&EPA
United States
Environmental Protection
Agency
Office of
Research and Development
Washington, DC 20460
EPA/600/9-91/034
September 1991
ariability
n
rotocols
-------
-------
FOREWORD
Today's rapidly developing and changing technologies and industrial products and
practices frequently carry with them the increased generation of materials that, if
improperly dealt with, can threaten both public health and the environment. The
U.S. Environmental Protection Agency is charged by Congress with protecting the
Nation's land, air, and water systems. Under a mandate of national environmental
laws, the Agency strives to formulate and to implement actions leading to a
compatible balance between human activities and the ability of natural systems to
support and to nurture life. These laws direct the EPA to perform research to define
our environmental problems, measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for the planning,
implementation, and management of research, development, and demonstration
programs to provide an authoritative, defensible engineering basis in support of the
policies, programs, and regulations of the EPA with respect to drinking water,
wastewater, pesticides, toxic substances, solid and hazardous wastes, and
Superfund-related activities. This publication is one of the products of a quality
assurance outreach program and provides a useful comparative index of several of
the more frequently employed chemical analytical methodologies.
Within almost any project, the two resources which always seem to be in the
shortest supply are time and money; to have more of either one is a welcome
occurrence. It is toward this end that the document Variability in Protocols has
been developed. By initially determining the objectives and requirements of a
project, then having the procedures in place to accomplish them, as well as the
quality control measures to ensure the reliability of the results, both time and money
may be conserved. The compilation and summarization of the analytical methods
contained in this document allow the user to compare the capabilities and
requirements of each, thereby simplifying the decision-making process regarding
which method to use in order to meet different requirements. In these ways,
Variability in Protocols can facilitate the accomplishment of a project's goals by
enabling more effective use of the allotted resources.
E. Timothy Oppelt, Director
Risk Reduction Engineering
Laboratory
in
-------
ABSTRACT
The EPA Risk Reduction Engineering Laboratory's Quality Assurance Office, which
published the popular pocket guide Preparing Perfect Project Plans,\s now
introducing another quality assurance reference aid. The document Variability in
Protocols (VIP) was initially designed as a quick reference for personnel
performing QA audits, but it also has found its place in serving as a reference
source for laboratory managers as well as personnel reviewing or developing QA
Project Plans.
Variability in Protocols contains tabular summaries of the quality control
differences and similarities for some of the most frequently used analytical methods
for water soils, and other environmental samples. The document has been prepared
in an attempt to bring together the separate methods that became a product of the
major environmental statutes.
Noticeable differences between methods are evidenced in.method detection limits,
calibration methods, blanks, spikes, and several other parameters included in this
summary The tabular format provides quick and easy access to important, needed
information - information that will increase one's knowledge about sets of methods
such as SW-846, EPA 500 and 600 Series, Standard Methods, and others.
VIP can provide "guidance when preparing Quality Assurance Project Plans.
Managers field sampling team, members, auditors, and laboratory personnel alike will
find this document helpful in determining the most suitable method of chemical
analysis for their various purposes. As a quick reference tool, this document gives
accurate information without the past necessity of searching through pages of
methods, saving both time and money.
Inconsistency in quality control protocols doesn't have to be an obstacle, and with
this creation, comparisons of methods can be effortless.
IV
-------
TABLE OF CONTENTS
Title
Page
Disclaimer ii
Foreword iii
Abstract iv
Table of Contents : v
Acknowledgement vi
References vii
Abbreviations viii
Organic Constituents;
Herbicides by GC - Chlorinated 1
Pesticides by GC - Organochlorine 3
PCBs by GC - 3
Semivolatile Organic Compounds by GC/MS 6
Volatile Organic Compounds by GC/MS 9
Volatile Organic Compounds by GC - Aromatic 12
Volatile Organic Compounds by GC - Halogenated 14
Inorganic Constituents:
Cyanide - Total & Amenable 16
Organic Carbon - Total 18
Trace Metals by FLAA and GFAA 19
Mercury by CVAA 21
Trace Metals by ICP 23
-------
ACKNOWLEDGEMENT
The extensive technical contributions of Tracey Vandermark of Maxwell
Laboratories and Lauren Drees of IT Corporation are gratefully acknowledged.
Contributors to and reviewers of this report were Thomas Clark of IT Corporation;
and Robert Danner and Ann Kern of the USEPA.
VI
-------
REFERENCES
CLP flnorganic SOW)
U.S. EPA Contract Laboratory Program (CLP), Statement of Work (SOW) for
Inorganics Analysis, Document Number ILMO1.0, March 1990.
CLP (Organic SQW1
U.S. EPA Contract Laboratory Program (CLP), Statement of Work (SOW) for
Organics Analysis, Document Number OLMO1.0, Revision April, 1991.
EPA Series
Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020,.1983.
EPA 500 Series
Methods for the Determination of Organic Compounds in Drinking Water,
EPA/600/4-88/039, December 1988.
EPA 600 Series
40 CFR, Part 136, Friday, October 26, 1984.
Standard Methods
Standard Methods for the Examination of Water and Wastewater, 17th Edition,
1989.
SW-846
U.S. EPA Test Methods for Evaluating Solid Waste, SW-846, Update I to Third
Edition.
VII
-------
ABBREVIATIONS
CCC Calibration Check Compound
CRDL Contract Required Detection Limit
CRQL Contract Required Quantitation Limit
CVAA Cold Vapor Atomic Absorption
EDL Estimated Detection Limit
EICP Extracted Ion Current Profile
EQL Estimated Quantitation Limit
FLAA Flame Atomic Absorption
GFAA Graphite Furnace Atomic Absorption
ICP Inductively Coupled Plasma
ICS Interference Check Standard
IDL Instrument Detection Limit
LSE Liquid-Solid Extraction
ID Identification
IS Internal Standard
MDL Method Detection Limit
MS Matrix Spike
MSA Method of Standard Additions
MSD Matrix Spike Duplicate
QC Quality Control
R Recovery
RF Response Factor
RPD Relative Percent Difference
RRT Relative Retention Time
RSD Relative Standard Deviation
RT Retention Time
SD Standard Deviation
SOW Statement of Work
SPCC System Performance Check Compound
SV Semivolatile
SVGA Semivolatile Organic Analysis
TCL Target Compound List
VGA Volatile Organic Analysis
VIII
-------
DETERMINATION OF CHLORINATED HERBICIDES BY GC
Method -
Parameter I
Applicability
Number of
Analytes (1)
Method
Validation (2)
QC Check
Standards
Method Detection
Limit
Standard Solution
Expiration (3)
Initial
Calibration
Continuing
Calibration
Surrogate
Standards
Internal Standards
Accuracy/
Precision
Blanks
Preservation/
Storage
Conditions
Holding Time (4)
Sample Volume
(5)
SW-846
Method 81 50 A
Groundwater, soils, sediments and
waste samples
10 total
Extract and analyze 4 replicates of QC
check standard. Compare accuracy
and precision results to Table 3 of
method.
If MS/MSD results fall outside the
ranges designated in Table 3 of
method, a QC check standard must
be analyzed and fall within those
ranges.
MDLs listed in Table 1 of method.
EQLs listed in Table 2 of method.
Stock standards: 1 year
Calibration standards: 6 months
Minimum of 5 levels, lowest near but
above MDL If % RSD<20, linearity
assumed and average RF used.
Mid-level calibration standard run
every 10 samples. If not within ±15%
of predicted response, recalibrate.
OneAwo surrogates added to each
sample (avoid use of deuterated
analogs). Results must fall within
laboratory established limits.
Optional; no standards specified.
One MS/MSD per 20 samples or each
batch of samples, whichever is more
frequent. Compare results -to Table 3
of method.
One method blank per 20 samples or
each batch of samples, whichever is
more frequent.
Sodium thiosulfate if residual chlorine
present. Store at 4"C.
Extraction: 7 days (aqueous)
14 days (solid)
Analysis: 40 days after extraction
1 liter (aqueous)
50 grams (solid)
EPA 500 Scries
Method 515.1
Groundwater, surface, and drinking
water
17 total
Extract and analyze a minimum of 4
replicates of QC check standard.
Results must be within ±30% of
values in Table 2 of method.
Analyze a QC check standard with
every 20 samples or one per sample
set (all samples extracted within a 24-
hour period). Compare %R to
laboratory established limits, if
available, or Table 2 of method.
EDLs listed In Table 2 of method.
Stock standards: 2 months
Calibration standards: not specified
Minimum of 3 levels (5
recommended), lowest near but
above ED L If %RSD<20, linearity
assumed and average RF used.
A calibration check standard must be
analyzed at the beginning and end of
analysis day (each at a different
level). If not within ±20% of predicted
response, recalibrate.
2,4-Dichlorophenylacetic acid (DCAA)
at 0.5 ug/ml extract.
%R = 70-130.
Optional. If used, 4,4'-
Dibromooctafluorobiphenyl (DBOB) at
0.25 iig/mL extract.
One MS per 10 samples or each
batch of samples. %R=70-130 or
laboratory established limits.
One method blank with each batch of
samples extracted or when new
reagents used.
Mercuric chloride as bacteriocide.
Sodium thiosulfate if residual chlorine
present. Protect from light. Store at
4'C.
Extraction: 14 days
Analysis: 28 days after extraction
1 liter
Standeird Methods
Method 6640
Surface waters, groundwater
Not specified (includes Silvex, 2,4-D,
2,4,5-T and "similar" chlorinated phenoxy
acid chemicals).
Not specified.
Periodically determine recovery efficiency
using QC check standard. Periodically Is
not defined in the method.
Varies with detector sensitivity, sample
size, extract concentration.
Not specified.
Prepare standard concentrations
according to detector sensitivity and
linearity. Number of standards used for
calibration not specified.
Inject same volume of herbicide methyl
esters frequently to insure optimum
operating conditions. Frequently is not
defined in the method.
Not specified.
Not specified.
Analyze one set of duplicates with each
batch of samples processed at the same
time.
Periodically analyze a control blank to
test the procedure:. Periodically is not
defined in the method.
Store at 4"C.
Extraction: 7 days
Analysis: 40 days after extraction
850 to 1000 mL
-------
DETERMINATION OF CHLORINATED HERBICIDES BY GC
Method -
Parameter l
Other Criteria
(Method Spcdflc)
SW-846
Method 8150A
When doubt exists in compound
Identification, second column
confirmation should be used.
QC for extraction and cleanup
according to specific methods
used.
EPA 500 Scries
Method 515.1
Laboratory Performance Check
Sample analyzed daily to monitor
instrument sensitivity, column
performance, and chromatographic
performance.
When doubt exists in compound
identification, second column
confirmation should be used.
Standard Methods
Method 6640
Use at least two columns for
identification and quantification.
'
Notes:
(1)
(2)
(3)
(4)
(5)
Analytc lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time, demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be
necessary.
Unless otherwise indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
-------
EPA/600/9-91/034
September 1991
V
I
p
ariability
n
rotocols
By
Guy F. Simes
Risk Reduction Engineering Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Printed on Recycled Paper
-------
DISCLAIMER
This material has been funded by the United States Environmental Protection
Agency. Although it has been subject to Agency review, and has been approved
for publication as an EPA document, it does not necessarily reflect EPA policy.
-------
DETERMINATION OF ORGANOCHLORINE PESTICIDES
AND PCBs BY GC
Method -
Parameter 1
Applicability
Number of
Analytes (1)
Method
Validation (2)
QC Check
Standards
Method
Detection
Limit
Standard
Solution
Expiration (3)
Initial
Calibration
Continuing
Calibration
Surrogate
Standards
SW-846
Method 8080A
Groundwater, soils,
sludges, and non-water
miscible wastes
26 total
Extract and analyze 4
replicates of QC check
standard. Compare
accuracy and precision
results to Table 3 of
method.
If MS/MSD results fall
outside ranges
designated in Table 3 of
method, a QC check
standard must be
analyzed and fali within
those ranges.
MDLs listed in Table 1
of method. EQLs listed
in Table 2 of method.
Stock standards: 1
year
Calibration standards:
6 months
Minimum of 5 levels,
lowest near but above
MDI_lf%RSD<20,
linearity assumed and
average RF used.
Mid-leve! calibration
standard run every 10
samples. If not within
±15% of predicted
response, recalibrate.
Two surrogates,
decachlorobiphenyl and
2,4,5,6-Tetrachloro-m-
xylene. Results must
fall within laboratory
established control
limits.
EPA 500 Series
Method 508
Groundwater and
finished drinking water
38 total (2 qualitative
only)
Extract and analyze a
minimum of 4 replicates
of QC check standard.
Results must be within
±30% of values
specified in Table 2 of
method.
Analyze a QC check
standard with every 20
samples or one per
sample set (all samples
extracted within a 24-
hour period). Compare
%R to established
limits, if available, or
Table 2 of method.
EDLs listed in Table 2 of
method.
Stock standards: 2
months
Calibration standards:
not specified
Minimum of 3 levels (5
recommended), lowest
near but above EDL If
%RSD<20. linearity
assumed and average
RF used.
A calibration check
standard must be
analyzed at the
beginning and end of
analysis day (each at a
different level). If not
within ±20% of
predicted response,
recalibrate.
4,4'-Dichlorobiphenyl
(DCB) or others if
acceptance criteria met.
%R=70-130.
EPA 600 Series
Method 608
Municipal and
industrial discharges
25 total
Extract and analyze
4 replicates of QC
check standards.
Compare accuracy
and precision results
to Table 3 of
method.
If MS results fall
outside ranges
designated in Table
3 of method, a QC
' check standard must
be analyzed and fall
within those ranges.
MDLs listed in Table
1 of method.
Stock standards: 6
months
Calibration
standards: not
specified.
Minimum of 3 levels,
lowest near but
above MDL If
%RSD<10, linearity
assumed and
average RF used.
One or more
calibration standards
analyzed daily. If not
within ±15% of
predicted response,
recalibrate.
Not specified.
Standard Methods
Method 6630
Drinking water,
surface and
groundwater
19 listed (others
possible). No PCBs.
•Not specified.
Periodically determine
extraction efficiency
'to test procedure.
Periodically, is not
defined in the method.
Varies with detector
sensitivity, extraction/
clean-up efficiency,
concentrations.
Not specified.
Prepare standard
concentrations
according to detector
sensitivity and
linearity. Number of
standards used for
calibration not
specified.
Inject standards
frequently to insure
optimum operating
conditions.
Frequently is not
defined in the method.
Not specified.
CLP
PEST
(Organic SOW)
Water, soil and
sediment
28 total
Not specified.
Not specified.
CRQLs for TCL
listed in Exhibit C of
SOW.
Stock standards: 6
months
Calibration
standards: not
specified
Three levels (except
multi-components
at one level) the
lowest at the CRQL
The %RSD must be
<20.
Blank and midpoint
calibration standard
are run once per 12
hour period.
Standard must be
within ±25% of
predicted response.
Two surrogates,
Decachlorobiphenyl
and 2,4,5,6-
Tetrachloro-m-
xylene. Advisory
limits=60-150%.
-------
DETERMINATION OF ORGANOCHLORINE PESTICIDES AND PCBs BY GC
Method -
Parameter 1
Internal
Standards
Accuracy/
Precision
Banks
Preservation/
Storage
Conditions
Holding Time
(4)
Sample
Volume
Required (5)
SW-&16
Method 8080A
Optional; no standards
specified.
One MS/MSD per 20
samples or each batch of
samples, whichever Is
more frequent. Compare
results to Table 3 of
method. —
One method blank per 20
samples or each batch of
samples
If residual chlorine present,
add sodium thiosulfate.
Store at 4'C.
Extraction: 7 days
(aqueous)
14 days (solids)
Analysis: 40 days after
extraction
1 liter (aqueous)
30 grams (low level solid)
2 grams (medium level
solid)
EPA 500 Scries
Method 508
Optional. If used, penta-
chloronitrobenzene or
others if acceptance criteria
met. Sample IS response
must be >70% of standard
response.
One MS per 10 samples or
each sample batch,
whichever is greater.
Compare %R to lab
established limits, if
available, or Table 2 of
method.
One method blank with
each batch of samples
extracted or when new
reagents used.
Mercuric chloride as
bacteriocide. Sodium
thiosulfate if residual
chlorine present. Store at
4'C.
Extraction: 7 days
Analysis: 14 days after
extraction
1 liter
EPA 600 Series
Method 60S
Optional; no
standards specified.
One MS per 10
samples from each
site or 1 MS per
month, whichever is
more frequent.
Compare %R to
Tabie 3 of method.
One method blank
with each batch of
samples extracted
or when new
reagents used.
Adjust pH to 5-9 if
extraction not to be
done within 72
hours of sampling.
Add sodium
thiosulfate if
residual chlorine
present and aldrin is
being determined.
Store at 4 'C.
Extraction: 7 days
Analysis: 40 days
after extraction
1 liter
Standard Methods
. Method 6630
Not specified.
Analyze one set of
duplicates with each
batch of samples
processed at the
same time.
Periodically analyze a
control blank to test
the procedure.
Periodically is not
defined in the
method.
Store at 4'C.
Extraction: 7 days
Analysis: 40 days
after extraction
1 liter
CLP
PEST
(Organic SOW)
•Not required.
One MS/MSD per
sample batch or
1 per 20
samples. Six
compounds are
used for spiking;
advisory limits in
Exhibit D, Section
III. Paragraph
16.4 of SOW.
One method
blank per case,
one per 20
samples, or one
per sample
batch. All
compounds <
CRQL
Protect from
light. Store at
4'C.
Extraction: 5
days of sample
receipt
(aqueous)
10 days of
sample receipt
(solid)
Analysis: 40
days after
extraction
1 liter (aqueous)
30 grams (low
level solid)
1 gram (medium
level solid)
-------
DETERMINATION OF ORGANOCHLORINE PESTICIDES AND PCBs BY GC
Method -
Parameter
1
Other Criteria
(Method
Specific)
SW-846
Method 8080A
When doubt exists in
compound
identification, second
column confirmation
should be used.
Check for dichlorodi-
phenyltrichioroethane
(DDT) and endrin
degradation. %
breakdown must be <
20.
EPA 500 Series
Method 508
Laboratory Performance
Check Sample analyzed
daily to monitor
instrument sensitivity,
column performance,
and chromatographic
performance.
When doubt exists in
compound identification,
second column
confirmation should be
used.
EPA 600 Series
Method 608
When doubt exists in
compound
identification, second
column confirmation
should be used.
Standard Methods
Method 6630
When doubt exists in
compound
Identification, second
column confirmation
should be used.
CLP
PEST
(Organic SOW)
Second column
confirmation is
mandatory.
Check for dichlorodi-
phenyltrichloroethane
(DDT) and endrin
degradation every 12
hours. % breakdown
must be < 20.
Analyze resolution
check mixture prior to
initial calibration.
Notes:
(1) Analyte lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
(2) Initial, one-time, demonstration of ability to generate acceptable accuracy and precision.
(3) Indicates maximum usage time. If comparisons of QC check standards indicate a problem, more frequent preparation may be
necessary.
(4) Unless otherwise indicated, holding times are from the date of sample collection.
(5) Minimum volume for analysis. Additional volumes are required for the generation of QC data.
5
-------
DETERMINATION OF SEMIVOIATILE ORGANIC COMPOUNDS BY GC/MS
Method -
Parameter 1
Applicability
Number of
Compounds (1)
Method
Validation (2)
QC Check
Standards
Method
Detection limit
Standard
Solution
Expiration (3)
Initial
CaSl) ration
Continuing
Calibration
Surrogate
Standards
SW-B46
Method 8270A
Qroundwaters. soils,
sediments, sludges, and
non-water mlscible
wastes
227 total
Extract and analyze 4
replicates of QC check
standard. Compare
accuracy and precision
results to Table 6 of
method.
If MS/MSD results fall
outside ranges
designated In Table 6 of
method, a QC check
standard must be
analyzed and fall within
those ranges.
EQLs listed in Table 2 of
method.
Stock standards: 1 year
Calibration standards: 1
year
Daily continuing
calibration standard: 1
week
Minimum of 5 levels,
lowest near but above
EDL. %RSDforCCCs<
30. RF for SPCCs> 0.05.
Mid-level calibration
standard run every 12
hours. RF for SPCCs >
0.05.
RF of CCCs must be <
30% difference from Initial
calibration.
Nitrobenzene-ds,
2-Fluorobiphenyl.
p-Terphenyl-dn,
Phenol-dg,
2-Fluorophenol. and
2,4,6-Trlbromophenol.
Recovery limits in Table 8
of method.
EPA 500 Series
Method 525
Drinking water and raw
source water
43 total
Extract and analyze 4-7
replicates of QC check
standard. %R=70-130.
%RSD<30.
Analyze a OC check
standard with every 20
samples or one per
sample set. %R=70-
130.
Analyze QC sample
from external source
quarterly.
MDLs listed in Tables 4,
5. and 6 of method.
Not specified.
Six levels. %RSD must
be < 30.
Mid-level calibration
standard analyzed at •
the beginning of each 8
hour shift. RF must be
within ± 30% of initial
calibration.
Perylene-d^2-
Optional: Caffeine-
15N^nd Pyrene-diQ.
EPA 600 Series
Method 625
Wastewater
81 total
Extract and analyze 4
replicates of QC
check standard.
Compare, accuracy
and precision results
to Table 6 of method.
If MS results fall
outside ranges in
Table 6 of method, a
QC check standard
must be analyzed
and fall within those
ranges.
MDLs listed in Tables
4 and 5 of method.
Stock standards: 6
months
Calibration
standards: not
specified
Minimum of 3 levels,
lowest near but
above MDU If %
RSD < 35. linearity
assumed arid
average RF used;
One or more
calibration standards
analyzed each day.
If not within ± 20% of
predicted response.
recalibrate.
Minimum of three
from Table 8 of
method. Results
must fall within
laboratory
established control
limits.
Standard
Methods
Method 6410
Domestic, industrial
wastewaters,
natural and potable
waters
81 total
Extract and analyze
4 replicates of QC
check standard.
Compare accuracy
and precision
results to Table
6410:V of method.
If MS results fall
outside ranges in
Table 6410:V of
method, a QC check
standard must be
analyzed and fall
within those ranges.
MDLs listed in
Tables 6410:1' and
6410:11 of method.
Stock standards: 6
months
Calibration
' standards: not
specified
Minimum of three
levels, one near but
above MDL If %
RSD < 35. linearity
assumed and
average RF used. -
One or more
calibration
standards analyzed
each day. If not
within ± 20% of
predicted response,
recalibrate.
Minimum of 3 from
Table 6410:IV of
method. Results
must fall within
laboratory
established control
limits.
CLP
SVQA
(Organic SOW)
Water, soil, and
sediment
64 total
Not specified.
Not specified.
CRQLs for TCL
listed in Exhibit C of
SOW.
Stock standards: 1
year
Calibration
standards: 1 year
Daily continuing
calibration
standard: 1 week
Five levels except
for 8 compounds
which only require 4
levels. Minimum
RRF and maximum
RSD criteria listed in
Table 5 of Exhibit
D/SV of SOW.
A mid-level
calibration standard
is run every 12
hours. The%
difference must be
<25 from Initial
calibration.
Same as 8270A
plus 2-
Fluorobiphenyl and
Chlorophenol-d4.
Recovery limits
listed in Table 6 of
Exhibit D/SV of
SOW.
-------
DETERMINATION OF SEMIVOLATILE ORGANIC COMPOUNDS BY GC/MS
Method-
Parameter I
Internal
Standards
Accuracy/
Precision
Blanks
Preservation/
Storage
Conditions
Holding Time
m
Sample
Volume (5)
SW-846
Method 8270A
1 ,4-DIchlorobenzene-
d^, Naphthalene-ds.
Acenaphthene-diQ.
Phenanthrene-.d^Q.
Chrysene-d i2-anc'
Perylene-d^2- ^
must be within ± 30
seconds from last
calibration; area must
be -50 to +100%.
One MS/MSD per 20
samples or each
batch of samples,
whichever is more
frequent Compare
results to Table 6 of
method.
One method blank
per 20 samples or
each batch of
samples, whichever
is more frequent.
Sodium thiosulfate
if residual chlorine.
Store at 4"C.
Extraction: 7 days
(aqueous)
14 days (solids)
Analysis: 40 days
after extraction.
1 liter (aqueous)
30 grams (low level
solid)
2 grams (medium
level solid)
EPA 500 Series
Method 525
Acenaphthene-D ^g,
Phenanthrene-D^g.
and Chrysene-D^2-
Sample IS response
must be >70% of
standard response.
One MS/MSD per 20
samples or each
batch of samples,
whichever is more
frequent. %R=70-130.
%RSD < 30.
Analyze duplicate QC
check standards.
quarterly.
One method blank
with each batch of
samples extracted.
If residual chlorine.
add sodium sulfite or
sodium arsenite.
Adjust pH Ł 2 with
HCI for unchlorinated
water. Store at 4"C.
Extraction: 7 days
Analysis: 30 days
after extraction.
1 liter
EPA 600 Series
Method 625
Optional. If used,
minimum of 3 from
Table 8 of method.
One MS per 20
samples from each
site or 1 MS per
month, whichever is
more frequent.
Compare %R to Table
6 of method.
One method blank
with each batch of
samples extracted or
when new reagents
used.
Sodium thiosulfate if
residual chlorine.
Store at 4'C.
Extraction: 7 days
Analysis: 40 days
after extraction.
1 liter
Standard Methods
Method 6410
Minimum of 3 (some
recommended in
Table 6410:IV of
method).
One MS per 20
samples from each
site. Compare
results to Table
6410:V of method.
Not specified.
Sodium thiosulfate if
residual chlorine.
Store at 4"C.
Extraction: 7 days
Analysis: 40 days
after extraction.
1 liter
CLP
SVGA
(Organic SOW)
1,4-Dichlorobenzene-d4,
Naphthalene-dg,
Acenapthene-d IQ.
Phenanthrene-d^Q,
Chrysene-di2-ar|d
Perylene-d^2- RT must
be within ± 30 seconds
from last calibration;
area must be -50 to
+100%.
One MS/MSD per 20
samples or each batch
of samples, whichever
is more frequent (only
11 compounds spiked).
Compare results to
Table 7 of Exhibit D/SV
of SOW. '
One method blank per
20 samples or each
batch of samples,
whichever is more
frequent. Concentration
< CRQL for all
compounds but
phthalates < 5X CRQL
Protect from light.
Store at 4'C.
Extraction: 5 days of
sample receipt
(aqueous)
10 days of sample
receipt (solid)
Analysis: 40 days"after
extraction.
1 liter (aqueous)
30 grams (low level
solid)
1 gram (medium level
solid)
-------
DETERMINATION OF SEMIVOLATILE ORGANIC COMPOUNDS BY GC/MS
Method -
Parameter t
Other Criteria
(Method
Specific)
SW-846
Method 8270A
Tuning: 50 ng
decafluorotriphenyl-
phosphlne (DFTPP)
initially and every 12
hours: acceptance
criteria in Table 3 of
method.
Qualitative ID: All
Ions > 10% Intensity
must be ± 20% of
standard; ± 0.06
RRT units of
standard RRT.
Library searches
may bo made for the
purpose of tentative
identification.
EPA 500 Series
Method 525
Tuning: 5 ng
decafluorotriphenyl-
phosphine (DFTPP) at
the beginning of each
8 hour shift;
acceptance criteria In
Table 1 of method.
Qualitative ID: All ions
> 10% Intensity must
be ± 20% of standard
ion; RT ± 10 seconds
of standard RT.
LSE cartridges must
be checked for
contamination.
EPA 600 Scries
Method 625
Tuning: 50 ng
decafluorotriphenyl-
phosphine (DFTPP)
at the beginning of
each day;
acceptance criteria
in Table 9 of
method.
Qualitative ID:
Characteristic ions
for each analyte
must maximize in
the same scan or
within 1 scan:
relative peak heights
of 3 characteristic
ions must be ± 20%
of standard; RT
(characteristic ions)
within ±30 seconds
RT of analyte.
Check column
performance daily
with benzidine and
pentachlorophenol.
Standard Methods
Method 6410
Tuning: 50 ng
decaftuorotriphenyl-
phosphine (DFTPP) at
the beginning of each
day; acceptance
criteria In Table
6410:111 of method.
Qualitative ID:
Characteristic masses
(Tables 6410:1 and II) -
each compound
maximizes in same
scan or within 1 scan;
RT within ± 30 •
seconds of RT of
standard; relative
peak heights of 3
characteristic masses
in EICPs within ± 20%
of relative intensities
of masses in
reference spectrum.
Check column
performance daily
with benzidine and
pentachlorophenol.
CLP
SVGA
(Organic SOW)
Tuning: 50 ng
decafluorotriphenyl-
phosphine (DFTPP) Ini-
tially and every 12
hours; acceptance
criteria in Table 1 of
Exhibit D of SOW.
Qualitative ID: same as
for 8270A.
Up to 20 compounds
with responses > 10%
of nearest internal
standard are tentatively
identified via a library
search.
Notes:
(D
(2)
(3)
CO
(S)
Analyte lists may vary among methods: a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be necessary.
Unless otherwise Indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
8
-------
CH
(pijos) suiBjB g
(snoanbB) s-jtu g
jdjaoaj sjdujBS
oioJisXepoi-
•O.frieajojs
•JU.6I1 uuojjjoajojd
~1OHO
XB > auoue}nq-3
'3UO130E 'aplJO|lp
au3|AiH3iu
inqiis jojioaO>
UOJIEJIU30UOO
•sjnou, zi A-iaAa
>lUE|q poqiaiu 3UQ
•MOS
jo VOA/Q JlPWXg jo
2 a|qs_L 0} sj|nsaj
ajsdujoo -(pa>)lds
spunoduioo
9 A'IUO) juanbajj
3joiu sj J3/\3UO|U.M
'sa|duJES jo upisq
L|OB3 JO S3|dUJBS
03 J3d SW auo
•%OOL
o; OS- gq lsniu
B3JB :uoi}Bjqi|BO
JSBI UJO4 spuooss
OE T aq isnui iu
•Sp-auazuaqojomo
pus
•au32uaqojon|j!p
-fr'l. 'auBLjjauj
-ojomoouiojg
CMOS ojueBJO)
VOA
cTIO
siui g
sXsp frL
'O.fr IB 3J01S
•aujjomo |snp|saj
jj ajejinsoim ujnipos
•|OH m™ Z ~ Hd
•Asp jad
>jUE|q po^aiu auo
•poq;auj
*o AIW29 3WBJL o;
sj|nsaj ajBduioo 'ays
H3B3 U10JJ S3|dUJES
02 J3d si/M 8UQ
•poqjaiu
io m:oi.Z9 aiqei
uiojj Ł jo ujnuiiui|/\i
OLZ9 polftBim
SpOlflDW PJEPUEJS
s-iiu g
sfep frL
'O.fr IE aJOJS
•3UUO|tjO |BnplS3J
}! ajB}|nsoiqj mnipos
•|OH 4HM 2 ~ Hd
•Aep
jsd >)UB|q poq;3UJ 3UQ
•poinauj jo g aiqsx oj
y% ajBdujoo '}U3nb34
3JOUJ sj jaAaqoiqAft
•IHUOUJ jad i. jo s;|s
U.OB3 U10JJ S3|dU!ES
OZJ3dsW8UO
•poiflsuu jo Ł 3|qsi
LUOJ; e jo lunujjutuj
'pssn j| 'isuoiido
frZ9 poiflow
sauas 009 Vd3
(paAaiqoE
aq USD STOW K P^sn
aq Asm nuig) iiu gz
S/BP 171
•O.fr JE ajojs
•a}EO||dnp
ui sajduiES ||E joanoo
•auuoiijo iBnpissj
J! pipy oiqjoosy
•|OH MUM z ~ Hd
•sa|duiBS jo i(o;Bq
jad >)uE|q p|aij 3UQ
•jaMjaBoi passaoojd
sa|dujES jo qojsq
J3d >jUEiq poqisui 3UQ
•^Ijspsnb
pszA|BUB spJBpuB;s
>)p3U.o oo 3lBO||dna
•psjinbsj SIN ON
•|BUOIjdO SpJBpUEJS
|BUJ3iU| JBUOjllppV
•suazuaqojony
ftZS poiflow
soyos DOS VdH
(P!|O'.0 SUJBJB g
(snoa'fibB) -jui g
sXBp^i.
"0,> IB 3J°1S
•auijo|tp lenpisaj
J! sjEjinsoim, ujnipos
MOM MJ!«v Z > Hd
•Ju3nb34
3JOUJ SI J3A3L|OIL|M
•sajdUJES jo ipisq
i)3Ba jo sa|duJBS OZ
jad >|UB|q p»qiauj auo
•poiflsiu jo 9 aiqBX
01 sunsaj ajEdujoo
•juanbajj SJOLU
s] jaAaupiu/rt 'sa|dujBS jo
qojBq qosa jo sa|duiBS
. QZ J3d QSIA1/SIAJ 8"0
•%OOL
O} OS- 8q ISnUJ B3JB
:uo!isjqi|B:i iss| uiojj
spuooas OE * sq jsniu
J.U 'Sp-3uazuaqojo|u.o
puB '3ua2uaqojon|j!p-t?'i.
'auBq}aujojci|Lpoujo)g
VOfrZO poiflSN
9t«-MS
(gjpojtnbou
aiunpA
ajdujES
(f)
aiuaBupioH
suoijipuoo
DBBJOJS
/UOflEAJDSaJd
S5|UE|a
poujan
uoisioajd
/AoEjnoov
SpJBpUBJS
[BUJ3]U|
t jo;oujB-red
-pomsui
A3
DIMVOHO 31IXV1OA JO
-------
•AAOSJOVOA/a
1WNX3 10 9 siqoj.
uj SIILUII XJSAOOOB
•8p,ousn|oi pun
• »p-aumnaojoiM3ia-E' 1.
'auazuaq
-ojonuoiuojg-tr
•uoncjqiioa
team UJOJJ gz>
aq jsniu asuajajjip %
at(i 'SKiou. zi. XJBAS
psz/imw s| pjppuois
ucjiujqipjo pAoi-pitu v
•MOS jo VOA/Q
J!<3 jo Z aiqox
U| paisji 0|J3«J3 QSU
utntuparai pun ddU
lunujiqw -sioAOiOAy
sniuow z
:$pjcpums su6 >pois
•sqi'jouj
g :(sa2c6 jdaaxa)
sp-Tpucis M30JS
•/WOSJOOlWItpgu!
paismauojs-iouo
•paypads ION
•paypads JON
IBJO» EE
juoiuipas
ptra 'ROS MajBM
OKOSOIuoOJO)
VOA
trio
•Sl!Ul||
IOJJUOD pau.s||qB)S3
XjoiEJoqEi
ujtniM ||Bj jsnui
sunsou -poinaiu
jo |||:oiZ9 3|qBjL
UJOJJ e jo iunuiiu|i«i
•pogjauj
jo Ai: asu%
11 -1QIM BAoqB jnq
JGDU auo 'SIDAOI
DOJm jo umuiiuiw
XOOM L ISpJBpUBJS
SC6 >)DOJS
•LHUOUJ
L :(sasB6 idasxa)
SPJBPUBJS H30JS
•poiusuJ
jo |:oi29 aiqei
u| pajsu snaw
•saEuBj
35014; UW1!M
I|B} pus pozX|eue
aq JGOUJ pjupusis
H33M30QB
•pomauj jo Ai:OlZ9
oiqni u| paiBu5|sop
soBuBJ ai|i apisino
HBJ sj|nS3J SW Jl
•poqjauj jo Ai:OLZ9
siqsj. o\ sj|nsaj
UO)S|33jd PUB
/CsBjnooo ajBduJOO
'PJBPUBJS ))33q3
OO JO S31B3||d3J
t» 3ZX|BUV
IBJOJ It
sajduiBS
J3)BM IBJU3U1
-UOJIAUO ;so^j
OlZSPOtflan
cpoijja/j pjepuns
•SHUUII
lOJiuoo pai|si|qe)S3
XjO)BJOQB| U1L|)1M
MBj isnuj sjinsau
•POI|131U JO C 3IQB1
luoj) Ł jo lunuu.uiyv
•pogjsiu jo g aiqEX
oj sjinsaj sjBdiuoo
•XBp BUJJIJOM
ipeo pazAjBUB *
pjBpusis >)oat|3 oo
•pssn ju
oBBJSAB pus paoinssB
Xj|jB3ui| 'se > QSH
%ji nawsAoqB
jnq JBOU JSOMOI
'S|3A3| Ł JO UinUJIUIlM
>|3aM i
:spjEpUEjs SBB >|3o;s
•qjuoiu
L :(s3ssB }daox3)
spjepuB;s >(3Ois
•poiftaui jo
t 3|qej. ui pajsii SHQIAJ
•S36UBJ asoq; uiqtiM
|{BJ PUB p3zX|Bue 3q
jsnoi pjEpuejs noaqo
OO B 'poiffaui jo
g 3|qsj. ui pajEuBisap
saBuej am apisjno
HBJ sjinssj SWI Jl
•pog»3Ui jo g 3|qej_
o; s»|nsaj uoisioajd
PUB XoBjnosB
ajEdujoo -pjBpuBjs
))03M3 OO jo sa;Bo!|d3j
fr 3ZX|BUB PUB lOBJpg
IBIOI ie
J31BM31SBM
f Z9 POiflow
sapas 009 Vd3
•p3U!33ds jou sjiiuii
XjaAooaa -|BUO!Jdo
sojEBoJjns |Euoi}ippv
•Vp- auazuaq
-OJOWSIQ-Z'I.
PUB
3uazuaqojon|joiuojg-t7
•UOIJBjqi|BO
|B!)|U! jo %oe » UIU.JIM
sq jsnui ja TJWS Jnoy
g l|oea }O BuiuuiBaq am
}B pazAjEUE pJBpUBJS
UOI}Ejqi|EO |3A3|-P!|A]
•pasn ja
aBsjaAE pus pauinsse
xjuBauii 'oz>asa% u
-1QIAI S3U1H OU-Z ;S3MO|
'(aBuEJ uoiiBjqi|EO
uo Buipuadop)
S|3A3| g JO > 'E
jnoM L- :spJBpus;s
uo[iBjq!|BD snosnbv
•>|aaM
L :spjEpuejs SE6 >IDOIS
*S^33M
t> :(sasBB idaoxa)
SpJEpUBIS UDOJS
•poqjauj jo
e aiqsjL U! pajsi| SIQIA)
•ozu
-08=H% '*3S S|dLUBS
J3d 3UO JO Sa|dLUES
OZ XJ3A3 mi/A PJBPUBJS
H03M3 OO B 3ZX|EUV
"oz>asa%
•OZL-08=a% -pJEpueis
>(Dai|D OO JO S3lBO]|d3J
2.-t7 3ZX|BUB PUB IOBJJX3
IBIO; Qfr
J31BM aojnos
MBJ 'J3JBM 6u|)(U|Ja
U'frZS poiflBW
sauas DOS Vd3
•poqjauj jo
g aiqBj. ui BIJUJII XJBAOSSH
•8p-3U3H|OJ. PUB
•Vp-auBmsojoinaia-z'i.
'3U3zu3qojon|jouiojg-t'
•UOIlBjqi|B3 IEIJIUI UJOJJ
33U3J3jj!p %gz > sq ;snuj
sODOJOdU -uoijBjqiiBS
IBIJIUI JOJ SB 3UJBS
soOdSJOJdd "sjnon
Z\. XJ3A3 Unj pJBpUBJS
uoi;Bjq||B3 |SAa|.pi[A|
(lujojoiuojq Joj sz'Q)
OE-0 sooo Joj asd%
naiM
3AOqB }nq JB3U JS3MO|
•s|3A3| g jo ujnai|U!|/\|
Xiiea
:SPJBPUBIS uoiJBjqiiso
•SLUUOLU
Z :spjEpuBis seB >)oois
•smuouj 9 :(S3SBB
ld30X3) SPJEPUB)S >|3OIS '
•pomsui
jo 2 3|qBi U) psisii SHO3
•saBuBJ asom
UiqilM ||BJ PUB P3ZX|EUB
L3q jsnui pJEpUBjs
>|33HO OO B 'poqjaui
jo 9 aiqBj. ,U| pa;BuB|ssp
saBusj am apisjno
l|Ej sjinsaj QSW/SIAJ Jl
•poiflauj
jo 9 aiqEj. o\ siinsaj
uoispajd puB AoBjnooE
SJBdlUOO tpJBpUBJS
H03M3 OO JO SSJEDjldSJ
t» 3ZX|BUE PUB JDBJJX3
IBJOJ W
ssiSBM aiqpsioi JSIBM
-uou 'saBpnjs 'sjuouiipas
•s||os 'sjajEMpunojg
VOfrZ9 poinaw
9V9-MS
spjBpueis
oiEfiojjns
UORBjqilBO
Buinujjuoo
uojiBjq![BO
|BB!U|
(E) uoijEJKtg
uo.qnios
pjBpunS
«uin
uopoapa
poifloiN
. SPJBPUE»S
M33MO OO
(Z) uogBpiiBA
poujan
(L) S31/IBUV
jo JoquinN
Xl!|ic|Boaddv
I jaiaujBjBd
-poujaiAJ
Ae saMiioawoD DINVOHO anxvioA .10
-------
DETERMINATION OF VOLATILE ORGANIC COMPOUNDS BY GC/MS
Method^
Parameter 1
Other Criteria
(Method Specific)
SW-846
Method 8240A
Tuning: 50 ng
bromofluorobenzene
(BFB) initially and every
12 hours; acceptance
criteria in Table 3 of
method.
Qualitative ID: All ions
> 10% intensity must
be ± 20% of standard;
± 0.06 RRT units of
standard RRT.
Library searches may
be made for the •
purpose of tentative
identification.
EPA 500 Series
Method 524.1
Tuning: 50 ng
bromofluoro-
benzene (BFB) at the
beginning of each 8
hour shift; acceptance
criteria in Table 2 of
method.
Qualitative ID: All ions
> 10% intensity must
be ± 20% of standard
ion; sample RT within 3
SD of RT in calibration.
-
EPA 600 Series
Method 624
Tuning: 50 ng
bromofluoro-
benzene (BFB)
initially and every 12
hours; acceptance
criteria in Table 2 of
method.
Qualitative ID: Three
characteristic ions
must be ± 20% of
standard & must
maximize within 1
scan.
Standard Mc'Jiods
Methods 6210
Tuning: 50 ng
bromofiuoro-
benzene (BFB) at the
beginning of each
day; acceptance
criteria in Table .
6210:11 of method.
Qualitative ID:
Characteristic
masses of each
compound must
reach the
maximization point in
same scan or within
1 scan: RT within 30
seconds of RT of
authentic compound;
relative peak height
of 3 characteristic
masses in EICP
within 20% of relative
intensities of masses
in reference
spectrum.
CLP
VGA
(Organic SOW)
Tuning: 50 ng
bromofluoro-
benzene (BFB) ini-
tially & every 12
hours; acceptance
criteria in Table 1
of Exhibit D/VOA of
SOW.
Qualitative ID:
Same as for
8240A.
Up to 20
compounds with
responses >10%
of nearest IS are •
tentatively
identified via a
library search.
Notes:
(1)
(2)
(3)
(4)
(5)
Analyte list may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time, demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage" time. If comparisons of QC check standards indicate a problem, more frequent preparation may be
necessary.
Unless otherwise indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
11
-------
DETERMINATION OF AROMATIC VOLATILE ORGANIC COMPOUNDS BY GC
Method -
Piiramctcr I
Applicability
Number of
Anar/te3(1}
Method
VoKdatlon (2)
QC Chock
Standard
Method
Detection
Umtt
Standard
Solution
Bplrationp)
Initial
Calibration
Continuing
CftKbraUon
Surrogate
Standards
Internal
Standards
Accuracy/
Precision
SW-846
Method 8020A
Groundwater. soils, sludges.
water-mlsclble and non-water
misclble wastes
7 total (same as 602 and 6220)
Analyze 4 replicates of QC
check standard. Compare
accuracy and precision results
to Table 3 of method.
If MS/MSD results fall outside
ranges designated In Table 3 of
method, a GC check standard
must be analyzed and fall within
those ranges.
MDU listed In Table 1 of
method.
Stock standards: 6 months
Calibration standards: 24 hours
with no headspace.
Minimum of 5 levels, lowest
near but above MDL If %RSD
< 20, linearity assumed and
average RF used.
Mid-level calibration standard
run every 10 samples. If not
within ±15% of predicted
response, recalibrate.
Add surrogates to encompass
range of temperature program
(five recommended surrogates
are given In Section 5.7 of
method).
Optional. If used, a.a.a-
Trifluorotoluene is
recommended.
One MS/MSD per 20 samples or
each batch of samples,
whichever is more frequent.
Compare results to Table 3 of
method.
EPA 500 Series
Method 503.1
Drinking water, raw source
water
26 total
Analyze 4-7 replicates of QC
check standard. %R=80-120. ,
%RSD < 20.
Analyze a QC check standard
with every 20 samples or one
per sample set. %R=80-120.
Analyze QC check standard
from external source quarterly.
MDLs listed in Table 2 of
method.
Stock standards: 4 weeks
Calibration standards: not
specified
3, 4. or 5 levels (depending on
calibration range), lowest 2-10
times MDL lf%RSD<10,
linearity assumed and average
RF used.
Mid-level calibration standard
analyzed at the beginning of
each 8 hour shift. RF must be
within ± 20% of initial
calibration.
Not specified.
Optional. If used, a.a.a-
Trifluorotoluene is
recommended.
No MS required.
Analyze duplicates daily.
EPA 600 Series
Method 602
Municipal and industrial
discharge water
7 total (same as 8020 A
and 6220)
Analyze 4 replicates of QC
check standard.
Compare accuracy and
precision results to Table
2 of method.
If MS results fall outside
ranges designated in
Table 2 of method, a QC
check standard must be
analyzed and fall within
those ranges.
MDLs listed in Table 1 of
method.
Stock standards: 1 month
Calibration standards:
daily
Minimum of 3 levels,
lowest near but above
MDL If %RSD < 10,
assume linearity and
average RF used.
QC check standard
analyzed each working
day. Compare results to
Table 2 of method.
Add surrogates to
encompass range of
temperature program
(a.a.a-Trifluorotoluene
is recommended).
Optional. If used,
a.a.a-Trifluorotoluene
is recommended.
One MS per 10 samples
from each site or 1 per
month, whichever is more
frequent. Compare %R to
Table 2 of method.
Standard Methods
Method 6220
Most environmental
water samples
7 total (same as 8020A
and 602)
Analyze 4 replicates of QC
check standard.
Compare accuracy and
precision results to Table
6220:ll of method.
If MS results fall outside
ranges designated In
Table 6220:ll of method.
a QC check standard
must be analyzed and fall
within those ranges.
MDLs listed in Table
6220:1 of method.
Stock standards: 4
weeks
Calibration standards: 24
hours if zero headspace
Minimum of 5 levels. If
%RSD<10, linearity
assumed and average RF
used.
Analyze one or more
calibration standards
daily. If not within ±20%
of predicted response,
recalibrate.
a.a.a-Trifluorotoluene
Optional. If used.
a.a.a-Trifluorotoluene
is recommended.
One MS per 10 samples
from each site or 1 per
month, whichever is more
frequent. Compare %R to
Table 6220:ll of method.
12
-------
DETERMINATION OF AROMATIC VOLATILE ORGANIC
COMPOUNDS BY GC
Method^
Parameter 1
Blanks
Preservation/
Storage Conditions
Holding Time (4)
Sample Volume
Required (5)
Other Criteria
(Method Specific)
SW-846
Method 6020A
One method blank per 20
samples or each batch of
samples.
pH Ł 2 with HCI. If residual
chlorine, add sodium
thiosulfate. Store at 4"C.
14 days
5 mLs (aqueous)
5 grams (solid)
Second column confirmation
is recommended.
EPA 500 Series
Method 503.1
One method blank per batch
of samples processed at the
same time.
One field blank per batch of
samples.
pH < 2 with HCI. If residual
chlorine, add ascorbic acid
or sodium thiosulfate. Store
at 4"C. Collect all samples in
duplicate.
14 days
S mLs
Second column confirmation
is recommended.
Retention times must vary
by <10% over 8 hour period.
EPA 600 Series
Method 602
One method blank per
day.
pH < 2 with HCI. If
residual chlorine, add
sodium thiosulfate.
Store at 4'C.
14 days
5 mLs
Second column
confirmation is
recommended.
Standard Methods
Method 6220
One method blank per day:
pH Ł 2 with HCI. Add
ascorbic acid if residual
chlorine. Store at 4'C.
14 days
5 mLs
Second column
confirmation is
recommended.
Notes
(1)
(2)
(3)
(4)
(5)
Analyte lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be
necessary.
Unless otherwise indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
13
-------
DETERMINATION OF HALOGENATED VOLATILE ORGANIC
COMPOUNDS BY GC
Method -
Parameter 1
AppScabBty
Number of
AnaJytcsfl)
Method VaHdalion
ra
OC Check
Standards
Method Detection
limit
Standard Solution
Expiration (3)
Initial
Calibration
Continuing
Castration
Surrogate
Standards
Internal Standards
Accuracy/
Precision
SW-846
Method 8010A
Groundwater, soils,
sludge, water mlsclble
liquid waste and non-
water mlsclble waste
34 total
Analyze 4 replicates of QC
check standard.
Compare accuracy and
precision results to Table
3 of method.
It MS results fall outside
the ranges designated in
Table 3 of method, a QC
check standard must be
analyzed and fall within
those ranges.
MDLs listed In Table 1 of
method. EQLs listed In
Table 2 of method.
Stock standards (except
gases): 6 months
Stock gas standards: 2
months
Calibration standards: 24
hours if zero headspace.
Minimum of 5 levels,
lowest near but above
MDL lf%RSD<20.
linearity assumed and
average RF used.
Mid-level calibration
standard run every 10
samples. If not within
±15% of predicted
response, recalibrate.
Bromochloromethane,
2-Bromo-1-
chloropropane, and
1 ,4-Dlchlorob utane.
Results within lab
established control limits.
Optional. If used, exact
compounds not
specified, though same
as used for surrogates
may be appropriate.
One MS/MSD per 20
samples or each batch of
samples, whichever is
more frequent. Compare
results to Table 3 of
method.
EPA 500 Series
Method 502.1
Drinking water, raw source
water ,
40 total
Analyze 4-7 replicates of QC
check standard. %R=80-120.
%RSD<20.
Analyze a QC check standard
with each sample batch.
%R=80-120.
Analyze a QC check standard
from an external source
quarterly.
MDLs listed in Table 2 of
method.
Stock standards: 4 weeks
Intermediate standards: 4
weeks
Calibration standards: not
specified
3, 4. or 5 levels (depending
on calibration range), lowest
2-10XMDL lf%RSD<10,
linearity assumed and
average RF used.
Analyze one or more
calibration standards daily. If
not within ±20% of predicted
response, recalibrate.
Not specified.
Optional. If used, 1,4-
Dichlorobutane or
2-Bromo-1-chloropropane.
Area must be ±3 SD of
calibration standards.
MS not required.
Analyze duplicates daily.
EPA 600 Series
Method 601
Municipal and industrial
discharge water
29 total (same as 6230)
Analyze 4 replicates of QC
check standard. Compare
accuracy and precision
results to Table 2 of
method.
If MS results fall outside the
ranges designated in Table
2 of method, a QC check
standard must be analyzed
and fall within those ranges.
MDLs listed in Table 1 of
method.
Stock standards, (except
gases and 2-
chloroethylvinyl ether): 1
month
Stock gas standards and 2-
chloroethylvinyl ether: 1
week
Calibration standards: 24
hours if zero headspace.
Minimum of 3 levels, lowest
near but above MDL If
%RSD<10, linearity
assumed and average RF
used.
QC check standard analyzed
each working day.
Compare results to Table 2
of method.
Bromochloromethane,
2-bromo-1 -chloropropane,
and 1,4-dichlorobutane
Optional. If used, surrogate
compounds have been
successfully used as
internal standards.
One MS per 10 samples
from each site or 1 per
month, whichever is more
frequent. Compare %R to
Table 2 of method.
Standard Methods
Method 6230
Most environmental water
samples
29 total (same as 601)
Analyze 4 replicates of QC
check standard. Compare
accuracy and precision
results to Table 6230:lll of
method.
If MS results fall outside the
ranges designated in Table
6230:ll of method, a QC,
check standard must be
analyzed and fall within
those ranges.
MDLs listed In Table 6230:1
of method ,
Stock standards, (except
gases and 2-chloroethylvinyl
ether): 1 month
Stock gas standards and 2-
chloroethylvinyl ether: 1
week
Calibration standards: 24
hours if zero headspace.
Minimum of 3 levels, lowest
near but above MDL If
%RSD<10, linearity assumed '
and average RF used.
QC check standard analyzed
each working day. Compare
results to Table 6230:lll of
method.
Bromochloromethane,
2-bromo-1-chloropropane,
and 1,4-dlchlorobutane
Optional. Select one or
more compounds similar in
analytical behavior to
compounds of Interest.
One MS per 10 samples
from each site or 1 per
month, whichever is more
frequent. Compare %R to
Table 6230:lll of method.
14 '
-------
DETERMINATION OF HALOGENATED VOLATILE ORGANIC
COMPOUNDS BY GC
Method^
Parameter I
Blanks
Preservation/
Storage
Conditions
Holding Time
(4)
Sample
Volume
Required (5)
Other Criteria
(Method
Specific)
SW-846
Method 801 OA
One method blank per 20
samples or each batch of
samples.
Sodium thiosulfate If residual
chlorine.
Store at 4"C.
14 days
5 mLs (aqueous)
5 grams (solid)
When doubt exists in
compound identification,. ,
second column confirmation
is recommended.
EPA 500 Series
Method 502.1
One method blank per batch of
samples processed at the
same time.
pH .< 2 with HCI. If residual
chlorine, add ascorbic acid or
sodium thiosulfate.
Store at 4'C. Collect all
samples in duplicate.
14 days
5 mLs
When doubt exists in
compound identification,
second column confirmation is
recommended.
EPA 600 Series
Method 601
One method blank per
day.
Sodium thiosulfate if
residual chlorine.
Store at 4"C.
14 days
5 mLs
When doubt exists in
compound identification.
second column
confirmation is
recommended.
Standard Methods
Method 6230
One method blank per day.
pH <. 2 with HCI. Add
ascorbic acid if residual
chlorine. Store at 4"C.
. 14 days
5 mLs
When doubt exists in
compound identification,
second column confirmation
is recommended.
Notes
(1)
(2)
(3)
(4)
(5)
Analyte lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be
necessary.
Unless otherwise indicted, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
15
-------
DETERMINATION OF TOTAL AND AMENABLE CYANIDE
Method -
Parameter l
Applicability
Number of Anolytcs
Method Validation
(1)
OC Check
Standards
Method Detection
Umlt
Standard Solution
Expiration (2)
InttJjl
Calibration
Continuing
CaEbraUon
Surrogate
Standards
Ifltcrnal Standards
Accuracy/
fi-ccfcton
Blanks
Reservation/
Storage Conditions
Holding Times (4)
SW-846
Methods 9010A/9011
Wastes and leachates
Total CN and CN
amenable to chlorlnation
Not specified.
Verify calibration with an
Independent check
standard. If not within ±
15% of expected value,
recalibrate.
0.02 mg/L
Stock standard: Not
specified
Calibration standards:
prepare daily
Colorlmetric: 6 levels plus
blank
Colorlmetric: verify curve
with every sample batch
by analyzing a mid-level
concentration standard.
Not applicable.
Not applicable.
One MS/MSD per sample
batch
Titratlon - One reagent
blank per sample batch
Colorimetric - Calibration
blank
No distillation blank
specified.
Aqueous: pH^ 12 with
NaOH. Sodium arsenlte or
ascorbic acid if oxidizing
agents. Store at 4"C.
Solid: Store at 4'C.
14 days
EPA Series
Methods 335.1. 335.2
Drinking, surface,
saline water,
domestic and
Industrial wastes.
Total CN and CN
amenable to
chlorination
Not specified.
Not specified.
0.02 mg/L
Stock standard: Not
specified
Calibration standards:
prepare daily
Colorimetric: 6 levels
plus blank
Not specified.
Not applicable.
Not applicable.
Do MS to check
sample distillation
efficiency: no
frequency specified.
Titration - One reagent
blank per sample
batch
Colorimetric -
Calibration blank
No distillation blank
specified.
pH> 12 with NaOH.
Ascorbic acid if
oxidizing agents.
Store at 4'C.
14 days (24 hours
when sulfide present)
Standard Methods
Methods 4500-CN C, D. E.
andG
Wastewater and groundwaters
Total CN and cyanide amenable
to chlorination
Not specified;
Not specified.
0.02 mg/L
Stock cyanide: check weekly
Calibration standards:
prepare dally
Colorimetric: Series of
standards over range 0.2 - 6 iig
CN plus blank
Colorimetric: Recheck
calibration curve periodically,
and each time new reagent
used. Periodically is not defined
in the method.
Not applicable.
Not applicable.
Not specified.
Titratlon: One reagent blank per
sample batch
Colorimetric: Calibration blank
No distillation blank specified.
pH = Ł12 with NaOH.
Store at 4"C in dark.
Sodium thiosulfate if oxidizing
agent present.
14 days (24 hours when sulfide
present)
CLPCN
(Inorganic SOW)
Water, soil, and sediments
Total CN only
Not specified.
Verify initial calibration with a
distilled independent
standard. %R=85-115%.
CRDL: 0.01 mg/L
Stock cyanide: not specified
Calibration standards:
prepare daily
Colorimetric: Minimum of 3
levels plus a blank (one
standard at CRDL).
Colorimetric: Calibration
checked after every 10
samples or 2 hours,
. whichever is more frequent.
%R=85-115%.
Not applicable.
Not applicable.
One MS and 1 duplicate for
each sample batch. %R=75-
125%. RPD<20%
Titration: One reagent blank
per sample batch
Colorlmetric: Calibration
blanks after every 10
samples or 2 hours,1
whichever is more frequent
Analyze a distillation blank
with each sample batch.
Aqueous: pH > 12 with
NaOH. Ascorbic acid if
oxidizing agents. Store at
4'C.'
Solid: Store at 4'C.
12 days from sample receipt
16
-------
DETERMINATION OF TOTAL AND AMENABLE CYANIDE
Method -
Parameter 1
Sample Volume
Required (5)
Other Criteria
(Method Specific)
SW-846
Methods 9010 A/9011
Aqueous: 500 mLs (1000
tnLs if both total and
amenable CN)
Solid: 1-5 grams (2-10 grams
if both total and amenable
CN)
Distill a high and a low
standard; results should be
±10% of undistilled
concentration.
If sulfides present, all
standards must be distilled.
If matrix interference, use
MSA.
EPA Series
Methods 335.1/335.2
500 mLs (1000 mLs if both
total and amenable CN)
Distill a high and a low
standard; results should be
±10% of undistilled
concentration.
If sulfides present, all
standards must be distilled.
Standard Methods
Methods 4500-CN C. D.
E.andG
500 mLs (1000 mLs if
both total and
amenable CN)
None.
CLPCN
(Inorganic SOW]
500 mLs (aqueous)
1-5 grams (solid)
Distill one mid-level
standard; results must be
±15% of undistilled
'Concentration.
Notes:
(1)
(2)
(3)
(4)
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be necessary.
Unless otherwise indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
17
-------
DETERMINATION OF TOTAL ORGANIC CARBON
Method -
Parameter 1
Applicability
Number of
Arulytcs
Method
VaMatton (1)
QC Check
Standards
Method
Detection Umtt
Standard
Solution
Expiration (2)
Initial
CaSb ration
Continuing
CoSb ration
Surrogate
Standards
Internal
Standards
Accuracy/
Precision
Blanks
Preservation/
Storage
CondHions
HcJcSngTImo
P)
Sample Volume
Required (4)
Otltcr Criteria
(Method
Specific)
SW-846
Method 9060A
Groundwater, surface and saline waters,
domestic and Industrial wastes
No specific compounds; Includes
natural sugars, mercaptans, alkanes,
low molecular weight alcohols and oils.
cellulose fibers, oily matter adsorbed on
silt.
Not specified.
Verify calibration with an Independently
prepared check standard. No criteria
specified.
1 mg/L
Not specified.
Per Instrument manufacturer's
specifications.
Not specified.
Not applicable.
Not applicable.
Analyze samples In quadruplicate.
Method blanks analyzed; frequency not
specified.
pH52withHCIorH2SO«.
Protect from light & atmospheric 02-
Store at 4*C.
ZSdays
Not specified.
None.
EPA Series
Method 41 5.1
Groundwater, surface and saline
waters; domestic and industrial wastes
No specific compounds; includes
natural sugars, mercaptans, alkanes,
low molecular weight alcohols and oils,
cellulose fibers, oily matter adsorbed
on silt.
Not specified.
Not specified.
1 mg/L
Not specified.
Per instrument manufacturer's
specifications.
Not specified.
Not applicable.
Not applicable.
Not specified.
Method blanks analyzed; frequency not
specified.
pH < 2 with HCI or H2SOv
Protect from light & atmospheric 02-
Store at 4'C.
28 days
Not specified.
None.
Standard Methods
Method 5310B
Ground and surface waters,
wastewater
No specific compounds; classes of
organic compounds not. specified.
Not specified.
Not specified.
1 mg/L
Not specified.
Per instrument manufacturer's
specifications.
Not specified.
Not applicable.
Not applicable.
Not specified.
Method blanks analyzed; frequency
not specified.
pH < 2 with h^SO^or H^PO^only if
inorganic carbon is later purged.
Protect from light. Store at 4"C.
28 days
Not specified.
None.
Notes:
(1) Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
(2) Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be necessary.
(3) Unless otherwise Indicated, holding times are from the date of sample collection.
(4) Minimum volume for analysis. Additional volumes are required for the generation of QC data.
18
-------
DETERMINATION OF TRACE METALS BY FLAME AND GRAPHITE FURNACE
ATOMIC ABSORPTION SPECTROSCOPY
Method-
Parameter I
Applicability
Number of Analytes
(1)
Method Validation (2)
QC Check Standards
Method Detection
Limit
Standard Solution
Expiration (3)
Initial Calibration
Continuing
Calibration
Surrogate Standards
Internal Standards
Accuracy/
Precision
Blanks
SW-846
Method 7000 Series
Drinking, surface, saline
waters, domestic and
industrial wastes, extracts,
soils, sludges, sediments,
industrial and other solid
wastes
27 total
Not specified.
Verify calibration with an
independent check
standard. %R=90-110.
Detection limits listed in
Table 1 of method 7000A;
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Minimum of 3 levels plus a
blank
Analyze a mid-level
. calibration .standard or QC,
check standard after every
10 samples.- %R=80-120.
Not applicable.
Not applicable.
One MS/MSD per batch of
samples processed at the
same time. %R=75-125.
%RPD<20.
One method blank per
batch of samples
processed at the same
time.
One calibration blank with
curve.
EPA Series
Method 200 Series
. Drinking, surface, and saline
waters; domestic and
industrial wastes
33 total
Not specified.
Performance Sample: One
(blind) sample analyzed per
year for metals being
determined; results within
EPA control limits.
OPTIONAL: Known reference
standards analyzed once
per quarter for metals being
determined
Detection limits listed in .
Table 1 of Metals
Introductory chapter.
Stock standards: Not
specified.
Calibration standards:
• Prepare fresh at time of
analysis.
Minimum of 3 levels plus a
blank
Analyze a low-level standard
daily orevery 20 samples, •
whichever is more frequent.
%R=90-110.
Not applicable.
Not applicable.
OPTIONAL: One duplicate
sample per every 10
samples, or per each set of
samples (if set contains <
10). Results within EPA
control limits.
Method blank not specified.
Calibration blank with curve.
Standard Methods
Method 3000 Series
Drinking, surface, saline,
groundwaters, and
wastewaters
38 total
Not specified.
Verify calibration with
independent check
standard.
%R=95-105.
FLAA: IDLs listed in Table
3111:1 of Method 311 1A.
GFAA: IDLs listed in Table
3113:11 of Method 3113A.
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Minimum of 3 levels plus a
blank
Analyze a mid-level
standard after every 10
samples. %R=90-110.
Not applicable.
Not applicable.
Spike samples prior to
digestion (frequency not
specified). %R=85-115.
GFAA only: analyze all
digestates in duplicate.
One method preparation
blank per batch of samples
processed at the same
time.
Analyze calibration blank
after every 10 samples.
CLP
(Inorganic SOW)
Water, soil, and sediment
13 total
Not specified.
Initial calibration verified
with independent standard.
%R=90-110.
Digested QC check ••.
standard analyzed with
each sample batch.
%R=80-120.
CRDLs listed in Exhibit C of
SOW.
IDLs determined quarterly.
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Minimum of 3 levels plus a
•blank (one standard at
CfiDL).
Analyze mid-level
calibration standard after
each 10 samples or every
2 hours, whichever is more
frequent. %R=90-110.
Not applicable.
Not applicable.
One MS and 1 duplicate per
20 samples or each sample
batch, whichever is more
frequent. %R=75-125.
%RPD<20.
One method blank with
very 20 samples or each
sample batch, whichever is
more frequent.
Analyze calibration blanks
after every 10 samples or 2
hours, whichever is more
frequent.
19
-------
DETERMINATION OF TRACE METALS BY FLAME AND GRAPHITE FURNACE
ATOMIC ABSORPTION SPECTROSCOPY
Method -
Parameter 1
Preservation/
Storage Conditions
HoWogTlmc(4)
Sample Volume
Required p)
Otlicr Criteria
(Mcthod-Spccffic)
SW-e46
Method 7000 Scries
Aqueous: pH < 2 with
HN03
Solid: Store at 4'C.
6 months
100 mLs (aqueous)
2 grams (solid)
Test for matrix interference
with each matrix using
serial dilution (if >25X
detection limit) or post-
digestion spike.
Use standard additions to
compensate for matrix
interferences.
EPA Series
Method 2000 Scries
pH < 2 with HNO3
6 months
100 mLs
For GFAA. verify the
absence of interferences
by diluting and spiking each
matrix. %R=90-110%.
Use standard addition to
compensate for matrix
interferences.
Standard Methods
Method 3000 Scries
pH 5 2 with HN03
6 months
100 mLs
Test for matrix
interference with each
1 matrix by analyzing ,
undiluted and diluted
samples.
CLP
(Inorganic S.O.W.)
Aqueous: pH <. 2 with HNC>3
Solid: Store at 4'C.
180 days from sample receipt
100 mLs (aqueous)
2 grams (solid)
CRDL standard run at
beginning and end of run, or
minimum of twice per 8
hours.
All GFAA digestates injected
in duplicate. %RPD<20.
All GFAA digestates spiked to
determine matrix
interferences. If verified, MSA
used.
Notes:
0)
C)
0)
<«)
(5)
Analyte lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to CC check standards indicate a problem, more frequent preparation may be necessary.
Unless otherwise indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
20
-------
DETERMINATION OF MERCURY BY COLD VAPOR
ATOMIC ABSORPTION SPECTROSCOPY
Method ~
Parameter I
Applicability
Number of
Analytes
Method
Validation (1)
QC Check
Standards
Method
Detection
Limit
Standard
Solution
Expiration (2)
Initial
Calibration
Continuing
Calibration
Surrogate
Standards
Internal
Standards
Accuracy/
Precision
SW-646
Methods 7470/7471 '
Drinking, surface, saline
waters, domestic and
industrial wastes, extracts,
soils, sludges, sediments,
industrial and other solid
wastes
Hg only
Not specified.
Verify calibration with an
independent check standard.
%R=90-110.
0.0002 mg/L
1
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of .
analysis.
Five levels plus a blank
Analyze a mid-level
calibration standard or QC
check standard after every 10
samples. %R=80-120.
Not applicable.
Not applicable.
One MS/MSD per batch of
samples processed at the
same time. %R=75-125.
%RPD<20.
EPA Series
Methods 245.1/245.5
Drinking, surface, and saline
waters, domestic and
industrial wastes, soils,
sediments, and sludges
Hg only
Not specified.
Performance Sample: One
(blind) sample analyzed per
year for metals being
determined; results within
EPA control limits.
OPTIONAL: Known reference
standards analyzed once per
quarter for metals being
determined.
0.0002 mg/L
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Six levels plus a blank
Analyze a low-level standard
daily or every 20 samples,
whichever is more frequent.
%R=90-110.
Not applicable.
Not applicable.
OPTIONAL; One duplicate
sample per every 10 samples,
or per each batch of samples .
(if batch contains < 10).
Results, within EPA control
limits.
Standard Methods
Method 3112B
Drinking, surface, saline,
groundwaters, and
wastewaters
Hg only
Not specified.
Verify calibration with
independent check
standard.
%R=95-105.
Not specified.
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Three levels plus a blank
Analyze a mid-level
standard after every 10
samples. %R=90-110.
Not applicable. . .
Not applicable.
Spike samples prior to
digestion (frequency not
specified). %R=85-115.
CLP
(Inorganic SOW)
Water, soil, and sediment
Hg only
Not specified.
Initial calibration verified with
independent standard.
%R=80-120.
• Digested QC check standard
analyzed with each sample
batch. %R=80-120.
CRDL: 0.0002 mg/L
Stock standards: Not
specified.
Calibration standards:
Prepare fresh at time of
analysis.
Four levels plus a blank
Analyze mid-level calibration
standard after each 10
samples or every 2 hours,
whichever is more frequent.
%R=80-120.
Not applicable.
Not applicable.
One MS and 1 duplicate per
20 samples or each sample
batch, whichever is more
frequent. %R=75-125.
%RPD<20.
21
-------
DETERMINATION OF MERCURY BY COLD VAPOR
ATOMIC ABSORPTION SPECTROSCOPY
Method -
Parameter 1
Blanks
Preservation/
Storage Conditions
Molding Time (3)
Sample Volume
Required (4)
Other Criteria
(Method-Specific)
SW-846
Methods 7470/7471
One method blank per batch
of samples processed at the
same time.
One calibration blank with
curve.
Aqueous: pH < 2 with HNC>3
Solid: Store at 4'C.
28 days
100 mLs (aqueous)
0.2 grams In triplicate (solids)
Use MSA to compensate for
matrix Interferences.
EPA Series
Methods 245.1/245.5
Method blank not
specified.
Calibration blank with
curve. "
Aqueous: pH < 2 with
HN03
Solid: Store at 4'C.
28 days
100 mLs (aqueous)
0.2 grams in triplicate
(solids)
Use MSA to compensate
for matrix interferences.
Standard Methods
Method 3112B
One calibration blank
with curve.
pH < 2 with HNO3
28 days
100 mLs
Use MSA to
compensate for matrix
interferences.
CLP
(Inorganic SOW)
One method blank with every
20 samples or each sample
batch, whichever is more
frequent.
Analyze calibration blanks
after every 10 samples or 2
hours, whichever is more
frequent.
Aqueous:- pH < 2 with HNO3
Solid: Store at 4'C.
26 days from sample receipt
100 mLs (aqueous)
0.2 grams in triplicate (solids)
CRDL standard run at
beginning and end of run, or
minimum of twice per 8
hours.
Notes:
(1)
(2)
(3)
(4)
Initial, one-tlmo demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standards indicate a problem, more frequent preparation may be necessary.
Unless otherwise Indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
22
-------
DETERMINATION OF TRACE METALS BY ICP
Method -
Parameter I
Applicability
Number of Analytes
CD
Method Validation (2)
QC Check Standards
Method Detection
Limit
Standard Solution
Expiration (3)
Initial
Calibration
Continuing
Calibration
Surrogate Standards .
Internal
Standards
Accuracy/
Precision
Blanks
SW-846
Method 6010
Nearly all matrices, including
groundwater, extracts,
industrial wastes, soils,
sludges, sediments and solid
wastes
26 total
Not specified.
Verify calibration with an
independently prepared
check standard.
IDLs listed in Table 1 of
method. MOLs vary by
matrix.
Not specified.
Per instrument
manufacturer's
specifications (should
consist of 3 levels and a
blank).
Analyze mid-level calibration
standard after each 10
samples. %R=90-110.
Npt applicable. . , ...
Not applicable.
One MS/MSO per 20
samples or each batch of
samples, whichever is more
frequent. %R=75-125.
%RPD<20.
One method blank per batch
of samples processed at the
same time.
Analyze calibration blank
after each 10 samples.
EPA Series
Method 200.7
Drinking water, surface,
saline and industrial and
domestic wastes
25 total (same as CLP)
Not specified.
Verify calibration with QC
check standard from
external source. If
recovery is not 95-105%.
recalibrate:
IDLs listed in Table 1 of
method. MDLs vary by
matrix.
Not specified.
Per instrument
manufacturer's
specifications.
Analyze mid-level
calibration standard after
each 10 samples. %R=95-
105.
Not applicable :••..',..
Not applicable.
Not specified.
One method blank per
batch of samples
processed at the same
time.
Analyze calibration blank
after each 10 samples.
Standard Methods
Method 3120
Water and wastewater
27 total
Not specified.
Analyze QC check
standard with each
sample batch.
%H=95-105 of
expected values.
IDLs listed in Table
3120:1 of method.
Not specified.
Per instrument
manufacturer's
specifications. •
Analyze 2 mg/L
instrument check
standard after each 10
samples. %R=95-105.
Not applicable. . .
Not applicable.
Not specified.
Method blank
analyzed; frequency
not specified.
CLP
(Inorganic SOW)
Water, soil, and
sediment
25 total (same as 200.7)
Not specified. •
initial calibration verified
with independent
standard. %R=90-110.
Digested QC check
standard analyzed with
each sample batch.
%R=80-120.
CRDLs list in Exhibit C of
SOW.
IDLs determined
quarterly.
Not specified.
Per instrument
manufacturer's
specifications.
Analyze mid-level
calibration standard after
each 10 samples or
every 2 hours, whichever
is more frequent.
%R=90-110.
Not applicable.
Not applicable.
One MS and one
duplicate per 20 samples
or each sample batch,
whichever is more
frequent. %R=75-125.
%RPD <20.
Analyze a method blank
with every 20 samples or
each sample batch,
whichever is more
frequent.
Analyze calibration
blanks after every 10
samples or 2 hours.
whichever is more
frequent.
23
-------
DETERMINATION OF TRACE METALS BY ICP
Method -
Parameter l
Preservation/
Storage
Coodfflons
Holding Tlmo
w
Sample Volume
Required (5)
Other Criteria
(Method
Spednc)
SW-O46
Method 6010
Aqueous: pH 5 2 with HNOs
Solid: Store at 4'C.
6 months
100 mLs (aqueous)
2 grams (solid)
Analyze ICS at beginning and
end of run or twice during 8
hour shift, whichever is more
frequent Results ±20% of
true value.
Reanalyze highest standard
after calibration. Results
±5% of true value.
For each new matrix^ if
analyte >10X IDU dilute 1:4.
Dilution should be ±10% of
original.
EPA Series
Method 200.7
pH < 2 with HN03
6 months .
100 mLs
Analyze ICS at beginning,
end and periodically
during run. Results within
1.5X SD of mean.
Standard Methods
Method3120
pHŁ2withHNO3
6 months
100 mLs
Determine interference
correction factors, each
time samples are
analyzed.
Test for matrix
interference with each
matrix using serial dilution
(>1 mg/L) or post-
digestion spike (<1mg/L).
CLP
(Inorganic SOW)
Aqueous: pH < 2 with HNC>3
Solid: Store at 4'C.
180 days from sample receipt.
100 mLs (aqueous)
2 grams (solid)
ICS analysis: same as 601 OA.
CRDL standard run at
beginning and end of run, or
minimum of twice per 8 hours.
Serial dilution analysis must
be performed on a sample
, from each matrix. If '
concentration >50X IDU must
agree within ±10% of original.
Verify linear ranges quarterly.
Notes:
(1)
(2)
(3)
(4)
(5)
Analyte lists may vary among methods; a smaller list in one method is not necessarily a subset of a larger list in another method.
Initial, one-time demonstration of ability to generate acceptable accuracy and precision.
Indicates maximum usage time. If comparisons to QC check standard indicate a problem, more frequent preparation may be necessary.
Unless otherwise Indicated, holding times are from the date of sample collection.
Minimum volume for analysis. Additional volumes are required for the generation of QC data.
24
-------
-------
m jo
O j* DO
co
8
> Til
-n
m
m
OJ
r-
ml
------- |