Document ID: EPA-HQ-OW-2003-0002-0120
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2003-03-12T05:00Z

Guidance
on
Evaluation,
Resolution,
and
Documentation
of
Analytical
Problems
Associated
with
Compliance
Monitoring
Prepared
by
Analytical
Methods
Staff
Engineering
and
Analysis
Division
Office
of
Science
and
Technology
Office
of
Water
U.
S.
Environmental
Protection
Agency
Washington,
DC
June,
1993
Disclaimer
This
report
has
been
reviewed
by
the
Analytical
Methods
Staff
within
the
Engineering
and
Analysis
Division
of
the
EPA
Office
of
Water.

Mention
of
trade
names
or
commercial
products
does
not
constitute
endorsement
or
recommendation
for
use.
i
i
i
Foreword
This
guidance
document
was
prepared
in
response
to
questions
directed
to
the
Environmental
Protection
Agency
(
EPA)
Headquarters
by
EPA
Regions
and
various
state
agencies
about
monitoring
compliance
with
the
Organic
Chemicals,
Plastics,
and
Synthetic
Fibers
(
OCPSF)
Effluent
Guideline
Limitations
promulgated
by
EPA
in
1987.
The
Engineering
and
Analysis
Division
(
EAD)
in
EPA's
Office
of
Science
and
Technology
within
the
Office
of
Water
is
responsible
for
promulgation
of
regulations
controlling
the
discharge
of
pollutants
into
surface
waters.
EAD
has
developed
analytical
methods
and
collected
and
validated
analytical
data
as
part
of
the
rulemaking
process.
To
support
compliance
monitoring,
EAD
provides
assistance
to
the
EPA
Regions
and
the
States
in
evaluating
claims
of
matrix
interference
problems
associated
with
OCPSF
and
other
proposed
and
promulgated
regulations.

Recognizing
that
the
guidance
necessary
to
deal
with
these
issues
goes
beyond
the
OCPSF
Rule
and
beyond
those
Regions
and
States
that
have
requested
assistance,
EAD
has
compiled
this
guidance
under
one
cover
for
use
by
permit
writers,
permittees,
laboratories,
and
other
interested
parties.
This
document
is
organized
into
six
chapters:

·
Data
required
to
document
matrix­
related
problems
·
Guidance
to
analysts
attempting
to
identify
pollutants
in
OCPSF
wastewaters
·
Cost
estimates
for
resolving
matrix­
related
problems
·
Guidance
for
review
of
data
from
EPA
600­
and
1600­
series
methods
for
organic
compounds
·
Case
histories
of
claims
of
matrix
interferences
·
Contracting
for
analytical
services
This
document
addresses
only
those
issues
related
to
the
analysis
of
organic
compounds
regulated
under
the
OCPSF
rule,
but
much
of
the
approach
can
be
applied
to
the
analysis
of
other
organics
as
well
as
to
metals.

This
document
presumes
knowledge
of,
or
access
to,
the
relevant
analytical
methods
under
discussion.
The
authors
have
found
it
necessary
to
sacrifice
some
level
of
detail
in
order
to
address
as
broad
a
range
of
situations
as
possible.
Some
analytical
problems
and
some
samples
are
not
addressed
in
these
pages.
However,
the
approaches
used
to
demonstrate
the
magnitude
of
problems
with
sample
matrices
can
be
applied
to
issues
not
specifically
addressed
here.

EPA's
Engineering
and
Analysis
Division
is
solely
responsible
for
the
content
of
this
document
The
document
was
prepared,
in
part,
by
DynCorp
Viar
Inc.,
under
U.
S.
EPA
Contract
68­
D0­

0083.
Comments,
suggestions,
and
requests
for
additional
copies
should
be
directed
to:

William
A.
Telliard,
Chief
Analytical
Methods
Staff
Engineering
and
Analysis
Division
Office
of
Science
and
Technology
U.
S.
Environmental
Protection
Agency
401
M
St.,
SW
Washington,
DC
20460
Table
of
Contents
Chapter
1
Checklist
of
Laboratory
Data
Required
to
Support
a
Claim
that
the
Permittee
was
Unable
to
Measure
Pollutants
Due
to
Matrix
Problems
.
.
.
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.
.
1
Chapter
2
Guidance
for
Analysts
Attempting
to
Identify
and
Quantify
Pollutants
in
Wastewaters
Discharged
from
Plants
Manufacturing
Organic
Chemicals,
Plastics,
and
Synthetic
Fibers
.
.
.
.
.
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.
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.
9
Chapter
3
Cost
Estimates
for
Resolving
Matrix
Interferences
.
.
.
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.
.
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.
.
19
Chapter
4
Guidance
for
Reviewing
Data
from
the
Analysis
of
Organic
Compounds
Using
EPA
600­
and
1600­
Series
Methods
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
21
Chapter
5
Case
Histories
of
Claims
of
Matrix
Interferences
Submitted
Under
the
OCPSF
Rule
.
.
.
.
.
.
.
.
.
.
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.
.
33
Chapter
6
Guidance
on
Contracting
for
Analytical
Services
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
39
1
Chapter
1
Checklist
of
Laboratory
Data
Required
to
Support
a
Claim
that
the
Permittee
was
Unable
to
Measure
Pollutants
Due
to
Matrix
Problems
The
Federal
Water
Pollution
Control
Act
(
FWPCA)
Amendments
of
1972,
later
amended
as
the
Clean
Water
Act
(
CWA),
require
that
all
facilities
that
discharge
wastewaters
to
the
surface
waters
of
the
United
States
maintain
a
permit
for
such
discharges
under
the
National
Pollutant
Discharge
Elimination
System
(
NPDES).
In
addition,
all
such
permitted
dischargers
(
permittees)
must
monitor
their
effluent
for
compliance
with
any
and
all
relevant
federal
and
state
discharge
limitations.

CWA
Section
304(
h)
requires
EPA
to
promulgate
test
procedures
appropriate
for
the
measurement
of
regulated
pollutants,
commonly
known
as
"
the
304(
h)
methods."
These
methods
are
then
published
at
40
CFR
Part
136.
Test
procedures
may
also
be
promulgated
by
EPA
under
the
authority
of
other
CWA
sections,
and
these
procedures
are
typically
incorporated
in
revisions
of
40
CFR
Part
136.
For
some
inorganic
analytes
and
some
organic
pesticides,
the
test
procedures
promulgated
under
Section
304(
h)
include
methods
sponsored
by
organizations
other
than
EPA,
such
as
the
American
Society
for
Testing
and
Materials
(
ASTM)
and
the
U.
S.
Geological
Survey
(
USGS).

The
permittee
must
use
the
304(
h)
methods
or
methods
promulgated
in
other
regulations
to
demonstrate
compliance
with
NPDES
permit
limitations.
The
304(
h)
methods
for
non­
pesticide
organic
compounds
promulgated
in
40
CFR
Part
136
(
49
FR
43234;
October
26,
1984,
and
later
corrections)
are
commonly
referred
to
as
the
"
600­
series"
and
"
1600­
series"
methods.
This
chapter
addresses
issues
related
to
the
analysis
of
organic
compounds,
but
much
of
the
general
approach
can
be
applied
to
the
analysis
of
metals
and
other
inorganics
as
well.

Table
1,
at
the
end
of
this
chapter,
lists
all
of
the
600­
and
1600­
series
methods,
indicating
each
method
number,
the
general
class
of
analytes
to
which
each
is
applicable,
the
instrumentation
required,
and
the
regulatory
status
of
each
method
(
promulgated,
proposed,
or
draft).
These
methods
were
designed
to
be
applicable
to
a
wide
range
of
industrial
effluents
and
were
used
to
generate
the
data
necessary
for
the
development
of
each
of
the
effluent
guidelines
promulgated
by
EPA.
Despite
this
wide
applicability,
EPA
recognizes
that
some
sample
matrices
may
fail
to
yield
useful
results
when
these
analytical
methods
are
employed.
Therefore,
EPA
is
prepared
to
consider
claims
that
the
effluent
is
compliant
in
those
instances
in
which
the
effects
of
the
sample
matrix
make
measurements
difficult
or
impossible.
All
such
claims
must
be
supported
by
specific
analytical
data;
stating
that
"
the
sample
could
not
be
analyzed"
is
not
acceptable
documentation.

This
chapter
outlines
the
analytical
data
and
other
information
required
by
EPA
to
evaluate
a
permittee's
claim
of
compliance
when
complex
matrices
preclude
measurement
of
the
pollutants
listed
in
the
permit.
The
data
required
are
identical
to
those
gathered
by
EPA
in
developing
the
regulation.

Since
different
instrumentation
provide
different
data
(
e.
g.,
GC/
MS
procedures
produce
plots
of
mass
intensities
while
GC
procedures
do
not),
the
specific
form
of
the
data
will
differ
according
to
the
method.
The
following
numbered
items
describe
the
data
required
to
support
a
claim
of
compliance
at
a
minimum.
Chapter
1:
Checklist
of
Laboratory
Data
Compliance
Monitoring
Guidance
2
1.
The
method
number
of
the
base
method
used
for
the
measurement.

The
methods
required
for
NPDES
compliance
monitoring
are
specified
in
40
CFR
Part
136
(
and
elsewhere,
as
explained
above).
Although
there
are
many
similarities
between
the
technical
details
of
methods
from
other
EPA
programs
and
from
other
sources,
it
is
not
acceptable
to
use
such
other
methods
for
NPDES
monitoring
in
place
of
a
304(
h)
method.
For
instance,
methods
from
the
Office
of
Solid
Waste
SW­
846
manual
are
not
acceptable
in
instances
where
a
304(
h)
method
exists,
unless
approved
by
the
permitting
authority
in
advance

The
600­
and
1600­
series
methods
do
provide
flexibility
to
improve
separations
and
reduce
the
costs
of
measurements,
but
method
performance
must
not
be
sacrificed.
The
purpose
of
this
flexibility
is
to
allow
for
improvements
in
analytical
technology,
in
part
to
address
matrix
effects.
In
order
to
invoke
this
flexibility,
the
analyst
must
start
with
one
of
the
base
600­
or
1600­
series
methods
and
improve
upon
it.
Example
improvements
include
the
use
of
additional
cleanup
techniques,
alternative
gas
chromatography
or
liquid
chromatography
columns,
and
more
specific
detectors.

Changing
to
an
alternative
method
for
the
sake
of
convenience
is
contrary
to
the
spirit
of
this
flexibility.
The
change
must
be
within
the
scope
of
the
method
used
and
must
be
for
the
sake
of
improvement,
and
this
improvement
must
be
supported
by
data
demonstrating
equivalent
performance
to
that
of
the
base
method.

2.
A
detailed
narrative
discussing
the
problems
with
the
analysis,
corrective
actions
taken,
and
the
changes
made
to
the
base
method
identified.

The
permittee
must
also
describe
the
reasons
for
the
change
to
the
base
method,
the
supporting
logic
behind
the
technical
approach
to
the
change,
and
the
result
of
the
change.

Many
compliance
monitoring
analyses
are
performed
by
contract
laboratories
on
behalf
of
the
permittee.
However,
the
responsibility
for
providing
the
information
to
EPA
rests
with
the
permittee.
The
permittee
must
therefore
impress
upon
its
contract
laboratories
the
need
for
detailed
technical
communication
of
problems
encountered
and
solutions
attempted.
The
narrative
should
be
authored
by
an
analytical
chemist
and
written
in
terms
that
another
analytical
chemist
can
understand.

3.
A
summary
level
report
or
data
reporting
forms
giving
the
pollutants
for
which
analyses
were
conducted
and
the
concentrations
detected.
For
the
pollutants
that
were
not
detected
the
detection
limits
or
estimated
detection
limits
must
be
provided.

Such
results
must
be
provided
for
each
field
sample
analyzed,
including
any
dilutions
and
reanalyses.

If
not
specified
in
the
base
method,
the
means
for
estimating
detection
limits
must
be
provided
in
the
narrative.
If
the
laboratory
uses
"
flags"
in
its
data
reporting,
the
definition
of
each
flag
must
be
provided
with
the
data.
Compliance
Monitoring
Guidance
Chapter
1:
Checklist
of
Laboratory
Data
3
4.
A
summary
of
all
quality
control
results
required
by
the
base
method.

These
results
include,
but
are
not
limited
to,
the
following:

·
Instrument
tuning
·
Calibration
·
Calibration
verification
·
Initial
precision
and
recovery
·
Ongoing
precision
and
recovery
·
Matrix
spike
matrix
spike
duplicate
results
·
Surrogate
recoveries
·
Labeled
compound
recoveries
(
isotope
dilution
methods
only)
·
Blank
results
·
Quality
control
charts
and
limits
5.
Raw
data
that
will
allow
an
independent
reviewer
to
validate
each
determination
and
calculation
performed
by
the
laboratory.

This
validation
should
consist
of
tracing
the
instrument
output
(
peak
height,
area,
or
other
signal
intensity)
to
the
final
result
reported.
The
raw
data
are
method
specific
and
may
include
any
of
the
following:

·
Sample
numbers
or
other
identifiers
used
by
the
both
the
permittee
and
the
laboratory
·
Extraction
dates
·
Analysis
dates
and
times
·
Sequence
of
analyses
or
run
logs
·
Sample
volume
·
Extract
volume
prior
to
each
cleanup
step
·
Extract
volume
after
each
cleanup
step
·
Final
extract
volume
prior
to
injection
·
Digestion
volume
·
Titration
volume
·
Percent
solids
or
percent
moisture
·
Dilution
data,
differentiating
between
dilution
of
a
sample
and
dilution
of
an
extract
or
digestate
·
Instrument(
s)
and
operating
conditions
·
GC
and/
or
GC/
MS
operating
conditions,
including
detailed
information
on
­
columns
used
for
determination
and
confirmation
(
column
length
and
diameter,
stationary
phase,
solid
support,
film
thickness,
etc.)
­
analysis
conditions
(
temperature
programs,
flow
rates,
etc.)
­
detectors
(
type,
operating
conditions,
etc.)
·
Chromatograms,
ion
current
profiles,
bar
graph
spectra,
library
search
results
·
Quantitation
reports,
data
system
outputs,
and
other
data
to
link
the
raw
data
to
the
results
reported.
(
Where
these
data
are
edited
manually,
explanations
of
why
manual
intervention
was
necessary
must
be
included)
·
Direct
instrument
readouts;
i.
e.,
strip
charts,
printer
tapes,
etc.,
and
other
data
to
support
the
final
results
·
Laboratory
bench
sheets
and
copies
of
all
pertinent
logbook
pages
for
all
sample
preparation
and
cleanup
steps,
and
for
all
other
parts
of
the
determination
Chapter
1:
Checklist
of
Laboratory
Data
Compliance
Monitoring
Guidance
Please
note
that
other
methods
for
the
analysis
of
organic
compounds
are
incorporated
by
reference
in
40
CFR
136.
1
4
The
raw
data
required
shall
be
provided
not
only
for
the
analysis
of
samples,
but
also
for
all
calibrations,
verifications,
blanks,
matrix
spikes
and
duplicates,
and
other
QC
analyses
required
by
the
base
method.
Data
must
be
organized
so
that
an
analytical
chemist
can
clearly
understand
how
the
analyses
were
performed.

6.
Example
calculations
that
will
allow
the
data
reviewer
to
determine
how
the
laboratory
used
the
raw
data
to
arrive
at
the
final
results.

Useful
examples
include
both
detected
compounds
and
undetected
compounds.
If
the
laboratory
or
the
method
employs
a
standardized
reporting
level
for
undetected
compounds,

this
should
be
made
clear
in
the
example,
as
should
adjustments
for
sample
volume,
dry
weight
(
solids
only),
etc.

7.
For
GC/
MS
and
other
instruments
involving
data
systems,
the
permittee
should
be
prepared
to
submit
raw
data
on
magnetic
tape
or
disk,
upon
request
by
EPA.

8.
The
names,
titles,
addresses,
and
telephone
numbers
of
the
analysts
who
performed
the
analyses
and
of
the
quality
control
officer
who
will
verify
the
analyses.

If
data
are
collected
by
a
contract
laboratory,
it
is
the
permittee's
responsibility
to
see
that
all
of
the
requirements
in
the
methods
are
met
by
the
contract
laboratory
and
that
all
data
listed
above
are
provided.
(
See
Chapter
6
for
guidance
on
writing
contracts
for
laboratory
services.)

Table
1.
600­
and
1660­
Series
Methods
for
Organics1
Method
Class
of
Analytes
Instrumentation
Status
601
Purgeable
Halocarbons
GC/
ELCD
Promulgated
602
Purgeable
Aromatics
GC/
PID
Promulgated
603
Acrolein
and
Acrylonitrile
GC/
FID
Promulgated
604
Phenols
GC/
FID,
GC/
ECD
Promulgated
604.1
Hexachlorophene
and
Dichlorophen
HPLC/
UV
Draft
605
Benzidines
HPLC/
Electrochemical
Promulgated
606
Phthalate
Esters
GC/
ECD
Promulgated
607
Nitrosamines
GC/
NPD,
ELCD
Promulgated
Compliance
Monitoring
Guidance
Chapter
1:
Checklist
of
Laboratory
Data
5
Table
1.
600­
and
1660­
Series
Methods
for
Organics
(
cont.)

Method
Class
of
Analytes
Instrumentation
Status
608
Organochlorine
Pesticides/
PCBs
GC/
ECD
Promulgated
609
Nitroaromatics
and
Isophorone
GC/
FID,
GC/
ECD
Promulgated
610
Polynuclear
Aromatic
Hydrocarbons
HPLC/
UV,
Fluorescence
Promulgated
611
Haloethers
GC/
ELCD/
ECD
Promulgated
612
Chlorinated
Hydrocarbons
GC/
ECD
Promulgated
613
2,3,7,8­
Tetrachlorodibenzo­
p­
dioxin
Low
Resolution
GC/
MS
Promulgated
614
Organophosphorus
Pesticides
GC/
FPD
Proposed
614.1
Organophosphorus
Pesticides
GC/
NPD
Proposed
615
Chlorinated
Herbicides
GC/
ECD
Proposed
616
C,
H,
and
O
Pesticides
GC/
FID
Proposed
617
Organohalide
Pesticides/
PCBs
GC/
ECD
Proposed
618
Chloropicrin
and
Ethylene
Dibromide
GC/
ECD
Proposed
619
Triazine
Pesticides
GC/
NPD
Proposed
620
Diphenylamine
GC/
NPD
Proposed
621
Carbamate
and
Urea
Pesticides
TLC
Draft
622
Organophosphorus
Pesticides
GC/
NPD
Proposed
624
Purgeable
Organics
GC/
MS
Promulgated
625
Base/
Neutral
and
Acid
Extractable
Organics
GC/
MS
Promulgated
626
Acrolein
and
Acrylonitrile
GC/
FID
Draft
627
Dinitroaniline
Pesticides
GC/
ECD
Proposed
629
Cyanazine
HPLC/
UV
Proposed
630
Dithiocarbamate
Pesticides
UV/
Vis,
by
CS
liberation
Proposed
2
630.1
Dithiocarbamate
Pesticides
GC/
Hall,
by
CS
liberation
Proposed
2
631
Benomyl
and
Carbendazim
HPLC/
UV
Proposed
632
Carbamate
and
Urea
Pesticides
HPLC/
UV
Proposed
632.1
Napropamide,
Propanil,
and
Vacor
HPLC/
UV
Proposed
633
Organonitrogen
Pesticides
GC/
NPD
Proposed
633.1
Neutral
Nitrogen­
Containing
Pesticides
GC/
NPD
Proposed
634
Thiocarbamate
pesticides
GC/
NPD
Proposed
635
Rotenone
HPLC/
UV
Proposed
Chapter
1:
Checklist
of
Laboratory
Data
Compliance
Monitoring
Guidance
Table
1.
600­
and
1660­
Series
Methods
for
Organics
(
cont.)

Method
Class
of
Analytes
Instrumentation
Status
Draft
Method
1618
has
been
supplanted
by
Methods
1656,
1657,
and
1658.
2
6
636
Bensulide
HPLC/
UV
Proposed
637
MBTS
and
TCMTB
HPLC/
UV
Proposed
638
Oryzalin
HPLC/
UV
Proposed
639
Bendiocarb
HPLC/
UV
Proposed
640
Mercaptobenzothiazole
HPLC
Proposed
641
Thiabendazole
HPLC/
Fluorescence
Proposed
642
Biphenyl
and
Orthophenyl
Phenol
HPLC/
UV
Proposed
643
Bentazon
HPLC/
UV
Proposed
644
Picloram
HPLC/
UV
Proposed
645
Amine
Pesticides
GC/
NPD
Proposed
646
Dinitro
Aromatic
Pesticides
GC/
ECD
Proposed
680
Organochlorine
Pesticides/
PCBs
GC/
MS
Draft
1613
Polychlorinated
Dibenzo­
p­
dioxins
and
High
Resolution
GC/
MS
Isotope
Proposed
Dibenzofurans
Dilution
1618
Organochlorine
Pesticides/
PCBs,
Organo­
GC/
ECD,
GC/
NPD
Draft
phosphorus
Pesticides,
and
Phenoxy­
Acid
Herbicides
2
1624
Volatile
Organics
GC/
MS
Isotope
Dilution
Promulgated
1625
Semivolatile
Organics
GC/
MS
Isotope
Dilution
Promulgated
1648
Organic
Halides
(
OX)
in
Solids
Neutron
Activation
Draft,
1/
91
1649
Organic
Halides
(
OX)
in
Solids
Combustion,
Coulometric
Titration
Draft,
1/
91
1650
Adsorbable
Organic
Halides
(
AOX)
in
Carbon
Adsorption,
Combustion,
Draft,
1/
91
Wastewaters
and
Coulometric
Titration
1651
Total
Oil
and
Diesel
Oil
in
Drilling
Muds
Retort,
Gravimetric
Proposed
Federal
Register
Part
VIII
EPA
40
CFR
Part
136
CI
CI
CI
CI
CI
CI
CI
CI
CI
OH
Compliance
Monitoring
Guidance
Chapter
1:
Checklist
of
Laboratory
Data
Table
1.
600­
and
1660­
Series
Methods
for
Organics
(
cont.)

Method
Class
of
Analytes
Instrumentation
Status
7
A
d
d
i
t
i
o
n
a
l
 
i
n
f
o
r
m
a
t
i
o
n
 
o
n
 
a
n
a
l
y
t
e
s
,
 
m
e
t
h
o
d
s
,
 
a
n
d
 
r
e
g
u
l
a
t
o
r
y
 
l
i
m
i
t
s
 
m
a
y
 
b
e
 
f
o
u
n
d
 
i
n
 
E
M
M
I
,
 
t
h
e
E
P
A
 
E
n
v
i
r
o
n
m
e
n
t
a
l
 
M
o
n
i
t
o
r
i
n
g
 
M
e
t
h
o
d
s
 
I
n
d
e
x
,
 
a
 
c
o
m
p
u
t
e
r
i
z
e
d
 
d
a
t
a
b
a
s
e
 
l
i
n
k
i
n
g
 
5
0
 
E
P
A
r
e
g
u
l
a
t
o
r
y
 
l
i
s
t
s
,
 
2
6
0
0
 
s
u
b
s
t
a
n
c
e
s
,
 
a
n
d
 
9
2
6
 
a
n
a
l
y
t
i
c
a
l
 
m
e
t
h
o
d
s
.
 
 
F
o
r
 
i
n
f
o
r
m
a
t
i
o
n
 
o
n
 
o
b
t
a
i
n
i
n
g
t
h
e
 
E
M
M
I
 
s
y
s
t
e
m
 
s
o
f
t
w
a
r
e
,
 
c
o
n
t
a
c
t
:
N
a
t
i
o
n
a
l
 
T
e
c
h
n
i
c
a
l
 
I
n
f
o
r
m
a
t
i
o
n
 
S
e
r
v
i
c
e
5
8
2
5
 
P
o
r
t
 
R
o
y
a
l
 
R
o
a
d
S
p
r
i
n
g
f
i
e
l
d
,
 
V
A
 
 
2
2
1
6
1
7
0
3
-
4
8
7
-
4
6
5
0
S
p
e
c
i
f
y
 
i
t
e
m
 
n
u
m
b
e
r
 
P
B
9
2
-
5
0
3
0
9
3
1652
Oil
and
Grease
by
Solid­
Phase
Extraction
Solid­
Phase
Extraction,
Gravimetric
Draft
12/
91
1653
Chlorinated
Phenolics
in
Wastewater
GC/
MS
Isotope
Dilution
Draft,
12/
91
1654
Diesel
Oil
in
Drilling
Muds
HPLC
Draft,
12/
91
1656
Organohalide
Pesticides
GC/
ECD,
GC/
ELCD,
Proposed
GC/
Microcoulometric
2
1657
Organophosphorus
Pesticides
GC/
FPD
Proposed2
1658
Phenoxy­
Acid
Herbicides
GC/
ECD,
GC/
ELCD,
Proposed
GC/
Microcoulometric
2
1659
Dazomet
GC/
NPD
Proposed
1660
Pyrethrins
and
Pyrethroids
HPLC/
UV
Proposed
1661
Bromoxynil
HPLC/
UV
Proposed
ed
by
Methods
1656,
1657,
and
1658.
Draft
Method
1618
has
been
supplant
2
To
obtain
copies
of
the
600­
series
methods,
write
or
call:
To
obtain
copies
of
the
1600­
series
methods,
write
or
call:

Chemical
Research
Division
USEPA
Sample
Control
Center
(
operated
by
Viar
USEPA
Environmental
Monitoring
Systems
Labo­
&
Co.)
ratory
P.
O.
Box
1407
26
Martin
Luther
King
Blvd.
Alexandria,
VA
22313
Cincinnati,
OH
45268
703­
557­
5040
513­
569­
7325
Note:
Some
1600­
series
methods
listed
as
"
draft"
may
not
be
available
through
the
Sample
Control
Center.
8
Chapter
2
Guidance
for
Analysts
Attempting
to
Identify
and
Quantify
Pollutants
in
Wastewaters
Discharged
from
Plants
Manufacturing
Organic
Chemicals,
Plastics,
and
Synthetic
Fibers
This
chapter
provides
guidance
to
analytical
chemists
having
difficulty
in
analyzing
complex
wastewaters
from
facilities
that
manufacture
organic
chemicals,
plastics,
and
synthetic
fibers.
This
guidance
illustrates
how
the
method
equivalency
and
flexibility
permitted
by
the
wastewater
methods
can
be
used
to
apply
other
analytical
techniques
to
matrix
problems.
This
guidance
specifically
addresses
the
determination
of
the
organic
pollutants
in
these
wastewaters.
Conventional
pollutants
and
metals
are
not
addressed
because
few
problems
have
been
encountered
in
measuring
these
analytes
in
these
wastewaters.

Table
2,
at
the
end
of
this
chapter,
lists
the
organic
priority
pollutants
regulated
in
wastewaters
from
organic
chemicals,
plastics,
and
synthetic
fibers
(
OCPSF)
industries
and
the
EPA
analytical
methods
relevant
to
monitoring
such
wastewaters.

Approved
Methods
for
Determination
of
Organic
Pollutants
Section
304(
h)
and
other
sections
of
the
CWA
authorize
the
EPA
Administrator
to
promulgate
test
procedures
for
monitoring
pollutants
in
wastewater
discharges.
Analytical
methods
(
test
procedures
to
monitor
organic
priority
pollutants
in
wastewater
were
proposed
on
December
3,
1979
(
44
FR
69494)
and
promulgated
in
40
CFR
Part
136
on
October
26,
1984
(
49
FR
43234).
These
methods
are
variously
known
as
the
304(
h)
methods,
the
600­
series
methods,
the
1600­
series
methods,
and
the
Cincinnati
methods.
Additional
methods
have
been
proposed
and/
or
promulgated
under
Section
304(
h)

since
1984.
The
304(
h)
methods
for
organics
are
listed
in
Chapter
1,
Table
1.
Information
on
obtaining
copies
of
these
methods
may
be
found
at
the
end
of
that
table.

The
approved
methods
are
based
on
recovery
of
organic
pollutants
from
a
wastewater
sample
by
a
purge­
and­
trap
technique
or
by
extraction
with
an
organic
solvent
such
as
methylene
chloride.
In
the
purge­
and­
trap
technique,
the
pollutants
are
purged
from
water
with
an
inert
gas
and
trapped
on
a
sorbent
column.
The
sorbent
column
is
then
heated
and
back­
flushed
to
desorb
the
pollutants
into
a
gas
chromatograph
(
GC).
The
pollutants
are
separated
by
the
GC
and
detected
by
a
conventional
detector
(
CD)
or
by
a
mass
spectrometer
(
MS).
Conventional
detectors
include
the
flame
ionization
detector
(
FID),
electron
capture
detector
(
ECD),
electrolytic
conductivity
detector
(
ELCD),
and
nitrogen­
phosphorous
detector
(
NPD).

Pollutants
extracted
from
wastewater
with
an
organic
solvent
are
concentrated
by
evaporation
of
the
solvent,
and
a
portion
of
the
concentrated
extract
is
injected
into
a
GC
or
high
performance
liquid
chromatograph
(
HPLC),
where
the
pollutants
are
separated
and
detected
by
a
CD
or
MS.
For
application
of
GC
and
HPLC
methods,
EPA
classified
the
organic
pollutants
into
twelve
groups
of
similar
chemical
and
physical
properties
allowing
each
group
to
be
measured
under
a
given
set
of
chromatographic
conditions.
Through
the
use
of
different
detectors,
several
methods
may
be
applicable
to
each
of
the
twelve
groups
of
pollutants.
Table
3
lists
the
304(
h)
methods
applicable
to
Compliance
Monitoring
Guidance
Chapter
2:
Guidance
for
Analysts
9
monitoring
those
pollutants
specifically
regulated
under
the
OCPSF
Rule,
provides
the
general
class
of
analytes
to
which
the
method
is
applicable,
and
specifies
the
applicable
instrumentation.

Flexibility
in
Analytical
Methods
In
promulgating
analytical
methods
for
measurement
of
pollutants,
EPA
has
provided
flexibility
for
dealing
with
interferences.
The
major
flexibility
options
are
discussed
in
the
preamble
to
the
40
CFR
Part
136
methods
(
49
FR
43234).
These
options
include
a
mechanism
for
obtaining
approval
of
an
alternative
test
procedure
on
a
nationwide
basis
and/
or
on
a
site­
specific
basis
(
40
CFR
Parts
136.4
and
136.5).
These
procedures
are
intended
to
encourage
development
of
new
analytical
methods
and
to
give
analysts
a
number
of
options
for
resolving
analytical
problems
that
may
be
unique
to
specific
wastewaters.
If
the
discharger
or
an
interested
third
party
wishes
to
pursue
the
option
of
an
alternative
test
procedure,
that
party
should
apply
to
the
Director
of
the
Environmental
Monitoring
and
Support
Laboratory
in
Cincinnati,
Ohio,
for
approval
of
an
nationwide
alternative
procedure,
or
should
apply
to
the
State
or
Regional
EPA
permitting
office
for
approval
of
a
limited
procedure.

In
addition
to
the
flexibility
provided
by
the
options
above,
flexibility
is
permitted
in
each
analytical
method.
The
analyst
is
permitted
to
"
improve
separations
or
lower
the
costs
of
analyses"

provided
that
the
results
obtained
are
not
less
precise
and
accurate
than
the
results
obtained
using
the
unmodified
method.
For
example,
the
analyst
is
allowed
to
use
professional
judgment
in
selecting
packed
or
open
tubular
columns,
operating
temperature
programs,
carrier
gas
or
solvent
flow
rates,
and
detectors.
Analysts
may
also
use
their
discretion
in
selecting
cleanup
procedures
and
extract
concentration
procedures.
The
flexibility
permitted
is
outlined
in
each
method
and
in
the
preamble
to
the
regulation.

EPA
believes
that
method
flexibility,
which
is
discussed
further
below,
should
permit
pollutant
identities
and
concentrations
to
be
determined
in
nearly
all
wastewaters,
but
recognizes
that
there
may
be
a
few
intractable
sample
matrices
that
do
not
yield
readily
to
extensive
analytical
efforts.
EPA
is
anxious
to
learn
of
the
steps
taken
by
the
analyst,
the
solutions
found,
and
the
instances
in
which
a
given
matrix
does
not
yield
to
known
analytical
techniques.
Stating
that
"
the
sample
couldn't
be
analyzed"
is
not
sufficient
and
will
not
be
accepted
as
justification
for
a
claim
of
matrix
interference.

Demonstrating
Equivalency
with
a
Given
Method
The
objective
in
modifying
a
method
is
to
make
it
more
specific
for
a
given
pollutant,
more
sensitive,
more
precise,
more
accurate,
or
in
some
other
way
to
improve
the
method.
However,
some
laboratories
have
interpreted
the
provision
to
modify
a
method
as
a
means
of
increasing
the
speed
of
analysis,
thus
reducing
the
analysis
time,
or
to
take
other
"
shortcuts"
to
reduce
cost,
resulting
in
a
compromise
of
method
performance.
In
regulating
the
wastewater
methods,
EPA
needed
a
means
to
preclude
this
compromise
in
performance,
yet
permit
the
flexibility
that
would
improve
method
performance.

EPA
resolved
this
issue
by
providing
limited
flexibility
within
the
methods,
so
that
improvements
could
be
made,
and
requiring
the
analyst
to
demonstrate
that
the
results
produced
by
any
modification
would
be
equal
to
or
better
than
results
obtained
with
the
unmodified
method.
The
yardsticks
by
which
this
performance
is
to
be
measured
are
precision
and
accuracy,
but
can
be
Chapter
2:
Guidance
for
Analysts
Compliance
Monitoring
Guidance
10
extended
to
include
detection
limit,
gas
chromatographic
resolution,
mass
spectral
resolution,
and
other
measures
of
method
performance.
The
spirit
of
the
regulation
concerning
methods
is
that
method
performance
must
be
improved
by
any
modification,
and
must
not
be
degraded
by
such
a
modification.

The
laboratory
must
perform
a
start­
up
test
prior
to
practicing
a
method,
and
the
results
of
the
start­
up
test
must
be
on
record
at
the
laboratory
for
inspection
by
EPA
if
desired.
The
start­
up
test
provides
an
initial
validation
of
the
performance
of
the
method
by
a
specific
laboratory.
It
is
described
in
detail
in
Section
8
of
the
600­
series
and
1600­
series
wastewater
methods
and
is
also
used
in
the
Office
of
Drinking
Water
500­
series
methods
and
the
Solid
Waste
SW­
846
methods.
The
test
consists
of
an
analysis
of
four
replicate
volumes
of
reagent
water
spiked
with
the
pollutants
of
interest
at
the
concentration
specified
in
the
method
or
at
5
 
10
times
the
detection
limit
of
the
method.

For
each
analyte,
the
precision
of
the
analysis
of
the
four
replicates,
as
determined
by
the
standard
deviation
of
the
four
measurements,
must
be
less
than
the
standard
deviation
specified
in
the
method.
Similarly,
for
each
analyte,
the
accuracy
of
the
analysis
of
the
four
replicates,
as
determined
by
the
average
percent
recovery
of
the
four
measurements,
must
fall
within
the
range
of
percent
recovery
specified
in
the
method.
If
either
the
precision
or
accuracy
test
is
failed,
the
test
must
be
repeated
until
the
laboratory
is
able
to
meet
the
precision
and
accuracy
requirements.

If
the
laboratory
modifies
a
method,
the
start­
up
test
must
be
repeated
with
the
modification
as
an
integral
part
of
the
method.
The
laboratory
must
demonstrate
that
the
precision
and
accuracy
specifications
in
the
method
can
be
met
with
the
modification;
otherwise,
the
modification
is
not
permitted.
The
laboratory
must
maintain
records
that
document
that
the
start­
up
test
was
performed
on
the
modified
method
and
that
the
precision
and
accuracy
requirements
were
met.

Examples
of
Solutions
to
Matrix
Problems
The
inability
to
measure
the
concentration
of
a
pollutant
in
a
specific
wastewater
is
often
attributed
to
"
matrix
problems."
Some
example
solutions
to
matrix
problems
are
described
below.

The
list
is
not
exhaustive
but
should
help
the
analyst
to
examine
the
specific
matrix
problems
at
hand
and
then
to
develop
solutions
to
such
problems.

Volatile
Organic
Pollutants
1.
Use
of
selective
GC
detectors
The
304(
h)
methods
for
volatiles
include
Methods
601,
602,
603,
624,
and
1624.
The
effluent
limits
in
the
OCPSF
regulation
are
all
greater
than
10
µ
g/
L.
The
selective
GC
detectors
in
Methods
601
and
602
cover
all
OCPSF
volatile
pollutants
regulated,
and
allow
detection
at
levels
well
below
the
effluent
limits
in
the
OCPSF
regulation.
The
specificity
provided
by
the
electrolytic
conductivity
detector
and
by
the
photoionization
detector
allow
detection
of
the
halogenated
and
aromatic
analytes,
respectively,
in
complex
matrices.

2.
Micro­
extraction
and
gas
chromatography
with
selective
detectors
The
selective
GC
detectors
in
Methods
601
and
602
provide
sensitivity
that
is
10
 
100
times
greater
than
that
required
to
detect
the
analytes
of
interest.
Some
of
this
sensitivity
can
Compliance
Monitoring
Guidance
Chapter
2:
Guidance
for
Analysts
Rhodes,
J.
W.,
and
Nulton,
C.
P.,
J.
Env.
Sci.
and
Health,
vol.
A15,
no.
5,
(
1980).
1
11
be
used
to
substitute
micro­
extraction
in
place
of
purge­
and­
trap.
The
advantage
of
microextraction
is
that
the
pH
of
the
water
can
be
adjusted
to
attempt
to
keep
the
interferences
in
the
water
while
the
analytes
of
interest
are
extracted.
1
3.
Sample
dilution
Methods
601
and
602
can
achieve
method
detection
limits
of
less
than
1
µ
g/
L
for
all
volatile
analytes
in
the
OCPSF
regulation,
and
of
less
than
0.1
µ
g/
L
for
many
of
these
analytes.
The
added
sensitivity
of
the
selective
GC
detectors
can
be
used
to
overcome
matrix
problems
by
diluting
the
sample
by
a
factor
of
10
 
100.
Even
with
this
dilution,
the
pollutants
can
be
detected
at
the
levels
required,
and
the
effects
of
the
interferences
will
be
reduced
or
eliminated.

4.
Isotope
dilution
Method
1624
employs
stable,
isotopically
labeled
analogs
of
the
pollutants
as
internal
standards
in
the
analysis.
The
use
of
these
labeled
compounds
frequently
permits
the
pollutant
to
be
determined
in
the
presence
of
interferences
because
the
unique
spectrum
of
the
labeled
compound
can
be
located
in
the
presence
of
these
interferences,
and
the
pollutant
can
then
be
located
by
reference
to
the
labeled
compound.

Semivolatile
Organic
Pollutants
1.
Use
of
selective
GC
detectors
Methods
604
through
612
employ
gas
chromatography
with
selective
detectors
and
high­
performance
liquid
chromatography
with
an
ultraviolet
(
UV)
or
electrochemical
detector
to
detect
pollutants
in
the
presence
of
interferences.
In
addition,
Method
604
employs
derivatization
and
a
halogen­
specific
detector
for
the
determination
of
phenols.
As
with
volatiles,
the
added
sensitivity
of
the
selective
detectors
permits
the
sample
to
be
diluted
by
a
factor
of
10
 
100
while
allowing
detection
of
the
analytes
at
the
effluent
limits
specified
in
the
OCPSF
regulation.

2.
pH
change
A
very
powerful
means
of
separating
the
pollutants
of
interest
from
interferences
is
to
adjust
the
pH
of
the
sample
to
keep
the
interferences
in
solution
while
allowing
the
pollutants
to
be
extracted
in
an
organic
solvent.
For
example,
neutral
pollutants
can
be
extracted
at
either
low
or
high
pH.
Therefore,
if
the
main
interferences
are
acidic,
the
pH
can
be
adjusted
to
>
13
and
the
acidic
interferences
will
remain
in
the
water
as
their
salts
while
the
neutral
pollutants
are
extracted
using
an
organic
solvent.
Chapter
2:
Guidance
for
Analysts
Compliance
Monitoring
Guidance
Jackson,
C.
B.
et.
al.,
J.
Env.
Sci.
and
Health,
vol.
A15,
no.
5,
(
1980).
2
Tessari,
J.
D.,
12th
Annual
EPA
Conference
on
Analysis
of
Pollutants
in
the
Environment,
Norfolk,
Virginia,
3
May
1989
(
copies
of
the
proceedings
may
be
available
through
the
EPA
Sample
Control
Center,
P.
O.
Box
1407,
Alexandria,
VA
22313,
703­
557­
5040).

12
Phenol
and
2,4­
dimethylphenol
can
be
extracted
at
high
pH
(
11
 
13)
using
continuous
liquid/
liquid
extractors,
as
described
in
Method
1625.
This
permits
phenol
and
2,4­

dimethylphenol
to
be
extracted
in
the
presence
of
other,
stronger
acids.
2
In
a
manner
analogous
to
the
pH
change
described
above,
the
extract
from
the
primary
extraction
can
be
back­
extracted
with
water
of
the
opposite
pH
to
remove
other
interferences.

To
keep
the
organic
pollutants
in
the
extract,
the
water
used
for
back­
extraction
can
be
saturated
with
salt
(
sodium
sulfate
and/
or
sodium
chloride).
Aqueous
solutions
containing
2%
of
each
of
these
salts
have
been
shown
to
be
effective
in
keeping
the
pollutants
of
interest
in
the
extract.

3.
Gel­
permeation
(
size­
exclusion)
chromatography
This
technique
is
described
in
Revision
C
of
Method
1625.
The
same
technique
is
used
in
the
Superfund
Contract
Laboratory
Program
(
CLP)
methods
and
SW­
846
methods,
and
has
been
shown
to
be
effective
for
removing
lipids
and
high­
molecular­
weight
interferences
that
can
degrade
GC
and
mass
spectrometer
performance.

4.
Solid­
phase
extraction
(
SPE)
cartridge
Although
not
fully
evaluated
at
this
time,
SPE
cleanup
appears
promising
for
not
only
neutral
species
but
also
for
acidic
and
basic
species.
It
has
been
shown
to
be
effective
in
removing
interferences
from
extracts
containing
pesticides
and
in
the
extraction
of
pollutants
from
drinking
waters
by
Method
525.
3
5.
Florisil,
alumina,
and
silica
gel
These
adsorbents
are
effective
in
separating
neutral
species
from
polar
interferences.

For
polar
analytes
of
interest,
the
adsorbent
must
be
evaluated
to
determine
if
the
analyte
will
be
recovered.
The
level
of
activation
of
the
adsorbent
plays
a
major
role
in
this
recovery
process.

6.
Isotope
dilution
Method
1625
permits
determination
of
pollutants
in
the
presence
of
interferences
in
semivolatile
samples
in
the
same
way
described
for
volatiles
above.
In
addition,
the
wide
range
of
recovery
of
the
labeled
analogs
permitted
in
the
method
allows
good
quantitation
of
the
pollutant
when
interferences
reduce
the
efficiency
of
the
extraction.
Compliance
Monitoring
Guidance
Chapter
2:
Guidance
for
Analysts
13
Determination
of
Phenol
as
a
Specific
Example
Phenol
is
a
commonly
occurring
pollutant
in
OCPSF
wastewaters.
The
protocols
below
are
suggested
as
approaches
to
the
determination
of
phenol
in
a
complex
sample
matrix.
After
a
protocol
has
been
found
to
be
effective,
the
laboratory
must
demonstrate
that
the
modification
has
equivalent
performance
to
the
original
method.
This
demonstration
involves
the
start­
up
tests
described
above.

The
specifications
in
the
original
method
must
be
met
before
proceeding
with
analysis
of
a
sample
for
compliance
monitoring.

1.
Base/
neutral
extraction,
acid
back
extraction,
and
isotope
dilution
GC/
MS
(
based
on
Method
1625)

1.1
Measure
1.0
L
of
well­
mixed
sample
into
a
graduated
cylinder
and
spike
with
labeled
phenol
per
Section
10
of
Method
1625.
Stir
and
equilibrate
per
this
method.
Quantitatively
transfer
the
sample
to
a
continuous
liquid/
liquid
extractor.
Adjust
the
pH
of
the
sample
to
11
 
13
and
extract
with
methylene
chloride
as
described
in
the
method.

1.2
Remove
the
extract
from
the
extractor
and
place
in
a
1
 
2
L
separatory
funnel.
Backextract
the
extract
sequentially
three
times
with
500­
mL
portions
of
salt­
saturated
reagent
water
(
pH
<
2),
discarding
the
reagent
water
after
each
back­
extraction.

1.3
Concentrate
the
extract
to
10
mL
and
clean
up
using
gel­
permeation
chromatography
(
GPC)
per
Section
10
of
Method
1625.

1.4
After
GPC,
concentrate
the
extract
to
0.5
mL
and
analyze
by
isotope
dilution
GC/
MS,
as
described
in
Method
1625.

1.5
Calculate
the
recovery
of
labeled
phenol
and
compare
to
the
performance
specifications
in
Method
1625.

2.
Dilution,
acid
extraction,
back­
extraction
with
base,
derivatization,
silica
gel
cleanup,
and
gas
chromatography
with
an
electrolytic
conductivity
detector
(
based
on
Method
604)

2.1
Measure
two
100­
mL
aliquots
of
well­
mixed
sample
into
1000­
mL
graduated
cylinders
Spike
one
of
the
aliquots
with
phenol
at
the
level
specified
in
Section
8
of
Method
604.
This
aliquot
serves
as
the
matrix
spike
sample
specified
in
the
method.
Dilute
both
aliquots
to
1.0
L
with
reagent
water.
Adjust
the
pH
of
each
aliquot
to
less
than
2
with
HCl.

2.2
Pour
each
aliquot
into
a
separate
1
 
2
L
separatory
funnel
and
sequentially
extract
three
times
with
methylene
chloride
per
Method
604.
Discard
the
aqueous
phase
and
return
the
extract
to
the
separatory
funnel.

2.3
Back­
extract
the
extract
sequentially
three
times
with
salt­
saturated
reagent
water,
discarding
the
reagent
water
after
each
back
extraction.

2.4
Concentrate,
derivatize,
and
clean
up
the
extract
per
Method
604.
Chapter
2:
Guidance
for
Analysts
Compliance
Monitoring
Guidance
14
2.5
Analyze
using
the
electrolytic
conductivity
detector.
This
detector
is
less
susceptible
to
interferences
than
the
electron
capture
detector
used
in
Method
604.
Newer
models
have
sensitivity
nearly
equivalent
to
the
electron
capture
detector.

2.6
Calculate
the
recovery
of
phenol
in
the
matrix
spike
aliquot
and
compare
this
recovery
to
the
specifications
in
Method
604.
Compliance
Monitoring
Guidance
Chapter
2:
Guidance
for
Analysts
15
Table
2.
Priority
Pollutants
Regulated
under
the
OCPSF
Rule
Priority
Pollutant
Applicable
304(
h)
Meth­
Priority
Pollutant
Applicable
304(
h)
ods
Methods
Acenaphthene
610,
625,
1625
Methylene
chloride
601,
624,
1624
Acrylonitrile
603,
624,
1624
Chloromethane
601,
624,
1624
Benzene
602,
624,
1624
Hexachlorobutadiene
612,
625,
1625
Carbon
tetrachloride
601,
624,
1624
Naphthalene
610,
625,
1625
Chlorobenzene
602,
625,
1625
Nitrobenzene
609,
625,
1625
1,2,4­
Trichlorobenzene
612,
625,
1625
2­
Nitrophenol
604,
625,
1625
Hexachlorobenzene
612,
625,
1625
4­
Nitrophenol
604,
625,
1625
1,2­
Dichloroethane
601,
624,
1624
2,4­
Dinitrophenol
604,
625,
1625
1,1,1­
Trichloroethane
601,
624,
1624
2­
Methyl­
4,6­
Dinitrophenol
604,
625,
1625
Hexachloroethane
612.
625,
1625
Phenol
604,
625,
1625
1,1­
Dichloroethane
601,
624,
1624
Bis(
2­
ethylhexyl)
phthalate
606,
625,
1625
1,1,2­
Trichloroethane
601,
624,
1624
Di­
n­
butyl
phthalate
606,
625,
1625
Chloroethane
601,
624,
1624
Diethyl
phthalate
606,
625,
1625
Chloroform
601,
624,
1624
Dimethyl
phthalate
606,
625,
1625
2­
Chlorophenol
604,
625,
1625
Benzo(
a)
anthracene
610,
625,
1625
1,2­
Dichlorobenzene
601,
602,
612,
Benzo(
a)
pyrene
610,
625,
1625
624,
625,
1625
1,3­
Dichlorobenzene
601,
602,
612,
3,4­
Benzofluoranthene
610,
625,
1625
624,
625,
1625
1,4­
Dichlorobenzene
601,
602,
612,
Benzo(
k)
fluoranthene
610,
625,
1625
624,
625,
1625
1,1­
Dichloroethylene
601,
624,
1624
Chrysene
610,
625,
1625
1,2­
trans­
Dichloroethylene
601,
624,
1624
Acenaphthylene
610,
625,
1625
2,4­
Dichlorophenol
604,
625,
1625
Anthracene
610,
625,
1625
1,2­
Dichloropropane
601,
624,
1624
Fluorene
610,
625,
1625
1,3­
Dichloropropylene
601,
624,
1624
Phenanthrene
610,
625,
1625
2,4­
Dimethylphenol
604,
625,
1625
Pyrene
610,
625,
1625
2,4­
Dinitrotoluene
609,
625,
1625
Tetrachloroethylene
601,
624,
1624
2,6­
Dinitrotoluene
609,
625,
1625
Toluene
602,
624,
1624
Ethylbenzene
602,
624,
1624
Trichloroethylene
601,
624,
1624
Fluoranthene
610,
625,
1625
Vinyl
chloride
601,
624,
1624
Chapter
2:
Guidance
for
Analysts
Compliance
Monitoring
Guidance
16
Table
3.
304(
h)
Methods
for
OCPSF
Organics
Method
Class
of
Analytes
Instrumentation
601
Purgeable
Halocarbons
GC/
ELCD
602
Purgeable
Aromatics
GC/
PID
603
Acrolein
and
Acrylonitrile
GC/
FID
604
Phenols
GC/
FID,
GC/
ECD
606
Phthalate
Esters
GC/
ECD
609
Nitroaromatics
and
Isophorone
GC/
FID,
GC/
ECD
610
Polynuclear
Aromatic
Hydrocarbons
GC/
FID/
HPLC/
UV,
Fluorescence
612
Chlorinated
Hydrocarbons
GC/
ECD
624
Purgeable
Organics
GC/
MS
625
Base/
Neutral
and
Acid
Extractable
Organics
GC/
MS
1624
Volatile
Organics
GC/
MS
Isotope
Dilution
1625
Semivolatile
Organics
GC/
MS
Isotope
Dilution
17
Chapter
3
Cost
Estimates
for
Resolving
Matrix
Interferences
Most
of
the
options
for
resolving
matrix
interferences
are
outlined
in
Chapter
2.
The
costs
associated
with
such
options
vary
from
laboratory
to
laboratory,
as
do
the
costs
of
the
basic
analysis.

However,
EPA
has
provided
some
guidance
in
Table
4
on
the
likely
added
costs
of
the
work
required
to
overcome
such
matrix
interferences.
These
estimates
are
based
on
EPA's
experience
in
contracting
for
analytical
services.

The
costs
are
estimated
for
repetitive
routine
monitoring
of
a
given
waste
stream.
The
estimates
do
not
include
the
development
costs
involved
in
modifying
a
given
method
to
overcome
a
complex
matrix
problem.
The
cost
estimates
also
do
not
include
the
costs
of
validating
the
use
of
additional
cleanup
techniques
through
the
"
start­
up"
tests
described
in
Chapter
2.
The
costs
of
method
modifications
cannot
be
estimated
because
each
complex
matrix
problem
must
be
evaluated
individually
EPA
believes
that
these
development
costs
could
range
between
several
hundred
and
several
thousand
dollars,
depending
on
the
complexity
of
the
wastewater
and
the
experience
of
the
laboratory
in
resolving
matrix
interferences.

Given
these
difficulties,
EPA
believes
that
the
prudent
course
is
to
begin
by
applying
the
cleanups
and
other
techniques
described
in
Chapter
2
to
the
existing
304(
h)
methods
before
embarking
on
a
major
modification
of
a
method.
The
cost
estimates
in
Table
4
are
based
on
EPA's
experience
through
1992
and
are
given
in
round
numbers.
Chapter
3:
Cost
Estimates
Compliance
Monitoring
Guidance
The
techniques
listed
in
this
table
are
discussed
in
Chapter
2.
1
18
Table
4.
Estimated
Incremental
Costs
Associated
with
Cleanup
Techniques
and
Other
Approaches
to
Resolving
Matrix
Interferences1
Interference­
reducing
technique
Estimated
incremental
cost
Use
of
GC
with
selective
detector
in
place
of
GC/
MS
No
increased
cost:

V
O
L
A
T
I
L
E
S
should
be
less
expensive
than
GC/
MS
Micro­
extraction
after
pH
adjustment
$
25
Sample
dilution
No
charge
if
known
prior
to
analysis
of
neat
sample,
otherwise
may
be
billable
as
another
analysis
Isotope
dilution
GC/
MS
(
Method
1624)
$
200
to
$
500
Use
of
GC
with
selective
detector
in
place
of
GC/
MS
No
increased
cost:

S
E
M
I
V
O
L
A
T
I
L
E
S
should
be
less
expensive
than
GC/
MS
pH
change
No
charge
Back­
extraction
$
25
Gel
permeation
cleanup
$
100
Solid
phase
extraction
cleanup
$
100
Florisil
column
cleanup
$
25
Alumina
column
cleanup
$
25
Silica
gel
column
cleanup
$
25
Sample
dilution
No
charge
if
known
prior
to
analysis
of
neat
sample,
otherwise
may
be
billable
as
another
analysis
Isotope
dilution
GC/
MS
(
Method
1625)
$
200
to
$
500
19
Chapter
4
Guidance
for
Reviewing
Data
from
the
Analysis
of
Organic
Compounds
Using
EPA
600­
and
1600­
Series
Methods
This
chapter
provides
guidance
for
reviewing
data
submitted
for
compliance
monitoring
purposes
under
the
National
Pollutant
Discharge
Elimination
System
(
NPDES)
and
data
submitted
to
EPA
and
State
authorities
under
the
Clean
Water
Act.
This
guidance
is
intended
to
aid
in
review
of
data
for
organic
compounds
regulated
under
the
OCPSF
Rule
and
collected
using
the
600­
series
and
1600­
series
wastewater
methods
under
40
CFR
Part
136
(
49
FR
43234).
The
principles
of
data
review
described
herein
are
also
applicable
to
data
from
the
500­
series
methods
and
the
SW­
846
methods.

The
guidance
is
technically
detailed
and
is
intended
for
data
reviewers
familiar
with
the
600­

and
1600­
series
methods
and
similar
analytical
methods.
Reviewers
unfamiliar
with
these
methods
should
review
the
methods
and
the
supporting
background
materials
provided
in
the
preamble
to
the
regulation
(
49
FR
43234).

Standardized
Quality
Assurance/
Quality
Control
In
developing
methods
for
the
determination
of
organic
pollutants
in
wastewater,
EPA
sought
scientific
and
technical
advice
from
many
sources,
including
EPA's
Science
Advisory
Board,
scientists
at
EPA's
environmental
research
laboratories,
scientists
in
industry
and
academia,
and
scientists,

managers,
and
legal
staff
at
EPA
Headquarters.
The
result
of
discussions
held
among
these
groups
was
the
standardized
quality
assurance
and
quality
control
(
QA/
QC)
approach
that
is
an
integral
part
of
the
600­
and
1600­
series
methods.
This
QA/
QC
takes
the
form
of
performance
specifications
for
each
method
and
contains
the
following
elements:

1.
Purity
and
traceability
of
reference
standards
2.
Number
of
calibration
points
3.
Linearity
of
calibration
4.
Calibration
verification
5.
Method
detection
limit
(
MDL)
or
minimum
level
6.
Initial
precision
and
recovery
7.
Analysis
of
blanks
8.
Recovery
of
analyte
spikes
into
the
sample
matrix
or
Recovery
of
labeled
compound
spikes
into
samples
(
Methods
1624
and
1625).
9.
Statements
of
data
quality
for
recovery
of
spikes
of
analytes
or
labeled
compounds
into
samples
10.
Ongoing
precision
and
recovery
(
Methods
1624
and
1625)
11.
Statements
of
data
quality
for
the
laboratory
In
reviewing
data
submitted
for
compliance,
the
permit
writer
or
other
individual
or
organization
has
the
authority
and
responsibility
to
assure
that
the
test
data
submitted
contain
the
elements
listed
above;
otherwise,
the
data
can
be
considered
noncompliant.
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
20
Provision
of
QA/
QC
Data
Permittees
and
other
organizations
submitting
test
data
under
the
CWA
or
other
acts
may
use
their
own
laboratories
or
contract
the
testing
to
laboratories
that
meet
the
requirements
specified
in
the
methods.
The
permit
writer
can
require
that
the
supporting
QA/
QC
data
described
above
be
submitted
with
results
or
that
it
be
on
record
at
the
permittee's
facility
or
at
the
testing
laboratory.

EPA
strongly
suggests
that
the
supporting
QA/
QC
data
be
submitted
along
with
the
analytical
results,
so
that
the
quality
of
the
data
can
be
evaluated
directly,
and
so
that
these
supporting
data
are
not
lost
between
the
time
of
submission
of
the
analytical
results
and
the
time
that
the
QA/
QC
data
are
required.

In
many
of
its
early
analytical
programs,
EPA
relied
upon
laboratories
to
maintain
records
of
the
QA/
QC
data.
This
practice
was
cumbersome
for
the
laboratories,
because
many
of
the
QA/
QC
data
were
common
to
the
analytical
results
for
a
variety
of
clients.
Retrieving
these
data
from
the
laboratory
to
resolve
questions
of
permit
compliance
was
time­
consuming
for
the
permittee
and
the
permit
writer.
More
importantly,
this
practice
occasionally
resulted
in
unscrupulous
laboratories
failing
to
perform
the
necessary
QA/
QC
testing,
or
performing
the
QA/
QC
testing
"
after
the
fact"
to
satisfy
an
audit
or
data
submission
request.
In
particular,
many
laboratories
did
not
perform
the
initial
precision
and
recovery
test
(
the
"
start­
up"
test)
prior
to
practice
of
the
method
and
did
not
perform
a
spike
of
the
analytes
into
the
sample
matrix
to
prove
that
the
method
would
work
on
a
particular
sample.

Therefore,
while
the
data
provided
by
those
laboratories
may
have
been
valid,
there
was
no
way
to
prove
their
validity.

When
collecting
data
for
the
development
of
a
regulation,
EPA
requires
that
the
supporting
QA/
QC
data
be
provided
along
with
the
results
for
the
sample
analyses.
If
an
individual
or
organization
submits
analytical
results
for
inclusion
into
EPA's
regulations,
EPA
similarly
requires
the
submission
of
the
QA/
QC
data.
The
sample
results
are
evaluated
relative
to
the
QA/
QC
specifications
in
the
method,
and
those
results
that
pass
the
QA/
QC
requirements
are
included
for
consideration.

EPA
believes
that
provision
of
the
QA/
QC
data
at
the
time
of
submission
of
the
analytical
results
is
essential
to
the
timely
and
effective
evaluation
of
permit
compliance
issues.

Details
of
Data
Review
The
details
of
the
data
review
process
depend
to
a
great
extent
upon
the
specific
analytical
methods
being
employed
for
compliance
monitoring.
Even
for
data
from
the
same
methods,
there
are
probably
as
many
specific
approaches
as
there
are
reviewers.
However,
given
the
standardized
QA/
QC
requirements
of
the
600­
and
1600­
series
EPA
methods,
a
number
of
basic
concepts
apply.

The
following
sections
provide
the
basic
details
for
reviewing
data
submitted
and
provide
some
of
EPA's
rationale
for
the
QA/
QC
tests.

1.
Purity
and
Traceability
of
Reference
Standards
The
accuracy
of
any
non­
absolute
empirical
measurement
is
dependent
on
the
reference
for
that
measurement.
In
determining
pollutants
in
water
or
other
sample
matrices,
the
analytical
instrument
and
analytical
process
must
be
calibrated
with
a
known
reference
mate­
Compliance
Monitoring
Guidance
Chapter
4:
Data
Review
21
rial.
The
600­
and
1600­
series
analytical
methods,
as
well
as
other
EPA
methods,
require
that
the
standards
used
for
calibration
and
other
purposes
be
of
known
purity
and
traceable
to
a
reliable
reference
source.

The
ultimate
source
for
reference
materials
is
typically
EPA
or
the
National
Institute
for
Standards
and
Technology
(
NIST,
formerly
NBS).
Permittees
and
their
supporting
laboratories
submitting
analytical
data
must
be
able
to
prove
traceability
of
the
reference
standards
used
in
the
analysis
to
EPA
or
NIST.
The
proof
of
this
traceability
is
a
written
certification
from
the
supplier
of
the
standard.

Documentation
of
the
purity
and
traceability
of
the
standards
need
not
be
provided
with
every
sample
analysis.
Rather,
it
should
be
maintained
on
file
at
the
laboratory
and
provided
on
request.
When
analyses
are
conducted
in
a
contract
laboratory,
such
documentation
ought
to
be
provided
to
the
permittee
the
first
time
that
a
laboratory
is
employed
for
specific
analyses
and
then
updated
as
needed.

2.
Number
of
Calibration
Points
The
600­
series
methods
specify
a
minimum
of
three
calibration
points.
The
lowest
of
these
points
is
required
to
be
near
the
MDL.
The
highest
is
required
to
be
near
the
upper
linear
range
of
the
analytical
system,
and
the
third
point
is
approximately
midway
between
the
two.
Methods
1624
and
1625
require
calibration
at
five
specific
concentrations
for
nearly
all
analytes,
and
three
or
four
specific
concentrations
for
the
remaining
analytes
for
which
the
methods
are
not
as
sensitive.

The
lowest
calibration
point
should
never
be
greater
than
five
times
the
MDL
and
should
ideally
be
within
three
times
the
MDL.
The
results
for
the
lowest
calibration
standard
are
the
principal
means
by
which
to
assure
that
measurements
at
levels
near
the
MDL
are
reliable.

The
flexibility
in
selecting
the
levels
of
the
calibration
points
in
the
600­
series
methods
has
led
to
a
wide
variety
of
calibration
ranges
as
each
laboratory
may
determine
its
own
calibration
range.
Some
laboratories
establish
a
relatively
narrow
calibration
range,
for
instance
a
five­
fold
increase
in
concentration,
because
it
makes
it
simpler
to
meet
the
linearity
specifications
of
the
600­
series
methods.
Other
laboratories
choose
wider
calibration
ranges
in
order
to
minimize
the
number
of
samples
that
have
to
be
diluted
and
reanalyzed
because
the
concentration
of
one
or
more
analytes
exceeds
the
calibration
range.

The
data
reviewer
must
make
certain
that
all
measurements
are
within
the
calibration
range
of
the
instrument.
Samples
with
analytes
outside
of
the
calibration
range
should
have
been
diluted
and
reanalyzed.
The
diluted
sample
results
need
only
apply
to
those
analytes
that
were
out
of
the
calibration
range
in
the
initial
analysis.
In
other
words,
it
is
acceptable
to
use
data
for
different
analytes
from
different
levels
of
dilution
within
the
same
sample.
Some
flexibility
may
be
exercised
in
acceptance
of
data
that
are
only
slightly
above
(<
10%)
the
calibration
range.
Such
data
are
generally
acceptable
as
calculated.

If
data
from
an
analysis
of
the
diluted
sample
are
not
provided,
limited
use
can
be
made
of
the
data
that
are
above
the
calibration
range
(>
10%).
The
response
of
the
analytical
instrument
to
concentrations
of
analytes
will
eventually
level
off
at
concentrations
above
the
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
22
calibration
range.
While
it
is
not
possible
to
specify
at
what
concentration
this
will
occur
from
the
calibration
data
provided,
it
is
generally
safe
to
assume
that
the
reported
concentration
above
the
calibrated
range
is
a
lower
limit
of
the
actual
concentration.
Therefore,
if
concentration
above
the
calibration
range
is
also
above
a
regulatory
limit,
it
is
highly
likely
that
the
actual
concentration
would
also
be
above
that
limit.

3.
Linearity
of
Calibration
The
relationship
between
the
response
of
an
analytical
instrument
to
the
concentration
or
amount
of
an
analyte
introduced
into
the
instrument
is
referred
to
as
the
"
calibration
curve."

An
analytical
instrument
can
be
said
to
be
calibrated
in
any
instance
in
which
an
instrumental
response
can
be
related
to
a
single
concentration
of
an
analyte.
The
response
factor
(
GC/
MS
methods)
or
calibration
factor
(
GC,
HPLC
methods)
is
the
ratio
of
the
response
of
the
instrument
to
the
concentration
(
or
amount)
of
analyte
introduced
into
the
instrument.

While
the
shape
of
calibration
curves
can
be
modeled
by
quadratic
equations
or
higher
order
mathematical
functions,
most
analytical
methods
focus
on
a
calibration
range
where
the
response
is
essentially
a
linear
function
of
the
concentration
of
the
analyte.
The
advantage
of
the
linear
calibration
is
that
the
response
factor
or
calibration
factor
represents
the
slope
of
the
calibration
curve
and
is
relatively
constant,
simplifying
the
calculations
and
the
interpretation
of
the
data.
Therefore,
all
the
600­
and
1600­
series
methods
specify
some
criterion
for
determining
the
linearity
of
the
calibration
curve.
When
this
criterion
is
met,
the
calibration
curve
is
sufficiently
linear
to
permit
the
laboratory
to
use
an
average
response
factor
or
calibration
factor,
and
it
is
assumed
that
the
calibration
curve
is
a
straight
line
that
passes
through
the
zero/
zero
calibration
point.
Linearity
is
determined
by
calculating
the
relative
standard
deviation
(
RSD)
of
the
response
factor
or
calibration
factor
for
each
analyte
and
comparing
this
RSD
to
the
limit
specified
in
the
method.
If
the
RSD
does
not
exceed
the
specification,
linearity
is
assumed.

In
the
600­
and
1600­
series
methods,
the
linearity
specification
varies
from
method
to
method,
depending
on
the
quantitation
technique.
The
typical
limits
on
the
RSD
are
as
follows:

·
15%
for
the
gas
chromatography
(
GC)
and
high­
performance
liquid
chromatography
(
HPLC)
methods
·
35%
for
analytes
determined
by
the
internal
standard
technique
in
the
gas
chromatography
mass
spectrometry
(
GC/
MS)
methods
(
624,
625,
1624,
and
1625)

·
20%
for
analytes
determined
by
isotope
dilution
in
Methods
1624
and
1625
If
the
calibration
is
not
linear,
as
determined
by
the
RSD
of
the
response
factor
or
calibration
factor,
a
calibration
curve
must
be
used.
This
means
that
a
regression
line
or
other
mathematical
function
must
be
employed
to
relate
the
instrument
response
to
the
concentration.

Properly
maintained
and
operated
lab
instrumentation
should
have
no
difficulty
in
meeting
linearity
specifications
for
600­
and
1600­
series
methods.
Compliance
Monitoring
Guidance
Chapter
4:
Data
Review
23
For
determination
of
nearly
all
of
the
organic
analytes
using
the
600­
and
1600­
series
methods,
the
calibration
curves
are
linear
over
a
concentration
range
of
20
 
100
times
the
nominal
concentration,
depending
on
the
detector
being
employed.
Whatever
calibration
range
is
used,
the
laboratory
must
provide
the
RSD
results
by
which
one
can
judge
linearity,
even
in
instances
where
the
laboratory
is
using
a
calibration
curve.
In
instances
where
the
laboratory
employs
a
curve
rather
than
an
average
response
factor
or
calibration,
the
data
reviewer
should
review
each
calibration
point
to
assure
that
the
response
increases
as
the
concentration
increases
If
it
does
not,
the
instrument
is
not
operating
properly,
or
the
calibration
curve
is
out
of
the
range
of
that
instrument,
and
data
are
not
considered
valid.

4.
Calibration
Verification
Calibration
verification
involves
the
analysis
of
a
single
standard,
typically
in
the
middle
of
the
calibration
range,
at
the
beginning
of
each
analytical
shift.
The
concentration
of
each
analyte
in
this
standard
is
determined
using
the
initial
calibration
data
and
compared
to
specifications
in
the
method.
If
the
results
are
within
the
specifications,
the
laboratory
is
allowed
to
proceed
with
analysis
without
recalibrating
and
use
the
initial
calibration
data
to
quantify
sample
results.

Calibration
verification,
used
in
the
600­
and
1600­
series
methods,
differs
in
concept
and
practice
from
"
continuing
calibration,"
which
is
used
in
the
CLP
and
SW­
846
methods.
In
continuing
calibration,
a
standard
is
analyzed
and
new
response
factors
or
calibration
factors
are
calculated
on
the
basis
of
that
analysis.
If
the
new
factors
are
close
to
the
average
from
the
initial
calibration,
all
subsequent
sample
analyses
are
conducted
using
the
new
response
or
calibration
factors.
The
degree
of
"
closeness"
is
generally
measured
as
the
percent
difference
between
the
old
and
new
factors.
The
problem
with
continuing
calibration
is
that
it
amounts
to
a
daily
single­
point
calibration.
Information
about
the
behavior
of
the
instrument
at
concentrations
above
and
below
this
single
standard
can
only
be
inferred
from
the
initial
multiplepoint
calibration.

Specifications
for
calibration
verification
are
generally
given
as
either
a
range
of
concentrations
or
as
a
percentage
difference
from
the
test
concentration.
For
the
600­
series
semivolatile
GC
and
HPLC
methods,
the
difference
must
be
within
±
15%.
For
Method
625,

the
difference
must
be
within
±
20%.
For
the
GC
and
GC/
MS
methods
for
volatiles
and
for
Method
1625,
a
range
of
concentrations
is
given
for
each
analyte.
These
ranges
are
based
on
interlaboratory
method
validation
studies.

If
calibration
cannot
be
verified,
the
laboratory
may
either
recalibrate
the
instrument
or
prepare
a
fresh
calibration
standard
and
make
a
second
attempt
to
verify
calibration.
If
calibration
cannot
be
verified
with
a
fresh
calibration
standard,
the
instrument
must
be
recalibrated.
If
calibration
is
not
verified,
subsequent
data
are
considered
to
be
invalid
until
the
instrument
is
recalibrated.
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
24
5.
Method
Detection
Limit
or
Minimum
Level
The
600­
and
1600­
series
methods
do
not
require
that
laboratories
determine
the
method
detection
limit
(
MDL)
for
each
analyte
(
40
CFR
Part
136,
Appendix
B).
However,

laboratories
that
wish
to
practice
any
method
on
a
routine
basis
must
prove
that
they
can
measure
pollutants
at
the
MDL
or
the
detection
limit
specified
in
the
method.
Performance
of
an
MDL
study
in
accordance
with
this
procedure
is
one
means
of
demonstrating
such
proficiency

The
ability
to
identify
and
quantify
compounds
at
the
"
minimum
levels"
specified
in
Methods
1624
and
1625
must
be
demonstrated
prior
to
the
practice
of
these
methods.
The
minimum
level
for
any
compound
is
the
concentration
in
a
sample
that
is
equivalent
to
the
concentration
of
the
lowest
calibration
standard
in
the
initial
calibration,
assuming
that
all
method­
specified
sample
weights,
volumes,
and
procedures
are
employed.
Therefore,
data
from
the
initial
calibration
must
be
submitted
in
order
to
demonstrate
that
the
required
sensitivity
has
been
achieved.

If
the
minimum
level
in
Methods
1624
and
1625
have
not
been
achieved
(
as
exemplified
by
calibration
data),
data
are
considered
to
be
invalid.

6.
Initial
Precision
and
Recovery
This
test
is
required
prior
to
the
use
of
the
method
by
the
laboratory.
It
is
sometimes
termed
the
"
start­
up
test."
The
laboratory
must
demonstrate
that
it
can
meet
the
specifications
in
the
method
for
the
recovery
of
analytes
spiked
into
a
reference
matrix
(
reagent
water).

EPA's
experience
has
been
that
laboratories
that
have
difficulty
passing
the
start­
up
test
have
such
marginal
performance
that
they
will
have
difficulty
in
the
routine
practice
of
the
method.

Performing
the
start­
up
test
"
after
the
fact"
is
not
acceptable
and
may
not
be
used
to
validate
data
that
have
been
considered
invalid
because
the
start­
up
test
was
not
performed.

The
test
consists
of
spiking
the
analytes
of
interest
into
a
set
of
four
aliquots
of
reagent
water
and
analyzing
these
four
aliquots.
The
mean
concentration
and
the
standard
deviation
of
the
concentration
are
calculated
for
each
analyte
and
compared
to
the
specifications
in
each
method.
If
the
mean
and
standard
deviation
are
within
the
limits,
the
laboratory
can
use
the
method
to
analyze
field
samples.
For
some
methods,
a
repeat
test
is
allowed
because
of
the
large
number
of
analytes
being
tested
simultaneously.

If
there
are
no
start­
up
test
data,
or
if
these
data
fail
to
meet
the
specifications
in
the
method,
all
data
produced
by
that
laboratory
using
that
method
are
not
considered
valid.
As
with
the
documentation
of
the
purity
of
the
standards,
the
start­
up
test
data
need
not
be
submitted
with
each
set
of
sample
results,
but
should
be
submitted
the
first
time
a
laboratory
is
employed
for
analyses,
and
updated
as
changes
to
the
method
necessitate
(
see
below).

It
is
important
to
remember
that
if
a
change
is
made
to
a
method,
the
start­
up
test
must
be
repeated
with
the
change
as
an
integral
part
of
the
method.
Such
changes
may
involve
alternative
extraction,
concentration,
or
cleanup
processes,
alternative
GC
columns,
GC
conditions
or
detectors,
or
other
steps
designed
to
address
a
particular
matrix
problem.
If
the
Compliance
Monitoring
Guidance
Chapter
4:
Data
Review
25
start­
up
test
is
not
repeated
when
these
steps
are
modified
or
added,
any
data
produced
by
the
modified
method
are
considered
not
valid.

7.
Analysis
of
Blanks
Blanks
are
required
to
be
analyzed
on
a
routine
basis,
when
any
part
of
the
analytical
process
has
been
changed,
and
when
contamination
of
the
laboratory
is
suspected.
The
600­

and
1600­
series
methods
require
that
a
blank
be
prepared
and
analyzed
with
each
set
of
samples.
The
size
of
a
"
set"
is
usually
limited
to
a
maximum
of
20
field
samples.
In
practice
this
means
that
on
each
day
that
a
laboratory
prepares
samples,
they
must
also
prepare
a
blank,

even
if
fewer
than
20
samples
are
prepared.
The
purpose
of
analyzing
a
blank
with
each
set
of
samples
is
to
determine
the
extent
of
possible
contamination
of
the
samples
while
in
the
laboratory.
If
the
blank
is
handled
by
the
same
analysts
in
the
same
way
as
the
samples
and
the
blank
shows
no
contamination,
it
is
likely
that
the
samples
will
not
have
been
contaminated
Requiring
a
blank
to
be
analyzed
after
the
analytical
process
has
been
changed
is
consistent
with
requiring
a
repeat
of
the
start­
up
test,
because
the
change
introduces
a
new
possibility
for
contamination
of
samples
through
the
use
of
the
new
procedures.

Contamination
in
the
laboratory
is
a
common
problem,
though
there
are
many
opinions
on
what
constitutes
contamination.
In
the
600­
and
1600­
series
methods,
any
concentration
of
a
compound
above
the
detection
limit
or
minimum
level
of
the
method
in
question
is
a
potential
cause
for
concern.
In
reality,
it
is
not
unusual
to
find
low
levels
of
common
laboratory
solvents,
phthalates,
and
other
ubiquitous
compounds
in
laboratory
blanks.

Controlling
laboratory
contamination
is
an
important
aspect
of
each
laboratory's
quality
assurance
plan.
The
laboratory
should
maintain
records,
typically
in
the
form
of
control
charts,
of
blank
contaminants.
These
records
should
prompt
corrective
action
by
the
laboratory
including
reanalysis
of
any
affected
samples.
Such
control
charts
may
be
requested
by
the
reviewer
in
evaluating
sample
results;
however,
they
are
not
routinely
submitted
with
sample
data.

Unfortunately,
by
the
time
that
data
on
contaminants
are
submitted,
it
is
usually
too
late
for
corrective
action.
Therefore,
the
reviewer
has
several
options
in
making
use
of
the
sample
data.
First,
if
a
contaminant
is
present
in
a
blank,
but
not
present
in
a
sample,
then
there
is
little
need
for
concern
about
the
sample
result,
though
it
may
be
useful
to
occasionally
review
the
raw
data
for
samples
without
the
contaminant
to
ensure
that
the
laboratory
did
not
edit
the
results
for
this
compound.

The
second
approach
deals
with
instances
where
the
blank
contaminant
is
also
reported
in
a
sample.
Some
general
guidance
will
help
you
determine
the
degree
to
which
the
contaminant
is
affecting
sample
results:

·
If
the
sample
contains
the
contaminant
at
levels
of
at
least
10
times
that
in
the
blank,
then
the
likely
contribution
to
the
sample
from
the
contaminant
in
the
laboratory
environment
is
at
most
10%.
Since
most
of
the
methods
in
question
are
no
more
accurate
than
that
level,
the
possible
contamination
is
negligible.
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
26
·
If
the
sample
contains
the
contaminant
at
levels
of
at
least
5
times
but
less
than
10
times
the
blank
result,
the
compound
is
probably
present
in
the
sample,
but
the
numerical
result
should
be
considered
an
upper
limit
of
the
true
concentration.

·
If
the
sample
contains
the
contaminant
at
levels
below
5
times
the
level
in
the
blank,
there
is
no
adequate
means
by
which
to
judge
whether
or
not
the
sample
result
is
attributable
to
laboratory
contamination.
The
results
for
that
compound
in
that
sample
then
become
unacceptable
for
compliance
monitoring.

There
are
two
difficulties
in
evaluating
sample
results
relative
to
blank
contamination.

First,
the
reviewer
must
be
able
to
associate
the
samples
with
the
correct
blanks.
For
analysis
of
volatiles
by
purge­
and­
trap
techniques,
where
no
sample
extraction
is
required,
the
blanks
and
samples
are
associated
by
analysis
date
and
time,
and
specific
to
the
instrument
as
well.

For
methods
involving
the
extraction
of
organic
compounds
from
the
samples,
the
blanks
and
samples
are
primarily
associated
by
the
date
on
which
they
were
extracted,
and
by
the
batch
of
samples
and
associated
lab
equipment
(
glassware,
reagents,
cleanup
media).

The
second
difficulty
involves
samples
that
have
been
diluted.
The
dilution
of
the
sample
with
reagent
water
or
the
dilution
of
the
extract
with
solvent
represents
an
additional
potential
source
of
contamination
that
will
not
be
reflected
in
the
results
for
the
blank
unless
the
blank
was
similarly
diluted.
Therefore,
in
applying
the
10­
times
rule,
the
concentration
of
the
sample
is
compared
to
the
blank
result
multiplied
by
the
dilution
factor
of
the
sample
or
sample
extract.
For
instance,
if
12
ppb
of
a
contaminant
are
found
in
the
blank,
and
the
associated
sample
extract
was
diluted
by
a
factor
of
6
relative
to
the
extract
from
the
blank
prior
to
analysis,
then
the
sample
result
would
have
to
be
greater
than
12
×
6
×
10,
or
720
ppb,
to
be
acceptable.
Between
360
ppb
and
720
ppb,
the
sample
result
would
best
be
considered
an
upper
limit
of
the
actual
concentration.
Below
360
ppb,
the
sample
result
is
not
acceptable
for
compliance
monitoring.

Many
laboratories
would
have
the
reviewer
believe
that
subtracting
the
concentration
of
the
analyte
in
the
blank
from
the
concentration
of
the
analyte
in
the
sample
is
a
reliable
method
of
determining
the
true
concentration
of
the
analyte
in
the
sample.
Unfortunately,

experience
indicates
that
this
practice
is
not
reliable.
The
obvious
problem
occurs
when
the
blank
concentration
is
higher
than
that
in
the
sample,
and
subtraction
would
yield
a
negative
concentration
value.
Using
the
10­
times
rule
above
provides
a
more
appropriate
means
of
evaluating
the
results
and
does
not
require
that
the
reviewer
alter
the
results
reported
by
the
laboratory.

8.
Recovery
of
Analyte
Spikes
into
the
Sample
Matrix
or
Recovery
of
Labeled
Compound
Spikes
into
Samples
(
Methods
1624
and
1625)

The
non­
isotope
dilution
methods
require
a
spike
of
the
analytes
of
interest
into
a
second
aliquot
of
the
sample
for
analysis
with
the
sample.
The
purpose
of
spiking
the
sample
(
often
termed
a
"
matrix
spike")
is
to
determine
if
the
method
is
applicable
to
the
sample
in
question.
The
majority
of
the
600­
and
1600­
series
methods
were
developed
for
the
analysis
of
effluent
samples
and
may
not
be
appropriate
for
in­
process
samples.
While
many
of
the
Compliance
Monitoring
Guidance
Chapter
4:
Data
Review
27
methods
were
tested
using
effluents
from
a
wide
variety
of
industries,
samples
from
some
sources
may
not
yield
acceptable
results.
It
is
therefore
important
to
evaluate
method
performance
in
the
sample
matrix
of
interest.

If
the
recovery
of
the
matrix
spike
is
within
the
limits
specified
in
the
method,
then
the
method
is
judged
to
be
applicable
to
that
sample
matrix.
If,
however,
the
recovery
of
the
spike
is
not
within
the
recovery
range
specified,
either
the
method
does
not
work
on
the
sample,
or
the
sample
preparation
process
is
out
of
control.

If
the
method
is
not
appropriate
for
the
sample
matrix,
then
changes
to
the
method
are
required.
Matrix
spike
results
are
necessary
in
evaluating
the
modified
method.
If
the
analytical
process
is
out
of
control,
the
laboratory
must
take
immediate
corrective
action
before
any
more
samples
are
analyzed.

To
separate
indications
of
method
performance
from
those
of
laboratory
performance,

the
laboratory
should
prepare
and
analyze
a
quality
control
check
standard
consisting
of
a
spike
of
the
analytes
in
reagent
water.
If
the
results
for
the
quality
control
standard
are
not
within
the
range
specified,
then
the
analytical
system
must
be
repaired
and
the
sample
and
spiked
sample
analyses
repeated.
If
the
recovery
of
this
spike
is
within
the
range
specified,

then
the
analytical
process
is
judged
to
be
in
control.
However,
the
results
of
the
sample
analysis
cannot
be
accepted
for
regulatory
compliance
purposes
because
the
matrix
spike
results
indicate
that
the
method
is
not
applicable
to
the
sample.

In
evaluating
matrix
spike
results,
the
data
reviewer
must
verify
the
following:

a.
The
unspiked
sample
has
been
analyzed.
b.
The
spiked
sample
has
been
analyzed.
c.
The
recovery
of
the
spike
is
within
the
range
specified.
d.
If
the
spike
recovery
is
not
within
the
range
specified,
a
QC
check
standard
has
been
analyzed.
e.
If
a
QC
check
standard
has
been
analyzed,
the
results
are
within
the
range
specified.

For
isotope
dilution
analyses,
the
evaluation
of
the
data
is
simpler
because
isotopically
labeled
analogs
of
the
pollutants
are
spiked
into
each
sample,
and
because
a
QC
check
standard
(
termed
the
"
ongoing
precision
and
recovery
standard,"
or
OPR)
is
analyzed
with
each
sample
set.

If
the
recovery
of
the
labeled
compound
spiked
into
the
sample
is
not
within
the
range
specified
in
the
method,
and
the
results
of
analysis
of
the
ongoing
precision
and
recovery
standard
are
within
the
respective
limits,
the
sample
results
are
considered
invalid.
When
labeled­
compound
recoveries
are
outside
of
the
method
specifications,
the
problem
may
be
related
to
the
sample
matrix.
The
isotope
dilution
methods
specify
that,
in
these
instances,
the
sample
must
be
diluted
with
reagent
water
and
reanalyzed.
If
the
labeled
compound
recoveries
meet
the
method
specifications
after
dilution
of
the
sample,
then
the
results
are
acceptable,

although
the
sensitivity
of
the
analysis
will
be
decreased
by
the
dilution.

Unfortunately,
for
some
sample
matrices,
even
dilution
will
not
resolve
the
problem,

and
for
other
matrices,
the
loss
of
sensitivity
will
preclude
the
use
of
the
results
for
determining
compliance.
In
these
instances,
additional
steps
need
to
be
taken
to
achieve
acceptable
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
28
results.
Guidance
as
to
what
steps
may
be
taken
when
the
results
of
matrix­
spike
or
labeledcompound
recoveries
are
not
within
the
limits
specified
in
the
methods
is
provided
in
Chapter
2.
This
guidance
consists
of
suggestions
for
more
extensive
extraction
and
cleanup
procedures
for
sample
dilution,
and
for
other
measures
that
can
be
taken
to
overcome
matrix
problems.

Using
either
non­
isotope
dilution
or
isotope
dilution
techniques,
in
instances
where
matrix
spike
or
labeled
compound
recoveries
are
not
within
the
specifications,
it
may
still
be
possible
to
use
the
sample
results
for
compliance
monitoring
purposes.
In
particular,
if
(
1)
the
recovery
of
the
spiked
compound
is
above
the
method
specifications
and
(
2)
the
compound
is
not
detected
in
the
sample
analysis,
it
is
unlikely
that
the
compound
is
present
in
the
sample.

This
is
because
the
factors
that
caused
the
analysis
to
over­
estimate
the
concentration
in
the
spiked
sample
would
not
likely
have
resulted
in
an
under­
estimate
in
the
unspiked
sample.

For
samples
in
which
the
compound
is
detected
but
the
matrix
spike
or
labeled
compound
recovery
is
above
the
method
specifications,
the
concentration
reported
in
the
unspiked
sample
is
likely
an
upper
limit
of
the
true
concentration.

9.
Statements
of
Data
Quality
for
Recovery
of
Spiked
Analytes
or
Labeled
Compounds
in
Samples
The
600­
and
1600­
series
methods
specify
that
after
the
analyses
of
five
spiked
samples,
a
statement
of
data
quality
is
constructed
for
each
analyte.
The
statement
of
data
quality
for
each
analyte
is
computed
as
the
mean
percent
recovery
plus
and
minus
two
times
the
standard
deviation
of
percent
recovery
for
each
analyte.
The
statements
of
data
quality
should
then
be
updated
by
the
laboratory
after
each
five
to
ten
subsequent
spiked
sample
analyses.

For
non­
isotope
dilution
results,
the
statement
of
data
quality
can
be
used
to
estimate
the
true
value
of
a
reported
result
and
to
construct
confidence
bounds
around
the
result.
For
example,
if
the
result
reported
for
analysis
of
phenol
is
25
µ
g/
L,
and
the
statement
of
data
quality
for
phenol
is
70%
±
30%
(
i.
e.,
the
mean
recovery
is
70%
and
the
standard
deviation
of
the
recovery
is
15%),
the
true
value
for
phenol
will
be
in
the
range
of
28
 
43
µ
g/
L,
with
95%

confidence.
This
range
is
derived
as
follows:

Lower
limit
=
[(
25
÷
0.7)
-
(
25
×
0.3)]
=
[
35.7
-
7.5]
=
28
µ
g/
L
Upper
limit
=
[(
25
÷
0.7)
+
(
25
×
0.3)]
=
[
35.7
+
7.5]
=
43
µ
g/
L
Many
laboratories
do
not
provide
the
data
quality
statements
with
the
sample
results,

in
which
case
the
data
reviewer
must
determine
if
the
data
quality
statements
are
being
maintained
for
each
analyte
and
may
need
to
obtain
the
data.
If
necessary,
the
reviewer
can
construct
the
data
quality
statement
from
the
individual
data
points.

Statements
of
data
quality
for
isotope
dilution
methods
are
based
on
the
recoveries
of
the
labeled
compounds.
Using
an
isotope
dilution
method,
the
sample
result
has
already
been
corrected
for
the
recovery
of
the
labeled
analog
of
the
compound.
Therefore,
for
a
reported
result
for
phenol
of
25
µ
g/
L
where
the
standard
deviation
of
the
labeled
phenol
recovery
is
Compliance
Monitoring
Guidance
Chapter
4:
Data
Review
29
15%,
the
true
value
for
phenol
will
be
in
the
range
of
17
 
32
µ
g/
L,
with
95%
confidence,

derived
as
follows:

Lower
limit
=
[
25
-
(
25
×
0.3)]
=
17
µ
g/
L
Upper
limit
=
[
25
+
(
25
×
0.3)]
=
32
µ
g/
L
The
lack
of
a
statement
of
data
quality
does
not
invalidate
results
but
makes
some
compliance
decisions
more
difficult.
If
statements
of
data
quality
are
not
being
maintained
by
the
laboratory,
there
may
be
increased
concern
about
both
specific
sample
results
and
the
laboratory's
overall
quality
assurance
program.

10.
Ongoing
Precision
and
Recovery
(
Methods
1624
and
1625)

Methods
1624
and
1625
require
that
an
"
ongoing
precision
and
recovery"
(
OPR)

standard
be
analyzed
with
each
sample
set,
and
that
the
results
of
this
standard
meet
the
acceptance
criteria
in
the
method
prior
to
the
analysis
of
blanks
and
samples.

The
data
reviewer
must
determine
if
the
ongoing
precision
and
recovery
standard
has
been
run
with
each
sample
set
and
if
all
criteria
have
been
met.
If
the
standard
was
not
run
with
a
given
set
of
samples,
or
if
the
criteria
are
not
met,
the
results
for
that
set
of
samples
are
considered
not
valid.

For
volatiles
analyses
by
Method
1624,
the
OPR
analysis
is
associated
with
the
samples
on
the
basis
of
the
analysis
date
and
time
and
the
specific
GC/
MS
system.
For
semivolatile
analyses
by
Method
1625,
OPR
results
are
associated
with
samples
extracted
at
the
same
time
as
the
OPR.

Because
of
the
large
number
of
compounds
being
tested
simultaneously
in
the
600­

and
1600­
series
methods,
there
is
a
small
probability
that
the
OPR
analysis
will
occasionally
fail
to
meet
the
specifications.
While
the
laboratory
is
supposed
to
correct
any
problems
and
analyze
another
OPR
aliquot,
it
may
still
be
possible
to
utilize
the
data
associated
with
an
OPR
aliquot
that
does
not
meet
all
of
the
method
specifications.

For
instance,
if
the
concentration
of
a
compound
in
the
OPR
is
above
the
method
specifications
but
that
compound
is
not
detected
in
an
associated
sample,
then
it
is
unlikely
that
the
sample
result
is
affected
by
the
failure
in
the
OPR.
If
the
concentration
in
the
OPR
is
below
the
method
specifications
but
that
compound
is
detected
in
an
associated
sample,
then
the
sample
result
is
likely
a
lower
limit
of
the
true
concentration
for
that
compound.

11.
Statements
of
Data
Quality
for
the
Laboratory
(
Methods
1624
and
1625)

In
addition
to
statements
of
data
quality
for
results
of
analyses
of
the
labeled
compounds
spiked
into
the
samples,
Methods
1624
and
1625
require
that
statements
of
data
quality
be
constructed
from
the
initial
and
ongoing
precision
and
recovery
data.
The
purpose
of
these
statements
is
to
assess
laboratory
performance
in
the
practice
of
the
method,
as
compared
to
the
assessment
of
method
performance
made
from
the
labeled
compound
results
for
the
Chapter
4:
Data
Review
Compliance
Monitoring
Guidance
30
samples.
Ideally,
the
two
statements
of
data
quality
would
be
the
same.
Any
difference
is
attributable
to
either
random
error
or
sample
matrix
effects.

If
the
laboratory
is
practicing
isotope
dilution
methods,
the
data
reviewer
should
review
the
statements
of
data
quality
for
the
laboratory.
If
the
laboratory
does
not
make
these
statements
available
for
the
reviewer,
they
may
be
requested.
If
the
laboratory
still
does
not
make
them
available,
it
does
not
necessarily
invalidate
any
data,
but
indicates
that
the
laboratory
may
not
be
following
the
method
as
written.
31
Chapter
5
Case
Histories
of
Claims
of
Matrix
Interferences
Submitted
Under
the
OCPSF
Rule
Chapter
1
described
the
data
that
would
be
required
to
demonstrate
that
a
matrix
problem
precluded
the
measurement
of
a
pollutant
regulated
under
a
NPDES
permit
limitation.
This
chapter
provides
case
histories
of
selected
claims
of
matrix
interference
problems
submitted
by
dischargers
regulated
under
the
OCPSF
rule.

Since
1991,
the
Engineering
and
Analysis
Division
(
EAD)
of
EPA
has
reviewed
data
provided
by
at
least
15
dischargers
regulated
under
the
categorical
pretreatment
standards
for
the
OCPSF
industry.
In
each
instance,
the
discharger
claimed
that
the
facility's
wastewater
could
not
be
monitored
for
compliance
with
the
pretreatment
standards
because
of
interferences.
EAD
was
asked
to
review
such
claims
of
matrix
interferences
by
either
the
Region
or
State
with
permitting
authority
for
the
facilities
in
question.
The
various
guidance
documents
collected
here
under
one
cover
are
an
offshoot
of
the
efforts
to
review
such
claims.

EAD's
review
focused
on
each
facility's
alleged
inability
to
determine
the
organic
analytes
in
its
wastewater
because
of
interferences.
This
chapter
presents
11
case
histories
of
EAD's
review
of
data
submitted
by
dischargers
claiming
interference
problems
and
provides
further
detail
as
to
how
these
dischargers
might
resolve
matrix
interference
problems.
None
of
the
dischargers
nor
any
of
the
laboratories
involved
are
identified
in
this
document.

Prior
to
reviewing
the
data,
each
of
the
permitting
authorities
was
provided
with
copies
of
the
following
draft
guidance
documents:

·
Draft
Checklist
of
Laboratory
Data
Required
to
Support
a
Claim
that
the
Permittee
was
Unable
to
Measure
Pollutants
Due
to
Matrix
Problems
(
the
"
Checklist,"
updated
as
Chapter
1
of
this
report)

·
Draft
Guidance
for
Analysts
Attempting
to
Identify
and
Quantify
Pollutants
in
Wastewaters
Discharged
from
Plants
Manufacturing
Organic
Chemicals,
Plastics,
and
Synthetic
Fibers
(
the
"
Guidance
for
Analysts,"
updated
as
Chapter
2
of
this
report)

·
Draft
Guidance
for
Permit
Writers
and
Others
Reviewing
Data
from
the
Analysis
of
Organic
Compounds
Determined
using
the
600­
and
1600­
series
Methods
(
the
"
Guidance
for
Permit
Writers,"
updated
as
Chapter
4
of
this
report)

It
was
EAD's
intention
that
these
draft
documents
be
provided
to
the
dischargers
and
in
turn
to
their
laboratories,
as
needed.
However,
the
review
revealed
that
the
documents
had
either
not
been
provided
by
the
States
and
Regions
or
were
not
followed.

In
general,
EAD's
review
of
the
claims
submitted
by
11
dischargers
revealed
the
following:

·
In
nearly
all
instances
where
data
were
submitted,
the
dischargers
and/
or
their
contract
laboratories
were
using
incorrect
analytical
methods
or
did
not
follow
the
procedures
required
in
40
CFR
Part
136.
Chapter
5:
Case
Histories
Compliance
Monitoring
Guidance
32
·
In
other
instances,
the
dischargers
and/
or
their
contract
laboratories
did
not
submit
data
necessary
to
document
that
the
methods
were
being
followed.

·
Finally,
the
dischargers
and/
or
their
contract
laboratories
did
not
submit
documentation
regarding
the
nature
of
interferences
and
the
attempts
(
if
any)
to
resolve
these
interferences

Case
Histories
Case
#
1:
This
discharger
used
a
contract
laboratory
for
its
analytical
work.
Information
submitted
by
the
laboratory
revealed
inconsistencies
with
the
stated
analytical
methods.

The
discharger
allowed
the
laboratory
to
either
(
1)
Use
alternative
methods
to
the
40
CFR
Part
136
methods,
or
(
2)
Modify
Methods
624
and
625.

Alternative
methods
are
allowed
under
40
CFR
Part
136.4
and
136.5
provided
that
the
facility
submits
the
alternative
methods
to
EPA's
Environmental
Monitoring
and
Support
Laboratory
in
Cincinnati,
Ohio,
(
EMSL­
Ci)
for
approval.
Otherwise,
alternative
methods
are
not
allowed.
EAD
found
no
reference
to
alternate
methods
approved
by
EMSL­
Ci.

If
Methods
624
and
625
were
modified
under
the
spirit
of
the
40
CFR
Part
136
rule,
these
modifications
were
not
documented
and
equivalence
was
not
demonstrated.
Modifications
that
the
laboratory
made
to
Methods
624
and
625
included:

·
Combining
acid
and
base/
neutral
fractions,
·
Using
a
fused­
silica
capillary
column
for
the
analysis
of
acid
and
base/
neutral
fractions
·
Using
alternative
internal
standards,
·
Using
alternative
surrogates,
·
Using
higher
detection
limits,
·
Using
fewer
matrix
spike
compounds,
and
·
Using
matrix
spike
amounts
inconsistent
with
regulatory
compliance,
background,
or
method­
specified
levels.

The
preamble
to
the
40
CFR
Part
136
methods
(
49
FR
43234,
October
26
1984)
states
that
a
method
is
considered
to
be
equivalent
if
its
performance
has
been
demonstrated
to
meet
or
exceed
the
specifications
in
the
original
method.
None
of
the
submitted
data
provided
any
evidence
supporting
method
equivalence.

EPA
recognizes
that
the
use
of
multiple
internal
standards
and
a
fused­
silica
capillary
column
for
the
base/
neutral/
acid
fraction
represent
improvements;
however,
EPA
does
not
accept
that
combining
fractions,
higher
detection
limits,
alternative
matrix
spike
compounds,
and
matrix
spike
amounts
inconsistent
with
background
or
regulatory
compliance
levels
represents
improvement.
On
the
contrary,
these
changes
degrade
method
performance
and
are
therefore
in
violation
of
both
the
spirit
and
letter
of
the
flexibility
permitted
in
the
600­
and
1600­
series
40
CFR
Part
136
organic
methods.
Compliance
Monitoring
Guidance
Chapter
5:
Case
Histories
33
Method
625
requires
the
analysis
of
separate
acid
and
base/
neutral
fractions
(
40
CFR
Part
136,

Appendix
A:
Method
625,
Sections
10
and
12
and
Tables
4
and
5).
Because
combining
these
fractions
can
compound
matrix
interference
problems,
the
acid
and
base/
neutral
fractions
should
not
have
been
combined
for
these
analyses.

The
matrix
spike
compounds
and
spiking
levels
used
by
the
laboratory
appeared
to
have
been
from
Office
of
Solid
Waste
(
OSW)
SW­
846
methods
or
from
Superfund
Contract
Laboratory
Program
(
CLP)
methods.
The
600­
and
1600­
series
wastewater
methods
require
the
matrix
spike
compounds
to
be
the
compounds
regulated
in
the
discharge
(
e.
g.,
40
CFR
Part
136,
Appendix
A:
Method
624,

Section
8.3)
and
require
that
the
spike
levels
be
at
(
1)
The
regulatory
compliance
level,
(
2)
1
 
5
times
the
background
level
of
the
analyte
in
the
sample,
or
(
3)
The
level
specified
in
the
method
(
e.
g.,
Method
624,
Section
8.3.1).

The
compounds
spiked
were
not
those
regulated
and
the
spikes
were
not
at
the
levels
required.

The
matrix
spike
was
performed
on
a
diluted
sample.
Had
the
matrix
spike
been
performed
as
specified
in
Method
624
or
625
(
e.
g.,
Method
624,
Section
8.4.3),
the
spike
would
likely
have
failed
the
specifications
in
the
method
and
the
associated
sample
result
could
not
have
been
reported
for
regulatory
compliance
purposes.
This
should
have
triggered
cleanup
procedures,
the
use
of
alternative
methods,
or
modification
of
Method
624
or
625
to
improve
method
performance,
as
detailed
in
the
draft
"
Guidance
for
Analysts."

The
QC
specifications
for
matrix
spike
recovery
used
by
the
laboratory
were
not
the
specifications
given
in
Methods
624
and
625.
The
specifications
in
the
wastewater
methods
(
40
CFR
Part
136,

Appendix
A:
Method
624,
Table
5;
and
Method
625,
Table
6)
must
be
used
for
compliance
monitoring
While
tighter
specifications
from
a
documented
source
may
be
acceptable
if
met,
use
of
wider
limits
without
documentation
would
never
be
acceptable.

The
detection
limits
reported
for
semivolatiles
were,
for
the
most
part,
twice
the
minimum
levels
given
in
Method
1625
and
were
approximately
10
 
20
times
the
method
detection
limits
(
MDLs)

given
in
Method
625.
No
explanation
for
the
increased
detection
limits
was
given,
nor
could
the
limits
be
derived
from
the
data
provided.

The
laboratory
made
no
attempt
to
clean
up
the
samples
using
pH
change,
gel
permeation
chromatography,
or
the
other
techniques
in
the
600­
and
1600­
series
methods
or
the
draft
"
Guidance
for
Analysts."

Case
#
2:
Information
provided
with
data
submitted
by
this
discharger
was
insufficient
for
a
detailed
review
(
as
outlined
in
the
"
Checklist
of
Laboratory
Data").

Despite
the
general
lack
of
data,
it
appeared
the
discharger
submitted
samples
to
a
contract
laboratory
for
analyses
by
a
GC/
MS
method
which
failed
to
produce
useful
results.
The
discharger
and/
or
the
laboratory
attributed
the
problems
to
large
concentrations
of
acetone
in
the
discharge,

though
this
problem
could
not
be
confirmed
from
the
information
provided.
The
analytical
contractor
proposed
to
the
discharger
that
Methods
601
and
602
be
used
for
the
volatiles
analysis
in
an
attempt
to
overcome
the
interference
problems.
Because
these
methods
are
both
more
sensitive
and
more
selective
than
a
GC/
MS
method,
the
analytes
regulated
should
be
measurable
in
the
presence
of
a
large
Chapter
5:
Case
Histories
Compliance
Monitoring
Guidance
34
concentration
of
acetone.
The
discharger
ignored
the
laboratory's
proposal
and
submitted
a
claim
of
matrix
interferences.
EPA
believes
that
the
approach
proposed
by
the
laboratory
is
workable
and
appropriate,
and
should
have
been
attempted.
If
Methods
601
and
602
were
used
(
as
with
any
other
methods
used),
the
analytical
laboratory
must
adhere
to
all
method
specifications.

Case
#
3:
This
discharger
used
several
contract
laboratories
for
analyses.
The
"
reports"
from
these
laboratories
consisted
of
summary
reporting
forms
showing
detection
limits
that
were
10
 
50
times
greater
than
the
MDLs
in
Methods
624
and
625.

There
were
no
QC
results,
no
details
of
how
the
analyses
were
performed,
and
no
documentation
of
interference
problems
or
steps
taken
to
overcome
interference
problems,
and
therefore
no
proof
that
an
interference
existed.
The
laboratory
may
have
chosen
to
dilute
samples
for
convenience.

The
discharger
and
its
laboratory
must
provide
the
data
listed
in
the
"
Checklist
of
Laboratory
Data"

and
attempt
to
solve
purported
interference
problems
using
the
techniques
discussed
in
the
"
Guidance
for
Analysts."

Case
#
4:
This
discharger
submitted
a
report
from
one
contract
laboratory
that
contained
insufficient
information
for
evaluation;
and
two
letters
from
a
second
contract
laboratory
describing
a
problem
with
4,6­
dinitro­
o­
cresol.

The
report
provided
by
the
first
laboratory
indicated
no
results
for
spikes
of
the
OCPSFregulated
analytes
into
samples,
no
details
of
how
the
analyses
were
performed,
what
interference
problems
were
encountered,
or
what
steps
were
taken
to
overcome
interference
problems.
In
addition,

it
appeared
that
the
contract
laboratory
combined
acid
and
base/
neutral
extracts,
thus
exacerbating
interference
effects.

The
letters
from
the
second
laboratory
describing
the
problem
with
4,6­
dinitro­
o­
cresol
asked
for
suggestions
on
how
to
determine
this
compound
in
the
presence
of
interferences.
The
"
Guidance
for
Analysts"
provides
general
suggestions
for
overcoming
matrix
interference
problems
and
specific
suggestions
for
determination
of
phenol.
The
specific
suggestions
for
determination
of
phenol
can
be
applied
to
4,6­
dinitro­
o­
cresol.

Other
reports
by
the
contract
laboratory
showed
high
detection
limits
for
the
substituted
phenols
because
of
a
huge
quantity
of
phenol
in
the
sample.
One
solution
to
this
analytical
problem
is
for
the
facility
to
reduce
the
level
of
phenol
in
the
wastewater.
The
analytical
laboratory
should
have
used
the
procedures
for
determination
of
phenol
detailed
in
the
"
Guidance
for
Analysts."

Case
#
5:
This
discharger
submitted
letters
and
reports
from
several
contract
laboratories.
One
report
contained
only
some
of
the
data
required
by
the
"
Checklist
of
Laboratory
Data."

Data
items
that
were
present
and
are
required
for
a
thorough
review
were
instrument
tunes,
run
chronologies,
chromatograms,
calibration
data,
calibration
verification
data,
results
for
blanks,

quantitation
reports
for
samples,
and
matrix
spike
data
run
against
the
QC
limits
for
Methods
624
and
625.
The
initial
precision
and
recovery
(
IPR)
data
that
demonstrate
method
equivalence
were
missing.
Compliance
Monitoring
Guidance
Chapter
5:
Case
Histories
35
The
semivolatile
matrix
spike
data
were
inconsistent.
The
results
of
the
unspiked
samples
indicated
that
some
of
the
acids
and
base/
neutrals
were
not
detected,
yet
the
results
for
the
spiked
samples
showed
large
concentrations
of
some
of
these
analytes
that
were
not
spiked
into
the
samples.

The
volatiles
matrix
spike
had
been
diluted
by
a
factor
of
200
and
spiked
after
dilution.

Diluting
and
spiking
will
not
show
matrix
interferences,
and
thus
these
data
are
of
no
value
in
evaluating
the
undiluted
sample
results.

Cases
#
6­#
11:
These
facilities
submitted
summary
reports
from
their
laboratories.

None
of
the
materials
contained
the
information
required
by
the
"
Checklist
of
Laboratory
Data,"
and
none
contained
explanations
of
the
nature
of
the
interferences
found
or
descriptions
of
attempts
to
overcome
these
interferences.
These
facilities
should
follow
the
guidance
provided
by
EPA
and
should
report
all
data
required
by
the
"
Checklist
of
Laboratory
Data"
and
the
"
Guidance
for
Permit
Writers."
36
Chapter
6
Guidance
on
Contracting
For
Analytical
Services
Most
businesses
and
government
organizations
have
procedures
and
policies
governing
the
purchase
of
services
and
supplies.
They
range
from
simply
assigning
responsibility
to
one
individual
("
Joe
handles
all
that...")
to
the
myriad
of
complex
procedures
set
forth
in
the
Federal
Acquisition
Regulations
(
FAR).
Once
established,
these
various
procedures
and
policies
may
be
applied
relatively
easily
to
purchases
of
office
supplies,
computers,
and
janitorial
services.
However,
most
organizations
experience
problems
when
they
attempt
to
apply
these
procedures
to
the
purchase
of
analytical
services.

At
the
heart
of
these
problems
is
the
difficulty
in
defining
the
services
that
are
required.
The
purpose
of
this
chapter
is
to
provide
a
basic
framework
with
which
to
define
the
technical
and
contractual
requirements
associated
with
purchasing
analytical
services
related
to
compliance
monitoring
under
the
National
Pollutant
Discharge
Elimination
System
(
NPDES).
The
procedures
outlined
here
are
presented
as
guidance
and
may
need
to
be
modified
to
meet
the
specific
policies
of
an
organization
The
level
of
detail
presented
is
not
sufficient
to
meet
all
of
the
requirements
of
the
FAR,
but
is
a
subset
of
the
procedures
used
by
several
EPA
offices
and
their
contractors.
The
procedures
may
represent
some
degree
of
"
overkill"
for
private
organizations;
however,
it
is
simpler
to
delete
the
unneeded
detail
in
those
instances
than
to
add
it
when
it
is
required.
The
procedures
are
designed
for
procuring
analytical
services
from
commercial
laboratories,
but
may
also
be
applied
to
requests
for
services
from
in­
house
laboratories.

Requirements
Analysis
Defining
what
services
are
required
is
often
the
most
difficult
step.
The
commercial
environmental
laboratory
business
has
grown
to
be
a
multi­
million­
dollar­
per­
year
enterprise
serving
the
diverse
needs
of
clients
regulated
under
a
variety
of
federal
and
state
environmental
statutes.
Many
laboratories
have
recognized
the
importance
of
customer
service
and
employ
staff
who
are
trained
to
assist
clients
in
defining
the
requirements.
Other
laboratories,
large
and
small,
rely
solely
on
the
client
to
define
the
specific
requirements.
Still
another
group
of
laboratories,
albeit
a
small
group,
perform
analyses
with
little
regard
to
the
client's
actual
needs.
One
of
the
problems
that
arises
when
the
client's
requirements
are
poorly
defined
is
the
use
of
inappropriate
methods.
As
noted
in
Chapter
1,

NPDES
compliance
monitoring
requires
that
the
304(
h)
methods
be
used.
It
is
not
the
laboratory's
place
to
decide
that
a
method
from
another
source,
even
another
EPA
source,
is
"
close
enough."

The
"
five
W's"
of
journalism
("
who,
what,
when,
where,
and
why,"
with
"
how"
thrown
in
for
good
measure)
are
a
first
step
in
defining
the
requirements.
"
Who"
is
the
name
of
the
client,

including
a
set
of
specific
contact
points.
The
laboratory
needs
to
know
the
name
of
the
person
who
will
be
taking
and
shipping
the
sample,
in
the
event
that
there
are
shipping
delays,
broken
samples,
etc.
The
laboratory
needs
the
name
of
a
technical
contact,
if
any,
in
the
event
that
there
are
analytical
questions
Compliance
Monitoring
Guidance
Chapter
6:
Contracting
37
that
need
to
be
resolved.
The
laboratory
also
needs
to
know
the
name
of
the
administrative
contact
who
will
handle
issues
of
billing,
payment,
etc.

"
What"
is
a
description
of
the
samples
to
be
analyzed,
including:

·
Number
of
samples,
·
Matrices
(
e.
g.,
wastewater,
sludge,
solids,
soils,
etc.),
and
·
Analyses
required
(
volatile
organics,
pesticides,
etc.).

"
What"
may
also
include
information
on
the
required
methodology,
the
reporting
format,
and
the
quality
assurance/
quality
control
(
QA/
QC)
requirements.
It
may
also
include
a
specific
description
of
the
"
product"
to
be
delivered
to
the
client.
EPA
recommends
(
Chapter
4)
that
the
client
receive
a
copy
of
all
data,
raw
and
summary,
associated
with
the
analyses.

"
When"
specifies
the
approximate
date
that
the
samples
will
be
shipped
to
the
laboratory,

including
the
means
of
shipment
(
hand­
delivered,
picked
up
by
the
laboratory,
overnight
air
freight,

etc.),
and
the
date
when
the
results
are
required
by
the
client.
It
should
also
specify
the
date
by
which
the
results
are
required.
The
"
turnaround
time"
is
the
length
of
time,
usually
in
calendar
days,
from
the
receipt
of
the
sample
at
the
laboratory
until
the
results
are
to
be
received
by
the
purchaser.
The
turnaround
time
is
often
a
function
of
a
reporting
deadline
under
a
permit.
One
can
often
save
cost
by
giving
the
laboratory
as
much
time
as
possible
to
provide
the
data.
Sampling
early
in
the
month
may
mean
that
one
has
more
time
before
the
data
must
be
reported
to
the
permitting
agency.

Obviously,
"
where"
includes
the
name
of
the
laboratory,
but
it
is
important
to
include
the
street
address
of
the
laboratory
to
which
the
samples
will
be
shipped
and
the
name
of
the
person
assigned
to
receive
the
samples.
It
is
also
important
to
include
the
name
and
address
of
the
laboratory's
administrative
personnel
handling
billing
and
payment
issues,
as
these
may
be
different
from
the
address
where
samples
are
shipped.

"
Why"
is
often
overlooked
by
people
who
assume
that
everyone
understands
the
purpose
of
the
analysis.
Simply
stating
that
"
the
analysis
of
X
wastewater
samples
for
NPDES
compliance
monitoring
is
required"
can
give
a
laboratory
a
wealth
of
information.
Among
other
things,
it
should
inform
the
laboratory
that
a
304(
h)
method
is
to
be
used;
however,
just
to
be
certain,
the
method
required
is
also
specified
elsewhere
(
see
"
how"
below).
In
contrast,
a
statement
about
"
groundwater
monitoring"
ought
to
lead
the
laboratory
to
inquire
as
to
the
purpose
of
the
analysis,
and
hence
what
methods
might
be
required,
as
304(
h)
methods
may
not
be
appropriate.
The
type
of
analyses
required
can
also
be
included,
further
clarifying
the
requirements.

The
last
requirement
to
be
explicitly
stated
is
"
how."
Although
information
about
the
analysis
is
included
in
"
what"
and
"
why,"
it
helps
to
be
specific,
stating
the
method
that
is
required
or
requested
It
is
also
important
to
specify
the
quality
assurance
and
quality
control
operations
that
will
be
performed
in
association
with
the
sample
analyses.
While
the
EPA
600­
and
1600­
series
methods
specify
the
level
of
QA/
QC
to
be
performed,
there
are
some
methods
from
other
sources
(
SW­
846,

ASTM,
AOAC,
etc.)
that
have
been
approved
under
Section
304(
h)
for
some
analytes,
and
these
methods
may
not
be
as
explicit
regarding
the
QA/
QC
requirements.
The
laboratory
also
needs
to
know
how
the
data
are
to
be
reported
and
how
many
copies
of
the
report
are
required.
Chapter
6:
Contracting
Compliance
Monitoring
Guidance
38
Identifying
Laboratories
and
Soliciting
Bids
Identifying
qualified
laboratories
can
be
a
time­
consuming
process.
While
many
laboratories
advertise
in
the
Yellow
Pages
and
in
various
directories
of
professional
services,
those
advertisements
may
not
tell
you
much
about
the
laboratory's
abilities
to
fulfill
your
specific
analytical
requirements.

However,
any
list
of
laboratories
is
better
than
none.
In
addition,
state
and
EPA
Regional
personnel
may
be
able
to
give
you
a
list
of
laboratories
in
your
area
or
nationwide,
depending
on
the
type
of
analyses
required.
Such
lists
are
not
an
endorsement
of
these
laboratories,
but
are
provided
as
a
starting
point.

If
your
procedures
require
that
you
obtain
competitive
bids
for
laboratory
services,
you
will
usually
have
to
identify
a
minimum
of
three
laboratories
from
which
to
solicit
bids.
If
you
are
not
required
to
obtain
competitive
bids,
it
may
still
be
useful
to
occasionally
compare
prices
from
competing
laboratories.

Determining
that
a
laboratory
is
qualified
to
perform
the
analyses
is
also
a
somewhat
daunting
task.
You
can
always
take
the
laboratory
director's
word
for
their
capabilities.
However,
you
then
have
to
evaluate
the
consequences
of
making
a
error
in
judgment.
While
EPA
is
currently
exploring
the
idea
of
a
national
laboratory
accreditation
program,
it
is
unlikely
that
such
a
program
will
be
in
place
for
several
years.
In
the
meantime,
you
can
begin
to
identify
qualified
laboratories
by
sending
them
a
list
of
your
requirements,
identified
above.
Ask
them
to
provide
information
regarding
their
qualifications
to
perform
such
work
(
SOQ).
Obviously,
this
needs
to
be
done
well
in
advance
of
your
need
for
actual
analytical
services.
The
laboratory
should
be
willing
to
discuss
your
specific
needs
with
you,
and
demonstrate
how
they
will
meet
those
needs.
While
not
normally
required
for
NPDES
compliance
monitoring,
it
is
not
unheard
of
to
perform
an
on­
site
inspection
of
a
laboratory
prior
to
using
their
services.
It
may
also
be
worthwhile
in
some
instances
to
send
performance
evaluation
samples
(
samples
of
known
composition)
to
a
laboratory
prior
to
utilizing
them
for
routine
analytical
work.
Performance
evaluation
samples
for
various
organic
and
inorganic
analytes
are
commercially
available
from
several
vendors.
These
vendors
may
also
prepare
custom
samples
that
focus
on
the
regulated
pollutants
at
a
specific
facility.

Once
you
have
identified
a
group
of
laboratories,
you
may
solicit
bids
by
simply
sending
them
a
request
for
a
bid,
including
the
detailed
requirements
identified
above.
One
possible
format
for
such
solicitations
is
included
with
this
report
as
an
attachment.
This
is
a
generic
version
of
a
format
that
several
EPA
contractors
have
used
for
some
time.

The
NPDES
compliance
monitoring
requirements
for
a
given
facility
may
only
require
the
analysis
of
a
small
number
of
samples
monthly
or
quarterly.
While
those
analyses
are
very
important
to
you
(
the
discharger),
they
may
not
represent
a
significant
source
of
revenue
for
a
given
laboratory.

At
some
level,
you
are
paying
for
all
the
quality
control
analyses
associated
with
your
small
number
of
samples.
As
a
result,
you
may
pay
higher
prices
per
sample.
One
way
to
address
the
cost
issue
is
to
pursue
a
longer­
term
contracting
arrangement.
Determine
how
many
analyses
of
what
types
you
will
need
for
the
next
year,
and
ask
laboratories
to
bid
on
the
entire
package.
To
do
this,
you
must
be
able
to
approximate
the
schedule
on
which
these
analyses
are
needed,
but
that
is
often
driven
by
permit
requirements.
The
advantages
to
you
are
(
1)
a
lower
price
and
(
2)
less
time
spent
arranging
for
Compliance
Monitoring
Guidance
Chapter
6:
Contracting
39
bids.
The
advantages
to
the
laboratory
are
(
1)
knowing
that
the
work
is
coming
and
(
2)
spending
less
time
getting
business.

Writing
a
Contract
Before
writing
a
contract
for
any
kind
of
services,
consult
with
the
appropriate
legal
staff
at
your
facility
or
firm.
They
will
obviously
know
the
ins
and
outs
of
contract
law
in
your
state.
A
well­
written
contract
will
include
the
"
five
W's"
outlined
above.
It
will
also
address
your
right
to
review
the
data
as
needed,
the
timeliness
of
payment
to
the
laboratory,
and
your
ultimate
right
to
determine
that
the
work
does
not
meet
the
requirements
established
in
the
contract.

The
required
data
turnaround
and
analytical
holding
time
must
be
stated
clearly
in
the
contract.
If
analytical
holding
times
are
applicable,
they
are
generally
stated
in
the
analytical
method.

However,
delays
in
sampling
and
sample
shipment
may
necessitate
specification
of
a
"
contract"

holding
time
that
is
based
on
the
analytical
holding
time
minus
any
time
required
for
sample
shipment.

Unless
you
can
guarantee
that
the
sample
will
be
delivered
as
soon
as
the
laboratory
opens
in
the
morning,
it
is
typical
to
specify
that
the
day
that
the
sample
is
received
at
the
laboratory
is
"
day
zero,"

and
the
counting
of
"
days"
begins
with
the
following
day
as
"
day
1."

In
addition
to
stating
the
time
that
the
laboratory
has
to
generate
and
deliver
the
data,
it
may
be
useful
to
assign
some
specific
consequences
to
the
possibility
of
late
delivery.
One
approach
is
to
assess
a
penalty
of
some
percentage
of
the
analytical
price
per
day
of
lateness.
In
the
past,
EPA
has
used
values
of
1
 
2%
per
day
after
the
due
date
that
the
data
were
delivered.

Obviously,
such
penalties
for
lateness
cannot
be
due
to
changes
in
the
requirements
made
after
the
samples
were
sent,
or
the
fact
that
the
methods
requested
were
not
applicable
to
the
samples.

Many
of
the
remedies
to
matrix
problems
discussed
in
Chapter
2
cannot
be
expected
to
be
carried
out
in
the
original
turnaround
time
assigned
to
the
sample.
However,
once
you
have
established
that
your
samples
can
routinely
be
analyzed
by
the
requested
methods,
lateness
becomes
an
issue
of
laboratory
management
practices,
not
sample
matrix.

From
time
to
time,
almost
every
laboratory
will
produce
data
that
are
of
little
use
for
the
intended
purpose
(
compliance
monitoring
in
this
instance).
While
well­
run
laboratories
will
contact
you
as
soon
as
they
identify
the
problem
and
work
with
you
to
make
the
best
of
a
bad
situation,
you
may
still
find
yourself
with
no
useful
data
and
a
deadline
approaching.

A
contract
should
stipulate
that
the
laboratory
will
reanalyze
samples
at
no
cost
to
the
client
if
the
problems
are
due
to
laboratory
error.
It
should
also
state
that
the
client
has
the
right
to
inspect
the
results,
and
if
they
do
not
meet
the
requirements
in
the
contract,
the
client
has
the
right
to
reject
the
data,
returning
them
to
the
laboratory
without
payment.
Rejection
of
data
should
be
based
on
sound
technical
review
of
the
results.
It
also
obligates
the
client
to
make
no
use
of
those
results
without
making
some
payment
to
the
laboratory.

The
contract
should
discuss
in
what
instances
dilutions
of
samples
and
reanalyses
are
considered
billable
by
the
purchaser.
Again,
a
laboratory
should
be
prepared
to
do
the
job
right
the
first
time
and
not
bill
for
reanalyses
required
due
to
their
errors.
In
contrast,
some
samples
may
need
to
be
diluted
and
reanalyzed
in
order
to
bring
the
results
within
the
demonstrated
calibration
range
of
the
instrumentation.
When
this
occurs,
the
laboratory
ought
to
be
paid
for
this
effort.
Such
reanalyses
Chapter
6:
Contracting
Compliance
Monitoring
Guidance
40
can
be
figured
into
the
original
price,
inflating
the
per­
sample
price
for
all
samples
to
account
for
the
need
to
reanalyze
some
samples,
or
it
can
be
broken
out
as
a
separate
cost.
Similarly,
for
analyses
involving
an
extraction
or
digestion
as
well
as
an
analysis,
it
may
be
useful
to
specify
the
price
for
the
extraction
step
and
the
analysis
separately,
as
a
reanalysis
may
not
require
an
additional
extraction.

The
contract
is
not
a
one­
sided
agreement,
and
as
such,
it
must
give
specific
rights
and
recourse
to
the
laboratory
as
well.
You
may
be
asked
to
negotiate
specific
contract
issues
with
the
laboratory
beforehand.
The
time
involved
in
this
process
will
obviously
vary,
and
one
of
the
benefits
of
contracting
over
longer
time
periods
than
the
immediate
need
for
one
analysis
is
that
these
negotiations
need
only
take
place
once
for
a
large
number
of
samples.

Combined
with
a
careful
analysis
of
the
requirements,
a
well­
written
contract
can
minimize
or
eliminate
many
common
problems
in
procuring
analytical
services.
It
should
enable
the
client
to
obtain
technically
sound,
legally
defensible,
and
timely
analytical
data
to
meet
a
variety
of
compliance
monitoring
needs.
41
Attachment:
Example
Analytical
Services
Request
The
following
is
an
example
of
a
generic
analytical
services
request
form.
Variations
on
this
form
have
been
used
by
several
EPA
offices
and
their
contractors
for
many
years.
This
form
is
intended
to
assist
the
client
in
identifying
and
specifying
their
analytical
requirements,
and
to
transmit
this
information
to
a
potential
supplier
of
analytical
services
in
a
consistent
format.
42
Analytical
Services
Request
Client
Name:

Point
of
Contact
(
name
and
telephone
number):

Date
of
Request:

1.
General
description
of
analytical
services
requested:

2.
Definition
and
number
of
samples
involved
(
specify
wastewater,
groundwater,
sludge,
soil,
etc.)

3.
Purpose
of
analysis
(
NPDES,
SDWA,
RCRA
compliance
monitoring,
etc.)

4.
Estimated
date(
s)
of
sample
collection:

5.
Estimated
date(
s)
and
method
of
shipment:

6.
Sampling/
shipping
contact
(
name
and
telephone
number):

7.
Holding
times
associated
with
analysis
(
specify
number
of
days,
or
state
"
per
method"):

8.
Number
of
days
after
sample
receipt
that
data
are
required:

9.
Analytical
method
required
(
specify
method
number,
source,
and
date,
and
attach
copy
where
practical):

10.
Special
technical
instructions
(
provide
information
on
known
problems,
possible
solutions,
matrix
effects,
etc.):

11.
Data
reporting
requirements
(
specify
format
of
data,
QA/
QC
reports,
number
of
copies,
etc.)

12.
Sensitivity
required
(
specify
"
per
requested
method,"
or
list
analyte
names,
CAS
numbers,
and
quantitation
limits
required):

13.
Quality
control
requirements
(
summarize
QC
operations
specified
in
the
referenced
method,
and
any
additional
requirements):

14.
Action
required
if
QC
limits
exceeded
(
specify
reanalysis,
contacting
client
immediately,
etc.):

15.
Other
(
use
additional
sheets
or
attach
supplementary
information,
as
needed):