Document ID: EPA-HQ-OW-2003-0002-0104
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2003-03-12T05:00Z

EPA
Response
to
Peer
Review
Comments
received
on
EPA's
Draft
Assessment
of
Detection
and
Quantitation
Limit
Concepts
February
25,
2003
February
25,
2003
Page
1
Introduction
In
August
2002
EPA
conducted
a
peer
review
of
a
draft
"
Technical
Support
Document
of
Detection
and
Quantitation
Regulations
under
the
Clean
Water
Act"
(
the
"
Assessment
Document").
This
peer
review
was
conducted
in
accordance
with
EPA's
peer
review
policies
described
in
the
Science
Policy
Council
Handbook
(
EPA
100­
B­
00­
001).
The
review
was
performed
by
two
experts
in
the
field
of
analytical
chemistry
and
two
experts
in
the
statistical
aspects
of
analytical
data
interpretation.
Each
reviewer
was
provided
with
a
draft
version
of
the
Assessment
Document,
which
documented
the
Agency's
approach
to
the
assessment
and
the
Agency's
preliminary
findings
and
conclusions.
Reviewers
also
were
provided
with
copies
of
all
data
evaluated
in
the
assessment,
statistical
programs
used
to
analyze
the
data,
and
copies
of
the
detection
and
quantitation
concepts
and
procedures
evaluated
by
EPA.
In
accordance
with
the
Agency's
peer
review
policies,
the
reviewers
were
provided
with
a
written
`
charge'
intended
to
ensure
the
evaluation
would
meet
EPA
needs.

In
its
charge
to
the
peer
reviewers,
EPA
requested
a
written
evaluation
of
whether
the
assessment
approach
described
by
EPA
was
valid
and
conceptually
sound.
Reviewers
also
were
asked
to
consider
and
address
eight
specific
questions
pertaining
to
the
adequacy
of
the
concepts
and
issues
considered,
the
evaluation
criteria
developed
by
EPA,
EPA's
assessment
and
conclusions,
the
data
used
to
perform
the
assessment,
suggested
improvements
to
the
procedures
discussed,
and
EPA's
consideration
of
interlaboratory
vs.
intralaboratory
issues.
Copies
of
all
materials
associated
with
the
peer
review,
including
the
peer
review
charge,
the
materials
provided
to
the
peer
reviewers
for
review,
and
complete
copies
of
the
peer
reviewers'
comments
are
provided
separately
in
the
public
docket
supporting
the
Agency's
assessment.
February
25,
2003
Page
2
Responses
to
Comments
Submitted
by
David
Rocke
EPA's
reassessment
is
complete
and
sound
(
DR­
1)

Comment:
The
list
of
detection
and
quantitation
concepts,
the
issues
laid
out
in
Chapter
3
of
the
peer
review
version
of
the
Assessment
Document,
and
the
evaluation
criteria
in
Chapter
4
are
sufficiently
complete
and
adequate
for
the
reassessment.
The
assessments
in
Chapter
5
are
sound.

Response:
EPA
appreciates
the
support
for
the
reassessment.

Purpose
of
detection
limit
(
DR­
2,
DR­
14)

Comment:
The
purpose
of
a
detection
limit
in
Criterion
4
of
the
peer
review
version
of
the
Assessment
Document
appears
from
the
description
and
the
discussion
to
be
a
mix
of
the
Currie
concepts
of
critical
value
(
CRV)
and
minimum
detectable
value
(
MDV).
What
should
appear
here
is
the
CRV
equivalent.
Here
is
a
suggested
re­
wording:
The
detection
level
concept
should
identify
the
signal
or
estimated
concentration
at
which
there
is
99%
confidence
that
the
substance
is
actually
present
when
the
analytical
method
is
performed
by
experienced
staff
in
a
well­
operated
laboratory.

Response:
EPA
agrees
and
has
revised
the
purpose
along
the
lines
that
the
peer
reviewer
suggests.

Quantitation
limits
are
misnomer
(
DR­
3,
DR­
9,
DR­
15)

Comment:
With
respect
to
the
limit
of
quantitation
concept,
the
EPA
ML
is
as
good
as
any
of
the
others
given.
However,
all
are
flawed
by
the
assumption
that
there
is
some
level
higher
than
the
Currie
critical
value
(
CRV)
needed
before
quantitative
assessments
can
be
made.
This
is
not
supported
in
this
document,
nor
anywhere
else
I
have
seen,
except
as
an
almost
unexamined
assumption.
After
all,
the
concentration
at
which
the
MDL
is
measured
must
generate
peaks
that
can
be
measured.
If
the
instrument
can
be
read,
and
the
spectra
can
be
recognized,
then
the
ML
is
exceeded,
regardless
of
the
other
issues.
The
entire
concept
of
a
quantitation
level
higher
than
the
CRV
should
be
immediately
discarded.

Criterion
5
of
the
peer
review
version
of
the
Assessment
Document
should
be
completely
changed
to
reflect
that
almost
all
implementations
of
limits
of
quantitation
have
nothing
to
do
with
whether
the
measurements
are
actually
quantitative.
No
arbitrary
standard
regarding
multiples
of
the
standard
deviation
at
zero
or
a
desired
CRV
is
appropriate
for
any
purpose
in
analytical
chemistry
or
the
regulation
of
toxic
substances.
This
includes
the
PQL,
the
AML
and
other
related
methods.
None
of
them
generate
a
useful
number.
Here
is
a
suggested
re­
wording:
February
25,
2003
Page
3
The
quantitation
limit
concept
should
identify
a
concentration
at
which
the
instrument
yields
a
measurable
signal
at
least
99%
of
the
time,
and
which
is
also
no
smaller
than
the
detection
level.
This
will
often
be
the
same
as
the
detection
level.

Response:
EPA
agrees
in
principle
but
does
not
want
to
create
a
conflict
with
historical
precedent
and
present
use
of
a
quantitation
limit
as
understood
and
used
by
the
analytical
community.
EPA
agrees
with
the
reviewer's
comments
that
all
results
above
the
critical
value
(
or
MDL)
are
quantitative
measurements.
At
issue
is
the
potential
degree
of
uncertainty
associated
with
a
specific
value.
While
there
are
many
who
advocate
reporting
all
results
down
to
the
MDL,
the
EPA
Office
of
Water
believes
that
in
a
regulatory
context,
the
greater
uncertainty
associated
with
measurements
at
the
MDL
warrants
the
use
of
a
"
quantitation
limit"
as
a
means
to
assure
that
the
uncertainty
of
a
reported
value
is
at
an
acceptable
level.
Therefore,
EPA
has
not
revised
Criterion
5
and
has
not
discarded
the
quantitation
limit.

MDL
is
reasonable
(
DR­
4,
DR­
16)

Comment:
The
MDL
is
a
reasonable
implementation
of
Currie's
critical
value
(
CRV)
concept
for
situations
in
which
the
instrument
may
not
yield
reliable
data
for
blanks.
With
a
slight
alteration
to
the
specifications
on
the
spike
concentration,
the
EPA
MDL
as
now
given
is
a
reasonable,
practical
implementation
of
a
limit
of
detection
concept
and
procedure.
None
of
the
other
procedures
is
an
improvement
on
this
overall.

Response:
EPA
agrees
and
thanks
the
reviewer.

Additional
data
sets
(
DR­
5)

Comment:
There
is
no
need
to
examine
additional
data
sets.

Response:
EPA
believes
that
the
data
sets
examined
for
the
peer
review
are
sufficient
to
allow
the
reassessment.
However,
EPA
is
soliciting
further
data
sets
in
the
proposal
in
the
event
that
there
could
be
more
definitive
data
sets
that
may
aid
in
further
assessing
detection
and
quantitation
limit
concepts.

Interlaboratory
variability
(
DR­
6,
DR­
12)

Comment:
EPA's
position
on
interlaboratory
vs.
intralaboratory
variability
is
reasonable.
If
a
laboratory
computes
a
CRV
using
a
procedure
such
as
the
MDL,
it
makes
no
sense
to
expand
this
to
account
for
interlaboratory
variability.
Whether
other
labs
can
or
cannot
detect
the
substance
with
a
signal
at
the
MDL
of
the
given
laboratory
is
irrelevant.
It
may
be
different
if
the
goal
is
precisely
to
determine
the
quantity
of
the
analyte
in
a
standard
sample.
In
this
case,
interlaboratory
variability
may
be
appropriately
considered.
It
should
not
be
considered
in
detection
decisions
unless
it
can
February
25,
2003
Page
4
be
shown
that
such
decisions
in
an
individual
laboratory
are
biased
and
may
over­
or
under­
estimate
the
true
critical
value
(
detection
threshold)
in
that
laboratory.

For
the
specific
purpose
of
determining
whether
a
given
sample
exceeds
the
safe
level,
a
general
interlaboratory
study
is
not
of
much
use,
since
it
may
be
influenced
by
the
performance
of
laboratories
at
levels
far
removed
from
the
point
at
issue.
If
the
safe
level
is
below
a
critical
value,
use
of
the
critical
value
is
appropriate
as
an
action
threshold.
If
the
safe
level
is
above
the
critical
value,
interlaboratory
variation
should
only
be
taken
into
account
if
it
can
be
shown
that
the
number
of
false
positives
when
the
analyte
is
present
at
the
safe
level
is
not
well
controlled
using
the
usual
intralaboratory
calibration
methods.

Response:
EPA
agrees.

Randomized
study
design
(
DR­
7)

Comment:
EPA's
tests
of
variability
vs
concentration
that
resulted
in
the
ICP/
MS,
Episode
6000,
and
6184
data
sets
were
conducted
in
sequence
from
high
to
low
concentration.
This
grouped
analysis
by
concentration
leads
to
anomalous
results.
If
all
samples
at
a
given
concentration
are
analyzed
in
sequence,
then
the
next
concentration,
and
so
on,
the
values
at
a
given
concentration
will
be
closer
together
than
would
be
the
case
if
they
were
analyzed
at
different
times,
or
interspersed
with
other
concentrations.
This
problem
should
be
fixed
by
using
a
proper
randomized­
order
design,
but
can
be
mitigated
by
always
looking
at
variability
around
the
calibration
line,
rather
than
around
the
mean
of
the
replicates.

Response:
The
reason
concentrations
were
not
randomized
was
because
of
a
concern
about
cross
contamination
of
low­
concentration
samples
by
highconcentration
samples.
For
example,
in
Episode
6000
study,
the
concentrations
ranged
from
0.1
to
100
times
the
initial
estimate
of
the
MDL,
or
a
concentration
range
of
a
factor
of
1000.
If
a
highest
concentration
sample
were
analyzed
and
followed
by
a
lowest
concentration
sample,
the
possibility
exists
that
some
of
the
analyte
would
be
carried
into
the
lowest
concentration
sample,
inflating
the
result,
and
increasing
the
apparent
variability
and
the
resulting
detection
and/
or
quantitation
limit
at
the
lowest
concentration.

Regarding
use
of
variability
around
the
calibration
line,
the
measured
concentrations
in
the
various
variability
vs
concentration
studies
were
determined
using
a
calibration
factor,
response
factor,
or
calibration
curve,
as
appropriate
to
the
analytical
technique
and
as
required
by
the
analytical
method.
This
means
of
determining
the
analyte
concentration
assured
that
the
variability
was
mitigated,
as
the
reviewer
suggests.
February
25,
2003
Page
5
In
response
to
this
reviewers
comment,
EPA
has
revised
the
Assessment
Document
to
further
explain
this
issue.

MDL
procedure
should
allow
use
of
blanks
(
DR­
8,
DR­
16)

Comment:
The
MDL
had
a
number
of
problems
that
needed
repair,
some
of
which
were
fixed
in
the
rewording
on
page
5­
4
of
the
peer
review
version
of
the
Assessment
Document.
The
basic
concept
of
Glaser
et
al.
(
1981)
that
the
"
MDL
is
considered
operationally
meaningful
only
when
the
method
is
truly
in
detection
mode,
i.
e.,
[
the]
analyte
must
be
present."
is
problematic.
For
methods
under
which
a
signal
is
generated
from
blanks,
this
is
not
at
all
necessary,
For
cases
in
which
the
blank
does
not
generate
a
signal
due
to
instrumental
limitations
(
such
as
inability
to
find
the
peak
to
integrate),
one
must
generate
the
MDL
using
positive
concentrations,
and
the
MDL
should
not
increase
the
CRV
much
over
what
would
be
obtained
using
true
blanks
if
that
were
possible.
Otherwise,
blank
samples
are
fine.

Response:
EPA
agrees
and
has
addressed
this
issue
by
revising
the
MDL
procedure
to
allow
use
of
blanks
in
which
the
analyte
is
present
for
determination
of
an
MDL.

Regulatory
levels
(
DR­
10)

Comment:
Obviously,
levels
of
a
toxic
substance
cannot
easily
be
regulated
below
the
level
at
which
there
is
an
instrumental
response
(
i.
e.,
a
signal
is
generated).
All
environmental
measurements
should
be
reported
as
measured,
and
should
only
be
reported
as
non­
detects
if
there
is
no
instrument
response.
If
a
value
is
generated
by
the
instrument,
it
should
be
reported,
with
an
indication
of
what
the
estimated
standard
deviation
is,
and
whether
the
measurement
shows
the
concentration
to
be
non­
zero
(
that
is,
whether
the
signal
is
above
the
CRV).

Response:
In
principle,
EPA
agrees
with
the
reviewer,
and
is
aware
that
several
organizations,
including
the
European
Union
and
others,
are
developing
procedures
for
estimating
the
uncertainty
associated
with
measured
results.
If
successful,
such
an
approach
would
eliminate
many
of
the
data
censoring
concerns
discussed
in
Section
3.3.2
of
the
Assessment
Document.
Given
the
difficulty
in
achieving
consensus
on
an
appropriate
means
of
establishing
a
detection
limit,
however,
EPA
believes
that
it
would
be
extremely
difficult
to
obtain
consensus
on
an
appropriate
means
for
estimating
the
uncertainty
associated
with
each
result
measured
on
each
environmental
sample.
In
addition,
analytical
chemists
have
used
and
believe
that
they
understand
a
quantitation
limit
to
mean
the
lowest
concentration
at
which
an
analyte
can
be
identified
and
determined
with
some
degree
of
certainty,
and
most
laboratories
are
reluctant
to
report
results
with
the
higher
error
at
a
detection
limit,
as
compared
to
a
quantitation
limit.
Therefore,
EPA
prefers
to
monitor
developments
by
the
February
25,
2003
Page
6
EU
and
others
on
this
subject,
and
if
appropriate,
re­
evaluate
this
issue
if
and
when
it
becomes
widely
accepted
by
the
environmental
laboratory
communities.
In
the
meantime,
EPA
believes
that
the
traditional
approach
of
defining
a
quantitation
limit
at
some
level
above
the
detection
limit
provides
a
data
user
with
a
reasonable
degree
of
confidence
in
the
reliability
of
the
measured
value
without
requiring
that
individual
estimates
of
uncertainty
be
developed
and
reported.
Therefore,
EPA
has
not
revised
Criterion
5
to
reflect
the
changes
suggested
by
this
peer
reviewer.

MDL
is
appropriate
CET
(
DR­
11)

Comment:
For
substances
for
which
the
toxic
level
is
well
below
the
CRV,
the
compliance
evaluation
threshold
should
be
at
the
critical
value
(
in
one
of
its
implementations
such
as
the
revised
MDL).

Response:
In
principle,
EPA
agrees
with
the
reviewer.
However,
EPA
has
suggested
that
the
compliance
evaluation
threshold
(
CET)
be
set
at
the
ML
because
of
added
reliability
of
measurements
at
the
ML.
States
that
wish
to
be
more
protective
of
the
environment
may
set
the
CET
to
the
MDL
or
other
limit
are
allowed
to
do
so
if
they
believe
is
will
be
more
protective.

Prediction
and
tolerance
intervals
(
DR­
13)

Comment:
Tolerance
intervals
are
inappropriate
for
environmental
monitoring.
The
main
issues
here
are
1)
is
the
true
concentration
greater
than
some
specified
safe
of
action
level,
with
sufficient
confidence,
and
2)
what
interval
of
possible
concentrations
is
consistent
with
one
or
a
series
of
measurements,
with
a
specified
degree
of
confidence.
Both
are
statements
about
a
given
sample
or
series
of
samples,
and
not
about
the
hypothetical
variability
of
future
estimates.
Suppose
that
one
has
a
sample
of
10
observations
with
mean
concentration
of
1
ppb
and
standard
deviation
of
0.5
ppb.
The
estimated
99%
CRV
is
(
2.326)(
0.5)
=
1.2
ppb.
One
may
choose
to
use
a
tscore
instead
of
a
normal
score
so
that
the
chance
that
a
future
observation
will
exceed
this
level
is
in
fact
99%.
In
this
case,
the
CRV
estimate
would
be
(
3.250)(
0.5)
=
1.6
ppb.
This
does
actually
correspond
to
a
prediction
interval
for
future
observations
from
a
zero
concentration
sample.

If
one
asked
instead
for
a
95%
confidence
interval
for
the
.99
percentage
point
of
the
true
distribution
of
measurements
(
assuming
normality)
when
the
true
quantity
is
zero,
this
can
be
calculated
approximately
using
a
chisquared
distribution
and
covers
the
interval
(
0.9
ppb,
2.4
ppb).
It
does
not,
however,
make
sense
to
use
2.4
ppb
as
a
threshold,
since
the
chance
of
a
future
observation
exceeding
2.4
ppb
when
the
true
mean
concentration
is
0
is
about
.0005,
far
smaller
than
the
intended
false­
positive
rate
of
.01.

Response:
EPA
agrees.
February
25,
2003
Page
7
Spike
to
MDL
ratio
(
DR­
17)

Comment:
Use
of
as
much
as
five
times
the
CRV
for
the
spike
concentration
could
be
problematic.
Inflation
of
the
MDL
by
using
a
spike
at
the
CRV
is
only
25%
for
a
method
with
a
coefficient
of
variation
of
20%
(
this
and
other
calculations
here
are
done
with
the
Rocke
and
Lorenzato
1995
variance
function
assuming
a
sample
size
of
7).
A
spike
concentration
of
3
times
the
CRV
inflates
the
MDL
to
a
value
140%
higher,
which
even
there
may
be
tolerable.
Use
of
a
value
5
times
the
CRV
gives
an
inflation
of
over
280%.
Thus
if
the
true
CRV
is
1
ppb,
then
the
use
of
1,
3,
and
5
times
the
CRV
for
spike
concentrations
in
determining
the
MDL
gives
likely
values
of
1.2
ppb,
2.4
ppb,
and
3.8
ppb,
respectively.
These
number
were
determined
as
follows:
Let
V(
y)
=
a2+
b2
:

2
.
Then
the
expected
MDL
if
blanks
were
used
is
approximately
ta,
where
t
is
the
appropriate
t­
statistic.
If
spikes
at
kta
are
used,
then
the
variance
at
that
level
of
:
is
a2+(
ktab)
2,
and
the
approximate
estimated
MDL
will
be
t
times
the
square
root
of
this
quantity,
so
that
the
ratio
of
the
MDL
with
blanks
to
the
MDL
at
spike
level
:
=
kta
is
%[
1+(
ktb)
2].
Thus,
I
would
recommend
that
the
procedure
be
altered
to
use
concentrations
that
are
no
more
than
3
times
the
detection
limit,
and
perhaps
to
permit
concentrations
lower
then
the
CRV,
including
possibly
blanks.

Response:
EPA
agrees
with
the
reviewer's
concern,
but
has
found
that,
in
practice,
the
disadvantages
associated
with
limiting
the
spike­
to­
MDL
ratio
to
three
outweigh
the
benefits.
Specifically,
EPA
initially
required
that
all
laboratories
participating
in
the
EPA's
Multi­
technique
Variability
Study
(
the
Episode
6000
Study)
achieve
a
spike­
to­
MDL
ratio
of
three.
After
attempting
to
meet
this
requirement,
two
of
laboratories
reported
that
a
large
number
of
iterations
would
be
required
in
order
to
achieved
a
the
lower
spike­
to­
MDL
ratio.
Given
the
costs
associated
with
each
iteration,
EPA
returned
to
a
ratio
of
5
as
was
stated
in
the
original
MDL
procedure.
EPA
is
retaining
a
ratio
of
5
in
the
revised
procedure
being
proposed.
February
25,
2003
Page
8
Responses
to
Comments
Submitted
by
Walter
Piegorsch
Peer­
review
was
complete
and
sound
(
WP­
1,
WP2­
7,
WP2­
13)

Comment:
The
peer
review
version
of
the
Assessment
Document
is
well­
organized
and
intelligently
thought­
out.
It
has
strong
scientific
merit
and
establishes
a
good
baseline
from
which
further
discussion
and
debate
may
continue
on
the
important
issue
of
detection
limits
and
quantification
of
contaminants
in
the
nation's
water
supply.
The
evaluation
criteria
in
Chapter
4
seem
reasonable.
The
description
of
the
IUPAC/
ISO
detection
limit
and
the
introduction
to
quantitative
assessment
of
the
ML
were
well
presented.
EPA's
willingness
to
consider
other
detection
and
quantification
approaches
is
admirable.

Response:
EPA
thanks
the
reviewer
for
the
support.

MDL
is
not
an
interval
estimator
(
WP­
3,
WP2­
2)

Comment:
Accepting
the
Assessment
Document's
interpretation
of
the
MDL
as
a
"
general
purpose
version
of
Currie's
critical
value
(
LC),"
I
am
concerned
that
the
operational
definition
MDL
=
t0.99(
df)
S,
where
df
is
an
appropriately­
chosen
value
for
the
degrees
of
freedom
and
S
is
an
associated
root
mean
square,
does
not
correspond
to
an
appropriate
form
of
interval
estimator.

Response:
The
MDL
is
not
intended
as
an
interval
estimator
but
rather
a
value
analogous
to
a
Currie
critical
value
(
CRV;
LC).
EPA
has
removed
all
references
to
interval
from
the
revised
version
of
the
MDL
procedure
being
proposed
as
a
result
of
this
assessment.

Correct
terminology
(
WP2­
3)

Comment:
The
peer
review
version
of
the
Assessment
Document,
and
I,
should
be
more
careful
in
the
use
of
statistical
terminology.
We
both
refer
often
to
confidence
"
intervals,"
when
in
fact
the
quantity
of
interest
is
a
confidence
limit
 
or
tolerance
limit,
etc.
 
on
some
underlying
parametric
quantity.

Response:
EPA
will
try
to
be
consistent
with
reference
to
limit,
and
has
revised
the
Assessment
Document
accordingly.

Critical
value
not
detection
limit
(
WP2­
6)

Comment:
There
seems
to
be
a
fair
amount
of
confusion
on
the
issue
in
the
analytical
chemistry
literature.
The
bottom
line
from
my
reading
of
the
Assessment
Document
is
that,
in
effect,
we
are
calculating
an
LC,
but
using
terminology
that
makes
some
readers
think
it's
an
LD
.
The
Agency
should
put
forth
an
effort
to
overcome
this
confusion
in
terminology.
February
25,
2003
Page
9
Response:
EPA
agrees
that
the
terminology
is
inconsistent,
and
to
help
overcome
confusion
arising
from
the
terminology
has
added
the
following
sentence
to
the
MDL
definition,
"
The
MDL
is
calculated
from
replicate
analyses
of
a
matrix
containing
the
analyte
and
is
functionally
analogous
to
the
"
critical
value"
described
by
Currie
(
1968,
1995)
and
the
Limit
of
Detection
(
LOD)
described
by
the
American
Chemical
Society
(
Keith
et
al.
1980,
MacDougall
et
al.
1983)."

Error
in
MDL
equation
in
the
draft
Assessment
Document
(
WP­
4,
WP2­
9)

Comment:
The
definition
of
S2
given
on
p.
5­
2
of
the
peer
review
version
of
the
Assessment
Document
is
in
error.
I
assume
that
this
a
typographical
error
and
not
a
more
serious
misinterpretation
of
statistical
principles.

Response:
EPA
thanks
the
reviewer
for
pointing
out
this
typographical
error
and
has
corrected
it
in
the
revised
version
of
the
Assessment
Document
included
in
the
Docket
for
today's
proposal.

MDL
confidence
interval
is
fallacious
(
WP­
5,
WP2­
10,
WP2­
14)

Comment:
The
idea
of
building
a
confidence
interval
for
the
MDL
is
fallacious
because
a
95%
confidence
interval
for
the
MDL
cannot
be
calculated.
The
suggestion
that
MDL
represents
a
95%
confidence
interval
is
spurious.

Response:
Although
EPA
asserts
that
a
confidence
interval
can
be
calculated
for
an
MDL,
we
have
deleted
all
references
to
a
confidence
or
other
interval
from
the
MDL
procedure
because,
operationally,
these
intervals
serve
no
purpose.

Prediction
and
Tolerance
Intervals
(
WP­
6,
WP2­
4)

Comment:
Some
authors
even
argue
that
the
Glaser
et
al.
model
and
definition
of
the
MDL
does
not
even
produce
a
valid
confidence,
prediction,
or
tolerance
interval.
Rather
than
join
the
fray
here,
however,
I
suggest
the
following
reconsideration:
Accepting
the
Assessment
Document's
argument
on
p.
3­
25
that
the
practical
value
of
tolerance
limits
for
this
sort
of
analyte
detection
is
limited,
one
naturally
thinks
to
view
the
MDL
as
a
prediction
limit.
But,
as
Gibbons
(
1994,
p.
98)
points
out,
a
single­
use
prediction
limit
of
such
a
form
should
contain
an
additional
term,
viz.
t0.99(
df)
S.
I
emphatically
encourage
the
EPA
to
revisit
its
definition
of
MDL
with
this
consideration
in
mind.

Response:
EPA
appreciates
and
has
considered
the
suggestion.
EPA
wishes
to
note
that,
although
there
have
been
suggestions
in
the
literature
concerning
prediction
and
tolerance
intervals,
neither
the
Currie
critical
value
(
CRV),
the
ACS
limit
of
detection
(
LOD),
nor
the
EPA
MDL
have
historically
included
allowance
for
a
prediction
or
tolerance
interval.
One
use
of
the
February
25,
2003
Page
10
MDL
(
and
other
detection
limit
approaches
that
are
based
on
the
standard
deviation
of
replicate
measurements)
is
to
characterize
the
performance
of
a
method
or
laboratory.
Because
there
is
no
intent
to
test
a
future
MDL
or
other
measurement
against
the
value
estimated
or
determined,
a
prediction
or
tolerance
interval
is
inappropriate.
EPA
acknowledges
that
a
prediction
or
tolerance
interval
may
be
applicable
if
the
MDL
were
to
be
applied
on
a
routine
basis;
e.
g.,
for
regulatory
compliance.
EPA
refers
the
reader
to
comment
DR­
13
above,
provided
by
another
peer
reviewer,
for
an
excellent
explanation
of
why
prediction
or
tolerance
intervals
are
inappropriate
for
environmental
monitoring
programs.

False
negatives
(
WP­
7,
WP2­
5)

Comment:
The
single
most
problematic
issue
in
developing
a
detection
limit
is
that
of
correction
for
false
negatives.
For
the
generic
problem
of
detecting
a
chemical
analyte,
the
incorporation
of
false
negatives
should
be
afforded
greater
importance
than
I
think
the
peer­
review
Assessment
Document
provides.

Response:
EPA
agrees
that
the
issue
is
problematic
and
attempted
to
address
the
issue
in
the
Assessment
Document.

MDL
not
adjusted
for
outliers
(
WP2­
11)

Comment:
It
is
good
to
mention
that
the
MDL
procedure
is
not
adjusted
for
outliers,
since
this
sort
of
subtlety
could
escape
the
casual
reader.

Response:
EPA
appreciates
the
positive
feedback.
EPA
also
notes
that,
based
on
feedback
from
other
reviewers
of
the
draft
Assessment
Document,
EPA
is
proposing
revisions
to
the
MDL
procedure
that
will
allow
removal
of
a
maximum
of
one
outlier
in
the
revised
MDL
procedure
and
include
guidance
on
the
outlier
removal
processes.
EPA
has
revised
the
Assessment
Document
to
further
discuss
this
issue.

Calibration
design
(
WP­
9)

Comment:
There
is
also
the
rather
strong
argument
that
instead
of
LC
calculation
from
a
single
concentration
design,
use
of
calibration
designs
is
considered
to
be
more
efficient
in
terms
of
deriving
effective
detection
limits
from
the
data.

Response:
EPA
is
not
opposed
to
the
"
calibration"
design
(
also
referred
to
as
the
"
concentration"
design)
on
scientific
principles;
EPA
is
opposed
to
use
of
the
calibration
design
to
establish
detection
and
quantitation
limits
on
practical
and
economic
grounds.
However,
EPA
is
proposing
to
allow
use
of
detection
and
quantitation
limits
developed
from
alternate
approaches
and
procedures,
including
the
"
calibration"
or
"
concentration"
design.
February
25,
2003
Page
11
IDE
procedure
is
complex
(
WP2­
12)

Comment:
It
is
worth
emphasizing
that
the
IDE
procedure
as
outlined
is
so
complex
as
to
make
simple
determination
of
error
rates
associated
with
it
untenable.

Response:
EPA
has
incorporated
this
reviewer's
comment
into
the
revised
version
of
the
Assessment
Document.

Draft
Assessment
Document
favors
MDL
(
WP­
10)

Comment:
The
evaluation
criteria
in
the
peer­
review
version
of
the
Assessment
Document
seem
reasonable
at
first
reading.
I
do
not
think
any
of
them
should
be
eliminated,
and
I
do
not
have
any
concrete
suggestions
for
addition.
In
passing,
however,
I
should
note
that
as
I
continued
through
the
chapter,
I
found
it
perchance­
less­
than­
coincidental
that
the
(
revised)
MDL
and
ML
approaches
seemed
to
satisfy
the
criteria
so
readily,
and
that
most
of
the
other
approaches
were
found
wanting.
(
A
cynical
reader
might
view
this
as
a
contrivance
that
elevates
the
MDL
and
ML
at
the
expense
of
the
other
methods,
and
perhaps
the
EPA
may
wish
to
proceed
with
caution
in
this
area.)

Response:
EPA
acknowledges
that
a
reader
of
the
draft
Assessment
Document
would
conclude
that
the
MDL
better
satisfies
the
evaluation
criteria
than
the
other
detection
and
quantitation
limit
approaches
evaluated.
The
reason
is
that
the
evaluation
criteria
were
constructed
around
EPA's
needs
and
uses
for
detection
and
quantitation
limits
and
approaches,
and
these
needs
have
scientific,
practical,
cost,
and
regulatory
components.
These
needs
have
not
changed
substantially
since
the
1980s
when
MDL
procedure
was
developed
and
adopted
to
support
them.
EPA
believes
that
if
other
approaches
had
been
developed
to
suit
Agency
needs,
these
approaches
would
have
better
satisfied
EPA's
evaluation
criteria.
As
an
example,
if
the
ISO/
IUPAC
critical
value
had
a
well­
defined
procedure
for
its
determination,
it
is
likely
that
the
critical
value
would
have
met
the
evaluation
criteria
equally
well
to
the
MDL.

Additional
data
sets
(
WP­
13,
WP2­
15)

Comment:
I
would
encourage
the
EPA
to
expand
its
search
and
consider
as
many
additional
data
sets
as
can
be
acquired
in
a
reasonable
period
of
time.
I
do
not
have
at
my
disposal
any
new
data
sets,
nor
am
I
working
with
anyone
currently
who
does.
I
cannot
give
EPA
any
new
sources
of
data.

Response:
EPA
continues
its
search
for
definitive
data
sets
that
may
further
assist
in
resolving
the
detection/
quantitation
limit
issue
and
is
soliciting
additional
data
sets
in
the
proposal.
February
25,
2003
Page
12
New
interlaboratory
study
(
WP­
14,
WP2­
16)

Comment:
The
issues
of
intralaboratory
and
interlaboratory
variation
are
quite
important,
and
I
applaud
the
Assessment
Document
for
its
consideration
of
them.
While
reasonably
addressed,
I
would
encourage
that
EPA
undertake,
commission,
or
actively
abet
a
formal
interlaboratory
study,
building
on
the
success
of
the
Method
1638
Interlaboratory
Validation
Study.
The
recognition
that
multiple
components
of
variation
can
exists
in
calculating
LC
(
or
any
other
form
of
detection/
decision
limit),
is
an
important
one,
and
such
calculations
must
be
based
on
appropriate
variance
components
for
the
model
under
study.
A
large,
carefully­
conducted
interlaboratory
study
would
make
a
major
contribution
towards
understanding
and
quantifying
these
components
for
use
in
future
detection
limit
calculations.

Response:
When
EPA
discussed
the
objectives
for
the
Multi­
technique
Variability
Study
(
the
Episode
6000
study)
in
1996,
the
purpose
was
to
create
a
database
that
would
help
answer
questions
concerning
detection
and
quantitation
limits.
The
study
was
conducted
using
7
replicates
at
16
concentration
levels
and
11
of
the
most
commonly
used
analytical
technologies.
EPA
considered
conducting
the
study
in
multiple
laboratories
at
the
time
but
the
additional
factor
of
6
to
10
in
cost
made
this
approach
cost­
prohibitive.
EPA
believes,
however,
that
the
Episode
6000
study
shows
that
detection
limits
can
be
variable
and
that
some
judgement
will
always
be
required
in
evaluating
detection
limit
determinations;
and
that
there
is
no
procedure
that
is
applicable
to
all
analytes
in
all
methods
under
all
circumstances.
If
an
organization
is
willing
to
conduct
more
extensive
studies
between
proposal
and
promulgation
of
a
final
rule,
EPA
would
appreciate
additional
data
so
long
as
it
doesn't
compromise
the
deadline
for
the
final
rule.

Composite
sampling
(
WP­
15,
WP2­
1)

Comment:
Aside
from
the
comments
given
above,
I
have
no
further
improvements
to
suggest.
I
do
have
one
general
question,
however:
has
EPA
studied
the
use
of
composite
sampling
methodology
(
primarily
from
a
statistical
perspective)
for
application
to
MDL
or
ML
determination?

Response:
EPA
has
considered
composite
sampling
in
its
various
regulatory
programs
and
other
data
gathering,
and
has
published
procedures
for
composite
sampling
in
regulations
and
analytical
methods.
Analysis
of
composite
samples
with
respect
to
detection
and
quantitation
is
not
fundamentally
different
from
analysis
of
individual
samples.
In
fact,
no
advantage
is
gained
with
respect
to
detection
and
quantitation
by
compositing
samples.
Compositing
a
number
of
samples
with
concentrations
below
detection
levels
with
one
or
a
few
samples
above
detection
levels
can
cause
the
composite
sample
to
have
a
concentration
below
detection.
Increased
February
25,
2003
Page
13
replicate
analysis
of
the
same
sample
would
be
a
better
means
of
improving
a
detection
limit
estimate.

A
new
approach
should
be
assessed
in
same
way
as
those
presented
(
WP2­
8)

Comment:
If
a
revised
MDL
or
some
other
new
limit
calculation
is
adopted,
it
should
be
assessed
in
the
same
way
that
the
various
approaches
have
been
assessed.

Response:
EPA
is
not
proposing
a
new
approach
in
today's
rule,
but
is
proposing
modifications
to
the
existing
MDL
and
ML
approaches.
These
modifications
are
included
in
the
assessment
detailed
in
the
Assessment
Document
that
supports
this
proposal.
EPA
also
is
soliciting
comments
on
a
new
approach
recently
suggested
by
the
Inter­
Industry
Analytical
Group
(
IIAG).
EPA
agrees
that
if
comments
suggest
further
consideration
of
the
IIAG
approach,
it
(
and
any
other
new
approach)
must
be
assessed
in
the
same
way
that
the
various
approaches
have
been
assessed
in
the
Assessment
Document.
February
25,
2003
Page
14
Responses
to
Comments
Submitted
by
Dallas
Wait
Data
Quality
Act
(
PL
106­
554),
(
DW­
1)

Comment:
The
Data
Quality
Act
mandates
that
the
Office
of
Management
and
Budget
(
OMB)
issue
guidance
to
federal
agencies
for
"
ensuring
and
maximizing
the
quality,
objectivity,
utility,
and
integrity
of
information
(
including
statistical
information)
disseminated
by
federal
agencies."
The
construct
of
EPA's
draft
Assessment
Document
is
consistent
with
the
spirit
of
this
act.

Response:
EPA
thanks
the
peer
reviewer
for
the
recognition.

Daubert
(
DW­
2)

Comment:
EPA
should
be
applauded
for
invoking
the
Daubert
factors
(
testing
and
validation,
peer
review,
rate
of
error,
and
general
acceptance
in
the
scientific
community).
Use
of
the
Daubert
approach
is
defensible
and
should
give
the
resultant
consensus
document
long­
term
standing.

Response:
EPA
appreciates
the
positive
feedback
and
agrees
that
the
Court's
definition
of
scientific
validity
has
been
helpful
in
evaluating
alternatives.

Resolution
of
detection/
quantitation
issues
(
DW­
3)

Comment:
Overall,
I
believe
the
Assessment
Document
effort
is
a
rigorous,
open
and
honest
attempt
by
EPA
to
resolve
a
technically
and
operationally
difficult
matter
in
a
manner
fair
to
all
sides.

Response:
EPA
appreciates
the
peer
reviewer's
opinion.

Literature
search
(
DW­
4)

Comment:
The
thoroughness
of
the
on­
line
search
for
relevant
documents
provided
in
the
Reference
Section
and
Appendix
A
of
the
Assessment
Document
was
impressive.
However,
on­
line
searches
often
don't
capture
information
contained
in
text
and
reference
books.
This
area
of
information
may
not
have
been
adequately
addressed.
EPA's
literature
search
was
extensive,
regardless
of
my
suggestions
to
examine
some
other
sources.

Response:
EPA
has
included
references
to
text
and
reference
books
in
the
revised
version
of
the
Assessment
Document
in
response
to
this
suggestion.
February
25,
2003
Page
15
Perception
of
detection/
quantitation
approaches
by
other
Federal
and
State
agencies
(
DW­
5)

Comment:
EPA
appears
to
have
closely
examined
the
detection
and
quantitation
approaches
by
professional
organizations.
Has
EPA
rigorously
examined
how
these
approaches
are
perceived
and
implemented
by
other
Federal
and
State
agencies
(
e.
g.,
USGS,
NRC,
FDA,
DOD,
DOE)?
For
example,
Chapter
19
of
the
recently
published
draft
document
entitled
"
Multi­
Agency
Radiological
Laboratory
Analytical
Protocols
Manual"
(
MARLAP)
discusses
detection
and
quantitation
issues.
It
would
be
useful
for
EPA
to
tabulate
the
approaches
used
by
federal
and
state
agencies
in
the
Assessment
Document.

Response:
In
response
to
this
comment,
EPA
has
added
a
new
section
on
"
Approaches
Advocated
by
Other
Governments"
to
Chapter
2
of
the
Assessment
Document
(
see
Section
2.3.4).
EPA
did
not
tabulate
use
by
federal
and
state
agencies
because
such
a
tabulation
would
be
a
formidable
task
that
is
unlikely
to
yield
new
information
or
improve
the
assessment.
For
example,
EPA
found
more
than
140
uses
by
more
than
50
organizations
in
developing
the
Environmental
Monitoring
Methods
Index
(
EMMI)
in
1995.
In
many
instances,
different
organizations
use
the
same
term
to
describe
different
things.
In
other
instances,
different
organizations
use
different
terms
to
describe
the
same
thing.
Also,
EPA
has
found
that
nearly
all
of
the
state
and
federal
"
uses"
are
merely
different
applications
(
i.
e.,
reporting
thresholds,
permit
limits,
certification
criteria,
etc.)
of
the
basic
approaches
that
EPA
evaluated
or
are
only
slightly
different
variants
of
these
approaches.
For
example,
the
U.
S.
Geological
Survey
has
adopted
something
called
a
longterm
MDL
that
is
based
on
many
of
the
same
fundamental
assumptions
as
the
MDL.
Therefore,
rather
than
tabulating
uses
by
different
organizations,
EPA
focused
the
assessment
on
the
most
widely
used
and
recognized
detection
and
quantitation
limit
approaches,
and
incorporated
a
consideration
of
state
and
local
implementation
of
these
approaches
into
it's
evaluation
criteria
(
see
Evaluation
Criterion
6)

Case
law
(
DW­
6)

Comment:
Another
source
of
information
may
be
Case
Law.
Has
EPA
examined
whether
there
is
a
legal
record
detailing
EPA
(
and
others,
e.
g.,
NEIC,
DOJ)
opinions
on
these
matters?
If
so,
their
opinions
and
those
of
the
Court
should
be
acknowledged.

Response:
EPA
has
not
done
a
rigorous
search
of
case
law
for
litigation
on
detection/
quantitation
limit
approaches
in
general,
and
has
instead
focused
its
assessment
on
the
scientific
basis
for
many
approaches
and
practical
aspects
of
implementing
those
approaches
to
meet
EPA
needs
under
the
Clean
Water
Act.
February
25,
2003
Page
16
Justification
for
seven
replicates
in
the
MDL
procedure
(
DW­
7)

Comment:
EPA
should
justify
why
seven
replicates
were
chosen
to
determine
MDLs
rather
than
six,
eight,
or
some
other
number.

Response:
During
development
of
the
MDL
procedure,
the
use
of
seven
replicates
was
selected
in
consultation
among
several
EPA
analysts
and
statisticians
based
on
(
1)
the
number
that
would
be
not
overly
burdensome
to
measure
in
the
laboratory
and
(
2)
the
point
at
which
the
multiplier
is
approaching
an
asymptote
in
Student's
t­
test.
There
is
no
absolute
justification
for
exactly
seven
replicates,
in
the
same
way
that
there
would
be
no
justification
for
exactly
six
or
exactly
eight
replicates.
In
response
to
this
peer
reviewer's
suggestion,
EPA
has
modified
Section
2.2.1
of
the
Assessment
Document
to
include
this
explanation.

Matrix
effects
(
DW­
8)

Comment:
Matrix
effects
are
an
extremely
critical
element
to
be
considered
when
generating
MDLs.
As
EPA
notes,
since
each
environmental
sample
is
unique,
it
would
be
impossible
to
conduct
a
MDL
study
on
each.
The
best
means
of
dealing
with
this
reality
is
by
employing
on
a
project
by
project
basis
a
graded
approach
to
verifying
MDLs.
The
EPA
data
quality
objectives
(
DQO)
process
is
an
efficient
mechanism
for
addressing
the
variability
of
MDLs
between
different
matrices.

Response:
EPA
agrees
that
the
DQO
process
would
be
an
effective
means
for
dealing
with
the
variability
of
MDLs
between
different
matrices.

Reference
matrices
(
DW­
9)

Comment:
EPA
states
that
it
believes
that
reference
matrices
should
be
used
to
establish
method
detection
and
quantitation
limits.
Has
EPA
considered
establishing
a
repository
of
"
typical"
matrices
where
low
background
concentrations
of
contaminants
are
thoroughly
characterized
similar
to
the
National
Institute
of
Standards
(
NIST)
Standard
Reference
Materials
(
SRMs)?
If
laboratories
had
the
option
of
evaluating
MDLs
using
matrices
similar
to
samples
they
were
studying
(
e.
g.,
POTW
wastewater,
salt
water,
river
sediment,
pond
sediment,
clay),
this
would
give
labs
an
option
in
demonstrating
their
analytical
capabilities
in
a
fashion
comparable
to
other
labs.
Use
of
these
low
level
matrices
would
be
determined
during
the
DQO
process.

Response:
EPA
has
considered,
at
various
times,
providing
reference
matrices
for
performance
evaluation
and
other
purposes.
Difficulties
include
(
1)
the
stability
of
aqueous
samples
and
the
holding
times
necessary
to
assure
stability,
(
2)
the
argument
that
no
reference
matrix
would
represent
all
possible
matrices,
even
within
a
given
industrial
category,
(
3)
making
and
February
25,
2003
Page
17
preserving
a
reference
matrix
requires
extensive
study,
as
evidenced
by
NIST's
experience,
(
4)
the
costs
involved
in
developing
and
maintaining
a
repository
of
reference
matrices,
and
(
5)
the
potential
conflict
with
NIST
and
with
non­
governmental
organizations
that
provide
reference
matrices.
In
addition,
the
ultimate
use
of
the
reference
material
would
be
for
performance
evaluation,
a
situation
likely
to
bring
contention
over
the
reliability
of
the
reference
material.
Given
all
of
these
difficulties,
EPA
believes
that
it
is
better
to
have
an
organization
with
experience
in
developing
SRMs,
such
as
NIST
provide
reference
materials.
In
response
to
this
reviewer's
comment,
EPA
has
added
a
section
titled
"
Repository
of
Reference
Matrices"
to
the
Assessment
Document
supporting
today's
proposed
rule
(
see
Chapter
3,
Section
3.1.3.2).

Allowance
for
use
of
a
different
detection/
quantitation
approach
by
a
laboratory
(
DW­
10)

Comment:
Section
3.2.4
of
the
Assessment
Document
discusses,
in
part,
the
option
of
using
performance
standards
over
prescriptive
standards,
which
would
allow
laboratories
and
others
the
freedom
to
use
a
variety
of
different
approaches
to
establish
limits.
Although
theoretically
this
sounds
agreeable,
operationally
this
would
be
a
nightmare
and
comparability,
a
QA
tenet,
would
be
jeopardized.
I'm
not
in
favor
of
this
approach.

Response:
EPA
is
committed
to
flexibility
in
analytical
measurements,
and
EPA's
water
programs
have
favored
a
reference
method
or
procedure
with
QC
acceptance
criteria
for
establishing
a
performance
benchmark.
However,
EPA
does
not
want
to
force
other
organizations
to
use
the
EPA
approach
for
detection
and
quantitation
because
other
approaches
may
also
be
suitable
for
CWA
applications.
Therefore,
in
this
instance,
EPA
believes
that
it
is
better
to
standardize
on
one
pair
of
procedures
(
detection
and
quantitation)
and
continue
to
accept
methods
that
use
alternate
procedures
when
the
method
provides
the
sensitivity
and
performance
needed
for
use
in
CWA
programs.
For
example,
EPA
would
continue
to
accept
a
Standard
Method
or
ASTM
method
that
specifies
a
different
type
of
detection
or
quantitation
limit,
provided
it
meets
EPA's
regulatory
needs.

Sources
of
variability
(
uncertainty)
(
DW­
11)

Comment:
Overall,
the
analytical
chemistry,
CWA
regulatory
issues,
and
statistical
issues
presented
in
Section
3
of
the
draft
Assessment
Document
are
comprehensive.
In
Section
3.3.1,
the
discussion
on
sources
of
variability
could
be
enhanced
to
address
the
impact
of
variability
at
the
MDL
and
how
this
variability
impacts
data
use.

Response:
EPA
agrees
and,
in
response
to
this
suggestion,
has
enhanced
the
discussion
in
Section
3.3.1
of
the
Assessment
Document.
February
25,
2003
Page
18
Measurement
quality
over
the
life
of
a
method
(
DW­
12)

Comment:
Although
informative,
Section
3.1.4
of
the
Assessment
Document,
which
discusses
measurement
quality
over
the
life
of
a
method,
could
probably
be
deleted
without
hurting
the
integrity
of
the
Chapter.

Response:
After
carefully
considering
this
comment,
as
well
as
comments
from
other
peer
reviewers,
EPA
has
decided
to
retain
the
section
(
which
now
appears
as
Section
3.1.5
of
the
revised
Assessment
Document).
EPA
discussed
the
issue
of
measurement
quality
over
the
life
of
an
analytical
method
in
the
context
of
detection
and
quantitation
because
method
performance,
including
the
ability
to
detect
and
quantify
to
lower
levels,
improves
with
time.
EPA
believes
this
is
an
important
point
that
is
worth
making
because
detection
and
quantitation
limits
published
in
the
methods
may
not
reflect
current
method
and
laboratory
capabilities.

Adequacy
of
evaluation
criteria
(
DW­
13)

Comment:
All
of
the
criteria
used
by
EPA
are
pertinent
to
the
evaluation
of
viable
detection
and
quantitation
limit
methods.
The
explanations
for
each
criterion
are
reasoned
and
persuasive.
I
would
not
remove
any
criteria
from
the
evaluation
process.
No
other
evaluation
criteria
are
apparent.

Response:
This
comment
was
consistent
with
comments
made
by
other
peer
reviewers.
EPA
appreciates
the
positive
feedback.

Validity
of
assessment
(
DW­
14)

Comment:
The
thorough
evaluation
process
used
by
EPA
is
excellent!
A
comprehensive
and
open
discussion
was
performed
for
all
five
detection
limit
approaches
and
four
quantitation
limit
approaches.
These
discussions
fairly
debate
the
pros
and
cons
of
each
approach.

Response:
EPA
thanks
the
peer
reviewer
for
the
comment.

Clarification
of
Step
1
of
the
MDL
procedure
(
DW­
15)

Comment:
In
Section
5.1.1.2.1
of
the
Assessment
Document,
EPA
astutely
notes
that
many
people
complain
that
MDLs
can
vary
depending
on
spike
levels
used,
based
on
the
mistaken
assumption
that
spike
levels
may
be
arbitrarily
selected.
I
have
witnessed
this
same
complaint
numerous
times.
EPA
also
properly
notes
that
Step
1
of
the
MDL
procedure
specifies
a
number
of
criteria
that
must
be
met
in
selecting
spike
levels.
Apparently
many
chemists
just
don't
get
it.
It
would
be
advantageous
for
EPA
to
embellish
Step
1,
possibly
with
examples,
to
make
the
requirement
clearer.
February
25,
2003
Page
19
Response:
EPA
agrees
and
is
proposing
revisions
to
the
MDL
procedure.
Among
these
clarifications
are
more
specific
instructions
at
Step
1.

Alternative
detection/
quantitation
procedures
(
DW­
16)

Comment:
The
Assessment
Document
is
not
clear
in
what
options
EPA
is
considering
and
what
alternative
approaches
and
procedures
EPA
will
accept.
Any
flexibility
in
approaches
and
procedures
could
lead
to
further
litigation.

Response:
EPA
has
included
the
following
statement
in
the
MDL
procedure
proposed
today:
"
An
alternative
procedure
may
be
used
(
e.
g.,
from
a
voluntary
consensus
standards
body)
to
establish
the
sensitivity
of
an
analytical
method,
provided
the
resulting
detection
limit
meets
the
sensitivity
needs
for
the
specific
application."
This
statement
allows
EPA
to
continue
to
accept
methods
from
VCSBs
with
detection
limits
other
than
MDLs.

EPA
does
not
believe
that
flexibility
in
detection
and
quantitation
approaches
and
procedures
would
necessarily
result
in
further
litigation.
EPA
has
already
approved
hundreds
of
methods
developed
by
other
organizations,
and
many
of
those
methods
cite
sensitivity
ranges
that
are
not
based
on
the
MDL.
In
considering
methods
for
approval
under
the
CWA,
EPA
considers
the
regulatory
needs
associated
with
the
method
and
all
available
performance
information,
including
information
concerning
method
sensitivity.
EPA
is
unlikely
to
approve
a
method
if
it
will
not
support
regulatory
needs.
If
supporting
information
is
not
adequate
to
justify
proposing
use
of
the
method,
EPA
requires
additional
information
from
the
method
developer
prior
to
approval.

Better
correlation
between
Table
6­
1
and
the
text
(
DW­
17)

Comment:
A
better
correlation
between
the
findings
in
Table
6­
1
of
the
Assessment
Document
and
the
associated
text
would
be
useful.
Within
Table
6­
1,
it
would
also
be
useful
to
reference
where
in
the
Assessment
Document
many
of
the
statistics
were
derived.
Also,
the
revised
MDL
procedures
presented
in
Appendix
D
should
be
mentioned.

Response:
EPA
agrees
and
has
made
the
recommended
changes
to
the
revised
version
of
the
Assessment
Document
released
today.

Additional
data
sets
(
DW­
17)

Comment:
EPA
has
requested
additional
data
sets.
During
the
1980s
numerous
interlaboratory
method
evaluation
studies
were
conducted
by
EPA's
ORD
group
in
Cincinnati,
some
of
which
may
have
looked
at
detection
limits.
Has
EPA
examined
any
of
their
historical
work
for
pertinent
MDL
information?
Also,
as
I
recall,
George
Stanko
of
Shell
presented
a
fairly
large
study
challenging
EPA's
detection
limits
for
volatile
organics
in
water
February
25,
2003
Page
20
at
EPA's
annual
Analytical
Symposium
in
Norfolk,
Virginia?
Has
EPA
petitioned
large
trade
associations,
such
as
the
American
Petroleum
Institute
(
API),
about
detection
and
quantitation
studies
they
may
have
sponsored?
Personally,
I
am
not
aware
of
any
additional
detection
and
quantitation
limit
data
sets
that
may
be
of
value
to
EPA.

Response:
The
interlaboratory
method
validation
studies
conducted
by
EPA's
laboratory
in
Cincinnati
were
not
directed
at
determining
detection
and
quantitation
limits
but
rather
at
characterizing
precision
and
recovery
across
the
analytical
range.
Regarding
studies
by
the
late
George
Stanko
of
Shell,
EPA
reviewed
the
minutes
of
the
Annual
Analytical
Symposia
and
found
the
papers
by
George
Stanko,
but
the
papers
did
not
include
data
that
could
be
used
to
evaluate
the
various
detection
and
quantitation
approaches.
Regarding
data
sets
from
studies
sponsored
by
trade
associations,
EPA
has
requested
such
information
in
discussions
with
the
Electric
Power
Research
Institute
(
EPRI),
the
Inter­
industry
Analytical
Group,
and
others.
The
Petitioners
and
Intervenor
provided
EPA
with
a
list
of
databases
for
consideration.
This
list,
and
EPA's
decision
regarding
each
of
the
recommended
databases,
is
discussed
in
the
revised
Assessment
Document.
In
addition,
EPA
is
soliciting
any
appropriate
data
sets
in
the
proposal.

Inter­
vs
intra­
laboratory
issues
(
DW­
18)

Comment:
Use
of
inter­
laboratory
measurements
is
important
for
a
general
understanding
of
the
laboratory
communities'
capabilities,
but
is
not
as
relatable
to
the
issues
that
EPA
must
consider
in
support
of
a
permittee's
CWA
requirements.
Intra­
laboratory
measurements
are
more
practical.
EPA's
approach
between
inter­
and
intra­
studies
is
balanced
and
reasonable.

Response:
EPA
appreciates
the
support.

Improvements
to
detection/
quantitation
procedures
(
DW­
19)

Comment:
The
MDL
and
ML
approaches
evaluated
in
the
Assessment
Document
are
shown
to
be
technically
sound
and
practical.
The
revised
MDL
procedure
provided
in
Appendix
D
is
streamlined
and
more
intelligible
than
the
previous
version,
although
a
reexamination
of
Step
1
to
aid
chemists
in
the
spiking
level
requirement
may
be
warranted.
The
detection
and
quantitation
approaches
I'm
aware
of
have
already
been
adequately
"
fleshed"
out
by
EPA.

Response:
EPA
appreciates
the
positive
feedback
and
has
added
detail
to
the
spiking
procedure,
as
the
peer
reviewer
suggests.
February
25,
2003
Page
21
Recommendations
for
improvements
to
the
Assessment
Document
(
DW­
20)

Comment:
Although
the
Assessment
Document
is
necessarily
long
and
dense
with
information,
it
is
well
written
and
flows
logically.
I
would
not
make
any
structural
changes
to
the
document.

Response:
EPA
appreciates
the
feedback,
and
has
retained
the
overall
structure
in
the
revised
version
of
the
Assessment
Document.

EPA's
Quality
System
(
DW­
21)

Comment:
Since
the
Assessment
Document
addresses
fundamental
quality
assurance
issues,
I'm
surprised
that
there
is
no
acknowledgment
or
reference
to
EPA's
Quality
System.
EPA
may
want
to
reexamine
the
Assessment
Document
and
update
as
appropriate
to
remain
consistent
with
Agency
directives.

Response:
In
response
to
this
comment,
EPA
Office
of
Water
staff
searched
the
Quality
System
documents
for
specific
information
regarding
detection
and
quantitation,
and
could
not
find
a
direct
reference.
EPA
believes,
however,
that
the
assessment
is
consistent
with
policies
embodied
in
EPA's
Quality
System.

Acronyms
and
abbreviations
(
DW­
22)

Comment:
A
listing
of
acronyms
and
abbreviations
would
be
useful.

Response:
EPA
agrees
and
will
add
a
list
to
the
final
Assessment
Document.

Typographical
errors
(
DW­
23)

Comment:
A
list
of
typographical
and
grammatical
errors
is
included.

Response:
EPA
thanks
the
commenter
for
the
list
and
has
corrected
the
typographical
and
grammatical
errors.

Information
that
EPA
could
add
to
the
Assessment
Document
(
DW­
24)

Comment:
A
list
of
additional
references
is
included.

Response:
EPA
thanks
the
commenter
for
the
list
and
has
added
the
references.
February
25,
2003
Page
22
Responses
to
Comments
Submitted
by
Marcus
Cooke
EPA
should
consider
European
approaches
to
detection
and
quantitation
and
treatment
of
analytical
data
(
MC­
1,
MC­
5)

Comment:
EPA
could
consider
method
verification,
data
reliability,
and
detection
approaches
that
have
been
developed
by
the
European
Union
(
EU).
One
example
is
the
application
of
the
operational
equivalent
of
EPA
Method
1613B
for
chlorinated
dibenzo­
p­
dioxins
and
dibenzofurans
(
CDDs/
CDFs).
Vegetable
foodstuffs
must
be
tested
at
levels
more
than
an
order
of
magnitude
below
the
method
detection
limit
(
MDL)
of
1­
5
parts­
per­
trillion
(
ppt)
in
EPA
Method
1613B.
EU
regulators
applied
an
"
Upper
Bound"
reporting
limit
where
non­
detects
are
found,
using
the
EPA
MDL
for
each
analyte.
This
forces
laboratories
to
achieve
levels
available
with
modern
instrumentation,
otherwise
the
"
Upper
Bound"
reporting
level
is
above
the
regulatory
compliance
level
and
the
data
(
or
foodstuffs)
are
rejected.

EPA
may
want
to
consider
recent
advances
in
the
statistical
treatment
of
analytical
method
data
that
has
evolved
in
Europe,
for
3
reasons:
(
1)
The
EU
is
conducting
the
largest
trace
chemical
analytical
program
in
the
world
(
EPA
is
the
record
holder
with
the
Contract
Laboratory
Program,
$
1.5B+);
(
2)
The
EU
has
applied
an
operational
equivalent
of
EPA
Method
1613B
to
a
regulatory
program
that
screens
all
food
and
animal
feed
used,
produced,
or
imported;
and
(
3)
The
subject
EU
program
has
developed
practical
solutions
to
applying
modern
ultra­
trace
measurements
(
and
statistical
verification)
in
a
legally­
based,
widely­
applied
testing
program.

Response:
EPA
has
revised
Chapters
2,
3
and
4
of
the
Assessment
Document
to
address
these
suggestions.
It
is
important
to
recognize
that
the
Upper
Bound
approach
described
by
the
reviewer
is
directed
at
reporting
limits,
rather
than
detection
or
quantitation
limits,
and
that
in
adopting
this
approach,
the
EU
has
essentially
1)
accepted
the
MDL
concept,
2)
used
the
MDL
as
a
reporting
limit,
and
3)
utilized
the
relatively
low
cost
and
ease
of
the
MDL
procedure
as
a
tool
for
encouraging
improvements
in
measurement
technology.
EPA
agrees
that
this
approach,
which
yields
a
"
worst­
case"
(
i.
e.,
highest
possible)
estimate
of
the
pollutant
concentration,
can
serve
as
a
useful
tool
for
encouraging
the
analytical
and
regulated
community
to
pursue
measurements
at
the
lowest
levels
necessary
to
protect
human
and
ecological
health.
EPA
believes
such
an
approach
may
be
useful
in
the
context
of
establishing
permit
limits,
but
that
the
approach
does
not
shed
new
light
on
the
issue
of
establishing
detection
and
quantitation
limits.

A
reference
material
would
aid
in
evaluating
"
trueness"
(
MC­
2)

Comment:
Many
EU
procedures
have
a
"
trueness"
criterion.
This
is
accuracy
determined
by
percent
recovery
of
an
accepted
reference
material.
In
order
to
incorporate
trueness
into
an
EPA
method
validation
study,
an
appropriate
February
25,
2003
Page
23
reference
material
would
need
to
be
developed
ahead
of
time
and
included
in
the
study.

Response:
For
method
validation
and
periodic
testing,
EPA
uses
reagent
water
as
the
reference
material
because
reagent
water
is
available
to
all
laboratories.
Where
possible,
EPA
requires
use
of
a
reference
material
for
periodic
method
performance
verification.
For
example,
with
each
analytical
batch
of
20
or
fewer
samples,
Section
9.5
of
EPA
Method
1631E
requires
analysis
of
mercury
spiked
into
reagent
water
(
the
"
ongoing
precision
and
recovery"
(
OPR)
sample),
and
Section
9.5
requires
analysis
of
a
quality
control
sample
(
QCS).
The
QCS
can
be
a
Standard
Reference
Material
(
SRM)
from
the
National
Institute
of
Standards
and
Technology
(
NIST)
or
other
material
obtained
from
a
different
source
than
the
calibration
standard
and
OPR
standard.
Recovery
of
the
OPR
must
be
within
the
QC
acceptance
criteria
in
EPA
Method
1631
and
recovery
of
the
SRM
or
other
QCS
must
be
within
the
limits
specified
by
the
organization
responsible
for
providing
the
material.

While
EPA
agrees
that
the
use
of
such
reference
materials
can
be
of
value
in
a
validation
study,
EPA
notes
that
the
universe
of
SRMs
or
certified
reference
materials
(
CRMs)
for
matrices
and
analytes
relevant
to
the
Clean
Water
Act
is
limited.
More
importantly,
few,
if
any,
SRMs
are
available
at
concentrations
in
the
region
of
interest
for
establishing
detection
and
quantitation
limits
of
a
given
method.
EPA
has
added
a
discussion
of
these
issues
to
Chapter
3
of
the
revised
Assessment
Document.

European
protocols
give
tools
for
uncertainty
evaluation
(
MC­
3)

Comment:
The
Eurachem
Guide
Quantifying
Uncertainty
in
Analytical
Measurement,
Second
Edition
(
QUAM:
2000.
P1),
provides
guidelines
to
evaluate
uncertainty
in
analytical
measurements.
These
elements
were
detailed
in
a
presentation
at
the
22nd
International
Symposium
on
Halogenated
Environmental
Organic
Pollutants
and
POPs
[
persistent
organic
pollutants]
(
the
"
22nd
International
Symposium).
United
Kingdom
Valid
Analytical
Measurement
Programme
(
VAM)
Project
3.2.1
Development
and
Harmonisation
of
Measurement
Uncertainty
Principles
(
LGC/
VAM/
1998/
088,
January
2000)
protocols
give
additional
tools
for
uncertainty
evaluation.

Response:
In
response
to
this
suggestion,
EPA
reviewed
the
Eurochem
and
VAM
documents
and
modified
Chapters
2
and
4
of
the
Assessment
Document
to
describe
EPA's
findings.
The
European
Union
(
EU)
guidance
advocates
reporting
all
results
along
with
an
estimate
of
the
uncertainty
associated
with
each
value.
In
its
discussion
of
the
issue,
the
EU
indicates
that
use
of
the
term
"
limit
of
detection"
only
implies
a
level
at
which
detection
becomes
problematic
and
is
not
associated
with
any
specific
definition.
Instead,
the
EU
focuses
its
attention
on
ways
to
estimate
uncertainty,
basing
February
25,
2003
Page
24
its
approach
on
the
ISO
Guide
to
the
Expression
of
Uncertainty
in
Measurements
(
1993).
The
EU
also
notes,
however,
that
the
use
of
uncertainty
estimates
in
compliance
statements
and
the
expression
and
use
of
uncertainty
at
low
levels
may
require
additional
guidance.
The
VAM
document,
published
by
the
United
Kingdom
(
UK),
uses
a
similar
approach.
Because
both
of
these
approaches
focus
on
estimating
uncertainty
rather
than
at
establishing
or
defining
limits
for
detection
and
quantitation,
EPA
does
not
believe
they
warrant
extensive
evaluation
as
part
of
the
Agency's
assessment
of
approaches
for
establishing
detection
and
quantitation
limits.
Moreover,
given
the
difficulty
in
achieving
consensus
on
an
appropriate
means
of
establishing
a
detection
limit,
EPA
believes
it
would
be
extremely
difficult
to
obtain
consensus
on
an
appropriate
means
for
estimating
the
uncertainty
associated
with
each
result
measured
on
each
environmental
sample.
EPA
will
continue
to
monitor
developments
by
the
EU
and
others
on
this
subject,
and
if
appropriate,
re­
evaluate
this
issue
if
and
when
it
becomes
widely
accepted
by
the
environmental
laboratory
community.

Contributions
to
uncertainty
(
MC­
4)

Comment:
In
another
presentation
at
the
22nd
International
Symposium,
contributions
to
measurement
uncertainty
for
CDD/
CDF
analysis
of
food
and
feed
were
presented.
The
major
contributions
were
from
precision,
trueness
(
bias),
purity
(
not
defined,
but
presumably
the
purity
of
the
reference
material
used
in
the
analysis),
and
[
sample]
homogeneity.

Response:
EPA
is
familiar
with
the
presentations
and
agrees
with
identified
contributions
to
measurement
uncertainty.
Sources
of
uncertainty
are
useful
for
understanding
the
analytical
process
so
that
analytical
methods
can
be
refined
in
an
attempt
to
reduce
uncertainty
and
thereby
lower
detection
and
quantitation
limits.

Quality
control
(
MC­
6)

Comment:
Chapter
3
of
the
Draft
Assessment
Document
addresses
20
technical
elements,
and
Chapter
6
addresses
6
directed
issues.
EPA
may
want
to
consider
the
additional
issues
of
quality
control
(
QC)
and
use
of
reference
materials.
These
issues
may
have
a
significant
effect
on
the
reliability
of
data
produced
at
ultra­
trace
levels,
whether
to
determine
the
initial
presence
of
an
analyte
like
mercury,
or
reliably
apply
regulations
at
a
discharge
limit.

Single
laboratories,
working
independently,
start
from
scratch
each
time
they
perform
a
method.
QC
should
be
sufficient
to
insure
reliability
in
single,
isolated
determinations
of
small
sample
sets,
as
well
as
in
large
commercial
laboratories
performing
many
tests.

Response:
The
methods
approved
for
use
under
the
Clean
Water
Act
include
a
standardized
suite
of
quality
control
procedures
and
analyses
that
are
February
25,
2003
Page
25
designed
to
ensure
that
the
analytical
results
can
be
assessed
and
their
reliability
can
be
determined,
regardless
of
the
size
of
the
laboratory
performing
the
analysis.
Where
practical,
analyses
of
reference
materials
form
a
portion
of
those
QC
procedures.
However,
as
noted
earlier,
the
universe
of
relevant
SRMs
in
limited,
and
their
relevance
to
establishing
detection
and
quantitation
limits
also
is
limited.

However,
in
response
to
this
suggestion,
EPA
has
revised
Chapter
3
of
the
Assessment
Document
to
include
additional
discussion
of
QC
and
reference
materials
in
Chapter
3
(
see
Section
3.1.3.2,
Repository
of
Reference
Matrices
and
Section
3.1.5,
Measurement
Quality
of
the
Life
of
a
Method).

Use
of
a
reference
material
for
calibration
(
MC­
7)

Comment:
Calibration
required
in
Method
1631B
could
be
enhanced
by
use
of
a
reference
material
which
contains
a
"
real
world"
matrix,
and
also
mercury
forms
known
to
exist
in
natural
samples.

Response:
Enhancements
to
EPA
Method
1631
are
outside
the
scope
of
the
assessment
that
is
the
subject
of
this
peer
review.
However,
EPA
will
consider
the
suggestion
during
any
future
revision
of
Method
1631.
For
the
record,
Section
7.7
of
EPA
Method
1631E
(
and
previous
revisions)
requires
that
the
stock
mercury
standard
be
the
NIST­
certified
10,000­
ppm
aqueous
Hg
solution
(
NIST­
3133).

Mercury
forms,
species,
and
compounds
(
MC­
8)

Comment:
Elemental
mercury
in
nature
often
converts
to
Cinnabar
or
meta­
Cinnabar,
forms
of
mercuric
sulfide.
These
are
very
stable,
innocuous
forms
of
mercury.
Ambient
samples
can
also
contain
organomercurials
that
have
elevated
human
toxicity.
EPA
might
consider
a
demonstration
study
to
show
how
"
safe"
or
"
unsafe"
mercury
forms
are
oxidized
by
BrCl,
and
are
subsequently
measured
by
Method
1631,
especially
at
low
concentrations
near
the
limit
of
detection.

Response:
EPA
appreciates
the
suggestion.
However,
further
evaluation
of
EPA
Method
1631
is
beyond
the
scope
of
the
assessment
that
is
the
subject
of
this
peer
review.

Cost
and
ease­
of­
use
(
MC­
9)

Comment:
The
complex
theoretical
treatments
defined
in
the
Assessment
Document
and
the
resultant
additional
analyses
required
in
regulatory
applications
of
Method
1631B
may
produce
significant
cost
due
to
new
supporting
analyses
needed
to
demonstrate
detection
and
data
reliability.
The
Assessment
Document
does
not
adequately
address
cost
to
users.
Considerations
of
ease­
of­
use
and
cost
should
be
included
in
any
final
revisions
arising
from
February
25,
2003
Page
26
this
process.
Cost
issues
should
be
fully
addressed
in
summary
reviews
of
the
Assessment
Document.

Response:
EPA
agrees
that
the
"
complex
theoretical
treatments"
involved
in
some
of
the
approaches
to
establishing
detection
and
quantitation
limits
would
raise
the
costs
of
establishing
such
limits.
Such
costs
would
be
incurred
by
the
developer
of
the
method
(
e.
g.,
EPA
or
another
organization).
EPA
is
even
more
concerned
about
increasing
the
costs
incurred
by
individual
laboratories
and,
therefore,
passed
on
to
their
clients
(
data
users)
if
each
laboratory
was
required
to
duplicate
the
"
treatments"
involved.
Therefore,
in
its
assessment,
EPA
favored
approaches
that
could
be
readily
applied
in
a
single
laboratory,
either
to
establish
or
verify
the
detection
and
quantitation
limits
associated
with
an
analyte.

In
response
to
this
comment,
EPA
included
an
enhanced
discussion
of
these
issues
in
Section
3.2.6
(
Cost
and
Implementation
Issues)
of
the
revised
Assessment
Document.

Background,
matrix
effects,
and
sources
of
variance
(
MC­
10)

Comment:
The
Assessment
Document
gives
considerable
discussion
to
the
problems
that
arise
from
background,
matrix
effects,
and
sources
of
variance.
Topics
such
as
instrument
maintenance,
reliability,
and
time
stability
of
calibration
standards,
anion
solubility
effects,
and
related
topics
are
also
important
to
implementation
of
a
method.
EPA
has
done
a
good
job
addressing
these
issues,
both
in
the
Assessment
Document
and
in
Method
1631B.

Response:
EPA
appreciates
the
reviewer's
positive
feedback.

QC
charts
(
MC­
11)

Comment:
Good
QC
would
include
QC
charts
that
identify
statistically
significant
loss
of
response
at
the
MDL
or
alternate
minimum
detection
level.
The
discussion
in
the
Assessment
Document
does
not
point
out
the
operational
difficulty
in
applying
a
method­
defined
MDL
to
single­
laboratory
determinations
of
a
few
samples.

The
evaluation
criteria
stated
in
Chapters
3
and
4
of
the
Assessment
Document
do
not
address
adequate
measures
to
estimate
increased
variability
near
the
limit
of
detection.
Nor
do
they
establish
rigorous
criteria
for
data
acceptance.
In
practical
laboratory
operations,
techniques
like
control
charts,
maintained
over
time,
would
provide
reliable
measures
of
variability
during
actual
laboratory
operations.

Response:
EPA
agrees
that
control
charts
are
instructive
in
tracking
variability
in
laboratory
performance
over
time.
However,
EPA
believes
they
have
two
potential
drawbacks:
(
1)
they
do
not
establish
an
absolute
limit
within
which
February
25,
2003
Page
27
analysis
must
operate,
and
(
2)
continued
improvement
could
lead
to
unusually
stringent
limits,
that
eventually
will
not
be
met.
To
compound
the
problem,
EPA
found
that
some
regulatory
authorities
are
penalizing
laboratories
that
do
not
keep
QC
charts
up
to
date,
even
though
laboratories
are
operating
within
the
QC
acceptance
criteria
(
limits)
of
a
method.
In
such
cases,
a
concept
that
is
intended
to
serve
as
a
useful
diagnostic
tool
for
the
laboratory
is
having
unanticipated
negative
consequences.
That
said,
however,
EPA
agrees
that
control
charts,
maintained
over
time,
can
be
instructive
in
identifying
statistically
significant
losses
of
analyte
responses
in
the
region
of
interest.
EPA
has
included
a
discussion
of
this
issue
in
Section
3.1.5,
Measurement
Quality
over
the
Life
of
a
Method,
of
the
revised
Assessment
Document.

However,
the
issue
of
"
applying
a
method­
defined
MDL
to
singlelaboratory
determinations
of
a
few
samples"
is
not
one
that
EPA
believes
can
be
addressed
by
the
use
of
control
charts.
As
noted
in
the
Assessment
Document,
EPA
is
not
promoting
the
use
of
the
MDL
as
a
reporting
limit.
EPA
believes
that
the
MDL,
as
a
measure
of
method
sensitivity,
is
an
important
consideration
in
the
selection
of
methods
to
meet
the
objectives
of
a
given
analytical
program
and
provides
a
potential
metric
for
judging
laboratory
performance
before
analyses
begin.
The
application
of
a
methoddefined
would
apply
to
any
limits
derived
using
any
of
the
procedures
considered
in
the
Assessment
Document.

EPA
also
notes
that
there
is
no
technical
problem
in
applying
an
MDL
(
or
other
detection
limit
concept)
to
single­
laboratory
determinations
of
a
few
samples.
The
problems
are
practicality
and
cost.
Because
the
MDL
is
usually
determined
using
seven
replicates,
application
to
a
few
samples
would
significantly
increase
the
cost
for
the
determination.
However,
nothing
in
the
Assessment
Document
suggests
that
the
MDL
be
determined
by
an
individual
laboratory
at
a
specific
frequency.

Plots
of
RSD
vs
concentration
(
MC­
12)

Comment:
Data
in
the
Assessment
Document
and
referenced
publications
cite
the
loss
of
precision
for
ultra­
trace
determinations
near
the
limit
of
detection.
This
effect
was
plotted
in
a
paper
presented
at
the
"
22nd
International
Symposium
and
shows
that
relative
standard
deviation
(
RSD)
decreases
rapidly
from
a
high
level
at
low
concentrations
and
reaches
an
asymptote
at
high
concentrations.

Response:
EPA
provided
plots
of
RSD
vs
concentration
in
Appendix
C
to
the
Assessment
Document.
For
nearly
all
analytes
and
determinative
techniques
these
plots
show
the
same
effect
as
the
plot
presented
at
the
22nd
International
Symposium.
EPA
considered
the
effects
of
these
plots
on
detection
and
quantitation
concepts
in
its
assessment.
February
25,
2003
Page
28
Outliers
(
MC­
13)

Comment:
The
subject
of
outliers
was
given
limited
attention
in
Chapter
3
of
the
Assessment
Document.
Outlier
treatment
is
a
statistically
valid
area
of
data
treatment.
Cochran's
test,
and
single/
double
Grubbs
tests
are
useful
in
evaluating
interlaboratory
data
sets
to
determine
outliers
and
stragglers.
Other
classical
outlier
tests
could
also
be
evaluated
in
examining
the
data
sets
used
in
the
Assessment
Document.

Response:
EPA
agrees
and
has
included
a
discussion
of
outlier
treatment
in
the
revised
MDL
procedure
being
proposed
today.

Prescriptive
vs
descriptive
use
of
lower
limits
of
measurement
(
MC­
14)

Comment:
EPA
typically
walks
a
thin
line
in
defining
descriptive
vs
prescriptive
procedures.
Regulatory
requirements
built
into
EPA
final
rules
are
very
difficult
to
change
and
cause
a
high
level
of
legal
liability
to
laboratories
and
data
users.
It
is
important
for
EPA
to
build
as
much
flexibility
as
possible
into
CWA
methods
in
order
to
prevent
"
locking"
unreasonable
or
unsound
procedures
into
final
rule
methods.

Response:
EPA
agrees
and
has
built
flexibility
in
recent
methods,
such
as
EPA
Method
1631.

National
vs
local
standards
of
measurement,
and
NPDES
uses
(
MC­
15)

Comment:
By
law,
local
restrictions
must
be
as
stringent
as
federal
rules.
This
process
is
addressed
in
current
law.
NPDES
permitting
is
well
established
in
the
U.
S.
There
should
not
be
any
unusual
legal
or
procedural
difficulties
that
arise
from
a
review
of
this
Assessment
Document.

Response:
EPA's
intent
in
mentioning
local
standards
of
measurement
was
to
determine
if
local
standards
should
be
a
consideration
in
detection
and
quantitation
limit
concepts.
EPA
agrees
with
the
peer
reviewer's
opinion
that
there
should
not
be
unusual
legal
or
procedural
difficulties
that
arise
from
EPA's
assessment
of
detection/
quantitation
limit
concepts.

Use
of
a
pair
of
procedures
(
MC­
16)

Comment:
EPA
has
stated
in
the
draft
Assessment
Document
that
one
primary
procedure
is
needed
for
clarity
and
to
avoid
confusion
among
stakeholders.
If
alternate
procedures
are
needed,
the
EPA
Clean
air
Act
system
of
reference
and
equivalent
methods
has
worked
well,
and
could
be
a
model
for
EPA
to
follow
under
the
Clean
Water
Act.

Response:
The
system
of
reference
methods
used
under
the
Clean
Air
Act
(
CAA)
is
similar
to
the
existing
"
alternate
test
procedure"
(
ATP)
program
for
February
25,
2003
Page
29
analytical
methods
currently
used
in
the
Clean
Water
Act
(
CWA)
and
the
Safe
Drinking
Water
Act
(
SDWA).
The
difference
between
the
ATP
program
and
the
use
of
alternate
procedures
for
establishing
detection
and
quantitation
limits,
is
that
in
an
ATP
program,
the
goal
is
clear
and
agreed
upon,
whereas
there
remain
fundamental
theoretical
issues
surrounding
detection
and
quantitation.

For
example,
when
a
test
procedure
is
developed
for
use
in
CAA
or
CWA
programs,
the
reference
method
is
designed
to
measure
Analyte
X,
in
Matrix
Y,
at
some
concentration
related
to
a
regulatory
need
(
e.
g.,
a
permit
limit).
Alternative
procedures
may
be
capable
of
making
measurements
of
Analyte
X
in
Matrix
Y,
at
the
level
of
concern
using
different
approaches.
Thus
the
demonstration
of
equivalency
between
the
reference
method
and
a
possible
alternative
method
is
judged
using
a
metric
that
consists
of
Analyte
X,
Matrix
Y,
and
the
level
of
concern,
as
well
as
other
aspects
of
method
performance.
In
contrast,
the
primary
differences
between
the
EPA
MDL/
ML
concepts
and
potential
alternatives,
such
as
the
ASTM
IDE
and
IQE,
are
related
to
different
interpretations
as
to
how
detection
and
quantitation
limits
should
be
derived
and
applied.
(
These
differences
are
described
in
the
Assessment
Document.)
Therefore,
EPA
does
not
believe
that
a
permutation
of
existing
ATP
programs
is
likely
to
be
an
effective
model
for
assessing
other
detection
and
quantitation
procedures.

However,
EPA
is
willing
to
consider
that
an
analytical
method
from
a
VCSB
or
other
source
may
be
acceptable
for
approval
at
40
CFR
part
136
and
use
in
CWA
programs
even
if
it
employs
an
alternative
procedure
for
establishing
method
sensitivity.
For
example,
consider
the
theoretical
situation
of
an
ASTM
method
for
the
determination
of
an
analyte
regulated
under
the
NPDES
program
that
uses
the
IDE
or
IQE
to
describe
method
sensitivity
and
for
which
the
value
of
the
IDE
or
IQE
was
below
the
relevant
regulatory
limit.
EPA
would
evaluate
the
overall
performance
of
such
a
method
for
approval
at
40
CFR
part
136,
despite
the
fact
that
the
method
did
not
contain
an
MDL
determined
using
the
Appendix
B
procedure.

In
response
to
this
comment,
EPA
enhanced
the
discussion
of
this
issue
in
the
revised
Assessment
Document.

VCSB
procedures
(
MC­
17)

Comment:
EPA
has
strived
to
include
voluntary
consensus
standards
body
(
VCSB)
detection
and
quantitation
concepts
in
the
Assessment
Document
and
has
conducted
an
extensive
review
and
discussion
of
VCSB
procedures.
International
VCSBs,
including
those
from
non­
governmental
organizations
(
NGOs)
should
be
included.
February
25,
2003
Page
30
Response:
EPA
has
included
international
VCSBs,
including
NGOs,
in
its
assessment
by
including
detection
and
quantitation
approaches
from
ASTMInternational
International
Organization
for
Standardization
(
ISO),
International
Union
of
Pure
and
Applied
Chemistry
(
IUPAC),
and
the
American
Chemical
Society
(
which
is
one
the
largest
international
scientific
organizations
in
the
world).
However,
as
discussed
in
the
Assessment
Document,
ASTM­
International
is
the
only
one
of
these
organizations
that
has
developed
detailed
procedures
for
determining
detection
and
quantitation
limits
(
i.
e.,
the
IDE
and
IQE).

Censoring
data
and
degradation
of
method
performance
over
time
(
MC­
18)

Comment:
Method
flexibility
is
discussed
in
the
Assessment
Document
and
considers
time­
dependent
modifications
to
rigid
methods.
EPA
is
gaining
experience
in
this
area
and
newer
methods
do
address
this
concern.
EPA
has
developed
an
evolving
method
development
process
that
has
been
shown
to
be
responsive
to
this
issue.

Response:
EPA
appreciates
the
positive
feedback.

Comments
on
the
Criteria
used
to
Evaluate
Detection
and
Quantitation
Limit
Concepts
(
MC­
19,
MC­
20,
MC­
21,
MC­
22,
MC­
23,
MC­
23b)

Comment:
The
six
criteria
should
provide
a
vigorous
review
of
the
conditions
set
out
in
the
draft
Assessment
Document.
(
MC­
23b)

Response:
EPA
agrees
and
appreciates
the
positive
feedback.

Comment:
Scientific
validity
is
defined
in
two
ways:
legal
reliability
and
scientific
practice.
Criterion
1
is
defined
by
U.
S.
Supreme
Court
decisions
defining
expert
testimony.
Scientific
validity
is
based
on
publication
in
the
open
literature,
competent
peer
review
and
general
acceptance
in
the
scientific
community.
The
primary
detection
and
quantitation
limit
procedures
evaluated
by
EPA
appear
to
meet
the
conditions
for
legal
reliability
and
scientific
practice
stated
in
Criterion
1
of
the
Assessment
Document.
One
open
question
concerns
"
standards."
The
Assessment
Document
interprets
this
condition
to
mean
well­
documented
methodology.
U.
S.
Constitutional
law
intended
metrology,
the
legal
recognition
of
reference
measures,
as
a
Federal
responsibility.
If
the
court's
intent
was
to
include
legal
measures
(
metrology)
as
part
of
expert
testimonial
evidence,
the
need
for
a
defined
reference
material,
or
EPA
audit
standard,
is
implied
and
should
be
considered.
This
reviewer
is
not
competent
to
answer
this
legal
question.
All
the
other
elements
of
Criterion
1
seem
to
be
addressed
in
the
Assessment
Document.
(
MC­
19)

Response:
EPA
appreciates
the
feedback.
EPA
wishes
to
emphasize
that
EPA
used
the
conditions
established
in
the
Daubert
decision
as
a
guideline
for
establishing
February
25,
2003
Page
31
scientific
validity
because
the
scientific
community
has
not
established
a
consensus
definition
of
term.
EPA
believes
that
some
flexibility
in
applying
these
conditions
to
an
evaluation
of
scientific
validity
is
reasonable.

Comment:
Criterion
2
(
demonstrated
method
performance)
appears
to
be
met
under
EPA
Method
1613B
and
other
EPA­
cited
methods
used
as
examples
in
the
Assessment
Document.
Measurement
of
variability
and
defined
method
expectations
may
require
a
special
study
that
addresses
all
candidate
alternate
procedures
and
parameters
that
interested
stakeholders
deem
significant.
(
MC­
20)

Response:
EPA
agrees
that
the
performance
of
any
method
developed
for
use
in
CWA
programs
should
be
studied
to
establish
method
performance
characteristics
(
including
sensitivity).
In
the
Assessment
Document,
EPA
reaffirms
use
of
the
MDL
and
ML
to
establish
sensitivity,
but
as
noted
in
the
response
to
a
previous
comment,
EPA
also
is
willing
to
approve
methods
submitted
by
other
organizations
that
rely
on
alternate
sensitivity
approaches.
In
such
cases,
EPA
would
require
that
method
performance
be
characterized
and
that
the
sensitivity
limits
established
in
the
subject
method
be
at
or
below
the
applicable
regulatory
limits.

Comment:
Criterion
3
addresses
performance
of
a
procedure
that
is
practical
and
affordable
for
use
by
a
single
laboratory.
This
criterion
is
important
because
it
isolates
theoretical
estimators
and
large
demonstration
studies
(
interlaboratory
and
intralaboratory
comparisons)
from
the
fundamental
application
of
any
EPA
method
for
single
or
small
numbers
of
determinations.
The
most
common
situation
is
a
laboratory
performing
many
types
of
analysis
but
must
perform
EPA
Method
1631
on
a
periodic
basis
where
reproducibility
is
poor.

Criterion
3
should
judge
method
ruggedness
and
appropriate
quality
control
to
make
a
method
reliable
and
well
as
"
laboratory
friendly."
Criterion
3
also
addresses
cost
which
is
very
important,
but
this
may
need
to
be
a
final
estimator
after
other
parameters
are
settled.
Criterion
3
should
be
strengthened
both
in
performance
discussions
and
proposed
method
modifications.
(
MC­
21)

Response:
EPA
agrees.
A
large
number
of
small
laboratories
operate
in
the
U.
S.,
and
these
small
laboratories
do
not
have
the
capability
of
conducting
interlaboratory
studies
to
establish
detection
and
quantitation
limits.
Therefore,
detection
and
quantitation
procedures
should
be
practical
and
affordable
for
use
by
a
single
laboratory.
In
response
to
this
reviewer's
suggestion,
EPA
has
revised
the
discussion
of
Criterion
3
in
the
Assessment
Document
(
Section
4.3)
to
address
the
need
for
a
"
laboratory
friendly"
procedure
and
enhance
the
discussion
of
method
ruggedness
and
appropriate
control,
particularly
as
it
relates
to
demonstrating
method
performance
in
real
world
matrices.
February
25,
2003
Page
32
Comment:
Criteria
4
and
5
address
the
primary
subject
matter
of
the
Assessment
Document:
detectability
(
assure
99%
detection
confidence
in
an
experienced
laboratory)
and
quantifiability
(
assure
reliable
quantification
limit
in
an
experienced
laboratory).
As
such,
they
are
significant
and
should
be
maintained.
(
MC­
22)

Response:
EPA
appreciates
the
positive
feedback.

Comment:
Criterion
6
addresses
conditions
in
the
method
that
meet
federal
limits
and
allow
for
more
stringent
application
by
local
regulatory
bodies.
This
criterion
is
essential
and
cannot
be
changed.
(
MC­
23)

Response:
EPA
agrees.

Conceptual
soundness
of
the
MDL
and
ML
(
MC­
24)

Comment:
The
MDL
and
ML
have
stood
the
test
of
time
and
provide
a
proven
methodology
which
meets
defined
evaluation
criteria
stated
in
the
Assessment
Document.

Response:
EPA
agrees
and
appreciates
the
positive
feedback.

EPA's
assessment
appears
to
be
valid
(
MC­
25)

Comment:
The
assessment
in
Chapter
5
of
the
Assessment
Document
appears
valid
based
on
the
stated
criteria.
Detection
using
the
MDL,
in
my
opinion,
is
valid.
Quantification
concepts
are
subject
to
a
higher
degree
of
scientific
challenge
and
interpretation.

Response:
EPA
appreciates
the
positive
feedback
and
agrees
that
the
use
of
quantitation
limits
are
likely
to
be
subject
to
a
higher
degree
of
challenge
and
interpretation.
For
example,
another
peer
reviewer
noted
that
nearly
all
quantitation
limit
approaches
have
nothing
do
with
whether
the
measurements
are
actual
quantitative,
and
that
"
the
only
real
criterion
for
a
quantitation
limit
is
that
the
instrument
generate
a
recognizable
signal."
EPA
has
revised
the
Assessment
Document
(
see
Section
4.4)
to
include
an
enhanced
discussion
of
this
issue,
and
in
today's
proposed
rule
is
soliciting
comments
on
whether
a
quantitation
limit
is
necessary
and,
if
yes,
whether
the
ML
is
an
appropriate
quantitation
limit.

Evaluation
of
alternate
procedures
(
MC­
26)

Comment:
The
review
process
might
be
strengthened
if
EPA
were
to
suggest
experiments
to
evaluate
alternate
detection­
quantitation
procedures.
To
completely
test
the
six
criteria
stated
in
the
Assessment
Document,
a
tailored
validation
study
would
need
to
be
designed
and
performed.
February
25,
2003
Page
33
Response:
An
objective
of
EPA's
variability
versus
concentration
studies
described
in
Sections
1.3.2.1
­
1.3.2.3
of
the
Assessment
Document
was
to
resolve
the
detection/
quantitation
issue.
The
study
covered
some
of
the
most
commonly
used
techniques
for
environmental
measurement
and
a
range
of
concentrations
from
0.1
to
100
times
the
MDL.
The
data
showed
that
detection
and
quantitation
limits
can
be
variable
and
greatly
dependent
on
the
data
set
used.
Based
on
results
from
these
and
other
studies,
EPA
concluded
that
judgment
is
required
in
setting
detection
and
quantitation
limits,
regardless
of
how
much
data
are
collected.
Therefore,
EPA
does
not
believe
that
additional
experiments
would
resolve
the
issue.

Agreement
with
EPA's
conclusions
in
Chapter
6
of
the
Assessment
Document
(
MC­
27)

Comment:
I
agree
with
EPA's
conclusions,
based
on
the
conditions
laid
out
in
Chapters
3,
4,
and
5.
Furthermore,
EPA
has
documented
that
the
MDL
is
a
sound
estimator
of
initial
signal
response
in
a
broad
range
of
analytical
methods.
The
MDL
has
stood
the
test
of
time
and
I
could
not
find
a
convincing
statistical
argument
to
replace
the
MDL.
However,
alternate
methods
do
demonstrate
potential
improvements
to
the
MDL
implementation
(
i.
e.,
criteria
for
initial
spike
determination
and
selection).
The
ML
and
other
candidate
procedures
for
quantitation
limits
show
significant
variability.

Response:
EPA
appreciates
the
support
for
the
MDL
and
is
proposing
further
improvements
to
the
MDL,
such
as
additional
criteria
for
initial
spike
determination
and
selection.

Maintaining
the
MDL
and
ML
(
MC­
28)

Comment:
The
overall
conclusion
from
reading
the
Assessment
Document
is
that
EPA
has
made
a
strong
case
for
maintaining
the
MDL
and
ML
as
reference
procedures.
Most
of
the
alternate
detection
and
quantitation
procedures
evaluated
in
the
Assessment
Document
are
rejected
because
they
have
not
been
tested
extensively
in
the
manner
that
EPA
challenges
its
internal
procedures
before
publication
for
regulatory
applications.
Candidate
alternate
procedures
were
drafted
by
non­
governmental
organizations
(
NGOs)
as
generally
applicable
without
consideration
for
the
legal
constraints
placed
on
EPA.
EPA
procedures
are
formed
around
legally
defined
analyte
lists
(
e.
g.,
the
Priority
Pollutant
List),
producing
limited
numbers
of
analytes
and
"
bright­
line"
legal
limits
that
define
compliance
vs
violation.
NGOs
usually
do
not
create
method
criteria
based
on
these
legal
constraints.
This
disconnect,
seen
between
EPA
and
candidate
alternate
procedures,
is
to
be
expected.
EPA
has
handled
this
problem
in
other
media
(
e.
g.,
the
Clean
Air
Act)
by
establishing
one
or
more
EPA
reference
procedures,
then
establishing
minimum
criteria
for
equivalency.
This
could
be
done
with
candidate
alternate
procedures
if
they
contain
statistically
sound
principles
that
allow
equivalent
performance.
February
25,
2003
Page
34
Response:
EPA
thanks
the
reviewer
for
acknowledging
that
EPA
has
made
a
strong
case
for
maintaining
the
MDL
and
ML
as
reference
procedures.
As
explained
in
a
previous
response,
the
acceptance
of
alternate
detection
and
quantitation
limit
approaches
cannot
be
exactly
compared
to
the
procedures
for
evaluating
and
accepting
alternate
test
procedures
under
the
Clean
Air
Act
or
Clean
Water
Act.
EPA
believes
that
rather
than
establishing
specific
criteria
for
demonstrating
the
validity
of
alternative
sensitivity
approaches,
it
may
be
better
to
simply
evaluate
methods
that
use
alternative
approaches
for
establishing
sensitivity.
A
test
method
would
be
accepted
if
the
sensitivity
(
and
overall
performance)
of
the
method
has
been
characterized
and
is
sufficient
to
meet
EPA's
regulatory
needs.

No
need
to
suspend
EPA
regulatory
programs
(
MC­
29)

Comment:
There
are
no
strong
statements
in
the
Assessment
Document
that
would
cause
a
level
of
concern
needed
to
suspend
EPA
regulatory
programs
or
methodology
pending
additional
review.

Response:
EPA
has
not
suspended
rulemaking
pending
resolution
of
the
detection/
quantitation
issue.

Variability
of
low­
level
data
(
MC­
30)

Comment:
Data
supplied
with
the
Assessment
Document
show
that
low­
level
samples
are
subject
to
higher
relative
variance
and
should
be
treated
differently
from
data
above
an
agreed
quantitation
limit.

Response:
EPA
has
suggested
that
data
below
the
quantitation
limit
should
not
be
used
for
setting
permit
limits
or
other
regulatory
purposes
in
EPA's
CWA
programs.
However,
EPA
recognizes
the
authority
of
the
States
to
use
the
detection
limit
or
other
threshold
when
necessary
to
protect
human
health
or
the
environment.

Aware
of
no
further
data
(
MC­
31)

Comment:
I
am
not
aware
of
any
specific
data
sets
that
could
elucidate
the
various
approaches
and
challenges
listed
in
the
Assessment
Document.
Even
if
such
databases
exist,
it
would
be
very
difficult
to
make
the
appropriate
computations
and
solicit
adequate
reviews
from
interested
parties
given
the
limitations
of
the
six
evaluation
criteria.

Response:
Because
the
reviewer
did
not
state
the
limitations
of
the
six
evaluation
criteria,
we
could
not
determine
the
potential
effect
of
the
comment
on
existing
or
postulated
databases.
February
25,
2003
Page
35
Interlaboratory
issues
(
MC­
32)

Comment:
EPA
has
done
an
adequate
job
showing
performance
of
EPA
methods,
especially
defining
detection
(
e.
g,
MDL).
EPA
has
presented
extensive
data
on
interlaboratory
studies
that
demonstrate
method
performance
for
a
number
of
EPA
regulatory
procedures.

Response:
EPA
thanks
the
reviewer
for
the
acknowledgment.

EPA
should
consider
the
need
for
a
tailored
demonstration
study
(
MC­
33)

Comment:
To
fully
evaluate
alternate
approaches,
a
cooperative
study
should
be
performed
that
is
designed
with
input
from
all
settlement
participants,
and
interested
outside
laboratory
professionals.
That
study
could
include
spike
levels,
blank
and
zero
determination,
intralaboratory
variability,
ruggedness
testing,
"
pairs"
determinations,
use
of
"
real
world"
samples,
evaluation
of
outlier
criteria,
sufficient
replicates
to
challenge
statistical
models,
and
reproducibility
versus
repeatability
(
e.
g.,
single
unbroken
series
of
determinations,
versus,
series
performed
on
different
dates
after
set
up
and
calibration).

Response:
As
noted
in
a
response
to
another
reviewer,
EPA's
objective
in
conducting
the
Multi­
Technique
Variability
Study
(
the
Episode
6000
study),
was
to
create
a
database
that
would
help
answer
questions
concerning
detection
and
quantitation
limits.
The
study
design
reflected
comments
and
concerns
raised
by
interested
and
concerned
parties
(
e.
g.,
settlement
participants,
laboratory
scientists,
statisticians,
and
regulatory
personnel)
at
various
meetings
and
conferences.
The
study
was
conducted
using
7
replicates
at
16
concentration
levels
and
11
of
the
most
commonly
used
analytical
techniques.
EPA
considered
conducting
the
study
at
multiple
laboratories
to
evaluate
interlaboratory
variability,
but
the
additional
factor
of
6
to
10
in
cost
made
this
approach
cost­
prohibitive.
EPA
believes,
however,
that
the
Episode
6000
study
shows
that
detection
limits
can
be
variable
and
that
some
judgement
will
always
be
required
in
evaluating
detection
limit
determinations,
regardless
of
how
much
data
is
collected.

EPA
also
notes
that
the
Agency
has
involved
all
interested
and
concerned
parties
in
development
of
all
recent
wastewater
methods.
For
example,
the
Electric
Power
Research
Institute
(
EPRI)
provided
funding
for
spikes
at
additional
concentrations
in
EPA's
interlaboratory
validation
of
EPA
Method
1631
and
EPA
involved
the
international
community
in
the
interlaboratory
validation
of
EPA
Method
1613.

EPA
should
consider
further
validation
of
EPA
Method
1631
(
MC­
34)

Comment:
Since
the
subject
legal
settlement
specifically
addressed
mercury
using
EPA
Method
1631B,
the
focus
of
any
collaborative
study
to
answer
questions
February
25,
2003
Page
36
raised
in
the
Assessment
Document
and
legal
challenges,
should
include
this
specific
method.
In
a
joint
validation
study,
it
would
be
useful
if
EPA
incorporated
uniform
procedures
to
be
followed
for
any
alternate
procedures
that
supplant
EPA
numbered
methods.

Response:
EPA
asserts
that
Method
1631
is
sufficiently
validated,
Revision
E
to
Method
1631
was
published
in
a
final
rule
on
October
29,
2002
(
67
FR
65876)
to
comply
with
requirements
of
the
Settlement
Agreement.
Results
from
the
interlaboratory
validation
of
Method
16311
were
used
in
the
Agency's
evaluation
of
detection
and
quantitation
limits,
as
described
in
the
revised
Assessment
Document.

EPA
should
consider
better
method
equivalency
and
method
flexibility
(
MC­
35)

Comment:
Simple
equivalency
procedures
are
routinely
specified
by
several
EPA
Offices.
For
air
determinations,
EPA
provides
a
generic
method
protocol
to
demonstrate
method
performance.
This
is
used
to
show
that
an
alternate
procedure
is
suitable
for
reporting
accurate
data
for
regulatory
purposes.
For
stack
methods,
four
(
4)
concurrent
determinations
in
the
same
source
are
required.
EPA
could
use
this
type
of
process
to
set
and
demonstrate
simplified
equivalency
criteria
for
existing
EPA
water
and
waste
water
methods.
Such
guidance
(
method
equivalency
and
flexibility)
will
become
more
critical
as
detection
limits
are
driven
lower,
additional
analytes
are
required,
and
more
complex
matrices
are
added
to
areas
of
regulatory
concern.

Response:
EPA
thanks
the
reviewer
for
the
comment,
but
notes
that
analytical
test
method
equivalency
and
flexibility
are
beyond
the
scope
of
this
assessment,
which
is
focused
solely
at
approaches
for
establishing
analytical
detection
and
quantitation
limits.

EPA
should
consider
the
need
for
an
approved
reference
material
and
audit
standard
(
MC­
36)

Comment:
Interlaboratory
performance
is
highly
variable
using
modern
ultra­
trace
methods
like
EPA
Method
1631.
When
small
batches
of
samples
arrive
at
most
environmental
laboratories,
they
are
scheduled
in
series
with
other
methods
and
different
analytes
than
mercury.
These
samples
must
be
checked
in,
records
verified,
and
proper
storage
and
chain­
of­
custody
implemented.
At
that
point
the
appropriate
equipment
must
be
started
and
calibrated.
This
process
is
the
worst
case,
intermittent
analyses
where
all
the
causes
of
variability,
and
sensitivity
loss,
are
maximized.
This
means
quality
control
on
every
batch
of
samples
becomes
critically
important.
EPA
validation
studies,
which
demonstrate
the
optimum
method
performance,
are
useful
guidance;
however,
one­
time
optimum
performance
does
not
reflect
batch­
to­
batch
data
quality
in
actual
operation.
In
the
real
February
25,
2003
Page
37
world
non­
optimum
operation
is
the
rule,
not
the
exception.
This
problem
is
exacerbated
with
ultra­
trace
methods.

Response:
EPA
thanks
the
reviewer
for
this
comment
and
will
consider
this
issue
during
future
method
development
and
revision
efforts.
EPA
also
wishes
to
note
that
Revision
E
to
EPA
Method
1631,
promulgated
on
October
29,
2002
(
67
FR
65876),
contains
more
extensive
batch
quality
control
(
QC)
than
any
EPA
wastewater
method
promulgated
to
date.
This
QC
is
mandatory.

Note:
In
addition
to
the
comments
detailed
above,
this
peer
reviewer
also
provided
a
suite
of
detailed
comments
and
suggestions
concerning
EPA
Method
1631B.
EPA
thanks
the
reviewer
for
these
detailed
comments,
but
notes
that
specific
analytical
test
methods
are
beyond
the
scope
of
this
assessment,
which
is
focused
solely
at
approaches
for
establishing
analytical
detection
and
quantitation
limits.
EPA
will
retain
the
reviewer's
comments
on
Method
1631
for
further
consideration
during
any
future
revision
of
that
test
method.