
4
6
a
MSDl
299.
EiC~
296.7299
7
(Ro518wBvlUSHoo29.0)
APCES
Negative
_.­_

6
8
10
­­­­­
,
,
,
0
2
4
MSD1
413,
ElC­
412.7'413.7
(RO518OOBvlUSHomS.
D)
API­
ES
Negative
Q
2
4
6
B
mid
Instrument
1
7/
10/
00
9:
45:
05
AM
kej
Page
1
of
2
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126
of
148
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TO
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3M
Environmental
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Report
No.
E00­
2192
I
..
.,'
..,...I
.,
.,..
2
4
6
8
10
mir
_l_

I
Batch
Run
#
30
of
62
Data
File
C:\
HPCHEM\
l\
DATA\
R051800B\
rushO03O.
D
Sample
Name:
0515­
PFOAfe­
12
========
33=====
5======­­
...............................................

Injection
Date
:
5/
18/
00
11:
38:
48
PM
Seq.
Line
:
30
Sample
Name
:
0515­
PFOAfe­
12
Vial
:
22
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODs\
RO518AX.
M
Last
changed
:
7/
10/
00
9:
45:
09
AM
by
k
e
j
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4
x
3
5
~.
(modified
after
loading)

25Mx)

175wo
~li..
0
MSD1
413,
EIC.
412.7:
413
2
I
.,
7
(RffilBWEWUSH0030
.
4
I
0)
'
I
,
API­
ES
Negative
6
1
.
'

::
i)*,
8
.
.
10
1
.
rnin
soOoo
25wo
0
­
1
125ooo
'
4
1M)
Ow
Insteument
1
71'10/
00
9:
45:
10
AM
kej
Page
1
of
2
Page
127
of
148
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TO
MAIN
3M
Environmental
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Report
No.
E00­
2192
I
"'
I
..'
I
'
.'
,~~
0
2
4
6
E
10
mlr
MSDI
413.
EICn41Z.
f:
413.7
(ROSl~
BWUSHGO31.0)
API­
ES
NeOallW
ISMKXIO
8
125wM,
1
lMxxxM
7
5
m
50oooO
250000
0
,
I
.)'
,'
..
I
,,
I
Batch
Run
#
31
of
62
Data
File
C:\
HPCHEM\
l\
DATA\
R0518OOB\
rushO03l.
D
Sample
Name:
0515­
PFOAfe­
13
............................................................................

Injection
Date
:
5/
18/
00
11:
57:
01
PM
Seq.
Line
:
31
Sample
Name
:
0515­
PFOAfe­
13
Vial
:
23
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHE!
M\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518AX.
M
Last
changed
:
7/
10/
00
9:
45:
13
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
'NG1
column,
4
x
3
5
~.
(modified
after
loading)

MSDl
263,
EIC1282.7:
203.7
(RO5laoOBvlUSHoo31.
D)
API­
ES
N
W
t
h
I
Exposed
­
72hrs
sample
Fe203
NoPcmxide
M
0
2
4
6
a
10
mln
I
"'
I
"'
I
"'

MSDl
363.
EIC=
38273363.7
(RO518MlBlRUSHW3l.
D)
API­
ES
Negative
10
min
14ooo
12m
low0
8wo
6wo
m
,...l
..,,..
'Imo
'­­­
./
f­­­
./­­­­
a­

0
2
4
6
6
MSOl
299.
EIC=
Z98.7:
299.7
(R051aoOBvlUSH0031
D)
API­
ES
Negative
Instrument
1
7/
10/
00
9:
45:
14
AM
kej
Page
1
of
2
Page
128
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
Batch
Run
#
31
of
62
Data
File
C:\
HPCHEM\
1\
DATA\
R051800B\
rush0037.
D
Sample
Name:
0515­
PFOAfe­
19
=======
S=
IPflP­===
CI*=~­========~=­==­~==~==­========~======~=~====~=

Injection
Date
:
5/
19/
00
1:
46:
30
AM
Seq.
Line
:
37
Sample
Name
:
0515­
PFOAfe­
19
Vial
:
29
Acq.
Operator
:
kej
Inj
:
1
Acq.
InstrLment
:
Rush
Inj
Volume
:
5
1.11
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516­
M
L
a
s
t
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
ROSlllAX.
M
L
a
s
t
changed
:
7/
10/
00
9:
45:
36
AM
by
kej
SIM
Ana1ysi.
s
(ES­)
f
o
r
PFOS/
PFBS/
PFOA
using
DiOneX
IonPac
NG1
column,
4
~3
5
m
.
(modified
after
loading)

I
MSDl
263,
EIC=
262.7263.7
(R05f&
3JBWUSHW37.!
3)
API­
ES
Negative
Enposed
­
72hB
Control
MilliQ
NO
Peroxide
I
0
2
4
8
10
ml
MSDl
383.
EIC­
362
7
383
7
(ROWeOO8WUSHCQ37
0)
AP1­
ES
N@
IW
12000
2w0
C
2
4
6
8
10
rn~
MSDl299.
EIC=
298
7299
7
(ROWsOa~
WUSUCU37
0)
APCES
N
e
g
a
h
25000
I
'
"
.
I
'
'
'
I
'
.
'
I
,
,
­
0
2
4
6
8
10
m
MSDl
413,
€IC~
41274137(
R~~
eOOB\
RUSHW370)
API­
ESNegak
Instrument
1
7/
10/
00
9:
45:
36
AM
kej
Page
1
of
2
Page
129
of
148
BACK
TO
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Environmental
Laboratory
Report
No.
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2192
7000
6000
Batch
Run
#
40
of
61
Data
File
C:\
HPCHEM\
1\
DATA\
RO5180OB\
rushOO91.
D
Sample
Name:
0515­
PFOAfe­
51
­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­
p===­­­­­­­­­­­­­­­­­­­====­
______­­­­­­­­­­_­_____________
­­­­­­­­_­­­­­­­
­=­­­_________
­_­­________
Injection
Date
:
5/
19/
00
6:
13:
39
PM
Seq.
Line
:
91
Sample
Name
:
0515­
PFOAfe­$
1
Vial
:
61
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518BX.
M
Last
changed
:
7/
10/
00
9:
16:
40
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)
(Results
are
from
a
previously
saved
Day
0
Blank
Fe203
No
Pemxtde
Instrument
1
7/
10/
00
9:
16:
40
AM
kej
Page
1
of
2
Page
130
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
Batch
Run
#
41
of
61
Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOO92.
D
Sample
Name:
0515­
PFOAfe­
52
=1=
1=
3==.==
1===
59~=====~========~~==*­­===~==========­===~=======~===

Injection
Date
:
5/
19/
00
6:
31:
53
PM
Seq.
Line
:
92
Sample
Name
:
0515­
PFOAfe­
52
Vial
:
62
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
pl
Acq.
Method
:
C:\
HPCHEM\
l\
METHoDS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
RO518BX.
M
Last
changed
:
7/
10/
00
9:
16:
44
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)

k
Spiked
Fez03
No
Peroxide
Instrument
1
7/
10/
00
9:
16:
44
AM
kej
Page
1
of
2
Page
131
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
12ooo
loo00
B
w
o
6003
4MM
zwo
Batch
Run
#
42
of
61
Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOO93.
D
Sample
Name:
0515­
PFOAfe­
53
­­
A+,
­­
I
I
'
.l
..,,.
4
­­­­­­
=======
iE=============
ii.
Ci=­~===~==­~=~==~=~===~====~=============­­­­­

Injection
Date
:
5/
19/
00
6:
50:
09
PM
Seq.
Line
:
93
Sample
Name
:
0515­
PFOAfe­
53
Vial
.:
63
Inj
:
1
Acq.
Operator
:
kej
Acq.
Instrument
:
Rush
Inj
Volume
:
5
p1
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOASl6.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518BX.
M
Last
changed
:
7/
10/
00
9:
16:
48
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35mm.
(modified
after
loading)

MSD1
28,
ElC=
2627263.7
(R051N10B~
lJSHW93.0)
API­
ES
Negath'e
Day
0
Sample
Fe203
NoPemxide
5Mx)

Instrument
1
7/
10/
00
9:
16:
48
AM
kej
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1
of
2
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No.
E00­
2192
b
2
4
6
ti
mi
MSDl
299,
EIC=
298.7299.7
(R0518WSWUSH0098.
D)
API­
ES
Negathw
­_

~~
1
0
2
l
'
*'
I
"'
I
.'
4
6
L
8
10
,;
mi
~~~
0
2
4
6
.
0
I
r
10
,
,
'
rniD
5
m
25000
0
­­,
,

MSD1
413,
ElC=
412.7:
413.7
(RC51800B\
RUSH~.
D)
API­
ES
Negafive
XXXXX]

2
m
0
­
Batch
Run
#
47
of
61
Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOO98.
D
Sample
Name:
0515­
PFOAfe­
58
======i
========i
l
==I
l
=====I
i
E
.=f
i
l
====3
~=­==~=======================

Injection
Date
:
5/
19/
00
8:
21:
32
PM
Seq.
Line
:
98
Sample
Name
:
0515­
PFOAfe­
58
Vial
:
68
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
p1
Acq.
Method
:
C:\
HPCHF,
M\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
RO518BX.
M
Last
changed
:
7/
10/
00
9:
16:
48
AM
by
kej
SIM
Analysis
(ES­)
f
o
r
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35m.
(modified
after
loading)

MSDl
263,
EIC.
zL62.72S3.7
(R05I@
OOBWUSHWW.
D)
API­
ES
Negative
Control
Millip
No
Peroxide
ml
Dayo
a
2
4
6
10
mi
MSDl
363,
ElC.
382.7383.7
(R051800BWUSHW98.
D)
APCES
Negative
I
Instrument
1
7/
10/
00
9:
17:
10
AM
kej
Page
1
of
2
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148
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Environmental
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No.
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'
I
Batch
Run
#
14
of
61
Data
File
C:\
HPCHEM\
1\
DATA\
RO51800B\
rush0065.
D
Sample
Name:
0515­
PFOAfe­
31
=i
==^=====I
L
==~===l
==i
l
=3
==F
==O
=C
.====E
===

Injection
Date
:
5/
19/
00
10:
17:
53
AM
Seq,
Line
:
65
Sample
Name
:
0515­
PFOAfe­
31
Vial
:
41
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Inj
Volume
:
5
p1
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518BX.
M
Last
changed
:
7/
10/
00
9:
15:
03
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35mm.
(modified
after
loading)
(Results
are
from
a
previously
saved
Instrument
1
7/
10/
00
9:
15:
03
AM
kej
Page
1
of
2
Page
134
of
148
BACK
TO
MAIN
Batch
Run
#
15
of
61
Data
File
C:\
HPCHEM\~\
DATA\
R
5
800B\
rush00
3M
Environmental
Laboratory
Report
No.
E00­
2192
6.
D
Sample
Name:
0515­
PFOAfe­
32
====
i=====
E=
3=
ii==
iEf==
l===
l=====
iS=
E===
iir===================
i=­­­­
­­­­­­
Injection
Date
:
5/
19/
00
10:
36:
09
AM
Seq.
Line
:
66
Sample
Name
:
0515­
PFOAfe­
32
Vial
:
42
Acq.
0pera:
or
:
kej
I
n
j
:
1
Acq.
Instrument
:
Rush
Acq.
Method
:
C:\
HPCHEM\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518BX.
M
Last
changed
:
7/
10/
00
9:
15:
07
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
calm,
4x35m
Inj
Volume
:
5
p
l
(modified
after
loading)

MSDl
263,
EIC=
282.7=.
7
(RO518WBRUSHCO66.
D)
API­
ES
N­
W
Unexpnscd
­
72hn
Blank
Spiked
FcZ03
No
Peroxide
0
­­
I­­
2
I
,
,
,
4
,
6
a.
8
10
MSDl
363,
ElC6627363.7
(RoS18ooEWJSH~.
D)
API­
ES
N@~
w
~"
L.
5wM)
25ooo
0
0
'
2
I
'
.
'
4
I
'
'
.
I
'
a
4
'

d;_
10
~%I
~'
0
MSDl
413,
ElC412.7413.7
'
2
I
,
(R
~l
~~\R
U
S
H
o
o
S
e
.D
)
"
4
I
'
,
APKS
NegaUvs
1
6
;
8
10
~­
0
2
4
6
8
A,,
10
I
­
MSD1
299,
ElC=
298.7:
290.7
(RWl8OOB\
RUsHOO66.
D)
APKS
N
e
~a
t
i
i
SWOD
25ooo
0
I
",I
...I
...t
,

Instrument
1
7/
10/
00
9:
15:
07
AM
kej
Page
1
of
2
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Batch
Run
#
16
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61
Data
File
C:\
HPCHEM\
1\
DATA\
R0518OOB\
rushOO67.
D
Sample
Name:
0515­
PFOAfe­
33
===========­­=..
ii~
e===
m==­
Eiil=
iD====­=*~===~=============­============~~=========

Injection
Date
:
5/
19/
00
10:
54:
22
AM
Seq.
Line
:
67
Sample
Name
:
0515­
PFOAfe­
33
Vial
:
43
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrnment
:
Rush
Acq.
Method
:
C:
\HPCHE&
l\
l\
METHODS\
PFOA516
.M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
R0518BX.
M
Last
changed
:
7/
10/
00
9:
15:
10
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4
~3
5
m
.
(modified
after
loading)
(Results
are
from
a
previously
saved
Unexposed
­
72hn
7
W
4
sample
Fez03
Noperoxide
r,

"

2
4
8
8
10
mi
t
­­.'
I
.'
.,
...,...,...,.,
0
MSDl
333,
EIC­
362.7J8.7
(RO518WBWJSHMwr.
D)
APCES
Negatlve
0
2
4
6
E
r'o
mi
MSDl
299.
EICE298.7:
299.7
(R0518M)
B\
RUSHWW.
D)
API­
ES
Negallve
­__.­­

2
4
5
8
10
mi
I
1woW
75000
5oMx)
25ooo
0
­
0
MSDl
413,
ElC42.7:
413.7
(ROSl800B\
RUSHOOW.
D)
APES
NqsUVe
0
­
,
.
.
.
I
,
.
,
,
.
.
,
.
7­­­
4
8
8
10
mil
0
2
Instrument
1
7/
10/
00
9:
15:
11
AM
kej
Page
1
of
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2192
lsMxyxl
125Mwo
SMXWX)
Batch
Run
#
21
of
61
Data
File
C:\
HPCHEM\
l\
DATA\
R0518OOB\
rush0072.
D
Sample
Name:
0515­
PFOAfe­
38
­
­
­­­­­­­­­­­­­_­­­_*===~=~~­====~=~====­­­­­­­­­­­­­­­­­
­­­­­­­­­­­­­­­­­
i____
­­­­
Injection
Date
:
5/
19/
00
12:
26:
11
PM
Seq.
Line
:
1
2
Sample
Name
:
0515­
PFOAfe­
38
Vial
:
48
'
Acq.
Operator
:
kej
Inj
:
1
Acq.
Instrument
:
Rush
Acq.
Method
:
C:\
HPCHW\
l\
METHODS\
PFOA516.
M
Last
changed
:
5/
18/
00
11:
35:
03
AM
by
kej
Analysis
Method
:
C:\
HPCHEM\
l\
METHODS\
RO518BX.
M
Last
changed
:
7/
10/
00
9:
15:
29
AM
by
kej
SIM
Analysis
(ES­)
for
PFOS/
PFBS/
PFOA
using
Dionex
IonPac
NG1
column,
4x35mm.
(modified
after
loading)
(Results
are
from
a
previously
saved
MSDl
263.
ElC=
262.7263.7
(RffilBWS\
RUSHW72.
D)
API­
ES
N@
b
0
i
4
6
a
10
mil
MSDI
363,
ElCW2.7369.7
(R0518WBWJSHW72.
D)
API­
ES
NWiIk
w.
3
0
2
4
6
6
10
rnl
MSDsDt
299,
EIC~
W.
7299.7
(ROSlBM)
B\
RUSHW72.0)
API­
ES
Negdive
2
4
6
a
fo
rn
Instrument
17/
10/
00
9:
15:
29
AM
kej
Page
1
of
2
Page
137
of
148
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TO
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Environmental
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Report
No.
E00­
2192
__~
­

Appendix
E:
Soil
Types
and
Characterizations
This
appendix
presents
the
physical
descriptions
and
chemical
characterizations
of
the
three
soils
used
in
the
present
investigation
Page
138
of
148
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No.
E00­
2192
STANDARD
LABORATORY
SQiLS
ST
cmlx
Eo,
y
s3
22000
<to
.
0.6
3000
4.5
8
36
12
20000
2mo
MK)

!j2
120
18
620
4
0
9
0
0
d9
8.14
0.68
'

297
0.03
42
28.3
0.1
1
0.04
<.?
IO
'
0.04
I'

61
2.00
84
1470
1.79
3.09
1S.
f
s.
7
5.7
0.98
22
44
34
LOAM
BDL
BO1
1.8
MOR?
COW
A
U
U
40000
<lo
4
.5
3oOo
co.
5
5
41
8.5
22wo
0.1
1
1500
84
M
14
150
4
0
4
0
0
47
?7
120
3.50
0.10
0.43
0.02
18
22.0
0.09
0.05
5
0.25
14
280
0.277
0.478
22.3
.4.8
4.5
1.1)
0.32
26
36
38
CLAY
LOAM
BDL
BDL
..
EPkSSM
4
n
o
loa
0.6
48000
'

.
86000
4.5
,

6
2J
13
18000
0.02
3OOOO
f10
92
13
7
l
O
4
0
em
47
220
.

26.1
0.18
3.58
lo0
21.3
0.20
0.05
15
1.80
6.0
2
s
O
M
0.805
0.08
,

16.0
7.7
7.5
NONE
0.68
22
26
52
SANDY
CLAY
LOAM
B
M
BDL
.­

Page
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148
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No.
E00­
2192
Appendix
F:
Light
Intensity
Measurements
at
45"
South
Latitude
(Miami
FL)

Page
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of
148
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.Environmental
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No.
E00­
2192
.I.

I
I
I
'

I
'da;,
.

CInA
:
I..
.
.
I
.

*Small
variations
are
possible,
depending
un
condition
oflamp
andfilters.

Page
141
of
148
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Environmental
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Report
No.
E00­
2192
Appendix
G:
Characteristics
of
the
Spectral
Output
of
the
Suntest
Instruments
This
appendix
contains
an
Excel
spreadsheet
of
the
characteristics
of
the
spectral
output
of
the
Suntest
Photoreactors
used
in
the
present
investigation.

Page
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No.
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2192
Suntest
Irradiance
in
W/
mA2*
nm
Assuming
the
use
of
300­
800nm
Global
Sensor
Only
Filters
Used
Wavelength
nm
250
252
254
256
258
260
262
264
266
268
270
272
274
276
278
280
282
284
286
288
290
292
294
296
298
300
302
304
306
308
31
0
312
314
31
6
31
8
320
322
324
326
328
IR
QlSuprax
(UV)
0.001
0
0
0
0.001
0
0
0
0
0
0
0
0
0
0
0
0
0
0.003
0.005
0.009
0.014
0.021
0.028
0.045
0.054
0.07
0.085
0.116
0.138
0.151
0.175
0.21
0.24
0.263
0.279
0.329
0.352
0.369
0.4
Irradiances
factored
to
yield
680
W/
mA2
in
300­
800nm
band
IR
QlSuDrax
IUV)
0.001
119
0
0
0
0.001
1
I
9
0
0
0
0
0
0
0
0
0
0
0
0
0
0.003357
0.005595
0.01
0071
0.01
5666
0.023499
0.031332
0.050355
0.060426
0.07833
0.0951
15
0.129804
0.154422
0.168969
0.195825
0.23499
0.26856
0.294297
0.312201
0.368151
0.393888
0.412911
0.4476
Page
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No.
E00­
2192
330
332
334
336
338
340
342
344
346
348
350
352
354
356
358
360
362
364
366
368
370
372
374
376
378
380
382
384
386
388
390
392
394
396
398
400
402
404
406
408
41
0
412
414
416
418
420
422
424
426
428
0.431
0.449
0.475
0.495
0.525
0.549
0.565
0.566
0.587
0.614
0.61
0.635
0.656
0.685
0.662
0.675
0.719
0.714
0.73
0.813
0.858
0.767
0.8
0.827
0.864
0.962
0.992
0.974
0.996
1.028
1.111
1.126
1.227
1.642
I
.552
1.243
1.228
1.241
I
.284
1.473
1.395
1.551
1.41
6
1.369
I
.426
1.644
1.453
I
.472
I
.462
1.466
0.482289
0.502431
0.531525
0.553905
0.587475
0.614331
0.632235
0.633354
0.656853
0.687066
0.68259
0.710565
0.734064
0.76651
5
0.740778
0.755325
0.804561
0.798966
0.81687
0.909747
0.9601
02
0.858273
0.8952
0.925413
0.966816
1.076478
1
.I
10048
I
.089906
1
.I
14524
I.
150332
1.243209
1.259994
1.373013
1.837398
1.736688
1.390917
1.374132
1.388679
1.436796
1.648287
1.561
005
1.735569
1.584504
1.53191
1
1.595694
1.839636
1.625907
1.647
1
68
1.635978
I
.640454
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144
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148
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MAIN
430
432
434
436
438
440
442
444
446
448
450
452
454
456
458
460
462
464
466
468
470
472
474
476
478
480
482
484
486
488
490
492
494
496
498
500
502
504
506
508
51
0
51
2
51
4
51
6
51
8
520
522
524
526
528
1.466
1.487
1.5
1.566
1.714
1.616
1.616
1.57
1.563
1.573
2.267
2.031
1.796
1.81
1
2.127
1.835
3.267
2.476
2.541
5.277
2.487
1.922
2.924
1.837
1.813
2.289
2.516
2.651
1.952
1.842
1.898
3.012
2.089
1.871
1.888
1.898
I
.973
2.005
1.94
1.927
1.934
I
.963
2.013
2.031
2.021
I
.995
1.971
1.98
1.966
1.978
3M
Environmental
Laboratory
Report
No.
E00­
2192
1.640454
1.663953
I
I
.6785
1.752354
1.91
7966
1.808304
1.808304
1.75683
1.748997
1.7601
87
2.536773
2.272689
2.009724
2.026509
2.3801
13
2.053365
3.655773
2.770644
2.843379
5.904963
2.782953
2.1
50718
3.271
956
2.055603
2.028747
2.561391
2.8
I
5404
2.966469
2.184288
2.061
198
2.123862
3.370428
2.337591
2.093649
2.1
12672
2.123862
2.207787
2.243595
2.1
7086
2.1
56313
2.1
641
46
2.196597
2.252547
2.272689
2.261499
2.232405
2.205549
2.21562
2.199954
2.2
1
3382
Page
145
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
530
532
534
536
538
540
542
544
546
548
550
552
554
556
558
560
562
564
566
568
570
572
574
576
578
580
582
584
586
588
590
592
594
596
598
600
602
604
606
608
610
612
614
616
61
8
620
622
624
626
628
I
.954
I
.932
1.942
2.008
2.014
2.113
1.996
1.977
1.962
1.921
1.876
1.84
1.938
2.17
2.106
1.936
1.912
1.749
1.706
1.77
1.997
2.032
1.802
1.624
1.572
1.654
2.215
2.034
1.738
2.118
2.159
1.996
2.185
1.607
1.492
1.471
I
.37
1.263
1.207
1.184
1.292
1.494
1.31
1.631
2.672
2.172
1.416
1.181
1.256
1.251
2.186526
2.161908
2.173098
2.246952
2.253666
2.364447
2.233524
2.21
2263
2.195478
2.149599
2.099244
2.05896
2.168622
2.42823
2.35661
4
2.166384
2.139528
1.9571
31
1
.go9014
1.98063
2.234643
2.273808
2.016438
1.81
7256
1.759068
1.850826
2.478585
2.276046
I
.944822
2.370042
2.415921
2.233524
2.44501
5
I
.798233
1.669548
1.646049
1.53303
I
.413297
1.350633
1.324896
1.445748
1.671786
1.46589
1.825089
2.989968
2.430468
I
.584504
1.321539
1.405464
1.399869
Page
146
of
148
BACK
TO
MAIN
3M
Environmental
Laboratory
Report
No.
E00­
2192
630
632
634
636
638
640
642
644
646
648
650
652
654
656
658
660
662
664
666
668
670
672
674
676
678
680
682
684
686
688
690
692
694
696
698
700
702
704
706
708
710
712
714
71
6
720
722
724
726
728
718
1.51
2.325
1.246
0.959
0.927
0.834
0.856
0.876
1.013
1.571
1.431
1.12
1.071
0.86
0.801
1.103
0.763
0.762
0.855
1.037
0.575
0.682
0.91
2
0.526
0.567
0.514
0.738
1.065
1.214
2.331
1.16
0.73
0.603
0.432
0.688
0.347
0.327
0.298
0.31
0.275
0.424
2.069
0.594
0.302
0.289
0.254
0.297
0.384
0.592
0.817
I
.68969
2.601675
1.394274
1.073121
1.037313
0.933246
0.957864
0.980244
I
.I
33547
1.757949
1.601
289
1.25328
1.
I
98449
0.96234
0.89631
9
1.234257
0.853797
0.852678
0.956745
I.
160403
0.643425
0.763158
1.020528
0.588594
0.634473
0.575166
0.825822
1
.I
91
735
1.358466
2.608389
1.29804
0.81687
0.674757
0.483408
0.769872
0.388293
0.365913
0.333462
0.34689
0.307725
0.474456
2.31521
1
0.664686
0.337938
0.323391
0.284226
0.332343
0.429696
0.662448
0.9
14223
Page
147
of
148
BACK
TO
MAIN
730
732
734
736
738
740
742
744
746
748
750
752
754
756
758
760
762
764
766
768
770
772
774
776
778
780
782
784
786
788
790
792
794
796
798
800
0.593
0.634
0.472
0.316
0.375
1.097
0.368
0.272
0.264
0.439
0.356
0.231
0.273
0.406
0.823
1.344
0.554
1.555
1.114
0.388
0.194
0.152
0.188
0.21
0.247
0.388
0.327
0.225
0.171
0.335
0.693
0.137
0.18
0.326
0.632
0.233
Total
Integrated
irradiance
in
300­
800nm
Wavelength
Band
607.6
W/
mA2
680.0
W/
mA2
3M
Environmental
Laboratory
Report
No.
E00­
2192
0.663567
0.709446
0.5281
68
0.353604
0.419625
I
.227543
0.41
1792
0.304368
0.295416
0.491241
0.398364
0.258489
0.305487
0.454314
0.920937
1.503936
0.619926
1.740045
1.246566
0.434172
0.21
7086
0.170088
0.210372
0.23499
0.276393
0.4341
72
0.365913
0.251
775
0.191
349
0.374865
0.775467
0.153303
0.20142
0.364794
0.707208
0.260727
Page
148
of
148
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