Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
U.
S.
Environmental
Protection
Agency
Office
of
Water
Office
of
Science
and
Technology
Engineering
and
Analysis
Division
Washington,
DC
20460
December
2000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
Acknowledgments
This
report
was
prepared
under
the
direction
of
William
A.
Telliard
and
Maria
Gomez­
Taylor
of
the
Engineering
and
Analysis
Division
within
the
U.
S.
Environmental
Protection
Agency's
(
EPA)
Office
of
Water.
The
report
was
prepared
by
DynCorp
I&
ET
with
assistance
from
Interface,
Inc.
and
Russell
Roegner.
EPA
also
acknowledges
the
efforts
of
the
referee
laboratory,
participant
laboratories,
and
especially
the
volunteer
laboratories
for
their
participation
in
the
Interlaboratory
Validation
Study.

Disclaimer
This
report
has
been
reviewed
by
the
Analytical
Methods
Staff
in
the
Engineering
and
Analysis
Division
within
the
U.
S.
EPA's
Office
of
Water.
Mention
of
company
names,
trade
names,
or
commercial
products
does
not
constitute
endorsement
or
recommendation
for
use.

Questions
or
comments
regarding
this
report
should
be
addressed
to:

Maria
Gomez­
Taylor
Analytical
Methods
Staff
(
4303)
Office
of
Science
and
Technology
U.
S.
Environmental
Protection
Agency
Ariel
Rios
Building
1200
Pennsylvania
Avenue,
N.
W.
Washington,
DC
20460
202­
260­
1639
Requests
for
additional
copies
should
be
directed
to:

USEPA
NSCEP
11029
Kenwood
Road
Cincinnati,
OH
45242
800­
490­
9198
http://
www.
epa.
gov/
ncepi
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
i
Draft
­
December
2000
TABLE
OF
CONTENTS
Acknowledgments
List
of
Tables
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iii
Executive
Summary
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v
Section
1
Background
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1
Section
2
Study
Design
and
Objectives
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1
2.1
Phase
1
­
Laboratory
Qualification
(
MDL
and
Blank
Analyses)
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1
2.2
Phase
2
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Sample
Collection,
Preparation,
and
Distribution
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2
2.3
Phase
3
­
Blind
Sample
and
QC
Sample
Analyses
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6
Section
3
Study
Management
and
Implementation
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6
Section
4
Data
Reporting
and
Validation
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10
4.1
Phase
1
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11
4.2
Phase
2
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11
4.3
Phase
3
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11
4.3.1
Calibration
Verification
Samples
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12
4.3.2
Initial
Precision
and
Recovery
Samples
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12
4.3.3
Ongoing
Precision
and
Recovery
Samples
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12
4.3.4
Blanks
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12
4.3.5
Matrix
Spike
and
Matrix
Spike
Duplicate
Samples
.
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13
4.3.6
Calibration
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13
4.3.7
Standard
Reference
Material
Analyses
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14
4.3.8
Additional
Deviations
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14
Section
5
Results
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15
5.1
Phase
1
Results
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16
5.2
Phase
2
Results
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20
5.2.1
Background
Concentrations
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20
5.2.2
Stability
Analyses
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20
5.3
Phase
3
Results
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21
5.3.1
Outlier
Screening
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21
5.3.2
Calibration
Linearity
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22
5.3.3
Calibration
Verification
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26
5.3.4
Initial
and
Ongoing
Precision
and
Recovery
(
IPR/
OPR)
.
.
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29
5.3.5
Matrix
Spike
and
Matrix
Spike
Duplicate
Analyses
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31
5.3.6
Method
Blank
Analyses
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36
5.3.7
Calibration
Blank
Analyses
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37
5.3.8
Standard
Reference
Material
Analyses
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38
5.3.9
Quality
Control
Samples
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41
5.4
Silver
Recoveries
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41
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
ii
Section
6
Development
of
QC
Acceptance
Criteria
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43
6.1
Method
Detection
Limit
(
MDL)
and
Minimum
Level
(
ML)
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43
6.2
Calibration
Linearity
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44
6.3
Calibration
Verification
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44
6.4
Initial
and
Ongoing
Precision
and
Recovery
(
IPR/
OPR)
.
.
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.
.
.
45
6.5
Matrix
Spike/
Matrix
Spike
Duplicate
(
MS/
MSD)
Recovery
and
Relative
Percent
Difference
(
RPD)
.
.
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47
Section
7
Data
Analysis
and
Discussion
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49
7.1
Matrix­
Specific
Performance
of
Method
1638
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49
7.2
Overall
Performance
of
Method
1638
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50
Section
8
Conclusion
and
Discussion
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57
Appendix
A
Study
Plan
for
Collaborative
Validation
of
Trace
Metals
Methods
1631,
1632,
1636,
1638,
1639,
and
1640
Appendix
B
Data
Submitted
in
the
Interlaboratory
Method
1638
Validation
Study
Appendix
C
Statistical
Methods
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
iii
Draft
­
December
2000
LIST
OF
TABLES
Table
2­
1:
Validation
Study
Samples
Sent
to
Participating
Laboratories
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3
Table
3­
1:
Laboratories
Participating
in
the
Method
1638
Validation
Study
.
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7
Table
4­
1:
Number
and
Type
of
Phase
3
Samples
Analyzed
by
Participating
Laboratories
.
.
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.
10
Table
5­
1:
Phase
1,
MDL
and
Method
Blank
Results
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17
Table
5­
2:
Youden
Outlier
Laboratories
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21
Table
5­
3.
Percentage
of
Sample
Results
Rejected
as
Grubbs
Outliers
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22
Table
5­
4.
Laboratory
3
Calibration
Results
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23
Table
5­
5.
Weighted
Linear
Regression
Results
.
.
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24
Table
5­
6.
Percent
Recoveries
for
Calibration
Verification
Samples
.
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26
Table
5­
7.
Precision
and
Recovery
Samples
.
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.
29
Table
5­
8.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Laboratories
.
.
.
.
.
.
31
Table
5­
9.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Matrices
.
.
.
.
.
.
.
.
.
33
Table
5­
10.
Method
Blank
Results
.
.
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.
37
Table
5­
11.
Calibration
Blank
Results
.
.
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38
Table
5­
12.
SRM
Sample
Results
.
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39
Table
5­
13.
Quality
Control
Sample
Results
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.
41
Table
5­
14.
Recovery
of
Silver
in
QC
and
Field
Samples
.
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.
42
Table
6­
1.
Revised
MDLs
and
MLs
.
.
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.
44
Table
6­
2.
Calibration
Verification
Acceptance
Criteria
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.
44
Table
6­
3.
IPR
Acceptance
Criteria
.
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.
46
Table
6­
4.
OPR
Verification
Acceptance
Criteria
.
.
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.
46
Table
6­
5.
MS/
MSD
Acceptance
Criteria
.
.
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.
47
Table
7­
1.
Pooled
Matrix
Specific
Precision
and
Recovery
.
.
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.
49
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
.
.
.
.
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.
.
.
.
52
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
iv
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
v
Draft
­
December
2000
Executive
Summary
This
report
presents
results
of
EPA's
interlaboratory
validation
study
of
draft
Method
1638
Determination
of
Trace
Elements
in
Ambient
Waters
by
Inductively
Coupled
Plasma­
Mass
Spectrometry
(
EPA
821­
R­
96­
005,
January
1996;
the
"
Method").

The
objectives
of
the
study
were
to
evaluate
the
performance
of
the
method
and
to
gather
data
to
allow
revision
of
detection
and
quantitation
limits
and
the
quality
control
(
QC)
acceptance
criteria
(
performance
specifications).

The
study
was
conducted
in
1999
and
managed
by
the
Analytical
Methods
Staff
in
EPA's
Office
of
Science
and
Technology.
Day­
to­
day
operations
during
the
study
were
managed
by
the
EPA
Sample
Control
Center
(
SCC),
operated
by
DynCorp
under
contract
to
EPA.

A
referee
laboratory
prepared
the
Study
samples
and
shipped
the
samples
to
the
laboratories.
Eight
laboratories
participated.
A
total
of
40,
16,
and
32
samples
were
analyzed
from
reagent
water,
wastewater,
and
ambient
water
matrices,
respectively.
Results
were
transmitted
to
SCC
where
they
were
verified
and
entered
into
a
database
for
statistical
analysis.
The
statistical
analysis
yielded
statements
of
Method
performance
and
revised
method
detection
limits
(
MDLs),
minimum
levels
of
quantitation
(
MLs)
and
QC
acceptance
criteria.

Study
results
demonstrated
that
Method
1638
produces
reliable
results
by
ICP­
MS
and
largely
supported
the
performance
specifications
given
in
the
draft
method.
The
study
also
provided
information
regarding
areas
of
the
method
that
can
be
further
clarified
to
ensure
that
all
laboratories
interpret
requirements
in
the
same
way
and
suggested
the
need
for
a
separate
study
of
silver
stability.

EPA
plans
to
revise
Method
1638
to
reflect
the
results
of
this
study
and
to
propose
the
revised
method
for
use
at
40
CFR
part
136.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
1Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1631,
March
1998.
Available
from
the
EPA
Sample
Control
Center,
6101
Stevenson
Ave.,
Alexandria,
VA
22304;
703/
461­
2100.

2Guidelines
for
Selection
and
Validation
of
U.
S.
EPA's
Measurement
Methods,
U.
S.
EPA
Office
of
Acid
Deposition,
Environmental
Monitoring
and
Quality
Assurance
(
OADEMQA),
Office
of
Research
and
Development,
U.
S.
EPA,
August
1987,
DRAFT.

3Standard
Practice
for
Determination
of
Precision
and
Bias
of
Applicable
Test
Methods
of
Committee
D­
19
on
Water
(
ASTM
D2777­
96),
September
1996.

4"
Guidelines
for
Collaborative
Study
Procedure
to
Validate
Characteristics
of
a
Method
of
Analysis,"
J.
Assoc.
Off.
Anal.
Chem.
72,
694­
704,
1989.

Draft
­
December
2000
1
Section
1
Background
This
report
presents
the
design,
results,
and
conclusions
of
an
interlaboratory
validation
study
of
EPA
Method
1638:
The
Method
was
developed
in
1995
by
EPA's
Office
of
Water
to
address
stakeholder
needs
for
measuring
metals
at
the
concentrations
specified
in
EPA
and
State
water
quality
criteria.

The
Office
of
Water
(
OW)
initiated
the
interlaboratory
validation
study
in
1997
as
part
of
a
larger
effort
to
validate
all
seven
of
the
EPA
1600­
series
trace
metals
draft
methods
for
application
to
aqueous
matrices.
Each
of
the
methods
had
been
widely
distributed
for
review
and
comment,
tested
in
several
single­
laboratory
studies,
and
revised
accordingly.

To
accommodate
stakeholder
interests,
and
to
expand
the
scope
of
the
study,
the
Electric
Power
Research
Institute
(
EPRI)
funded
the
distribution
of
additional
samples
to
study
laboratories.
EPA
also
prioritized
its
validation
efforts
to
reflect
the
most
pressing
needs
of
the
stakeholder
community.
Results
of
the
Method
1631
study
already
have
been
reported
(
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1631,
March
1998),
and
results
of
the
remaining
studies
will
be
reported
as
the
studies
are
completed.
1
The
remainder
of
this
report
focuses
on
the
design,
implementation,
and
results
of
the
Method
1638
Interlaboratory
Study
(
the
"
Study").

Section
2
Study
Design
and
Objectives
The
primary
objectives
of
the
study
were
to
1)
characterize
the
performance
of
Method
1638
and
2)
evaluate
and,
if
appropriate,
revise
the
quality
control
(
QC)
acceptance
criteria
based
on
study
results.
The
study
was
designed
in
accordance
with
interlaboratory
validation
study
procedures
published
by
EPA,
2
ASTM,
3
and
AOAC­
International.
4
Details
of
the
study
design
are
summarized
in
Sections
2.1
through
2.3
below.
Additional
details
can
be
found
in
the
Study
Plan
for
Collaborative
Validation
of
Trace
Metals
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640,
February
1997
(
the
"
Study
Plan")
provided
as
Appendix
A
to
this
report.

The
study
was
conducted
in
three
phases:
(
1)
Laboratory
Qualification,
(
2)
Sample
Collection,
Preparation,
and
Distribution,
and
(
3)
Blind
Sample
and
QC
Sample
Analyses.

2.1
Phase
1
­
Laboratory
Qualification
(
MDL
and
Blank
Analyses)

The
objective
of
Phase
1
was
to
identify
a
minimum
of
nine
laboratories
capable
of
analyzing
aqueous
samples
using
Method
1638.
This
number
was
selected
as
a
conservative
figure
likely
to
yield
at
least
six
sets
of
useable
data
after
all
outlier
and
data
quality
analyses
had
been
completed.
It
was
not
considered
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
2
necessary
for
each
laboratory
to
have
extensive
experience
with
the
method;
rather,
laboratories
were
to
have
experience
representative
of
the
federal,
state,
local,
and
private
laboratories
that
ultimately
would
use
Method
1638
to
measure
antimony,
cadmium,
copper,
lead,
nickel,
selenium,
silver,
thallium,
and
zinc
(
the
"
target
analytes")
under
the
Clean
Water
Act
and
other
environmental
programs.
EPA
identified
eleven
laboratories
that
met
these
criteria.
To
assure
that
these
laboratories
were
capable
of
performing
the
method,
laboratories
were
provided
up
to
30
days
to
review
Method
1638
and
to
perform
method
detection
limit
(
MDL)
studies
and
blank
analyses
for
the
target
analytes.
Laboratories
interested
in
participating
on
a
volunteer
basis
were
encouraged
but
not
required
to
submit
MDL
study
data.

MDL
studies
were
performed
according
to
the
requirements
given
at
40
CFR
136,
Appendix
B,
Definition
and
Procedure
for
the
Determination
of
the
Method
Detection
Limit,
Revision
1.11.
Reagent
water
was
chosen
as
the
reference
matrix
because
it
is
homogeneous,
readily
available,
and
included
as
an
option
in
the
EPA
MDL
procedure.
In
accordance
with
these
requirements,
10
of
the
11
laboratories
prepared
and
analyzed
a
minimum
of
7
replicate
samples
containing
each
of
the
target
analytes.
Based
on
the
MDL
determinations,
eight
laboratories
were
identified
to
participate
in
Phase
3.
Efforts
to
identify
a
ninth
laboratory
were
determined
to
be
unnecessary
given
the
study
schedule
and
costs.

2.2
Phase
2
­
Sample
Collection,
Preparation,
and
Distribution
The
study
design
included
the
use
of
a
referee
laboratory
to
collect,
prepare
and
distribute
samples
to
each
of
the
participating
laboratories.
The
primary
objectives
in
using
a
referee
laboratory
were
to
1)
collect,
prepare,
and
distribute
freshwater,
effluent,
and
reagent
water
samples
that
contained
the
target
analytes
of
interest
at
the
desired
concentration
levels,
and
2)
minimize
variability
within
each
of
the
sample
matrices
distributed
to
the
participant
laboratories.

In
implementing
Phase
2,
the
referee
laboratory
was
directed
to
perform
all
sample
collection,
preparation,
and
distribution
activities
in
accordance
with
sample
handling
and
analysis
procedures
outlined
in
Method
1669:
Sampling
Ambient
Water
for
Trace
Metals
at
EPA
Water
Quality
Criteria
Levels
(
EPA
821­
R­
96­
008,
July
1996)
and
Method
1638.
The
referee
laboratory
also
was
instructed
to
collect
a
sufficient
volume
of
each
sample
to
allow
for
1)
distribution
of
the
various
water
samples
to
each
of
the
eight
participating
laboratories,
2)
stability
analyses
by
the
referee
laboratory,
3)
analysis
of
matrix
spike
(
MS)
and
matrix
spike
duplicate
(
MSD)
samples
by
each
of
the
eight
laboratories,
and
4)
extra
volume
in
case
of
sample
breakage,
lost
shipments,
or
other
unforeseen
problems.

After
collecting
bulk
sample
volumes
from
freshwater
and
effluent
sources,
the
referee
laboratory
thoroughly
homogenized
each
sample
matrix
before
dividing
it
into
sample
aliquots
for
background
determination
and
spiking
under
controlled
clean
room
conditions.
Background
concentrations
of
each
target
analyte
in
filtered
freshwater,
and
filtered
and
unfiltered
effluent
were
determined
by
the
referee
laboratory.
Background
concentrations
of
the
target
analytes
in
reagent
water
were
assumed
to
be
zero.
Spiking
levels
of
each
analyte
in
each
matrix
were
determined
according
to
background
levels,
the
analytical
range
of
the
method,
and
water
quality
criteria.

The
study
was
designed
so
that
each
participating
laboratory
would
analyze
sample
pairs
of
each
matrix
of
interest
at
concentrations
that
would
span
the
analytical
range
of
the
method.
Accordingly,
the
referee
laboratory
prepared
a
total
of
11
sets
of
sample
pairs
for
each
participating
laboratory
in
accordance
with
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
5Youden,
W.
J.
and
E.
H.
Steiner,
1975.
Statistical
Manual
of
the
Association
of
Official
Analytical
Chemists,
AOAC,
1111
North
19th
Street,
Suite
210,
Arlington,
VA
22209.

Draft
­
December
2000
3
ASTM
procedures
and
Youden
guidelines.
5
Samples
were
prepared
as
either
duplicates
or
Youden
pairs
and
distributed
to
the
participating
laboratories
as
blind
samples
(
e.
g.,
the
laboratories
did
not
know
the
matrix
or
concentration
of
the
analytes).
The
matrices
and
concentrations
of
each
of
the
11
sample
pairs
distributed
to
the
participating
laboratories
are
shown
in
Table
2­
1.

The
referee
laboratory
shipped
11
sample
pairs
(
22
samples
total)
to
each
of
8
participating
laboratories,
for
a
total
of
176
blind
samples.
The
participating
laboratories
also
were
provided
instructions
concerning
sample
handling,
analysis,
and
data
reporting.
To
measure
the
recovery
and
precision
of
the
analytical
system,
and
to
monitor
matrix
interferences,
the
laboratories
were
instructed
to
analyze
matrix
spike
and
matrix
spike
duplicate
(
MS/
MSD)
samples
on
specified
field
samples
in
each
filtered
and
unfiltered
matrix.

Table
2­
1:
Validation
Study
Samples
Sent
to
Participating
Laboratories
Analyte
Matrix
Background
Concentration
(
µ
g/
L)
Expected
Concentration
(
µ
g/
L)
Total
Pairs/
Lab
Total
Pairs/
Matrix
Sb
Filtered
Freshwater
0.1241
0.1241
0.2041/
0.2441
0.4041/
0.5041
0.8041/
1.0041
4
32
Filtered
Effluent
0.9661
1.0000
1
8
Unfiltered
Effluent
0.4066
10.0000
1
8
Reagent
Water
0.0000
0
0.1000/
0.1200
1.000
5.000
20.000
5
40
Cd
Filtered
Freshwater
0.0000
0
0.0400/
0.0500
0.1200/
0.1400
0.2500
4
32
Filtered
Effluent
0.1080
0.3000
1
8
Unfiltered
Effluent
0.1250
0.5000
1
8
Reagent
Water
0.0000
0
0.0500/
0.0600
0.1000
1.0000
10.0000
5
40
Cu
Filtered
Freshwater
1.0300
1.0300
1.5300/
1.7300
2.5300/
3.0300
4.5300/
5.0300
4
32
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
2­
1:
Validation
Study
Samples
Sent
to
Participating
Laboratories
Analyte
Matrix
Background
Concentration
(
µ
g/
L)
Expected
Concentration
(
µ
g/
L)
Total
Pairs/
Lab
Total
Pairs/
Matrix
Draft
­
December
2000
4
Filtered
Effluent
13.8000
13.8000
1
8
Unfiltered
Effluent
15.1000
15.1000
1
8
Reagent
Water
0.0000
0
0.2000/
0.2400
0.5000
2.0000
20.0000
5
40
Pb
Filtered
Freshwater
0.0128
0.0128
0.0528/
0.0628
0.2000
0.3128/
0.3628
4
32
Filtered
Effluent
0.4585
0.5000
1
8
Unfiltered
Effluent
1.0557
1.0557
1
8
Reagent
Water
0.0000
0
0.0300/
0.03600
0.1000
0.5000
5.0000
5
40
Ni
Filtered
Freshwater
0.3100
0.3100
1.6100/
1.8100
3.3100/
4.0100
6.0000
4
32
Filtered
Effluent
2.6000
7.0000
1
8
Unfiltered
Effluent
2.7100
8.0000
1
8
Reagent
Water
0.0000
0
0.5000/
0.6000
1.0000
10.0000
100.0000
5
40
Se
Filtered
Freshwater
0.3810
0.3810
0.9810/
1.1810
1.9810/
2.3810
4.0000
4
32
Filtered
Effluent
0.3277
5.0000
1
8
Unfiltered
Effluent
0.3440
6.0000
1
8
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
2­
1:
Validation
Study
Samples
Sent
to
Participating
Laboratories
Analyte
Matrix
Background
Concentration
(
µ
g/
L)
Expected
Concentration
(
µ
g/
L)
Total
Pairs/
Lab
Total
Pairs/
Matrix
Draft
­
December
2000
5
Reagent
Water
0.0000
0
1.0000/
1.2000
5.0000
20.0000
100.0000
5
40
Ag
Filtered
Freshwater
0.0000
0
0.0700/
0.0800
0.2000
0.3000/
0.3600
4
32
Filtered
Effluent
0.4780
0.4780
1
8
Unfiltered
Effluent
2.8800
2.8800
1
8
Reagent
Water
0.0000
0
0.2000/
0.2400
0.1000
1.0000
10.0000
5
40
Tl
Filtered
Freshwater
0.0010
0.0010
0.0210/
0.0240
0.0600
0.1010/
0.1210
4
32
Filtered
Effluent
0.0020
0.2000
1
8
Unfiltered
Effluent
0.0020
0.9000
1
8
Reagent
Water
0.0000
0
0.0400/
0.0500
0.1000
0.5000
2.0000
5
40
Zn
Filtered
Freshwater
0.9743
0.9743
1.1043/
1.3043
1.5000
1.7943/
2.1943
4
32
Filtered
Effluent
43.8250
43.8250
1
8
Unfiltered
Effluent
48.0100
48.0100
1
8
Reagent
Water
0.0000
0
2.0000/
2.4000
0.5000
5.0000
50.0000
5
40
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
6The
Sample
Control
Center
(
SCC)
is
operated
by
DynCorp
under
EPA
Contract
No.
68­
C­
98­
139.
All
SCC
activities
were
performed
under
the
direction
and
guidance
of
the
EPA
Analytical
Methods
Staff.

Draft
­
December
2000
6
To
demonstrate
the
stability
of
samples
throughout
the
study,
the
referee
laboratory
randomly
selected
and
analyzed
aliquots
of
each
matrix
type.
Initial
stability
analyses
were
performed
when
samples
were
shipped
to
the
participating
laboratories
and
final
stability
analyses
were
performed
30
­
35
days
following
sample
shipment.
Results
of
the
stability
analyses
were
submitted
to
the
Sample
Control
Center
(
SCC)
for
assessment
of
instability
or
possible
contamination.
6
2.3
Phase
3
­
Blind
Sample
and
QC
Sample
Analyses
The
objective
of
Phase
3
was
to
evaluate
the
performance
of
Method
1638
in
multiple
laboratories.
A
secondary
objective
was
to
evaluate
and,
if
appropriate,
revise
the
QC
acceptance
criteria
in
the
draft
method.

Because
the
study
was
used
to
evaluate
method
performance
under
routine
laboratory
conditions,
laboratories
participating
in
Phase
3
were
prohibited
from
performing
multiple
analyses
to
improve
results.
Laboratories,
however,
were
permitted
to
implement
corrective
action
and
reanalyses
for
QC
failures
attributable
to
analyst
error
or
to
instrument
failure.

Laboratories
participating
in
Phase
3
were
required
to
analyze
each
of
the
22
blind
samples
sent
by
the
referee
laboratory
under
Phase
2.
The
laboratories
also
were
required
to
perform
all
required
Method
1638
QC
analyses,
including
initial
precision
and
recovery
(
IPR),
ongoing
precision
and
recovery
(
OPR),
method
blanks,
calibration
blanks,
and
matrix
spike/
matrix
spike
duplicate
(
MS/
MSD)
pairs.

Each
laboratory
was
required
to
prepare
and
analyze
one
MS
and
one
MSD
sample
for
filtered
freshwater,
filtered
effluent,
and
unfiltered
effluent
for
a
total
of
three
MS/
MSD
sample
pairs.
Samples
to
be
used
for
MS/
MSD
analyses
were
identified
by
the
referee
laboratory
on
the
sample
bottles
and
sample
tracking
documents.
Participating
laboratories
were
instructed
to
spike
aliquots
of
indicated
MS/
MSD
samples
at
1­
5
times
the
background
concentration
of
the
analytes
determined
by
analysis
of
an
unspiked
aliquot
of
the
sample.

Laboratories
were
required
to
submit
sample
results,
raw
data,
run
chronologies,
chromatograms,
example
equations,
and
narrative
discussions
to
EPA
for
review
and
validation.

Section
3
Study
Management
and
Implementation
The
Study
was
designed
and
managed
by
EPA
Office
of
Water's
Analytical
Methods
Staff
(
AMS),
with
participation
by
the
Electric
Power
Research
Institute
(
EPRI).
Day­
to­
day
coordination
of
activities
was
performed
by
SCC.
Phase
1
activities
associated
with
determination
of
the
MDL
were
performed
by
10
laboratories.
Phase
2
activities
associated
with
collection,
background
determination,
stability
analyses,
preparation,
and
distribution
of
samples
were
performed
by
Frontier
Geosciences,
Inc.
(
the
referee
laboratory)
operating
under
direction
and
guidance
from
SCC
and
EPRI.
Phase
3
activities
associated
with
analysis
of
blind
sample
pairs
and
associated
QC
samples
were
performed
by
eight
participant
laboratories
operating
either
on
a
voluntary
basis
or
under
contract
to
EPA.
The
referee
laboratory
and
eight
participant
laboratories
are
listed
in
Table
3­
1.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
7
Table
3­
1:
Laboratories
Participating
in
the
Method
1638
Validation
Study
Battelle
Marine
Sciences
Laboratory
1529
West
Sequim
Bay
Road
Sequim,
WA
98382
360­
681­
3650
Commonwealth
of
Virginia
Bureau
of
Analytical
Services
Division
of
Consolidated
Lab
Services
1
North
14th
Street
Richmond,
VA
23219
804­
786­
7755
USEPA
Region
10
Manchester
Laboratory
7411
Beach
Drive
Port
Orchard,
WA
98366
360­
871­
8706
Hampton
Roads
Sanitation
District
1432
Air
Rail
Avenue
Virginia
Beach,
VA
23455
757­
460­
4203
University
of
Iowa
State
Hygienic
Laboratory
H.
A.
Wallace
Building
900
East
Grand
Avenue
Des
Moines,
IA
50319
515­
281­
5371
Southwest
Research
Institute
6220
Culebra
Road
San
Antonio,
TX
78238­
5166
210­
522­
5428
University
of
Notre
Dame
Department
of
Civil
Engineering
&
Geology
106
Cushing
Notre
Dame,
IN
46556
219­
631­
9049
Texas
A&
M
Department
of
Oceanography
100
Bizzell
Eller
Bldg.,
Room
403
College
Station,
TX
77843­
3146
409­
845­
5137
Frontier
Geosciences,
Inc.
(
referee
lab)
414
Pontius
North
Seattle,
WA
98109
206­
622­
6960
Note:
The
primary
purpose
of
this
study
was
to
evaluate
the
performance
of
Method
1638.
While
the
data
submitted
by
these
laboratories
were
assessed
for
this
purpose,
no
attempt
was
made
to
assess
laboratory
performance.
No
endorsement
of
these
laboratories
is
implied,
nor
should
any
be
inferred.
Laboratories
have
been
assigned
random
numbers
from
1
to
8
for
purposes
of
reporting
data
in
the
tables
or
lists
included
in
this
report.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
8
The
study
was
implemented
as
described
in
the
February
1997
Study
Plan
with
the
following
exceptions:

C
EPA
was
able
to
obtain
only
eight
laboratories
based
on
the
Phase
1
study
instead
of
the
minimum
of
nine
laboratories
recommended
in
the
Study
Plan.
Of
this,
EPA
funded
participation
of
five
laboratories,
and
three
additional
laboratories
participated
on
a
voluntary
basis.
This
was
considered
to
be
a
sufficient
number
to
meet
overall
study
objectives.

C
Laboratories
that
voluntarily
participated
in
Phase
3
of
the
study
were
encouraged
but
not
required
to
participate
in
Phase
1
as
well.

C
The
Study
Plan
recommended
that
MDLs
be
determined
by
analysis
of
at
least
seven
replicates
known
to
contain
the
analytes
of
interest
at
a
concentration
of
1
to
5
times
the
estimated
MDL.
This
recommendation
was
included
to
ensure
that
the
MDLs
are
not
artificially
high
due
to
high
spiking
levels.
Although
some
laboratories
did
not
meet
this
specification,
they
did
meet
the
requirements
of
the
EPA
MDL
procedure
given
at
40
CFR
136,
Appendix
B.

C
The
referee
laboratory
did
not
collect
or
analyze
field
blanks
with
matrix
samples.
When
collecting
field
samples
for
regulatory
purposes,
EPA
believes
it
is
important
that
field
blanks
be
collected
to
rule
out
contamination
during
the
collection
procedure.
However,
EPA
did
not
require
field
blank
collection
for
this
Study.
The
purpose
of
this
study
was
to
evaluate
method
performance
rather
than
to
characterize
a
field
sample.

C
The
Study
Plan
called
for
each
participant
laboratory
to
analyze
three
pairs
of
reagent
water
samples
and
one
pair
each
of
filtered
freshwater,
filtered
effluent,
and
unfiltered
effluent.
Funding
provided
by
EPRI
allowed
inclusion
of
four
additional
blind
sample
pairs:
three
filtered
freshwater
and
one
reagent
water.
EPA
also
increased
the
number
of
samples
sent
to
each
participant
laboratory
by
adding
an
additional
reagent
water
sample
pair.

C
The
stability
analysis
in
Phase
2
covered
the
planned
length
(
30
days)
of
Phase
3,
but
did
not
cover
the
actual
length
of
Phase
3.
Due
to
contract
delays,
laboratories
3,
6,
and
7
analyzed
Phase
3
samples
after
the
final
stability
analysis
was
performed,
but
within
the
holding
times
for
the
samples.

C
The
referee
laboratory
did
not
prepare
sufficient
volume
of
unfiltered
effluent
to
allow
each
participant
laboratory
to
perform
MS/
MSD
analyses.
In
order
to
maintain
the
integrity
of
the
study,
the
participant
laboratories
were
directed
to
digest
30­
mL
aliquots
rather
than
100­
mL
aliquots
for
total
recoverable
metals.
Because
only
a
sub­
aliquot
of
the
digested
sample
is
injected
into
the
instrument,
this
change
was
acceptable
for
the
purposes
of
this
study.

C
The
referee
laboratory
requested
approval
to
run
a
single
calibration
for
total
and
dissolved
metals
using
HNO3/
HCl
(
Draft
Method
1638
specifies
HNO3/
HCl
and
HNO3
for
total
recoverable
and
dissolved
metals
respectively).
EPA
approved
this
modification
and
requested
that
all
participant
laboratories
prepare
calibration
standards,
method
blanks,
other
applicable
QC
samples,
and
both
dissolved
and
total
recoverable
samples,
with
the
appropriate
acids
at
the
appropriate
concentrations
using
the
total
recoverable
metals
procedure.
This
involved
the
addition
of
nitric
and
hydrochloric
acids
to
all
samples
for
dissolved
metal
determinations.

C
Following
Phase
1,
five
participant
laboratories
requested
permission
to
calibrate
with
linear
regression
instead
of
response
factors.
Because
response
factor
calibration
is
statistically
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
9
equivalent
to
weighted
linear
regression
forced
through
zero,
EPA
approved
this
calibration
technique.
Weighted
linear
regression
with
a
non­
zero
y­
intercept
also
was
accepted;
this
approach
can
be
considered
equivalent
to
the
response
factor
calibration
technique
because
the
instrument
response
is
weighted
in
the
same
way.
These
alternate
calibration
approaches
were
allowed
because
ICP/
MS
instruments
typically
utilize
software
with
an
option
to
calibrate
with
linear
regression,
but
response
factor
calibration
requires
export
of
raw
data
from
the
instrument.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
10
Section
4
Data
Reporting
and
Validation
Data
reports
were
submitted
to
SCC
for
review
and
validation.
The
reports
included
MDL
study
results
(
Phase
1),
background
determination,
sample
analysis,
and
sample
stability
results
(
Phase
2),
and
study
data
packages
(
Phase
3).
Data
packages
included
sample
tracking
logs,
results
summaries,
QC
summaries,
raw
data,
sample
calculations,
laboratory
narratives,
and
electronic
data
reporting
spreadsheets.

Seven
of
the
eight
participant
laboratories
submitted
Phase
1
data
packages.
Laboratory
4
chose
not
to
participate
in
the
MDL
study.

The
referee
laboratory
submitted
a
complete
data
package
describing
all
Phase
2
activities
and
results,
including
sample
collection
and
preparation
information,
analytical
results
of
background
determinations,
analytical
results
of
post­
spiking
sample
concentrations,
results
from
sample
stability
analyses,
and
copies
of
all
hardcopy
sample
tracking
documentation.

All
eight
participant
laboratories
submitted
Phase
3
data
packages.
Results
were
submitted
for
all
176
samples
distributed
(
22
sample
results
from
each
of
8
laboratories)
yielding
a
100%
laboratory
completion
rate.
Results
also
were
submitted
for
most
of
the
required
QC
analyses.
The
type
and
number
of
study
samples
analyzed
and
reported
by
each
laboratory
in
Phase
3
are
listed
in
Table
4­
1.
Laboratories
also
reported
spike
amounts,
percent
recoveries,
and
true
values
for
QC
samples.
For
those
instances
in
which
Study
Plan
requirements
were
not
met,
an
explanation
was
provided
or
the
situation
resolved
through
discussions
with
the
laboratory.

Table
4­
1:
Number
and
Type
of
Phase
3
Samples
Analyzed
by
Participating
Laboratories
Lab
Runs1
Blind
Samples
MS/
MSD
QCS2
SRM3
IPR
OPR
Cal
Ver
Method
Blanks
Cal
Blanks
non­
zero
CAL4/
Run
1
1
22
3/
3
0
1
to
2
4
2
5
10
0
3
2
6
22
4/
4
3
to
6
2
to
6
4
7
to
15
10
to
20
9
to
19
12
to
26
4
to
5
3
2
22
4/
4
0
1
4
3
10
to
14
3
10
to
14
4
4
2
22
4/
4
7
to
9
5
to
8
12
5
to
8
2
to
5
2
to
4
9
to
10
5
to
7
5
4
22
4/
4
10
4
8
10
9
1
9
3
to
7
6
1
22
3/
0
0
2
6
0
0
0
4
6
7
1
22
3/
3
0
3
to
6
4
3
7
3
6
3
8
1
22
5/
5
3
1
4
3
7
3
7
3
1
"
Run"
is
defined
as
a
group
of
samples
associated
with
a
calibration.
2
Quality
control
samples
(
QCSs)
are
required
by
Method
1638,
but
were
not
required
for
this
study.
3
SRMs
are
not
required
by
Method
1638
but
at
least
one
analysis
was
required
for
this
study.
4
A
minimum
of
three
non­
zero
calibration
standards
(
CAL)
are
required
by
Method
1638.

Data
were
reviewed
against
the
requirements
of
the
Study
Plan
and
against
the
specifications
in
Method
1638.
Data
completeness
was
verified
by
ensuring
all
required
data
were
present,
including
results
of
all
required
tests,
sample
lists,
run
chronologies,
summaries
of
analytical
results,
raw
data,
and
copies
of
laboratory
notebook
entries.
Data
verification
was
performed
by
comparing
each
data
element
to
the
requirements
of
the
Study
Plan.
This
included
verification
that:
reagent
water,
freshwater,
and
effluent
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
11
samples
were
analyzed
as
appropriate;
proper
spike
levels
were
used
in
the
MDL
studies
and
QC
analyses;
the
analytical
system
was
properly
calibrated;
and
the
MDLs
were
calculated
in
accordance
with
the
MDL
procedure
at
40
CFR
136,
Appendix
B.

4.1
Phase
1
Phase
1
results
were
used
to
pre­
qualify
laboratories
for
participation
in
Phase
3
and
to
revise
draft
Method
1638
MDLs
(
Section
6.1).
Based
on
the
SCC
data
review
and
discussions
with
the
laboratories
to
resolve
discrepancies,
Phase
1
data
from
7
of
the
10
laboratories
were
considered
to
be
of
acceptable
quality.

Three
laboratories
did
not
submit
acceptable
Phase
1
data.
One
laboratory
submitted
level
of
quantitation
(
LOQ)
results
instead
of
an
MDL
study
and
used
only
one
calibration
point
instead
of
the
required
three.
A
second
laboratory
was
unable
to
meet
draft
method
MDLs
for
six
of
the
nine
analytes
and
reported
antimony
and
lead
contamination
in
their
blanks.
The
third
laboratory
was
unable
to
meet
draft
method
MDLs
for
seven
of
the
nine
analytes,
and
method
blanks
were
greater
than
the
MDL
for
all
nine
analytes,
indicating
laboratory
contamination.

All
MDLs
reported
were
determined
according
to
the
procedure
at
40
CFR
part
136,
Appendix
B.
The
Study
Plan
recommended
that
MDLs
determined
in
Phase
1
be
within
a
factor
of
five
of
the
level
spiked
so
that
the
determined
MDLs
would
not
be
artificially
high
due
to
high
spiking
levels.
Although
some
MDLs
did
not
meet
this
objective,
they
did
meet
all
requirements
of
the
EPA
MDL
procedure
given
at
40
CFR
136,
Appendix
B.
Therefore,
all
data
were
used
to
evaluate
the
MDLs
in
Method
1638.
Results
for
Phase
1
are
presented
in
Section
5.1.

As
part
of
Phase
1,
laboratories
also
were
required
to
analyze
at
least
one
method
blank.
All
laboratories
analyzed
one
method
blank
except
Laboratory
8,
which
analyzed
two
method
blanks.
Phase
1
method
blank
results
are
presented
in
Table
5­
1.

4.2
Phase
2
Based
on
data
review
and
discussions
with
the
referee
laboratory
to
resolve
discrepancies,
all
Phase
2
data
were
considered
to
be
of
acceptable
quality.
Phase
2
results
were
used
to
determine
spiking
levels
and
sample
stability.
Phase
2
results
also
were
used
as
the
basis
for
determining
percent
recoveries
in
the
Phase
3
data.

During
Phase
2,
the
referee
laboratory
determined
the
mass­
to­
charge
ratios
(
m/
z)
that
it
determined
should
be
used
for
quantitation
based
on
the
results
of
individual
analytical
runs.
As
a
result,
some
of
the
data
reported
were
not
quantified
using
m/
z's
recommended
in
Method
1638.
Specifically,
in
the
stability
study,
the
laboratory
reported
all
data
using
114Cd,
121Sb,
65Cu,
and
68Zn.
EPA
believes
that
there
is
no
adverse
impact
to
this
use
of
alternate
m/
z's
because
the
m/
z's
in
Method
1638
are
recommended
but
not
required.

4.3
Phase
3
Data
submitted
for
Phase
3
met
study
and
method
requirements.
Sections
4.3.1
through
4.3.8
detail
deviations
from
these
requirements.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
7EPA
Guide
to
Method
Flexibility
and
Approval
of
EPA
Water
Methods,
EPA
821­
D­
96­
004,
December
1996.

Draft
­
December
2000
12
4.3.1
Calibration
Verification
Samples
Method
1638
requires
the
laboratory
to
verify
instrument
calibration
immediately
following
calibration
and
after
every
ten
samples.
Calibration
is
verified
by
analysis
of
the
mid­
point
calibration
standard.
Several
laboratories
did
not
analyze
the
mid­
point
standard,
but
did
analyze
a
standard
in
the
middle
of
their
calibration
range.
Other
laboratories
analyzed
calibration
samples
that
were
not
in
the
middle
of
the
calibration
range,
or
were
greater
than
the
calibration
range.
All
calibration
verification
samples
that
were
within
the
laboratory
calibration
ranges
were
included
in
the
assessment
of
the
QC
acceptance
criteria
for
the
method.

Laboratory
6
did
not
analyze
calibration
verification
samples,
but
instead
analyzed
SRMs
(
SLRS­
2)
at
the
beginning
and
end
of
each
analytical
run.
Analytical
results
for
SRMs
can
be
used
to
verify
calibration,
so
long
as
analyte
concentrations
are
in
the
calibration
range.
The
analytical
results
for
SRMs
showed
acceptable
recoveries
and,
therefore,
calibration
was
considered
verified.
Results
for
the
SRMs
were
not
used
for
development
of
calibration
verification
QC
acceptance
criteria.
The
results
are
presented
in
Table
5­
6.

4.3.2
Initial
Precision
and
Recovery
Samples
Draft
Method
1638
requires
laboratories
to
spike
each
initial
precision
and
recovery
(
IPR)
sample
with
each
analyte
at
a
concentration
two
to
three
times
the
ML
for
that
analyte.
EPA
intends
to
revise
Method
1638
to
specify
that
the
concentration
of
IPR
sample
aliquots
be
at
one
to
five
times
the
ML
in
order
to
make
the
method
consistent
with
EPA's
Guide
to
Method
Flexibility
and
Approval
of
EPA
Water
Methods7
(
the
"
Streamlining
Guide"),
which
was
published
after
the
release
of
draft
Method
1638.
All
IPR
samples
spiked
at
the
draft
method
ML
or
greater
were
included
in
EPA's
assessment
of
the
IPR
QC
acceptance
criteria,
even
if
the
levels
spiked
were
higher
than
specified
in
the
method.

Laboratories
4
and
6
submitted
IPR
results
for
more
than
the
method­
specified
minimum
of
four
replicates.
Laboratory
4
analyzed
a
total
of
sixteen
IPR
samples.
Laboratory
6
analyzed
six
IPR
samples.
These
two
laboratories
also
analyzed
their
IPR
samples
after
the
Phase
3
samples.
The
data
were
considered
acceptable
for
use
in
evaluating
method
performance
because
the
data
were
collected
in
the
same
way
as
IPR
data
run
prior
to
sample
analyses
were
collected.
Results
for
IPR
samples
are
provided
in
Appendix
B,
Table
4.

4.3.3
Ongoing
Precision
and
Recovery
Samples
Draft
Method
1638
requires
laboratories
to
spike
each
OPR
sample
at
a
level
two
to
three
times
the
ML
for
each
analyte.
As
with
the
IPR
requirements,
EPA
intends
to
revise
Method
1638
to
specify
that
the
concentration
of
OPR
sample
aliquots
be
one
to
five
times
the
ML
in
order
to
make
the
method
consistent
with
the
Streamlining
Guide.
All
OPR
samples
spiked
at
the
draft
method
ML
or
greater
were
included
in
EPA's
assessment
of
the
OPR
QC
acceptance
criteria,
even
if
the
levels
spiked
were
higher
than
specified
in
the
method.
Laboratory
6
did
not
analyze
OPR
samples.
OPR
sample
results
are
provided
in
Appendix
B,
Table
4.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
13
4.3.4
Blanks
Method
1638
requires
laboratories
to
analyze
1)
method
blanks
with
every
sample
batch,
and
2)
calibration
blanks
following
calibration
verification.
The
concentration
of
each
target
analyte
in
the
blanks
must
be
below
the
MDL
for
that
analyte.
Alternatively,
if
three
or
more
blanks
are
analyzed
to
characterize
the
nature
of
a
blank,
the
average
concentration
plus
two
standard
deviations
must
be
less
than
the
regulatory
compliance
limit.
Negative
values
are
common
when
using
ICP/
MS
to
analyze
samples
that
have
concentrations
below
the
MDL.
Although
not
specified
in
the
draft
method,
it
is
widely
understood
that
extreme
negative
values
can
indicate
signs
of
instrument
drift
or
other
problems
that
can
result
in
negative
bias.
Further
revisions
of
Method
1638
will
address
this
issue.
For
the
purposes
of
this
study,
SCC
compared
the
absolute
value
of
blank
results
to
the
revised
MDLs.

Laboratory
1
did
not
analyze
calibration
blanks
and
Laboratory
6
did
not
analyze
method
blanks.
Results
from
these
laboratories
were
assessed
for
possible
contamination
by
examining
QC
sample
results
(
e.
g.,
calibration
blanks,
IPR/
OPR,
calibration
verification,
SRMs).
Quality
control
sample
results
from
these
laboratories
met
method
specifications,
suggesting
no
evidence
of
a
high
bias
that
would
be
observed
if
contamination
were
present
in
the
laboratories.
Similarly,
a
comparison
of
field
sample
results
reported
by
these
laboratories
showed
no
evidence
of
high
bias
compared
to
results
reported
by
other
laboratories.
Based
on
these
factors,
EPA
considered
data
reported
by
these
laboratories
to
be
acceptable
for
study
purposes
unless
otherwise
noted
in
this
report.
Blank
results
were
assessed
by
comparison
to
the
revised
MDLs
(
determined
using
Phase
1
data).
Results
of
the
comparison
are
given
in
Sections
5.3.6
and
5.3.7.
Blank
results
are
listed
in
Appendix
B,
Table
5.

4.3.5
Matrix
Spike
and
Matrix
Spike
Duplicate
Samples
The
referee
laboratory
identified
samples
to
be
used
for
MS/
MSD
analysis
on
sample
labels
and
traffic
reports.
Five
of
the
participant
laboratories
analyzed
additional
MS/
MSD
samples.
Laboratories
2,
3,
4,
and
5
each
analyzed
an
additional
set
of
filtered
freshwater
MS/
MSD
samples.
Laboratory
8
analyzed
a
set
of
MS/
MSD
reagent
water
samples.
Laboratory
6
performed
MS
analyses
on
the
samples
identified
but
did
not
analyze
corresponding
MSD
samples.
When
revising
Method
1638
to
reflect
study
findings,
EPA
intends
to
revisit
the
language
contained
in
Section
9.3
of
the
method
to
ensure
that
laboratories
clearly
understand
the
requirement
to
analyze
both
MS
and
MSD
samples.

Laboratories
were
directed
to
spike
MS/
MSD
samples
at
one
to
five
times
the
ML
or
one
to
five
times
the
background
concentration
in
the
sample,
whichever
was
greater.
Several
laboratories
did
not
meet
this
spiking
requirement.
MS/
MSD
samples
spiked
at
the
draft
method
ML
or
greater
were
included
in
EPA's
assessment
of
the
MS/
MSD
QC
acceptance
criteria.

Results
for
MS/
MSD
samples
are
provided
in
Appendix
B,
Table
3
with
associated
spiking
levels.

4.3.6
Calibration
All
laboratories
complied
with
method
requirements
for
instrument
calibration
using
a
calibration
blank
and
at
least
three
non­
zero
standards.
Method
1638
also
directs
laboratories
to
calibrate
their
instruments
using
response
factors
(
height
or
area
at
the
analyte
m/
z
divided
by
the
analyte
concentration).

Upon
request
from
the
participant
laboratories,
two
changes
to
the
calibration
procedure
were
approved
for
this
study:
C
Due
to
the
variety
of
linear
dynamic
ranges
(
LDR)
across
instruments
and
because
the
sensitivity
of
certain
instruments
could
be
adversely
affected
by
injection
of
high
concentration
calibration
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
14
solutions,
the
laboratories
were
instructed
to
prepare
the
high
calibration
standard
as
high
as
was
practical.
C
Many
ICP­
MS
instruments
use
software
that
allows
for
weighted
linear
regression
but
not
response
factor
calibration.
EPA
agreed
that
laboratories
could
calibrate
using
weighted
linear
regression.

Laboratory
3
used
a
response
factor
calibration
as
specified
in
the
method.
Laboratories
4
and
6
submitted
data
calculated
using
unweighted
linear
regression.
All
other
laboratories
used
weighted
linear
regression
calibration.
Although
not
specifically
approved,
the
data
generated
using
unweighted
linear
regression
also
were
considered
valid
for
use
in
this
study
(
this
calibration
technique
is
widely
practiced
as
the
industry
standard
for
metals
determinations
in
environmental
samples).

Draft
Method
1638
also
requires
that
the
lowest
non­
zero
standard
be
at
the
minimum
level
(
ML),
and
the
high
standard
be
near
the
upper
end
of
the
linear
dynamic
range.
Several
laboratories
did
not
consistently
use
a
low
standard
at
the
minimum
levels,
however,
most
laboratories
encompassed
the
ML
by
using
one
standard
below
the
ML
and
a
mid­
level
standard
above
the
ML.
Seven
laboratories
analyzed
field
and
QC
samples
with
concentrations
exceeding
those
in
the
laboratory's
high
standard.
Sample
results
outside
a
laboratory's
calibration
range
(
i.
e.,
below
the
lowest
calibration
standard
or
above
the
highest
calibration
standard)
were
not
used
to
assess
the
performance
of
Method
1638.

4.3.7
Standard
Reference
Material
Analyses
Each
participant
laboratory
received
and
analyzed
the
National
Institute
of
Science
and
Technology
(
NIST)
standard
reference
material
(
SRM)
1643d.
Laboratories
1
and
7
analyzed
an
additional
SRM
(
SLRS­
4)
from
the
Canadian
National
Research
Council
(
NRC),
containing
six
of
the
nine
target
analytes
(
excluding
silver,
selenium,
and
thallium)
at
lower
levels
than
1643d.
The
cadmium
concentration
in
SLRS­
4
is
below
the
draft
and
the
revised
method
MDL.
Percent
recoveries
of
SRM
samples
analyzed
by
the
participant
laboratories
are
presented
in
Table
5­
12.

4.3.8
Additional
Deviations
Additional
deviations
from
study
requirements
that
are
not
related
to
the
specific
QC
detailed
in
Sections
4.3.1
through
4.3.7
are
listed
below.
In
most
cases,
the
deviations
did
not
warrant
data
removal.

C
Laboratory
1
prepared
two
OPRs
and
analyzed
each
OPR
multiple
times.
Only
the
first
analytical
result
for
each
OPR
was
used
to
develop
OPR
QC
acceptance
criteria.

C
Laboratory
2
analyzed
an
OPR
with
a
1050%
selenium
recovery.
The
laboratory
suspected
the
result
was
an
anomaly
and
immediately
repeated
the
analysis.
Laboratory
2
prepared
and
analyzed
eight
additional
OPR
samples
and
reported
recoveries
for
these
OPR
sample
analyses
ranging
from
84­
127
%
recovery.
Because
eight
of
the
nine
OPR
sample
results
were
within
the
draft
method
specifications,
EPA
agreed
with
the
laboratory's
assessment
that
the
data
were
an
anomaly.
EPA
did
not
use
the
elevated
selenium
recovery
concentration
to
assess
method
performance.

C
Method
1638
requires
that
a
method
blank
be
prepared
and
analyzed
with
each
analytical
batch.
Laboratory
3
analyzed
three
method
blanks
under
the
first
calibration
and
no
method
blanks
under
the
second
calibration.
All
three
method
blanks
were
analyzed
during
the
first
of
eight
batches
instead
of
one
method
blank
per
batch.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
15
(
)
(
)
(
)
Pb
Pb
Pb
Pb
total
=
+
+
0
241
0
221
0
524
206
207
208
.
*
.
*
.
*
C
Laboratory
4
analyzed
all
samples
twice.
The
first
run
was
used
to
screen
samples
for
concentration.
Although
the
laboratories
were
instructed
not
to
repeatedly
analyze
samples
to
improve
performance,
they
were
not
precluded
from
implementing
such
a
screening
approach.
(
To
the
contrary,
such
an
approach
is
often
used
to
ensure
that
elevated
sample
concentrations
do
not
contaminate
clean
equipment
and
to
determine
spiking
levels).
Therefore
EPA
chose
to
ignore
the
screening
data
and
consider
results
from
only
the
second
run
for
all
analytes
except
dissolved
silver.
The
laboratory
determined
that
spike
recoveries
for
dissolved
silver
were
not
acceptable
on
the
second
day
of
analysis
based
on
analysis
of
prepared
standards,
and
thus
reported
dissolved
silver
and
associated
QC
samples
from
the
first
day.
Additional
details
on
problems
associated
with
silver
recoveries
are
presented
in
Section
5.4.

C
In
Laboratory
5,
sample
preparation
and
analysis
was
not
performed
in
a
clean
room
or
clean
area.
The
laboratory
indicated
that
samples
high
in
target
analytes
were
analyzed
at
the
same
site
and
on
the
same
instrument
on
a
routine
basis.
Not
surprisingly,
Laboratory
5
reported
total
recoverable
OPR
samples
with
elevated
recoveries
for
copper
(
510
%)
and
lead
(
514
%).
The
laboratory
attributed
the
elevated
recoveries
to
possible
contamination,
noting
that
they
frequently
analyzed
samples
high
in
copper
and
lead.
The
OPR
samples
for
copper
and
lead
were
not
used
for
development
of
QC
specifications
for
the
method.

C
Laboratory
5
analyzed
the
MS/
MSD
for
sample
46534
three
times;
once
undiluted,
once
diluted
2X,
and
once
diluted
10X.
Copper
and
antimony
spike
recoveries
were
close
to
zero
for
both
the
undiluted
and
2X
dilution
samples,
and
the
laboratory
reported
the
results
for
the
10X
dilution.
The
laboratory
stated
that
there
may
have
been
a
matrix
effect
causing
the
poor
recoveries.
EPA
compared
background
results
for
the
undiluted
sample
to
results
reported
by
the
other
laboratories
and
found
that
there
were
no
indications
of
matrix
effects.
Because
of
the
inability
of
the
laboratory
to
discern
the
matrix
effects,
EPA
decided
not
to
include
the
copper
and
antimony
MS/
MSD
results
from
this
sample
in
the
assessment
of
method
performance.

C
Laboratory
6
did
not
perform
the
recommended
correction
equation
to
account
for
the
variability
of
lead
isotopes.
The
laboratory
reported
separate
concentrations
for
206Pb,
207Pb,
and
208Pb.
EPA
applied
the
following
correction
equation
to
the
laboratory's
data
to
account
for
the
natural
abundance
of
the
lead
isotopes:

C
Laboratory
7
submitted
results
for
each
analyte
calculated
using
several
different
internal
standards.
Only
one
internal
standard
is
recommended
in
the
method.
During
data
review,
EPA
chose
the
most
appropriate
method­
specified
internal
standard
and
re­
calculated
the
results.

C
Method
blank
and
OPR
sample
results
submitted
by
Laboratory
8
exhibited
zinc
contamination.
The
laboratory
was
unsure
of
the
source
of
contamination.
The
method
blanks,
OPRs,
and
associated
field
samples
are
footnoted
in
this
report.
The
QC
samples
were
not
used
for
development
of
OPR
QC
acceptance
criteria.

All
data
deemed
inappropriate
for
development
of
QC
acceptance
criteria
are
identified
in
Section
5.
In
addition,
data
that
were
not
used
are
included
as
footnoted
sample
results
in
Appendix
B.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
16
Section
5
Results
Results
submitted
for
Phase
1
are
discussed
in
Section
5.1.
These
results
were
used
to
assess
laboratory
capability
and
to
either
validate
the
MDL's
specified
in
the
draft
method
or
develop
revised
MDLs
when
the
draft
method
MDL
was
not
supported
by
study
results.

Results
submitted
for
Phase
2
are
presented
in
Section
5.2
and
in
Appendix
B,
Table
1.
These
results
were
used
to
establish
background
and
expected
concentrations
for
each
study
sample
and
to
assess
sample
stability
for
each
target
analyte.

Phase
3
results
are
presented
in
Section
5.3
and
in
Appendix
B,
Table
2.
These
results
were
used
to
evaluate
method
performance
in
real­
world
matrices
and
develop
performance
criteria
for
Method
1638.

5.1
Phase
1
Results
All
laboratories
followed
the
40
CFR
136,
Appendix
B
MDL
procedure
for
Phase
1
MDL
determinations.
Results
of
the
Phase
1
MDL
and
method
blank
assessments
are
given
in
Table
5­
1.
Laboratory
6
analyzed
10
replicates
to
determine
their
MDLs;
all
other
laboratories
analyzed
the
minimum
requirement
of
7
replicates.
MDLs
were
calculated
using
the
appropriate
Student's
t
value
to
reflect
the
actual
number
of
replicates
(
n)
used.
These
MDLs
were
evaluated
and
used
to
either
confirm
the
draft
method
MDLs
or
to
calculate
a
revised
MDL
as
appropriate.

Absolute
values
of
method
blanks
reported
during
Phase
1
were
evaluated
based
on
these
confirmed
or
revised
MDLs.
Of
the
71
Phase
1
method
blank
results
reported,
more
than
80%
were
below
the
confirmed
or
revised
MDLs.
Laboratory
4
agreed
to
participate
in
the
study
after
the
completion
of
Phase
1
and
did
not
participate
in
Phase
1
of
the
study.
17
Table
5­
1:
Phase
1,
MDL
and
Method
Blank
Results
Analyte
Lab
Spiking
Concentration
(
µ
g/
L)
MDL
Results
(
µ
g/
L)
Method
Blank
Results
(
µ
g/
L)
1
2
3
4
5
6
7
8
9
10
Mean
(
µ
g/
L)
s
MDL
(
µ
g/
L)

Antimony
1
0.02
0.014
0.017
0.011
0.014
0.022
0.018
0.017
­
­
­
0.016
0.003
0.011
0.103
2
0.03
0.028
0.037
0.037
0.031
0.027
0.040
0.032
­
­
­
0.033
0.005
0.016
0.004
3
0.05
0.033
0.033
0.027
0.027
0.033
0.029
0.027
­
­
­
0.030
0.003
0.009
­
0.016
5
0.02
0.019
0.017
0.015
0.018
0.020
0.017
0.017
­
­
­
0.018
0.002
0.005
0.014
6
0.051
0.048
0.043
0.041
0.046
0.039
0.038
0.043
0.031
0.044
0.037
0.041
0.005
0.014
0.004
7
0.01
0.011
0.007
0.008
0.009
0.010
0.005
0.007
­
­
­
0.008
0.002
0.007
­
0.005
8
0.1
0.089
0.063
0.057
0.051
0.043
0.046
0.056
­
­
­
0.058
0.015
0.048
­
0.081
­
0.032
Cadmium
1
0.02
0.031
0.035
0.028
0.035
0.036
0.029
0.025
­
­
­
0.031
0.004
0.013
0.159
2
0.3
0.311
0.327
0.341
0.323
0.291
0.369
0.319
­
­
­
0.326
0.024
0.077
0.027
3
0.025
0.021
0.017
0.020
0.022
0.025
0.020
0.024
­
­
­
0.021
0.003
0.008
­
0.002
5
0.1
0.097
0.087
0.093
0.082
0.092
0.100
0.082
­
­
­
0.090
0.007
0.022
0.018
6
0.041
0.064
0.041
0.053
0.045
0.035
0.043
0.043
0.032
0.048
0.054
0.046
0.009
0.026
0.006
7
0.05
0.020
0.018
0.021
0.023
0.019
0.014
0.020
­
­
­
0.019
0.003
0.009
­
0.033
8
0.05
0.013
0.011
0.013
0.008
0.014
0.013
0.024
­
­
­
0.014
0.005
0.016
­
0.040
­
0.025
Copper
1
0.05
0.039
0.048
0.047
0.047
0.046
0.038
0.058
­
­
­
0.046
0.007
0.021
0.002
2
0.3
0.361
0.342
0.374
0.346
0.342
0.349
0.414
­
­
­
0.361
0.026
0.081
­
0.052
3
0.025
0.036
0.032
0.025
0.029
0.030
0.030
0.033
­
­
­
0.031
0.003
0.011
­
0.025
5
0.2
0.179
0.195
0.195
0.196
0.194
0.188
0.200
­
­
­
0.192
0.007
0.022
0.176
6
1.016
1.034
1.013
1.016
0.906
0.966
1.035
1.063
1.003
1.060
1.028
1.013
0.047
0.132
0.094
7
0.1
0.089
0.084
0.085
0.085
0.084
0.086
0.081
­
­
­
0.085
0.003
0.008
­
0.006
8
0.05
0.055
0.050
0.043
0.054
0.047
0.048
0.054
­
­
­
0.050
0.005
0.014
0.027
0.018
Lead
1
0.02
0.023
0.022
0.024
0.019
0.022
0.024
0.021
­
­
­
0.022
0.002
0.005
0.009
2
0.05
0.067
0.061
0.070
0.065
0.065
0.064
0.065
­
­
­
0.065
0.003
0.009
0.100
3
0.025
0.021
0.021
0.019
0.021
0.020
0.021
0.022
­
­
­
0.021
0.001
0.003
0.000
Table
5­
1:
Phase
1,
MDL
and
Method
Blank
Results
Analyte
Lab
Spiking
Concentration
(
µ
g/
L)
MDL
Results
(
µ
g/
L)
Method
Blank
Results
(
µ
g/
L)
1
2
3
4
5
6
7
8
9
10
Mean
(
µ
g/
L)
s
MDL
(
µ
g/
L)

18
5
0.05
0.035
0.040
0.044
0.043
0.035
0.043
0.041
­
­
­
0.040
0.004
0.012
0.019
6
0.051
0.048
0.048
0.044
0.045
0.038
0.044
0.042
0.042
0.041
0.040
0.043
0.003
0.009
0.007
7
0.025
0.026
0.025
0.025
0.025
0.026
0.026
0.026
­
­
­
0.026
0.001
0.002
0.002
8
0.1
0.087
0.092
0.095
0.098
0.098
0.098
0.097
­
­
­
0.095
0.004
0.013
­
0.005
0.000
Nickel
1
0.1
0.084
0.084
0.094
0.091
0.065
0.069
0.092
­
­
­
0.083
0.011
0.036
0.000
2
0.1
0.233
0.215
0.208
0.224
0.211
0.203
0.205
­
­
­
0.214
0.011
0.034
0.015
3
0.025
0.022
0.022
0.027
0.023
0.029
0.026
0.022
­
­
­
0.024
0.003
0.009
­
0.005
5
0.5
0.355
0.370
0.414
0.436
0.383
0.331
0.376
­
­
­
0.381
0.035
0.111
1.130
6
1.036
0.976
0.932
0.935
0.986
0.992
1.014
1.036
1.003
1.009
1.025
0.991
0.035
0.099
0.110
7
0.5
0.475
0.474
0.471
0.479
0.475
0.463
0.474
­
­
­
0.473
0.005
0.015
0.010
8
0.05
0.034
0.038
0.037
0.042
0.035
0.039
0.041
­
­
­
0.038
0.003
0.010
0.007
0.003
Selenium
1
0.5
0.310
0.516
0.503
0.578
0.968
0.545
0.403
­
­
­
0.546
0.207
0.652
0.250
2
No
data
submitted
by
laboratory
3
1
0.703
0.805
0.821
0.888
0.956
0.779
0.768
­
­
­
0.817
0.083
0.261
­
0.146
5
1
0.796
0.696
0.777
0.949
0.958
0.622
0.884
­
­
­
0.812
0.127
0.398
0.885
6
2.499
2.237
2.143
1.882
2.060
1.432
1.495
1.589
2.133
2.227
1.652
1.885
0.316
0.891
0.710
7
2.5
2.401
2.417
2.282
2.333
2.369
2.313
2.336
­
­
­
2.350
0.048
0.151
­
0.027
8
0.5
0.466
0.617
0.430
0.467
0.522
0.605
0.601
­
­
­
0.530
0.078
0.245
­
0.027
0.020
Silver
1
0.02
0.025
0.027
0.032
0.028
0.024
0.026
0.027
­
­
­
0.027
0.003
0.008
0.011
2
0.05
0.065
0.056
0.067
0.051
0.062
0.059
0.052
­
­
­
0.059
0.006
0.019
0.018
3
0.05
0.019
0.019
0.014
0.022
0.018
0.017
0.020
­
­
­
0.019
0.002
0.008
­
0.022
5
0.02
0.010
0.013
0.011
0.008
0.007
0.010
0.011
­
­
­
0.010
0.002
0.006
0.023
6
0.091
0.098
0.087
0.081
0.067
0.089
0.076
0.079
0.070
0.077
0.080
0.080
0.009
0.026
0.019
7
0.05
0.054
0.050
0.051
0.052
0.051
0.048
0.049
­
­
­
0.051
0.002
0.006
0.002
Table
5­
1:
Phase
1,
MDL
and
Method
Blank
Results
Analyte
Lab
Spiking
Concentration
(
µ
g/
L)
MDL
Results
(
µ
g/
L)
Method
Blank
Results
(
µ
g/
L)
1
2
3
4
5
6
7
8
9
10
Mean
(
µ
g/
L)
s
MDL
(
µ
g/
L)

19
8
0.1
0.095
0.106
0.110
0.110
0.113
0.116
0.110
­
­
­
0.108
0.007
0.021
0.024
0.017
Thallium
1
0.02
0.025
0.024
0.024
0.023
0.023
0.023
0.021
­
­
­
0.023
0.001
0.004
0.006
2
0.02
0.017
0.018
0.018
0.028
0.026
0.026
0.026
­
­
­
0.023
0.005
0.015
­
0.019
3
0.005
0.003
0.003
0.003
0.003
0.003
0.003
0.003
­
­
­
0.003
0.000
0.001
­
0.002
5
0.02
0.024
0.018
0.019
0.019
0.020
0.020
0.022
­
­
­
0.020
0.002
0.006
0.010
6
0.051
0.042
0.045
0.042
0.042
0.045
0.044
0.042
0.040
0.042
0.042
0.043
0.002
0.005
0.001
7
0.01
0.010
0.010
0.011
0.011
0.011
0.010
0.010
­
­
­
0.010
0.000
0.001
0.000
8
0.05
0.040
0.040
0.040
0.038
0.041
0.042
0.042
­
­
­
0.040
0.001
0.004
­
0.008
­
0.004
Zinc
1
0.2
0.124
0.139
0.155
0.154
0.121
0.172
0.149
­
­
­
0.145
0.018
0.057
0.000
2
0.5
0.548
0.521
0.527
0.510
0.510
0.580
0.533
­
­
­
0.533
0.025
0.078
0.042
3
0.1
0.100
0.108
0.103
0.114
0.154
0.145
0.154
­
­
­
0.125
0.024
0.077
­
0.040
5
0.5
0.935
0.951
0.976
0.998
0.981
0.916
1.190
­
­
­
0.992
0.092
0.288
0.544
6
1.026
1.106
1.075
1.031
1.071
1.070
1.005
1.199
1.116
1.052
1.150
1.087
0.057
0.161
0.096
7
0.25
0.233
0.218
0.221
0.228
0.248
0.216
0.249
­
­
­
0.231
0.014
0.043
­
0.017
8
0.5
0.523
0.527
0.557
0.530
0.544
0.538
0.494
­
­
­
0.530
0.020
0.062
0.244
0.207
20
5.2
Phase
2
Results
5.2.1
Background
Concentrations
Background
concentrations
of
the
target
analytes
in
the
freshwater
and
effluent
matrices
were
determined
by
the
referee
laboratory.
The
background
concentration
of
the
reagent
water
was
assumed
to
be
zero.
The
background
concentrations
were
used
to
determine
appropriate
spiking
levels
for
each
target
analyte
in
the
blind
samples
distributed
to
the
participating
laboratories.
Background
concentrations
are
listed
in
Table
2­
1.

5.2.2
Stability
Analyses
Aliquots
from
each
batch
of
filtered
and
unfiltered
samples
were
analyzed
at
the
beginning
and
end
of
the
30­
to
35­
day
stability
test
period,
the
expected
duration
of
Phase
3.
Results
were
submitted
with
full
QC
data
to
SCC
for
assessment
of
instability
or
possible
contamination.
Sample
stability
was
assessed
by
comparing
analytical
results
against
the
expected
concentration.
Mean
percent
recoveries
for
both
initial
analyses
and
final
analyses
were
based
on
the
expected
analyte
concentrations,
and
are
presented
in
Appendix
B,
Table
1.
Relative
percent
differences
(
RPD)
of
mean
percent
recoveries
were
used
to
assess
analyte
concentration
stability
during
Phase
3
of
the
study.

Stability
could
not
be
quantitatively
assessed
for
samples
having
expected
analyte
concentrations
below
the
MLs
determined
in
Phase
1
(
Table
6­
1).
These
samples
are
flagged
in
Appendix
B,
Table
1,
and
include
(
1)
unspiked
reagent
water
samples,
(
2)
many
of
the
Youden
pairs
that
EPRI
included
in
the
study,
and
(
3)
one
freshwater
pair
for
antimony.
EPA
did,
however,
verify
that
these
samples
remained
at
or
near
this
threshold
over
the
30
to
35­
day
stability
test
period.
All
but
three
of
the
low
concentration
sample
pairs
provided
by
EPRI
were
consistently
below
the
ML.
The
three
remaining
pairs
closely
bracketed
the
ML.
For
example,
antimony
was
initially
reported
at
the
ML
(
0.20
ug/
L)
in
a
freshwater
sample
and
slightly
below
the
ML
(
0.17
ug/
L)
for
the
final
stability
analysis.
The
expected
concentration
of
antimony
was
reported
to
be
at
the
ML
(
0.20).

Of
the
117
non­
zero
samples
assessed
for
stability,
32
were
removed
from
the
assessment
because
the
expected
concentrations
were
below
the
revised
method
MLs.
Of
the
remaining
85
samples,
only
four
indicated
possible
instability.

C
Reagent
Water
Pair
2
(
silver)
­
The
RPD
between
silver
measurements
at
the
beginning
and
end
of
the
stability
period
was
25.4%.
The
expected
concentration
of
this
sample
pair
was
at
the
method
ML
for
silver
(
0.1
µ
g/
L).
C
Freshwater
Pair
­
High
(
silver)
­
The
RPD
between
silver
measurements
was
121%.
Final
stability
assessment
yielded
recovery
of
silver
at
less
than
a
third
of
the
expected
and
initial
analyses
concentrations.
C
Freshwater
Pair
­
Low
(
silver)
­
The
RPD
between
silver
measurements
was
134%.
Final
stability
assessment
yielded
recovery
of
silver
at
less
than
a
third
of
the
expected
and
initial
analyses
concentrations.
C
Unfiltered
Effluent
Pair
(
silver)
­
Initial
stability
assessment
yielded
52%
recovery
and
the
final
stability
assessment
yielded
53%
recovery.
The
RPD
between
silver
measurements
was
3%
and
the
silver
concentration
was
considered
stable
for
the
study
period.

For
all
samples
in
which
analyte
concentrations
were
consistently
reported
above
the
ML,
EPA
determined
that
concentrations
remained
sufficiently
stable
during
Phase
3
of
the
study.
Results
of
stability
analyses
and
assessment
are
shown
in
Table
1
of
Appendix
B.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
21
5.3
Phase
3
Results
5.3.1
Outlier
Screening
Sample
results
were
screened
for
outliers
in
accordance
with
laboratory
ranking
and
individual­
point
procedures
described
by
AOAC­
International
and
ASTM
D
2777­
96.
The
laboratories
were
ranked
and
screened
according
to
Youden's
test
for
outlying
laboratories
to
identify
laboratories
with
significantly
higher
or
lower
results
than
the
majority
of
laboratories.
For
each
analyte
and
sample
type
(
analyte/
matrix/
concentration),
laboratories
were
ranked
according
to
the
distance
between
the
analyte
concentration
determined
by
that
laboratory
and
the
mean
concentration
over
all
laboratories
for
the
corresponding
sample
type
and
analyte.
One
of
the
eight
Phase
3
data
packages
was
rejected
for
each
analyte
following
application
of
the
Youden
laboratory
ranking
test
at
the
5
percent
significance
level
leaving
7
full
datasets
for
each
analyte
for
determination
of
method
performance.
Laboratory
data
packages
that
were
removed
for
each
analyte
are
listed
in
Table
5­
2.

Table
5­
2:
Youden
Outlier
Laboratories
Analyte
Outlier
Laboratory
Antimony
Laboratory
1
Cadmium
Laboratory
6
Copper
Laboratory
1
Lead
Laboratory
1
Nickel
Laboratory
2
Selenium
Laboratory
6
Silver
Laboratory
4
Thallium
Laboratory
7
Zinc
Laboratory
5
After
identifying
the
Youden
outlying
laboratories,
the
data
were
screened
for
outliers
using
the
statistical
procedures
attributed
to
Grubbs
in
the
AOAC
and
ASTM
procedures.
This
screening
was
conducted
separately
for:
1)
the
development
of
the
QC
acceptance
criteria
and
2)
the
assessment
of
method
performance.
For
development
of
QC
acceptance
criteria,
an
objective
was
to
use
as
much
data
as
possible.
All
field
and
sample
results
that
were
above
the
draft
method
ML
were
used
in
the
development
of
QC
acceptance
criteria.
Therefore,
results
that
were
below
the
draft
method
ML
were
removed
from
the
data
set
prior
to
applying
the
Grubbs
outlier
test.
For
assessment
of
method
performance,
all
results
that
were
above
the
revised
method
ML
(
see
Table
6­
1)
were
used.
This
required
a
separate
application
of
the
Grubbs
outlier
test
prior
to
conducting
the
method
performance
assessment
presented
in
Section
7.

The
Phase
3
field
sample
(
excluding
Youden
pairs),
IPR/
OPR,
and
calibration
verification
results
were
screened
for
outliers
using
Grubbs
test
for
outlying
observations.
The
Grubbs
outlier
test
allows
for
identification
and
removal
of
up
to
10
percent
of
the
samples
for
each
matrix/
concentration/
analyte
combination.
Because
there
were
fewer
than
10
results
for
any
given
combination
of
method/
concentration/
analyte
in
the
MS/
MSD
and
Youden
pair
samples,
application
of
the
Grubbs
test
to
these
samples
could
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
22
not
be
performed
because
removal
of
any
sample
would
violate
the
10%
removal
limit
specified
for
the
Grubbs
test.
However,
two
results
from
Youden
pairs
were
removed
due
to
exceedingly
high
recoveries
(
3000%
for
sample
47292
Cd,
and
1000%
for
sample
47245
Cu).
Results
remaining
after
removal
of
the
Youden
outlying
laboratory,
the
Grubbs
outliers,
and
the
two
Youden
pair
outliers
were
used
for
development
of
QC
acceptance
criteria.

The
percentages
of
sample
results
that
were
rejected
as
outliers
from
the
7
full
data
sets
for
each
analyte
are
listed
in
Table
5­
3.
Rejected
outlying
results
are
identified
in
Appendix
B,
Tables
2
and
4.

Table
5­
3.
Percentage
of
Sample
Results
Rejected
as
Grubbs
Outliers
Analyte
Phase
3
Field
(%)
Precision
and
Recovery
(%)
Calibration
Verification
(%)
Method
Performance
Precision
and
Recovery
(%)

Sb
0
7
2
6
Cd
0
1
0
2
Cu
4
5
8
6
Pb
6
3
0
1
Ni
3
2
0
2
Se
0
1
6
1
Ag
0
0
0
0
Tl
2
1
0
1
Zn
1
2
0
3
5.3.2
Calibration
Linearity
Method
1638
stipulates
that
calibration
is
performed
using
response
factors.
For
this
study,
both
weighted
and
unweighted
linear
regression
also
were
accepted
(
see
Section
3
for
more
information).
EPA
intends
to
revise
Method
1638
to
recommend
use
of
response
factor
or
weighted
linear
regression
calibrations,
allowing
unweighted
linear
regression
as
an
acceptable
calibration
technique.

Method
1638
requires
each
laboratory
to
calibrate
the
instrument
with
three
or
more
non­
zero
calibration
standards.
All
laboratories
followed
this
requirement.
Five
of
the
eight
laboratories
used
weighted
linear
regression
with
a
non­
zero
y­
intercept.
Of
the
remaining
three
laboratories,
Laboratories
4
and
6
used
unweighted
linear
regression,
and
Laboratory
3
used
response
factors.
Calibration
data
were
pooled
for
development
of
QC
acceptance
criteria
and
method
performance
evaluation
regardless
of
calibration
technique.

For
response
factor
(
RF)
calibration,
the
laboratory
computes
1)
the
RF
for
each
calibration
point,
2)
the
mean
response
factor
(
RFm),
and
3)
the
relative
standard
deviation
(
RSD)
of
the
response
factors.
Method
1638
specifies
a
maximum
criterion
of
20
percent
RSD
of
the
RFs
for
each
calibration
run.
Results
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
23
submitted
by
Laboratory
3
(
the
only
laboratory
to
calibrate
using
response
factors)
are
shown
in
Table
5­
4.
The
RSDs
of
all
mean
RFs
were
well
below
the
maximum
criteria
of
20
percent.

Table
5­
4.
Laboratory
3
Calibration
Results
Analyte
RFm
s
RSD
Antimony
1.73
0.03
1.82
1.75
0.06
3.52
Cadmium
1.97
0.05
2.75
Copper
8.30
0.51
6.18
8.25
0.73
8.90
Lead
12.12
0.24
1.96
12.08
0.59
4.90
Nickel
3.52
0.12
3.28
3.53
0.09
2.66
Selenium
0.07
0.00
1.68
Silver
4.05
0.13
3.15
Thallium
8.96
0.21
2.38
Zinc
1.93
0.06
2.88
2.01
0.12
6.03
For
weighted
and
unweighted
linear
regression,
the
laboratory
calculates
1)
the
slope,
2)
the
y­
intercept,
and
3)
the
correlation
coefficient
(
R2).
EPA
assessed
the
data
relative
to
a
lower
limit
of
0.995
for
the
correlation
coefficient
and
set
upper
intercept
limits
at
the
MDLs.
For
all
labs
that
used
weighted
and
unweighted
linear
regression,
reported
correlation
coefficients
were
always
greater
than
0.995,
except
for
Laboratory
1.
Laboratory
1
reported
lower
correlation
coefficients
for
selenium
and
antimony,
however,
these
correlation
coefficients
were
above
0.990
and
all
data
were
considered
acceptable
for
the
study.
All
y­
intercepts
were
less
than
the
MDLs
with
the
exception
of
one
result
for
lead.
Calibration
linearity
was
considered
acceptable
for
each
lab
for
the
purposes
of
the
study.

In
order
to
evaluate
method
performance
using
a
weighted
linear
regression,
EPA
re­
calculated
calibrations
using
instrument
response
data
submitted
by
all
laboratories
except
Laboratory
2.
Laboratory
2
did
not
submit
raw
instrument
responses
and
was
unable
to
provide
them
upon
request.

It
is
to
be
expected
that
correlation
coefficients
using
weighted
linear
regression
would
be
lower
than
coefficients
using
unweighted
linear
regression
because
of
the
effect
of
equal
weighting
of
all
points
in
the
weighted
approach.
Of
the
67
weighted
correlation
coefficients
calculated
by
EPA,
70
percent
were
greater
than
0.995.
The
lowest
correlation
coefficient
was
0.874
for
lead.
Lead
most
frequently
had
a
correlation
coefficient
below
0.995
(
6
percent
of
the
total
correlation
coefficients).
Results
of
the
weighted
linear
regression
assessment
are
shown
in
Table
5­
5.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
24
Table
5­
5.
Weighted
Linear
Regression
Results
Analyte
Lab
Slope
Intercept
R2
Antimony
1
1.49
­
0.000018
0.986
2
Data
not
available
3
1.75
­
0.000028
1.000
1.77
­
0.000037
0.999
4
0.22
0.000033
0.992
5
0.18
0.000030
0.996
0.17
0.000036
0.997
6
Youden
outlying
laboratory
7
0.39
­
0.001834
1.000
8
0.89
­
0.000070
1.000
Cadmium
1
0.62
­
0.000006
0.990
2
Data
not
available
3
1.94
0.000054
1.000
4
0.09
0.000034
0.988
5
Youden
outlying
laboratory
6
0.08
0.000007
1.000
7
0.67
­
0.003960
1.000
8
0.44
­
0.000017
1.000
Copper
1
Youden
outlying
laboratory
2
Data
not
available
3
8.62
­
0.000511
0.999
8.71
­
0.000727
0.999
4
1.64
0.002584
0.987
5
0.39
0.000365
0.986
0.39
0.000334
0.996
6
0.58
­
0.002473
0.999
7
0.39
­
0.006303
1.000
8
1.12
­
0.000050
1.000
Analyte
Lab
Slope
Intercept
R2
Lead
1
Youden
outlying
laboratory
2
Data
not
available
3
12.27
­
0.000253
1.000
12.34
­
0.000415
0.998
4
0.77
0.000385
0.991
5
1.23
0.000067
0.975
1.23
­
0.000112
0.981
6
0.62
­
0.000915
0.874
7
1.68
­
0.015948
1.000
8
5.95
0.000048
0.999
Nickel
1
0.74
0.000043
0.992
2
Youden
outlying
laboratory
3
3.52
0.000007
0.999
3.55
­
0.000033
0.999
4
0.22
0.000129
0.989
5
0.17
0.000175
0.998
0.17
­
0.000153
1.000
6
0.26
­
0.000032
1.000
7
0.16
­
0.001399
1.000
8
0.56
­
0.000036
1.000
Selenium
1
0.03
0.000067
0.985
2
Data
not
available
3
0.07
0.000007
1.000
4
0.07
0.000156
0.984
5
0.01
0.000140
0.995
0.01
0.000123
0.988
6
Youden
outlying
laboratory
7
0.01
­
0.000713
1.000
8
0.04
­
0.000045
1.000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
25
Table
5­
5.
Weighted
Linear
Regression
Results
Analyte
Lab
Slope
Intercept
R2
Silver
1
2.54
­
0.000050
0.992
2
Data
not
available
3
4.13
­
0.000126
1.000
4
Youden
outlying
laboratory
5
0.41
0.000069
0.998
0.41
­
0.000009
0.997
6
0.34
0.003306
0.995
7
0.67
­
0.003960
1.000
8
1.85
­
0.000094
1.000
Thallium
1
Youden
outlying
laboratory
2
Data
not
available
3
9.05
­
0.000149
1.000
4
0.54
­
0.000018
0.989
5
0.84
0.000062
0.997
0.86
0.000004
0.999
6
0.99
0.000596
1.000
7
0.91
­
0.000446
1.000
8
4.40
­
0.000099
1.000
Zinc
1
0.41
­
0.000377
0.991
2
Data
not
available
3
1.90
0.000509
1.000
2.04
­
0.000437
0.996
4
0.46
0.011896
0.919
5
Youden
outlying
laboratory
6
0.07
­
0.000079
0.996
7
0.12
­
0.000573
1.000
8
0.34
0.000673
1.000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
26
5.3.3
Calibration
Verification
Method
1638
requires
that
each
laboratory
analyze
calibration
verification
(
CalVer)
samples
immediately
following
calibration
and
after
every
ten
samples.
The
calibration
verification
is
conducted
by
analyzing
the
mid­
point
calibration
standard.
Of
the
514
calibration
verification
results
reported,
510
were
within
the
draft
Method
1638
QC
acceptance
criteria.
Calibration
verification
results
were
subjected
to
outlier
testing
before
being
used
to
develop
revised
QC
acceptance
criteria
(
Section
6.3).
CalVer
samples
that
were
used
for
acceptance
criteria
development
are
summarized
in
Table
5­
6.
CalVer
sample
results
are
shown
in
Appendix
B,
Table
7.

Table
5­
6.
Percent
Recoveries
for
Calibration
Verification
Samples
Analyte
Lab1
n
Average
Recovery
(%)
Recovery
Range
%

Sb
1
Youden
Outlying
Laboratory2
2
11
99
95­
102
3
14
101
95­
107
4
2
91
90­
91
5
8
103
101­
105
7
7
101
98­
104
8
7
98
94­
100
Cd
1
5
101
100­
104
2
16
99
95­
102
3
10
100
97­
103
4
2
105
105­
105
5
9
103
100­
108
6
Youden
Outlying
Laboratory2
7
7
103
101­
105
8
7
99
96­
101
Cu
1
Youden
Outlying
Laboratory2
2
12
100
92­
112
3
14
101
93­
110
4
2
109
108­
110
5
5
97
94­
99
7
7
95
92­
99
8
7
95
90­
99
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
6.
Percent
Recoveries
for
Calibration
Verification
Samples
Analyte
Lab1
n
Average
Recovery
(%)
Recovery
Range
%

Draft
­
December
2000
27
Pb
1
Youden
Outlying
Laboratory2
2
10
99
95­
100
3
14
101
98­
107
4
2
102
101­
102
5
9
102
98­
105
7
7
99
98­
100
8
7
101
98­
104
Ni
1
5
100
99­
103
2
Youden
Outlying
Laboratory2
3
14
97
91­
104
4
2
105
103­
107
5
9
95
88­
102
7
7
94
91­
100
8
7
96
93­
99
Se
1
5
101
97­
106
2
11
98
94­
103
3
10
104
99­
110
4
2
108
107­
109
5
6
98
86­
108
7
7
96
93­
100
8
7
99
95­
102
Ag
1
5
96
93­
99
2
20
99
92­
107
3
10
103
95­
105
4
Youden
Outlying
Laboratory2
5
9
104
101­
108
7
7
102
101­
103
8
7
100
98­
102
Tl
1
5
101
99­
103
2
18
99
91­
110
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
6.
Percent
Recoveries
for
Calibration
Verification
Samples
Analyte
Lab1
n
Average
Recovery
(%)
Recovery
Range
%

Draft
­
December
2000
28
3
10
100
97­
107
4
2
90
89­
90
5
9
104
100­
107
7
Youden
Outlying
Laboratory2
8
7
102
97­
105
Zn
1
5
101
99­
103
2
16
97
88­
106
3
14
99
92­
107
4
2
103
102­
104
5
Youden
Outlying
Laboratory2
7
7
97
95­
101
8
7
98
94­
100
1Laboratory
5
did
not
prepare
and
analyze
calibration
verification
samples
2The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
29
5.3.4
Initial
and
Ongoing
Precision
and
Recovery
(
IPR/
OPR)

Draft
Method
1638
required
each
laboratory
to
analyze
at
least
four
reagent
water
samples
spiked
with
the
analytes
of
interest
prior
to
use
of
the
method
(
IPR
analyses)
and
one
reagent
water
sample
spiked
with
the
analytes
of
interest
with
each
analytical
batch
(
OPR
analyses).
Laboratories
reported
results
for
as
many
as
12
IPR
analyses
and
as
many
as
15
OPR
analyses.

The
IPR/
OPR
sample
results
were
screened
for
outliers
before
being
used
to
develop
QC
acceptance
criteria.
In
addition,
all
results
generated
from
IPR/
OPR
samples
spiked
below
the
draft
method
ML
were
excluded.
The
precision
and
recovery
data
used
in
development
of
IPR/
OPR
QC
acceptance
criteria
(
Section
6.4)
are
summarized
in
Table
5­
7.
Table
4
in
Appendix
B
contains
all
IPR
and
OPR
data
submitted
for
this
study.

Table
5­
7.
Precision
and
Recovery
Samples
Analyte
QC
attribute
Lab1
Overall2
1
2
3
4
5
6
7
8
Sb
IPR
Mean
Rec.
(%)

Youden
Outlying
Laboratory3
108
110
125
114
110
102
107
114
Std
dev
5
2
13
2
6
2
3
8
N
4
4
11
6
6
4
4
39
OPR
Mean
Rec.
(%)
99
11
97
119
­
91
94
104
Std
dev
12
2
1
20
­
5
10
13
N
10
3
5
9
­
2
3
32
Cd
IPR
Mean
Rec.
(%)
100
98
98
103
110
Youden
Outlying
Laboratory3
85
87
100
Std
dev
6
8
3
5
5
1
5
5
N
4
4
4
12
8
4
4
40
OPR
Mean
Rec.
(%)
99
102
101
107
121
85
99
105
Std
dev
18
10
3
1
7
2
10
8
N
2
12
3
5
9
3
3
37
Cu
IPR
Mean
Rec.
(%)

Youden
Outlying
Laboratory3
115
Spiked
below
draft
method
ML
4
115
125
110
94
Spiked
below
draft
method
ML
4
113
Std
dev
21
11
18
4
1
13
N
4
12
6
6
4
32
OPR
Mean
Rec.
(%)
117
110
100
­
92
107
Std
dev
15
2
8
­
2
10
N
8
5
9
­
3
25
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
7.
Precision
and
Recovery
Samples
Analyte
QC
attribute
Lab1
Overall2
1
2
3
4
5
6
7
8
Draft
­
December
2000
30
Pb
IPR
Mean
Rec.
(%)

Youden
Outlying
Laboratory3
125
97
107
137
102
99
103
111
Std
dev
3
2
3
8
2
1
1
4
N
3
4
12
8
6
4
4
41
OPR
Mean
Rec.
(%)
105
93
106
114
­
108
106
107
Std
dev
19
2
2
4
­
14
4
11
N
7
3
5
9
­
3
3
30
Ni
IPR
Mean
Rec.
(%)
107
Youden
Outlying
Laboratory2
Spiked
below
draft
method
ML
4
104
99
103
96
Spiked
below
draft
method
ML
4
102
Std
dev
2
2
8
3
1
4
N
4
12
8
6
4
34
OPR
Mean
Rec.
(%)
98
105
98
­
92
99
Std
dev
2
2
5
­
2
4
N
2
5
9
­
3
19
Se
IPR
Mean
Rec.
(%)

Spiked
below
draft
method
ML
4
90
106
103
90
Youden
Outlying
Laboratory3
96
103
98
Std
dev
8
2
4
11
1
3
6
N
4
4
12
8
4
4
36
OPR
Mean
Rec.
(%)
123
94
105
108
96
92
106
100
Std
dev
2
14
9
2
23
2
6
15
N
2
8
3
5
10
3
3
34
Ag
IPR
Mean
Rec.
(%)
103
104
85
Youden
Outlying
Laboratory3
115
107
101
108
105
Std
dev
4
1
0
3
3
2
4
4
N
4
4
4
8
6
4
8
34
OPR
Mean
Rec.
(%)
93
98
86
119
­
100
104
103
Std
dev
10
4
3
18
­
2
1
10
N
2
15
3
10
­
3
3
36
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
7.
Precision
and
Recovery
Samples
Analyte
QC
attribute
Lab1
Overall2
1
2
3
4
5
6
7
8
Draft
­
December
2000
31
Tl
IPR
Mean
Rec.
(%)
104
133
102
96
126
96
Youden
Outlying
Laboratory3
98
107
Std
dev
7
4
1
3
10
9
4
6
N
4
4
4
12
8
6
4
42
OPR
Mean
Rec.
(%)
93
83
103
93
119
­
110
98
Std
dev
11
13
7
1
15
­
4
12
N
2
14
3
5
9
­
3
36
Zn
IPR
Mean
Rec.
(%)
90
129
104
115
Youden
Outlying
Laboratory3
90
99
116
107
Std
dev
4
15
1
14
9
1
10
11
N
4
4
4
12
6
4
4
38
OPR
Mean
Rec.
(%)
95
103
104
102
­
98
116
103
Std
dev
4
22
3
2
­
4
8
16
N
2
12
3
5
­
3
2
27
1
Lab
6
did
not
prepare
and
analyze
OPR
samples.
2Overall
numbers
were
calculated
as:
1)
total
number
of
results,
2)
mean
recovery
of
all
individual
recoveries,
3)
weighted
mean
of
standard
deviations.
2The
laboratory's
data
package
was
identified
as
an
outlying
laboratory
for
this
analyte
using
Youden's
laboratory
ranking.

5.3.5
Matrix
Spike
and
Matrix
Spike
Duplicate
Analyses
Method
1638
requires
each
laboratory
to
prepare
and
analyze
MS/
MSD
samples
for
each
sample
batch.
Spiking
concentrations
must
be
one
to
five
times
the
background
or
one
to
five
times
the
ML,
whichever
is
greater.
In
developing
QC
acceptance
criteria,
EPA
used
results
from
all
MS/
MSD
pairs
that
were
spiked
above
the
draft
method
ML
and
were
within
the
laboratory's
calibration
range.
Laboratory
6
reported
only
MS
results,
precluding
calculation
of
RPDs.
Therefore,
MS
results
from
Laboratory
6
were
not
used
in
developing
MS/
MSD
acceptance
criteria.
The
two
MS/
MSD
samples
prepared
by
Laboratory
8
on
the
reagent
water
matrix
also
were
excluded
from
the
QC
acceptance
criteria
calculations
because
such
spikes
more
closely
represent
an
OPR
sample
than
a
matrix
spike
sample.

MS/
MSD
sample
results
were
subjected
to
Youden
outlier
analysis
before
being
used
to
develop
QC
acceptance
criteria.
MS/
MSD
sample
results
used
for
development
of
QC
acceptance
criteria
are
summarized
in
Table
5­
8
across
laboratories,
in
Table
5­
9
across
matrices,
and
in
Figure
1
below.
Table
3
in
Appendix
B
contains
all
MS/
MSD
data
submitted
by
the
laboratories.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
32
Table
5­
8.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Laboratories
Analyte
QC
attribute
Lab
Overall1
1
2
3
4
5
7
8
Sb
Mean
Recovery
(%)

Youden
Outlying
Laboratory2
98
105
94
101
106
102
100
Recovery
Range
(%)
85­
104
89­
114
91­
95
85­
138
102­
116
86­
109
85­
138
Mean
RPD
(%)
2
2
2
8
3
5
3
RPD
Range
(%)
1­
2
1­
3
1­
4
1­
15
0­
9
1­
13
0­
15
Number
of
Pairs
4
3
4
2
3
3
19
Cd
Mean
Recovery
(%)
103
103
96
102
87
101
98
98
Recovery
Range
(%)
99­
110
92­
115
90­
103
99­
105
43­
103
100­
103
92­
105
43­
115
Mean
RPD
(%)
2
6
1
1
8
1
1
3
RPD
Range
(%)
0­
4
2­
13
0­
1
1­
2
2­
19
0­
1
0­
1
0­
19
Number
of
Pairs
3
4
4
4
4
3
3
25
Cu
Mean
Recovery
(%)

Youden
Outlying
Laboratory2
108
98
100
86
92
89
96
Recovery
Range
(%)
97­
122
98­
99
94­
102
63­
158
90­
95
82­
103
63­
158
Mean
RPD
(%)
1
0
1
9
1
2
3
RPD
Range
(%)
1­
2
0­
0
0­
1
1­
18
1­
1
2­
3
0­
18
Number
of
Pairs
3
1
4
3
3
3
17
Pb
Mean
Recovery
(%)

Youden
Outlying
Laboratory2
94
95
99
93
90
103
96
Recovery
Range
(%)
88­
99
87­
105
96­
101
86­
97
77­
99
99­
111
77­
111
Mean
RPD
(%)
2
1
1
1
1
2
1
RPD
Range
(%)
0­
3
0­
4
0­
2
0­
2
0­
1
1­
4
0­
4
Number
of
Pairs
4
4
4
3
3
3
21
Ni
Mean
Recovery
(%)
96
Youden
Outlying
Laboratory2
83
95
78
92
92
89
Recovery
Range
(%)
92­
103
79­
87
88­
98
47­
92
88­
98
89­
98
47­
103
Mean
RPD
(%)
1
0
2
2
1
1
1
RPD
Range
(%)
1­
2
0­
0
0­
4
0­
5
1­
1
0­
2
0­
5
Number
of
Pairs
3
2
4
4
3
3
19
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
8.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Laboratories
Analyte
QC
attribute
Lab
Overall1
1
2
3
4
5
7
8
Draft
­
December
2000
33
Se
Mean
Recovery
(%)
111
100
108
103
67
95
97
97
Recovery
Range
(%)
98­
129
90­
105
99­
114
100­
105
31­
100
89­
107
91­
104
31­
129
Mean
RPD
(%)
4
4
2
2
6
3
1
3
RPD
Range
(%)
3­
7
1­
9
0­
5
1­
3
2­
12
2­
5
0­
2
0­
12
Number
of
Pairs
3
4
4
4
4
3
3
25
Ag
Mean
Recovery
(%)
94
90
93
Youden
Outlying
Laboratory2
89
98
98
93
Recovery
Range
(%)
84­
100
85­
96
85­
99
59­
106
97­
100
89­
122
59­
122
Mean
RPD
(%)
3
2
1
2
0
6
2
RPD
Range
(%)
1­
5
1­
4
1­
2
1­
3
0­
0
1­
13
0­
13
Number
of
Pairs
3
4
4
4
3
3
21
Tl
Mean
Recovery
(%)
102
101
104
88
113
Youden
Outlying
Laboratory2
105
102
Recovery
Range
(%)
98­
105
88­
107
99­
110
84­
90
57­
140
97­
111
57­
140
Mean
RPD
(%)
1
3
2
1
6
2
3
RPD
Range
(%)
1­
3
0­
6
0­
4
0­
2
1­
14
1­
3
0­
14
Number
of
Pairs
3
4
4
4
4
3
22
Zn
Mean
Recovery
(%)
96
104
91
99
Youden
Outlying
Laboratory2
98
102
99
Recovery
Range
(%)
95­
97
91­
114
77­
106
96­
102
92­
106
80­
164
77­
164
Mean
RPD
(%)
3
2
5
1
1
4
2
RPD
Range
(%)
3­
3
0­
4
1­
15
0­
1
0­
1
0­
10
0­
15
Number
of
Pairs
1
4
4
4
3
3
19
1Overall
numbers
were
calculated
as:
1)
mean
recovery
of
all
individual
recoveries,
2)
overall
recovery
range,
3)
weighted
mean
RPD
of
all
laboratory
mean
RPDs,
4)
overall
RPD
range,
and
5)
total
number
of
pairs.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
34
Table
5­
9.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Matrices
Analyte
QC
attribute
Matrix
Overall1
Filtered
Freshwater
Filtered
Effluent
Unfiltered
Effluent
Sb
Mean
Recovery
(%)
101
98
102
100
Recovery
Range
(%)
85­
138
85­
116
94­
107
85­
138
Mean
RPD
(%)
4
3
1
3
RPD
Range
(%)
0­
15
1­
9
0­
2
0­
15
Number
of
Pairs
10
5
4
19
Cd
Mean
Recovery
(%)
101
99
95
98
Recovery
Range
(%)
90­
108
86­
110
43­
115
43­
115
Mean
RPD
(%)
2
2
6
3
RPD
Range
(%)
0­
4
0­
7
0­
19
0­
19
Number
of
Pairs
11
7
7
25
Cu
Mean
Recovery
(%)
95
93
99
96
Recovery
Range
(%)
63­
122
82­
99
64­
158
63­
158
Mean
RPD
(%)
3
1
3
3
RPD
Range
(%)
0­
18
0­
3
1­
9
0­
18
Number
of
Pairs
8
4
5
17
Pb
Mean
Recovery
(%)
97
95
94
96
Recovery
Range
(%)
86­
111
87­
104
77­
105
77­
111
Mean
RPD
(%)
1
1
2
1
RPD
Range
(%)
0­
4
0­
2
1­
4
0­
4
Number
of
Pairs
10
6
5
21
Ni
Mean
Recovery
(%)
93
89
84
89
Recovery
Range
(%)
85­
103
79­
98
47­
98
47­
103
Mean
RPD
(%)
1
2
1
1
RPD
Range
(%)
0­
3
0­
4
0­
5
0­
5
Number
of
Pairs
8
6
5
19
Se
Mean
Recovery
(%)
101
95
93
97
Recovery
Range
(%)
73­
129
61­
107
31­
112
31­
129
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
5­
9.
MS/
MSD
Percent
Recoveries
and
Relative
Percent
Differences
Across
Matrices
Analyte
QC
attribute
Matrix
Overall1
Filtered
Freshwater
Filtered
Effluent
Unfiltered
Effluent
Draft
­
December
2000
35
Mean
RPD
(%)
3
2
4
3
RPD
Range
(%)
0­
10
0­
5
2­
12
0­
12
Number
of
Pairs
11
7
7
25
Ag
Mean
Recovery
(%)
99
90
88
93
Recovery
Range
(%)
85­
122
84­
97
59­
98
59­
122
Mean
RPD
(%)
3
2
1
2
RPD
Range
(%)
0­
13
0­
5
0­
2
0­
13
Number
of
Pairs
9
6
6
21
Tl
Mean
Recovery
(%)
103
107
96
102
Recovery
Range
(%)
88­
130
84­
140
57­
107
57­
140
Mean
RPD
(%)
4
1
2
3
RPD
Range
(%)
0­
14
0­
3
0­
5
0­
14
Number
of
Pairs
10
6
6
22
Zn
Mean
Recovery
(%)
100
98
97
99
Recovery
Range
(%)
77­
164
87­
107
80­
114
77­
164
Mean
RPD
(%)
4
1
1
2
RPD
Range
(%)
0­
15
0­
2
0­
2
0­
15
Number
of
Pairs
9
5
5
19
1Overall
numbers
were
calculated
as:
1)
mean
recovery
of
all
individual
recoveries,
2)
overall
recovery
range,
3)
weighted
mean
RPD
of
all
laboratory
mean
RPDs,
and
4)
overall
RPD
range,
and
5)
total
number
of
pairs.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
36
80.0
90.0
100.0
110.0
120.0
Ag
(

n=

42)
Cd
(

n=

50)
Cu
(

n=

34)
Ni
(

n=

38)
Pb
(

n=

42)
Sb
(

n=

38)
Se
(

n=

50)
Tl
(

n=

44)
Zn
(

n=

38)
Distribution
of
MS/
MSD
Recoveries
Analyte
Percent
Recovery
Figure
1.
Distribution
of
MS/
MSD
Recoveries
5.3.6
Method
Blank
Analyses
Method
1638
requires
the
analysis
of
method
blanks
with
each
sample
batch.
The
method
states
that
the
target
analyte
may
not
be
present
in
the
method
blank
at
a
level
equal
to
or
greater
than
the
MDL.
If
the
concentration
exceeds
the
MDL,
the
laboratory
must
identify
the
source
of
contamination,
correct
the
problem,
and
re­
analyze
the
method
blank
and
all
associated
samples.
In
order
to
assess
both
potential
contamination
and
instrument
drift
resulting
in
negative
bias,
method
blanks
were
assessed
by
comparing
the
absolute
value
of
the
method
blank
result
to
the
revised
MDL
for
the
corresponding
analyte.

Table
5­
10
summarizes
the
results
of
all
method
blanks
excluding
Youden
outliers.
Of
the
275
method
blank
results
reported,
more
than
93
percent
were
below
the
MDL
for
the
corresponding
analyte.
Lead
was
the
analyte
most
commonly
reported
in
method
blank
exceedances.
All
method
blank
results
are
given
in
Table
5
of
Appendix
B.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
37
Table
5­
10.
Method
Blank
Results
Analyte
Revised
MDL
Mean
Method
Blank
(
µ
g/
L)
Minimum
Method
Blank
(
µ
g/
L)
Maximum
Method
Blank
(
µ
g/
L)
n
Number
Exceeding
Revised
MDL
Antimony
0.05
0.002
­
0.019
0.028
24
0
Cadmium
0.08
0.005
­
0.037
0.292
36
1
Copper
0.13
0.328
­
0.037
6.364
26
2
Lead
0.015
0.033
­
0.022
0.859
25
6
Nickel
0.11
0.057
­
0.002
1.168
22
1
Selenium
0.9
­
0.001
­
0.827
0.519
31
0
Silver
0.03
0.018
­
0.004
0.391
39
5
Thallium
0.015
0.000
­
0.010
0.015
37
0
Zinc
0.3
0.102
­
0.245
2.127
35
2
5.3.7
Calibration
Blank
Analyses
Method
1638
requires
laboratories
to
analyze
a
calibration
blank
after
every
calibration
verification
to
demonstrate
that
there
is
no
carryover
and
that
the
analytical
system
is
free
from
contamination.
The
target
analytes
must
not
be
present
in
the
calibration
blank
at
a
level
equal
to
or
greater
than
the
MDL.
If
the
concentration
exceeds
the
MDL,
the
laboratory
must
identify
the
source
of
contamination,
correct
the
problem,
verify
the
calibration,
and
repeat
the
analysis.
Calibration
blanks
were
assessed
by
comparing
the
absolute
value
of
the
calibration
blank
results
to
the
revised
MDL
for
the
corresponding
analyte.

Table
5­
11
summarizes
the
results
of
all
calibration
blanks.
More
than
93
percent
of
the
539
calibration
blank
results
reported,
were
below
the
MDL
for
the
corresponding
analyte.
As
was
observed
with
the
method
blanks,
lead
had
the
highest
number
of
calibration
blank
exceedances.
All
calibration
blank
results
are
given
in
Table
5
of
Appendix
B.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
38
Table
5­
11.
Calibration
Blank
Results
Analyte
Revised
MDL
Mean
Calibration
Blank
(
µ
g/
L)
Minimum
Calibration
Blank
(
µ
g/
L)
Maximum
Calibration
Blank
(
µ
g/
L)
n
Number
Exceeding
Revised
MDL
Antimony
0.05
0.012
­
0.024
0.400
65
3
Cadmium
0.08
0.005
­
0.130
0.070
62
1
Copper
0.13
­
0.006
­
0.109
0.084
62
0
Lead
0.015
0.003
­
0.085
0.029
59
13
Nickel
0.11
­
0.003
­
0.165
0.130
49
4
Selenium
0.9
­
0.024
­
1.162
0.516
58
1
Silver
0.03
0.001
­
0.464
0.049
62
10
Thallium
0.015
­
0.003
­
0.200
0.014
62
1
Zinc
0.3
­
0.018
­
0.429
0.248
60
2
5.3.8
Standard
Reference
Material
Analyses
Each
laboratory
was
required
to
analyze
the
National
Institute
of
Science
and
Technology
(
NIST)
standard
reference
material
(
SRM)
1643d
at
least
once
during
Phase
3
of
this
study.
Laboratories
1
and
7
analyzed
an
additional
SRM
(
SLRS­
4)
from
the
Canadian
National
Research
Council
(
NRC).
SLRS­
4
contained
six
of
the
nine
target
analytes
(
excluding
silver,
selenium,
and
thallium)
at
lower
levels
than
1643d.
The
concentration
of
cadmium
was
below
the
analytical
range
of
the
method
and
was
not
considered
for
evaluation
of
Method
performance.
SRM
results
are
summarized
in
Table
5­
12
and
presented
in
Figure
2.
All
SRM
analyses
are
reported
in
Appendix
B,
Table
6.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
39
Table
5­
12.
SRM
Sample
Results
Analyte
SRM
Concentration
(
ug/
L
)
Mean
%
Recovery
Standard
Deviation
Number
of
Sample
Analyses
Number
of
Labs
Antimony
NIST­
1643
D
54.1
98
4
12
5
SLRS­
4
0.23
114
7
3
1
Cadmium
NIST­
1643
D
6.47
94
3
18
6
Copper
NIST­
1643
D
20.5
102
9
19
7
SLRS­
4
1.8
111
3
3
1
Lead1
NIST­
1643
D
18.15
93
12
15
6
Nickel
NIST­
1643
D
58.1
95
2
11
4
SLRS­
4
0.67
106
4
4
2
Selenium
NIST­
1643
D
11.43
94
14
18
7
Silver
NIST­
1643
D
1.27
98
6
18
7
Thallium
NIST­
1643
D
7.28
91
10
16
7
Zinc
NIST­
1643
D
72.48
95
7
16
6
SLRS­
4
0.93
99
3
4
2
1The
analytical
results
from
Laboratory
7
showed
poor
recoveries
(~
5%)
for
lead.
NIST
1643d
contains
bismuth,
and
the
laboratory
used
bismuth
as
an
internal
standard
for
lead.
The
lead
results
for
Laboratory
7
were
excluded
from
this
summary
information.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
40
80.0
90.0
100.0
110.0
120.0
Ag
(

n=

18)
Cd
(

n=

18)
Cu
(

n=

22)
Ni
(

n=

11)
Pb
(

n=

18)
Sb
(

n=

15)
Se
(

n=

18)
Tl
(

n=

16)
Zn
(

n=

20)
Distribution
of
SRM
Recoveries
Analyte
Percent
Recovery
Figure
2.
Distribution
of
SRM
Recoveries
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
41
5.3.9
Quality
Control
Samples
Method
1638
requires
laboratories
to
analyze
a
quality
control
sample
(
QCS)
when
beginning
use
of
the
method,
quarterly,
or
as
required
to
meet
data
quality
needs.
Although
QCS
analysis
was
not
required
for
this
study,
four
laboratories
analyzed
at
least
one
QCS.
QCS
results
are
summarized
in
Table
5­
13,
excluding
data
from
Youden
outlying
laboratories,
and
given
in
Appendix
B,
Table
6.

Table
5­
13.
Quality
Control
Sample
Results
Analyte
Mean
%
Recovery
Number
of
Samples
Number
of
Samples
<
90%
Recovery
Number
of
Samples
>
110%
Recovery
Antimony
120
12
0
5
Cadmium
103
14
0
0
Copper
107
16
0
5
Lead
103
16
0
0
Nickel
99
12
0
0
Selenium
105
14
0
2
Silver
101
10
0
0
Thallium
98
14
4
2
Zinc
99
13
1
2
5.4
Silver
Recoveries
Since
initiating
this
study,
EPA
has
learned
of
potential
problems
and
interferences
in
quantifying
silver.
Laboratory
4
reported
silver
concentration
data
for
two
days
of
analyses,
and
noted
poor
MS/
MSD
recoveries
for
silver
on
the
second
day.
The
laboratory
attributed
the
poor
recoveries
to
degradation
of
the
10
mg/
L
multi­
element
standard
used
to
spike
the
samples.
Analysis
of
the
standard
by
ICP­
AES
confirmed
that
the
silver
concentration
was
not
stable.
The
laboratory
suggested
that
the
problem
might
be
that
standards
prepared
in
0.4%
HCl
+
0.8%
HNO3
acid
are
not
as
stable
as
standards
prepared
in
1%
nitric
acid.
Laboratory
4
was
identified
as
the
Youden
outlying
laboratory
for
silver
and
was
not
included
for
development
of
silver
QC
acceptance
criteria.
Table
5­
15
shows
that
all
other
laboratories
reported
acceptable
silver
recovery
for
QC
samples
spiked
in
the
laboratory.

Because
the
QC
acceptance
criteria
developed
in
this
study
are
based
on
QC
results
and
the
QC
sample
results
do
not
show
low
silver
recoveries,
the
QC
acceptance
criteria
developed
in
this
study
are
considered
valid.
The
field
sample
results
show
low
silver
recovery
when
compared
to
the
expected
sample
concentration
determined
in
Phase
2.
EPA
recognizes
that
further
study
may
be
needed
to
assess
potential
interferences
and
the
stability
of
silver
in
the
presence
of
acid
preservatives.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
42
Table
5­
14.
Recovery
of
Silver
in
QC
and
Field
Samples
Lab
Mean
IPR
(%
Rec)
Mean
OPR
(%
Rec)
Mean
QCS
(%
Rec)
Mean
Cal
Ver
(%
Rec)
Mean
MS/
MSD
(%
Rec)
Mean
Field
Dups
(%
Rec)
Mean
Youden
Pairs
(%
Rec)

1
103
93
­
96
94
46
12
2
104
98
102
99
91
64
12
3
85
86
­
103
91
85
84
4
Youden
laboratory
outlier
5
115
119
101
104
84
55
26
6
107
­
­
­
­
70
27
7
101
100
­
102
98
46
6
8
108
104
101
100
98
45
6
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
8EPA
Guide
to
Method
Flexibility
and
Approval
of
EPA
Water
Methods,
EPA
821­
D­
96­
004,
December
1996.

Draft
­
December
2000
43
Section
6
Development
of
QC
Acceptance
Criteria
QC
acceptance
criteria
for
Method
1638
were
developed
using
ASTM
and
AOAC­
International
procedures
and
procedures
given
in
Chapter
3
of
EPA's
Guide
to
Method
Flexibility
and
Approval
of
EPA
Water
Methods.
8
Development
of
these
criteria
is
described
in
Sections
6.1
through
6.5.
Details
of
statistical
analyses
are
given
in
Appendix
C.

6.1
Method
Detection
Limit
(
MDL)
and
Minimum
Level
(
ML)

The
latest
water
quality
criteria
(
WQC)
published
by
EPA
are
those
listed
in
the
National
Toxics
Rule
(
57
FR
60848)
and
the
Stay
of
Federal
Water
Quality
Criteria
for
Metals
(
60
FR
22228).
These
rules
include
water
quality
criteria
for
13
metals
including
the
nine
target
analytes
for
Method
1638.
In
developing
Method
1638,
EPA
set
a
goal
that
analytical
methods
be
developed
that
are
capable
of
achieving
MDLs
that
are
one
tenth
the
lowest
EPA
WQC
for
that
metal.
This
goal
was
designed
to
avoid
the
need
for
blank
subtraction
by
ensuring
any
contributions
from
contaminant
sources
(
as
measured
by
blanks)
were
insignificant
(
i.
e.,
<
10%
of
total
sample
result)
at
potential
regulatory
compliance
levels.

To
establish
MDLs
for
Method
1638,
EPA
used
results
generated
during
Phase
1
(
presented
in
Table
5­
1).
After
removing
Youden
outlying
laboratories,
pooled
MDLs
for
each
analyte
were
calculated
and
the
pooled
and
highest
MDLs
were
compared
to
the
MDLs
listed
in
the
draft
method
and
to
the
lowest
Water
Quality
Criterion
for
each
metal.
Table
6­
1
presents
these
values.
When
revising
Method
1638,
EPA
intends
to
specify
the
highest
MDL
achieved
among
the
seven
participating
laboratories
as
the
MDL
criterion
for
the
method.
Such
MDLs
allow
for
detection
of
nearly
all
target
metals
at
least
10
times
below
the
lowest
EPA
water
quality
criterion
for
that
metal.
It
is
important
to
note
that
the
data
suggest
most
laboratories
can
achieve
lower
MDLs.
Laboratories
and
regulatory
authorities
should
consider
this
capability
when
using
Method
1638.

The
equations
used
to
calculate
pooled
MDLs
are
presented
in
Appendix
C.
MLs
for
each
analyte
were
determined
by
multiplying
the
MDL
by
3.18
(
or
by
the
appropriate
multiplier
if
the
laboratory
used
more
than
7
replicates
to
determine
the
MDL),
and
rounding
to
the
number
nearest
to
(
1,
2,
or
5)
x
10n,
where
n
is
a
positive
or
negative
integer.
The
3.18
multiplier
is
the
ratio
between
the
10
sigma
multiplier
used
to
establish
the
American
Chemical
Society's
(
ACS)
limit
of
quantitation
and
the
Student's
t
multiplier.
The
revised
MDLs
and
MLs
are
given
in
Table
6­
1.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
44
Table
6­
1.
Revised
MDLs
and
MLs
Analyte
Draft
MDL
(
µ
g/
L)
1/
10
WQC
(
µ
g/
L)
Pooled
MDL
(
µ
g/
L)
Highest
MDL
(
µ
g/
L)
Revised
MDL
(
µ
g/
L)
Revised
ML
(
µ
g/
L)

Sb
0.0097
1.4
0.016
0.048
0.05
0.2
Cd
0.025
0.037
0.025
0.077
0.08
0.2
Cu
0.087
0.24
0.056
0.132
0.13
0.5
Pb
0.015
0.054
0.007
0.013
0.015
0.05
Ni
0.33
0.82
0.051
0.111
0.11
0.5
Se
0.45
0.5
0.450
0.892
0.90
2.0
Ag
0.029
0.032
0.013
0.026
0.03
0.1
Tl
0.0079
0.17
0.005
0.015
0.015
0.05
Zn
0.14
3.2
0.109
0.288
0.30
1.0
6.2
Calibration
Linearity
EPA
intends
to
revise
the
calibration
section
in
Method
1638
to
recommend
use
of
response
factor
or
weighted
linear
regression
and
allow
unweighted
linear
regression
as
acceptable
calibration
techniques.
To
ensure
that
the
calibration
is
linear,
the
correlation
coefficients
for
unweighted
and
weighted
linear
regression
must
be
greater
than
0.995
and
0.990,
respectively,
and
the
intercept
must
have
an
absolute
value
less
than
the
MDL.
A
correlation
coefficient
of
0.995
is
the
standard
limit
for
assessing
calibration
linearity
using
an
unweighted
regression
in
analytical
methods
for
metals
and
a
correlation
coefficient
of
0.990
was
judged
to
allow
for
equal
weighting
in
the
weighted
regression.

6.3
Calibration
Verification
Calibration
verification
QC
acceptance
criteria
were
developed
using
all
calibration
verification
sample
results
remaining
after
data
validation
(
Section
4)
and
outlier
analysis
(
Section
5.3.1).
Calculations
used
to
develop
QC
acceptance
criteria
are
detailed
in
Appendix
C
and
encompass
both
between­
laboratory
and
within­
laboratory
variability.
In
general,
the
calculated
recovery
limits,
shown
in
Table
6­
2,
support
the
calibration
verification
limits
specified
in
the
draft
method.
Results
of
the
study
suggested
the
need
for
slightly
wider
limits
for
cadmium
and
silver;
EPA
intends
to
modify
the
draft
specifications
accordingly.
Revised
calibration
verification
QC
acceptance
criteria
reflecting
these
changes
are
listed
in
the
last
column
of
Table
6­
2.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
45
Table
6­
2.
Calibration
Verification
Acceptance
Criteria
Analyte
Draft
Recovery
Limits
(%)
Calculated
Recovery
Limits
(%)
Revised
Recovery
Limits
(%)

Antimony
90­
111
90­
111
90­
111
Cadmium
91­
105
95­
107
91­
107
Copper
76­
120
86­
111
76­
120
Lead
91­
120
96­
105
91­
120
Nickel
86­
116
87­
107
86­
116
Selenium
69­
127
89­
111
69­
127
Silver
81­
107
92­
108
81­
108
Thallium
82­
118
89­
111
82­
118
Zinc
76­
121
89­
108
76­
121
6.4
Initial
and
Ongoing
Precision
and
Recovery
(
IPR/
OPR)

QC
acceptance
criteria
for
IPR/
OPR
were
developed
using
all
IPR/
OPR
sample
results
remaining
after
data
validation
and
outlier
analysis.
Calculations
were
modified
from
ASTM
guidelines
and
EPA's
Guide
to
Method
Flexibility
and
Approval
of
EPA
Water
Methods
to
handle
a
different
number
of
results
per
laboratory.
ASTM
and
EPA
guidelines
concerning
the
development
of
QC
acceptance
criteria
for
IPR/
OPR
results
assume
that
all
labs
generate
the
same
number
of
results
(
i.
e.,
a
constant
"
n"
among
labs).
To
allow
development
of
criteria
based
on
all
valid
IPR/
OPR
data
submitted
by
each
laboratory,
the
ASTM
and
EPA
guidelines
were
slightly
modified
and
degrees
of
freedom
were
calculated
using
Satterthwaite's
method.
Calculations
used
to
develop
QC
acceptance
criteria
are
detailed
in
Appendix
C
and
encompass
both
between­
laboratory
and
within­
laboratory
variability.
In
general,
the
calculated
recovery
limits,
shown
in
Table
6­
3,
support
the
calibration
verification
limits
specified
in
the
draft
method.
Results
of
the
study
suggested
the
need
for
wider
recovery
limits
for
antimony,
cadmium,
and
silver;
EPA
intends
to
modify
the
draft
specifications
accordingly.
Revised
IPR/
OPR
QC
acceptance
criteria
reflecting
these
changes
are
listed
in
the
last
column
in
Table
6­
3
and
6­
4.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
46
Table
6­
3.
IPR
Acceptance
Criteria
Analyte
Draft
Recovery
and
Standard
Deviation
Limits
Calculated
Recovery
and
Standard
Deviation
Limits
Revised
Recovery
and
Standard
Deviation
Limits
s
X
s
X
s
X
Antimony
20
81­
120
19
90­
128
20
81­
128
Cadmium
13
85­
112
12
79­
126
13
79­
126
Copper
43
55­
141
20
89­
132
43
55­
141
Lead
30
75­
140
15
87­
132
30
75­
140
Nickel
30
71­
131
7
90­
112
30
71­
131
Selenium
41
63­
145
19
79­
119
41
63­
145
Silver
19
82­
120
13
81­
127
19
81­
127
Thallium
30
66­
134
23
78­
128
30
66­
134
Zinc
43
55­
142
22
83­
128
43
55­
142
Table
6­
4.
OPR
Verification
Acceptance
Criteria
Analyte
Draft
Recovery
Limits
(%)
Calculated
Recovery
Limits
(%)
Revised
Recovery
Limits
(%)

Antimony
79­
122
81­
138
79­
138
Cadmium
84­
113
77­
128
77­
128
Copper
51­
145
80­
141
51­
145
Lead
72­
143
82­
137
72­
143
Nickel
68­
134
89­
113
68­
134
Selenium
59­
149
72­
126
59­
149
Silver
74­
119
78­
130
74­
130
Thallium
64­
137
68­
137
64­
137
Zinc
46­
146
73­
138
46­
146
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
47
6.5
Matrix
Spike/
Matrix
Spike
Duplicate
(
MS/
MSD)
Recovery
and
Relative
Percent
Difference
(
RPD)

QC
acceptance
criteria
for
MS/
MSD
precision
and
recovery
were
developed
using
MS/
MSD
sample
results
remaining
after
data
validation
and
outlier
analysis.
These
samples
included
filtered
freshwater,
filtered
effluent,
and
unfiltered
effluent
matrices.
Calculations
used
to
develop
QC
acceptance
criteria
are
detailed
in
Appendix
C
and
encompass
both
between­
laboratory
and
within­
laboratory
variability.
These
calculations
reflect
the
statistical
procedures
recommended
by
ASTM
and
EPA
guidance
with
modifications
to
allow
for
calculation
of
degrees
of
freedom
using
Satterthwaite's
method.
Details
of
these
calculations
are
presented
in
Appendix
C,
and
the
calculated
MS/
MSD
QC
acceptance
criteria
are
listed
in
Table
6­
4.

In
most
cases,
the
calculated
recovery
and
RPD
limits
for
the
spiked
matrix
samples
supported
the
limits
given
in
the
draft
method.
EPA
intends
to
retain
the
draft
specifications
where
supported
by
the
data
from
this
study.
EPA
intends
to
slightly
widen
some
specifications
to
reflect
study
results
and
ensure
that
neither
the
upper
or
lower
recovery
limits
for
the
matrix
spike
samples
are
more
restrictive
than
their
corresponding
limit
in
the
OPR
samples
(
which
are
prepared
in
reagent
water).

Table
6­
5.
MS/
MSD
Acceptance
Criteria
Analyte
Draft
Recovery
and
RPD
Limits
Calculated
Recovery
and
RPD
Limits
Revised
Recovery
RPD
Limits
RPD
X
RPD
X
RPD
X
Antimony
NA
79­
122
29
79­
122
29
79­
138
Cadmium
NA
84­
113
17
75­
122
17
75­
128
Copper
NA
51­
145
52
59­
132
52
51­
145
Lead
NA
72­
143
11
81­
111
11
72­
143
Nickel
NA
68­
134
7
64­
115
7
64­
134
Selenium
NA
59­
149
17
57­
137
17
57­
149
Silver
NA
74­
119
11
70­
117
11
70­
130
Thallium
NA
64­
137
17
70­
133
17
64­
137
Zinc
NA
46­
146
31
68­
129
31
46­
146
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
48
Section
7
Data
Analysis
and
Discussion
Data
were
gathered
in
this
study
to
characterize
the
overall
performance
of
Method
1638
and
to
identify
areas
of
the
method,
including
QC
acceptance
criteria,
requiring
further
revision.
Areas
requiring
revision
were
discussed
previously
in
this
report
and
are
summarized
in
Section
8.
The
remainder
of
this
section
focuses
on
overall
method
performance.
Section
7.1
discusses
performance
of
the
method
in
each
of
the
matrices
tested
during
the
study;
Section
7.2
discusses
the
method's
performance
across
matrices
and
laboratories.

7.1
Matrix­
Specific
Performance
of
Method
1638
In
conducting
this
study,
EPA
sought
to
determine
if
Method
1638
was
capable
of
yielding
reliable
results
in
the
variety
of
matrices
to
which
the
method
might
be
applied,
including
ambient
freshwater
samples,
and
filtered
and
unfiltered
point
source
discharges.
To
assess
the
method's
performance
in
each
matrix,
percent
recoveries
were
determined
for
each
sample
at
each
concentration
in
each
matrix.
Mean
percent
recoveries
and
standard
deviations
(
SDs)
were
then
determined
for
each
matrix
in
each
laboratory.
The
standard
deviations
determined
by
calculating
the
square
root
of
the
weighted
mean
of
all
laboratory
variances
in
a
given
matrix.
The
average
percent
recoveries
were
determined
by
calculating
the
mean
of
all
laboratory
mean
recoveries
for
a
given
matrix.
Table
7­
1
presents
the
results
of
this
analysis
using
1)
field
samples
only,
2)
MS/
MSD
samples
only,
and
3)
a
combination
of
field
and
MS/
MSD
samples.
These
results
demonstrate
that
the
method
performs
comparably
across
matrix
types.

Table
7­
1.
Pooled
Matrix
Specific
Precision
and
Recovery
Field
Samples
MS/
MSD
Samples
Field
+
MS/
MSD
Samples
Analyte
Matrix
Mean
%
Rec1
Precision
(
SD)
n
Mean
%
Rec
Precision
(
SD)
n
Mean
%
Rec1
Precision
(
SD)
n
Antimony
Filtered
Effluent
105
8
13
98
4
10
102
7
23
Unfiltered
Effluent
95
1
11
102
1
8
98
4
19
Freshwater
99
8
42
99
2
8
99
8
50
Reagent
Water
78
12
40
 
 
 
78
12
40
Cadmium
Filtered
Effluent
95
18
14
99
4
14
97
18
28
Unfiltered
Effluent
95
3
14
95
8
14
95
21
28
Freshwater
101
6
14
101
3
14
101
9
28
Reagent
Water
97
3
28
 
 
 
97
3
28
Copper
Filtered
Effluent
103
3
12
92
2
6
99
7
18
Unfiltered
Effluent
110
8
14
99
30
10
105
19
24
Freshwater
116
74
55
96
8
14
112
67
69
Reagent
Water
113
31
41
 
 
 
113
31
41
Lead
Filtered
Effluent
124
11
14
95
1
12
110
18
26
Unfiltered
Effluent
108
2
13
94
3
10
102
5
23
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Table
7­
1.
Pooled
Matrix
Specific
Precision
and
Recovery
Field
Samples
MS/
MSD
Samples
Field
+
MS/
MSD
Samples
Analyte
Matrix
Mean
%
Rec1
Precision
(
SD)
n
Mean
%
Rec
Precision
(
SD)
n
Mean
%
Rec1
Precision
(
SD)
n
Draft
­
December
2000
49
Freshwater
135
41
41
98
3
12
123
44
61
Reagent
Water
109
21
39
 
 
 
109
21
39
Nickel
Filtered
Effluent
96
3
13
89
2
12
92
6
25
Unfiltered
Effluent
96
5
14
84
2
10
91
15
24
Freshwater
99
8
42
94
2
10
98
9
52
Reagent
Water
92
1
23
 
 
 
92
1
23
Selenium
Filtered
Effluent
141
4
14
95
4
14
118
32
28
Unfiltered
Effluent
136
6
14
93
5
14
114
30
28
Freshwater
92
10
22
103
7
14
96
12
36
Reagent
Water
99
5
38
 
 
 
99
5
38
Silver
Filtered
Effluent
77
10
14
90
3
12
83
13
26
Unfiltered
Effluent
46
2
14
88
1
12
65
26
26
Freshwater
43
20
28
99
6
12
60
35
40
Reagent
Water
45
36
42
 
 
 
45
36
42
Thallium
Filtered
Effluent
98
4
13
111
2
10
103
11
23
Unfiltered
Effluent
98
4
14
96
9
12
97
11
26
Freshwater
96
4
28
105
4
12
99
8
40
Reagent
Water
94
6
48
 
 
 
94
6
48
Zinc
Filtered
Effluent
100
5
14
98
2
10
99
5
24
Unfiltered
Effluent
102
1
13
97
3
10
100
7
23
Freshwater
110
47
42
99
16
12
108
43
54
Reagent
Water
102
14
42
 
 
 
102
14
42
*
Percent
recoveries
of
field
samples
were
calculated
using
expected
concentrations
in
Table
2­
1
and
Appendix
B,
Table
1.

7.2
Overall
Performance
of
Method
1638
Mean
precision
and
recovery
results
for
IPR,
OPR,
QCS,
MS/
MSD,
blind
duplicate
and
Youden
sample
pairs
analyzed
by
each
of
the
participating
laboratories
during
Phase
3
are
summarized
in
Table
7­
2,
along
with
the
pooled
results
across
laboratories.
In
addition,
the
distribution
of
field
duplicates
RPDs
is
presented
in
Figure
3.
With
the
exception
of
the
antimony
and
copper
QCS
values
reported
by
Laboratory
4
the
mean
percent
recoveries
of
all
QC
samples
were
within
the
revised
QC
acceptance
criteria.
With
the
exception
of
pooled
antimony
recovery,
the
results
of
all
QC
acceptance
criteria
pooled
across
laboratories
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
50
0.0
10.0
20.0
30.0
Ag
(

n=

35)
Cd
(

n=

35)
Cu
(

n=

38)
Ni
(

n=

31)
Pb
(

n=

37)
Sb
(

n=

31)
Se
(

n=

40)
Tl
(

n=

40)
Zn
(

n=

34)
Distribution
of
Field
Duplicate
RPDs
Analyte
Relative
Percent
Difference
also
were
within
the
revised
QC
acceptance
criteria
These
results
support
application
of
Method
1638
to
the
determination
of
trace
levels
of
antimony,
cadmium,
copper,
lead,
nickel,
selenium,
silver,
thallium,
and
zinc
in
all
study
matrices.

Figure
3.
Distribution
of
Field
Duplicate
RPDs
51
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
Analyte
Lab
IPR
OPR
QCS
SRM
Cal
Ver
MS/
MSD
Phase
3
Duplicates
Phase
3
Youden
Pairs
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Antimony
1
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

2
108
5
96
7
103
2
99
­
99
2
96
2
86
2
96
2
3
­
­
­
­
­
­
­
­
101
3
102
2
84
3
97
1
4
­
­
97
1
130
26
95
1
91
1
94
1
86
4
96
1
5
91
47
­
­
­
­
­
­
103
1
87
1
73
1
96
3
6
­
­
­
­
­
­
99
3
­
­
­
­
92
6
101
4
7
­
­
­
­
­
­
107
9
101
2
108
5
86
3
100
1
8
107
3
94
11
107
1
107
­
98
2
107
1
88
2
108
10
Pooled
100
34
96
6
120
21
101
6
100
2
99
2
86
3
99
3
Cadmium
1
100
6
99
18
­
­
94
­
101
2
103
2
92
5
­
­

2
98
8
102
10
101
2
93
6
99
2
106
7
94
13
­
­

3
­
­
­
­
­
­
­
­
100
2
94
1
102
3
­
­

4
103
5
107
1
105
2
95
1
105
0
102
1
96
14
­
­

5
110
5
121
6
102
2
94
2
103
2
83
10
117
3
­
­

6
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

7
85
1
85
3
­
­
91
0
103
2
101
1
85
6
­
­

8
­
­
­
­
104
7
91
­
99
3
98
1
94
3
­
­

Pooled
101
5
106
8
104
4
94
3
101
2
98
3
97
7
­
­

Copper
1
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
Analyte
Lab
IPR
OPR
QCS
SRM
Cal
Ver
MS/
MSD
Phase
3
Duplicates
Phase
3
Youden
Pairs
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
52
2
115
18
117
13
109
8
107
8
100
6
108
1
163
26
106
7
3
­
­
­
­
­
­
103
­
101
5
98
0
113
10
92
5
4
115
9
110
2
112
4
112
1
109
1
102
1
127
18
113
10
5
125
15
100
8
99
1
96
4
97
2
88
5
107
5
141
37
6
110
3
­
­
­
­
97
3
­
­
­
­
117
20
100
2
7
­
­
­
­
­
­
102
10
95
2
92
1
98
2
94
1
8
­
­
­
­
98
4
92
­
95
3
89
2
96
2
92
2
Pooled
116
11
109
9
106
5
103
7
99
5
96
2
118
12
105
9
Lead
1
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

2
134
14
105
18
100
3
71
13
99
2
96
2
118
9
225
24
3
97
2
93
2
­
­
102
­
101
2
94
2
114
4
138
6
4
107
3
106
2
106
3
98
2
102
1
98
1
109
6
120
3
5
137
6
114
4
100
1
86
6
102
2
92
1
128
13
139
28
6
102
2
­
­
­
­
108
3
­
­
­
­
118
2
141
3
7
99
1
108
13
­
­
­
­
99
1
90
1
98
1
114
1
8
103
1
106
4
101
1
97
­
101
2
103
2
103
3
101
3
Pooled
113
5
107
10
103
3
93
5
101
2
96
1
112
5
140
10
Nickel
1
107
1
98
2
­
­
104
­
100
2
96
1
93
5
102
3
2
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
Analyte
Lab
IPR
OPR
QCS
SRM
Cal
Ver
MS/
MSD
Phase
3
Duplicates
Phase
3
Youden
Pairs
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
53
3
­
­
­
­
­
­
92
­
97
5
79
0
93
2
99
4
4
104
2
105
2
99
4
96
1
105
3
95
2
103
2
112
4
5
99
8
98
5
100
2
­
­
95
6
74
2
103
5
118
1
6
103
3
­
­
­
­
96
4
­
­
­
­
85
11
69
2
7
96
1
92
2
­
­
100
8
94
3
92
1
94
1
99
3
8
­
­
­
­
101
5
­
­
96
2
92
1
96
2
104
2
Pooled
102
4
99
4
100
4
98
6
97
4
89
1
95
4
100
3
Selenium
1
­
­
123
2
­
­
111
­
101
4
111
4
134
6
96
2
90
9
94
15
101
7
85
31
98
3
102
3
114
9
53
3
106
2
105
9
­
­
101
­
104
4
107
2
123
2
95
4
103
4
108
1
108
2
107
2
108
2
102
2
110
2
88
5
90
12
96
24
95
­
88
8
98
9
64
8
113
3
111
6
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

7
96
1
92
2
­
­
83
3
96
3
95
3
95
2
85
8
103
3
106
6
103
1
89
­
99
2
97
1
99
5
91
Pooled
98
7
100
16
105
3
94
12
100
4
97
3
112
4
93
Silver
1
103
3
93
10
­
­
83
­
96
2
94
3
46
5
12
51
2
104
1
98
5
102
3
96
4
99
4
91
3
64
8
12
78
3
85
1
86
4
­
­
94
­
103
3
91
1
85
4
84
9
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
Analyte
Lab
IPR
OPR
QCS
SRM
Cal
Ver
MS/
MSD
Phase
3
Duplicates
Phase
3
Youden
Pairs
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
54
4
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

5
115
3
119
15
101
1
99
4
104
2
84
1
55
11
26
23
6
107
3
­
­
­
­
109
4
­
­
­
­
70
4
27
41
7
101
2
100
2
­
­
99
1
102
1
98
0
46
20
6
31
8
108
7
104
1
101
3
100
­
100
2
98
6
45
53
6
101
Pooled
105
3
103
9
102
3
98
3
100
3
93
2
59
15
25
48
Thallium
1
104
7
93
11
­
­
103
­
101
2
102
1
87
4
86
1
2
133
3
83
16
103
6
79
9
99
5
105
3
100
8
101
5
3
102
1
103
6
­
­
100
­
100
3
105
2
101
3
101
2
4
96
3
93
1
90
4
91
2
90
1
90
0
88
2
87
0
5
126
8
119
13
­
­
98
­
104
2
111
4
98
3
98
3
6
96
10
­
­
­
­
106
2
­
­
­
­
102
3
103
3
7
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

8
98
4
110
4
110
14
98
­
102
3
105
2
96
2
90
1
Pooled
107
6
98
13
98
7
91
5
100
4
104
2
96
4
95
2
Zinc
1
90
4
95
5
­
­
­
­
101
2
96
3
93
5
94
10
2
129
12
95
13
104
8
95
3
97
6
105
2
129
14
130
13
3
104
1
104
2
­
­
108
­
99
5
90
2
103
7
100
7
4
115
12
102
2
96
9
99
1
103
1
98
0
99
5
91
29
Table
7­
2.
Laboratory
Precision
and
Recovery
Performance
Using
EPA
Method
1638
Analyte
Lab
IPR
OPR
QCS
SRM
Cal
Ver
MS/
MSD
Phase
3
Duplicates
Phase
3
Youden
Pairs
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RSD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
Mean
%
Rec
RPD
55
5
The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

6
90
10
­
­
­
­
96
3
­
­
­
­
112
24
106
4
7
99
1
98
4
­
­
83
3
97
2
98
1
93
1
85
3
8
­
­
­
­
94
8
94
­
98
2
102
4
134
8
85
4
Pooled
106
10
98
10
98
8
95
2
98
5
98
2
109
9
99
10
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Draft
­
December
2000
56
Section
8
Conclusion
and
Discussion
Results
of
this
study
demonstrate
the
ability
of
EPA
Method
1638
to
provide
reliable
data
for
determination
of
target
analytes
in
reagent
water,
freshwater,
and
effluent
with
slight
modifications
to
clarify
certain
QC
requirements
and
to
adjust
QC
acceptance
criteria.
The
Study
results
also
suggest
that
further
investigation
of
stability
of
silver
in
the
presence
of
acid
preservatives
is
needed.

Specific
modifications
suggested
by
this
study
include:
C
Revision
of
the
calibration
requirements
(
Section
10.0)
to
recommend
response
factor
or
weighted
linear
regressions
and
allow
for
unweighted
linear
regression.
C
Revision
of
the
IPR
and
OPR
analyses
(
Sections
9.2.2
and
9.7,
respectively)
to
require
laboratories
to
spike
IPR
and
OPR
samples
at
1­
5
times
the
ML
instead
of
2­
3
times
the
ML.
This
change
will
standardize
the
method
with
current
EPA
OW
policies.
C
Clarification
of
the
OPR
requirements
to
require
an
OPR
to
be
prepared
and
analyzed
with
each
analytical
batch.
C
Clarification
of
the
MS/
MSD
requirements
(
Section
9.3)
to
explicitly
that
an
MSD
sample
must
be
prepared
and
analyzed;
C
Revision
of
the
method
and
calibration
blank
requirements
(
Sections
9.6.1
and
10.6
respectively)
will
be
revised
to
require
that
the
absolute
value
of
the
blanks
for
the
target
analytes
be
less
than
the
MDL;
and
C
Method
blank
requirements
will
be
clarified
to
require
a
method
blank
to
be
prepared
and
analyzed
with
each
analytical
batch.

With
these
results,
EPA
Method
1638
can
be
considered
valid
for
the
determination
of
dissolved
and
total
antimony,
cadmium,
copper,
lead,
nickel,
selenium,
silver,
thallium,
and
zinc
in
aqueous
matrices
at
water
quality
criteria
levels.
Draft
­
December
2000
Appendix
A
Study
Plan
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
A­
1
Study
Plan
for
Collaborative
Validation
of
Trace
Metals
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640
Prepared
for
William
A.
Telliard
U.
S.
Environmental
Protection
Agency
Office
of
Water
Office
of
Science
and
Technology
Engineering
and
Analysis
Division
(
4303)
401
M
Street,
SW
Washington,
D.
C.
20460
Prepared
by
DynCorp
Environmental
300
North
Lee
Street
Alexandria,
Virginia
22314
Prepared
under
EPA
Sample
Control
Center
Contract
No.
68­
C3­
0337
February
1997
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
2
Draft
­
December
2000
Acknowledgments
This
study
plan
was
prepared
under
the
direction
of
William
A.
Telliard
of
the
Engineering
and
Analysis
Division
within
the
U.
S.
Environmental
Protection
Agency
(
EPA)
Office
of
Water.
It
was
prepared
by
DynCorp
Environmental
under
EPA
Contract
No.
68­
C3­
0337.

Disclaimer
This
document
has
been
reviewed
and
approved
by
the
EPA
Engineering
and
Analysis
Division.
Mention
of
company
names,
trade
names,
or
commercial
products
does
not
constitute
endorsement
or
recommendation
for
use.
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
3
TABLE
OF
CONTENTS
SECTION
1:
INTRODUCTION
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
1
SECTION
2:
OBJECTIVES
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
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.
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.
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.
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.
.
.
.
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.
.
.
.
.
.
.
2
2.1
Phase
1
Objectives
­
Laboratory
Qualification
and
Selection
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
2
2.1.1
Method
Blank
Analysis
Results
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
3
2.1.2
Method
Detection
Limit
Studies
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
3
2.1.3
Provision
of
Time
for
Gaining
Familiarity
with
the
Methods
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
4
2.2
Phase
2
Objectives
­
Sample
Collection
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
4
2.2.1
Collect
Samples
that
Represent
Multiple
Matrices
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
4
2.2.2
Minimize
Contamination
.
.
.
.
.
.
.
.
.
.
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.
4
2.2.3
Ensure
Homogeneity
and
Characterize
Stability
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
4
2.2.4
Collect
Filtered
and
Unfiltered
Samples
.
.
.
.
.
.
.
.
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.
.
.
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.
.
.
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.
.
.
.
.
5
2.2.5
Collect
Samples
that
Represent
Multiple
Concentration
Ranges
.
.
.
.
.
.
.
.
.
.
.
.
.
5
2.2.6
Collect
Samples
to
Allow
Evaluation
of
Intralaboratory
Precision
.
.
.
.
.
.
.
.
.
.
.
5
2.3
Phase
3
Objectives
­
Method
Performance
Evaluation
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
6
2.4
Data
Quality
Objectives
for
Phases
1
through
3
.
.
.
.
.
.
.
.
.
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.
.
.
.
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.
.
7
SECTION
3:
STUDY
MANAGEMENT
.
.
.
.
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.
.
8
SECTION
4:
TECHNICAL
APPROACH
.
.
.
.
.
.
.
.
.
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.
.
8
4.1
Phase
1
Technical
Approach
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
.
.
.
.
8
4.1.1
Method
Blank
Analysis
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
.
.
.
.
9
4.1.2
Method
Detection
Limit
Study
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
9
4.2
Phase
2
Technical
Approach
.
.
.
.
.
.
.
.
.
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.
.
.
.
10
4.2.1
Equipment
Cleaning
and
Preparation
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
11
4.2.2
Field
Sampling
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
11
4.2.3
Sample
Filtration,
Sample
Preservation,
and
Sample
Shipment
.
.
.
.
.
.
.
.
.
.
.
.
12
4.2.4
Determination
of
Field
Sample
Concentrations
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
12
4.2.5
Generation
of
Sample
Pairs
and
Homogenization
of
Samples
.
.
.
.
.
.
.
.
.
.
.
.
.
13
4.2.6
Stability
Analysis
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
14
4.3
Phase
3
Technical
Approach
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
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.
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.
.
.
.
.
14
SECTION
5:
DATA
REPORTING
AND
EVALUATION
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
16
SECTION
6:
LIMITATIONS
.
.
.
.
.
.
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.
.
.
.
.
17
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
4
Draft
­
December
2000
SECTION
1:
INTRODUCTION
The
Clean
Water
Act
requires
that
ambient
water
quality
criteria
(
WQC)
published
by
the
United
States
Environmental
Protection
Agency
(
EPA)
reflect
the
latest
scientific
knowledge
concerning
the
physical
fate
of
pollutants,
the
effects
of
pollutants
on
ecological
and
human
health
and
welfare,
and
the
effect
of
pollutants
on
biological
community
diversity,
productivity,
and
stability.

The
EPA
Office
of
Water
(
OW),
EPA
Regions,
and
state
permitting
authorities
are
increasing
their
emphasis
on
water
qualitySbased
permitting
under
the
National
Pollutant
Discharge
Elimination
System.
However,
ambient
WQC
levels
for
trace
metals
require
measurement
capabilities
at
levels
as
much
as
280
times
lower
than
those
required
to
support
technology­
based
permit
limits.
The
WQC
associated
with
trace
metals
are
presented
in
the
National
Toxics
Rule,
published
at
57
FR
60848.
Although
the
Agency
has
long
held
that
analytical
detection
limits
should
not
be
a
consideration
when
calculating
WQC
(
because
detection
limits
are
not
related
to
actual
environmental
impacts),
the
ability
to
make
reliable
measurements
at
WQC
levels
is
an
obvious
goal.
This
study
plan
is
designed
to
validate
seven
1600­
series
trace
metals
methods
that
have
been
developed
in
response
to
the
low­
level
WQC
requirements.

In
1993,
OW's
Engineering
and
Analysis
Division
(
EAD),
within
the
Office
of
Science
and
Technology,
began
researching
analytical
methodology
believed
to
be
capable
of
making
measurements
at
or
near
WQC
levels.
In
developing
these
methods,
EAD
sought
to
utilize
existing
instrumentation
and
technology
to
the
maximum
extent
possible.
EAD
also
sought
to
ensure
that
the
methods
would
provide
the
quality
control
(
QC)
requirements
necessary
to
demonstrate
the
reliability
of
data
gathered
at
the
low
concentrations
associated
with
WQC.
Finally,
EAD
sought
to
minimize
method
development
costs
by
basing
its
approaches
on
techniques
already
in
use
by
marine
chemists
familiar
with
measuring
metals
at
ambient
levels.

In
1994,
EAD
developed
preliminary
drafts
of
EPA
sampling,
analysis,
and
data
reporting
procedures
that
could
be
used
to
collect
reliable
metals
data
for
use
in
water
qualitySbased
permitting.
EAD
conducted
several
studies
in
1995
and
1996
aimed
at
developing
new
procedures
and
validating
the
preliminary
procedures
in
the
draft
sampling
and
analysis
guidance
documents.
Results
of
those
studies
were
used
to
develop
seven
draft
EPA
methods
for
the
analysis
of
trace
metals.

EAD's
Analytical
Method's
Staff
(
AMS)
updated
draft
versions
of
these
methods
in
1996
to
reflect
minor
editorial
corrections
and
final
WQC
values
published
in
May
1995
under
the
Stay
of
Federal
Water
Quality
Criteria
for
Metals
(
60
FR
22228).
Two
of
the
methods
(
Methods
1631
and
1632)
were
further
revised
to
reflect
results
of
several
single­
laboratory
studies
that
were
completed
in
early
1996.
Current
versions
of
the
seven
draft
methods
are
as
follows:

°
Method
1631:
Mercury
in
Water
by
Oxidation,
Purge
and
Trap,
and
CVAFS.
EPA
821­
R­
96­
001,
July
1996
°
Method
1632:
Inorganic
Arsenic
in
Water
by
Hydride
Generation
Quartz
Furnace
AA.
EPA
821­
R­
96­
002,
July
1996
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
5
°
Method
1636:
Determination
of
Hexavalent
Chromium
by
Ion
Chromatography.
EPA
821­
R­
96­
003,
January
1996
°
Method
1637:
Determination
of
Trace
Elements
in
Ambient
Waters
by
Chelation
Preconcentration
with
Graphite
Furnace
Atomic
Absorption.
EPA
821­
R­
96­
004,
January
1996
°
Method
1638:
Determination
of
Trace
Elements
in
Ambient
Waters
by
Inductively
Coupled
Plasma­
Mass
Spectrometry.
EPA
821­
R­
96­
005,
January
1996
°
Method
1639:
Determination
of
Trace
Elements
in
Ambient
Waters
by
Stabilized
Temperature
Graphite
Furnace
Atomic
Absorption.
EPA
821­
R­
96­
006,
January
1996
°
Method
1640:
Determination
of
Trace
Elements
in
Ambient
Waters
by
On­
Line
Chelation
Preconcentration
and
Inductively
Coupled
Plasma­
Mass
Spectrometry.
EPA
821­
R­
96­
007,
January
1996
EAD's
next
step
in
the
development
of
the
seven
draft
methods
is
to
evaluate
their
performance
through
a
collaborative
(
round­
robin)
laboratory
study
on
real­
world
matrices.
The
design
of
this
study
is
articulated
below.

SECTION
2:
OBJECTIVES
The
primary
objective
of
the
collaborative
study
is
to
determine
the
performance
capabilities
of
the
seven
1600
series
trace
metals
methods.
A
secondary
objective
is
to
evaluate,
and
if
appropriate,
revise
the
QC
acceptance
criteria
for
data
generated
by
each
method.
To
accomplish
these
objectives,
this
study
will
be
conducted
in
three
phases.
Phase
1
will
focus
on
pre­
qualification
of
laboratories;
Phase
2
will
focus
on
collection
of
natural­
matrix
samples
for
use
in
the
collaborative
study;
and
Phase
3
will
focus
on
analysis
of
standard
reference
materials,
reagent
water,
and
natural­
matrix
samples
to
validate
each
method
of
interest
in
applicable
sample
matrices.
Specific
objectives
for
each
phase
are
described
below
in
Sections
2.1
through
2.3.
Data
quality
objectives
are
described
in
Section
2.4.

2.1
Phase
1
Objectives
­
Laboratory
Qualification
and
Selection
The
objective
of
Phase
1
is
to
ensure
that
laboratories
participating
in
the
collaborative
study
are
familiar
with
the
methods
being
validated
and
capable
of
demonstrating
acceptable
performance
prior
to
actual
implementation
of
the
collaborative
study
design.
Ideally,
a
full
collaborative
study
on
each
of
the
seven
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
1
Guidelines
for
Selection
and
Validation
of
US
EPA's
Measurement
Methods,
U.
S.
EPA
Office
of
Acid
Deposition,
Environmental
Monitoring
and
Quality
Assurance
(
OADEMQA),
Office
of
Research
and
Development,
U.
S.
Environmental
Protection
Agency,
August
1987
DRAFT.

2
"
Report
of
the
Committee
on
Collaborative
Interlaboratory
Studies,"
J.
Assoc.
Offic.
Anal.
Chem.,
67,
(
2),
1984
3
ASTM
Standard
D2777­
94,
"
Standard
Practice
for
Determination
of
Precision
and
Bias
of
Methods
of
Committee
D­
19
on
Water,"
11.01,
Water
(
1)
Annual
Book
of
ASTM
Standards,
American
Society
of
Testing
and
Materials,
Philadelphia,
PA
19103.

A­
6
Draft
­
December
2000
methods
should
yield
a
minimum
of
six
complete
and
useable
datasets.
1,2,3
To
ensure
a
useable
number
of
data
sets,
an
objective
of
Phase
1
is
to
identify
at
least
nine
qualified
laboratories
that
are
interested
in,
and
capable
of,
validating
each
method
in
each
of
the
five
matrices
of
interest.
Due
to
a
variety
of
factors,
such
as
instrument
limitations,
and
scheduling
constraints,
it
is
unlikely
that
nine
laboratories
will
be
capable
of
validating
all
seven
methods
in
each
matrix
of
interest.
Therefore,
individual
laboratories
will
be
allowed
to
select
specific
methods
that
they
wish
to
validate,
and
allowed
to
perform
analyses
on
either
the
ambient
and
effluent
matrices
or
the
marine
matrices,
or
both.
The
following
steps
will
be
taken
to
ensure
that
the
laboratories
selected
to
take
part
in
the
study
are
qualified
to
perform
trace
metals
analyses
by
the
methods
they
select
to
validate.

2.1.1
Method
Blank
Analysis
Results
Each
laboratory
must
submit
results
from
a
method
blank
analysis
for
each
method
they
are
interested
in
performing.
The
blanks
must
be
performed
according
to
the
method
procedures
and
must
be
performed
specifically
for
this
study.
Blank
analysis
results
will
be
submitted
with
the
laboratory's
bid
and
will
be
used
to
identify
contamination
levels
at
the
laboratory.

2.1.2
Method
Detection
Limit
Studies
Each
laboratory
will
be
required
to
submit
MDL
study
results
for
each
method
they
are
interested
in
performing.
The
MDL
study
results
will
be
used
to
demonstrate
the
laboratory's
ability
to
perform
the
method
effectively.
The
MDL
study
ideally
will
be
conducted
in
response
to
this
study.
However,
results
from
MDL
studies
for
the
relevant
methods
conducted
within
the
past
year
also
will
be
acceptable.
EAD
will
evaluate
MDL
study
results
as
part
of
its
identification
of
qualified
laboratories.

MDL
studies
on
reagent
water,
ambient
water,
or
effluent
will
be
required
for
laboratories
interested
in
validating
method
performance
in
ambient
water
and
effluent
matrices.
MDL
studies
on
marine
water
will
be
required
for
laboratories
interested
in
validating
method
performance
in
marine
matrices.
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
7
2.1.3
Provision
of
Time
for
Gaining
Familiarity
with
the
Methods
Because
the
primary
purpose
of
the
collaborative
study
is
to
determine
the
performance
capabilities
of
each
method,
it
is
important
that
laboratories
participating
in
the
study
be
familiar
with
method
requirements
and
procedures.
It
is
not
necessary,
however,
for
each
laboratory
to
have
extensive
experience
with
each
method.
Rather,
laboratories
participating
in
the
study
should
have
experience
that
is
representative
of
the
federal,
state,
local,
and
private
laboratories
that
subsequently
will
use
the
method.
To
achieve
this
objective,
laboratories
will
be
provided
with
a
period
of
21
­
30
days,
depending
on
scheduling
constraints,
to
perform
the
required
MDL
studies
and
blank
analyses.
This
period
provides
laboratories
that
have
little
to
no
experience
with
the
method
with
sufficient
time
to
review
their
methods
of
choice
and
perform
any
preliminary
analyses
necessary
to
become
familiar
with
the
requirements
and
procedures.

2.2
Phase
2
Objectives
­
Sample
Collection
The
objective
of
Phase
2
is
to
collect
appropriate,
uncontaminated
natural­
matrix
samples
for
use
in
the
round­
robin
study.
In
order
to
ensure
that
the
samples
collected
are
appropriate
for
use
in
a
collaborative
study,
the
following
secondary
objectives
will
be
pursued
in
this
phase:

2.2.1
Collect
Samples
that
Represent
Multiple
Matrices
All
seven
1600
series
methods
are
believed
to
be
applicable
to
ambient
water
and
effluent
samples.
Four
of
the
methods
 
Methods
1631,
1632,
1637,
and
1640
 
also
are
believed
to
be
applicable
to
marine
samples.
In
addition,
reagent
water
will
be
analyzed
for
all
methods
to
establish
a
baseline
characterization
of
the
precision
and
bias
of
the
methods.
Therefore,
an
objective
of
Phase
2
is
to
collect
or
prepare
ambient
water,
effluent,
marine
water,
and
reagent
water
samples.

2.2.2
Minimize
Contamination
To
control
variability
among
results
and
to
ensure
that
trace
metals
detected
in
the
study
are
not
the
result
of
contamination
during
sampling,
it
is
critical
that
contamination
be
strictly
controlled
during
implementation
of
Phase
2.
Therefore,
Phase
2
sampling
activities
and
preparation
of
sampling
equipment
and
bottles
will
be
conducted
in
accordance
with
the
procedures
described
in
EPA
Method
1669:
Sampling
Ambient
Water
for
Trace
Metals
at
EPA
Water
Quality
Criteria
Levels
(
EPA
821­
R­
96­
008,
July
1996)
and
in
accordance
with
Sections
4.2.1
­
4.2.3
of
this
study
plan.
In
addition,
field
blanks
will
be
collected
with
each
group
of
samples
and
will
be
analyzed
by
a
referee
laboratory
to
verify
that
the
samples
are
free
from
contamination.

2.2.3
Ensure
Homogeneity
and
Characterize
Stability
Samples
used
in
the
collaborative
study
should
be
homogeneous
in
the
form
and
amount/
volume
to
be
tested.
All
participant
laboratories
will
receive
the
same
sample
volumes.
The
referee
laboratory(
ies)
will
agitate
the
field
carboys
when
creating
test
samples
in
an
attempt
to
ensure
homogeneity
among
the
samples.
The
referee
laboratory(
ies)
also
will
analyze
all
sample
types
by
all
methods
over
a
time
period
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
4
Youden,
W.
J.
and
E.
H.
Steiner,
1975.
Statistical
Manual
of
the
Association
of
Official
Analytical
Chemists,
AOAC,
1111
North
19th
Street,
Suite
210,
Arlington,
VA
22209
A­
8
Draft
­
December
2000
equivalent
to
that
covering
the
study,
or
at
the
conclusion
of
the
study,
to
assure
stability
of
the
test
samples.

2.2.4
Collect
Filtered
and
Unfiltered
Samples
To
verify
that
each
method
is
applicable
to
analysis
of
total
recoverable
metals
and
to
dissolved
metals,
an
unfiltered
aliquot
of
effluent,
marine,
and
reagent
water
sample
matrices
will
be
collected
for
subsequent
total
recoverable
metals
determinations,
and
a
filtered
aliquot
of
ambient
water,
effluent,
and
marine
matrices
will
be
collected
for
dissolved
metals
determinations.

2.2.5
Collect
Samples
that
Represent
Multiple
Concentration
Ranges
To
the
extent
feasible,
an
objective
of
Phase
2
is
to
collect
samples
that
represent
the
concentration
ranges
of
interest.
Specifically,
the
samples
collected
should
represent
levels
that
are
typical
of
the
matrices
to
which
the
methods
will
be
applied
and
of
the
anticipated
regulatory
action
levels.
Regulatory
action
levels
will
typically
be
equal
to
the
WQC
levels,
the
minimum
levels
(
MLs)
specified
in
the
method,
or
the
technology­
based
permitting
levels.
In
general,
WQC
levels
are
above
both
the
MDL
and
the
ML,
concentrations
found
in
most
ambient
waters
are
near
the
MDL
or
ML,
and
concentrations
found
in
effluents
are
near
the
ML
or
the
technology­
based
permitting
level.

Therefore,
EAD
believes
that
a
combination
of
ambient
samples
and
effluent
samples
will
adequately
represent
the
concentration
ranges
of
interest.
Collection
and
subsequent
analysis
of
marine
samples
by
some
of
the
methods
may
provide
additional
concentration
ranges
for
those
methods
applicable
to
marine
water
matrices.
Finally,
the
reagent
water
samples
prepared
for
this
study
will
be
spiked
at
three
concentrations
across
the
working
range
of
the
methods
to
characterize
method
performance
and
confirm
the
linear
response
of
the
methods.
To
ensure
that
natural­
matrix
samples
collected
are
within
appropriate
concentration
ranges,
EAD
also
will
spike
all
of
the
natural
matrix
samples
as
necessary
to
achieve
the
desired
range(
s).

2.2.6
Collect
Samples
to
Allow
Evaluation
of
Intralaboratory
Precision
To
enable
EPA
to
evaluate
intralaboratory
precision,
but
preclude
laboratories
from
anticipating
results
of
true
replicate
samples,
a
pair
of
samples
will
be
generated
for
each
of
the
six
matrices
in
the
study
according
to
guidelines
developed
by
Youden.
4
Results
from
analysis
of
these
samples
will
be
used
to
generate
within­
laboratory
precision
estimates.
In
this
study,
two
batches
of
spiked
samples
will
be
generated
for
each
of
the
natural
matrices.
Each
laboratory
in
the
study
will
receive
one
sample
from
each
batch
(
a
sample
pair)
for
each
method
they
will
be
performing
and
each
matrix
they
will
be
analyzing.
EAD
will
prepare
six
batches
of
samples
for
the
reagent
water
matrix
 
two
batches
for
each
of
the
three
concentrations
across
the
working
range
of
the
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
9
methods.
Each
laboratory
in
the
study
will
receive
three
pairs
of
reagent
water
samples
for
each
method
they
will
be
performing.

2.3
Phase
3
Objectives
­
Method
Performance
Evaluation
The
objective
of
Phase
3
is
to
evaluate
the
performance
of
the
seven
1600­
series
trace
metals
in
multiple
laboratories.
In
previous,
single­
laboratory
studies,
MDLs,
MLs,
and
QC
acceptance
criteria
were
established
for
each
method.
Further
method
optimization
is
not
the
goal
of
this
study.
The
objective
of
the
round­
robin
study
is
to
provide
a
realistic
estimate
of
the
attributes
of
each
method,
particularly
the
systematic
and
random
deviations,
to
be
expected
when
the
method
is
used
in
actual
practice.
A
secondary
objective
is
to
evaluate
the
QC
acceptance
criteria
established
in
the
draft
methods.
If
appropriate,
results
from
Phase
3
will
be
used
to
modify
these
acceptance
criteria.

Because
this
study
will
be
used
to
evaluate
method
performance
under
routine
laboratory
conditions,
laboratories
will
be
prohibited
from
performing
multiple
analyses
to
improve
recoveries.
Laboratories
will,
however,
be
allowed
to
implement
corrective
action
and
reanalysis
for
QC
failures
that
are
attributable
to
analyst
error,
such
as
incorrect
spiking
levels,
or
to
instrument
failure.
In
addition,
many
methods
for
trace
metals
require
replicate
injections
into
the
instrument.
Such
replicate
injections
will
be
allowed,
but
in
such
cases,
laboratories
participating
in
the
study
will
be
required
to
identify
the
instrument
on
which
replicate
injections
were
made,
and
to
report
the
calculation
procedures
employed
by
the
instrument
to
report
sample
concentrations.
For
example,
some
instruments
may
be
programmed
to
average
results
of
multiple
background
determinations
and
subtract
that
average
from
the
results
of
replicate
sample
analyses.
Other
instruments
may
be
programmed
to
subtract
a
single
background
determination
from
the
average
of
replicate
sample
analyses.

To
meet
the
objectives
of
Phase
3,
laboratories
in
the
study
will
analyze
pairs
of
real­
world
samples,
representing
up
to
five
different
matrices,
pairs
of
reagent
water
samples,
representing
three
concentrations
across
the
working
range
of
the
methods,
and
up
to
two
standard
reference
materials
(
SRMs).
The
five
real­
world
matrices
include
filtered
ambient
water,
unfiltered
and
filtered
effluent,
and
unfiltered
and
filtered
marine
water.
Laboratories
will
analyze
the
following:

C
A
pair
of
effluent
water
samples
and
three
pairs
of
reagent
water
samples
for
total
recoverable
metals
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640
C
A
pair
of
ambient
water
samples
and
a
pair
of
effluent
water
samples
for
dissolved
metals
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640
C
A
pair
of
marine
water
samples
for
dissolved
and
total
recoverable
metals
using
Methods
1631,
1632,
1637,
and
1640
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
10
Draft
­
December
2000
2.4
Data
Quality
Objectives
for
Phases
1
through
3
In
addition
to
the
overall
objectives
described
above,
EAD
has
three
principle
data
quality
objectives
(
DQOs)
for
this
study:

1.
All
samples
and
data
produced
under
this
study
must
be
generated
according
to
the
analytical
and
QA/
QC
procedures
defined
in
the
relevant
method.
Alternatively,
the
data
must
be
the
result
of
preapproved
and
documented
changes
to
these
procedures.
This
will
allow
EAD
to
use
the
results
of
the
round­
robin
study
to
identify
the
need
for
further
revision
of
the
method.

2.
All
data
produced
under
this
phase
of
the
study
must
be
capable
of
being
verified
by
an
independent
person
reviewing
the
analytical
data
package.

3.
The
MDLs
determined
in
Phase
1
of
this
study
must
be
within
a
factor
of
five
of
the
level
spiked
to
ensure
that
MDLs
determined
in
the
study
are
neither
overstated
nor
understated.

To
meet
study
DQOs,
the
laboratories
will
be
required
to
have
a
comprehensive
QA
program
in
place
and
operating
throughout
the
study.
This
will
ensure
that
the
data
produced
are
of
appropriate
and
documented
quality.

During
Phase
1
of
the
study,
the
laboratories
will
be
required
to
follow
all
QC
procedures
defined
in
the
methods
they
are
interested
in
validating,
with
the
following
exceptions:

C
Demonstration
of
initial
and
ongoing
precision
and
recovery
will
not
be
required
during
Phase
1.

C
Performance
of
matrix
spike
(
MS)
and
matrix
spike
duplicate
(
MSD)
analyses
will
not
be
required
during
Phase
1.

C
Analysis
of
field
blanks
and
equipment
blanks
will
not
be
required
during
Phase
1.

C
Instrument
calibration
must
be
performed
at
a
range
that
will
encompass
the
minimum
level
(
ML)
specified
in
the
method
during
Phase
1.

During
Phases
2
and
3
of
the
study,
laboratories
will
be
required
to
follow
all
QC
procedures
defined
in
the
methods.
No
exceptions
will
be
allowed.
All
analyses
performed
in
each
phase
of
the
study
must
be
performed
on
a
calibrated
instrument,
and
calibration
verification
must
be
performed
at
the
frequency
specified
in
each
method.

SECTION
3:
STUDY
MANAGEMENT
The
study
described
in
this
document
will
be
managed
by
AMS.
Day­
to­
day
management
and
coordination
of
study
activities
will
be
performed
by
the
contractor­
operated
Sample
Control
Center
(
SCC)
under
AMS
guidance.
Collection
of
samples
under
Phase
2
of
the
study
will
be
performed
by
either
SCC
or
a
referee
laboratory
not
participating
in
Phase
3
of
the
study.
This
referee
laboratory
will
have
extensive
experience
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
11
with
the
procedures
used
in
the
methods
and
may
be
funded
through
one
of
EAD's
existing
contracts.
If
a
single
laboratory
with
extensive
experience
using
all
seven
methods
is
not
available
to
support
this
study,
more
than
one
referee
laboratory
will
be
sought,
such
that
one
referee
laboratory
is
available
for
each
method.

The
total
number
of
laboratories
participating
in
Phase
3
of
this
study
will
depend
upon
laboratory
capability
(
as
determined
in
Phase
1)
and
availability,
cost,
and
scheduling
constraints.
Laboratories
participating
in
Phase
3
of
this
study
may
include
commercial
laboratories,
academic
laboratories,
state
laboratories,
EPA
laboratories,
and/
or
municipal
laboratories.
To
ensure
that
study
schedules
are
maintained,
EPA
will
issue
a
small
purchase
order
or
will
issue
a
delivery
order
to
one
or
more
of
its
current
contract
laboratories
following
a
competitive
bidding
process.
The
awarded
laboratory(
ies)
and
their
subcontractors
must
fulfill
the
Phase
1
prequalification
requirements
as
part
of
their
bidding
process.
This
approach
will
be
used
to
ensure
that
appropriate
controls
on
study
schedule
and
data
quality
can
be
imposed.
These
controls
include
the
required
Phase
1
method
familiarization
and
pre­
qualification
requirements,
explicit
schedule
and
performance
requirements,
and
the
imposition
of
liquidated
damages
for
failing
to
follow
study
requirements
and/
or
meet
study
schedules.
Additional
laboratory
support
will
be
sought
from
EPA
Regional
laboratories,
state
laboratories,
and/
or
municipal
laboratories
on
a
voluntary
basis.
If
necessary,
and
if
feasible,
these
government
laboratories
may
be
reimbursed
for
their
costs
of
participating
in
the
study.

SCC
will
coordinate
sample
collection
and
laboratory
analysis,
and
will
receive
and
validate
all
analytical
data
and
perform
statistical
analyses.
AMS
will
draw
conclusions
from
the
results
and
produce
a
report
providing
the
results
of
the
study.
If
appropriate,
AMS
will
revise
one
or
more
methods
evaluated
in
the
study
as
necessary
to
reflect
study
findings.
AMS
also
will
share
data
and
results
with
all
interested
parties
upon
request.

SECTION
4:
TECHNICAL
APPROACH
4.1
Phase
1
Technical
Approach
Phase
1
entails
the
evaluation
of
laboratory
capability
based
on
blank
analysis
results
and
MDL
studies.

4.1.1
Method
Blank
Analysis
Each
laboratory
will
be
required
to
submit
results
from
the
analysis
of
a
laboratory
(
method)
blank
for
each
method
they
are
interested
in
performing.
These
blank
determinations
will
be
used
to
determine
if
each
laboratory
is
capable
of
maintaining
contamination
within
acceptable
levels
for
this
study.
EPA
will
evaluate
each
laboratory's
blank
results
against
historical
values
produced
with
the
method
and
with
other
laboratories'
results.
Laboratories
submitting
blanks
with
unacceptable
levels
may
have
the
opportunity
to
analyze
additional
blanks
to
reduce
the
uncertainty
regarding
their
capacity
to
produce
acceptable
data
at
low
concentrations.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
12
Draft
­
December
2000
4.1.2
Method
Detection
Limit
Study
Each
laboratory
must
submit
results
of
an
MDL
study
for
each
method
they
are
interested
in
performing.
The
MDL
study
must
be
performed
in
accordance
with
the
procedure
described
in
Federal
Register
Vol.
49
No.
209,
Friday,
October
26,
1984,
Appendix
B
to
Part
136
­
Definition
and
Procedure
for
the
Determination
of
the
Method
Detection
Limit
­
Revision
1.11.
This
procedure
involves
the
analysis
of
at
least
seven
replicate
samples
that
are
known
to
contain
the
target
analyte(
s)
at
a
concentration
of
one
to
five
times
the
estimated
MDL.

Acceptance
of
Method
Detection
Limit
Studies
Performed
Within
the
Past
Year.
Laboratories
that
have
performed
MDL
studies
within
the
past
year
for
one
or
more
of
the
seven
targeted
methods
are
permitted
to
submit
those
results
instead
of
performing
new
MDL
studies.
However,
if
changes
that
could
affect
method
performance
have
occurred
at
the
laboratory
since
an
MDL
study
was
performed,
those
MDL
study
results
cannot
be
used.
Acceptable
MDL
study
matrices
for
laboratories
interested
in
performing
analyses
on
ambient
and
effluent
matrices
include
reagent
water,
ambient
water,
and
effluent.
Acceptable
MDL
study
matrices
for
laboratories
interested
in
performing
analyses
on
marine
matrices
are
limited
to
marine
water.

Procedure
for
Method
Detection
Limit
Studies
Performed
for
this
Study.
For
each
method,
laboratories
interested
in
performing
analyses
on
ambient
and
effluent
matrices
will
spike
reagent
water,
ambient
water,
or
effluent
with
the
analyte(
s)
listed
in
the
method
to
produce
a
synthetic
sample
that
can
be
divided
into
at
least
seven
replicates.
Laboratories
interested
in
performing
analyses
on
marine
samples
will
spike
marine
samples
with
the
analyte(
s)
listed
in
the
method
to
produce
a
synthetic
sample
that
can
be
divided
into
at
least
seven
replicates.

To
ensure
that
the
laboratory
is
spiking
at
the
appropriate
level,
it
is
recommended
that
the
laboratory
follow
the
two­
aliquot
test
described
in
Section
4b
of
the
MDL
procedure.
If
these
measurements
indicate
that
a
sample
concentration
is
in
the
desired
range
for
determination
of
the
MDL,
a
laboratory
may
proceed
with
five
additional
aliquots
for
a
total
of
seven
aliquots.
All
seven
measurements
will
be
used
for
calculation
of
the
MDL.
If
the
first
two
measurements
indicate
that
the
sample
concentration
is
not
in
the
correct
range,
the
laboratory
will
be
required
to
repeat
Section
4b
(
analysis
of
two
spiked
aliquots)
until
the
desired
spike
level
is
achieved.
Application
of
the
two
aliquot
test
is
recommended
to
minimize
the
possibility
of
repeating
the
MDL
study
in
order
to
obtain
an
MDL
that
is
within
a
factor
of
five
of
the
level
spiked.

If
a
laboratory's
MDL
resulting
from
its
study
is
not
within
a
factor
of
five
of
the
level
spiked,
then
the
spiking,
measurement,
and
calculation
processes
will
be
repeated
until
the
measured
MDL
is
within
a
factor
of
five,
as
given
in
the
MDL
procedure.
If
the
laboratory
obtains
non­
detect
results
during
their
MDL
study,
that
laboratory
must
increase
the
spike
level
and
repeat
the
test.
The
objective
of
these
requirements
is
to
ensure
that
MDLs
resulting
from
the
study
are
not
artificially
high
or
low
due
to
inappropriate
spiking
levels.
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
13
The
analytical
portion
of
each
MDL
study
will
be
performed
in
accordance
with
the
procedures
described
in
the
applicable
1600­
series
method.
Each
laboratory
will
submit
MDL
study
results
in
an
MDL
summary
table
that
groups
data
under
the
following
categories:

C
Spiked
concentration
in
each
of
the
seven
replicates
C
Measured
concentration
in
each
of
the
seven
replicates
C
The
mean
of
the
seven
measured
concentrations
C
The
standard
deviation
of
these
measurements
C
The
Student's
t­
value
used
C
The
calculated
MDL
for
the
technique
Other
reporting
requirements
are
detailed
in
Section
5
of
this
study
plan.

4.2
Phase
2
Technical
Approach
Samples
will
be
collected
with
bottles
and
equipment
that
have
been
pre­
cleaned
by
a
laboratory
experienced
in
the
analysis
of
trace
metals
at
ambient
water
quality
criteria
levels.
Samples
will
be
collected
by
EAD
and
SCC
staff
or
by
the
selected
referee
laboratory(
ies)
using
procedures
detailed
in
Method
1669
for
ambient
and
marine
samples
or
procedures
based
on
the
principles
outlined
in
Method
1669
as
adapted
to
effluent
sampling.

The
sampling
team
will
collect
sufficient
volume
of
each
real­
world
matrix
to
allow
for
distribution
of
filtered
and
unfiltered
sample
pairs
to
each
laboratory,
to
allow
for
analysis
of
MS
and
MSD
samples,
and
to
provide
extra
volume
in
case
of
sample
breakage,
lost
shipments,
or
other
unforeseen
problems.
The
referee
laboratory(
ies)
will
prepare
sufficient
unfiltered
reagent
water
volume
to
allow
for
distribution
of
three
sample
pairs
per
method
to
each
laboratory
and
provide
extra
volume
in
case
of
sample
breakage,
lost
shipments,
or
other
unforeseen
problems.

In
addition,
the
sampling
team
will
collect
separate
aliquots
for
analysis
of
trivalent
and
hexavalent
chromium.
The
field
team
will
follow
the
procedures
outlined
in
Method
1669
for
preservation
of
trivalent
and
hexavalent
chromium
to
preserve
these
parameters
immediately
upon
collection.
To
minimize
sample
handling
in
the
field,
aliquots
for
all
other
parameters
will
be
preserved
immediately
upon
receipt
by
the
referee
laboratory.

All
samples
will
be
homogenized
and
divided
into
batches
under
controlled
clean
room
conditions
by
the
referee
laboratory(
ies).
The
referee
laboratory(
ies)
will
analyze
random
samples
to
ensure
that
concentration
levels
found
in
the
natural
matrices
are
appropriate
for
this
study.
The
referee
laboratory(
ies)
will
report
results
of
these
analyses
to
SCC
for
review.
If
problems
are
identified,
SCC
will
notify
EAD
to
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
14
Draft
­
December
2000
discuss
and
implement
appropriate
corrective
actions,
including
resampling,
additional
homogenization,
sample
spiking,
sample
dilution,
and/
or
other
procedures.
In
addition,
the
referee
laboratory(
ies)
will
reanalyze
samples
during
the
study
period
or
at
the
conclusion
of
the
study
to
verify
the
stability
of
test
samples.
These
results
will
be
reported
to
SCC
for
review.
Specific
activities
associated
with
the
sample
collection
and
preparation
tasks
are
described
below.

4.2.1
Equipment
Cleaning
and
Preparation
Prior
to
commencement
of
field­
sampling
activities,
sample
bottles
and
necessary
sampling
equipment
will
be
obtained
from
an
experienced
cleaning
facility.
The
cleaning
facility
will
utilize
the
guidance
stated
in
Method
1669
and
the
associated
trace
metals
analysis
methods
to
thoroughly
clean,
store,
and
ship
all
required
equipment
to
organization
responsible
for
sample
collection
and
will
implement
QC
protocols
necessary
to
verify
and
certify
that
the
bottles
and
sampling
equipment
are
free
of
any
target
metals
at
the
levels
of
interest
in
this
study.

4.2.2
Field
Sampling
A
total
of
five
real­
world
sample
matrices
will
be
collected
in
the
field:
filtered
ambient
water
samples;
unfiltered
effluent
samples,
filtered
effluent
samples;
unfiltered
marine
samples,
and
filtered
marine
samples.
All
sampling
activities
to
be
performed
under
this
study
will
be
performed
by
SCC
or
referee
laboratory
staff
who
have
observed
and
been
trained
in
the
collection
of
samples
using
the
"
clean
hands/
dirty
hands"
techniques
described
in
Method
1669,
as
adapted
for
effluent
sampling
where
necessary.
These
techniques
entail
using
two
sampling
team
members
(
designated
"
clean
hands"
and
"
dirty
hands")
for
different
aspects
of
the
sample
collection
and
filtering
tasks
to
minimize
contamination.
If
feasible,
a
third
individual
will
be
responsible
for
performing
all
sample
documentation
activities.
The
sampling
team
will
process
trivalent
and
hexavalent
chromium
samples
in
a
clean,
contaminant­
free
area.

To
simplify
documentation,
specific
sample
numbers
will
be
pre­
assigned
to
each
sampling
point
and
bottle
prior
to
collection.
The
number
of
each
sample
bottle
will
be
documented
and
associated
with
the
preassigned
sample
number
in
a
field
log
prior
to
commencement
of
sampling
activities.
The
pre­
assigned
sample
number
will
be
pre­
recorded
on
the
outside
storage
bag
used
to
store
the
sample
bottle.
Once
in
the
field,
the
"
dirty
hands"
team
member
will
read
the
sample
number
printed
on
the
outside
bag
to
the
documentation
team
member.
After
"
clean
hands"
has
removed
the
sample
bottle
from
the
inside
storage
bag,
"
clean
hands"
will
read
the
bottle
number
to
the
documentation
team
member.
In
this
way,
the
documentation
team
member
can
minimize
actual
field
transcription
yet
verify
that
the
appropriate
bottle
is
being
utilized.
The
team
member
will
record
the
time
that
the
sample
is
collected,
field
conditions,
and
any
problems
or
other
issues
noted
by
the
"
clean
hands/
dirty
hands"
team
during
collection.

4.2.3
Sample
Filtration,
Sample
Preservation,
and
Sample
Shipment
Filtration:
Trace
metals
samples,
including
mercury
samples,
will
be
filtered
in
the
field
according
to
the
filtration
procedure
described
in
Section
8.3
of
Method
1669.
In
brief,
samples
will
be
collected
using
a
peristaltic
pump
and
new,
cleaned
tubing
that
terminates
in
a
0.45­
µ
m
capsule
filter.
The
sampling
team
will
assemble
the
filtration
system
inside
a
contaminant­
free
glove
bag,
and
flush
the
system
with
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
15
approximately
200
mL
of
reagent
water.
After
the
system
is
flushed,
the
team
will
collect
a
blank
sample,
and
then
collect
in
carboys
the
volume
needed
for
the
filtered
trace
metals
samples.
The
capsule
filter
will
be
replaced
after
each
carboy
is
filled,
and
the
sampling
team
will
flush
the
system
and
take
a
blank
sample
before
samples
are
collected
using
a
new
filter.

Preservation:
The
techniques
described
in
Sections
8.4.4
and
8.4.5
of
Method
1669
will
be
used
to
preserve
aliquots
for
trivalent
and
hexavalent
chromium.
Briefly,
the
sampling
team
will
preserve
trivalent
chromium
by
pipetting
1
mL
of
chromium
(
III)
extraction
solution
to
a
100­
mL
sample
aliquot
and
shaking
the
sample.
The
team
will
vacuum­
filter
the
resulting
precipitate
through
a
0.4­
µ
m
pretreated
polycarbonate
filter
membrane
and
rinse
the
filter
holder.
The
filter
will
be
folded
and
transferred
to
a
fluoropolymer
vial
with
ultrapure
nitric
acid.
The
sampling
team
will
preserve
hexavalent
chromium
by
pipetting
1
mL
of
NaOH
to
a
125­
mL
sample
aliquot.

Shipping:
All
samples
will
be
shipped
to
the
referee
laboratory(
ies)
via
overnight
courier.
Immediately
after
sample
shipment
(
i.
e.,
as
soon
as
samples
are
in
the
custody
of
the
carrier),
the
sampling
team
will
call
SCC
and
provide
information
on
the
shipment,
including
sample
numbers,
numbers
of
coolers,
and
courier
and
airbill
number.
SCC
will
notify
the
referee
laboratory
when
samples
will
arrive.

4.2.4
Determination
of
Field
Sample
Concentrations
SCC
will
ship
carboys
of
field
samples
to
the
referee
laboratory
for
homogenization
and
generation
of
individual
samples
for
analysis
by
the
participant
laboratories.
SCC
will
ship
multiple
carboys
for
the
following
five
sample
matrix
types
to
the
referee
laboratory:
filtered
ambient
water,
unfiltered
effluent,
filtered
effluent,
unfiltered
marine
water,
and
filtered
marine
water.
The
referee
laboratory
will
analyze
volume
from
a
representative
carboy
for
each
of
the
five
matrix
types
to
ensure
that
concentration
levels
found
in
the
natural
matrices
are
appropriate
for
this
study.
To
ensure
homogeneity
in
each
carboy
sampled,
the
referee
laboratory
will
collect
samples
from
the
field
carboys
while
continually
agitating
the
carboys.

The
referee
laboratory
shall
analyze
one
filtered
ambient
water
sample,
one
unfiltered
effluent
sample,
and
one
filtered
effluent
sample
per
method
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640.
The
referee
laboratory
also
will
analyze
one
unfiltered
marine
water
sample
and
one
filtered
marine
water
sample
per
method
for
Methods
1631,
1632,
1637,
and
1640.

The
referee
laboratory
shall
report
the
results
of
these
analyses
to
SCC
for
review.
If
problems
are
identified,
SCC
will
notify
EAD
to
discuss
and
implement
appropriate
corrective
actions,
including
resampling,
sample
spiking,
sample
dilution,
and/
or
other
procedures.
EAD
and/
or
SCC
will
inform
the
referee
laboratory
of
any
actions
needed
before
volume
in
the
field
carboys
is
aliquoted
into
sample
pairs.

4.2.5
Generation
of
Sample
Pairs
and
Homogenization
of
Samples
Sample
pairs
prepared
according
to
Youden's
guidance
will
be
generated
for
each
real­
world
matrix
by
splitting
the
volume
collected
for
each
matrix
and
spiking
(
as
necessary)
each
of
the
two
split
sample
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
16
Draft
­
December
2000
volumes
with
target
analytes.
Prior
to
aliquoting
test
samples
from
the
field
carboys,
the
reference
laboratory(
ies)
will
split
the
carboys
for
each
matrix
into
two
batches.
The
referee
laboratory(
ies)
will
spike
each
batch
with
target
analytes
in
the
desired
concentration
range.
All
samples
within
a
batch
will
therefore
contain
identical
levels
of
target
analytes.
For
each
real­
world
matrix,
one
sample
from
each
batch
will
be
sent
to
each
laboratory
as
a
pair.

In
addition
to
generating
two
batches
of
samples
for
each
real­
world
matrix,
the
referee
laboratory(
ies)
also
will
prepare
six
batches
of
reagent
water
samples,
which
will
be
used
to
create
pairs
of
reagent
water
samples
in
three
concentrations.
The
referee
laboratory
will
split
the
six
reagent
water
batches
into
three
sets
of
two.
Reagent
water
in
the
sets
will
be
spiked
with
the
analytes
of
interest
at
three
different
concentrations
across
the
working
range
of
the
methods
to
yield
one
set
(
two
batches)
of
reagent
water
for
each
of
the
three
concentrations.
For
each
set,
the
referee
laboratory(
ies)
will
spike
each
batch
with
target
analytes
in
the
desired
concentration
range.
All
samples
within
a
batch
will
therefore
contain
identical
levels
of
target
analytes.
For
each
set
(
concentration)
of
reagent
water,
one
sample
from
each
batch
will
be
sent
to
each
laboratory
as
a
pair,
yielding
three
pairs
of
reagent
water
samples.

To
ensure
homogeneity
of
the
samples
in
each
batch
of
real­
world
matrices
and
reagent
water,
the
referee
laboratory(
ies)
will
aliquot
samples
from
the
carboys
while
continually
agitating
the
carboys
in
an
attempt
to
ensure
homogeneity.
After
the
referee
laboratory(
ies)
aliquot
all
of
the
test
samples
from
the
field
carboys,
the
laboratory(
ies)
will
analyze
randomly
selected
samples
across
each
of
the
sample
series
prepared
for
the
study
to
assure
among­
sample
homogeneity.

The
referee
laboratory(
ies)
will
test
samples
for
homogeneity
in
a
clean
room,
using
equipment
that
has
been
cleaned
according
to
Method
1669
and
demonstrated
to
be
free
from
contamination.
The
referee
laboratory(
ies)
will
generate
acceptable
equipment
blanks
and
laboratory
blanks
to
demonstrate
that
the
facility
was
free
of
contamination
during
the
homogeneity
testing.

The
referee
laboratory(
ies)
will
report
the
results
of
their
subsampling
analyses
to
SCC.
SCC
will
review
the
data,
consult
with
EPA,
and
issue
further
directions
to
the
referee
laboratory
regarding
distribution
of
samples
to
the
study
participants.
If
the
data
indicate
that
samples
are
not
homogenous,
SCC
will
issue
corrective
action
instructions
to
the
referee
laboratory(
ies).

4.2.6
Stability
Analysis
The
referee
laboratory(
ies)
also
will
analyze
all
sample
types
by
all
methods
to
assure
stability
of
the
test
samples.

To
assess
stability
of
the
test
samples,
the
referee
laboratory(
ies)
will
analyze
samples
from
each
matrix
and
concentration
using
each
analytical
method
over
a
time
period
equivalent
to
that
covering
the
study.
Specifically,
the
referee
laboratory(
ies)
will
analyze
at
least
one
filtered
ambient
water
sample,
at
least
one
unfiltered
effluent
sample,
at
least
one
filtered
effluent
sample,
and
at
least
one
reagent
water
sample
at
each
concentration
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and
1640.
The
referee
laboratory(
ies)
will
analyze
at
least
one
unfiltered
marine
water
sample
and
at
least
one
filtered
marine
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
17
water
sample
per
method
for
Methods
1631,
1632,
1637,
and
1640.
The
referee
laboratory
will
submit
the
results
of
these
analyses
to
SCC
for
evaluation
and
comparison
with
the
pre­
study
results.

4.3
Phase
3
Technical
Approach
Phase
3
entails
the
use
of
1600­
series
methods
at
multiple
laboratories
to
analyze
real­
world
samples,
reagent
water
samples,
and
standard
reference
materials
for
trace
metals.
AMS
will
use
the
results
of
these
analyses
to
assess
the
performance
of
each
method
under
routine
conditions.
As
noted
in
Phase
1,
each
laboratory
may
be
approved
to
perform
one,
several,
or
all
of
the
1600­
series
methods.
Laboratories
may
elect
to
analyze
a
combination
of
ambient
water,
effluent,
and
reagent­
water
samples
and/
or
marine
water
samples
for
each
of
the
methods
they
are
approved
to
perform.
Laboratories
will
not
be
allowed
to
analyze
ambient
water,
effluent,
or
reagent­
water
samples
alone;
these
matrices
must
be
analyzed
as
a
set.

The
general
approach
to
the
round­
robin
study
entails
the
following
analyses
at
each
laboratory:

C
Qualified
round­
robin
laboratories
will
analyze
a
pair
of
filtered
ambient
water
samples
for
dissolved
metals
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and/
or
1640.

C
Qualified
round­
robin
laboratories
will
analyze
a
pair
of
filtered
effluent
water
samples
for
dissolved
metals
and
a
pair
of
unfiltered
effluent
water
samples
for
total
recoverable
metals
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and/
or
1640.

C
Qualified
round­
robin
laboratories
will
analyze
three
pairs
of
reagent
water
samples
for
total
recoverable
metals
using
Methods
1631,
1632,
1636,
1637,
1638,
1639,
and/
or
1640.

C
Qualified
round­
robin
laboratories
will
analyze
a
pair
of
filtered
marine
water
samples
for
dissolved
metals
and
a
pair
of
unfiltered
marine
water
samples
for
total
recoverable
metals
using
Methods
1631,
1632,
1637
and/
or
1640.
Note:
To
prevent
loss
of
sensitivity,
laboratories
analyzing
marine
water
samples
using
Method
1631
will
be
required
to
modify
the
procedure
at
Section
11.1.1.
Laboratories
will
add
0.2
mL
of
bromine
monochloride
(
BrCl)
to
100
mL
of
sample
instead
of
the
0.5
to
5
mL
of
BrCl
required
by
the
method.

C
Qualified
laboratories
performing
analyses
on
ambient
and
effluent
samples
will
periodically
analyze
an
SRM
for
ambient
water.
Qualified
laboratories
performing
analyses
on
marine
water
samples
will
periodically
analyze
an
SRM
for
marine
water.
If
EAD
funding
permits,
EPA
will
purchase
the
SRMs
for
the
study
and
distribute
them
to
the
participant
laboratories
with
the
test
samples.
If
this
plan
is
cost­
prohibitive,
EAD
will
require
the
participant
laboratories
to
purchase
specific
SRMs
identified
by
EAD.

The
following
specific
requirements
apply
to
analyses
by
each
method:
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
18
Draft
­
December
2000
C
With
the
exception
of
the
modification
to
Method
1631
for
marine
water
samples
noted
above,
all
laboratories
must
follow
the
methods
exactly.
Any
deviation,
such
as
the
necessity
to
substitute
reagents,
apparatus,
or
instruments,
must
be
recorded
at
the
time
and
reported.

C
All
laboratories
must
follow
all
QC
procedures
and
the
analytical
sequence
defined
in
the
methods
they
are
performing.

C
Each
portion
of
the
sample
pair
will
be
analyzed
once,
as
replication
defeats
the
purpose
of
the
design,
except
where
the
method
requires
replicate
injections
(
see
next
bullet).

C
If
analytical
results
appear
unreasonable,
laboratories
should
investigate
possible
causes
immediately,
first
by
checking
for
transcription
and
calculation
mistakes,
and
then
by
reanalysis.
Although
laboratories
will
be
prohibited
from
performing
multiple
analyses
to
improve
recoveries,
they
will
be
allowed
to
implement
corrective
action
and
reanalysis
for
QC
failures
that
are
attributable
to
analyst
error,
such
as
incorrect
spiking
levels,
or
to
instrument
failure.
In
addition,
many
methods
for
trace
metals
require
replicate
injections
into
the
instrument.
Such
replicate
injections
will
be
allowed,
but
in
such
cases,
laboratories
participating
in
the
study
will
be
required
to
identify
the
instrument
on
which
such
replicate
injections
were
made,
and
to
report
the
calculation
procedures
employed
by
the
instrument
to
report
sample
concentrations.
For
example,
some
instruments
may
be
programmed
to
average
results
of
multiple
background
determinations
and
subtract
that
average
from
the
results
of
replicate
sample
analyses.
Other
instruments
may
be
programmed
to
subtract
a
single
background
determination
from
the
average
of
replicate
sample
analyses.

C
All
laboratories
analyzing
the
set
of
ambient
water,
effluent,
and
reagent
water
samples
must
prepare
and
analyze
MS
and
MSD
samples
for
one
member
of
each
of
the
effluent
pairs
(
one
MS/
MSD
for
filtered
effluent
and
one
MS/
MSD
for
unfiltered
effluent).
All
laboratories
analyzing
marine
water
samples
must
prepare
and
analyze
MS
and
MSD
samples
for
one
member
of
each
of
the
marine
water
pairs
(
one
MS/
MSD
for
filtered
marine
water
and
one
MS/
MSD
for
unfiltered
marine
water).
To
control
variability
in
the
study,
SCC
will
designate
which
samples
should
be
used
for
MS/
MSD
analysis
and
the
concentrations
that
should
be
spiked
into
each
sample.

C
All
laboratories
will
analyze
materials
within
sample
holding
times.

C
All
laboratories
must
conduct
exactly
the
number
of
determinations
stated
in
the
instructions.
Any
other
number
complicates
the
statistical
analysis.

C
All
laboratories
must
report
individual
values,
including
blanks.
Laboratories
will
not
average
or
do
other
data
manipulations
unless
required
by
a
method's
instructions.
When
results
are
below
the
MDL,
laboratories
should
report
the
actual
calculated
result,
regardless
of
its
value.
Results
of
the
Interlaboratory
Study
of
EPA
Method
1638
Appendix
A
Draft
­
December
2000
A­
19
SECTION
5:
DATA
REPORTING
AND
EVALUATION
The
laboratories
will
be
required
to
submit
both
summary
level
and
raw
data
in
hardcopy
format.
Summary
level
data
also
must
be
provided
in
electronic
format.
The
laboratories
also
will
be
required
to
submit
detailed
explanations
of
any
approved
modifications
to
the
analytical
techniques
specified
in
the
methods
and
used
in
this
study.
Specific
reporting
requirements
are
or
will
be
detailed
in
each
laboratory's
analytical
statement
of
work
and
are
summarized
below.

Upon
the
receipt
of
a
laboratory
data
package,
SCC
will
review
the
data
to
ensure
that
they
were
generated
in
accordance
with
the
required
procedures.
Laboratory
comments
and
suggestions
also
will
be
used
to
identify
further
revisions
that
should
be
made
to
the
methods.

The
following
rules
should
be
followed
in
reporting
results:

1.
Quantitative
results
above
or
at
the
MDL
­
report
value
2.
Quantitative
results
below
the
MDL
­
report
value
but
flag
with
footnote
giving
the
MDL
3.
Nonquantitative
results
­
report
as
less
than
the
MDL
value
and
state
the
MDL
value
4.
The
terms
"
zero,"
"
trace,"
or
"
ND
(
not
detected)"
are
not
to
be
used
5.
Laboratories
must
report
concentrations
as
F
g/
L
and
report
data
to
three
significant
figures
The
laboratory
shall
report
the
following
data,
at
a
minimum:

1.
Summary
reports
of
all
analytical
results.

2.
A
list
of
samples
analyzed
and
a
run
chronology.

3.
Copies
of
all
raw
data,
including
quantitation
reports,
strip
charts,
spectra,
bench
sheets,
and
laboratory
notebooks
showing
tare
and
sample
weights,
sample
volumes,
and
other
data
that
will
allow
verification
of
the
calculations
performed
and
will
allow
the
final
results
reported
to
be
traced
to
the
raw
data.
Each
data
element
shall
be
clearly
identified
in
the
laboratory's
data
package.

4.
A
written
report
that
details
any
problems
associated
with
analysis
of
the
samples.
The
written
report
also
shall
provide
comments
on
the
performance
of
any
part
of
a
method.

5.
A
detailed
written
description
of
any
modifications
to
the
procedures
specified
in
the
methods.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
A
A­
20
Draft
­
December
2000
SECTION
6:
LIMITATIONS
Size
of
study:
To
avoid
excessively
large
confidence
limits
around
the
precision
(
variance),
and
bias
(
mean
recovery)
statements,
this
round­
robin
study
should
yield
a
minimum
of
six
complete
and
useable
data
sets.
Therefore,
the
number
of
laboratories
participating
in
a
study
should
be
increased
sufficiently
beyond
six
to
assure
a
that
at
least
six
sets
of
complete
and
useable
data
are
available
after
outliers
and
non­
usable
data
are
removed.
Participation
by
a
minimum
of
six
laboratories
is
recommended
by
ASTM
and
AOAC.

Assuming
a
25%
data
loss,
a
minimum
of
nine
laboratories
are
needed
to
participate
in
the
study
to
obtain
at
least
six
sets
of
useable
data.
Ideally,
this
study
will
consist
of
as
many
as
15
laboratories,
including
at
least
6
commercial
laboratories
funded
by
EPA.
EPA
funding
of
commercial
laboratories
will
provide
a
level
of
enforceability,
helping
to
ensure
timely
submission
of
data.
EPA
anticipates
that
government,
academic,
and
utility
laboratories
will
comprise
the
balance
of
the
participant
laboratories.
These
laboratories
are
anticipated
to
participate
voluntarily
or
through
funding
by
interested
organizations,
such
as
ASTM
and
EPRI.

Normally,
it
is
desirable
to
allow
participation
by
only
one
analyst
in
each
laboratory
to
avoid
potential
cross­
talk
and
sharing
of
reagents,
standards,
or
instruments
within
a
laboratory.
It
may
be
impossible
to
obtain
nine
qualified
participant
laboratories
for
this
study,
so
it
may
be
necessary
to
allow
multiple
analysts
per
laboratory.
If
such
a
contingency
is
necessary,
safeguards
will
be
developed
to
assure
the
independence
of
the
two
analytical
processes,
including
separate
reagents,
instrumentation,
sample
preparation,
and
analyses.

Effluent
variability:
Effluent
matrices
vary,
particularly
pretreated
effluents
(
indirect
dischargers)
and
treated
effluents
(
direct
dischargers).
Effluent
samples
for
this
study
will
be
collected
from
the
treated
effluent
stream
at
a
well­
designed,
well­
operated,
best­
available­
technology
publicly
owned
treatment
works.
Untreated
effluent
will
not
be
collected
or
analyzed
because
the
matrix
may
overload
the
analytical
methods
and
will
not
be
representative
of
any
other
untreated
effluent,
limiting
the
usefulness
of
any
analytical
results.
Draft
­
December
2000
Appendix
B
Data
Submitted
in
the
Interlaboratory
Method
1638
Validation
Study
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
B­
1
Draft
­
December
2000
Table
1:
Phase
2,
Sample
Stability
Results
Analyte
Matrix
Expected
(
µ
g/
L)
Initial
(
1)
(
µ
g/
L)
Initial
(
2)
(
µ
g/
L)
Average
%
Recovery
Final
(
1)
(
µ
g/
L)
Final
(
2)
(
µ
g/
L)
Average
%
Recover
y
%
Recovery
RPD
Antimony
ML
=
0.2
Reagent
Pair
1
0.0000
0.0081
0.0015
­
­
0.0234
­
0.0285
­
­

Reagent
Pair
2
1.0000
0.9680
0.9664
97
0.9081
0.9116
91
6­

Reagent
Pair
3
5.0000
4.8800
4.8740
98
4.7280
4.7130
94
3­

Reagent
Pair
4
20.0000
19.7400
19.1513
97
19.0600
19.0100
95
2­

*
Reagent
Pair
5
(
low)
0.1000
0.0831
­
­
0.0072
­
­
­

*
Reagent
Pair
5
(
high)
0.1200
0.1073
­
­
0.0723
­
­
­

*
Freshwater
Pair
1
0.1241
0.1526
0.1349
­
0.1014
0.1036
­
­

Freshwater
Pair
2
(
low)
0.2041
0.2002
­
98
0.1650
­
81
19­

Freshwater
Pair
2
(
high)
0.2441
0.2346
­
96
0.2009
­
82
15­

Freshwater
Pair
3
(
low)
0.4041
0.3866
­
96
0.3603
­
89
7­

Freshwater
Pair
3
(
high)
0.5041
0.4695
­
93
0.4550
­
90
3­

Freshwater
Pair
4
(
low)
0.8041
0.7768
­
97
0.7366
­
92
5­

Freshwater
Pair
4
(
high)
1.0041
0.9612
­
96
0.9464
­
94
2­

Unfiltered
Effluent
10.0000
9.5000
9.556
95
9.399
9.375
94
1­

Filtered
Effluent
1.0000
1.0210
1.0350
103
0.9807
0.9850
98
4­

Cadmium
ML
­
0.2
µ
g/
L
Reagent
Pair
1
0.0000
­
0.0048
­
0.0041
­
­
0.0021
­
0.0029
­
­

*
Reagent
Pair
2
0.1000
0.0946
0.0935
­
0.0973
0.0958
­
­

Reagent
Pair
3
1.0000
0.9793
0.9561
97
0.9637
0.9689
97
0­

Reagent
Pair
4
10.0000
9.5820
9.6810
96
9.5710
9.5830
96
1­

*
Reagent
Pair
5
(
low)
0.0500
0.0431
­
­
0.0502
­
­
­

*
Reagent
Pair
5
(
high)
0.0600
0.0508
­
­
0.0567
­
­
­

Freshwater
Pair
1
0.2500
0.2439
0.2393
97
0.2419
0.2418
97
0+

Freshwater
Pair
2
0.0000
­
0.0081
­
­
0.0016
­
­
­

*
Freshwater
Pair
3
(
low)
0.0400
0.0321
­
­
0.0398
­
­
­

*
Freshwater
Pair
3
(
high)
0.0500
0.0412
­
­
0.0492
­
­
­

*
Freshwater
Pair
4
(
low)
0.1200
0.1069
­
­
0.1163
­
­
­

*
Freshwater
Pair
4
(
high)
0.1400
0.1325
­
­
0.1369
­
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
1:
Phase
2,
Sample
Stability
Results
Analyte
Matrix
Expected
(
µ
g/
L)
Initial
(
1)
(
µ
g/
L)
Initial
(
2)
(
µ
g/
L)
Average
%
Recovery
Final
(
1)
(
µ
g/
L)
Final
(
2)
(
µ
g/
L)
Average
%
Recover
y
%
Recovery
RPD
Draft
­
December
2000
B­
2
Unfiltered
Effluent
0.5000
0.5053
0.5086
101
0.4948
0.4972
99
2­

Filtered
Effluent
0.3000
0.3150
0.3095
104
0.3206
0.3228
107
3+

Copper
ML
=
0.5
µ
g/
L
Reagent
Pair
1
0.0000
0.0249
0.0186
­
0.0271
0.0229
­
­

Reagent
Pair
2
0.5000
0.5383
0.5408
108
0.5118
0.5186
103
5­

Reagent
Pair
3
2.0000
2.1440
2.1060
106
2.0450
2.0260
102
4­

Reagent
Pair
4
20.0000
20.5400
20.6700
103
20.2300
20.0400
101
2­

*
Reagent
Pair
5
(
low)
0.2000
0.2000
­
­
0.2134
­
­
­

*
Reagent
Pair
5
(
high)
0.2400
0.2700
­
­
0.2552
­
­
­

Freshwater
Pair
1
1.0300
1.2080
1.1680
115
1.1290
1.0950
108
7­

Freshwater
Pair
2
(
low)
1.5300
1.5975
­
104
1.5600
­
102
2­

Freshwater
Pair
2
(
high)
1.7300
1.7596
­
102
1.735
­
100
1­

Freshwater
Pair
3
(
low)
2.5300
2.5467
­
101
2.519
­
100
1­

Freshwater
Pair
3
(
high)
3.0300
3.0903
­
102
3.092
­
102
0+

Freshwater
Pair
4
(
low)
4.5300
4.5065
­
99
4.449
­
98
1­

Freshwater
Pair
4
(
high)
5.0300
4.9809
­
99
4.937
­
98
1­

Unfiltered
Effluent
15.1000
15.8600
15.5000
104
14.5600
14.4200
96
8­

Filtered
Effluent
13.8000
14.6300
14.3500
105
13.3100
13.3700
97
8­

Lead
ML
=
0.05
µ
g/
L
Reagent
Pair
1
0.0000
­
0.0926
­
0.0915
­
­
0.0030
­
0.0048
­
­

Reagent
Pair
2
0.1000
0.0874
0.0939
91
0.0898
0.0917
91
0+

Reagent
Pair
3
0.5000
0.4015
0.4029
80
0.4799
0.4775
96
17+

Reagent
Pair
4
5.0000
4.9610
4.944
99
4.9080
4.856
98
1­

*
Reagent
Pair
5
(
low)
0.0300
0.0236
­
­
0.0327
­
­
­

*
Reagent
Pair
5
(
high)
0.0360
0.0341
­
­
0.0365
­
­
­

Freshwater
Pair
1
0.2000
0.1997
0.2014
100
0.2047
0.2032
102
2+

*
Freshwater
Pair
2
0.0128
0.0205
0.0206
­
0.0229
0.0214
­
­

Freshwater
Pair
3
(
low)
0.0528
0.0559
­
106
0.0577
­
109
3+

Freshwater
Pair
3
(
high)
0.0628
0.0679
­
108
0.0676
­
108
0­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
1:
Phase
2,
Sample
Stability
Results
Analyte
Matrix
Expected
(
µ
g/
L)
Initial
(
1)
(
µ
g/
L)
Initial
(
2)
(
µ
g/
L)
Average
%
Recovery
Final
(
1)
(
µ
g/
L)
Final
(
2)
(
µ
g/
L)
Average
%
Recover
y
%
Recovery
RPD
B­
3
Draft
­
December
2000
Freshwater
Pair
4
(
low)
0.3128
0.3105
­
99
0.2976
­
95
4­

Freshwater
Pair
4
(
high)
0.3628
0.3663
­
101
0.3410
­
94
7­

Unfiltered
Effluent
1.0557
0.9966
1.0214
96
1.0260
1.019
97
1+

Filtered
Effluent
0.5000
0.4427
0.4448
89
0.5188
0.5249
104
16+

Nickel
ML
=
0.5
µ
g/
L
Reagent
Pair
1
0.0000
0.0575
0.0544
­
­
0.0026
­
0.0011
­
­

Reagent
Pair
2
1.0000
1.0830
1.0980
109
1.0310
1.0090
102
7­

Reagent
Pair
3
10.0000
10.4600
10.2500
104
10.1500
10.1800
102
2­

Reagent
Pair
4
100.0000
99.6100
99.1500
99
100.4000
99.1600
100
0+

Reagent
Pair
5
(
low)
0.5000
0.4887
­
98
0.4908
­
98
0+

Reagent
Pair
5
(
high)
0.6000
0.5897
­
98
0.6039
­
101
2+

Freshwater
Pair
1
6.0000
6.1420
6.1450
102
6.0500
6.0460
101
2­

*
Freshwater
Pair
2
0.3100
0.2329
0.2378
­
0.2906
0.2899
­
­

Freshwater
Pair
3
(
low)
1.6100
1.4841
­
92
1.578
­
98
6+

Freshwater
Pair
3
(
high)
1.8100
1.7226
­
95
1.771
­
98
3+

Freshwater
Pair
4
(
low)
3.3100
3.1507
­
95
3.171
­
96
1+

Freshwater
Pair
4
(
high)
4.0100
3.8920
­
97
3.939
­
98
1+

Unfiltered
Effluent
8.0000
7.1960
7.0580
89
7.3110
7.1570
90
1+

Filtered
Effluent
7.0000
6.5580
6.3820
92
6.5620
6.5190
93
1+

Selenium
ML
=
2.0
µ
g/
L
Reagent
Pair
1
0.0000
­
0.3436
­
0.3890
­
­
0.0003
0.0647
­
­

Reagent
Pair
2
5.0000
4.6870
4.6990
94
5.0970
5.0704
102
8+

Reagent
Pair
3
20.0000
20.2300
19.5700
100
20.5200
20.7600
103
4+

Reagent
Pair
4
100.0000
98.8000
99.8200
99
103.5000
104.8000
104
5+

*
Reagent
Pair
5
(
low)
1.0000
0.7650
­
­
1.284
­
­
­

*
Reagent
Pair
5
(
high)
1.2000
0.8625
­
­
1.635
­
­
­

Freshwater
Pair
1
4.0000
3.7050
3.7000
93
3.9250
3.9410
98
6+

*
Freshwater
Pair
2
0.3810
0.0640
0.0876
­
0.3224
0.2985
­
­

*
Freshwater
Pair
3
(
low)
0.9810
0.6790
­
­
0.9400
­
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
1:
Phase
2,
Sample
Stability
Results
Analyte
Matrix
Expected
(
µ
g/
L)
Initial
(
1)
(
µ
g/
L)
Initial
(
2)
(
µ
g/
L)
Average
%
Recovery
Final
(
1)
(
µ
g/
L)
Final
(
2)
(
µ
g/
L)
Average
%
Recover
y
%
Recovery
RPD
Draft
­
December
2000
B­
4
*
Freshwater
Pair
3
(
high)
1.1810
0.9591
­
­
1.245
­
­
­

*
Freshwater
Pair
4
(
low)
1.9810
1.7130
­
­
2.192
­
­
­

Freshwater
Pair
4
(
high)
2.3810
2.0686
­
87
2.669
­
112
25­

Unfiltered
Effluent
6.0000
5.2160
5.3430
88
6.0240
6.0250
100
13+

Filtered
Effluent
5.0000
4.4890
4.5590
90
4.9530
5.0250
100
10+

Silver
ML
=
0.1
µ
g/
L
Reagent
Pair
1
0.0000
0.0050
­
0.0025
­
­
0.0135
­
0.0236
­
­

Reagent
Pair
2
0.1000
0.1070
0.1413
124
0.0938
0.0986
96
25­

Reagent
Pair
3
1.0000
1.0110
1.025
102
1.1020
1.101
110
8+

Reagent
Pair
4
10.0000
10.3000
10.56
104
11.2700
11.21
112
7+

*
Reagent
Pair
5
(
low)
0.0400
0.2161
­
­
­
0.0542
­
­
­

*
Reagent
Pair
5
(
high)
0.0500
0.2603
­
­
­
0.0107
­
­
­

Freshwater
Pair
1
0.2000
0.2666
0.2257
123
0.2107
2.169
107
14­

Freshwater
Pair
2
0.0000
0.0475
0.0359
­
­
0.0592
­
0.0618
­
­

*
Freshwater
Pair
3
(
low)
0.0700
0.0935
­
­
­
0.0316
­
­
­

*
Freshwater
Pair
3
(
high)
0.0800
0.1018
­
­
­
0.0219
­
­
­

Freshwater
Pair
4
(
low)
0.3000
0.3123
­
104
0.0800
­
27
118­

Freshwater
Pair
4
(
high)
0.3600
0.3851
­
107
0.0761
­
21
134­

Unfiltered
Effluent
2.8800
1.4980
1.4780
52
1.4960
1.5590
53
3+

Filtered
Effluent
0.4780
0.4675
0.4721
98
0.4523
0.4613
96
3­

Thallium
ML
=
0.05
µ
g/
L
Reagent
Pair
1
0.0000
0.0064
0.0021
­
­
0.0005
­
0.0008
­
­

Reagent
Pair
2
0.1000
0.1047
0.1020
103
0.0966
0.0993
98
5­

Reagent
Pair
3
0.5000
0.5074
0.5109
102
0.4898
0.4925
98
4­

Reagent
Pair
4
2.0000
2.0530
2.048
103
1.997
1.991
100
3­

*
Reagent
Pair
5
(
low)
0.0400
0.0404
­
­
0.0434
­
­
­

Reagent
Pair
5
(
high)
0.0500
0.0503
­
101
0.0521
­
104
4+

Freshwater
Pair
1
0.0600
0.0629
0.0598
102
0.0589
0.0583
98
5­

*
Freshwater
Pair
2
0.0010
0.0006
­
0.0005
­
0.0073
0.0067
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
1:
Phase
2,
Sample
Stability
Results
Analyte
Matrix
Expected
(
µ
g/
L)
Initial
(
1)
(
µ
g/
L)
Initial
(
2)
(
µ
g/
L)
Average
%
Recovery
Final
(
1)
(
µ
g/
L)
Final
(
2)
(
µ
g/
L)
Average
%
Recover
y
%
Recovery
RPD
B­
5
Draft
­
December
2000
*
Freshwater
Pair
3
(
low)
0.0210
0.0170
­
­
0.0238
­
­
­

*
Freshwater
Pair
3
(
high)
0.0240
0.0218
­
­
0.0278
­
­
­

Freshwater
Pair
4
(
low)
0.1010
0.0993
­
98
0.0985
­
98
1­

Freshwater
Pair
4
(
high)
0.1210
0.1192
­
99
0.1151
­
95
3­

Unfiltered
Effluent
0.9000
0.8872
0.9007
99
0.8347
0.8283
92
7+

Filtered
Effluent
0.2000
0.1863
0.1972
96
0.1804
0.1818
91
6­

Zinc
ML
=
1.0
µ
g/
L
Reagent
Pair
1
0.0000
­
0.0255
­
0.0037
­
­
0.1395
­
0.1686
­
­

*
Reagent
Pair
2
0.5000
0.4474
0.4703
­
0.0000
0.3390
­
­

Reagent
Pair
3
5.0000
4.9600
4.9190
99
4.8190
4.8310
97
2­

Reagent
Pair
4
50.0000
49.3000
50.3500
100
49.6800
50.5700
100
1+

Reagent
Pair
5
(
low)
2.0000
1.9613
­
98
2.248
­
112
14+

Reagent
Pair
5
(
high)
2.4000
2.4299
­
101
2.409
­
100
1­

Freshwater
Pair
1
1.5000
1.4110
1.4320
95
1.4870
1.3870
96
1+

*
Freshwater
Pair
2
0.9743
0.8387
0.8804
­
0.8819
0.8671
­
­

Freshwater
Pair
3
(
low)
1.1043
0.9463
­
86
0.9517
­
86
1+

Freshwater
Pair
3
(
high)
1.3043
1.1676
­
90
1.0830
­
83
8­

Freshwater
Pair
4
(
low)
1.7943
1.6480
­
92
1.593
­
89
3­

Freshwater
Pair
4
(
high)
2.1943
2.0561
­
94
2.034
­
93
1­

Unfiltered
Effluent
48.0100
52.4800
52.93
110
53.2500
51.72
109
0­

Filtered
Effluent
43.8250
46.7800
46.8900
107
47.62
46.98
108
1+

*
Expected
concentration
is
below
the
revised
ML
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Draft
­
December
2000
B­
6
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Antimony
46750
1
Reagent
Water
0.0000
0.0000
Outlying
Laboratory
Antimony
46751
1
Reagent
Water
0.0000
0.0000
Outlying
Laboratory
Antimony
46752
1
Reagent
Water
1.0000
0.6190
Outlying
Laboratory
Antimony
46753
1
Reagent
Water
1.0000
0.6800
Outlying
Laboratory
Antimony
46754
1
Reagent
Water
5.0000
3.7500
Outlying
Laboratory
Antimony
46755
1
Reagent
Water
5.0000
3.8800
Outlying
Laboratory
Antimony
46774
1
Reagent
Water
20.0000
17.1000
Outlying
Laboratory
Antimony
46775
1
Reagent
Water
20.0000
16.9000
Outlying
Laboratory
Antimony
46776
1
Unfiltered
Effluent
10.0000
9.7600
Outlying
Laboratory
Antimony
46777
1
Unfiltered
Effluent
10.0000
9.6000
Outlying
Laboratory
Antimony
46778
1
Filtered
Effluent
1.0000
1.0900
Outlying
Laboratory
Antimony
46779
1
Filtered
Effluent
1.0000
0.9940
Outlying
Laboratory
Possible
contamination1
Antimony
46780
1
Filtered
Freshwater
0.1241
0.1240
Outlying
Laboratory
Antimony
46781
1
Filtered
Freshwater
0.1241
0.1190
Outlying
Laboratory
Antimony
47285
1
Filtered
Freshwater
0.2041
0.2000
Outlying
Laboratory
Antimony
47286
1
Filtered
Freshwater
0.2441
0.2260
Outlying
Laboratory
Possible
contamination1
Antimony
47287
1
Filtered
Freshwater
0.4041
0.3720
Outlying
Laboratory
Possible
contamination2
Antimony
47288
1
Filtered
Freshwater
0.5041
0.4660
Outlying
Laboratory
Possible
contamination2
Antimony
47289
1
Filtered
Freshwater
0.8041
0.7460
Outlying
Laboratory
Antimony
47290
1
Filtered
Freshwater
1.0041
0.9420
Outlying
Laboratory
Antimony
47291
1
Reagent
Water
0.1000
0.0338
Outlying
Laboratory
Antimony
47292
1
Reagent
Water
0.1200
0.0957
Outlying
Laboratory
Antimony
46504
2
Filtered
Freshwater
0.1241
0.1588
Antimony
46505
2
Filtered
Freshwater
0.1241
0.1116
Antimony
46506
2
Filtered
Effluent
1.0000
0.9923
Antimony
46507
2
Filtered
Effluent
1.0000
1.0330
Antimony
46509
2
Unfiltered
Effluent
10.0000
9.0020
Antimony
46510
2
Reagent
Water
0.0000
­
0.0041
Antimony
46511
2
Reagent
Water
0.0000
­
0.0158
Antimony
46512
2
Reagent
Water
1.0000
0.6302
Antimony
46513
2
Reagent
Water
1.0000
0.6413
Antimony
46514
2
Reagent
Water
5.0000
4.2280
Antimony
46515
2
Reagent
Water
5.0000
4.2610
Antimony
46516
2
Reagent
Water
20.0000
18.9000
Antimony
46517
2
Reagent
Water
20.0000
18.4100
Antimony
47231
2
Filtered
Freshwater
0.2041
0.2013
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
7
Draft
­
December
2000
Antimony
47232
2
Filtered
Freshwater
0.2441
0.2331
Antimony
47233
2
Filtered
Freshwater
0.4041
0.3645
Antimony
47234
2
Filtered
Freshwater
0.5041
0.4666
Antimony
47235
2
Filtered
Freshwater
0.8041
0.7920
Antimony
47236
2
Filtered
Freshwater
1.0041
0.9939
Antimony
47237
2
Reagent
Water
0.1000
0.0461
Antimony
47238
2
Reagent
Water
0.1200
0.0518
Antimony
46722
3
Filtered
Freshwater
0.1241
0.1300
Antimony
46723
3
Filtered
Freshwater
0.1241
0.1246
Antimony
46724
3
Filtered
Effluent
1.0000
1.0195
Antimony
46725
3
Filtered
Effluent
1.0000
0.9876
Antimony
46726
3
Unfiltered
Effluent
10.0000
9.0936
Antimony
46727
3
Unfiltered
Effluent
10.0000
9.2436
Antimony
46728
3
Reagent
Water
0.0000
0.0027
Antimony
46729
3
Reagent
Water
0.0000
0.0017
Antimony
46730
3
Reagent
Water
1.0000
0.6640
Antimony
46731
3
Reagent
Water
1.0000
0.7064
Antimony
46732
3
Reagent
Water
5.0000
3.9114
Antimony
46733
3
Reagent
Water
5.0000
3.9958
Antimony
46734
3
Reagent
Water
20.0000
16.1164
Antimony
46735
3
Reagent
Water
20.0000
16.3849
Antimony
47213
3
Filtered
Freshwater
0.2041
0.2053
Antimony
47214
3
Filtered
Freshwater
0.2441
0.2454
Antimony
47215
3
Filtered
Freshwater
0.4041
0.3884
Antimony
47216
3
Filtered
Freshwater
0.5041
0.4765
Antimony
47217
3
Filtered
Freshwater
0.8041
0.7639
Antimony
47218
3
Filtered
Freshwater
1.0041
0.9755
Antimony
47219
3
Reagent
Water
0.1000
0.0426
Antimony
47220
3
Reagent
Water
0.1200
0.1099
Antimony
46594
4
Reagent
Water
0.0000
0.0260
Antimony
46595
4
Reagent
Water
0.0000
0.0240
Antimony
46596
4
Reagent
Water
20.0000
16.5480
Antimony
46597
4
Reagent
Water
20.0000
16.6010
Antimony
46598
4
Reagent
Water
5.0000
4.1680
Antimony
46599
4
Reagent
Water
5.0000
4.1230
Antimony
46600
4
Reagent
Water
1.0000
0.6990
Antimony
46601
4
Reagent
Water
1.0000
0.7120
Antimony
46602
4
Filtered
Freshwater
0.1241
0.1410
Antimony
46603
4
Filtered
Freshwater
0.1241
0.1380
Antimony
46604
4
Filtered
Effluent
1.0000
0.9800
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
8
Antimony
46605
4
Filtered
Effluent
1.0000
1.1340
Antimony
46606
4
Unfiltered
Effluent
10.0000
8.7510
Antimony
46607
4
Unfiltered
Effluent
10.0000
8.9420
Antimony
47239
4
Filtered
Freshwater
0.2041
0.2070
Antimony
47240
4
Filtered
Freshwater
0.2441
0.2460
Antimony
47241
4
Filtered
Freshwater
0.4041
0.3880
Antimony
47242
4
Filtered
Freshwater
0.5041
0.4820
Antimony
47243
4
Filtered
Freshwater
0.8041
0.7440
Antimony
47244
4
Filtered
Freshwater
1.0041
0.9060
Antimony
47245
4
Reagent
Water
0.1000
0.0500
Antimony
47246
4
Reagent
Water
0.1200
0.0620
Antimony
46532
5
Filtered
Freshwater
0.1241
0.1102
Antimony
46533
5
Filtered
Freshwater
0.1241
0.1050
Antimony
46535
5
Filtered
Effluent
1.0000
1.0284
Antimony
46536
5
Unfiltered
Effluent
10.0000
10.5392
Concentration
>
cal
range
Antimony
46537
5
Unfiltered
Effluent
10.0000
9.7860
Concentration
>
cal
range
Antimony
46538
5
Reagent
Water
0.0000
­
0.0132
Antimony
46539
5
Reagent
Water
0.0000
­
0.0108
Antimony
46702
5
Reagent
Water
1.0000
0.6278
Antimony
46703
5
Reagent
Water
1.0000
0.6425
Antimony
46704
5
Reagent
Water
5.0000
4.1322
Antimony
46705
5
Reagent
Water
5.0000
4.1184
Antimony
46706
5
Reagent
Water
20.0000
18.7491
Concentration
>
cal
range
Antimony
46707
5
Reagent
Water
20.0000
18.6683
Concentration
>
cal
range
Antimony
47223
5
Filtered
Freshwater
0.2041
0.1984
Antimony
47224
5
Filtered
Freshwater
0.2441
0.2290
Antimony
47225
5
Filtered
Freshwater
0.4041
0.3728
Antimony
47226
5
Filtered
Freshwater
0.5041
0.4789
Antimony
47227
5
Filtered
Freshwater
0.8041
0.7774
Antimony
47228
5
Filtered
Freshwater
1.0041
0.9871
Antimony
47229
5
Reagent
Water
0.1000
0.0691
Antimony
47230
5
Reagent
Water
0.1200
0.0424
Antimony
46554
6
Filtered
Effluent
1.0000
1.0240
Antimony
46555
6
Filtered
Effluent
1.0000
1.1957
Antimony
46556
6
Filtered
Freshwater
0.1241
0.2055
Antimony
46557
6
Filtered
Freshwater
0.1241
0.1388
Antimony
46558
6
Reagent
Water
0.0000
0.0115
Antimony
46559
6
Reagent
Water
0.0000
0.0131
Antimony
46560
6
Unfiltered
Effluent
10.0000
9.9574
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
9
Draft
­
December
2000
Antimony
46561
6
Unfiltered
Effluent
10.0000
9.6147
Antimony
46562
6
Reagent
Water
1.0000
0.7091
Antimony
46563
6
Reagent
Water
1.0000
0.6579
Antimony
46564
6
Reagent
Water
5.0000
4.4013
Antimony
46565
6
Reagent
Water
5.0000
4.5073
Antimony
46566
6
Reagent
Water
20.0000
19.0607
Antimony
46567
6
Reagent
Water
20.0000
19.0956
Antimony
47247
6
Filtered
Freshwater
0.2041
0.2307
Antimony
47248
6
Filtered
Freshwater
0.2441
0.2563
Antimony
47249
6
Filtered
Freshwater
0.4041
0.4046
Antimony
47250
6
Filtered
Freshwater
0.5041
0.4759
Antimony
47251
6
Filtered
Freshwater
0.8041
0.7725
Antimony
47252
6
Filtered
Freshwater
1.0041
0.9653
Antimony
47253
6
Reagent
Water
0.1000
0.0971
Antimony
47254
6
Reagent
Water
0.1200
0.1484
Antimony
46846
7
Reagent
Water
0.0000
­
0.0017
Antimony
46847
7
Reagent
Water
0.0000
­
0.0006
Antimony
46848
7
Reagent
Water
1.0000
0.6017
Antimony
46849
7
Reagent
Water
1.0000
0.5732
Antimony
46850
7
Reagent
Water
5.0000
3.7466
Antimony
46851
7
Reagent
Water
5.0000
3.7478
Antimony
46852
7
Reagent
Water
20.0000
18.0506
Antimony
46853
7
Reagent
Water
20.0000
18.1348
Antimony
46854
7
Filtered
Effluent
1.0000
1.1239
Antimony
46855
7
Filtered
Effluent
1.0000
1.0088
Antimony
46856
7
Filtered
Freshwater
0.1241
0.1419
Antimony
46857
7
Filtered
Freshwater
0.1241
0.1326
Antimony
47267
7
Unfiltered
Effluent
10.0000
9.8225
Antimony
47268
7
Unfiltered
Effluent
10.0000
9.9053
Antimony
47269
7
Filtered
Freshwater
0.2041
0.2136
Antimony
47270
7
Filtered
Freshwater
0.2441
0.2490
Antimony
47271
7
Filtered
Freshwater
0.4041
0.3957
Antimony
47272
7
Filtered
Freshwater
0.5041
0.4948
Antimony
47273
7
Filtered
Freshwater
0.8041
0.7850
Antimony
47274
7
Filtered
Freshwater
1.0041
0.9860
Antimony
47275
7
Reagent
Water
0.1000
0.0564
Antimony
47276
7
Reagent
Water
0.1200
0.1016
Antimony
46540
8
Filtered
Effluent
1.0000
1.0597
Antimony
46541
8
Filtered
Effluent
1.0000
1.0647
Antimony
46542
8
Unfiltered
Effluent
10.0000
9.9690
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
10
Antimony
46543
8
Unfiltered
Effluent
10.0000
9.8699
Antimony
46544
8
Reagent
Water
20.0000
18.4290
Antimony
46545
8
Reagent
Water
20.0000
18.7830
Antimony
46546
8
Filtered
Freshwater
0.1241
0.1514
Antimony
46547
8
Filtered
Freshwater
0.1241
0.1352
Antimony
46548
8
Reagent
Water
0.0000
0.0409
Antimony
46549
8
Reagent
Water
0.0000
0.0109
Antimony
46550
8
Reagent
Water
1.0000
0.6547
Antimony
46551
8
Reagent
Water
1.0000
0.6252
Antimony
46552
8
Reagent
Water
5.0000
3.8980
Antimony
46553
8
Reagent
Water
5.0000
3.8641
Antimony
47259
8
Filtered
Freshwater
0.2041
0.2939
Antimony
47260
8
Filtered
Freshwater
0.2441
0.2723
Antimony
47261
8
Filtered
Freshwater
0.4041
0.4069
Antimony
47262
8
Filtered
Freshwater
0.5041
0.4886
Antimony
47263
8
Filtered
Freshwater
0.8041
0.7861
Antimony
47264
8
Filtered
Freshwater
1.0041
0.9654
Antimony
47265
8
Reagent
Water
0.1000
0.0662
Antimony
47266
8
Reagent
Water
0.1200
0.0992
Cadmium
46750
1
Reagent
Water
0.0000
0.0000
Cadmium
46751
1
Reagent
Water
0.0000
0.0000
Cadmium
46752
1
Reagent
Water
0.1000
0.0672
Cadmium
46753
1
Reagent
Water
0.1000
0.0786
Cadmium
46754
1
Reagent
Water
1.0000
0.9460
Cadmium
46755
1
Reagent
Water
1.0000
0.8640
Cadmium
46774
1
Reagent
Water
10.0000
8.6700
Cadmium
46775
1
Reagent
Water
10.0000
8.7400
Cadmium
46776
1
Unfiltered
Effluent
0.5000
0.4620
Cadmium
46777
1
Unfiltered
Effluent
0.5000
0.4940
Cadmium
46778
1
Filtered
Effluent
0.3000
0.3040
Cadmium
46779
1
Filtered
Effluent
0.3000
0.2910
Cadmium
46780
1
Filtered
Freshwater
0.2500
0.2080
Cadmium
46781
1
Filtered
Freshwater
0.2500
0.2180
Cadmium
47285
1
Filtered
Freshwater
0.0000
0.0000
Cadmium
47286
1
Filtered
Freshwater
0.0000
0.0001
Cadmium
47287
1
Filtered
Freshwater
0.0400
0.0224
Cadmium
47288
1
Filtered
Freshwater
0.0500
0.0576
Cadmium
47289
1
Filtered
Freshwater
0.1200
0.1190
Cadmium
47290
1
Filtered
Freshwater
0.1400
0.1510
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
11
Draft
­
December
2000
Cadmium
47291
1
Reagent
Water
0.0500
0.0469
Cadmium
47292
1
Reagent
Water
0.0600
1.8400
Cadmium
46504
2
Filtered
Freshwater
0.2500
0.2926
Cadmium
46505
2
Filtered
Freshwater
0.2500
0.2465
Cadmium
46506
2
Filtered
Effluent
0.3000
0.1854
Cadmium
46507
2
Filtered
Effluent
0.3000
0.2856
Cadmium
46508
2
Unfiltered
Effluent
0.5000
0.4082
Cadmium
46509
2
Unfiltered
Effluent
0.5000
0.4050
Cadmium
46510
2
Reagent
Water
0.0000
0.0170
Cadmium
46511
2
Reagent
Water
0.0000
0.0123
Cadmium
46512
2
Reagent
Water
0.1000
0.1233
Cadmium
46513
2
Reagent
Water
0.1000
0.1166
Cadmium
46514
2
Reagent
Water
1.0000
1.0400
Cadmium
46515
2
Reagent
Water
1.0000
1.0600
Cadmium
46516
2
Reagent
Water
10.0000
9.8920
Cadmium
46517
2
Reagent
Water
10.0000
9.9640
Cadmium
47231
2
Filtered
Freshwater
0.0000
­
0.0634
Cadmium
47232
2
Filtered
Freshwater
0.0000
0.0042
Cadmium
47233
2
Filtered
Freshwater
0.0400
0.0582
Cadmium
47234
2
Filtered
Freshwater
0.0500
0.0699
Cadmium
47235
2
Filtered
Freshwater
0.1200
0.1212
Cadmium
47236
2
Filtered
Freshwater
0.1400
0.1466
Cadmium
47237
2
Reagent
Water
0.0500
0.0678
Cadmium
47238
2
Reagent
Water
0.0600
0.0785
Cadmium
46722
3
Filtered
Freshwater
0.2500
0.2497
Cadmium
46723
3
Filtered
Freshwater
0.2500
0.2538
Cadmium
46724
3
Filtered
Effluent
0.3000
0.3243
Cadmium
46725
3
Filtered
Effluent
0.3000
0.3054
Cadmium
46726
3
Unfiltered
Effluent
0.5000
0.5163
Cadmium
46727
3
Unfiltered
Effluent
0.5000
0.5320
Cadmium
46728
3
Reagent
Water
0.0000
0.0038
Cadmium
46729
3
Reagent
Water
0.0000
0.0031
Cadmium
46730
3
Reagent
Water
0.1000
0.0987
Cadmium
46731
3
Reagent
Water
0.1000
0.0981
Cadmium
46732
3
Reagent
Water
1.0000
0.9950
Cadmium
46733
3
Reagent
Water
1.0000
0.9564
Cadmium
46734
3
Reagent
Water
10.0000
10.0214
Cadmium
46735
3
Reagent
Water
10.0000
9.9182
Cadmium
47213
3
Filtered
Freshwater
0.0000
0.0040
Cadmium
47214
3
Filtered
Freshwater
0.0000
0.0048
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
12
Cadmium
47215
3
Filtered
Freshwater
0.0400
0.0424
Cadmium
47216
3
Filtered
Freshwater
0.0500
0.0635
Cadmium
47217
3
Filtered
Freshwater
0.1200
0.1281
Cadmium
47218
3
Filtered
Freshwater
0.1400
0.1426
Cadmium
47219
3
Reagent
Water
0.0500
0.0541
Cadmium
47220
3
Reagent
Water
0.0600
0.0633
Cadmium
46594
4
Reagent
Water
0.0000
0.0050
Cadmium
46595
4
Reagent
Water
0.0000
­
0.0010
Cadmium
46596
4
Reagent
Water
10.0000
10.0840
Cadmium
46597
4
Reagent
Water
10.0000
10.1590
Cadmium
46598
4
Reagent
Water
1.0000
1.0180
Cadmium
46599
4
Reagent
Water
1.0000
1.0490
Cadmium
46600
4
Reagent
Water
0.1000
0.1100
Cadmium
46601
4
Reagent
Water
0.1000
0.0980
Cadmium
46602
4
Filtered
Freshwater
0.2500
0.2750
Cadmium
46603
4
Filtered
Freshwater
0.2500
0.2600
Cadmium
46604
4
Filtered
Effluent
0.3000
0.1990
Cadmium
46605
4
Filtered
Effluent
0.3000
0.3680
Cadmium
46606
4
Unfiltered
Effluent
0.5000
0.3690
Cadmium
46607
4
Unfiltered
Effluent
0.5000
0.3580
Cadmium
47239
4
Filtered
Freshwater
0.0000
­
0.0090
Cadmium
47240
4
Filtered
Freshwater
0.0000
­
0.0070
Cadmium
47241
4
Filtered
Freshwater
0.0400
0.0320
Cadmium
47242
4
Filtered
Freshwater
0.0500
0.0530
Cadmium
47243
4
Filtered
Freshwater
0.1200
0.1140
Cadmium
47244
4
Filtered
Freshwater
0.1400
0.1320
Cadmium
47245
4
Reagent
Water
0.0500
0.0470
Cadmium
47246
4
Reagent
Water
0.0600
0.0600
Cadmium
46532
5
Filtered
Freshwater
0.2500
0.3067
Cadmium
46533
5
Filtered
Freshwater
0.2500
0.3099
Cadmium
46534
5
Filtered
Effluent
0.3000
0.3996
Cadmium
46535
5
Filtered
Effluent
0.3000
0.4038
Cadmium
46536
5
Unfiltered
Effluent
0.5000
0.6642
Cadmium
46537
5
Unfiltered
Effluent
0.5000
0.6992
Cadmium
46538
5
Reagent
Water
0.0000
0.0895
Cadmium
46539
5
Reagent
Water
0.0000
0.0715
Cadmium
46702
5
Reagent
Water
0.1000
0.1595
Cadmium
46703
5
Reagent
Water
0.1000
0.1717
Cadmium
46704
5
Reagent
Water
1.0000
0.9707
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
13
Draft
­
December
2000
Cadmium
46705
5
Reagent
Water
1.0000
1.0440
Cadmium
46706
5
Reagent
Water
10.0000
9.1160
Cadmium
46707
5
Reagent
Water
10.0000
9.3767
Cadmium
47223
5
Filtered
Freshwater
0.0000
0.0420
Cadmium
47224
5
Filtered
Freshwater
0.0000
0.0360
Cadmium
47225
5
Filtered
Freshwater
0.0400
0.1028
Cadmium
47226
5
Filtered
Freshwater
0.0500
0.1133
Cadmium
47227
5
Filtered
Freshwater
0.1200
0.1829
Cadmium
47228
5
Filtered
Freshwater
0.1400
0.1926
Cadmium
47229
5
Reagent
Water
0.0500
0.0977
Cadmium
47230
5
Reagent
Water
0.0600
0.1210
Cadmium
46554
6
Filtered
Effluent
0.3000
0.3644
Outlying
Laboratory
Cadmium
46555
6
Filtered
Effluent
0.3000
0.3490
Outlying
Laboratory
Cadmium
46556
6
Filtered
Freshwater
0.2500
0.2666
Outlying
Laboratory
Cadmium
46557
6
Filtered
Freshwater
0.2500
0.2657
Outlying
Laboratory
Cadmium
46558
6
Reagent
Water
0.0000
0.0088
Outlying
Laboratory
Cadmium
46559
6
Reagent
Water
0.0000
0.0148
Outlying
Laboratory
Cadmium
46560
6
Unfiltered
Effluent
0.5000
0.5390
Outlying
Laboratory
Cadmium
46561
6
Unfiltered
Effluent
0.5000
0.5277
Outlying
Laboratory
Cadmium
46562
6
Reagent
Water
0.1000
0.1240
Outlying
Laboratory
Cadmium
46563
6
Reagent
Water
0.1000
0.1038
Outlying
Laboratory
Cadmium
46564
6
Reagent
Water
1.0000
1.0202
Outlying
Laboratory
Cadmium
46565
6
Reagent
Water
1.0000
1.1519
Outlying
Laboratory
Cadmium
46566
6
Reagent
Water
10.0000
10.0737
Outlying
Laboratory
Cadmium
46567
6
Reagent
Water
10.0000
10.1802
Outlying
Laboratory
Cadmium
47247
6
Filtered
Freshwater
0.0000
0.0132
Outlying
Laboratory
Cadmium
47248
6
Filtered
Freshwater
0.0000
0.0157
Outlying
Laboratory
Cadmium
47249
6
Filtered
Freshwater
0.0400
0.0349
Outlying
Laboratory
Cadmium
47250
6
Filtered
Freshwater
0.0500
0.0640
Outlying
Laboratory
Cadmium
47251
6
Filtered
Freshwater
0.1200
0.1414
Outlying
Laboratory
Cadmium
47252
6
Filtered
Freshwater
0.1400
0.1570
Outlying
Laboratory
Cadmium
47253
6
Reagent
Water
0.0500
0.0558
Outlying
Laboratory
Cadmium
47254
6
Reagent
Water
0.0600
0.0977
Outlying
Laboratory
Cadmium
46846
7
Reagent
Water
0.0000
­
0.0348
Cadmium
46847
7
Reagent
Water
0.0000
­
0.0347
Cadmium
46848
7
Reagent
Water
0.1000
0.0726
Cadmium
46849
7
Reagent
Water
0.1000
0.0598
Cadmium
46850
7
Reagent
Water
1.0000
0.9869
Cadmium
46851
7
Reagent
Water
1.0000
0.9937
Cadmium
46852
7
Reagent
Water
10.0000
10.0357
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
14
Cadmium
46853
7
Reagent
Water
10.0000
10.1000
Cadmium
46854
7
Filtered
Effluent
0.3000
0.1585
Cadmium
46855
7
Filtered
Effluent
0.3000
0.1832
Cadmium
46856
7
Filtered
Freshwater
0.2500
0.2298
Cadmium
46857
7
Filtered
Freshwater
0.2500
0.2180
Cadmium
47267
7
Unfiltered
Effluent
0.5000
0.4040
Cadmium
47268
7
Unfiltered
Effluent
0.5000
0.3690
Cadmium
47269
7
Filtered
Freshwater
0.0000
­
0.0373
Cadmium
47270
7
Filtered
Freshwater
0.0000
­
0.0370
Cadmium
47271
7
Filtered
Freshwater
0.0400
­
0.0008
Cadmium
47272
7
Filtered
Freshwater
0.0500
0.0108
Cadmium
47273
7
Filtered
Freshwater
0.1200
0.0816
Cadmium
47274
7
Filtered
Freshwater
0.1400
0.1053
Cadmium
47275
7
Reagent
Water
0.0500
0.0162
Cadmium
47276
7
Reagent
Water
0.0600
0.0222
Cadmium
46540
8
Filtered
Effluent
0.3000
0.2916
Cadmium
46541
8
Filtered
Effluent
0.3000
0.2988
Cadmium
46542
8
Unfiltered
Effluent
0.5000
0.4775
Cadmium
46543
8
Unfiltered
Effluent
0.5000
0.4846
Cadmium
46544
8
Reagent
Water
10.0000
9.4199
Cadmium
46545
8
Reagent
Water
10.0000
9.5763
Cadmium
46546
8
Filtered
Freshwater
0.2500
0.2322
Cadmium
46547
8
Filtered
Freshwater
0.2500
0.2185
Cadmium
46548
8
Reagent
Water
0.0000
­
0.0208
Cadmium
46549
8
Reagent
Water
0.0000
­
0.0170
Cadmium
46550
8
Reagent
Water
0.1000
0.0840
Cadmium
46551
8
Reagent
Water
0.1000
0.0857
Cadmium
46552
8
Reagent
Water
1.0000
0.9206
Cadmium
46553
8
Reagent
Water
1.0000
0.9097
Cadmium
47259
8
Filtered
Freshwater
0.0000
­
0.0218
Cadmium
47260
8
Filtered
Freshwater
0.0000
­
0.0203
Cadmium
47261
8
Filtered
Freshwater
0.0400
0.0127
Cadmium
47262
8
Filtered
Freshwater
0.0500
0.0194
Cadmium
47263
8
Filtered
Freshwater
0.1200
0.0942
Cadmium
47264
8
Filtered
Freshwater
0.1400
0.1121
Cadmium
47265
8
Reagent
Water
0.0500
0.0207
Cadmium
47266
8
Reagent
Water
0.0600
0.0349
Copper
46750
1
Reagent
Water
0.0000
0.0000
Outlying
Laboratory
Copper
46751
1
Reagent
Water
0.0000
0.0000
Outlying
Laboratory
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
15
Draft
­
December
2000
Copper
46752
1
Reagent
Water
0.5000
0.4490
Outlying
Laboratory
Copper
46753
1
Reagent
Water
0.5000
0.4420
Outlying
Laboratory
Copper
46754
1
Reagent
Water
2.0000
1.7700
Outlying
Laboratory
Copper
46755
1
Reagent
Water
2.0000
1.8000
Outlying
Laboratory
Copper
46774
1
Reagent
Water
20.0000
17.9000
Outlying
Laboratory
Copper
46775
1
Reagent
Water
20.0000
18.1000
Outlying
Laboratory
Copper
46776
1
Unfiltered
Effluent
15.1000
14.8000
Outlying
Laboratory
Copper
46777
1
Unfiltered
Effluent
15.1000
14.4000
Outlying
Laboratory
Copper
46778
1
Filtered
Effluent
13.8000
14.0000
Outlying
Laboratory
Copper
46779
1
Filtered
Effluent
13.8000
13.0000
Outlying
Laboratory
Copper
46780
1
Filtered
Freshwater
1.0300
0.9110
Outlying
Laboratory
Copper
46781
1
Filtered
Freshwater
1.0300
0.9870
Outlying
Laboratory
Copper
47285
1
Filtered
Freshwater
1.5300
1.4400
Outlying
Laboratory
Copper
47286
1
Filtered
Freshwater
1.7300
1.6900
Outlying
Laboratory
Copper
47287
1
Filtered
Freshwater
2.5300
2.4000
Outlying
Laboratory
Copper
47288
1
Filtered
Freshwater
3.0300
2.8800
Outlying
Laboratory
Copper
47289
1
Filtered
Freshwater
4.5300
4.3400
Outlying
Laboratory
Copper
47290
1
Filtered
Freshwater
5.0300
4.7200
Outlying
Laboratory
Copper
47291
1
Reagent
Water
0.2000
0.1750
Outlying
Laboratory
Copper
47292
1
Reagent
Water
0.2400
0.2460
Outlying
Laboratory
Copper
46504
2
Filtered
Freshwater
1.0300
6.2910
Copper
46505
2
Filtered
Freshwater
1.0300
1.4400
Copper
46506
2
Filtered
Effluent
13.8000
13.8600
Copper
46507
2
Filtered
Effluent
13.8000
13.1800
Copper
46508
2
Unfiltered
Effluent
15.1000
15.5200
Copper
46509
2
Unfiltered
Effluent
15.1000
15.2000
Copper
46510
2
Reagent
Water
0.0000
0.1589
Copper
46511
2
Reagent
Water
0.0000
0.1326
Copper
46512
2
Reagent
Water
0.5000
1.0490
Copper
46513
2
Reagent
Water
0.5000
0.8788
Copper
46514
2
Reagent
Water
2.0000
2.2070
Copper
46515
2
Reagent
Water
2.0000
2.1410
Copper
46516
2
Reagent
Water
20.0000
19.9900
Copper
46517
2
Reagent
Water
20.0000
20.2300
Copper
47231
2
Filtered
Freshwater
1.5300
1.8150
Copper
47232
2
Filtered
Freshwater
1.7300
1.8170
Copper
47233
2
Filtered
Freshwater
2.5300
2.5870
Copper
47234
2
Filtered
Freshwater
3.0300
3.2650
Copper
47235
2
Filtered
Freshwater
4.5300
4.5170
Copper
47236
2
Filtered
Freshwater
5.0300
5.1440
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
16
Copper
47237
2
Reagent
Water
0.2000
0.4544
Copper
47238
2
Reagent
Water
0.2400
0.2860
Copper
46722
3
Filtered
Freshwater
1.0300
1.0159
Copper
46723
3
Filtered
Freshwater
1.0300
1.0749
Copper
46724
3
Filtered
Effluent
13.8000
14.6823
Copper
46725
3
Filtered
Effluent
13.8000
15.2322
Copper
46726
3
Unfiltered
Effluent
15.1000
17.6339
Copper
46727
3
Unfiltered
Effluent
15.1000
16.2906
Copper
46728
3
Reagent
Water
0.0000
0.0323
Copper
46729
3
Reagent
Water
0.0000
0.0481
Copper
46730
3
Reagent
Water
0.5000
0.6168
Copper
46731
3
Reagent
Water
0.5000
0.6020
Copper
46732
3
Reagent
Water
2.0000
2.1453
Copper
46733
3
Reagent
Water
2.0000
3.2563
Copper
46734
3
Reagent
Water
20.0000
19.4746
Copper
46735
3
Reagent
Water
20.0000
19.7283
Copper
47213
3
Filtered
Freshwater
1.5300
1.5634
Copper
47214
3
Filtered
Freshwater
1.7300
1.6089
Copper
47215
3
Filtered
Freshwater
2.5300
2.2561
Copper
47216
3
Filtered
Freshwater
3.0300
2.8573
Copper
47217
3
Filtered
Freshwater
4.5300
3.9508
Copper
47218
3
Filtered
Freshwater
5.0300
4.3348
Copper
47219
3
Reagent
Water
0.2000
0.3242
Copper
47220
3
Reagent
Water
0.2400
0.2824
Copper
46594
4
Reagent
Water
0.0000
0.0440
Copper
46595
4
Reagent
Water
0.0000
0.0260
Copper
46596
4
Reagent
Water
20.0000
21.0530
Copper
46597
4
Reagent
Water
20.0000
21.3540
Copper
46598
4
Reagent
Water
2.0000
2.1880
Copper
46599
4
Reagent
Water
2.0000
2.2190
Copper
46600
4
Reagent
Water
0.5000
1.1720
Copper
46601
4
Reagent
Water
0.5000
0.5570
Copper
46602
4
Filtered
Freshwater
1.0300
1.2270
Copper
46603
4
Filtered
Freshwater
1.0300
1.2380
Copper
46604
4
Filtered
Effluent
13.8000
16.1150
Copper
46605
4
Filtered
Effluent
13.8000
17.7950
Individual
Outlier
Copper
46606
4
Unfiltered
Effluent
15.1000
17.5450
Possible
contamination2
Copper
46607
4
Unfiltered
Effluent
15.1000
20.1940
Possible
contamination2
Copper
47239
4
Filtered
Freshwater
1.5300
1.7160
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
17
Draft
­
December
2000
Copper
47240
4
Filtered
Freshwater
1.7300
1.8940
Copper
47241
4
Filtered
Freshwater
2.5300
2.7240
Copper
47242
4
Filtered
Freshwater
3.0300
3.4490
Copper
47243
4
Filtered
Freshwater
4.5300
5.8480
Copper
47244
4
Filtered
Freshwater
5.0300
5.2620
Copper
47245
4
Reagent
Water
0.2000
2.0470
Copper
47246
4
Reagent
Water
0.2400
0.9950
Copper
46532
5
Filtered
Freshwater
1.0300
1.1891
Possible
contamination1
Copper
46533
5
Filtered
Freshwater
1.0300
8.0865
Individual
Outlier
Possible
contamination1
Copper
46535
5
Filtered
Effluent
13.8000
14.4274
Possible
contamination1
Copper
46536
5
Unfiltered
Effluent
15.1000
18.9784
Possible
contamination1
Copper
46537
5
Unfiltered
Effluent
15.1000
17.9623
Possible
contamination1
Copper
46538
5
Reagent
Water
0.0000
0.5282
Possible
contamination1
Copper
46539
5
Reagent
Water
0.0000
0.6445
Possible
contamination1
Copper
46702
5
Reagent
Water
0.5000
0.5643
Possible
contamination1
Copper
46703
5
Reagent
Water
0.5000
0.6304
Possible
contamination1
Copper
46704
5
Reagent
Water
2.0000
1.9111
Possible
contamination1
Copper
46705
5
Reagent
Water
2.0000
1.8558
Possible
contamination1
Copper
46706
5
Reagent
Water
20.0000
18.6020
Possible
contamination1
Copper
46707
5
Reagent
Water
20.0000
18.8151
Possible
contamination1
Copper
47223
5
Filtered
Freshwater
1.5300
1.7400
Possible
contamination1
Copper
47224
5
Filtered
Freshwater
1.7300
5.4500
Possible
contamination1
Copper
47225
5
Filtered
Freshwater
2.5300
2.5788
Possible
contamination1
Copper
47226
5
Filtered
Freshwater
3.0300
3.6508
Possible
contamination1
Copper
47227
5
Filtered
Freshwater
4.5300
4.3961
Possible
contamination1
Copper
47228
5
Filtered
Freshwater
5.0300
4.7973
Possible
contamination1
Copper
47229
5
Reagent
Water
0.2000
0.6310
Possible
contamination1
Copper
47230
5
Reagent
Water
0.2400
0.4641
Copper
46554
6
Filtered
Effluent
13.8000
12.7543
Copper
46555
6
Filtered
Effluent
13.8000
13.7450
Copper
46556
6
Filtered
Freshwater
1.0300
1.3090
Copper
46557
6
Filtered
Freshwater
1.0300
1.1262
Copper
46558
6
Reagent
Water
0.0000
0.1286
Copper
46559
6
Reagent
Water
0.0000
0.3061
Copper
46560
6
Unfiltered
Effluent
15.1000
17.4718
Copper
46561
6
Unfiltered
Effluent
15.1000
14.4560
Copper
46562
6
Reagent
Water
0.5000
0.5794
Copper
46563
6
Reagent
Water
0.5000
0.6422
Copper
46564
6
Reagent
Water
2.0000
2.2046
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
18
Copper
46565
6
Reagent
Water
2.0000
3.5277
Copper
46566
6
Reagent
Water
20.0000
18.5092
Copper
46567
6
Reagent
Water
20.0000
43.9433
Individual
Outlier
Copper
47247
6
Filtered
Freshwater
1.5300
1.6680
Copper
47248
6
Filtered
Freshwater
1.7300
1.8756
Copper
47249
6
Filtered
Freshwater
2.5300
2.4713
Copper
47250
6
Filtered
Freshwater
3.0300
2.9969
Copper
47251
6
Filtered
Freshwater
4.5300
4.3591
Copper
47252
6
Filtered
Freshwater
5.0300
4.5801
Copper
47253
6
Reagent
Water
0.2000
0.3025
Copper
47254
6
Reagent
Water
0.2400
0.5329
Copper
46846
7
Reagent
Water
0.0000
0.0161
Copper
46847
7
Reagent
Water
0.0000
0.0160
Copper
46848
7
Reagent
Water
0.5000
0.4596
Copper
46849
7
Reagent
Water
0.5000
0.4643
Copper
46850
7
Reagent
Water
2.0000
1.9044
Copper
46851
7
Reagent
Water
2.0000
1.8799
Copper
46852
7
Reagent
Water
20.0000
18.5410
Copper
46853
7
Reagent
Water
20.0000
18.9762
Copper
46854
7
Filtered
Effluent
13.8000
14.6566
Copper
46855
7
Filtered
Effluent
13.8000
14.7489
Copper
46856
7
Filtered
Freshwater
1.0300
1.0672
Copper
46857
7
Filtered
Freshwater
1.0300
1.0314
Copper
47267
7
Unfiltered
Effluent
15.1000
15.1818
Copper
47268
7
Unfiltered
Effluent
15.1000
15.3126
Copper
47269
7
Filtered
Freshwater
1.5300
1.4750
Copper
47270
7
Filtered
Freshwater
1.7300
1.6631
Copper
47271
7
Filtered
Freshwater
2.5300
2.3944
Copper
47272
7
Filtered
Freshwater
3.0300
2.8477
Copper
47273
7
Filtered
Freshwater
4.5300
4.1560
Copper
47274
7
Filtered
Freshwater
5.0300
4.6702
Copper
47275
7
Reagent
Water
0.2000
0.1925
Copper
47276
7
Reagent
Water
0.2400
0.2383
Copper
46540
8
Filtered
Effluent
13.8000
13.8010
Copper
46541
8
Filtered
Effluent
13.8000
13.6680
Copper
46542
8
Unfiltered
Effluent
15.1000
15.4382
Copper
46543
8
Unfiltered
Effluent
15.1000
15.5194
Copper
46544
8
Reagent
Water
20.0000
18.1127
Copper
46545
8
Reagent
Water
20.0000
18.5166
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
19
Draft
­
December
2000
Copper
46546
8
Filtered
Freshwater
1.0300
1.0520
Copper
46547
8
Filtered
Freshwater
1.0300
1.0250
Copper
46548
8
Reagent
Water
0.0000
0.0173
Copper
46549
8
Reagent
Water
0.0000
0.0180
Copper
46550
8
Reagent
Water
0.5000
0.4540
Copper
46551
8
Reagent
Water
0.5000
0.4798
Copper
46552
8
Reagent
Water
2.0000
1.7638
Copper
46553
8
Reagent
Water
2.0000
1.8114
Copper
47259
8
Filtered
Freshwater
1.5300
1.4739
Copper
47260
8
Filtered
Freshwater
1.7300
1.6273
Copper
47261
8
Filtered
Freshwater
2.5300
2.3142
Copper
47262
8
Filtered
Freshwater
3.0300
2.8229
Copper
47263
8
Filtered
Freshwater
4.5300
4.0287
Copper
47264
8
Filtered
Freshwater
5.0300
4.5219
Copper
47265
8
Reagent
Water
0.2000
0.1719
Copper
47266
8
Reagent
Water
0.2400
0.2100
Lead
46750
1
Reagent
Water
0.0000
0.0004
Outlying
Laboratory
Lead
46751
1
Reagent
Water
0.0000
0.0035
Outlying
Laboratory
Lead
46752
1
Reagent
Water
0.1000
0.0790
Outlying
Laboratory
Lead
46753
1
Reagent
Water
0.1000
0.0832
Outlying
Laboratory
Lead
46754
1
Reagent
Water
0.5000
0.4540
Outlying
Laboratory
Lead
46755
1
Reagent
Water
0.5000
0.4510
Outlying
Laboratory
Lead
46774
1
Reagent
Water
5.0000
4.2700
Outlying
Laboratory
Lead
46775
1
Reagent
Water
5.0000
4.2600
Outlying
Laboratory
Lead
46776
1
Unfiltered
Effluent
1.0557
0.9680
Outlying
Laboratory
Lead
46777
1
Unfiltered
Effluent
1.0557
0.9730
Outlying
Laboratory
Lead
46778
1
Filtered
Effluent
0.5000
0.5310
Outlying
Laboratory
Lead
46779
1
Filtered
Effluent
0.5000
0.4870
Outlying
Laboratory
Lead
46780
1
Filtered
Freshwater
0.2000
0.1570
Outlying
Laboratory
Lead
46781
1
Filtered
Freshwater
0.2000
0.2200
Outlying
Laboratory
Lead
47285
1
Filtered
Freshwater
0.0128
0.0160
Outlying
Laboratory
Lead
47286
1
Filtered
Freshwater
0.0128
0.0131
Outlying
Laboratory
Lead
47287
1
Filtered
Freshwater
0.0528
0.0487
Outlying
Laboratory
Lead
47288
1
Filtered
Freshwater
0.0628
0.1090
Outlying
Laboratory
Possible
contamination2
Lead
47289
1
Filtered
Freshwater
0.3128
0.2690
Outlying
Laboratory
Lead
47290
1
Filtered
Freshwater
0.6328
0.3220
Outlying
Laboratory
Lead
47291
1
Reagent
Water
0.0300
0.0366
Outlying
Laboratory
Lead
47292
1
Reagent
Water
0.0360
0.0271
Outlying
Laboratory
Lead
46504
2
Filtered
Freshwater
0.2000
0.3806
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
20
Lead
46505
2
Filtered
Freshwater
0.2000
0.4883
Individual
Outlier
Lead
46506
2
Filtered
Effluent
0.5000
0.6331
Lead
46507
2
Filtered
Effluent
0.5000
0.7302
Lead
46508
2
Unfiltered
Effluent
1.0557
1.1380
Lead
46509
2
Unfiltered
Effluent
1.0557
1.1410
Lead
46510
2
Reagent
Water
0.0000
0.1292
Lead
46511
2
Reagent
Water
0.0000
0.0541
Lead
46512
2
Reagent
Water
0.1000
0.2634
Individual
Outlier
Lead
46513
2
Reagent
Water
0.1000
0.1817
Lead
46514
2
Reagent
Water
0.5000
0.6876
Lead
46515
2
Reagent
Water
0.5000
0.5714
Lead
46516
2
Reagent
Water
5.0000
5.1920
Lead
46517
2
Reagent
Water
5.0000
5.0520
Lead
47231
2
Filtered
Freshwater
0.0128
0.0852
Lead
47232
2
Filtered
Freshwater
0.0128
0.0770
Lead
47233
2
Filtered
Freshwater
0.0528
0.1464
Lead
47234
2
Filtered
Freshwater
0.0628
0.2292
Lead
47235
2
Filtered
Freshwater
0.3128
0.3636
Lead
47236
2
Filtered
Freshwater
0.6328
0.5197
Lead
47237
2
Reagent
Water
0.0300
0.1964
Lead
47238
2
Reagent
Water
0.0360
0.0852
Lead
46722
3
Filtered
Freshwater
0.2000
0.2403
Lead
46723
3
Filtered
Freshwater
0.2000
0.2358
Lead
46724
3
Filtered
Effluent
0.5000
0.6978
Lead
46725
3
Filtered
Effluent
0.5000
0.6215
Lead
46726
3
Unfiltered
Effluent
1.0557
1.2198
Lead
46727
3
Unfiltered
Effluent
1.0557
1.1774
Lead
46728
3
Reagent
Water
0.0000
0.0103
Lead
46729
3
Reagent
Water
0.0000
0.0145
Lead
46730
3
Reagent
Water
0.1000
0.1167
Lead
46731
3
Reagent
Water
0.1000
0.1194
Lead
46732
3
Reagent
Water
0.5000
0.5013
Lead
46733
3
Reagent
Water
0.5000
0.5341
Lead
46734
3
Reagent
Water
5.0000
4.9543
Lead
46735
3
Reagent
Water
5.0000
5.0154
Lead
47213
3
Filtered
Freshwater
0.0128
0.0437
Lead
47214
3
Filtered
Freshwater
0.0128
0.0486
Lead
47215
3
Filtered
Freshwater
0.0528
0.0835
Lead
47216
3
Filtered
Freshwater
0.0628
0.1106
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
21
Draft
­
December
2000
Lead
47217
3
Filtered
Freshwater
0.3128
0.3460
Lead
47218
3
Filtered
Freshwater
0.6328
0.3924
Lead
47219
3
Reagent
Water
0.0300
0.0605
Lead
47220
3
Reagent
Water
0.0360
0.0519
Lead
46594
4
Reagent
Water
0.0000
0.0070
Lead
46595
4
Reagent
Water
0.0000
0.0040
Lead
46596
4
Reagent
Water
5.0000
5.1970
Lead
46597
4
Reagent
Water
5.0000
5.2670
Lead
46598
4
Reagent
Water
0.5000
0.5160
Lead
46599
4
Reagent
Water
0.5000
0.5170
Lead
46600
4
Reagent
Water
0.1000
0.1060
Lead
46601
4
Reagent
Water
0.1000
0.1030
Lead
46602
4
Filtered
Freshwater
0.2000
0.2200
Lead
46603
4
Filtered
Freshwater
0.2000
0.2220
Lead
46604
4
Filtered
Effluent
0.5000
0.5650
Lead
46605
4
Filtered
Effluent
0.5000
0.7330
Lead
46606
4
Unfiltered
Effluent
1.0557
1.0530
Lead
46607
4
Unfiltered
Effluent
1.0557
1.0840
Lead
47239
4
Filtered
Freshwater
0.0128
0.0280
Lead
47240
4
Filtered
Freshwater
0.0128
0.0310
Lead
47241
4
Filtered
Freshwater
0.0528
0.0690
Lead
47242
4
Filtered
Freshwater
0.0628
0.0820
Lead
47243
4
Filtered
Freshwater
0.3128
0.3540
Lead
47244
4
Filtered
Freshwater
0.6328
0.3860
Lead
47245
4
Reagent
Water
0.0300
0.0670
Lead
47246
4
Reagent
Water
0.0360
0.0390
Lead
46532
5
Filtered
Freshwater
0.2000
0.3552
Possible
contamination1
Lead
46533
5
Filtered
Freshwater
0.2000
0.2326
Possible
contamination1
Lead
46534
5
Filtered
Effluent
0.5000
0.5874
Possible
contamination1
Lead
46535
5
Filtered
Effluent
0.5000
0.5899
Possible
contamination1
Lead
46536
5
Unfiltered
Effluent
1.0557
1.7818
Possible
contamination1
Lead
46537
5
Unfiltered
Effluent
1.0557
2.7456
Individual
Outlier
Possible
contamination1
Lead
46538
5
Reagent
Water
0.0000
0.0594
Possible
contamination1
Lead
46539
5
Reagent
Water
0.0000
0.1421
Possible
contamination1
Lead
46702
5
Reagent
Water
0.1000
0.1596
Possible
contamination1
Lead
46703
5
Reagent
Water
0.1000
0.1953
Possible
contamination1
Lead
46704
5
Reagent
Water
0.5000
0.4931
Possible
contamination1
Lead
46705
5
Reagent
Water
0.5000
0.5157
Possible
contamination1
Lead
46706
5
Reagent
Water
5.0000
4.7988
Possible
contamination1
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
22
Lead
46707
5
Reagent
Water
5.0000
4.8011
Possible
contamination1
Lead
47223
5
Filtered
Freshwater
0.0128
0.0630
Possible
contamination1
Lead
47224
5
Filtered
Freshwater
0.0128
0.1640
Possible
contamination1
Lead
47225
5
Filtered
Freshwater
0.0528
0.0958
Possible
contamination1
Lead
47226
5
Filtered
Freshwater
0.0628
0.0835
Possible
contamination1
Lead
47227
5
Filtered
Freshwater
0.3128
0.4236
Possible
contamination1
Lead
47228
5
Filtered
Freshwater
0.6328
0.3797
Possible
contamination1
Lead
47229
5
Reagent
Water
0.0300
0.1422
Possible
contamination1
Lead
47230
5
Reagent
Water
0.0360
0.1253
Possible
contamination1
Lead
46554
6
Filtered
Effluent
0.5000
0.6123
Lead
46555
6
Filtered
Effluent
0.5000
0.6286
Lead
46556
6
Filtered
Freshwater
0.2000
0.2493
Lead
46557
6
Filtered
Freshwater
0.2000
0.2500
Lead
46558
6
Reagent
Water
0.0000
0.0208
Lead
46559
6
Reagent
Water
0.0000
0.0291
Lead
46560
6
Unfiltered
Effluent
1.0557
1.1253
Lead
46561
6
Unfiltered
Effluent
1.0557
1.1737
Lead
46562
6
Reagent
Water
0.1000
0.1160
Lead
46563
6
Reagent
Water
0.1000
0.1135
Possible
contamination2
Lead
46564
6
Reagent
Water
0.5000
0.5201
Lead
46565
6
Reagent
Water
0.5000
2.4625
Individual
Outlier
Lead
46566
6
Reagent
Water
5.0000
5.0285
Lead
46567
6
Reagent
Water
5.0000
6.3171
Individual
Outlier
Lead
47247
6
Filtered
Freshwater
0.0128
0.0603
Possible
contamination1
Lead
47248
6
Filtered
Freshwater
0.0128
0.1225
Possible
contamination2
Lead
47249
6
Filtered
Freshwater
0.0528
0.0890
Possible
contamination1
Lead
47250
6
Filtered
Freshwater
0.0628
0.1112
Possible
contamination2
Lead
47251
6
Filtered
Freshwater
0.3128
0.3379
Lead
47252
6
Filtered
Freshwater
0.6328
0.3967
Lead
47253
6
Reagent
Water
0.0300
0.0528
Possible
contamination1
Lead
47254
6
Reagent
Water
0.0360
0.0777
Possible
contamination1
Lead
46846
7
Reagent
Water
0.0000
0.0051
Lead
46847
7
Reagent
Water
0.0000
0.0052
Lead
46848
7
Reagent
Water
0.1000
0.0996
Lead
46849
7
Reagent
Water
0.1000
0.0974
Lead
46850
7
Reagent
Water
0.5000
0.4792
Lead
46851
7
Reagent
Water
0.5000
0.4807
Lead
46852
7
Reagent
Water
5.0000
4.8454
Lead
46853
7
Reagent
Water
5.0000
4.8580
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
23
Draft
­
December
2000
Lead
46854
7
Filtered
Effluent
0.5000
0.5339
Lead
46855
7
Filtered
Effluent
0.5000
0.5326
Lead
46856
7
Filtered
Freshwater
0.2000
0.2166
Lead
46857
7
Filtered
Freshwater
0.2000
0.2143
Lead
47267
7
Unfiltered
Effluent
1.0557
0.8502
Lead
47268
7
Unfiltered
Effluent
1.0557
0.8549
Lead
47269
7
Filtered
Freshwater
0.0128
0.0280
Lead
47270
7
Filtered
Freshwater
0.0128
0.0278
Lead
47271
7
Filtered
Freshwater
0.0528
0.0678
Possible
contamination1
Lead
47272
7
Filtered
Freshwater
0.0628
0.0791
Possible
contamination1
Lead
47273
7
Filtered
Freshwater
0.3128
0.3156
Lead
47274
7
Filtered
Freshwater
0.6328
0.3653
Lead
47275
7
Reagent
Water
0.0300
0.0375
Lead
47276
7
Reagent
Water
0.0360
0.0366
Lead
46540
8
Filtered
Effluent
0.5000
0.6138
Lead
46541
8
Filtered
Effluent
0.5000
0.5709
Lead
46542
8
Unfiltered
Effluent
1.0557
1.1202
Lead
46543
8
Unfiltered
Effluent
1.0557
1.1145
Lead
46544
8
Reagent
Water
5.0000
4.8273
Lead
46545
8
Reagent
Water
5.0000
4.9817
Lead
46546
8
Filtered
Freshwater
0.2000
0.2203
Lead
46547
8
Filtered
Freshwater
0.2000
0.2217
Lead
46548
8
Reagent
Water
0.0000
­
0.0016
Lead
46549
8
Reagent
Water
0.0000
0.0004
Lead
46550
8
Reagent
Water
0.1000
0.0943
Lead
46551
8
Reagent
Water
0.1000
0.0921
Lead
46552
8
Reagent
Water
0.5000
0.4677
Lead
46553
8
Reagent
Water
0.5000
0.4772
Lead
47259
8
Filtered
Freshwater
0.0128
0.0180
Lead
47260
8
Filtered
Freshwater
0.0128
0.0211
Lead
47261
8
Filtered
Freshwater
0.0528
0.0550
Lead
47262
8
Filtered
Freshwater
0.0628
0.0670
Lead
47263
8
Filtered
Freshwater
0.3128
0.2972
Lead
47264
8
Filtered
Freshwater
0.6328
0.3550
Lead
47265
8
Reagent
Water
0.0300
0.0239
Lead
47266
8
Reagent
Water
0.0360
0.0290
Nickel
46750
1
Reagent
Water
0.0000
0.0000
Nickel
46751
1
Reagent
Water
0.0000
0.0000
Nickel
46752
1
Reagent
Water
1.0000
0.9190
Nickel
46753
1
Reagent
Water
1.0000
0.8190
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
24
Nickel
46754
1
Reagent
Water
10.0000
8.9500
Nickel
46755
1
Reagent
Water
10.0000
8.8200
Nickel
46774
1
Reagent
Water
100.0000
87.1000
Concentration
>
cal
range
Nickel
46775
1
Reagent
Water
100.0000
86.9000
Concentration
>
cal
range
Nickel
46776
1
Unfiltered
Effluent
8.0000
7.5900
Nickel
46777
1
Unfiltered
Effluent
8.0000
7.6000
Nickel
46778
1
Filtered
Effluent
7.0000
7.1100
Nickel
46779
1
Filtered
Effluent
7.0000
6.5200
Nickel
46780
1
Filtered
Freshwater
6.0000
5.1800
Nickel
46781
1
Filtered
Freshwater
6.0000
5.7500
Nickel
47285
1
Filtered
Freshwater
0.3100
0.4940
Nickel
47286
1
Filtered
Freshwater
0.3100
0.5130
Nickel
47287
1
Filtered
Freshwater
1.6100
1.7200
Nickel
47288
1
Filtered
Freshwater
1.8100
1.8800
Nickel
47289
1
Filtered
Freshwater
3.3100
3.2800
Nickel
47290
1
Filtered
Freshwater
4.0100
3.8600
Nickel
47291
1
Reagent
Water
0.5000
0.4200
Nickel
47292
1
Reagent
Water
0.6000
0.5230
Nickel
46504
2
Filtered
Freshwater
6.0000
6.9970
Outlying
Laboratory
Nickel
46505
2
Filtered
Freshwater
6.0000
6.7370
Outlying
Laboratory
Nickel
46506
2
Filtered
Effluent
7.0000
7.0590
Outlying
Laboratory
Nickel
46507
2
Filtered
Effluent
7.0000
7.3030
Outlying
Laboratory
Nickel
46508
2
Unfiltered
Effluent
8.0000
7.6590
Outlying
Laboratory
Possible
contamination1
Nickel
46509
2
Unfiltered
Effluent
8.0000
7.8510
Outlying
Laboratory
Nickel
46510
2
Reagent
Water
0.0000
0.0303
Outlying
Laboratory
Nickel
46511
2
Reagent
Water
0.0000
0.0256
Outlying
Laboratory
Nickel
46512
2
Reagent
Water
1.0000
1.4040
Outlying
Laboratory
Nickel
46513
2
Reagent
Water
1.0000
0.9972
Outlying
Laboratory
Nickel
46514
2
Reagent
Water
10.0000
10.1900
Outlying
Laboratory
Nickel
46515
2
Reagent
Water
10.0000
10.6900
Outlying
Laboratory
Nickel
46516
2
Reagent
Water
100.0000
98.7800
Outlying
Laboratory
Nickel
46517
2
Reagent
Water
100.0000
99.2600
Outlying
Laboratory
Nickel
47231
2
Filtered
Freshwater
0.3100
0.8529
Outlying
Laboratory
Nickel
47232
2
Filtered
Freshwater
0.3100
0.7177
Outlying
Laboratory
Nickel
47233
2
Filtered
Freshwater
1.6100
1.9840
Outlying
Laboratory
Nickel
47234
2
Filtered
Freshwater
1.8100
2.2680
Outlying
Laboratory
Nickel
47235
2
Filtered
Freshwater
3.3100
3.7520
Outlying
Laboratory
Nickel
47236
2
Filtered
Freshwater
4.0100
4.4710
Outlying
Laboratory
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
25
Draft
­
December
2000
Nickel
47237
2
Reagent
Water
0.5000
0.5463
Outlying
Laboratory
Nickel
47238
2
Reagent
Water
0.6000
0.6395
Outlying
Laboratory
Nickel
46722
3
Filtered
Freshwater
6.0000
6.1251
Nickel
46723
3
Filtered
Freshwater
6.0000
5.8139
Nickel
46724
3
Filtered
Effluent
7.0000
6.6059
Nickel
46725
3
Filtered
Effluent
7.0000
6.3867
Nickel
46726
3
Unfiltered
Effluent
8.0000
7.0975
Nickel
46727
3
Unfiltered
Effluent
8.0000
7.1137
Nickel
46728
3
Reagent
Water
0.0000
0.0069
Nickel
46729
3
Reagent
Water
0.0000
0.0152
Nickel
46730
3
Reagent
Water
1.0000
0.9903
Nickel
46731
3
Reagent
Water
1.0000
0.9264
Nickel
46732
3
Reagent
Water
10.0000
9.2682
Nickel
46733
3
Reagent
Water
10.0000
9.3891
Nickel
46734
3
Reagent
Water
100.0000
91.9907
Nickel
46735
3
Reagent
Water
100.0000
94.0182
Nickel
47213
3
Filtered
Freshwater
0.3100
0.6528
Nickel
47214
3
Filtered
Freshwater
0.3100
0.6711
Nickel
47215
3
Filtered
Freshwater
1.6100
1.6941
Nickel
47216
3
Filtered
Freshwater
1.8100
1.9425
Nickel
47217
3
Filtered
Freshwater
3.3100
3.1383
Nickel
47218
3
Filtered
Freshwater
4.0100
3.5813
Nickel
47219
3
Reagent
Water
0.5000
0.4731
Nickel
47220
3
Reagent
Water
0.6000
0.5952
Nickel
46594
4
Reagent
Water
0.0000
0.0010
Nickel
46595
4
Reagent
Water
0.0000
0.0030
Nickel
46596
4
Reagent
Water
100.0000
97.5750
Nickel
46597
4
Reagent
Water
100.0000
97.7140
Nickel
46598
4
Reagent
Water
10.0000
10.2880
Individual
Outlier
Nickel
46599
4
Reagent
Water
10.0000
9.9170
Nickel
46600
4
Reagent
Water
1.0000
0.9670
Nickel
46601
4
Reagent
Water
1.0000
0.9890
Nickel
46602
4
Filtered
Freshwater
6.0000
6.2400
Nickel
46603
4
Filtered
Freshwater
6.0000
6.1380
Nickel
46604
4
Filtered
Effluent
7.0000
6.8580
Nickel
46605
4
Filtered
Effluent
7.0000
7.1600
Nickel
46606
4
Unfiltered
Effluent
8.0000
8.9260
Nickel
46607
4
Unfiltered
Effluent
8.0000
8.7740
Nickel
47239
4
Filtered
Freshwater
0.3100
0.6570
Nickel
47240
4
Filtered
Freshwater
0.3100
0.6600
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
26
Nickel
47241
4
Filtered
Freshwater
1.6100
1.9240
Nickel
47242
4
Filtered
Freshwater
1.8100
2.1060
Nickel
47243
4
Filtered
Freshwater
3.3100
3.5990
Nickel
47244
4
Filtered
Freshwater
4.0100
4.1060
Nickel
47245
4
Reagent
Water
0.5000
1.5430
Nickel
47246
4
Reagent
Water
0.6000
0.6310
Nickel
46532
5
Filtered
Freshwater
6.0000
6.9102
Possible
contamination1
Nickel
46533
5
Filtered
Freshwater
6.0000
6.2185
Possible
contamination1
Nickel
46534
5
Filtered
Effluent
7.0000
6.9976
Possible
contamination1
Nickel
46535
5
Filtered
Effluent
7.0000
7.0286
Possible
contamination1
Nickel
46536
5
Unfiltered
Effluent
8.0000
9.0821
Possible
contamination1
Nickel
46537
5
Unfiltered
Effluent
8.0000
8.5336
Possible
contamination1
Nickel
46538
5
Reagent
Water
0.0000
3.3073
Possible
contamination1
Nickel
46539
5
Reagent
Water
0.0000
­
0.0714
Nickel
46702
5
Reagent
Water
1.0000
0.8445
Possible
contamination1
Nickel
46703
5
Reagent
Water
1.0000
0.9866
Possible
contamination1
Nickel
46704
5
Reagent
Water
10.0000
9.0384
Possible
contamination1
Nickel
46705
5
Reagent
Water
10.0000
9.3564
Possible
contamination1
Nickel
46706
5
Reagent
Water
100.0000
91.7845
Concentration
>
cal
range
Nickel
46707
5
Reagent
Water
100.0000
92.9108
Concentration
>
cal
range
Nickel
47223
5
Filtered
Freshwater
0.3100
0.9110
Possible
contamination1
Nickel
47224
5
Filtered
Freshwater
0.3100
3.1600
Possible
contamination1
Nickel
47225
5
Filtered
Freshwater
1.6100
2.0831
Possible
contamination1
Nickel
47226
5
Filtered
Freshwater
1.8100
2.3118
Possible
contamination1
Nickel
47227
5
Filtered
Freshwater
3.3100
3.5877
Possible
contamination1
Nickel
47228
5
Filtered
Freshwater
4.0100
4.2850
Possible
contamination1
Nickel
47229
5
Reagent
Water
0.5000
0.4734
Nickel
47230
5
Reagent
Water
0.6000
0.5540
Possible
contamination1
Nickel
46554
6
Filtered
Effluent
7.0000
4.5314
Individual
Outlier
Nickel
46555
6
Filtered
Effluent
7.0000
5.1111
Nickel
46556
6
Filtered
Freshwater
6.0000
5.6038
Nickel
46557
6
Filtered
Freshwater
6.0000
4.6596
Nickel
46558
6
Reagent
Water
0.0000
0.0312
Nickel
46559
6
Reagent
Water
0.0000
0.2107
Nickel
46560
6
Unfiltered
Effluent
8.0000
6.6759
Nickel
46561
6
Unfiltered
Effluent
8.0000
5.3956
Nickel
46562
6
Reagent
Water
1.0000
0.8887
Nickel
46563
6
Reagent
Water
1.0000
0.9097
Nickel
46564
6
Reagent
Water
10.0000
8.9976
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
27
Draft
­
December
2000
Nickel
46565
6
Reagent
Water
10.0000
9.4099
Nickel
46566
6
Reagent
Water
100.0000
87.9207
Nickel
46567
6
Reagent
Water
100.0000
89.4755
Nickel
47247
6
Filtered
Freshwater
0.3100
0.0000
Nickel
47248
6
Filtered
Freshwater
0.3100
0.0000
Nickel
47249
6
Filtered
Freshwater
1.6100
1.0149
Nickel
47250
6
Filtered
Freshwater
1.8100
1.1366
Nickel
47251
6
Filtered
Freshwater
3.3100
2.4122
Nickel
47252
6
Filtered
Freshwater
4.0100
3.0205
Nickel
47253
6
Reagent
Water
0.5000
0.4697
Nickel
47254
6
Reagent
Water
0.6000
0.8110
Nickel
46846
7
Reagent
Water
0.0000
0.0077
Nickel
46847
7
Reagent
Water
0.0000
0.0025
Nickel
46848
7
Reagent
Water
1.0000
0.9141
Nickel
46849
7
Reagent
Water
1.0000
0.9261
Nickel
46850
7
Reagent
Water
10.0000
9.3127
Nickel
46851
7
Reagent
Water
10.0000
9.1843
Nickel
46852
7
Reagent
Water
100.0000
90.3164
Nickel
46853
7
Reagent
Water
100.0000
92.2033
Nickel
46854
7
Filtered
Effluent
7.0000
6.9029
Nickel
46855
7
Filtered
Effluent
7.0000
6.8971
Nickel
46856
7
Filtered
Freshwater
6.0000
5.7563
Nickel
46857
7
Filtered
Freshwater
6.0000
5.7324
Nickel
47267
7
Unfiltered
Effluent
8.0000
7.3304
Nickel
47268
7
Unfiltered
Effluent
8.0000
7.4195
Nickel
47269
7
Filtered
Freshwater
0.3100
0.4790
Nickel
47270
7
Filtered
Freshwater
0.3100
0.4592
Nickel
47271
7
Filtered
Freshwater
1.6100
1.6675
Nickel
47272
7
Filtered
Freshwater
1.8100
1.8115
Nickel
47273
7
Filtered
Freshwater
3.3100
3.1570
Nickel
47274
7
Filtered
Freshwater
4.0100
3.8903
Nickel
47275
7
Reagent
Water
0.5000
0.4378
Nickel
47276
7
Reagent
Water
0.6000
0.5348
Nickel
46540
8
Filtered
Effluent
7.0000
6.9385
Nickel
46541
8
Filtered
Effluent
7.0000
6.7290
Nickel
46542
8
Unfiltered
Effluent
8.0000
7.6763
Nickel
46543
8
Unfiltered
Effluent
8.0000
7.7658
Nickel
46544
8
Reagent
Water
100.0000
92.6188
Nickel
46545
8
Reagent
Water
100.0000
91.9590
Nickel
46546
8
Filtered
Freshwater
6.0000
6.0458
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
28
Nickel
46547
8
Filtered
Freshwater
6.0000
5.8885
Nickel
46548
8
Reagent
Water
0.0000
0.0083
Nickel
46549
8
Reagent
Water
0.0000
0.0055
Nickel
46550
8
Reagent
Water
1.0000
0.9131
Nickel
46551
8
Reagent
Water
1.0000
0.9435
Nickel
46552
8
Reagent
Water
10.0000
9.1786
Nickel
46553
8
Reagent
Water
10.0000
9.1672
Nickel
47259
8
Filtered
Freshwater
0.3100
0.6062
Nickel
47260
8
Filtered
Freshwater
0.3100
0.6288
Nickel
47261
8
Filtered
Freshwater
1.6100
1.8047
Nickel
47262
8
Filtered
Freshwater
1.8100
1.9671
Nickel
47263
8
Filtered
Freshwater
3.3100
3.2257
Nickel
47264
8
Filtered
Freshwater
4.0100
3.9768
Nickel
47265
8
Reagent
Water
0.5000
0.4448
Nickel
47266
8
Reagent
Water
0.6000
0.5525
Selenium
46750
1
Reagent
Water
0.0000
0.0000
Selenium
46751
1
Reagent
Water
0.0000
0.0000
Selenium
46752
1
Reagent
Water
5.0000
5.6400
Selenium
46753
1
Reagent
Water
5.0000
5.3500
Selenium
46754
1
Reagent
Water
20.0000
22.4000
Selenium
46755
1
Reagent
Water
20.0000
22.3000
Selenium
46774
1
Reagent
Water
100.0000
107.0000
Concentration
>
cal
range
Selenium
46775
1
Reagent
Water
100.0000
111.0000
Concentration
>
cal
range
Selenium
46776
1
Unfiltered
Effluent
6.0000
9.9700
Selenium
46777
1
Unfiltered
Effluent
6.0000
11.0000
Selenium
46778
1
Filtered
Effluent
5.0000
8.8700
Selenium
46779
1
Filtered
Effluent
5.0000
8.6700
Selenium
46780
1
Filtered
Freshwater
4.0000
3.7900
Selenium
46781
1
Filtered
Freshwater
4.0000
4.1900
Selenium
47285
1
Filtered
Freshwater
0.3810
0.2890
Selenium
47286
1
Filtered
Freshwater
0.3810
0.1760
Selenium
47287
1
Filtered
Freshwater
0.9810
0.9890
Selenium
47288
1
Filtered
Freshwater
1.1810
1.0400
Selenium
47289
1
Filtered
Freshwater
1.9810
1.4000
Selenium
47290
1
Filtered
Freshwater
2.3810
2.2900
Selenium
47291
1
Reagent
Water
1.0000
0.9430
Selenium
47292
1
Reagent
Water
1.2000
1.0700
Selenium
46504
2
Filtered
Freshwater
4.0000
3.9550
Selenium
46505
2
Filtered
Freshwater
4.0000
3.5530
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
29
Draft
­
December
2000
Selenium
46506
2
Filtered
Effluent
5.0000
7.2890
Selenium
46507
2
Filtered
Effluent
5.0000
7.5030
Selenium
46508
2
Unfiltered
Effluent
6.0000
8.4000
Selenium
46509
2
Unfiltered
Effluent
6.0000
9.1760
Selenium
46510
2
Reagent
Water
0.0000
0.4753
Selenium
46511
2
Reagent
Water
0.0000
0.2495
Selenium
46512
2
Reagent
Water
5.0000
4.5400
Selenium
46513
2
Reagent
Water
5.0000
5.9650
Selenium
46514
2
Reagent
Water
20.0000
18.7500
Selenium
46515
2
Reagent
Water
20.0000
19.3300
Selenium
46516
2
Reagent
Water
100.0000
95.3600
Selenium
46517
2
Reagent
Water
100.0000
96.5400
Selenium
47231
2
Filtered
Freshwater
0.3810
0.1495
Selenium
47232
2
Filtered
Freshwater
0.3810
­
0.2973
Selenium
47233
2
Filtered
Freshwater
0.9810
0.0069
Selenium
47234
2
Filtered
Freshwater
1.1810
1.4730
Selenium
47235
2
Filtered
Freshwater
1.9810
1.3650
Selenium
47236
2
Filtered
Freshwater
2.3810
1.2640
Selenium
47237
2
Reagent
Water
1.0000
0.9426
Selenium
47238
2
Reagent
Water
1.2000
0.6453
Selenium
46722
3
Filtered
Freshwater
4.0000
3.7678
Selenium
46723
3
Filtered
Freshwater
4.0000
3.9146
Selenium
46724
3
Filtered
Effluent
5.0000
8.0103
Selenium
46725
3
Filtered
Effluent
5.0000
8.1828
Selenium
46726
3
Unfiltered
Effluent
6.0000
9.4909
Selenium
46727
3
Unfiltered
Effluent
6.0000
9.7532
Selenium
46728
3
Reagent
Water
0.0000
0.0862
Selenium
46729
3
Reagent
Water
0.0000
­
0.1122
Selenium
46730
3
Reagent
Water
5.0000
5.0323
Selenium
46731
3
Reagent
Water
5.0000
4.9782
Selenium
46732
3
Reagent
Water
20.0000
20.9289
Selenium
46733
3
Reagent
Water
20.0000
21.1048
Selenium
46734
3
Reagent
Water
100.0000
113.2210
Selenium
46735
3
Reagent
Water
100.0000
113.7347
Selenium
47213
3
Filtered
Freshwater
0.3810
0.1444
Selenium
47214
3
Filtered
Freshwater
0.3810
0.1777
Selenium
47215
3
Filtered
Freshwater
0.9810
0.7959
Selenium
47216
3
Filtered
Freshwater
1.1810
1.1142
Selenium
47217
3
Filtered
Freshwater
1.9810
2.0142
Selenium
47218
3
Filtered
Freshwater
2.3810
2.2558
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
30
Selenium
47219
3
Reagent
Water
1.0000
1.1618
Selenium
47220
3
Reagent
Water
1.2000
1.3055
Selenium
46594
4
Reagent
Water
0.0000
­
0.0010
Selenium
46595
4
Reagent
Water
0.0000
0.0100
Selenium
46596
4
Reagent
Water
100.0000
106.7670
Selenium
46597
4
Reagent
Water
100.0000
106.0850
Selenium
46598
4
Reagent
Water
20.0000
21.1320
Selenium
46599
4
Reagent
Water
20.0000
21.1440
Selenium
46600
4
Reagent
Water
5.0000
5.0620
Selenium
46601
4
Reagent
Water
5.0000
4.9660
Selenium
46602
4
Filtered
Freshwater
4.0000
3.7410
Selenium
46603
4
Filtered
Freshwater
4.0000
3.7900
Selenium
46604
4
Filtered
Effluent
5.0000
6.2770
Selenium
46605
4
Filtered
Effluent
5.0000
6.3980
Selenium
46606
4
Unfiltered
Effluent
6.0000
7.3640
Selenium
46607
4
Unfiltered
Effluent
6.0000
7.6150
Selenium
47239
4
Filtered
Freshwater
0.3810
0.1020
Selenium
47240
4
Filtered
Freshwater
0.3810
0.1380
Selenium
47241
4
Filtered
Freshwater
0.9810
0.6450
Selenium
47242
4
Filtered
Freshwater
1.1810
0.9580
Selenium
47243
4
Filtered
Freshwater
1.9810
1.8240
Selenium
47244
4
Filtered
Freshwater
2.3810
2.1020
Selenium
47245
4
Reagent
Water
1.0000
0.8750
Selenium
47246
4
Reagent
Water
1.2000
1.2170
Selenium
46532
5
Filtered
Freshwater
4.0000
3.8992
Selenium
46533
5
Filtered
Freshwater
4.0000
3.9011
Selenium
46534
5
Filtered
Effluent
5.0000
8.0251
Selenium
46535
5
Filtered
Effluent
5.0000
7.4642
Selenium
46536
5
Unfiltered
Effluent
6.0000
7.9873
Selenium
46537
5
Unfiltered
Effluent
6.0000
7.6959
Selenium
46538
5
Reagent
Water
0.0000
­
0.0605
Selenium
46539
5
Reagent
Water
0.0000
0.1500
Selenium
46702
5
Reagent
Water
5.0000
4.5147
Selenium
46703
5
Reagent
Water
5.0000
4.4402
Selenium
46704
5
Reagent
Water
20.0000
17.8544
Selenium
46705
5
Reagent
Water
20.0000
18.3850
Selenium
46706
5
Reagent
Water
100.0000
89.2289
Concentration
>
cal
range
Selenium
46707
5
Reagent
Water
100.0000
91.3304
Concentration
>
cal
range
Selenium
47223
5
Filtered
Freshwater
0.3810
0.4310
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
31
Draft
­
December
2000
Selenium
47224
5
Filtered
Freshwater
0.3810
0.0000
Selenium
47225
5
Filtered
Freshwater
0.9810
1.4480
Selenium
47226
5
Filtered
Freshwater
1.1810
1.4273
Selenium
47227
5
Filtered
Freshwater
1.9810
2.2191
Selenium
47228
5
Filtered
Freshwater
2.3810
2.6318
Selenium
47229
5
Reagent
Water
1.0000
1.6423
Selenium
47230
5
Reagent
Water
1.2000
1.7892
Selenium
46554
6
Filtered
Effluent
5.0000
24.8955
Outlying
Laboratory
Selenium
46555
6
Filtered
Effluent
5.0000
27.6746
Outlying
Laboratory
Possible
contamination1
Selenium
46556
6
Filtered
Freshwater
4.0000
27.4137
Outlying
Laboratory
Possible
contamination1
Selenium
46557
6
Filtered
Freshwater
4.0000
23.3279
Outlying
Laboratory
Selenium
46558
6
Reagent
Water
0.0000
20.6772
Outlying
Laboratory
Selenium
46559
6
Reagent
Water
0.0000
20.3840
Outlying
Laboratory
Selenium
46560
6
Unfiltered
Effluent
6.0000
35.2663
Outlying
Laboratory
Possible
contamination1
Selenium
46561
6
Unfiltered
Effluent
6.0000
26.0733
Outlying
Laboratory
Selenium
46562
6
Reagent
Water
5.0000
24.9791
Outlying
Laboratory
Selenium
46563
6
Reagent
Water
5.0000
24.8939
Outlying
Laboratory
Possible
contamination1
Selenium
46564
6
Reagent
Water
20.0000
37.9875
Outlying
Laboratory
Possible
contamination1
Selenium
46565
6
Reagent
Water
20.0000
39.8635
Outlying
Laboratory
Possible
contamination1
Selenium
46566
6
Reagent
Water
100.0000
110.3332
Concentration
>
cal
range
Selenium
46567
6
Reagent
Water
100.0000
110.4997
Concentration
>
cal
range
Selenium
47247
6
Filtered
Freshwater
0.3810
19.7109
Outlying
Laboratory
Possible
contamination1
Selenium
47248
6
Filtered
Freshwater
0.3810
19.0204
Outlying
Laboratory
Possible
contamination1
Selenium
47249
6
Filtered
Freshwater
0.9810
20.3957
Outlying
Laboratory
Possible
contamination1
Selenium
47250
6
Filtered
Freshwater
1.1810
20.7004
Outlying
Laboratory
Possible
contamination1
Selenium
47251
6
Filtered
Freshwater
1.9810
21.1349
Outlying
Laboratory
Possible
contamination1
Selenium
47252
6
Filtered
Freshwater
2.3810
20.6159
Outlying
Laboratory
Possible
contamination1
Selenium
47253
6
Reagent
Water
1.0000
21.7354
Outlying
Laboratory
Possible
contamination1
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
32
Selenium
47254
6
Reagent
Water
1.2000
20.3721
Outlying
Laboratory
Possible
contamination1
Selenium
46846
7
Reagent
Water
0.0000
0.0101
Selenium
46847
7
Reagent
Water
0.0000
0.0261
Selenium
46848
7
Reagent
Water
5.0000
4.3423
Selenium
46849
7
Reagent
Water
5.0000
4.1599
Selenium
46850
7
Reagent
Water
20.0000
18.1392
Selenium
46851
7
Reagent
Water
20.0000
18.1058
Selenium
46852
7
Reagent
Water
100.0000
89.5153
Selenium
46853
7
Reagent
Water
100.0000
91.3544
Selenium
46854
7
Filtered
Effluent
5.0000
5.5799
Selenium
46855
7
Filtered
Effluent
5.0000
5.4285
Selenium
46856
7
Filtered
Freshwater
4.0000
3.4203
Selenium
46857
7
Filtered
Freshwater
4.0000
3.5249
Selenium
47267
7
Unfiltered
Effluent
6.0000
6.5611
Selenium
47268
7
Unfiltered
Effluent
6.0000
6.5048
Selenium
47269
7
Filtered
Freshwater
0.3810
0.1985
Selenium
47270
7
Filtered
Freshwater
0.3810
0.2125
Selenium
47271
7
Filtered
Freshwater
0.9810
0.7142
Selenium
47272
7
Filtered
Freshwater
1.1810
0.8711
Selenium
47273
7
Filtered
Freshwater
1.9810
1.5490
Selenium
47274
7
Filtered
Freshwater
2.3810
2.0332
Selenium
47275
7
Reagent
Water
1.0000
0.8322
Selenium
47276
7
Reagent
Water
1.2000
0.9676
Selenium
46540
8
Filtered
Effluent
5.0000
5.3906
Selenium
46541
8
Filtered
Effluent
5.0000
5.7788
Selenium
46542
8
Unfiltered
Effluent
6.0000
6.3760
Selenium
46543
8
Unfiltered
Effluent
6.0000
6.4850
Selenium
46544
8
Reagent
Water
100.0000
92.8644
Selenium
46545
8
Reagent
Water
100.0000
97.3893
Selenium
46546
8
Filtered
Freshwater
4.0000
3.4754
Selenium
46547
8
Filtered
Freshwater
4.0000
3.6753
Selenium
46548
8
Reagent
Water
0.0000
0.1219
Selenium
46549
8
Reagent
Water
0.0000
0.1280
Selenium
46550
8
Reagent
Water
5.0000
4.6020
Selenium
46551
8
Reagent
Water
5.0000
4.9030
Selenium
46552
8
Reagent
Water
20.0000
19.0698
Selenium
46553
8
Reagent
Water
20.0000
18.7166
Selenium
47259
8
Filtered
Freshwater
0.3810
0.2646
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
33
Draft
­
December
2000
Selenium
47260
8
Filtered
Freshwater
0.3810
0.2360
Selenium
47261
8
Filtered
Freshwater
0.9810
0.8178
Selenium
47262
8
Filtered
Freshwater
1.1810
1.0490
Selenium
47263
8
Filtered
Freshwater
1.9810
1.8828
Selenium
47264
8
Filtered
Freshwater
2.3810
2.1701
Selenium
47265
8
Reagent
Water
1.0000
1.0135
Selenium
47266
8
Reagent
Water
1.2000
1.2068
Silver
46750
1
Reagent
Water
0.0000
0.0000
Silver
46751
1
Reagent
Water
0.0000
0.0000
Silver
46752
1
Reagent
Water
0.1000
0.0000
Silver
46753
1
Reagent
Water
0.1000
0.0000
Silver
46754
1
Reagent
Water
1.0000
0.0370
Silver
46755
1
Reagent
Water
1.0000
0.0357
Silver
46774
1
Reagent
Water
10.0000
6.7900
Silver
46775
1
Reagent
Water
10.0000
6.5800
Silver
46776
1
Unfiltered
Effluent
2.8800
1.2000
Silver
46777
1
Unfiltered
Effluent
2.8800
1.1400
Silver
46778
1
Filtered
Effluent
0.4780
0.3550
Silver
46779
1
Filtered
Effluent
0.4780
0.3270
Possible
contamination1
Silver
46780
1
Filtered
Freshwater
0.2000
0.0974
Silver
46781
1
Filtered
Freshwater
0.2000
0.0934
Silver
47285
1
Filtered
Freshwater
0.0000
0.0052
Silver
47286
1
Filtered
Freshwater
0.0000
0.0000
Silver
47287
1
Filtered
Freshwater
0.0700
0.0109
Silver
47288
1
Filtered
Freshwater
0.0800
0.0221
Silver
47289
1
Filtered
Freshwater
0.3000
0.0546
Silver
47290
1
Filtered
Freshwater
0.3600
0.1100
Silver
47291
1
Reagent
Water
0.2000
0.0000
Silver
47292
1
Reagent
Water
0.2400
0.0000
Silver
46504
2
Filtered
Freshwater
0.2000
0.1545
Silver
46505
2
Filtered
Freshwater
0.2000
0.1189
Silver
46506
2
Filtered
Effluent
0.4780
0.3787
Silver
46507
2
Filtered
Effluent
0.4780
0.3816
Silver
46508
2
Unfiltered
Effluent
2.8800
1.2830
Silver
46509
2
Unfiltered
Effluent
2.8800
1.3120
Silver
46510
2
Reagent
Water
0.0000
0.0020
Silver
46511
2
Reagent
Water
0.0000
­
0.0009
Silver
46512
2
Reagent
Water
0.1000
0.0091
Silver
46513
2
Reagent
Water
0.1000
0.0038
Silver
46514
2
Reagent
Water
1.0000
0.3276
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
34
Silver
46515
2
Reagent
Water
1.0000
0.3034
Silver
46516
2
Reagent
Water
10.0000
9.3500
Silver
46517
2
Reagent
Water
10.0000
9.4880
Silver
47231
2
Filtered
Freshwater
0.0000
0.0052
Silver
47232
2
Filtered
Freshwater
0.0000
0.0021
Silver
47233
2
Filtered
Freshwater
0.0700
0.0139
Silver
47234
2
Filtered
Freshwater
0.0800
0.0269
Silver
47235
2
Filtered
Freshwater
0.3000
0.0289
Silver
47236
2
Filtered
Freshwater
0.3600
0.0618
Silver
47237
2
Reagent
Water
0.2000
0.0347
Silver
47238
2
Reagent
Water
0.2400
0.0139
Silver
46722
3
Filtered
Freshwater
0.2000
0.1929
Silver
46723
3
Filtered
Freshwater
0.2000
0.1901
Silver
46724
3
Filtered
Effluent
0.4780
0.4471
Silver
46725
3
Filtered
Effluent
0.4780
0.4172
Silver
46726
3
Unfiltered
Effluent
2.8800
1.3798
Silver
46727
3
Unfiltered
Effluent
2.8800
1.3991
Silver
46728
3
Reagent
Water
0.0000
0.0003
Silver
46729
3
Reagent
Water
0.0000
0.0010
Silver
46730
3
Reagent
Water
0.1000
0.0870
Silver
46731
3
Reagent
Water
0.1000
0.0908
Silver
46732
3
Reagent
Water
1.0000
0.9276
Silver
46733
3
Reagent
Water
1.0000
0.8484
Silver
46734
3
Reagent
Water
10.0000
10.0446
Silver
46735
3
Reagent
Water
10.0000
9.9293
Silver
47213
3
Filtered
Freshwater
0.0000
0.0028
Silver
47214
3
Filtered
Freshwater
0.0000
0.0015
Silver
47215
3
Filtered
Freshwater
0.0700
0.0636
Silver
47216
3
Filtered
Freshwater
0.0800
0.0640
Silver
47217
3
Filtered
Freshwater
0.3000
0.2361
Silver
47218
3
Filtered
Freshwater
0.3600
0.3016
Silver
47219
3
Reagent
Water
0.2000
0.1611
Silver
47220
3
Reagent
Water
0.2400
0.2192
Silver
46594
4
Reagent
Water
0.0000
0.0050
Outlying
Laboratory
Silver
46595
4
Reagent
Water
0.0000
0.0050
Outlying
Laboratory
Silver
46596
4
Reagent
Water
10.0000
9.9770
Outlying
Laboratory
Silver
46597
4
Reagent
Water
10.0000
10.1060
Outlying
Laboratory
Silver
46598
4
Reagent
Water
1.0000
0.9000
Outlying
Laboratory
Silver
46599
4
Reagent
Water
1.0000
0.9400
Outlying
Laboratory
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
35
Draft
­
December
2000
Silver
46600
4
Reagent
Water
0.1000
0.0970
Outlying
Laboratory
Silver
46601
4
Reagent
Water
0.1000
0.0840
Outlying
Laboratory
Silver
46602
4
Filtered
Freshwater
0.2000
0.1910
Outlying
Laboratory
Silver
46603
4
Filtered
Freshwater
0.2000
0.2040
Outlying
Laboratory
Silver
46604
4
Filtered
Effluent
0.4780
0.4720
Outlying
Laboratory
Silver
46605
4
Filtered
Effluent
0.4780
0.5090
Outlying
Laboratory
Silver
46606
4
Unfiltered
Effluent
2.8800
1.5160
Outlying
Laboratory
Silver
46607
4
Unfiltered
Effluent
2.8800
1.4980
Outlying
Laboratory
Silver
47239
4
Filtered
Freshwater
0.0000
0.0420
Outlying
Laboratory
Silver
47240
4
Filtered
Freshwater
0.0000
0.0090
Outlying
Laboratory
Silver
47241
4
Filtered
Freshwater
0.0700
0.0800
Outlying
Laboratory
Silver
47242
4
Filtered
Freshwater
0.0800
0.0940
Outlying
Laboratory
Silver
47243
4
Filtered
Freshwater
0.3000
0.2930
Outlying
Laboratory
Silver
47244
4
Filtered
Freshwater
0.3600
0.3580
Outlying
Laboratory
Silver
47245
4
Reagent
Water
0.2000
0.1560
Outlying
Laboratory
Silver
47246
4
Reagent
Water
0.2400
0.2280
Outlying
Laboratory
Silver
46532
5
Filtered
Freshwater
0.2000
0.1265
Possible
contamination1
Silver
46533
5
Filtered
Freshwater
0.2000
0.1113
Possible
contamination1
Silver
46534
5
Filtered
Effluent
0.4780
0.3230
Possible
contamination1
Silver
46535
5
Filtered
Effluent
0.4780
0.3182
Possible
contamination1
Silver
46536
5
Unfiltered
Effluent
2.8800
1.6205
Possible
contamination1
Silver
46537
5
Unfiltered
Effluent
2.8800
1.4659
Possible
contamination1
Silver
46538
5
Reagent
Water
0.0000
0.0576
Silver
46539
5
Reagent
Water
0.0000
0.0540
Silver
46702
5
Reagent
Water
0.1000
0.0542
Silver
46703
5
Reagent
Water
0.1000
0.0515
Silver
46704
5
Reagent
Water
1.0000
0.0935
Silver
46705
5
Reagent
Water
1.0000
0.0713
Silver
46706
5
Reagent
Water
10.0000
8.8829
Silver
46707
5
Reagent
Water
10.0000
8.4280
Silver
47223
5
Filtered
Freshwater
0.0000
0.0460
Silver
47224
5
Filtered
Freshwater
0.0000
0.0450
Silver
47225
5
Filtered
Freshwater
0.0700
0.0640
Silver
47226
5
Filtered
Freshwater
0.0800
0.0671
Silver
47227
5
Filtered
Freshwater
0.3000
0.0972
Silver
47228
5
Filtered
Freshwater
0.3600
0.0880
Silver
47229
5
Reagent
Water
0.2000
0.0510
Silver
47230
5
Reagent
Water
0.2400
0.0510
Silver
46554
6
Filtered
Effluent
0.4780
0.4657
Silver
46555
6
Filtered
Effluent
0.4780
0.4473
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
36
Silver
46556
6
Filtered
Freshwater
0.2000
0.1373
Silver
46557
6
Filtered
Freshwater
0.2000
0.1275
Silver
46558
6
Reagent
Water
0.0000
0.0105
Silver
46559
6
Reagent
Water
0.0000
0.0078
Silver
46560
6
Unfiltered
Effluent
2.8800
1.4265
Silver
46561
6
Unfiltered
Effluent
2.8800
1.4569
Silver
46562
6
Reagent
Water
0.1000
0.0107
Silver
46563
6
Reagent
Water
0.1000
0.0082
Silver
46564
6
Reagent
Water
1.0000
0.3156
Silver
46565
6
Reagent
Water
1.0000
0.3295
Silver
46566
6
Reagent
Water
10.0000
10.4827
Silver
46567
6
Reagent
Water
10.0000
10.2625
Silver
47247
6
Filtered
Freshwater
0.0000
0.0115
Silver
47248
6
Filtered
Freshwater
0.0000
0.0217
Silver
47249
6
Filtered
Freshwater
0.0700
0.0189
Silver
47250
6
Filtered
Freshwater
0.0800
0.0178
Silver
47251
6
Filtered
Freshwater
0.3000
0.0637
Silver
47252
6
Filtered
Freshwater
0.3600
0.0508
Silver
47253
6
Reagent
Water
0.2000
0.0879
Silver
47254
6
Reagent
Water
0.2400
0.0697
Silver
46846
7
Reagent
Water
0.0000
0.0096
Silver
46847
7
Reagent
Water
0.0000
0.0038
Silver
46848
7
Reagent
Water
0.1000
0.0019
Silver
46849
7
Reagent
Water
0.1000
0.0040
Silver
46850
7
Reagent
Water
1.0000
0.0061
Silver
46851
7
Reagent
Water
1.0000
0.0027
Silver
46852
7
Reagent
Water
10.0000
8.5905
Silver
46853
7
Reagent
Water
10.0000
8.9060
Silver
46854
7
Filtered
Effluent
0.4780
0.3379
Silver
46855
7
Filtered
Effluent
0.4780
0.3065
Silver
46856
7
Filtered
Freshwater
0.2000
0.0637
Silver
46857
7
Filtered
Freshwater
0.2000
0.0646
Silver
47267
7
Unfiltered
Effluent
2.8800
1.2007
Silver
47268
7
Unfiltered
Effluent
2.8800
1.3045
Silver
47269
7
Filtered
Freshwater
0.0000
0.0107
Silver
47270
7
Filtered
Freshwater
0.0000
0.0080
Silver
47271
7
Filtered
Freshwater
0.0700
0.0200
Silver
47272
7
Filtered
Freshwater
0.0800
0.0261
Silver
47273
7
Filtered
Freshwater
0.3000
0.0453
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
37
Draft
­
December
2000
Silver
47274
7
Filtered
Freshwater
0.3600
0.0396
Silver
47275
7
Reagent
Water
0.2000
­
0.0015
Silver
47276
7
Reagent
Water
0.2400
­
0.0005
Silver
46540
8
Filtered
Effluent
0.4780
0.3964
Silver
46541
8
Filtered
Effluent
0.4780
0.2275
Silver
46542
8
Unfiltered
Effluent
2.8800
1.0881
Silver
46543
8
Unfiltered
Effluent
2.8800
1.2143
Silver
46544
8
Reagent
Water
10.0000
7.7363
Silver
46545
8
Reagent
Water
10.0000
7.3608
Silver
46546
8
Filtered
Freshwater
0.2000
0.0826
Silver
46547
8
Filtered
Freshwater
0.2000
0.0839
Silver
46548
8
Reagent
Water
0.0000
0.0177
Silver
46549
8
Reagent
Water
0.0000
0.0126
Silver
46550
8
Reagent
Water
0.1000
0.0015
Silver
46551
8
Reagent
Water
0.1000
0.0012
Silver
46552
8
Reagent
Water
1.0000
0.0012
Silver
46553
8
Reagent
Water
1.0000
0.0960
Silver
47259
8
Filtered
Freshwater
0.0000
0.0022
Silver
47260
8
Filtered
Freshwater
0.0000
0.0017
Silver
47261
8
Filtered
Freshwater
0.0700
0.0142
Silver
47262
8
Filtered
Freshwater
0.0800
0.0171
Silver
47263
8
Filtered
Freshwater
0.3000
0.0380
Silver
47264
8
Filtered
Freshwater
0.3600
0.0448
Silver
47265
8
Reagent
Water
0.2000
0.0014
Silver
47266
8
Reagent
Water
0.2400
0.0000
Thallium
46750
1
Reagent
Water
0.0000
0.0000
Thallium
46751
1
Reagent
Water
0.0000
0.0000
Thallium
46752
1
Reagent
Water
0.1000
0.0838
Thallium
46753
1
Reagent
Water
0.1000
0.0888
Thallium
46754
1
Reagent
Water
0.5000
0.4290
Thallium
46755
1
Reagent
Water
0.5000
0.4330
Thallium
46774
1
Reagent
Water
2.0000
1.7600
Thallium
46775
1
Reagent
Water
2.0000
1.7300
Thallium
46776
1
Unfiltered
Effluent
0.9000
0.7830
Thallium
46777
1
Unfiltered
Effluent
0.9000
0.7750
Thallium
46778
1
Filtered
Effluent
0.2000
0.1830
Thallium
46779
1
Filtered
Effluent
0.2000
0.1720
Thallium
46780
1
Filtered
Freshwater
0.0600
0.0496
Thallium
46781
1
Filtered
Freshwater
0.0600
0.0544
Thallium
47285
1
Filtered
Freshwater
0.0010
0.0000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
38
Thallium
47286
1
Filtered
Freshwater
0.0010
0.0000
Thallium
47287
1
Filtered
Freshwater
0.0210
0.0168
Thallium
47288
1
Filtered
Freshwater
0.0240
0.0175
Thallium
47289
1
Filtered
Freshwater
0.1010
0.0867
Thallium
47290
1
Filtered
Freshwater
0.1210
0.1050
Thallium
47291
1
Reagent
Water
0.0400
0.0345
Thallium
47292
1
Reagent
Water
0.0500
0.0457
Thallium
46504
2
Filtered
Freshwater
0.0600
0.0670
Thallium
46505
2
Filtered
Freshwater
0.0600
0.0590
Thallium
46506
2
Filtered
Effluent
0.2000
0.2092
Thallium
46507
2
Filtered
Effluent
0.2000
0.1841
Thallium
46508
2
Unfiltered
Effluent
0.9000
0.8521
Thallium
46509
2
Unfiltered
Effluent
0.9000
0.9424
Thallium
46510
2
Reagent
Water
0.0000
0.0012
Thallium
46511
2
Reagent
Water
0.0000
0.0002
Thallium
46512
2
Reagent
Water
0.1000
0.0962
Thallium
46513
2
Reagent
Water
0.1000
0.0999
Thallium
46514
2
Reagent
Water
0.5000
0.5734
Individual
Outlier
Thallium
46515
2
Reagent
Water
0.5000
0.4985
Thallium
46516
2
Reagent
Water
2.0000
2.0030
Thallium
46517
2
Reagent
Water
2.0000
2.0140
Thallium
47231
2
Filtered
Freshwater
0.0010
0.0086
Thallium
47232
2
Filtered
Freshwater
0.0010
0.0012
Thallium
47233
2
Filtered
Freshwater
0.0210
0.0229
Thallium
47234
2
Filtered
Freshwater
0.0240
0.0305
Thallium
47235
2
Filtered
Freshwater
0.1010
0.1041
Thallium
47236
2
Filtered
Freshwater
0.1210
0.1190
Thallium
47237
2
Reagent
Water
0.0400
0.0502
Thallium
47238
2
Reagent
Water
0.0500
0.0500
Thallium
46722
3
Filtered
Freshwater
0.0600
0.0620
Thallium
46723
3
Filtered
Freshwater
0.0600
0.0600
Thallium
46724
3
Filtered
Effluent
0.2000
0.2019
Thallium
46725
3
Filtered
Effluent
0.2000
0.2119
Thallium
46726
3
Unfiltered
Effluent
0.9000
0.9219
Thallium
46727
3
Unfiltered
Effluent
0.9000
0.9505
Thallium
46728
3
Reagent
Water
0.0000
0.0001
Thallium
46729
3
Reagent
Water
0.0000
0.0002
Thallium
46730
3
Reagent
Water
0.1000
0.1005
Thallium
46731
3
Reagent
Water
0.1000
0.0968
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
39
Draft
­
December
2000
Thallium
46732
3
Reagent
Water
0.5000
0.4960
Thallium
46733
3
Reagent
Water
0.5000
0.5049
Thallium
46734
3
Reagent
Water
2.0000
2.0253
Thallium
46735
3
Reagent
Water
2.0000
2.0039
Thallium
47213
3
Filtered
Freshwater
0.0010
0.0009
Thallium
47214
3
Filtered
Freshwater
0.0010
0.0009
Thallium
47215
3
Filtered
Freshwater
0.0210
0.0208
Thallium
47216
3
Filtered
Freshwater
0.0240
0.0243
Thallium
47217
3
Filtered
Freshwater
0.1010
0.1028
Thallium
47218
3
Filtered
Freshwater
0.1210
0.1211
Thallium
47219
3
Reagent
Water
0.0400
0.0394
Thallium
47220
3
Reagent
Water
0.0500
0.0489
Thallium
46594
4
Reagent
Water
0.0000
0.0010
Thallium
46595
4
Reagent
Water
0.0000
0.0010
Thallium
46596
4
Reagent
Water
2.0000
1.8130
Thallium
46597
4
Reagent
Water
2.0000
1.8310
Thallium
46598
4
Reagent
Water
0.5000
0.4510
Thallium
46599
4
Reagent
Water
0.5000
0.4500
Thallium
46600
4
Reagent
Water
0.1000
0.0890
Thallium
46601
4
Reagent
Water
0.1000
0.0830
Thallium
46602
4
Filtered
Freshwater
0.0600
0.0520
Thallium
46603
4
Filtered
Freshwater
0.0600
0.0530
Thallium
46604
4
Filtered
Effluent
0.2000
0.1730
Thallium
46605
4
Filtered
Effluent
0.2000
0.3200
Individual
Outlier
Thallium
46606
4
Unfiltered
Effluent
0.9000
0.7610
Thallium
46607
4
Unfiltered
Effluent
0.9000
0.7680
Thallium
47239
4
Filtered
Freshwater
0.0010
0.0000
Thallium
47240
4
Filtered
Freshwater
0.0010
0.0010
Thallium
47241
4
Filtered
Freshwater
0.0210
0.0180
Thallium
47242
4
Filtered
Freshwater
0.0240
0.0200
Thallium
47243
4
Filtered
Freshwater
0.1010
0.0880
Thallium
47244
4
Filtered
Freshwater
0.1210
0.1050
Thallium
47245
4
Reagent
Water
0.0400
0.0360
Thallium
47246
4
Reagent
Water
0.0500
0.0400
Thallium
46532
5
Filtered
Freshwater
0.0600
0.0551
Thallium
46533
5
Filtered
Freshwater
0.0600
0.0537
Thallium
46534
5
Filtered
Effluent
0.2000
0.1961
Thallium
46535
5
Filtered
Effluent
0.2000
0.1948
Thallium
46536
5
Unfiltered
Effluent
0.9000
1.0243
Thallium
46537
5
Unfiltered
Effluent
0.9000
0.9540
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
40
Thallium
46538
5
Reagent
Water
0.0000
­
0.0050
Thallium
46539
5
Reagent
Water
0.0000
­
0.0056
Thallium
46702
5
Reagent
Water
0.1000
0.0917
Thallium
46703
5
Reagent
Water
0.1000
0.0877
Thallium
46704
5
Reagent
Water
0.5000
0.4848
Thallium
46705
5
Reagent
Water
0.5000
0.4820
Thallium
46706
5
Reagent
Water
2.0000
2.0090
Thallium
46707
5
Reagent
Water
2.0000
2.0679
Thallium
47223
5
Filtered
Freshwater
0.0010
0.0000
Thallium
47224
5
Filtered
Freshwater
0.0010
0.0000
Thallium
47225
5
Filtered
Freshwater
0.0210
0.0131
Thallium
47226
5
Filtered
Freshwater
0.0240
0.0155
Thallium
47227
5
Filtered
Freshwater
0.1010
0.0977
Thallium
47228
5
Filtered
Freshwater
0.1210
0.1202
Thallium
47229
5
Reagent
Water
0.0400
0.0358
Thallium
47230
5
Reagent
Water
0.0500
0.0387
Thallium
46554
6
Filtered
Effluent
0.2000
0.2119
Thallium
46555
6
Filtered
Effluent
0.2000
0.2188
Thallium
46556
6
Filtered
Freshwater
0.0600
0.0680
Thallium
46557
6
Filtered
Freshwater
0.0600
0.0640
Thallium
46558
6
Reagent
Water
0.0000
0.0041
Thallium
46559
6
Reagent
Water
0.0000
0.0039
Thallium
46560
6
Unfiltered
Effluent
0.9000
0.9264
Thallium
46561
6
Unfiltered
Effluent
0.9000
0.9030
Thallium
46562
6
Reagent
Water
0.1000
0.1005
Thallium
46563
6
Reagent
Water
0.1000
0.0966
Thallium
46564
6
Reagent
Water
0.5000
0.4782
Thallium
46565
6
Reagent
Water
0.5000
0.4851
Thallium
46566
6
Reagent
Water
2.0000
1.9235
Thallium
46567
6
Reagent
Water
2.0000
1.9254
Thallium
47247
6
Filtered
Freshwater
0.0010
0.0116
Thallium
47248
6
Filtered
Freshwater
0.0010
0.0080
Thallium
47249
6
Filtered
Freshwater
0.0210
0.0266
Thallium
47250
6
Filtered
Freshwater
0.0240
0.0269
Thallium
47251
6
Filtered
Freshwater
0.1010
0.1056
Thallium
47252
6
Filtered
Freshwater
0.1210
0.1229
Thallium
47253
6
Reagent
Water
0.0400
0.0425
Thallium
47254
6
Reagent
Water
0.0500
0.0609
Thallium
46846
7
Reagent
Water
0.0000
0.0002
Outlying
Laboratory
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
41
Draft
­
December
2000
Thallium
46847
7
Reagent
Water
0.0000
0.0001
Outlying
Laboratory
Thallium
46848
7
Reagent
Water
0.1000
0.1051
Outlying
Laboratory
Thallium
46849
7
Reagent
Water
0.1000
0.1042
Outlying
Laboratory
Thallium
46850
7
Reagent
Water
0.5000
0.5151
Outlying
Laboratory
Thallium
46851
7
Reagent
Water
0.5000
0.5243
Outlying
Laboratory
Thallium
46852
7
Reagent
Water
2.0000
2.1066
Outlying
Laboratory
Thallium
46853
7
Reagent
Water
2.0000
2.1338
Outlying
Laboratory
Thallium
46854
7
Filtered
Effluent
0.2000
0.2089
Outlying
Laboratory
Thallium
46855
7
Filtered
Effluent
0.2000
0.2067
Outlying
Laboratory
Thallium
46856
7
Filtered
Freshwater
0.0600
0.0695
Outlying
Laboratory
Thallium
46857
7
Filtered
Freshwater
0.0600
0.0673
Outlying
Laboratory
Thallium
47267
7
Unfiltered
Effluent
0.9000
0.9770
Outlying
Laboratory
Thallium
47268
7
Unfiltered
Effluent
0.9000
0.9665
Outlying
Laboratory
Thallium
47269
7
Filtered
Freshwater
0.0010
0.0013
Outlying
Laboratory
Thallium
47270
7
Filtered
Freshwater
0.0010
0.0008
Outlying
Laboratory
Thallium
47271
7
Filtered
Freshwater
0.0210
0.0218
Outlying
Laboratory
Thallium
47272
7
Filtered
Freshwater
0.0240
0.0245
Outlying
Laboratory
Thallium
47273
7
Filtered
Freshwater
0.1010
0.1050
Outlying
Laboratory
Thallium
47274
7
Filtered
Freshwater
0.1210
0.1298
Outlying
Laboratory
Thallium
47275
7
Reagent
Water
0.0400
0.0423
Outlying
Laboratory
Thallium
47276
7
Reagent
Water
0.0500
0.0500
Outlying
Laboratory
Thallium
46540
8
Filtered
Effluent
0.2000
0.1887
Thallium
46541
8
Filtered
Effluent
0.2000
0.1904
Thallium
46542
8
Unfiltered
Effluent
0.9000
0.8704
Thallium
46543
8
Unfiltered
Effluent
0.9000
0.8559
Thallium
46544
8
Reagent
Water
2.0000
1.8590
Thallium
46545
8
Reagent
Water
2.0000
1.9596
Thallium
46546
8
Filtered
Freshwater
0.0600
0.0611
Thallium
46547
8
Filtered
Freshwater
0.0600
0.0594
Thallium
46548
8
Reagent
Water
0.0000
0.0000
Thallium
46549
8
Reagent
Water
0.0000
0.0000
Thallium
46550
8
Reagent
Water
0.1000
0.0970
Thallium
46551
8
Reagent
Water
0.1000
0.0995
Thallium
46552
8
Reagent
Water
0.5000
0.4630
Thallium
46553
8
Reagent
Water
0.5000
0.4665
Thallium
47259
8
Filtered
Freshwater
0.0010
0.0006
Thallium
47260
8
Filtered
Freshwater
0.0010
0.0000
Thallium
47261
8
Filtered
Freshwater
0.0210
0.0179
Thallium
47262
8
Filtered
Freshwater
0.0240
0.0206
Thallium
47263
8
Filtered
Freshwater
0.1010
0.0911
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
42
Thallium
47264
8
Filtered
Freshwater
0.1210
0.1097
Thallium
47265
8
Reagent
Water
0.0400
0.0352
Thallium
47266
8
Reagent
Water
0.0500
0.0429
Zinc
46750
1
Reagent
Water
0.0000
0.0713
Zinc
46751
1
Reagent
Water
0.0000
0.2800
Zinc
46752
1
Reagent
Water
0.5000
0.4650
Zinc
46753
1
Reagent
Water
0.5000
0.4740
Zinc
46754
1
Reagent
Water
5.0000
4.4600
Zinc
46755
1
Reagent
Water
5.0000
4.5800
Zinc
46774
1
Reagent
Water
50.0000
43.2000
Zinc
46775
1
Reagent
Water
50.0000
43.4000
Zinc
46776
1
Unfiltered
Effluent
48.0100
48.5000
Zinc
46777
1
Unfiltered
Effluent
48.0100
48.2000
Zinc
46778
1
Filtered
Effluent
43.8250
45.8000
Zinc
46779
1
Filtered
Effluent
43.8250
41.0000
Zinc
46780
1
Filtered
Freshwater
1.5000
1.2800
Zinc
46781
1
Filtered
Freshwater
1.5000
1.4000
Zinc
47285
1
Filtered
Freshwater
0.9743
0.8690
Zinc
47286
1
Filtered
Freshwater
0.9743
0.7900
Zinc
47287
1
Filtered
Freshwater
1.1043
0.9050
Zinc
47288
1
Filtered
Freshwater
1.3043
1.3700
Zinc
47289
1
Filtered
Freshwater
1.7943
1.6300
Zinc
47290
1
Filtered
Freshwater
2.1943
2.0000
Zinc
47291
1
Reagent
Water
2.0000
1.8900
Zinc
47292
1
Reagent
Water
2.4000
2.3600
Zinc
46504
2
Filtered
Freshwater
1.5000
4.3210
Zinc
46505
2
Filtered
Freshwater
1.5000
2.3680
Zinc
46506
2
Filtered
Effluent
43.8250
44.3000
Zinc
46507
2
Filtered
Effluent
43.8250
42.7000
Zinc
46508
2
Unfiltered
Effluent
48.0100
49.4400
Zinc
46509
2
Unfiltered
Effluent
48.0100
50.5500
Zinc
46510
2
Reagent
Water
0.0000
0.6914
Zinc
46511
2
Reagent
Water
0.0000
0.4415
Zinc
46512
2
Reagent
Water
0.5000
4.0300
Zinc
46513
2
Reagent
Water
0.5000
1.1550
Zinc
46514
2
Reagent
Water
5.0000
6.0460
Zinc
46515
2
Reagent
Water
5.0000
5.6360
Zinc
46516
2
Reagent
Water
50.0000
51.0000
Zinc
46517
2
Reagent
Water
50.0000
51.3700
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
43
Draft
­
December
2000
Zinc
47231
2
Filtered
Freshwater
0.9743
1.9980
Zinc
47232
2
Filtered
Freshwater
0.9743
1.3810
Zinc
47233
2
Filtered
Freshwater
1.1043
1.4150
Zinc
47234
2
Filtered
Freshwater
1.3043
1.8460
Zinc
47235
2
Filtered
Freshwater
1.7943
2.1890
Zinc
47236
2
Filtered
Freshwater
2.1943
2.5790
Zinc
47237
2
Reagent
Water
2.0000
3.0660
Zinc
47238
2
Reagent
Water
2.4000
2.8680
Zinc
46722
3
Filtered
Freshwater
1.5000
1.5506
Zinc
46723
3
Filtered
Freshwater
1.5000
1.3816
Zinc
46724
3
Filtered
Effluent
43.8250
42.7116
Zinc
46725
3
Filtered
Effluent
43.8250
44.2443
Zinc
46726
3
Unfiltered
Effluent
48.0100
49.6040
Zinc
46727
3
Unfiltered
Effluent
48.0100
49.7807
Zinc
46728
3
Reagent
Water
0.0000
0.0697
Zinc
46729
3
Reagent
Water
0.0000
0.1315
Zinc
46730
3
Reagent
Water
0.5000
0.7130
Zinc
46731
3
Reagent
Water
0.5000
0.6415
Zinc
46732
3
Reagent
Water
5.0000
4.9954
Zinc
46733
3
Reagent
Water
5.0000
5.8975
Zinc
46734
3
Reagent
Water
50.0000
52.5187
Zinc
46735
3
Reagent
Water
50.0000
51.9073
Zinc
47213
3
Filtered
Freshwater
0.9743
1.0036
Zinc
47214
3
Filtered
Freshwater
0.9743
0.9580
Zinc
47215
3
Filtered
Freshwater
1.1043
0.9369
Zinc
47216
3
Filtered
Freshwater
1.3043
1.1144
Zinc
47217
3
Filtered
Freshwater
1.7943
2.0570
Zinc
47218
3
Filtered
Freshwater
2.1943
2.0747
Zinc
47219
3
Reagent
Water
2.0000
2.1609
Zinc
47220
3
Reagent
Water
2.4000
2.6430
Zinc
46594
4
Reagent
Water
0.0000
­
0.2020
Zinc
46595
4
Reagent
Water
0.0000
­
0.2190
Zinc
46596
4
Reagent
Water
50.0000
50.4520
Zinc
46597
4
Reagent
Water
50.0000
50.7220
Zinc
46598
4
Reagent
Water
5.0000
4.9730
Zinc
46599
4
Reagent
Water
5.0000
4.9380
Zinc
46600
4
Reagent
Water
0.5000
0.2510
Zinc
46601
4
Reagent
Water
0.5000
0.2380
Zinc
46602
4
Filtered
Freshwater
1.5000
1.4320
Possible
contamination1
Zinc
46603
4
Filtered
Freshwater
1.5000
1.1660
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
44
Zinc
46604
4
Filtered
Effluent
43.8250
44.9860
Zinc
46605
4
Filtered
Effluent
43.8250
45.2430
Zinc
46606
4
Unfiltered
Effluent
48.0100
50.6250
Zinc
46607
4
Unfiltered
Effluent
48.0100
52.3870
Zinc
47239
4
Filtered
Freshwater
0.9743
0.5140
Zinc
47240
4
Filtered
Freshwater
0.9743
0.4470
Zinc
47241
4
Filtered
Freshwater
1.1043
0.6370
Zinc
47242
4
Filtered
Freshwater
1.3043
0.9220
Zinc
47243
4
Filtered
Freshwater
1.7943
1.6130
Zinc
47244
4
Filtered
Freshwater
2.1943
1.8390
Zinc
47245
4
Reagent
Water
2.0000
3.2120
Zinc
47246
4
Reagent
Water
2.4000
2.0620
Zinc
46532
5
Filtered
Freshwater
1.5000
3.5617
Outlying
Laboratory
Possible
contamination1
Zinc
46533
5
Filtered
Freshwater
1.5000
14.3135
Outlying
Laboratory
Possible
contamination1
Zinc
46534
5
Filtered
Effluent
43.8250
60.3392
Outlying
Laboratory
Possible
contamination1
Zinc
46535
5
Filtered
Effluent
43.8250
40.1084
Concentration
>
cal
range
Zinc
46536
5
Unfiltered
Effluent
48.0100
59.7132
Concentration
>
cal
range
Zinc
46537
5
Unfiltered
Effluent
48.0100
53.4459
Concentration
>
cal
range
Zinc
46538
5
Reagent
Water
0.0000
1.7024
Outlying
Laboratory
Possible
contamination1
Zinc
46539
5
Reagent
Water
0.0000
4.5007
Outlying
Laboratory
Possible
contamination1
Zinc
46702
5
Reagent
Water
0.5000
2.1957
Outlying
Laboratory
Possible
contamination1
Zinc
46703
5
Reagent
Water
0.5000
3.4642
Outlying
Laboratory
Possible
contamination1
Zinc
46704
5
Reagent
Water
5.0000
5.7298
Outlying
Laboratory
Possible
contamination1
Zinc
46705
5
Reagent
Water
5.0000
6.3932
Outlying
Laboratory
Possible
contamination1
Zinc
46706
5
Reagent
Water
50.0000
47.7843
Concentration
>
cal
range
Zinc
46707
5
Reagent
Water
50.0000
48.1602
Concentration
>
cal
range
Zinc
47223
5
Filtered
Freshwater
0.9743
19.9924
Outlying
Laboratory
Possible
contamination1
Zinc
47224
5
Filtered
Freshwater
0.9743
2.6400
Outlying
Laboratory
Possible
contamination1
Zinc
47225
5
Filtered
Freshwater
1.1043
2.2861
Outlying
Laboratory
Possible
contamination1
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
B­
45
Draft
­
December
2000
Zinc
47226
5
Filtered
Freshwater
1.3043
2.8336
Outlying
Laboratory
Possible
contamination1
Zinc
47227
5
Filtered
Freshwater
1.7943
3.3408
Outlying
Laboratory
Possible
contamination1
Zinc
47228
5
Filtered
Freshwater
2.1943
3.6014
Outlying
Laboratory
Possible
contamination1
Zinc
47229
5
Reagent
Water
2.0000
3.7071
Outlying
Laboratory
Possible
contamination1
Zinc
47230
5
Reagent
Water
2.4000
4.2327
Outlying
Laboratory
Possible
contamination1
Zinc
46554
6
Filtered
Effluent
43.8250
43.3113
Zinc
46555
6
Filtered
Effluent
43.8250
47.8295
Zinc
46556
6
Filtered
Freshwater
1.5000
2.1583
Zinc
46557
6
Filtered
Freshwater
1.5000
1.5672
Zinc
46558
6
Reagent
Water
0.0000
0.2636
Zinc
46559
6
Reagent
Water
0.0000
0.4230
Zinc
46560
6
Unfiltered
Effluent
48.0100
62.0914
Individual
Outlier
Zinc
46561
6
Unfiltered
Effluent
48.0100
48.8716
Zinc
46562
6
Reagent
Water
0.5000
0.7293
Zinc
46563
6
Reagent
Water
0.5000
0.8695
Zinc
46564
6
Reagent
Water
5.0000
4.8052
Zinc
46565
6
Reagent
Water
5.0000
6.4784
Zinc
46566
6
Reagent
Water
50.0000
45.8536
Zinc
46567
6
Reagent
Water
50.0000
59.8960
Zinc
47247
6
Filtered
Freshwater
0.9743
1.0932
Zinc
47248
6
Filtered
Freshwater
0.9743
1.6887
Zinc
47249
6
Filtered
Freshwater
1.1043
1.1470
Zinc
47250
6
Filtered
Freshwater
1.3043
1.4080
Zinc
47251
6
Filtered
Freshwater
1.7943
1.8281
Zinc
47252
6
Filtered
Freshwater
2.1943
2.2378
Zinc
47253
6
Reagent
Water
2.0000
2.1349
Zinc
47254
6
Reagent
Water
2.4000
2.7856
Zinc
46846
7
Reagent
Water
0.0000
­
0.0374
Zinc
46847
7
Reagent
Water
0.0000
­
0.0397
Zinc
46848
7
Reagent
Water
0.5000
0.4118
Zinc
46849
7
Reagent
Water
0.5000
0.4133
Zinc
46850
7
Reagent
Water
5.0000
4.6699
Zinc
46851
7
Reagent
Water
5.0000
4.5940
Zinc
46852
7
Reagent
Water
50.0000
46.6399
Zinc
46853
7
Reagent
Water
50.0000
46.6981
Zinc
46854
7
Filtered
Effluent
43.8250
42.9109
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
2.
Field
Sample
Results
Analyte
Sample
Number
Lab
Matrix
Expected
Concentration
(
µ
g/
L)
Amount
Comment
Draft
­
December
2000
B­
46
Zinc
46855
7
Filtered
Effluent
43.8250
42.8596
Zinc
46856
7
Filtered
Freshwater
1.5000
1.3056
Zinc
46857
7
Filtered
Freshwater
1.5000
1.2636
Zinc
47267
7
Unfiltered
Effluent
48.0100
45.5374
Zinc
47268
7
Unfiltered
Effluent
48.0100
46.2510
Zinc
47269
7
Filtered
Freshwater
0.9743
0.7638
Zinc
47270
7
Filtered
Freshwater
0.9743
0.7708
Zinc
47271
7
Filtered
Freshwater
1.1043
0.8760
Zinc
47272
7
Filtered
Freshwater
1.3043
1.0735
Zinc
47273
7
Filtered
Freshwater
1.7943
1.4933
Zinc
47274
7
Filtered
Freshwater
2.1943
1.8992
Zinc
47275
7
Reagent
Water
2.0000
1.7942
Zinc
47276
7
Reagent
Water
2.4000
2.1073
Zinc
46540
8
Filtered
Effluent
43.8250
42.8472
Zinc
46541
8
Filtered
Effluent
43.8250
45.3330
Zinc
46542
8
Unfiltered
Effluent
48.0100
49.5120
Zinc
46543
8
Unfiltered
Effluent
48.0100
48.7990
Zinc
46544
8
Reagent
Water
50.0000
44.7807
Zinc
46545
8
Reagent
Water
50.0000
50.4607
Zinc
46546
8
Filtered
Freshwater
1.5000
4.6312
Possible
contamination2
Zinc
46547
8
Filtered
Freshwater
1.5000
3.8415
Possible
contamination2
Zinc
46548
8
Reagent
Water
0.0000
1.1251
Possible
contamination1
Zinc
46549
8
Reagent
Water
0.0000
0.9461
Zinc
46550
8
Reagent
Water
0.5000
0.6587
Zinc
46551
8
Reagent
Water
0.5000
1.0679
Possible
contamination1
Zinc
46552
8
Reagent
Water
5.0000
4.4630
Possible
contamination2
Zinc
46553
8
Reagent
Water
5.0000
4.4245
Possible
contamination2
Zinc
47259
8
Filtered
Freshwater
0.9743
0.6552
Zinc
47260
8
Filtered
Freshwater
0.9743
0.8136
Zinc
47261
8
Filtered
Freshwater
1.1043
1.0597
Possible
contamination1
Zinc
47262
8
Filtered
Freshwater
1.3043
1.1635
Possible
contamination1
Zinc
47263
8
Filtered
Freshwater
1.7943
1.3807
Possible
contamination1
Zinc
47264
8
Filtered
Freshwater
2.1943
1.7278
Possible
contamination1
Zinc
47265
8
Reagent
Water
2.0000
1.6577
Possible
contamination1
Zinc
47266
8
Reagent
Water
2.4000
2.0357
Possible
contamination1
1Sample
result
is
less
than
five
times
an
associated
blank
result
that
is
higher
than
the
revised
MDL.
2Sample
result
is
between
five
and
ten
times
an
associated
blank
result
that
is
higher
than
the
revised
MDL.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
B­
47
Draft
­
December
2000
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Draft
­
December
2000
B­
48
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
Sb
46504
2
Freshwater
0.50000
0.66600
0.67510
Sb
46507
2
Filtered
Effluent
5.00000
5.36800
5.30200
Sb
46508
2
Unfiltered
Effluent
30.00000
38.40000
39.28000
Sb
46533
5
Freshwater
0.06000
0.18800
0.16100
Incorrect
spiking
level
Sb
46534
5
Filtered
Effluent
1.20000
NR
NR
Sb
46537
5
Unfiltered
Effluent
0.20000
10.00490
10.02850
Sample
>
high
std,
Incorrect
spiking
level
Sb
46540
8
Filtered
Effluent
4.00000
5.32460
5.43900
Sb
46543
8
Unfiltered
Effluent
8.00000
18.23900
18.37400
Incorrect
spiking
level
Sb
46544
8
Reagent
Water
50.00000
73.05000
77.47500
Sample
>
high
std
Sb
46547
8
Freshwater
1.00000
0.9904
1.12970
Incorrect
spiking
level
Sb
46552
8
Reagent
Water
5.00000
8.81430
9.09030
Sb
46555
6
Filtered
Effluent
5.06600
6.16310
NR
Sb
46556
6
Freshwater
0.50100
0.66650
NR
Sb
46560
6
Unfiltered
Effluent
50.37300
60.80580
NR
Incorrect
spiking
level
Sb
46602
4
Freshwater
30.00000
27.49600
28.52000
Incorrect
spiking
level
Sb
46605
4
Filtered
Effluent
30.00000
29.35700
29.53900
Incorrect
spiking
level
Sb
46606
4
Unfiltered
Effluent
40.00000
46.69000
46.37200
Sb
46722
3
Freshwater
0.25000
0.41516
0.40604
Sb
46724
3
Filtered
Effluent
0.83300
1.81551
1.76042
Incorrect
spiking
level
Sb
46726
3
Unfiltered
Effluent
15.00000
22.05490
22.12027
Sample
>
high
std
Sb
46776
1
Unfiltered
Effluent
25.00000
37.10000
37.30000
Sb
46779
1
Filtered
Effluent
1.00000
2.08000
2.15000
Sb
46780
1
Freshwater
1.00000
1.26000
1.25000
Incorrect
spiking
level
Sb
46855
7
Filtered
Effluent
5.00000
6.78910
6.20430
Sb
46856
7
Freshwater
5.00000
5.22960
5.22980
Incorrect
spiking
level
Sb
47213
3
Freshwater
0.25000
0.48044
0.48619
Sb
47223
5
Freshwater
0.06000
0.24946
0.25177
Incorrect
spiking
level
Sb
47231
2
Freshwater
1.00000
1.21400
1.23700
Sb
47239
4
Freshwater
30.00000
28.23400
28.61700
Incorrect
spiking
level
Sb
47268
7
Unfiltered
Effluent
5.00000
15.26020
15.22170
Incorrect
spiking
level
Cd
46504
2
Freshwater
1.00000
1.31200
1.37200
Cd
46507
2
Filtered
Effluent
0.90000
1.23300
1.27200
Cd
46508
2
Unfiltered
Effluent
1.00000
1.36200
1.55900
Cd
46533
5
Freshwater
0.30000
0.59849
0.61586
Incorrect
spiking
level
Cd
46534
5
Filtered
Effluent
0.30000
0.70712
0.65900
Incorrect
spiking
level
Cd
46537
5
Unfiltered
Effluent
1.00000
1.36099
1.12498
Cd
46540
8
Filtered
Effluent
1.00000
1.25810
1.26240
Cd
46543
8
Unfiltered
Effluent
2.00000
2.32460
2.34800
Cd
46544
8
Reagent
Water
50.00000
59.74590
61.94750
Incorrect
spiking
level
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
B­
49
Draft
­
December
2000
Cd
46547
8
Freshwater
0.25000
0.47980
0.47800
Cd
46552
8
Reagent
Water
1.25000
2.12950
2.17620
Cd
46555
6
Filtered
Effluent
2.07300
2.76780
NR
Incorrect
spiking
level
Cd
46556
6
Freshwater
2.03800
2.60300
NR
Incorrect
spiking
level
Cd
46560
6
Unfiltered
Effluent
4.00500
5.16080
NR
Incorrect
spiking
level
Cd
46602
4
Freshwater
30.00000
31.03900
31.28600
Incorrect
spiking
level
Cd
46605
4
Filtered
Effluent
30.00000
30.37900
30.20400
Incorrect
spiking
level
Cd
46606
4
Unfiltered
Effluent
2.00000
2.42200
2.47400
Incorrect
spiking
level
Cd
46722
3
Freshwater
0.25000
0.47483
0.47955
Cd
46724
3
Filtered
Effluent
0.83300
1.11517
1.09906
Cd
46726
3
Unfiltered
Effluent
1.66700
2.13707
2.12629
Cd
46776
1
Unfiltered
Effluent
1.00000
1.56000
1.50000
Cd
46779
1
Filtered
Effluent
1.00000
1.28000
1.28000
Cd
46780
1
Freshwater
1.00000
1.27000
1.23000
Incorrect
spiking
level
Cd
46855
7
Filtered
Effluent
5.00000
5.16680
5.19450
Incorrect
spiking
level
Cd
46856
7
Freshwater
5.00000
5.37660
5.31360
Incorrect
spiking
level
Cd
47213
3
Freshwater
0.25000
0.26045
0.26184
Cd
47223
5
Freshwater
0.30000
0.34679
0.34020
Cd
47231
2
Freshwater
3.00000
2.73800
2.68300
Incorrect
spiking
level
Cd
47239
4
Freshwater
30.00000
30.79800
31.05500
Incorrect
spiking
level
Cd
47268
7
Unfiltered
Effluent
5.00000
5.44840
5.46780
Incorrect
spiking
level
Cu
46504
2
Freshwater
20.00000
30.60000
30.08000
Cu
46507
2
Filtered
Effluent
50.00000
67.45000
66.04000
Sample
>
high
std
Cu
46508
2
Unfiltered
Effluent
50.00000
68.38000
69.03000
Cu
46533
5
Freshwater
30.00000
36.20700
30.39800
Cu
46534
5
Filtered
Effluent
0.60000
NR
NR
Cu
46537
5
Unfiltered
Effluent
2.00000
21.13220
19.24933
Incorrect
spiking
level,
Possible
contamination1
Cu
46540
8
Filtered
Effluent
21.00000
32.06890
31.11890
Cu
46543
8
Unfiltered
Effluent
22.00000
33.58530
34.17510
Cu
46544
8
Reagent
Water
50.00000
63.83030
68.14100
Sample
>
high
std
Cu
46547
8
Freshwater
0.25000
1.26160
1.28250
Incorrect
spiking
level
Cu
46552
8
Reagent
Water
1.25000
2.95670
3.00510
Incorrect
spiking
level
Cu
46555
6
Filtered
Effluent
50.36800
58.83320
NR
Cu
46556
6
Freshwater
5.04000
5.96880
NR
Cu
46560
6
Unfiltered
Effluent
45.34700
57.15260
NR
Cu
46602
4
Freshwater
30.00000
31.87400
31.93400
Incorrect
spiking
level
Cu
46605
4
Filtered
Effluent
30.00000
46.58600
46.03500
Cu
46606
4
Unfiltered
Effluent
80.00000
98.74500
97.71000
Cu
46722
3
Freshwater
5.00000
4.92250
5.04088
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
Draft
­
December
2000
B­
50
Cu
46724
3
Filtered
Effluent
15.00000
29.47470
29.33254
Cu
46726
3
Unfiltered
Effluent
15.00000
30.40590
29.97278
Sample
>
high
std,
Incorrect
spiking
level
Cu
46776
1
Unfiltered
Effluent
25.00000
38.50000
38.10000
Cu
46779
1
Filtered
Effluent
25.00000
36.20000
36.30000
Cu
46780
1
Freshwater
1.00000
2.01000
1.96000
Cu
46855
7
Filtered
Effluent
5.00000
19.49870
19.33470
Incorrect
spiking
level
Cu
46856
7
Freshwater
5.00000
5.55870
5.61690
Cu
47213
3
Freshwater
4.00000
5.14713
5.10406
Sample
>
high
std
Cu
47223
5
Freshwater
0.60000
2.11824
2.12930
Incorrect
spiking
level
Cu
47231
2
Freshwater
5.00000
6.65700
6.69100
Cu
47239
4
Freshwater
30.00000
32.37900
32.06900
Incorrect
spiking
level
Cu
47268
7
Unfiltered
Effluent
5.00000
19.84730
20.04080
Incorrect
spiking
level
Pb
46504
2
Freshwater
1.50000
1.83300
1.85900
Pb
46507
2
Filtered
Effluent
6.00000
6.31900
6.43700
Incorrect
spiking
level
Pb
46508
2
Unfiltered
Effluent
5.00000
5.83600
6.00100
Pb
46533
5
Freshwater
0.15000
0.36858
0.36114
Incorrect
spiking
level
Pb
46534
5
Filtered
Effluent
0.15000
0.72938
0.73001
Incorrect
spiking
level
Pb
46537
5
Unfiltered
Effluent
0.50000
2.68804
2.03289
Incorrect
spiking
level,
Possible
contamination1
Pb
46540
8
Filtered
Effluent
1.00000
1.65550
1.62380
Pb
46543
8
Unfiltered
Effluent
2.00000
3.08900
3.11640
Pb
46544
8
Reagent
Water
50.00000
53.86860
57.38300
Sample
>
high
std,
Incorrect
spiking
level
Pb
46547
8
Freshwater
0.25000
0.48220
0.49970
Pb
46552
8
Reagent
Water
1.25000
1.74170
1.75740
Pb
46555
6
Filtered
Effluent
2.61300
3.56030
NR
Pb
46556
6
Freshwater
1.04100
1.40000
NR
Pb
46560
6
Unfiltered
Effluent
5.04300
6.72090
NR
Pb
46602
4
Freshwater
30.00000
30.33200
30.48700
Incorrect
spiking
level
Pb
46605
4
Filtered
Effluent
30.00000
29.48200
29.42900
Incorrect
spiking
level
Pb
46606
4
Unfiltered
Effluent
5.00000
6.02200
5.90100
Pb
46722
3
Freshwater
0.25000
0.47231
0.47460
Pb
46724
3
Filtered
Effluent
0.83300
1.43216
1.42094
Pb
46726
3
Unfiltered
Effluent
1.66700
2.96845
2.84953
Pb
46776
1
Unfiltered
Effluent
1.00000
1.96000
1.98000
Pb
46779
1
Filtered
Effluent
1.00000
1.45000
1.48000
Pb
46780
1
Freshwater
1.00000
1.18000
1.18000
Incorrect
spiking
level
Pb
46855
7
Filtered
Effluent
5.00000
5.30240
5.33680
Incorrect
spiking
level
Pb
46856
7
Freshwater
5.00000
5.13580
5.15180
Incorrect
spiking
level
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
B­
51
Draft
­
December
2000
Pb
47213
3
Freshwater
0.25000
0.29194
0.29363
Pb
47223
5
Freshwater
0.15000
0.20901
0.20639
Pb
47231
2
Freshwater
1.50000
1.40300
1.39900
Incorrect
spiking
level
Pb
47239
4
Freshwater
30.00000
29.93000
30.31800
Incorrect
spiking
level
Pb
47268
7
Unfiltered
Effluent
5.00000
4.68640
4.74020
Incorrect
spiking
level
Ni
46504
2
Freshwater
20.00000
26.07000
26.51000
Ni
46507
2
Filtered
Effluent
20.00000
25.80000
25.25000
Ni
46508
2
Unfiltered
Effluent
20.00000
27.98000
28.34000
Ni
46533
5
Freshwater
3.00000
8.78263
8.90238
Incorrect
spiking
level
Ni
46534
5
Filtered
Effluent
3.00000
9.46807
9.50236
Incorrect
spiking
level
Ni
46537
5
Unfiltered
Effluent
10.00000
13.90000
13.20000
Ni
46540
8
Filtered
Effluent
11.00000
17.08750
16.70990
Ni
46543
8
Unfiltered
Effluent
12.00000
18.42300
18.39400
Ni
46544
8
Reagent
Water
50.00000
140.55300
144.31170
Sample
>
high
std,
Incorrect
spiking
level
Ni
46547
8
Freshwater
5.25000
10.96610
11.05030
Incorrect
spiking
level
Ni
46552
8
Reagent
Water
11.25000
20.22080
20.41270
Ni
46555
6
Filtered
Effluent
40.66500
41.73010
NR
Incorrect
spiking
level
Ni
46556
6
Freshwater
39.41600
41.85090
NR
Incorrect
spiking
level
Ni
46560
6
Unfiltered
Effluent
36.17900
41.05830
NR
Incorrect
spiking
level
Ni
46602
4
Freshwater
30.00000
34.88600
35.44400
Ni
46605
4
Filtered
Effluent
30.00000
35.11100
33.58600
Ni
46606
4
Unfiltered
Effluent
40.00000
47.98000
48.01700
Ni
46722
3
Freshwater
10.00000
14.94980
15.18900
Ni
46724
3
Filtered
Effluent
10.00000
14.47040
14.53703
Ni
46726
3
Unfiltered
Effluent
10.00000
15.35150
14.90455
Sample
>
high
std
Ni
46776
1
Unfiltered
Effluent
25.00000
31.00000
30.70000
Ni
46779
1
Filtered
Effluent
25.00000
30.00000
29.80000
Ni
46780
1
Freshwater
11.00000
16.50000
16.20000
Ni
46855
7
Filtered
Effluent
5.00000
11.78900
11.62450
Incorrect
spiking
level
Ni
46856
7
Freshwater
5.00000
10.15630
10.22660
Incorrect
spiking
level
Ni
47213
3
Freshwater
4.00000
4.09522
4.11498
Ni
47223
5
Freshwater
3.00000
3.63898
3.65862
Ni
47231
2
Freshwater
3.00000
3.70900
3.81300
Ni
47239
4
Freshwater
30.00000
29.25600
30.04200
Incorrect
spiking
level
Ni
47268
7
Unfiltered
Effluent
5.00000
11.94710
12.05380
Incorrect
spiking
level
Se
46504
2
Freshwater
20.00000
24.88000
24.28000
Incorrect
spiking
level
Se
46507
2
Filtered
Effluent
30.00000
37.96000
37.76000
Se
46508
2
Unfiltered
Effluent
30.00000
39.92000
37.91000
Se
46533
5
Freshwater
3.00000
6.89461
6.26332
Incorrect
spiking
level
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
Draft
­
December
2000
B­
52
Se
46534
5
Filtered
Effluent
3.00000
10.08730
9.86675
Incorrect
spiking
level
Se
46537
5
Unfiltered
Effluent
10.00000
12.17660
10.83706
Se
46540
8
Filtered
Effluent
20.00000
24.88270
24.98520
Se
46543
8
Unfiltered
Effluent
40.00000
42.94000
43.62500
Incorrect
spiking
level
Se
46544
8
Reagent
Water
50.00000
145.28700
150.13680
Incorrect
spiking
level
Se
46547
8
Freshwater
5.00000
8.72800
8.89340
Se
46552
8
Reagent
Water
25.00000
43.70890
43.57400
Se
46555
6
Filtered
Effluent
40.21700
70.50910
NR
Se
46556
6
Freshwater
19.59000
42.25390
NR
Incorrect
spiking
level
Se
46560
Unfiltered
Effluent
49.96700
78.79980
NR
Se
46602
4
Freshwater
30.00000
33.78100
34.82000
Incorrect
spiking
level
Se
46605
4
Filtered
Effluent
30.00000
37.09100
36.45200
Se
46606
4
Unfiltered
Effluent
40.00000
49.42100
48.49200
Incorrect
spiking
level
Se
46722
3
Freshwater
5.00000
9.27212
9.30843
Se
46724
3
Filtered
Effluent
16.66700
25.08210
24.56035
Se
46726
3
Unfiltered
Effluent
33.33300
46.75420
44.56386
Se
46776
1
Unfiltered
Effluent
25.00000
37.80000
36.80000
Se
46779
1
Filtered
Effluent
25.00000
33.10000
34.10000
Se
46780
1
Freshwater
11.00000
16.80000
18.00000
Se
46855
7
Filtered
Effluent
5.00000
10.75750
10.19860
Incorrect
spiking
level
Se
46856
7
Freshwater
5.00000
8.00300
7.87230
Se
47213
3
Freshwater
5.00000
5.82826
5.85295
Se
47223
5
Freshwater
3.00000
2.61802
2.66777
Se
47231
2
Freshwater
20.00000
18.19000
19.86000
Incorrect
spiking
level
Se
47239
4
Freshwater
30.00000
31.62400
31.20600
Incorrect
spiking
level
Se
47268
7
Unfiltered
Effluent
5.00000
11.12110
11.39860
Incorrect
spiking
level
Ag
46504
2
Freshwater
0.50000
0.57790
0.60240
Ag
46507
2
Filtered
Effluent
1.50000
1.68100
1.74700
Ag
46508
2
Unfiltered
Effluent
5.00000
6.09200
6.05800
Ag
46533
5
Freshwater
0.30000
0.42385
0.41300
Ag
46534
5
Filtered
Effluent
0.30000
0.58482
0.59225
Incorrect
spiking
level
Ag
46537
5
Unfiltered
Effluent
1.00000
2.05768
2.06904
Incorrect
spiking
level
Ag
46540
8
Filtered
Effluent
1.00000
1.28370
1.33170
Ag
46543
8
Unfiltered
Effluent
2.00000
2.98640
3.03120
Ag
46544
8
Reagent
Water
50.00000
57.92000
57.33130
Sample
>
high
std,
Incorrect
spiking
level
Ag
46547
8
Freshwater
0.25000
0.34080
0.39010
Ag
46552
8
Reagent
Water
1.25000
1.26840
1.24430
Incorrect
spiking
level
Ag
46555
6
Filtered
Effluent
2.03700
2.67120
NR
Ag
46556
6
Freshwater
4.96300
5.71270
NR
Incorrect
spiking
level
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
B­
53
Draft
­
December
2000
Ag
46560
6
Unfiltered
Effluent
4.97400
6.77840
NR
Ag
46602
4
Freshwater
30.00000
31.95000
32.32000
Incorrect
spiking
level
Ag
46605
4
Filtered
Effluent
30.00000
31.81000
31.95500
Incorrect
spiking
level
Ag
46606
4
Unfiltered
Effluent
1.00000
2.54300
2.51400
Incorrect
spiking
level
Ag
46722
3
Freshwater
0.25000
0.43178
0.42855
Ag
46724
3
Filtered
Effluent
0.83300
1.20005
1.18966
Ag
46726
3
Unfiltered
Effluent
1.66700
2.85547
2.80148
Ag
46776
1
Unfiltered
Effluent
1.00000
2.15000
2.17000
Ag
46779
1
Filtered
Effluent
1.00000
1.17000
1.23000
Ag
46780
1
Freshwater
1.00000
1.10000
1.08000
Incorrect
spiking
level
Ag
46855
7
Filtered
Effluent
5.00000
5.15150
5.16810
Incorrect
spiking
level
Ag
46856
7
Freshwater
5.00000
5.04890
5.06850
Incorrect
spiking
level
Ag
47213
3
Freshwater
0.25000
0.24888
0.25035
Ag
47223
5
Freshwater
0.30000
0.36322
0.35513
Ag
47231
2
Freshwater
3.00000
2.68400
2.71400
Incorrect
spiking
level
Ag
47239
4
Freshwater
30.00000
32.20000
32.17000
Incorrect
spiking
level
Ag
47268
7
Unfiltered
Effluent
5.00000
6.19960
6.21590
Tl
46504
2
Freshwater
0.30000
0.36230
0.38350
Tl
46507
2
Filtered
Effluent
1.00000
1.25200
1.23200
Incorrect
spiking
level
Tl
46508
2
Unfiltered
Effluent
4.00000
5.13800
5.11300
Tl
46533
5
Freshwater
0.06000
0.13174
0.12431
Tl
46534
5
Filtered
Effluent
0.06000
0.27980
0.27765
Incorrect
spiking
level
Tl
46537
5
Unfiltered
Effluent
0.20000
1.12679
1.06809
Incorrect
spiking
level
Tl
46540
8
Filtered
Effluent
0.40000
0.61770
0.59670
Tl
46543
8
Unfiltered
Effluent
0.80000
1.63210
1.67530
Incorrect
spiking
level
Tl
46544
8
Reagent
Water
50.00000
48.86510
52.97590
Sample
>
high
std,
Incorrect
spiking
level
Tl
46547
8
Freshwater
0.10000
0.16930
0.17060
Tl
46552
8
Reagent
Water
0.50000
0.97730
0.99430
Tl
46555
6
Filtered
Effluent
1.01700
1.39560
NR
Tl
46556
6
Freshwater
0.25200
0.36340
NR
Tl
46560
6
Unfiltered
Effluent
5.02700
6.67280
NR
Incorrect
spiking
level
Tl
46602
4
Freshwater
30.00000
26.97500
27.00900
Incorrect
spiking
level
Tl
46605
4
Filtered
Effluent
30.00000
25.45500
25.86600
Incorrect
spiking
level
Tl
46606
4
Unfiltered
Effluent
4.00000
4.37400
4.35800
Incorrect
spiking
level
Tl
46722
3
Freshwater
0.25000
0.31796
0.32170
Tl
46724
3
Filtered
Effluent
0.83300
1.11400
1.11939
Tl
46726
3
Unfiltered
Effluent
1.66700
2.57114
2.65728
Tl
46776
1
Unfiltered
Effluent
1.00000
1.81000
1.82000
Tl
46779
1
Filtered
Effluent
1.00000
1.16000
1.15000
Incorrect
spiking
level
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
3:
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)
Results
Analyte
Field
Sample
Number
Lab
Matrix
Water
Spike
Level
(
µ
g/
L)
MS
Amount
(
µ
g/
L)
MSD
Amount
(
µ
g/
L)
Comments
Draft
­
December
2000
B­
54
Tl
46780
1
Freshwater
1.00000
1.10000
1.07000
Incorrect
spiking
level
Tl
46855
7
Filtered
Effluent
5.00000
5.56780
5.55920
Incorrect
spiking
level
Tl
46856
7
Freshwater
5.00000
5.40260
5.43650
Incorrect
spiking
level
Tl
47213
3
Freshwater
0.25000
0.25262
0.26162
Incorrect
spiking
level
Tl
47223
5
Freshwater
0.06000
0.06604
0.07559
Tl
47231
2
Freshwater
0.60000
0.56500
0.53640
Incorrect
spiking
level
Tl
47239
4
Freshwater
30.00000
26.43400
27.03200
Incorrect
spiking
level
Tl
47268
7
Unfiltered
Effluent
5.00000
6.42950
6.41260
Incorrect
spiking
level
Zn
46504
2
Freshwater
10
13.4
13.95
Zn
46507
2
Filtered
Effluent
200
255.6
257.5
Zn
46508
2
Unfiltered
Effluent
100
162.6
163.3
Zn
46533
5
Freshwater
75
80.414
75.911
Incorrect
spiking
level
Zn
46534
5
Filtered
Effluent
75
114.657
120.643
Zn
46537
5
Unfiltered
Effluent
5
61.9461
54.91673
Incorrect
spiking
level
Zn
46540
8
Filtered
Effluent
54
89.9293
89.6455
Zn
46543
8
Unfiltered
Effluent
58
95.062
96.355
Possible
contamination1
Zn
46544
8
Reagent
Water
50
93.8834
98.25
Zn
46547
8
Freshwater
1
5.4825
4.9435
Incorrect
spiking
level
Zn
46552
8
Reagent
Water
5
9.408
9.3926
Zn
46555
6
Filtered
Effluent
101.182
145.687
NR
Zn
46556
6
Freshwater
9.956
12.0011
NR
Zn
46560
6
Unfiltered
Effluent
90.389
150.34
NR
Zn
46602
4
Freshwater
30
31.501
31.551
Incorrect
spiking
level
Zn
46605
4
Filtered
Effluent
30
74.413
73.988
Incorrect
spiking
level
Zn
46606
4
Unfiltered
Effluent
100
147.955
148.982
Zn
46722
3
Freshwater
2.5
3.51249
3.48278
Zn
46724
3
Filtered
Effluent
100
142.046
138.908
Zn
46726
3
Unfiltered
Effluent
100
144.966
142.37
Zn
46776
1
Unfiltered
Effluent
50
95.7
95.4
Sample
>
high
std
Zn
46779
1
Filtered
Effluent
50
88.2
88
Sample
>
high
std
Zn
46780
1
Freshwater
11
12
11.7
Incorrect
spiking
level
Zn
46855
7
Filtered
Effluent
5
48.0539
47.8124
Incorrect
spiking
level
Zn
46856
7
Freshwater
5
5.8806
5.8837
Zn
47213
3
Freshwater
2.5
3.64438
3.13855
Zn
47223
5
Freshwater
75
77.844
63.122
Zn
47231
2
Freshwater
5
7.016
7.175
Zn
47239
4
Freshwater
30
30.892
31.204
Incorrect
spiking
level
Zn
47268
7
Unfiltered
Effluent
5
51.0495
51.5702
Incorrect
spiking
level
1
Results
may
be
elevated
due
to
contamination
noted
in
the
accompanying
QC
samples
B­
55
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
Antimony
1
IPR
0.05
0.060
0.059
0.067
0.073
­
­
­
­
­
­

OPR
0.05
0.1321
0.036
­
­
­
­
­
­
­
­

Antimony
2
OPR
0.06
0.048
0.068
­
­
­
­
­
­
­
­

IPR
0.23
0.213
0.204
0.227
0.221
­
­
­
­
­
­

OPR
0.23
0.241
0.216
0.197
0.180
0.178
0.187
0.197
0.193
­
­

Antimony
3
IPR
0.1
0.112
0.108
0.113
0.108
­
­
­
­
­
­

OPR
0.1
0.109
0.111
0.113
­
­
­
­
­
­
­

Antimony
4
IPR
0.06
0.072
0.087
0.087
0.074
0.064
0.065
0.074
0.068
0.108
0.079
0.080
0.078
­
­
­
­
­
­
­
­

OPR
53
4.829
4.779
4.901
4.832
4.927
­
­
­
­
­

Antimony
5
OPR
0.06
0.078
0.063
0.059
0.084
0.072
0.062
0.060
0.070
0.093
­

OPR
0.23
0.108
­
­
­
­
­
­
­
­
­

IPR
0.33
0.337
0.069
0.065
0.352
0.343
0.350
0.340
0.338
­
­

Antimony
62
IPR
0.061
0.064
0.068
0.071
0.067
0.070
0.062
­
­
­
­

Antimony
7
IPR
0.04
0.041
0.042
0.040
0.040
­
­
­
­
­
­

OPR
0.04
0.035
0.075
0.038
­
­
­
­
­
­
­

Antimony
8
IPR
0.53
0.530
0.518
0.549
0.546
­
­
­
­
­
­

OPR
0.53
0.525
0.431
0.449
­
­
­
­
­
­
­

Cadmium
1
IPR
0.2
0.187
0.196
0.202
0.215
­
­
­
­
­
­

OPR
0.3
0.260
­
­
­
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
56
OPR
0.553
0.615
­
­
­
­
­
­
­
­
­

Cadmium
2
IPR
0.3
0.320
0.308
0.274
0.273
­
­
­
­
­
­

OPR
0.3
0.314
0.333
0.289
0.303
0.279
0.257
0.333
0.259
0.309
0.305
0.352
0.336
­
­
­
­
­
­
­
­

Cadmium
3
IPR
0.1
0.101
0.097
0.095
0.100
­
­
­
­
­
­

OPR
0.1
0.099
0.101
0.104
­
­
­
­
­
­
­

Cadmium
4
IPR
0.3
0.280
0.320
0.320
0.280
0.310
0.310
0.320
0.300
0.330
0.300
0.310
0.310
­
­
­
­
­
­
­
­

OPR
53
5.442
5.425
5.321
5.277
5.370
­
­
­
­
­

Cadmium
52
IPR
0.3
0.323
0.345
0.344
0.319
0.346
0.313
0.310
0.345
­
­

OPR
0.3
0.339
0.687
0.346
0.331
0.347
0.372
0.382
0.384
0.380
0.378
Cadmium
6
IPR
0.304
0.304
0.304
0.289
0.320
0.364
0.351
­
­
­
­

Cadmium
7
IPR
0.2
0.169
0.171
0.171
0.169
­
­
­
­
­
­

OPR
0.2
0.170
0.165
0.174
­
­
­
­
­
­
­

Cadmium
8
IPR
0.125
0.101
0.114
0.115
0.105
­
­
­
­
­
­

OPR
0.125
0.133
0.129
0.110
­
­
­
­
­
­
­

Copper
12
IPR
0.2
0.209
0.206
0.204
0.193
­
­
­
­
­
­

OPR
0.55
0.505
0.513
­
­
­
­
­
­
­
­

Copper
2
IPR
0.6
0.676
0.646
0.862
0.565
­
­
­
­
­
­

OPR
0.6
0.605
0.612
0.842
0.652
0.834
0.737
0.672
0.682
­
­

Copper
3
IPR
0.13
0.106
0.100
0.101
0.104
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
57
OPR
0.13
0.102
0.104
0.096
­
­
­
­
­
­
­

Copper
4
IPR
0.6
0.650
0.670
0.690
0.710
0.640
0.770
0.780
0.660
0.640
0.810
0.610
0.650
­
­
­
­
­
­
­
­

OPR
53
5.508
5.421
5.574
5.481
5.640
­
­
­
­
­

Copper
5
IPR
0.6
0.663
0.666
0.690
0.693
1.0901
1.5001
0.901
0.872
­
­

OPR
0.6
0.518
3.0651,
4
0.668
0.567
0.558
0.599
0.617
0.626
0.607
0.645
Copper
6
IPR
0.639
0.715
0.670
0.687
0.731
0.726
0.699
­
­
­
­

Copper
7
IPR
0.4
0.370
0.378
0.376
0.373
­
­
­
­
­
­

OPR
0.4
0.375
0.370
0.360
­
­
­
­
­
­
­

Copper
8
IPR
0.1253
0.127
0.123
0.126
0.126
­
­
­
­
­
­

OPR
0.1253
0.129
0.164
0.118
­
­
­
­
­
­
­

Lead
12
IPR
0.05
0.045
0.055
0.045
0.042
­
­
­
­
­
­

OPR
0.15
0.158
0.134
­
­
­
­
­
­
­
­

Lead
2
IPR
0.15
0.2441
0.182
0.191
0.190
­
­
­
­
­
­

OPR
0.15
0.159
0.152
0.189
0.155
0.198
0.120
0.130
­
­
­

Lead
3
IPR
0.05
0.048
0.050
0.048
0.048
­
­
­
­
­
­

OPR
0.05
0.047
0.046
0.046
­
­
­
­
­
­
­

Lead
4
IPR
0.15
0.160
0.170
0.170
0.160
0.160
0.160
0.160
0.160
0.150
0.160
0.160
0.160
­
­
­
­
­
­
­
­

OPR
53
5.341
5.397
5.254
5.263
5.144
­
­
­
­
­

Lead
5
IPR
0.15
0.196
0.195
0.201
0.205
0.229
0.204
0.215
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
58
OPR
0.15
0.164
0.7711,
4
0.183
0.176
0.171
0.166
0.168
0.167
0.165
0.172
Lead
6
IPR
0.4743
0.496
0.494
0.474
0.470
0.476
0.482
­
­
­
­

Lead
7
IPR
0.1
0.099
0.100
0.099
0.098
­
­
­
­
­
­

OPR
0.1
0.099
0.100
0.124
­
­
­
­
­
­
­

Lead
8
IPR
0.125
0.130
0.126
0.127
0.129
­
­
­
­
­
­

OPR
0.125
0.133
0.137
0.126
­
­
­
­
­
­
­

Nickel
1
IPR
1
1.060
1.080
1.080
1.050
­
­
­
­
­
­

OPR
2.55
2.480
­
­
­
­
­
­
­
­
­

OPR
5.053
5.030
­
­
­
­
­
­
­
­
­

Nickel
22
IPR
3
2.870
2.868
2.866
2.737
­
­
­
­
­
­

OPR
3
3.156
3.093
2.991
3.008
2.887
2.591
2.845
2.760
2.606
2.562
2.617
2.663
­
­
­
­
­
­
­
­

Nickel
3
IPR
0.13
0.095
0.097
0.099
0.097
­
­
­
­
­
­

OPR
0.13
0.102
0.093
0.085
­
­
­
­
­
­
­

Nickel
4
IPR
3
3.020
3.100
3.090
3.050
3.160
3.190
3.080
3.200
3.230
3.150
3.190
3.140
­
­
­
­
­
­
­
­

OPR
5
5.364
5.142
5.295
5.213
5.345
­
­
­
­
­

Nickel
5
IPR
3
3.100
3.190
3.220
3.220
2.750
2.820
2.670
2.830
­
­

OPR
3
2.830
4.7761
2.680
2.837
2.970
3.075
3.092
3.036
3.018
2.950
Nickel
6
IPR
3.078
3.011
3.179
3.157
3.139
3.194
3.273
­
­
­
­

Nickel
7
IPR
2
1.924
1.933
1.934
1.892
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
59
OPR
2
1.878
1.862
1.798
­
­
­
­
­
­
­

Nickel
8
IPR
0.1253
0.130
0.120
0.128
0.123
­
­
­
­
­
­

OPR
0.1253
0.126
0.153
0.127
­
­
­
­
­
­
­

Selenium
1
IPR
0.53
0.310
0.516
0.503
0.578
­
­
­
­
­
­

OPR
2.55
3.190
­
­
­
­
­
­
­
­
­

OPR
5.053
6.150
­
­
­
­
­
­
­
­
­

Selenium
2
IPR
3
2.749
2.719
2.974
2.412
­
­
­
­
­
­

OPR
3
3.041
2.529
2.752
3.796
2.604
2.551
2.694
2.552
31.520
1
­

Selenium
3
IPR
2
2.132
2.062
2.092
2.175
­
­
­
­
­
­

OPR
2
1.983
2.008
2.307
­
­
­
­
­
­
­

Selenium
4
IPR
3
3.000
3.100
3.000
3.200
3.100
3.300
3.100
3.100
3.200
3.100
2.900
3.000
­
­
­
­
­
­
­
­

OPR
5
5.419
5.475
5.274
5.421
5.419
­
­
­
­
­

Selenium
5
IPR
3
2.790
3.070
2.800
3.130
2.410
2.410
2.260
2.630
­
­

OPR
3
2.900
2.260
2.123
1.850
3.649
3.748
3.099
2.484
2.930
3.670
Selenium
62
IPR
15.0123
16.190
16.041
14.993
16.199
15.334
16.012
­
­
­
­

Selenium
7
IPR
103
9.591
9.692
9.606
9.440
­
­
­
­
­
­

OPR
103
9.296
9.362
8.964
­
­
­
­
­
­
­

Selenium
8
IPR
2.5
2.640
2.623
2.516
2.511
­
­
­
­
­
­

OPR
2.5
2.504
2.796
2.649
­
­
­
­
­
­
­

Silver
1
IPR
0.1
0.100
0.107
0.106
0.101
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
60
OPR
0.3
0.258
­
­
­
­
­
­
­
­
­

OPR
0.553
0.547
­
­
­
­
­
­
­
­
­

Silver
2
IPR
0.3
0.310
0.308
0.314
0.317
­
­
­
­
­
­

OPR
0.3
0.302
0.307
0.282
0.319
0.285
0.310
0.275
0.280
0.287
0.295
0.288
0.278
0.285
0.291
0.308
­
­
­
­
­

Silver
3
IPR
0.1
0.086
0.085
0.085
0.086
­
­
­
­
­
­

OPR
0.1
0.084
0.086
0.090
­
­
­
­
­
­
­

Silver
42
IPR
0.3
0.280
0.270
0.320
0.290
0.280
0.290
0.390
0.290
0.300
0.300
0.300
0.300
­
­
­
­
­
­
­
­

OPR
13
1.017
1.026
1.020
­
­
­
­
­
­
­

OPR
53
5.240
5.199
5.154
5.336
5.333
­
­
­
­
­

Silver
5
IPR
0.3
0.337
0.342
0.363
0.352
0.343
0.350
0.340
0.338
­
­

OPR
0.3
0.373
0.392
0.375
0.363
0.366
0.370
0.373
0.368
0.372
­

OPR
13
0.681
­
­
­
­
­
­
­
­
­

Silver
6
IPR
0.3
0.325
0.330
0.311
0.315
0.330
0.312
­
­
­
­

Silver
7
IPR
0.2
0.205
0.204
0.198
0.202
­
­
­
­
­
­

OPR
0.2
0.196
0.205
0.198
­
­
­
­
­
­
­

Silver
8
IPR
0.125
0.138
0.146
0.133
0.122
­
­
­
­
­
­

OPR
0.125
0.130
0.131
0.128
­
­
­
­
­
­
­

Thallium
12
IPR
0.05
0.055
0.050
0.055
0.048
­
­
­
­
­
­

OPR
0.05
0.050
0.043
­
­
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
61
Thallium
2
IPR
0.06
0.080
0.079
0.084
0.078
­
­
­
­
­
­

OPR
0.06
0.056
0.058
0.053
0.061
0.058
0.054
0.049
0.051
0.043
0.055
0.040
0.042
0.036
0.041
­
­
­
­
­
­

Thallium
3
IPR
0.05
0.051
0.051
0.051
0.052
­
­
­
­
­
­

OPR
0.05
0.051
0.049
0.055
­
­
­
­
­
­
­

Thallium
4
IPR
0.06
0.056
0.058
0.058
0.058
0.061
0.057
0.058
0.059
0.057
0.060
0.055
0.056
­
­
­
­
­
­
­
­

OPR
53
4.679
4.724
4.655
4.629
4.549
­
­
­
­
­

Thallium
5
IPR
0.06
0.078
0.075
0.081
0.085
0.068
0.071
0.070
0.075
­
­

OPR
0.06
0.073
0.1101
0.080
0.080
0.086
0.065
0.063
0.067
0.063
0.063
Thallium
6
IPR
0.06
0.064
0.064
0.057
0.055
0.055
0.050
­
­
­
­

Thallium
7
IPR
0.04
0.042
0.041
0.042
0.040
­
­
­
­
­
­

OPR
0.04
0.040
0.042
0.044
­
­
­
­
­
­
­

Thallium
8
IPR
0.05
0.047
0.052
0.048
0.050
­
­
­
­
­
­

OPR
0.05
0.053
0.057
0.055
­
­
­
­
­
­
­

Zinc
1
IPR
1
0.899
0.945
0.857
0.916
­
­
­
­
­
­

OPR
1.05
0.964
1.030
­
­
­
­
­
­
­
­

Zinc
2
IPR
1.5
2.213
1.915
1.658
1.938
­
­
­
­
­
­

OPR
1.5
1.727
1.728
2.034
1.584
2.231
1.371
1.374
1.420
1.172
1.278
1.353
1.309
­
­
­
­
­
­
­
­

Zinc
3
IPR
1
1.026
1.059
1.040
1.029
­
­
­
­
­
­
Table
4:
Initial
and
Ongoing
Precision
and
Recovery
Samples
Analyte
Lab
Type
Spike
Amount
(
µ
g/
L)

1
2
3
4
5
6
7
8
9
10
B­
62
OPR
1
1.047
1.055
1.007
­
­
­
­
­
­
­

Zinc
4
IPR
1.5
1.790
2.200
2.100
1.600
1.630
1.730
1.690
1.580
1.580
1.520
1.730
1.560
­
­
­
­
­
­
­
­

OPR
53
5.128
4.944
5.081
5.064
5.214
­
­
­
­
­

Zinc
52
IPR
1.5
1.610
1.670
1.620
1.650
2.570
2.950
3.030
3.030
­
­

OPR
1.5
1.220
2.360
1.258
1.280
1.094
1.165
1.205
1.263
1.180
­

OPR
53
6.039
­
­
­
­
­
­
­
­
­

Zinc
6
IPR
1.525
1.625
1.386
1.314
1.246
1.262
1.418
­
­
­
­

Zinc
7
IPR
1
0.992
0.979
0.994
0.977
­
­
­
­
­
­

OPR
1
0.942
0.973
1.014
­
­
­
­
­
­
­

Zinc
8
IPR
0.5
0.585
0.544
0.647
0.539
­
­
­
­
­
­

OPR
0.5
1.9661,
4
0.551
0.606
­
­
­
­
­
­
­

1
This
data
point
was
determined
to
be
an
outlier
using
Grubbs
outlier
test.

2
This
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.

3
These
samples
were
not
spiked
at
one
to
five
times
the
ML.

4
After
contacting
the
laboratory,
it
was
determined
that
the
elevated
concentration
was
probably
due
to
contamination.
B­
63
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
Sb
1
MB
0.000
0.064
0.000
0.000
0.031
0.004
0.024
0.082
0.242
0.076
2
MB
­
0.006
­
0.009
­
0.016
­
0.019
0.010
0.012
­
0.004
­
0.010
­
0.005
­
0.018
­
0.014
­
0.014
­
­
­
­
­
­
­
­
2
CB
­
0.006
0.000
­
0.012
­
0.018
­
0.014
­
0.012
­
0.012
­
0.008
­
0.003
­
0.005
0.001
­
0.002
­
0.005
0.006
­
0.002
0.019
­
­
­
­

3
MB
0.004
0.006
0.009
­
­
­
­
­
­
­
3
CB
0.001
0.000
0.005
0.001
0.000
0.001
0.001
­
0.001
­
0.001
0.001
0.007
0.001
0.000
­
0.000
­
­
­
­
­
­

4
MB
0.026
0.020
­
­
­
­
­
­
­
­

CB
0.011
0.017
0.017
0.017
0.019
0.013
0.053
0.035
0.018
­

5
MB
0.028
­
­
­
­
­
­
­
­
­

CB
0.053
­
0.015
­
0.014
­
0.024
­
0.009
­
0.010
­
0.007
­
0.017
­
0.009
­

61
CB
0.043
0.030
0.022
0.013
­
­
­
­
­
­

7
MB
0.023
­
0.005
­
0.000
­
­
­
­
­
­
­

CB
0.000
0.002
0.002
0.005
0.027
0.005
­
­
­
­

8
MB
0.026
­
0.010
0.006
­
­
­
­
­
­
­

CB
0.008
0.034
0.014
0.033
­
0.008
0.002
0.022
­
­
­

Cd
1
MB
0.000
0.000
0.004
0.000
0.008
0.000
0.000
0.000
0.000
0.000
2
MB
0.011
­
0.001
0.007
0.006
0.016
0.019
­
0.016
­
0.025
0.012
­
0.003
­
0.014
­
0.029
­
0.004
0.016
­
­
­
­
­
­

CB
0.000
0.047
0.006
0.008
0.018
0.006
0.008
0.024
0.011
­
0.004
0.018
­
0.023
­
0.005
0.028
0.011
0.013
­
0.034
­
0.002
0.013
­
0.007
0.003
­
­
­
­
­
­
­
­
­
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
64
3
MB
­
0.001
0.001
0.004
­
­
­
­
­
­
­

CB
0.001
0.000
0.001
0.000
0.002
0.002
0.000
0.002
0.002
­
0.001
4
MB
0.004
0.004
­
­
­
­
­
­
­
­

CB
0.008
0.013
0.019
0.019
0.019
­
0.130
­
0.008
0.022
0.005
­

51
MB
0.292
­
­
­
­
­
­
­
­
­

CB
0.067
0.069
0.058
0.068
0.035
0.038
0.030
0.064
0.028
­

6
CB
0.010
0.016
0.011
0.009
­
­
­
­
­
­

7
MB
­
0.037
­
0.034
­
0.033
­
­
­
­
­
­
­

CB
­
0.012
­
0.033
­
0.031
­
0.029
­
0.032
­
0.022
­
­
­
­

8
MB
­
0.004
­
0.021
0.012
­
­
­
­
­
­
­

CB
­
0.024
­
0.023
­
0.015
­
0.023
­
0.009
0.000
0.006
­
­
­

Cu
11
MB
0.045
0.042
0.037
0.041
0.000
0.057
0.050
0.054
0.068
0.048
2
MB
0.001
0.018
­
0.008
­
0.007
­
0.032
­
0.037
0.056
0.016
0.034
0.020
0.002
0.009
0.004
­
0.018
­
­
­
­
­
­

CB
­
0.001
0.010
0.048
­
0.040
­
0.041
­
0.006
0.000
0.031
­
0.006
0.004
­
0.004
0.042
0.001
­
­
­
­
­
­
­

3
MB
­
0.001
­
0.004
­
0.001
­
­
­
­
­
­
­

CB
­
0.002
0.005
­
0.004
­
0.003
­
0.004
­
0.002
0.000
­
0.001
­
0.001
­
0.002
­
0.002
­
0.004
­
0.003
­
0.001
­
­
­
­
­
­

4
MB
0.003
2.127
­
­
­
­
­
­
­
­

CB
0.012
0.005
0.006
0.001
0.014
0.015
0.014
0.018
0.006
­

5
MB
6.364
­
­
­
­
­
­
­
­
­

CB
­
0.073
­
0.079
­
0.099
­
0.109
­
0.059
­
0.061
­
0.058
­
0.063
­
0.109
­
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
65
6
CB
0.076
0.084
0.055
0.066
­
­
­
­
­
­

7
MB
­
0.006
­
0.007
­
0.006
­
­
­
­
­
­
­

CB
0.001
­
0.009
­
0.009
­
0.009
­
0.006
0.001
­
­
­
­

8
MB
­
0.004
­
0.003
0.008
­
­
­
­
­
­
­

CB
0.001
0.000
­
0.002
0.002
0.002
0.003
0.006
­
­
­

Pb
11
MB
0.032
0.011
0.030
0.028
0.000
0.010
0.011
0.015
0.024
0.010
2
MB
­
0.002
­
0.001
­
0.000
­
0.022
0.001
­
0.002
­
0.000
­
0.000
­
0.013
­
0.016
­
0.001
­
0.015
­
0.004
­
­
­
­
­
­
­

CB
­
0.003
0.001
­
0.004
0.000
­
0.001
0.002
­
0.005
­
0.007
0.010
­
0.001
3
MB
­
0.001
­
0.002
­
0.002
­
­
­
­
­
­
­

CB
­
0.001
­
0.001
­
0.002
­
0.002
­
0.001
­
0.001
­
0.004
­
0.004
­
0.003
­
0.001
­
0.002
­
0.002
­
0.002
­
0.001
­
­
­
­
­
­

4
MB
0.003
0.017
­
­
­
­
­
­
­
­

CB
0.000
0.004
0.004
­
0.001
­
0.003
0.001
0.008
0.005
0.001
­

5
MB
0.859
­
­
­
­
­
­
­
­
­

CB
0.028
­
0.085
0.024
0.023
0.018
0.026
0.029
0.018
0.029
­

6
CB
0.016
0.018
0.016
0.020
­
­
­
­
­
­

7
MB
0.032
0.001
0.002
­
­
­
­
­
­
­

CB
0.002
0.002
0.004
0.002
0.002
0.004
­
­
­
­

8
MB
­
0.006
­
0.006
0.002
­
­
­
­
­
­
­

CB
­
0.004
­
0.001
­
0.007
­
0.007
­
0.005
­
0.004
0.001
­
­
­

Ni
1
MB
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
21
MB
0.051
0.797
0.070
0.012
0.378
0.001
0.006
0.042
­
0.006
0.038
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
66
­
0.006
0.004
­
0.010
1.958
­
­
­
­
­
­

CB
0.011
­
0.016
­
0.002
­
0.011
­
0.014
­
0.011
­
0.004
­
0.006
­
0.012
­
0.017
­
0.061
­
0.109
­
0.002
0.009
0.015
0.010
­
0.016
­
0.005
0.013
0.054
0.00
­
­
­
­
­
­
­
­
­

3
MB
­
0.002
0.001
­
0.002
­
­
­
­
­
­
­

CB
0.001
0.003
0.003
0.002
0.001
0.001
0.002
0.000
­
0.000
0.002
­
0.002
­
0.001
0.000
­
0.001
­
­
­
­
­
­

4
MB
0.002
0.046
­
­
­
­
­
­
­
­

CB
0.004
0.006
0.002
0.000
0.005
0.000
0.002
0.003
­
0.001
­

5
MB
1.168
­
­
­
­
­
­
­
­
­

CB
0.028
­
0.122
­
0.024
­
0.025
­
0.086
­
0.112
­
0.165
­
0.000
­
0.030
­

6
CB
0.051
0.130
0.039
0.040
­
­
­
­
­
­

7
MB
0.002
0.009
0.010
­
­
­
­
­
­
­

CB
0.013
0.008
0.009
0.009
0.012
0.012
­
­
­
­

8
MB
0.001
0.003
0.010
­
­
­
­
­
­
­

CB
0.005
0.006
0.003
0.005
0.006
0.004
0.005
­
­
­

Se
1
MB
0.000
0.000
0.096
0.019
0.000
0.000
0.092
0.000
0.000
0.153
2
MB
­
0.187
­
0.446
0.519
0.180
­
0.161
0.132
0.071
0.066
0.127
­

CB
0.112
­
0.190
0.004
0.210
­
0.163
­
0.280
­
0.242
­
0.322
­
0.138
­
0.058
­
0.316
0.123
0.516
0.108
0.443
0.059
­
­
­
­

3
MB
­
0.036
­
0.083
­
0.037
­
­
­
­
­
­
­

CB
­
0.066
­
0.071
­
0.032
­
0.092
­
0.000
­
0.088
­
0.047
­
0.145
­
0.007
­
0.015
4
MB
­
0.024
­
0.037
­
­
­
­
­
­
­
­
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
67
CB
­
0.044
­
0.025
0.051
0.001
0.035
0.017
0.014
0.071
0.047
­
0.028
5
MB
­
0.827
­
­
­
­
­
­
­
­
­

CB
­
0.417
0.012
­
0.347
0.118
­
0.126
­
1.162
0.467
0.505
­
0.210
­

61
CB
22.166
19.771
20.057
18.555
­
­
­
­
­
­

7
MB
0.026
0.016
­
0.027
­
­
­
­
­
­
­

CB
0.099
­
0.034
­
0.012
­
0.055
0.037
0.095
­
­
­
­

8
MB
0.111
0.109
0.103
­
­
­
­
­
­
­

CB
0.036
0.131
0.116
0.063
0.052
0.151
0.032
­
­
­

Ag
1
MB
0.011
0.015
0.017
0.012
0.014
0.000
0.036
0.034
0.144
0.026
2
MB
­
0.000
­
0.001
­
0.002
­
0.004
0.000
­
0.002
­
0.001
­
0.004
­
0.000
0.002
0.000
0.002
0.004
­
0.004
­
0.002
­
0.000
0.001
0.003
­
0.000
­

CB
0.002
0.000
0.000
0.003
­
0.001
0.000
­
0.003
­
0.000
0.000
0.000
0.001
0.005
0.003
­
0.001
0.000
0.001
0.000
0.001
­
0.000
0.001
­
0.000
­
0.002
­
0.003
­
0.001
0.002
0.010
­
­
­
­

3
MB
­
0.003
­
0.004
­
0.002
­
­
­
­
­
­
­

CB
­
0.001
­
0.002
­
0.002
­
0.001
­
0.001
­
0.001
­
0.002
­
0.000
­
0.002
­
0.001
41
MB
0.005
0.002
0.003
0.004
­
­
­
­
­
­

CB
0.003
0.009
0.009
0.003
0.002
0.000
0.003
0.003
0.002
­

5
MB
0.391
­
­
­
­
­
­
­
­
­

CB
­
0.464
0.049
0.048
0.048
0.043
0.046
0.044
0.048
0.045
­

6
CB
0.010
0.007
0.014
0.012
­
­
­
­
­
­

7
MB
0.003
0.002
0.002
­
­
­
­
­
­
­

CB
0.004
0.006
0.007
0.008
0.009
0.028
­
­
­
­
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
68
8
MB
0.001
0.002
0.005
­
­
­
­
­
­
­

CB
0.002
0.001
0.001
0.005
0.017
0.004
0.006
­
­
­

Tl
11
MB
0.000
0.000
0.004
0.002
0.000
0.002
0.001
0.001
0.000
0.000
2
MB
­
0.007
­
0.001
0.002
­
0.008
­
0.010
­
0.009
­
0.001
0.002
0.002
0.000
­
0.001
0.001
0.001
0.004
0.004
0.003
0.001
0.002
­
­

CB
0.003
0.004
0.002
­
0.008
0.002
0.003
­
0.001
­
0.003
­
0.007
­
0.007
0.003
­
0.007
­
0.007
­
0.010
­
0.009
­
0.009
­
0.008
­
0.006
­
0.005
0.002
0.014
0.000
0.002
­
­
­
­
­
­
­

3
MB
0.000
0.000
0.001
­
­
­
­
­
­
­

CB
­
0.000
0.001
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.002
4
MB
0.002
­
0.001
­
­
­
­
­
­
­
­

CB
­
0.001
0.002
0.000
­
0.001
0.000
0.000
­
0.001
0.001
0.002
­

5
MB
0.015
­
­
­
­
­
­
­
­
­

CB
0.003
0.004
­
0.006
0.004
­
0.006
­
0.004
­
0.004
­
0.006
0.001
­

6
CB
0.005
0.007
0.005
0.006
­
­
­
­
­
­

7
MB
0.000
0.000
0.001
­
­
­
­
­
­
­

CB
0.010
0.005
0.005
0.004
0.004
0.006
­
­
­
­

8
MB
­
0.001
0.002
0.003
­
­
­
­
­
­
­

CB
0.006
0.004
0.005
­
0.001
0.004
0.000
0.009
­
­
­

Zn
1
MB
0.111
0.096
0.123
0.179
0.008
0.076
0.047
0.009
0.012
0.067
2
MB
0.012
0.007
­
0.002
­
0.010
­
0.018
­
0.030
0.098
0.020
0.006
0.019
0.002
0.030
0.026
0.033
­
­
­
­
­
­

CB
­
0.025
­
0.028
­
0.016
­
0.022
0.004
­
0.007
0.001
­
0.029
0.012
0.054
Table
5:
Method
Blank
(
MB)
and
Calibration
Blank
(
CB)
Results
Analyte
Lab
Type
1
2
3
4
5
6
7
8
9
10
B­
69
­
0.012
0.018
0.040
­
0.012
­
0.004
0.003
­
0.012
­
0.025
0.069
­
0.016
0.10
­
­
­
­
­
­
­
­
­

3
MB
­
0.003
­
0.002
­
0.009
­
­
­
­
­
­
­

CB
­
0.006
­
0.021
­
0.018
0.017
­
0.004
­
0.005
­
0.009
­
0.010
­
0.009
­
0.008
­
0.008
­
0.011
­
0.013
­
0.003
­
­
­
­
­
­

4
MB
­
0.245
2.127
­
­
­
­
­
­
­
­

CB
­
0.161
­
0.157
­
0.429
­
0.204
­
0.258
­
0.387
­
0.062
­
0.069
0.043
­

51
MB
11.418
­
­
­
­
­
­
­
­
­

CB
0.056
­
0.006
­
0.017
­
0.000
0.054
0.035
­
0.012
­
0.009
0.017
­

6
CB
0.248
0.178
0.168
0.138
­
­
­
­
­
­

7
MB
0.016
­
0.015
­
0.017
­
­
­
­
­
­
­

CB
­
0.018
­
0.014
­
0.015
­
0.009
0.003
0.023
­
­
­
­

8
MB
­
0.020
0.040
0.759
­
­
­
­
­
­
­

CB
0.055
0.066
­
0.070
­
0.059
­
0.045
0.002
­
0.185
­
­
­

1This
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Draft
­
December
2000
B­
70
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
Sb
1
SRM
0.23
0.239
­
­
­
­

54.1
58.5001
­
­
­
­

Sb
2
QCS
10
10.5701
10.420
10.190
­
­

SRM
54.1
56.4701
58.7401
54.1001
53.560
­

Sb
3
SRM
54.1
55.9721
­
­
­
­

Sb
4
QCS
0.06
0.081
0.079
0.068
0.095
0.110
30
27.777
­
­
­
­

40
37.892
­
­
­
­

SRM
54.1
50.316
51.975
51.946
52.089
51.43
4
Sb
5
QCS
10
10.8941
11.0071
­
­
­

20
21.8001
­
­
­
­

50
53.2611
54.7011
56.5001
57.3001
­

100
104.3401
­
­
­
­

200
208.7141
212.4021
­
­
­

SRM
54.1
54.4201
55.0181
52.7001
55.6001
­

Sb
62
SRM
54.1
52.741
54.868
­
­
­

Sb
7
SRM
0.23
0.249
0.279
0.262
­
­

54.1
52.826
53.448
53.966
­
­

Sb
8
QCS
0.2
0.211
­
­
­
­

10
10.820
10.810
­
­
­

SRM
54.1
57.750
­
­
­
­

Cd
1
SRM
0.012
0.000
­
­
­
­

6.47
6.110
­
­
­
­

Cd
2
QCS
5
5.129
­
­
­
­

10
10.3101
10.240
9.917
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
B­
71
Draft
­
December
2000
SRM
6.47
5.741
5.791
6.246
6.416
­

Cd
3
SRM
6.47
6.3351
­
­
­
­

Cd
4
QCS
0.3
0.317
0.319
0.308
0.325
0.317
2
2.137
­
­
­
­

30
30.421
­
­
­
­

SRM
6.47
6.059
6.195
6.123
6.236
6.148
Cd
52
QCS
10
10.358
10.041
­
­
­

20
20.3001
­
­
­
­

50
51.3771
50.3161
53.5001
51.9001
­

100
100.6491
­
­
­
­

200
198.2061
193.7441
­
­
­

SRM
6.47
6.162
6.166
5.890
6.210
­

Cd
6
SRM
6.47
6.360
6.413
­
­
­

Cd
7
SRM
0.012
­
0.013
­
0.017
­
0.022
­
­

6.47
5.923
5.888
5.941
­
­

Cd
8
QCS
0.05
0.056
­
­
­
­

10
9.969
9.985
­
­
­

SRM
6.47
5.909
­
­
­
­

Cu
12
SRM
1.81
1.760
­
­
­
­

20.5
20.900
­
­
­
­

Cu
2
QCS
5
5.184
­
­
­
­

10
10.710
12.260
10.290
­
­

SRM
20.5
20.350
23.860
21.500
­
­

Cu
3
SRM
20.5
21.164
­
­
­
­

Cu
4
QCS
0.6
0.681
0.658
0.701
0.666
0.695
30
31.751
­
­
­
­

80
86.576
­
­
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
Draft
­
December
2000
B­
72
SRM
20.5
22.611
22.986
23.072
23.219
22.51
4
Cu
5
QCS
10
10.041
9.930
­
­
­

20
19.500
­
­
­
­

50
49.1841
49.1471
50.8001
50.8001
­

100
96.1731
­
­
­
­

200
198.1061
195.2991
­
­
­

SRM
20.5
20.322
20.322
18.500
19.900
­

Cu
6
SRM
20.5
20.288
19.486
­
­
­

Cu
7
SRM
1.81
2.068
2.004
1.966
­
­
7
20.5
19.554
18.984
18.328
­
­

Cu
8
QCS
0.05
0.051
­
­
­
­
8
10
9.505
9.673
­
­
­

SRM
20.5
18.905
­
­
­
­

Pb
12
SRM
0.086
0.050
­
­
­
­

18.15
18.400
­
­
­
­

Pb
2
QCS
5
5.097
­
­
­
­

10
10.110
9.674
­
­
­

SRM
18.15
11.620
14.070
­
­
­

Pb
3
SRM
18.15
18.537
­
­
­
­

Pb
4
QCS
0.15
0.164
0.163
0.155
0.164
0.156
5
5.146
­
­
­
­

30
30.648
­
­
­
­

SRM
18.15
18.329
17.841
17.470
17.473
17.92
3
Pb
5
QCS
10
9.893
9.968
­
­
­

20
20.000
­
­
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
B­
73
Draft
­
December
2000
50
50.3061
50.7441
51.1001
51.5001
­

100
98.5371
­
­
­
­

200
179.9931
180.4811
­
­
­

SRM
18.15
16.446
16.594
14.800
14.800
­

Pb
6
SRM
18.15
19.066
20.026
­
­
­

Pb
7
SRM
0.086
0.079
0.081
0.079
­
­

18.15
0.9253
0.9223
0.9203
­
­

Pb
8
QCS
0.05
0.050
­
­
­
­

10
10.084
10.241
­
­
­

SRM
18.15
17.671
­
­
­
­

Ni
1
SRM
0.67
0.697
­
­
­
­

58.1
57.9001
­
­
­
­

Ni
22
QCS
5
5.428
­
­
­
­

10
10.810
9.935
9.693
­
­

SRM
58.1
60.0701
59.760
52.890
56.390
­

Ni
3
SRM
58.1
53.394
­
­
­
­

Ni
4
QCS
3
2.884
2.954
2.925
2.979
2.895
30
30.406
­
­
­
­

40
42.645
­
­
­
­

SRM
58.1
55.674
55.209
55.925
56.626
55.59
9
Ni
5
QCS
10
9.970
10.151
­
­
­

20
19.600
­
­
­
­

50
49.2841
48.9301
51.9001
52.4001
­

100
96.6891
­
­
­
­

200
201.0601
197.9361
­
­
­

SRM
58.1
54.5251
55.8501
51.4001
52.8001
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
Draft
­
December
2000
B­
74
Ni
6
SRM
58.1
57.211
54.236
­
­
­

Ni
7
SRM
0.67
0.754
0.700
0.702
­
­

58.1
55.707
54.287
52.328
­
­

Ni
8
QCS
0.05
0.054
­
­
­
­

10
9.786
9.893
­
­
­

SRM
58.1
55.2891
­
­
­
­

Se
1
SRM
11.43
12.700
­
­
­
­

Se
2
QCS
10
10.680
10.340
9.347
­
­

SRM
11.43
10.980
11.810
6.311
­
­

Se
3
SRM
11.43
11.562
­
­
­
­

Se
4
QCS
3
3.256
3.206
3.243
3.196
3.305
30
31.679
­
­
­
­

40
44.394
­
­
­
­

SRM
11.43
12.102
12.387
12.014
12.439
12.05
5
Se
5
QCS
20
19.000
­
­
­
­

50
47.9231
48.1351
49.7461
52.2021
­

100
93.8781
­
­
­
­

200
221.2311
218.3301
­
­
­

250
253.0001
264.0001
­
­
­

SRM
11.43
9.647
11.297
9.400
9.860
­

Se
62
SRM
11.43
13.272
11.353
­
­
­

Se
7
SRM
11.43
9.706
9.437
9.169
­
­

Se
8
QCS
1
1.032
­
­
­
­

10
10.411
10.148
­
­
­

SRM
11.43
10.187
­
­
­
­

Ag
1
SRM
1.27
1.050
­
­
­
­
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
B­
75
Draft
­
December
2000
Ag
2
QCS
5
5.009
­
­
­
­

10
9.990
10.260
10.500
10.010
10.70
0
SRM
1.270
1.182
1.295
1.184
1.222
1.170
1.261
­
­
­
­

Ag
3
SRM
1.270
1.193
1.309
1.292
1.319
1.311
1.301
1.329
1.335
1.302
­

Ag
42
QCS
0.3
0.313
0.315
0.312
0.302
0.323
1
1.084
­
­
­
­

30
30.7731
31.0601
32.2401
­
­

Ag
5
QCS
10
10.120
10.011
­
­
­

20
20.3001
­
­
­
­

50
47.5621
47.4531
52.0001
51.6001
­

100
92.1371
­
­
­
­

200
180.6551
176.6021
­
­
­

SRM
1.27
1.304
1.290
1.200
1.230
­

Ag
6
SRM
1.27
1.416
1.345
­
­
­

Ag
7
SRM
1.27
1.261
1.261
1.246
­
­

Ag
8
QCS
0.05
0.052
­
­
­
­

10
9.880
9.935
­
­
­

SRM
1.27
1.273
­
­
­
­

Tl
12
SRM
7.28
7.470
­
­
­
­

Tl
2
QCS
5
5.027
­
­
­
­

10
10.2201
10.290
9.816
11.210
­

SRM
7.28
4.956
5.863
5.856
5.791
6.449
Tl
3
SRM
7.28
7.300
­
­
­
­

Tl
4
QCS
0.06
0.056
0.053
0.050
0.055
0.052
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
Draft
­
December
2000
B­
76
4
3.760
­
­
­
­

30
26.893
­
­
­
­

SRM
7.28
6.770
6.683
6.442
6.503
6.575
Tl
5
QCS
10
10.6001
10.5881
­
­
­

20
21.2001
­
­
­
­

50
52.8901
53.5951
54.5001
54.5001
­

100
103.7471
­
­
­
­

200
187.1401
187.6401
­
­
­

SRM
7.28
7.0931
6.4801
6.4601
7.140
­

Tl
6
SRM
7.28
7.567
7.818
­
­
­

Tl
7
SRM
7.28
7.959
8.073
8.171
­
­

Tl
8
QCS
0.02
0.026
­
­
­
­

10
10.075
10.124
­
­
­

SRM
7.28
7.136
­
­
­
­

Zn
1
SRM
0.93
0.926
­
­
­
­

72.48
71.1001
­
­
­
­

Zn
2
QCS
5
5.618
­
­
­
­

10
11.020
9.903
9.440
­
­

SRM
72.48
67.230
69.510
70.960
67.010
­

Zn
3
SRM
72.48
78.480
­
­
­
­

Zn
4
QCS
1.5
1.590
1.285
1.354
1.353
1.410
30
30.354
­
­
­
­

100
107.537
­
­
­
­

SRM
72.48
71.747
72.471
72.091
73.360
70.78
9
Zn
52
QCS
10
9.941
9.943
­
­
­

20
19.200
­
­
­
­
Table
6:
Standard
Reference
Material
(
SRM)
and
Quality
Control
Standard
(
QCS)
Results
Analyte
Lab
Type
Spike
Conc.
(
µ
g/
L)
Amount
(
µ
g/
L)

1
2
3
4
5
50
48.7921
48.9681
51.1001
50.8001
­

100
95.1671
­
­
­
­

200
222.5701
220.5771
­
­
­

SRM
72.48
66.7381
67.5831
57.3001
66.1001
­

Zn
6
SRM
72.48
67.690
70.933
­
­
­

Zn
7
SRM
0.93
0.947
0.889
0.926
­
­

72.48
61.430
59.953
58.124
­
­

Zn
8
QCS
0.2
0.171
­
­
­
­

10
9.718
9.841
­
­
­
8
SRM
72.48
68.259
­
­
­
­

1
The
sample
concentration
was
greater
than
the
high
calibration
standard.
2
The
laboratory's
data
package
was
rejected
using
the
Youden
outlying
laboratory
ranking
test.
3
The
laboratory
used
bismuth
as
the
internal
standard
for
lead.
The
SRM
contained
bismuth,
causing
poor
recoveries
for
lead.
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Draft
­
December
2000
B­
78
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Sb
1
10.710
10
107
11.000
10
110
26.500
25
106
26.400
25
106
26.100
25
104
Sb
2
10.150
10
102
10.190
10
102
9.604
10
96
4.912
5
98
4.947
5
99
4.885
5
98
4.762
5
95
4.827
5
97
10.060
10
101
9.806
10
98
5.068
5
101
Sb
3
0.246
0.25
99
0.254
0.25
102
0.259
0.25
104
0.249
0.25
99
0.268
0.25
107
0.255
0.25
102
0.258
0.25
103
0.255
0.25
102
0.261
0.25
104
0.253
0.25
101
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
79
Draft
­
December
2000
0.251
0.25
100
0.261
0.25
104
1.920
2
96
1.891
2
95
Sb
4
27.068
30
90
27.307
30
91
Sb
5
1.043
1
104
1.047
1
105
1.040
1
104
1.010
1
101
1.008
1
101
1.038
1
104
1.200
1
120
Grubbs
Outlier
1.028
1
103
1.034
1
103
Sb
7
19.677
20
98
19.868
20
99
20.014
20
100
20.308
20
102
20.433
20
102
20.708
20
104
20.833
20
104
Sb
8
9.890
10
99
9.845
10
98
9.867
10
99
9.973
10
100
9.585
10
96
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
80
9.413
10
94
9.836
10
98
Cd
1
9.970
10
100
10.200
10
102
25.500
25
102
25.000
25
100
25.900
25
104
Cd
2
9.972
10
100
10.150
10
102
10.180
10
102
10.000
10
100
10.090
10
101
10.010
10
100
9.763
10
98
4.901
5
98
4.930
5
99
4.930
5
99
4.769
5
95
4.762
5
95
10.130
10
101
9.873
10
99
9.677
10
97
5.037
5
101
Cd
3
0.245
0.25
98
0.254
0.25
101
0.253
0.25
101
0.258
0.25
103
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
81
Draft
­
December
2000
0.253
0.25
101
0.255
0.25
102
0.251
0.25
101
0.252
0.25
101
0.250
0.25
100
0.388
0.4
97
Cd
4
31.475
30
105
31.461
30
105
Cd
5
1.040
1
104
Youden
Outlying
Laboratory1
1.005
1
100
1.039
1
104
1.080
1
108
1.033
1
103
1.030
1
103
1.020
1
102
1.009
1
101
1.008
1
101
Cd
7
20.237
20
101
20.228
20
101
20.351
20
102
20.566
20
103
20.846
20
104
20.969
20
105
20.930
20
105
Cd
8
2.530
2.5
101
2.415
2.5
97
2.529
2.5
101
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
82
2.459
2.5
98
2.392
2.5
96
2.394
2.5
96
2.524
2.5
101
Cu
1
10.100
10
101
Youden
Outlying
Laboratory1
10.100
10
101
25.400
25
102
25.500
25
102
25.500
25
102
Cu
2
24.510
25
98
23.070
25
92
23.660
25
95
23.450
25
94
25.370
25
101
25.410
25
102
27.750
25
111
9.580
10
96
24.620
25
98
25.100
25
100
28.000
25
112
9.849
10
98
Cu
3
0.254
0.25
102
0.256
0.25
102
0.264
0.25
106
0.255
0.25
102
0.275
0.25
110
0.241
0.25
96
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
83
Draft
­
December
2000
0.234
0.25
93
0.234
0.25
94
0.242
0.25
97
0.265
0.25
106
0.265
0.25
106
0.267
0.25
107
1.949
2
97
2.024
2
101
Cu
4
32.279
30
108
32.902
30
110
Cu
5
1.297
1
130
1.218
1
122
1.431
1
143
Grubbs
Outlier
0.983
1
98
0.978
1
98
0.989
1
99
0.975
1
98
1.230
1
123
0.938
1
94
Cu
7
19.714
20
99
19.239
20
96
18.965
20
95
18.811
20
94
18.458
20
92
18.495
20
92
18.647
20
93
Cu
8
2.401
2.5
96
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
84
2.326
2.5
93
2.430
2.5
97
2.363
2.5
95
2.283
2.5
91
2.256
2.5
90
2.485
2.5
99
Pb
1
9.970
10
100
Youden
Outlying
Laboratory1
10.200
10
102
25.000
25
100
24.700
25
99
25.500
25
102
Pb
2
9.996
10
100
9.945
10
99
9.859
10
99
9.855
10
99
9.990
10
100
10.020
10
100
9.469
10
95
9.933
10
99
9.994
10
100
9.699
10
97
Pb
3
0.244
0.25
98
0.251
0.25
101
0.250
0.25
100
0.252
0.25
101
0.255
0.25
102
0.252
0.25
101
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
85
Draft
­
December
2000
0.248
0.25
99
0.251
0.25
100
0.251
0.25
101
0.252
0.25
101
0.250
0.25
100
0.254
0.25
102
2.105
2
105
2.136
2
107
Pb
4
30.652
30
102
30.429
30
101
Pb
5
1.040
1
104
1.033
1
103
1.049
1
105
0.983
1
98
1.022
1
102
1.017
1
102
1.010
1
101
1.038
1
104
0.992
1
99
Pb
7
19.761
20
99
19.655
20
98
19.680
20
98
19.980
20
100
20.011
20
100
19.568
20
98
19.735
20
99
Pb
8
2.529
2.5
101
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
86
2.566
2.5
103
2.590
2.5
104
2.531
2.5
101
2.486
2.5
99
2.441
2.5
98
2.567
2.5
103
Ni
1
9.900
10
99
9.980
10
100
25.000
25
100
25.000
25
100
25.800
25
103
Ni
2
48.980
50
98
Youden
Outlying
Laboratory1
46.380
50
93
47.180
50
94
46.640
50
93
25.190
25
101
24.850
25
99
25.390
20
127
11.590
12.5
93
11.380
12.5
91
11.870
12.5
95
11.600
12.5
93
11.650
12.5
93
49.160
50
98
24.960
25
100
25.700
25
103
12.020
12.5
96
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
87
Draft
­
December
2000
9.591
10
96
Ni
3
0.240
0.25
96
0.251
0.25
100
0.258
0.25
103
0.257
0.25
103
0.238
0.25
95
0.239
0.25
96
0.230
0.25
92
0.230
0.25
92
0.228
0.25
91
0.258
0.25
103
0.259
0.25
104
0.246
0.25
98
4.729
5
95
4.767
5
95
Ni
4
32.182
30
107
30.912
30
103
Ni
5
4.544
5
91
4.565
5
91
4.730
5
95
5.059
5
101
4.948
5
99
4.436
5
89
4.397
5
88
4.831
5
97
5.099
5
102
Ni
7
20.076
20
100
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
88
19.200
20
96
18.907
20
95
18.592
20
93
18.231
20
91
18.308
20
92
18.435
20
92
Ni
8
2.378
2.5
95
2.463
2.5
99
2.442
2.5
98
2.396
2.5
96
2.325
2.5
93
2.367
2.5
95
2.487
2.5
99
Se
1
9.850
10
98
9.680
10
97
26.600
25
106
25.800
25
103
25.000
25
100
Se
2
49.330
50
99
51.440
50
103
51.220
50
102
24.720
25
99
23.630
25
95
23.940
25
96
25.200
25
101
23.560
25
94
48.520
50
97
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
89
Draft
­
December
2000
50.710
50
101
23.970
25
96
Se
3
4.937
5
99
5.303
5
106
5.358
5
107
5.167
5
103
5.015
5
100
5.485
5
110
5.453
5
109
5.146
5
103
5.313
5
106
2.013
2
101
Se
4
32.002
30
107
32.785
30
109
Se
5
4.295
5
86
3.818
5
76
3.420
5
68
Grubbs
Outlier
5.395
5
108
4.776
5
96
4.477
5
90
3.670
5
73
5.336
5
107
5.017
5
100
Se
7
20.077
20
100
19.217
20
96
19.175
20
96
19.097
20
95
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
90
18.731
20
94
18.596
20
93
18.885
20
94
Se
8
50.036
50
100
50.174
50
100
50.263
50
101
49.300
50
99
47.720
50
95
48.720
50
97
51.230
50
102
Ag
1
9.740
10
97
9.880
10
99
24.000
25
96
23.300
25
93
24.000
25
96
Ag
2
9.962
10
100
9.761
10
98
9.853
10
99
9.817
10
98
9.814
10
98
9.873
10
99
9.838
10
98
10.670
10
107
4.741
5
95
4.681
5
94
4.711
5
94
4.608
5
92
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
91
Draft
­
December
2000
4.592
5
92
10.330
10
103
9.972
10
100
10.030
10
100
10.110
10
101
10.590
10
106
4.805
5
96
10.260
10
103
Ag
3
0.253
0.25
101
0.260
0.25
104
0.258
0.25
103
0.258
0.25
103
0.257
0.25
103
0.262
0.25
105
0.263
0.25
105
0.258
0.25
103
0.258
0.25
103
0.946
1
95
Ag
4
5.073
5
101
Youden
Outlying
Laboratory1
5.108
5
102
5.066
5
101
30.922
30
103
31.352
30
105
Ag
5
1.036
1
104
1.030
1
103
1.028
1
103
1.030
1
103
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
92
1.040
1
104
1.042
1
104
1.080
1
108
1.007
1
101
1.027
1
103
Ag
7
20.338
20
102
20.426
20
102
20.296
20
101
20.491
20
102
20.535
20
103
20.685
20
103
20.689
20
103
Ag
8
2.550
2.5
102
2.484
2.5
99
2.483
2.5
99
2.475
2.5
99
2.462
2.5
98
2.447
2.5
98
2.553
2.5
102
Tl
1
9.910
10
99
Youden
Outlying
Laboratory1
10.100
10
101
25.700
25
103
25.000
25
100
25.700
25
103
Tl
2
9.925
10
99
9.962
10
100
9.954
10
100
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
93
Draft
­
December
2000
9.812
10
98
9.996
10
100
9.906
10
99
9.634
10
96
10.960
10
110
4.747
5
95
4.699
5
94
4.631
5
93
4.550
5
91
4.564
5
91
9.884
10
99
10.090
10
101
10.150
10
102
10.960
10
110
4.921
5
98
Tl
3
0.249
0.25
99
0.246
0.25
98
0.251
0.25
100
0.257
0.25
103
0.252
0.25
101
0.246
0.25
99
0.244
0.25
98
0.251
0.25
100
0.244
0.25
97
2.140
2
107
Tl
4
27.098
30
90
26.654
30
89
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
94
Tl
5
1.023
1
102
1.015
1
101
1.019
1
102
1.030
1
103
1.044
1
104
1.072
1
107
1.060
1
106
1.004
1
100
1.066
1
107
Tl
7
19.962
20
100
21.024
20
105
21.142
20
106
21.269
20
106
21.570
20
108
21.653
20
108
21.935
20
110
Tl
8
1.025
1
103
1.043
1
104
1.036
1
104
1.000
1
100
0.991
1
99
0.975
1
97
1.049
1
105
Zn
1
9.970
10
100
9.880
10
99
25.800
25
103
25.200
25
101
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
95
Draft
­
December
2000
25.200
25
101
Zn
2
49.070
50
98
47.470
50
95
48.950
50
98
47.880
50
96
105.300
100
105
105.900
100
106
52.730
50
105
22.980
25
92
22.040
25
88
22.160
25
89
22.070
25
88
22.700
25
91
49.760
50
100
101.800
100
102
51.810
50
104
23.730
25
95
Zn
3
2.477
2.5
99
2.500
2.5
100
2.564
2.5
103
2.516
2.5
101
2.456
2.5
98
2.357
2.5
94
2.392
2.5
96
2.394
2.5
96
2.377
2.5
95
2.675
2.5
107
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
Draft
­
December
2000
B­
96
2.594
2.5
104
2.683
2.5
107
0.923
1
92
0.977
1
98
Zn
4
31.254
30
104
30.614
30
102
Zn
5
1.211
1
121
Youden
Outlying
Laboratory1
1.210
1
121
1.487
1
149
0.978
1
98
0.989
1
99
1.034
1
103
1.030
1
103
1.240
1
124
0.866
1
87
Zn
7
20.227
20
101
19.562
20
98
19.264
20
96
19.259
20
96
19.142
20
96
18.964
20
95
19.091
20
95
Zn
8
9.829
10
98
9.759
10
98
9.950
10
99
9.762
10
98
9.431
10
94
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
B
Table
7.
Calibration
Verification
(
CalVer)
Results
Analyte
Lab
Conc.
(
µ
g/
L)
Spike
(
µ
g/
L)
Recovery
(%)
Comments
B­
97
Draft
­
December
2000
9.607
10
96
9.926
10
99
1The
laboratory's
data
package
was
rejected
for
this
analyte
using
Youden's
laboratory
ranking
Draft
­
December
2000
Appendix
C
Statistical
Analyses
Evaluation
of
Quality
Control
(
QC)
Acceptance
Criteria
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
C
Draft
­
December
2000
C­
1
1.0
Method
Detection
Limit
(
MDL)
and
Minimum
Level
of
Quantitation
(
ML)

The
pooled
MDL
was
calculated
using
the
following
equation:

MDL
d
MDL
t
d
MDL
t
d
MDL
t
d
d
d
t
Pooled
Lab
d
Lab
d
L
LabL
d
L
d
d
d
L
L
=
+
+
+
+
+
+
+
+
+
1
1
2
0
99
2
2
2
0
99
2
0
99
1
2
0
99
1
2
1
2
(
)
(
)
...
(
)

...
(
)

(
.
,
)
(
)

(
.
,
)
(
)

(
.
,
)
(
.
,
...
)

Where:
L
=
the
number
of
laboratories,
and
di
=
one
less
than
the
number
of
replicates
used
by
lab
i
to
derive
the
MDL.

MLs
were
determined
by
multiplying
the
MDL
by
3.18.
This
3.18
value
is
the
ratio
between
the
10
sigma
multiplier
used
to
establish
the
American
Chemical
Society
(
ACS)
and
International
Union
of
Pure
and
Applied
Chemistry
(
IUPAC)
limit
of
quantitation
(
LOQ)
and
the
Student's
t
multiplier
used
to
determine
an
MDL
(
i.
e.,
10
÷
3.143
=
3.18).
The
interim
MLs
were
rounded
to
the
number
nearest
to
(
1,
2,
or
5)
x
10n,
where
n
is
a
positive
or
negative
integer.
The
lowest
calibration
point
for
analytical
systems
is
at
the
ML,
and
the
use
of
a
rounded
number
simplifies
calibration.
Calculated
MDLs
and
MLs
are
listed
below.

2.0
Initial
Precision
and
Recovery
(
IPR)
and
Ongoing
Precision
and
Recovery
(
OPR)

QC
acceptance
criteria
were
calculated
using
the
recoveries
of
the
IPR
and
OPR
samples
for
each
laboratory,
and
a
linear
combination
of
between­
laboratory
and
within­
laboratory
variability.

Estimates
of
each
variance
component
(
between
laboratory
and
within
laboratory)
were
calculated
using
PROC
VARCOMP
from
SAS
6.12
using
the
maximum
likelihood
method
of
estimation.
Details
on
the
maximum
likelihood
estimation
can
be
found
in
SAS/
STAT
User's
Guide,
Volume
2,
published
by
the
SAS
Institute.

Estimates
of
between
laboratory
variance
and
within
laboratory
variance
were
labeled
s2
L
and
s2
w,
respectively.

The
combined
standard
deviation
for
IPR
(
isc)
is:

is
n
n
s
n
s
c
i
i
L
T
L
T
w
=
+
+
+
=
å
(
)
(
)
1
1
4
1
2
1
2
2
2
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
C
Draft
­
December
2000
C­
2
Where:
L
=
the
number
of
labs
(
7),
ni
=
the
number
of
combined
IPR
and
OPR
samples
for
laboratory
I,
and
nT
is
the
total
number
of
IPR
and
OPR
results
from
all
laboratories.

Upper
and
lower
limits
for
IPR
samples
were
then
calculated
as:

X
t
is
Mean
idf
c
±
(
.
;
)
*
0
975
Where
the
degrees
of
freedom
(
idf)
were
estimated
(
based
on
Satterthwaite's
degree
of
freedom
correction)
and
are
based
on
the
calculation
below:

idf
is
n
n
s
L
n
s
n
L
c
i
i
L
T
L
T
w
T
=
+
æ
è
ç
ç
ç
ç
ö
ø
÷
÷
÷
÷
é
ë
ê
ê
ê
ê
ù
û
ú
ú
ú
ú
-
+
+
æ
è
ç
ö
ø
÷
é
ë
ê
ù
û
ú
-
=
å
4
2
1
2
2
2
2
2
2
1
1
1
4
1
*
*

The
combined
standard
deviation
(
osc)
for
OPR
is:

os
n
n
s
n
s
c
i
i
L
T
L
T
w
=
+
+
+
=
å
(
)
(
)
1
1
1
2
1
2
2
2
Where:
n
i
=
the
number
of
IPR
and
OPR
samples
for
lab
i,
L
=
the
number
of
labs,
and
nT
is
the
total
number
of
IPR
and
OPR
results
from
all
laboratories.

Upper
and
lower
limits
for
OPR
samples
were
then
calculated
as:

X
t
os
Mean
odf
c
±
(
.
;
)
*
0
975
Where
the
degrees
of
freedom
(
odf)
were
estimated
(
based
on
Satterthwaite's
degree
of
freedom
correction)
and
are
based
on
the
calculation
below:
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
C
Draft
­
December
2000
C­
3
odf
os
n
n
s
L
n
s
n
L
c
i
i
L
T
L
T
w
T
=
+
æ
è
ç
ç
ç
ç
ö
ø
÷
÷
÷
÷
é
ë
ê
ê
ê
ê
ù
û
ú
ú
ú
ú
-
+
+
æ
è
ç
ö
ø
÷
é
ë
ê
ù
û
ú
-
=
å
4
2
1
2
2
2
2
2
1
1
1
1
*
*

The
precision
criterion
for
IPR
samples
was
calculated
as
a
maximum
relative
standard
deviation,
using
the
pooled
within­
laboratory
standard
deviation
sw
calculated
previously.

The
pooled
RSD
was
first
calculated
as:

RSD
s
X
Pool
w
Mean
=
(
)
*
100%

The
maximum
relative
standard
deviation
was
then
calculated
as:

RSD
F
RSD
Max
n
L
Pool
T
=
-
(
.
;
,
)
*
0
95
3
Where:
nT
is
the
total
number
of
IPR
and
OPR
results
from
all
laboratories,
and
m
is
the
number
of
laboratories.

3.0
Calibration
Verification
QC
acceptance
criteria
were
calculated
using
the
recoveries
of
the
ICV
and
CCV
samples
for
each
laboratory,
and
a
linear
combination
of
between­
laboratory
and
within­
laboratory
variability.

Estimates
of
each
variance
component
(
between
laboratory
and
within
laboratory)
were
calculated
using
PROC
VARCOMP
from
SAS
6.12
using
the
maximum
likelihood
method
of
estimation.
Details
on
the
maximum
likelihood
estimation
can
be
found
in
SAS/
STAT
User's
Guide,
Volume
2,
published
by
the
SAS
Institute.

Estimates
of
between
laboratory
variance
and
within
laboratory
variance
were
labeled
s2
L
and
s2
w,
respectively.

The
combined
standard
deviation
(
sc)
is:
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
C
Draft
­
December
2000
C­
4
s
n
n
s
n
s
c
i
i
L
T
L
T
w
=
+
+
+
=
å
(
)
(
)
1
1
1
2
1
2
2
2
Where:
n
i
=
the
number
of
ICV
and
CCV
samples
for
lab
i,
L
=
the
number
of
labs,
and
nT
is
the
total
number
of
ICV
and
CCV
results
from
all
laboratories.

Upper
and
lower
limits
were
then
calculated
as:

X
t
s
Mean
df
c
±
(
.
;
)
*
0
975
Where
the
degrees
of
freedom
(
df)
were
estimated
(
using
Satterthwaite's
degree
of
freedom
correction)
based
on
the
calculation
below:

df
s
n
n
s
L
n
s
n
L
c
i
i
L
T
L
T
w
T
=
+
æ
è
ç
ç
ç
ç
ö
ø
÷
÷
÷
÷
é
ë
ê
ê
ê
ê
ù
û
ú
ú
ú
ú
-
+
+
æ
è
ç
ö
ø
÷
é
ë
ê
ù
û
ú
-
=
å
4
2
1
2
2
2
2
2
1
1
1
1
*
*

4.0
Matrix
Spike
(
MS)
and
Matrix
Spike
Duplicate
(
MSD)

QC
acceptance
criteria
were
calculated
using
the
matrix
spike
and
matrix
spike
duplicate
samples
from
each
analyte.

Estimates
of
each
variance
component
(
between
laboratory,
between
matrix,
between
laboratoryby
matrix,
and
within
laboratory­
and­
matrix)
were
calculated
using
PROC
VARCOMP
from
SAS
6.12
using
the
maximum
likelihood
method
of
estimation.
Details
on
the
maximum
likelihood
estimation
can
be
found
in
SAS/
STAT
User's
Guide,
Volume
2,
published
by
the
SAS
Institute.

Estimates
of
between
laboratory
variance,
between
matrix
variance,
between
laboratory­
by­
matrix
variance,
and
within
laboratory­
and­
matrix
variance
were
labeled
s2
l,
s2
m,
s2
lm,
and
s2
w,
respectively.

The
combined
standard
deviation
is:
Results
of
the
Interlaboratory
Validation
Study
of
EPA
Method
1638
Appendix
C
Draft
­
December
2000
C­
5
s
L
s
M
s
L
M
s
L
M
N
s
c
L
M
LM
w
=
+
+
+
+
+
+
+
(
)
(
)
(
*
)
(
*
*
)
1
1
1
1
1
1
1
1
2
2
2
2
Where:

is
the
average
number
of
labs
per
matrix
for
the
given
analyte,
L
C
M
=
is
the
average
number
of
matrices
per
lab
for
the
given
analyte,
M
C
L
=
is
the
average
number
of
replicates
per
lab/
matrix
group,
N
n
C
T
=
C
is
the
total
number
of
lab/
matrix
groups,
and
nT
is
the
total
number
of
replicates
over
all
labs
and
matrices.

The
degrees
of
freedom
were
estimated
(
based
on
Satterthwaite's
degree
of
freedom
correction)
based
on
the
calculation
below:

df
s
L
s
L
M
s
M
L
M
s
L
M
L
M
N
s
L
M
N
c
L
M
LM
w
=
+
-
+
+
-
+
+
-
-
+
+
-
4
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
((
)
)
((
)
)
((
*
)
)

(
)(
)
((
*
*
)
)

*
*(
)

Upper
and
lower
limits
for
MS/
MSD
samples
were
then
calculated
as:

X
t
s
Mean
df
c
=
±
(
.
;
)
*
0
975
Where:
Xmean
=
the
mean
recovery
of
all
MS
and
MSD
samples.

In
order
to
calculate
the
precision
criterion
for
MS/
MSD
samples,
the
pooled
RSD
was
calculated
using
the
estimated
within
laboratory­
and­
matrix
standard
deviation
sw
calculated
previously.
The
pooled
RSD
was
calculated
as:

RSD
s
X
Pool
w
Mean
=
The
maximum
relative
percent
difference
was
calculated
as:

RPD
F
RSD
Max
L
M
Pool
=
2
0
95
1
*
*
(
.
;
,
*
)
