c
INTERLABORATORY VALIDATION OF U.S. ENVIRONMENTAL
PROTECTION AGENCY METHOD 1625A
Draft Final Report
June 1984
Prepared by:
Barrett P. Eynon
Christopher Maxwell
Alfonso Valdes
Prepared for:
JRB Associates
8400 Westpark Drive
McLean, Virginia 22102
SRI Project 7149
Work Assignment 1
Under Subcontract 2-834-37-632
to JRB Associates
Sponsored by the
U.S. Environmental Protection Agency
under EPA Contract 68-01-6192
SRI International
333 Ravenswood Avenue
Menlo Park, CA 94025
(415) 326-6200
TWX: 334-486
SRI)
International/
333 Ravenswood Ave. "• Menlo Park, CA 94025
(415 326-6200 • TWX: 910-373-2046 • Telex: 334-486
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EXECUTIVE SUMMARY
The U.S. Environmental Protection Agency 1s developing methods for the
chemical analysis of pollutants In wastewater. This report describes the
validation of Revision A of Method 1625 in laboratories which perform
routine analysis of wastewater samples. The report gives the design of the
validation study, the details of preparation of the samples used in the
study, the results of the study, and laboratory performance specifications
determined from the laboratory data using Method 1625A.
Method 1625A is designed to measure semi volatile toxic organic
pollutants in water by gas chromatography-mass spectrometry (GCMS). .The
method employs Isotope dilution, a technique 1n which stable Isotopically
labeled analogues of the pollutants are added to each water sample and
serves to reduce the variability of the analysis and correct for recovery
bias. The method also permits use of Internal standard and external
standard analytical techniques, and therefore permits comparison of method
performance by three techniques.
In order to evaluate Method 1625A and to aid in the selection of
contract laboratories for future wastewater analyses, EPA invited 26
laboratories, including EPA regional laboratories and commercial
laboratories, to participate in the Effluent Guidelines Division June 1983
Performance Evaluation. Each laboratory was sent an identical set of
standard solutions and a water sample, plus instructions specifying a series
of 11 calibrations and quantitations to be performed. These standards,
prepared by one central laboratory, contained known amounts of priority
pollutants and their labeled analogues, and were used for preparation of
calibration, verification, recovery, blank, and aqueous performance
standards. The contents of the water sample, prepared by a central
laboratory, were not revealed to the laboratories. Fourteen laboratories
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submitted analysis reports.* Three data formats were allowed for
.submission: magnetic tape, a hard-copy version of the magnetic tape format,
or data sheets provided 1n the Instructions. Data submitted on magnetic
tape was extracted by the EPA Sample Control Center (SCO; the remainder of
the submitted data was coded by SRI and then submitted to the SCC for entry.
The data were validated and screened for outlier values to produce a
final data set. This final data set was then analyzed to provide estimates
of the precision and accuracy of Method 1625A. Results of the
Interlaboratory validation revealed superior performance of the Isotope
dilution technique. The median absolute value of the relative accuracy
taken across all compounds In the study was Improved from 22.3 percent for
the Internal standard method to 7.6 percent for Isotope dilution, and the
median precision across all compounds was Improved from 29.8 percent for
Internal standard to 14.3 percent for Isotope dilution. Thus Isotope
dilution methods were found to be considerably more precise and accurate
than Internal standard methods. However, there was also some Indication
that Isotope dilution requires more care In Its application, since the
median proportion of laboratories that could not quantify or could not
detect compounds in the aqueous performance sample rose from 15.4 percent
for the Internal standard method to 23.1 percent for the Isotope dilution
method. These problems may be expected to diminish as the laboratories gain
experience with the Isotope dilution method, and with Increased use of
direct computer submission of data on magnetic media, which should eliminate
transcription and coding as a source of error.
The data from the study were used to develop specifications to be used
in a subsequent revision of Method 1625 and other EPA methods.
Specifications were developed for calibration linearity, initial precision
and accuracy, calibration verification, ongoing accuracy, and absolute and
relative retention time accuracy. These specifications will also be applied
to data received by EPA 1n Its analytical programs.
One laboratory submitted analyses on two different instruments. These
were treated as separate laboratories for the analysis, for a total of
15 data sets.
11
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CONTENTS
EXECUTIVE SUMMARY 1
LIST OF ILLUSTRATIONS 1v
LIST OF TABLES v
ACKNOWLEDGMENTS vl
I INTRODUCTION 1
II STUDY DESIGN 7
III CALIBRATION LINEARITY 21
IV DATA SCREENING 39
V METHOD PRECISION AND ACCURACY
VI QUALITY CONTROL LIMITS 55
VII CONCLUSIONS AND FURTHER WORK 81
APPENDICES
A METHOD 1625 REVISION A A-l
B INSTRUCTIONS FOR PREPARATION AND ANALYSIS OF
PERFORMANCE EVALUATION SAMPLES B-l
C TASK ORDER FOR PREPARATION OF PERFORMANCE
EVALUATION SAMPLES C-l
D QUANTITATION REPORTS ON MAGNETIC TAPE D-l
E EFFLUENT GUIDELINES DIVISION (EGO) DATA ELEMENTS . . E-l
F EVALUATION OF PRR SAMPLE F-l
G LABORATORY EXTREMAL RANK SCREENING G-l
H OUTLIER SCREENING METHODS H-l
I ESTIMATION OF VARIANCE COMPONENTS 1-1
J BINOMIAL CALCULATIONS FOR MULTIPLE TESTS J-l
K DERIVATION OF QUALITY CONTROL LIMITS FOR ACCURACY . . K-l
L DERIVATION OF QUALITY CONTROL LIMITS FOR PRECISION . L-l
M METHOD 1625 REVISION B M-l
REFERENCES R-l
111
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ILLUSTRATIONS
II-l Flow Chart for Extraction/Concentration of
Precision and Recovery Standard, Blank, and
Sample by Method 1625
1 1-2 Quantltation Data Sheet Format .. ........... 18
V-l Method Precision, APS Sample ............. 53
V-2 Method Accuracy, APS Sample ............. 54
VI-1 Column Temperature Programs Used ........... 71
iv
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TABLES
1-1 Participating Laboratories . . 4
1-2 Information Concordance 5
II-l Samples and Analyses 11
I1-2 Compounds, Compound Numbers, and
Mass/Charge Ratios 13
III-l Calibration Limits - Internal Standard
and Isotope Dilution 27
III-2 Calibration Limits - External Standard 31
III-3 Frequencies of Calibration Results 35
II1-4 Summary of Coefficient of Variation Limits
for Calibration Linearity 37
IY-1 Laboratory Ranking Results 41
IV-2 Summary of Laboratory Ranking Results 45
V-l Precision and Accuracy Evaluation - Aqueous
Performance Standard „ 49
VI-1 Start-up Limits for Accuracy and Precision 58
VI-2 Ongoing Calibration Verification Limits 61
VI-3 Ongoing Quality Assurance Limits 68
VI-4 Retention Time 73
VI-5 Relative Retention Time 77
H-l Simulation Results for Outlier Screening Methods . . H-2
1-1 Results of Variance Components Analysis 1-3
J-l Probability of Failing Quality Control Test J-2
J-2 First-Round Cutoffs for Two-Round Testing J-4
L-l Percentiles of the Standard Deviation of
Four Observations from LN(0, o2) L-3
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ACKNOWLEDGMENTS
This work was conducted for the Analytical Branch of EPA's Effluent
Guidelines Division. Special thanks are due to William A. Telllard,
Analytical Branch Chief, and Russell Roegner, Statistician. Mr. Telllard
was the EPA Project Officer for the interlaboratory validation; Mr. Roegner
was the EPA Task Officer for statistical analysis of the results. Many
thanks also to Dale Rushneck of Interface, Inc. for his contributions and
suggestions; and to John Morris of VIar & Co. and Bob Elder of JRB
Associates for their valued comments. Finally, the laboratories which
participated In this study should be acknowledged for their contribution to
the advancement of techniques for the analysis of pollutants In
environmental samples.
vl
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I INTRODUCTION
In 1976 the U.S. Supreme Court Issued a consent decree requiring the
U.S. Environmental Protection Agency (EPA) to measure and limit 65 compounds
and classes of compounds In discharged waters. The list of 65 was
subsequently refined by EPA to a list of 129 specific parameters termed the
"priority pollutants." In addition, EPA is responsible for developing
methods for measuring toxic pollutant concentrations In water and other
media. Within EPA's Office of Water, the Effluent Guidelines Division (EGO)
Is responsible for promulgation of nationwide standards for allowable
concentrations of these pollutants in discharges from municipal and
industrial facilities. To support these standards, the Division has been
Involved in the development of the latest, state-of-the-art methods of
chemical analysis. Method 1625 employs isotope dilution gas chromatography-
mass spectrometry (GCNS) to measure the concentrations of toxic sealvolatile
organic pollutants in water and wastewater. Revision A of Method 1625
permits measurements by Isotope dilution,- Internal standard, and external
standard techniques, and employs a capillary chromatographic column to aid
in resolution of complex mixtures. Isotope dilution methods differ from
previously proposed internal and external standard methods in two important
ways: (1) for each compound to be measured, a specific stable, isotopically
labeled analogue of the compound is used for reference, and (2) this
reference compound is added to each water sample prior to extraction.
Because the reference compound behaves chemically in a way identical to the
pollutant, losses in pollutant concentration during the analysis process are
compensated for by losses in the reference compound. As a result, the true
value of the pollutant is known more accurately when isotope dilution is
used.
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With isotope dilution, as with other chemical analysis techniques,
there is an error inherent in every measurement. This error can come from
variations in the analytical conditions (temperature, pressure, flow rate),
from variations in electrical signals, from imprecise operations performed
by the chemist, or from other sources. In order to develop performance
specifications for the method, method performance must be assessed in
laboratories that will use the method. This "interlaboratory" validation is
necessary because results obtainable in a single laboratory do not represent
performance in all laboratories, and specifications resulting from
single-laboratory data often reflect better precision and sometimes reflect
better accuracy than results from laboratories as a group. This fact is
especially true when the laboratory that develops the method determines the
specification, because this laboratory may achieve better performance by
using techniques that are not well documented for the method.
Interlaboratory validation of Method 1625 was one of the objectives of the
study reported here. The other objective was to evaluate laboratories to
determine which laboratories were qualified to perform work for EGD. Those
laboratories not meeting minimum standards, as determined by specifications
resulting from the validation, would be disqualified from performing EGD
work.
In order to evaluate Method 1625A and to aid in the selection of
contract laboratories for future wastewater analyses, EPA invited 26
laboratories, including EPA regional laboratories and commercial
laboratories, to participate in the June 1983 Performance Evaluation. Each
laboratory was sent an identical set of standard solutions plus one unknown
water sample, and was asked to perform five calibrations and six analyses.
A detailed set of instructions was given to the laboratories, along with a
copy of the method, a listing of the data elements to be reported, and a
specification for reporting results on magnetic tape. These documents are
attached as appendices to this report. Also included in the appendices is
the task order for preparation of the performance evaluation standards and
sample.
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The 14 laboratories listed 1n Table 1-1 responded to EGD's request for
participation. Data were received in the forms of quantisation reports on
magnetic tape, hard copy of quantitation reports, and data reporting
sheets. The data elements collected were aimed at assessing data quality.
Upon receipt of data from the laboratories, the data elements were entered
into a data base in the IBM computer at EPA's National Computer Center. The
EPA computer was chosen over alternates so that all data would be available
for future use by the Agency. Data were preserved in the state in which
they were received so that editing rules other than those used in this study
can be applied, If required. These data were then verified and cleaned
through editing and error-checking procedures. The verified data were used
to produce the analysis results presented in this report. Because of its
length, a listing of the data from this study Is not included in this
report. Separate computer listings of the data have been submitted to EPA.
The final data set was used to provide estimates of the precision and
accuracy in the interlaboratory validation. The data were also used to
construct quality control limits specified in Method 1625B, and to be
applied to quality assurance tests for data received by EGD. These limits
are given in the tables in sections III and VI. In some cases, parallel
sets of numbers were generated for analysis by the internal standard
method. These numbers may be used by EPA in setting quality control
specifications for Method 625 for priority pollutants by internal standard.
These numbers are also given in the tables in sections III and VI.
Table 1-2 has been provided to assist readers of this report seeking
information on a particular subject. This table provides an added link
between the body of the report and the appendices, so that Information on a
given subject can be located easily.
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Table 1-1
PARTICIPATING LABORATORIES
Radian Corp.
S-CUBED
EMS Laboratories, Inc.
ACUREX Corp.
Envlrodyne
Southern Research Institute
IT Analytical Services
Arthur D. Little
Gulf South Research Institute
Environmental Science and Engineering
Shell
Midwest Research Institute
EPA Region II
EPA Region VII
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Table 1-2
INFORMATION CONCORDANCE
Reference
Subject
Accuracy of analysis (median)
Calibration
Techniques
External standard
Internal standard
Isotope dilution
Linearity
Log-Log
Compound m/z
Compound number (EDG, CAS, NPDES)
Reference
Data
Elements
Formats
Screening
Kurtosls (FSCREEN)
Laboratory ranking
Robust (QSCREEN)
Description of analyses
Injections for perf. evaluation
Not detected entries
Participating laboratories
Submitting results
Precision of analysis (median)
Retention time outlier labs
Specifications
Accuracy
Start-up
On-going
Calibration
Linearity
Verification
Precision
Start-up
Retention time
Standard preparation
Report
page
11, 47
21-23
21
22
22
24-26
26, 34
13
10
15-16
17
17
39-45
40
39
40
9, 11-12
9
19
3, 4
17
11, 48
70, 71
56-59
67-69
25-33
60-67
56-59
70-80
10
Method
1625A
7 '
7
7
7
Tbl 6,7
Tbl 1,8
Tbl 3,4
•
6-14
7.10
12
7
12
7.10
12
6
section
1625B
7
7
7
7
Tbl 6,7
Tbl 1,8
Tbl 3,4
6-14
Tbl 8
Tbl 8
7
Tbl 8
Tbl 8
Tbl 3,4
6
Appendix
B and E
B and D
H
G
H
B
J.K.L
K
J.K.L
H
C
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II STUDY DESIGN
The Effluent Guidelines Division (EDG) June 1983 Laboratory Performance
Evaluation and Interlaboratory Method Validation was designed around the use
of Method 1625A by laboratories performing analysis of water and wastewater
samples. EPA had proposed methods for the analysis of water and wastewater
In the Federal Register In December of 1979. Method 625 1s a GCMS method
for the analysis of the priority pollutants 1n water and wastewater which
closely parallels Method 1625 (see the December 9, 1979 Federal Register for
details of this method). The methods proposed 1n the Federal Register In
1979 have been validated In the Intervening years through Interlaboratory
studies. The 1979 proposed methods did not contain quality control/quality
assurance (QA/QC) specifications Internal to each method, but a suggested
QA/QC program was given 1n the proposed method package. Therefore, an
objective of the Interlaboratory validation studies for the proposed methods
was to develop performance specifications for the methods, so that the QA/QC
could be stated within each method. In developing Isotope dilution methods
for the analysis of pollutants 1n water, EGO recognized the need to develop
QA/QC specifications for these methods, also. Thus, a major objective of
the work described 1n this report was to produce performance specifications
for Method 1625A. The specifications resulting from the Interlaboratory
evaluation of Method 1625A are explained 1n detail below, and are developed
1n subsequent sections of this report and In the Appendices. The resulting
method which Includes these specifications (Method 1625B) Is also given In
an Appendix.
Calibration Linearity—used to specify under which circumstances the
response of the GCMS Instrument to a given compound would be linear, or that
a calibration curve was to be used. Specifications were to be developed for
calibration by Isotope dilution, Internal standard, and external standard
calibration techniques. The study design Included the requirement to
-------
calibrate the Instrument by Injecting the pollutants at concentrations of
10, 20, 50, 100, and 200 ug/mL along with the labeled compounds at a
constant concentration of 100 ug/mL.
Calibration Verification—used to periodically verify that the GCMS
Instrument remains 1n calibration. Specifications were to be developed to
measure the allowable deviation from a single point on the calibration
curve. The study design required that the laboratory verify calibration of
the GCMS Instrument by analyzing the 100 ug/mL calibration solution after
the Instrument has been calibrated.
Retention Time Precision—used to aid 1n the Identification of a
pollutant, and to determine that sufficient time would be allowed for
separation of pollutants 1n complex mixtures. Specifications were to be
developed for the absolute retention time of the Internal standard, for the
relative retention time of each labeled compound to the Internal standard,
and for the relative retention time of each pollutant to Its labeled
analogue. The study design required each laboratory to report the retention
time for each compound 1n every analysis performed.
Initial Precision and Accuracy, and On-going Accuracy—used to
determine that the laboratory could perform analyses of the pollutants and
labeled compounds 1n a reagent water matrix. Specifications were to be
developed for the precision and recovery of four replicate analyses of
100 ug/L samples of the pollutants and labeled compounds 1n reagent water,
and for periodic single analyses of a reagent water sample containing all
pollutants and labeled compounds at this concentration. (Because of the
necessity to allow for the simultaneous test of a large number of compounds
in Method 1625A, the specifications were subsequently modified to permit two
sets of four analyses for the Initial precision and accuracy test, and one
set of two analyses for the on-going accuracy test. The details of these
modifications are given later 1n this report.) The study required that each
laboratory spike and analyze a single reagent water sample containing all
pollutants and labeled compounds at this concentration.
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NOTE: The use of a fixed concentration (100 ug/L) and of a reagent water
matrix (rather than an actual wastewater matrix) was based on the rationale
that laboratory performance 1s best quantified by repetitive analysis of the
same sample under the same analysis condltoons.
Labeled Compound Recovery—used to assess that the method would perform
properly on any particular sample tested. A specification was to be
developed for the permlssable range of recovery for each labeled compound
from each sample. The study design used the recovery for labeled compound
from the reagent waters under test to develop this specification.
NOTE: The application of specifications developed from reagent water data
to actual wastewater samples was based on the rationale that treated
wastewaters behave very similar to reagent water, that wastewaters which did
not behave similarly to reagent water would be diluted with reagent water so
that they would (see section 15 of Method 1625A or B), and that data
obtained on wastewaters which did not behave similarly to reagent water
after dilution could not be reported for regulatory compliance purposes (see
section 15 of Method 1625B).
The Performance Evaluation was Implemented by requiring a series of 11
Injections Into a GCMS Instrument by each laboratory. The purposes of the
11 Injections were for calibration, calibration verification, measurement of
the performance response ratio,* and analysis of extracts of a standard, a
blank, and a sample of unknown composition. Further details of the 11
Injections are given by the method description, attached to this report as
Appendix A, and the "Instructions for Preparation and Analysis of
Performance Evaluation Samples," attached as Appendix B. The 11 Injections
were to simulate the steps a laboratory would take when applying the Method
to analysis of water samples; I.e., the laboratory would first obtain
spectra of the pollutants and labeled compounds, then calibrate, then
analyze samples. Periodic calibration verification would be used to show
Ratio of peak area for the compound to peak area for the labeled compound.
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that Instrument performance had not changed. Table II-l lists the Injections
and analyses. The solutions to be Injected for calibration were to be
prepared by combining appropriate amounts of solutions of the pollutants and
of the labeled compounds, diluting this mixture to the appropriate volume,
then adding the Internal standard. The solution to be used for measurement
of the response ratio was to be prepared by measuring out a known volume of
the solution provided and adding a known volume of the Internal standard.
Preparation of the solutions to be used for the blank, aqueous performance
standard, and the sample are detailed In the flow chart 1n Figure II-l.
Table II-2 lists the pollutants Included In this study, and the
numbering scheme used for the quantltatlon reports to distinguish the
compound and analysis method. The first digit of the three-digit compound
number Indicates the method and pollutant type: 0 Indicates priority
pollutants measured by the Internal standard method; 1 Is used only for
compound 164 (2,2-d1fluorob1phenyl), the reference compound for the Internal
standard method; 2 Indicates the labeled analogue of a priority pollutant,
measured by the Internal standard method; 3 Indicates priority pollutants
measured by the Isotope dilution method; 5 Indicates other non-prlorlty-
pollutant compounds, analyzed by the Internal standard method; 6 Indicates
labeled analogues of the other compounds, measured by Internal standard; and
7 Indicates the other compounds measured by Isotope dilution. This
numbering scheme permits Identification of the quantltatlon method and the
compound simultaneously, so that confusion over the quantltatlon method or
spelling of compound names 1s avoided.
All standards were prepared by a central laboratory to eliminate
variability from this source. The labeled compounds were furnished to the
central laboratory from EPA's supply of these compounds at the Sample
Control Center. The labeled compounds were from the same lot as those used
for analyses In EGD's analytical programs. The standards for the pollutants
were obtained from commercial sources and were analyzed by GCMS to certify
their purity. The standards and sample were prepared according to the "Task
Order for Preparation of Performance Evaluation Samples" (attached to this
report as Appendix C).
10
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Table II-l
SAMH.ES AND ANALYSES
Unlabeled (Native) Labeled (Isotope)
Sample
lOug/mt calibration
ZOug/mL calibration
50ug/mL calibration
IQOug/mL calibration
200ug/mL calibration
Performance response
ratio
Verification
Blank
Aqueous performanceY,
-'Standard — ~--~^
Test sample
Designation
CAL 10
CAL 20
. CAL SO
CAL 100
CAL ZOO
PRR
VER
BLK
APS
EPA
Compound
Concentration
lOug/rt.
ZOugM.
SOug/rt.
lOOug/M.
ZOOugM.
lOOug/H.
lOOugM.
0
lOOug/L
Various**
Compound
Concentrattoa
lOOugM
lOOugM
100ug/ML
lOOugM.
100ug/ML
100ug/ML
lOOugM.
iOOug/L
lOOug/L
lOOug/L
Operations
Injection
Injection
Injection
Injection
Injection
Injection
Injection
Extraction and
Injection
Extraction and
Injection
Extraction and
Injection
Fractions
Analyzed*
C
C
C
C
C
C
C
C
C
A. B
A . Acid, B . Base/Neutral, C • Combined fraction
Up to 30 pollutants prepared at 10-ZOOug/L by the central laboratory.
-------
STANDARD BUNK SAMPLE
S'
ORG/
> f
1 L REAGENT
WATER
1 L REAQENT
WATER
1L ALIQUOT
X J* J*
SPIKE 500 uL
OF 200 ug/mL
ISOTOPES
i
SPIKE TO
1.0 mt
OF STANDARDS
1
STIR AND
EQUILIBRATE
SPIKE 600 JJL
OF 200 pg/mL
ISOTOPES
•__^^_^
SPIKE SOO uL
OF 200 ug/mL
ISOTOPES
/ *
STIR AND
EQUILIBRATE
CANDARD OR BLANK
EXTRACT BASE/
NEUTRAL
kNIC
CONCENTRATE
TO 2-4 mL
f
STIR AND
EQUILIBRATE
1
EXTRACT BASE/
NEUTRAL
AQI IEOUS ORGANIC AQUEOUS
Ju
. EX'. R ACT ACID
i
CONCENTRATE
TO 2-4 mL
1
J,
CONCENTRATE
TO 1.0 mL
I
ADO INTERNAL
STANDARD
INJECT
CONCENTRATE
TOLOmL
^
EXTRACT ACID
\ *
CONCENTRATE
TO 1.0 mL
i
ADD INTERNAL
STANDARD
I
ADD INTERNAL
STANDARD
1
INJECT
I
INJECT
[10.1.1J
[10.1.2]
[10.1.3]
[10.1.4]
[10.21
[10.3]
[10.4^1
(10,4,10,5]
[11-3J
[11.41
Fi gure 11 -1 ROW Chart for Extraction/Concentration of Precision and Recovery Standard, Blank,
and Sample by Method 1625. Numbers in Brackets [ ] Refer to Section Numbers in the Method.
12
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Table 11-2
COMPOUNDS, COMPOUND NUMBERS, AND MASS/CHARGE RATIOS
COMPOUND
001B ACENAPHTHENE
005B BENZZOZNE
0088 1,2,4-TRICHLOROBEKZENE
009B HEXACHLOROBENZENE
012B HEXACHLOROETHANE
0168 BISI2-CHLOROETHYL>ETHER
020B 2-CHLORONAPHTHALENE
021A 2i4,6-TRICHLOROPHENOL
022A P-CHLORO-M-CRESOL
024A 2-CHLOROPHENOL
025B 1,2-OICHLOROBENZENE
026B 1,3-DXCHLOROBENZENE
027B 1,4-DXCHLOROBENZENE
0288 3,3'-DXCHLOROBENZXDZNE
031A 2,4-DXCHLOROPHENOL
034A 2,4-OIMETHYLPHENOL
035B 2.4-OINXTROTOLUENE
036B 2,6-OXNXTROTOLUENE
037B 1,2-DZPHENYLHYDRAZINE
039B FLUORANTHENE
040B 4-CHLOROPHENYL PHENYL ETH
0418 4-BROMOPHENYL PHENYL ETHE
042B BZS (2-CHLOROISOPROPYL) E
052B HEXACHLOROBUTAOIENE
053B HEXACHLOROCYCLOPENTAOZENE
054B XSOPHORONE
0558 NAPHTHALENE
OS6B NITROBENZENE
057A 2-NITRPPHENOL
058A 4-NZTPOPHENOL
059A 2.4-OZNITROPHENOL
060A 4,6-DZNZTRO-O-CRESOL
062B N-NZTROSODZPHENYLAMINE
064A PENTA'-HLOROPHENOL
065A PHENOL
066B BZS (2-ETHYLHEXYL1 PHTHAL
0688 OI-N-BUTYL PHTHAUTE
0698 DZ-H-OCTYL PHTHAUTE
0708 OZETHYL PHTHALATE
0718 DIMETHYL PHTHAUTE
072B BENZOfAJANTHRANCENE
073B BENZO(A)PYRENE
0748 BENZO(B)FLUORANTHENE
0758 BEHZOIK1FLUORANTHENE
0768 CHRYSENE
0778 ACENAPHTHYLENE
078E> ANTHRACENE
079E BEHZOI GHI(PERYLENE
080B FLUOREl.t
061B PHENANTHRi.NE
084B PYRENE
1648 2.2'-DIFLUOROBIPHENYL
164B 2,2'-DIFLUOPOBIPHENYL
2018 ACENAFHTHEHE-D10
EPA
PRAI
i
E
REF
:TION CMPD
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
'164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
) 164
1 164
CORRECT
M/Z
154
104
180
264
201
93
162
196
107
128
146
146
146
252
162
122
165
165
77
202
204
248
• 121
225
237
62
126
123
139
139
184
196
169
266
94
149
149
149
149
163
228
252
252
252
228
152
178
276
166
178
202
190
190
164
ALTERNATE
M/Z
.
,
,
,
,
.
f
,
#
,
f
•
•
^
f
.
,
•
.
.
m
9
f
^
f
.
^
f
f
+
f
.
,
f
f
f
9
f
9
f
f
,
f
f
,
.
.
.
.
^
.
m
.
13
-------
Table II-2 (Continued)
COMPOUND EPA • REF CORRECT ALTERNATE
FRACTION CMPO M/Z M/Z
205B BEVZIOINE-08 (RINGS-081 B 164 192
ZO&, l,i!,4-TRICHLOROBENZENE-D3 B 164 183
20?£ HEXACH-.CKOBENZENE-13C6 B 164 292
2:ZB HEXACHLCWSTHANE-1-13C B 164 204
218B BI5t2-CHVO«0£THYL)-Oa ETH B 164 101
220B 2-CHLORONAPHTHALENE-D7 B 164 169
221A 2,4.6-TRICHLOROPHE;ff>L-3,5 A 164 200 202
222A 4-CHLORO-3-HETHYLPHENOL-2 A 164 109
224A 2-CHLOROPHENOL-3.4,5.6-04 A 164 132
225B 1.2-DICHIOROBEHZENE-04 B 164 152 150
226B 1.3-OICHLOROBENZENE-04 B 164 152 150
227B 1.4-OICHLOROBENZENE-D4 B 164 152 150
228B 3,3'-OICHLOROBENZIOZNE-06 B 164 25A
231A 2,4-DICHLOROPHENOL-3,5,6- A 164 167 165
234A 2,4-DIMETHYLPHEHOL-3,5,6- B 164 125
23SB 2,4-DINITROTOLUENE-3.5,6- B 164 166
236B 2.6-OINITROTOLUENE-D3 B 164 167
237B 1,2-OIPHENYL-DlO-HYORAZIN B 164 82
239B FLUORANTHENE-D10 B 164 212
2408 4-CHLOROPHENYL PHENYL-D5 B 164 209
242B BISI2-CHLOROISOPROPYDETH B 164 131
252B HEXACHLORO-1.3-BUTAOIENE- B 164 231
253B HEXACHLOROCYCLOPENTADIENE B 164 241
254B ISOPHORONE-08 B 164 88
255B NAPHTHALENE-08 B 164 136
256B NITROBENZENE-05 B 164 128
257A 2-NITROPHENOL-3,4,5,6-04 A 164 143
258A 4-NITROPHENOL-2,3,5,6-04 A 164 143
259A 2,4-OINITROPHEMOL-3.5,6-0 A 164 187
260A 4.6-OINITRO-0-CRESOL-D2 A 164 200
262B N-NITROSODIPHENYLAniNE-06 B 164 175
264A PENTACHLOROPHENOL-13C6 A 164 272 274
265A PHENOL-2.3,4,5,6-D5 B 164 99
266B BIS(2-£THYLHEXYL)PHTHALAT B 164 153
268B 01 N-BUTY'. PHTHALATE-04 B 164 153
269B OI-N-OCTYL PHTHALATE-04 B 164 153
270B OIETHYL PHTHAUTE-3,4,5.6 B 164 153
C71B DIMETHYL PHTHALATE-3,4,5. B 164 167
272B BENZO(A)ANTHRACENE-012 B 164 240
273B BENZO(A)PYRENE-D12 B 164 264
274B BENZO(B)FLUCRANTHENE-D12 B 164 264
275B BENZO
-------
Table II-2 (Continued)
COMPOUND
318B BIS(2-CHLOROETHYL)ETHER
320B 2-CHLORONAPHTHALENE
321* 2.4,6-TRICHLOROPHENOL
322A P-CHLORO-H-CRESOL
324A 2-CHU3ROP; -fwL
325B 1,2-DICHLOROBENZENE
326B 1,3-DICHLOROBEHZENE
327B 1,4-DICHLOROBENZENE
3208 3.3--OXCHLOR08ENZIDXNE
331A 2.4-OICHLOROPHEMOL
334A 2,4-DInETHYLF-HEHOL
33SB 2,4-OINITROTOLUENE
336P 2,6-OINITROTOLUENE
337B 1.2-OIPHENYLHrDRAZINE
339B FUJORANTHENE
340B 4-CHLOROP.IENYL PHEMYL ETH
3428 BIS (2-CHLOROISOPROPYU E
3528 HEXACHLOROBUTAOIENE
353B HEXACHUJROCYCLOPENTADXEN*
3548 ISOPHOROHE
355B NAPHTHALENE
3S6B NITROBENZENE
357A 2-NXTROPHENOL
358A 4-NTTROPHENOL
359A 2>4-DIMITROPHENOL
360A 4,6-OINITRO-O-CRE5OL
3628 N-NITROS0DIPHENYLAHINE
364A PENTACHLOROPHENOL
365A PHENOL
3<6B BIS 12-ETHTLHEXYL) PK/HAL
3668 DI-N-BUTYL PHTHALATE
3698 DI-N-OCTYL PHTHALATE
3708 OIETHYL PHTHALATE
371fl OITCTWYL PHTHALATE
372» BEHZO(AIANTHRAtCENE
373H BENZOtAHTRENE
37 «B BENZOiBlFLUORANTHEtiE
375B BENZOIKIFIUORANTHENE
3768 CHRTSENE
377B ACENAPHTHTLENE
3788 ANTHRACENE
3798 BEMZOI6HI1PERYLENE
3808 FLUORENE
381B PHENANTHRENE
384B PTRENE
5028 BETA NAPHTHTLAHINE
5038 ALPHA PICOUNE
5048 DIBENZOTHIOPHENE
505B DIBENZCFURAN
506B N-OOOECANE
507B DIPHENTLAniNE
5088 OIPHENTLETHER
§098 ALPHA TERPINEOL
108 STTRENE
EPA
FRAC
1
I
REF
moN cnpo
218
220
221
222
224
225
226
227
22S
231
234
235
236
237
239
240
242
252
253
254
255
256
257
250
259
260
262 '
264
265
266
268
269
270
27i
272
273
274
275
276
277
278
279
280
281
284
164
16A
164
164
164
164
164
1 164
i 164
CORRECT
M/Z
93
162
196
107
128
146
146
146
252
162
122
165
165
77
202
204
121
225
237
82
128
123
139
139
184
198
169
266
94
149
149
149
149
163
228
252
252
252
228
152
178
276
166
178
202
143
93
184
168
57
169
170
59
104
ALTERNATE
It/Z
9
u
f
f
9
m
m
• ,
f
f
*
*
•
•
„
f
f
,
*
f
r
f
.
.
f
f
*
m
f
.
f
v
r
f
f
r
m
,
f
m
f
.
r
,
.
.
,
.
.
f
^
.
-------
Table II-2 (Concluded)
COMPOUND
SUB DI-N-BUTYL AMINE
SUB BIPHENYL
513B P-CYMENE
517B N-DECANE CIO
519B N-HEXAOECANE C16
SZ1B N-EICOSANE CZO
58SB N-TETRACOSANE CZ4
5Z6B N-TRIACONTANE C30
6028 Z-NAPHTHYL-D7-AHINE
603B Z-METHYLPYRIDINE-07
604B DIBENZOTHIOPHENE-Oa
6058 DIBENZOFURAN-08
606B N-OOOECANE-D26
6078 DIPHENYL-D10-AMINE
6088 OIFHENYL-010 ETHER
609B ALPHA-TERPINEOL-D3
6IOB STYRENE-e,3.4.5,6-05
611B DI-N-BUTYL-016-AHINE
6128 DIPHENYL-D10
613B P-CYMENE-014
6176 N-DECANE-022
619B N-HEXADECANE-D34
6218 N-EICOSANE-04Z
6Z3B N-TETRACOSANE-DSO
6268 N-TRIACONTANE-D6Z
7028 BETA NAPHTHYLAMINE
703B ALPHA PXCOUNE
70*8 DIBEKZOTHIOPHENE
70SB DIBENZOFURAN
706B N-OODECANE CtZ
7078 DIPHENYLAMINE
7088 OIPHENYLETHER
7098 ALPHA TERPINEOL
71CB STYRENE
71IB OI-N-BUTYL AMINE
7128 6IPHENYL
71SB P-CYMENE
7178 N-OECANE CIO
719B N-HEXACcCANE C16
7Z1B N-EICOSANE CZO
7238 N-TETRACOSANE CZ4
7Z6B N-TRIACONTANE C30
EPA
FRACTION
B
B
B
B
B
REF
CMPD
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
60Z
603
604
605
606
607
608
609
610
611
61Z
613
617
619
621
623
6Z6
CORRECT
H/Z
66
154
119
57
57
57
57
57
150
100
19Z
176
66
179
180
62
109
96
164
130
66
66
66
66
66
143
93
164
166
57
169
170
59
104
86
154
119
57
57
57
57
57
ALTERNATE
H/Z
16
-------
Fourteen laboratories, Including the central laboratory,* submitted
data. One laboratory submitted two complete sets of data on different
analytical equipment, which were treated as separate data sets for the
purposes of this study. For study purposes, each set of data was assigned a
letter code, from A to 0, for use 1n reporting study data. In this report
this code cannot be correlated with any of the data; I.e., the order of data
presentation Is not the same as the 11st of the laboratories in Table 1-1.
Three data formats were allowed for submissions: quantification
reports on magnetic tape, a hard copy version of the magnetic tape format,
or data sheets provided in the instructions. The tape format, specified in
"Quantitation Reports on Magnetic Tape," (attached to this report as
Appendix D) Is a specific data format which Is being developed by EPA for
computer-readable submission of GCMS quantltatlon reports. Fields In this
format are specified to allow the submission of complete information on the
quantltatlon process, including time and date extracted and analyzed,
method, column type and temperature program, reference compound, peak area,
retention time, mass-to-charge ratio, calculated amount, and units, plus
reference library Information. A specific definition of the data elements
collected in the study is given 1n "Effluent Guidelines Division (EGO) Data
Elements" (attached to this report as Appendix E). Participating
laboratories were encouraged to use the tape format to test this method of
data submission and to reduce coding time and transcription errors. Six
laboratories submitted data on magnetic tape and three laboratories
submitted data in hard copy equivalent to the tape format. The remaining
laboratories submitted data in the format shown in Figure II-2. Data
submitted on magnetic tape was extracted by the EPA Sample Control Center
(SCC). The remainder of the data was coded and verified by SRI, then joined
with the tape data to form the raw data set.
*
The central laboratory, S-CUBED, was exempted from the laboratory
evaluation, but submitted analyses for use in the method evaluation.
17
-------
Figure II-l
QUANTITATION'DATA SHEET FORMAT
18
-------
In addition to the quantltatlon reports, each laboratory submitted
library spectrum Information for each compound 1n the study. Including at a
minimum the five highest spectral peaks and any additional peaks greater
than I/10th the size of the highest peak. This data was not analyzed for
this report but may be subsequently analyzed.
A number of processing steps were then necessary to complete the data
set before analysis. In particular, laboratories were allowed to report
only detected compounds 1n their quantltatlon reports, and to report only
the Isotope dilution results (or Internal standard 1f Isotope dilution was
not possible). For study purposes, "not detected" entries were created for
compounds which were not reported, and parallel entries were created for
both the Isotope dilution and Internal standard methods for each compound.
A data frame was constructed by taking the list of compounds measured
1n this study (216, counting labeled compounds and the standard, and
counting compounds measured by Internal standard and by Isotope dilution
twice), and crossing 1t with the list of 15* laboratories and with the 11st
of 11 Injections. The data frame was then compared with the study data from
the raw data base so that (1) compounds 1n the frame that were not reported
by a laboratory were entered as "not detected" (peak area » 0), and (2)
references to compounds outside of the frame were removed. Frame records
for cases that were not reported (I.e. CAL 200 samples for one laboratory,
labeled analogues for another laboratory, and EPA, APS, and BLK samples for
a third laboratory, plus all records for compound 341, which had no labeled
analogue) were deleted so that no artificial entries were generated.
Table II-2 Includes the mass/charge value that was specified for use In
quantltatlon of the compound. Analyses submitted using the wrong ratio were
discarded; however, alternative mass/charge ratios were accepted for a few
compounds, because of the absence of background Interference 1n the prepared
Counting the two analysis sets from one laboratory, on different
equipment, as separate laboratories.
19
-------
study samples. Alternative rations are also listed In Table 11 -2. For the
EPA samples, type A (acid fraction) compounds measured In the B
(base/neutral) fraction and type B compounds measured 1n the A fraction were
discarded. (Type A compounds are those with a nominal fraction of A on the
compound list, except for phenol [65] and 2,4 dimethyl phenol [34], which
were treated as type B.)
Entries were created for both the Internal standard and Isotope
dilution method measurements for each compound, carrying the peak area and
retention time Information from whichever type of record was actually
reported. The correct reference compound numbers were also generated, being
compound 164 for all Internal standard records and the compound number minus
100 for Isotope dilution records.
20
-------
Ill CALIBRATION LINEARITY
The purpose of this chapter 1s to describe how statistical limits for
testing calibration linearity were developed, and how calibration curves
were constructed and applied to the data In this study. The concentration
amounts calculated and reported by the laboratories on the quantltatlon
reports were not reproducible because of variation 1n the calibration
schemes for different analytical Instruments and laboratories; and
therefore, were not used In this study. As described below, a uniform
calibration methodology was applied to the peak area measurements for each
compound at each laboratory to obtain quantified amount values for use 1n
this study.
Calibration Curves
In order to calculate the concentration of each compound In a sample, a
calibration curve Is applied to the peak area of the compound and of the
reference compound obtained from the gas chromatograph. This calibration
curve 1s constructed by the analysis of a series of calibration samples at
known concentrations.
The form of the calibration curve 1s defined by the specific analytical
method. For external standard methods, the calibration curve directly
relates the peak area (A) for the compound and the known concentration (C)
in the calibration sample by
A = fES(C) .
The Inverse of the calibration curve is applied to obtain the neasured
concentration of an unknown sample, i.e.,
C = f~* (A) .
21
-------
For Internal standard methods, the ratios of the peak areas and
concentrations to those of a reference compound are used for calibration,
I.e.,
A/Apef. fIS(C/Cref) .
and the unknown concentration 1n a sample Is constructed from the area ratio
and the known level of the standard spiked Into the sample by
Isotope dilution methods use a calibration formula parallel to that of
Internal standard methods, except the reference compound for each compound
Is Its labeled analogue, rather than a single Internal standard for all
compounds.
In estimating the calibration curve, a range of calibration samples are
used In order to evaluate the response of the Instrumentation over Its
performance range. Method 1625 specifies five calibration standards for
Isotope dilution; Method 625 specifies three calibration standards for
Internal standard methods. In this study, five calibration points were
obtained for each compound at each laboratory, at 10, 20, 50, 100, and 200
ug/mL. Because of the Inherent variability 1n the measurement of Individual
samples, the determination of the calibration curve Is subject to
measurement error. Therefore, the more calibration samples used 1n the
determination of the calibration curve, and the simpler the functional form
of the curve (1n terms of the number of parameters of the curve to be
estimated), the more accurate the calibration curve and sample measurements
will be. The simplest form of the response curve Is a proportional
("linear") response curve
f(x) = ax
Because this function represents the theoretical response of a perfect
instrument and contains only one parameter to estimate, this form of the
calibration curve would be preferred in any case where the calibration data
do not indicate nonlinearity in the response.
22
-------
The random variation 1n the calibration response can be assumed to have
a proportional error structure, I.e. for repeated measurements the area ratio
A/Aref (A for external standard) Is distributed around fls (C/Cref) (or
fgs (C) for external standard) as
fis(c/cref) (i * «)
where c has mean zero and variance
-------
Linearity Tests
Statistical goodness-of-f1t tests for a particular functional form are
constructed by a comparison of the residual error of the fitted function
("lack of fit") to an estimate of error of the function obtained from
replicate measurements at one value ("pure error") (see, for example, Draper
and Smith, pp. 33-42). For this study, goodness-of-fit linearity limits
were needed both for calibration of the study samples and for use In final
method specifications. The replicate calibration-type samples available 1n
this study were the CAL 100, VER, and PRR samples. The CAL 100 and VER
samples were constructed by each laboratory by diluting the prepared Isotope
and priority pollutant standards supplied for the study, to produce samples
containing 100ug/mL of priority pollutant and labeled compounds. The PRR
sample was obtained from the solution of 100ng/mL mixed standards provided
by the central laboratory. Therefore, the contents of the PRR sample should
be Identical to those of the CAL 100 and VER samples, though constructed by
a slightly different process. Because of the similarity of the PRR sample
to the CAL 100 and VER samples, and because the PRR results provide
additional data values (I.e. degrees of freedom) for estimation of pure
error, these three samples were considered as replicates, subject to a check
for bias relative to the CAL 100 and VER samples. Details of the tests
applied to the PRR sample are given In Appendix F.
The linearity test was constructed by calculation of the average
intralaboratory variation in the standardized response factor of the three
replicates across all laboratories in the study. Then, for each laboratory,
the coefficient of variation of the five calibration samples was calculated
and compared with the test specification. If the coefficient of variation
was smaller than the test criterion, a linear calibration was used for that
compound at that laboratory. If the linearity test was not passed, an
alternate method of calibration was used, as described in the "Log-Log
Calibration" section.
24
-------
Linearity Specification Calculations
For each record, Information was obtained from the record for the
appropriate reference compound, and the following ratios were computed (1f
their components were all reported):
Area ratio = peak area/peak area (reference)
Input ratio = Input concentration/Input concentration (reference)
Response factor = area ratio/Input ratio.
The area ratios (AR), response factors (RF), and Input ratios (IR) for
the CAL, VER, and PRR samples were then used to calculate the calibration
curves. In order to prevent undue Influences of outliers, a mild
prescreenlng of the response factors was done (a QSCREEN of each set of
seven values at level .0001; see Chapter IV). The 345 values (out.of
approximately 20,000 values screened) Identified were set to "missing" for
all future calculations. Then, appropriate limits for testing the goodness
of fit of a linear calibration were obtained. For each compound and -""""I
laboratory, the variance among NF1QQ* RF(vERlLand Wyp^-ww^e'terinlned,
and standardized by the square of the meur respDBSgrfactor foj*all seven
samples (the five CAL samples, PRR, and VER). This standardized
was then averaged across all laboratories, weighted by the degrees of
freedom* for each laboratory, to come up with an overall standardized
2
variance of response factors a , with OF total degrees of freedom. Then
for calibration, assuming the response is truly linear with proportional
error structure, the test for linearity used was to compare the coefficient
of variation of RF
1Q...
RF200 with
CV Limit = 100
Number of points (up to 3) minus 1. \°~r-
25
-------
where N 1s the number of nonmlsslng RF10... ^200' F *s the
-------
CALIBRATION LIMITS - INTERNAL STANDARD AND ISOTOPE DILUTION
COMPOUND
OEMOH DEGR
OF FREEDOM
CV IIMIT
is POIHTSI
CV IIHIT
14 POINTS)
CV LIMIT
(3 ponnsi
106 LIMIT
(5 POIHTSI
LOG LIMIT
14 POINTS!
LOG LIMIT
13 POINTS)
ro
•sj
00 IB
OOSB
008B
009B
OI2B
0188
020B
021 A
022A
024A
OZ5B
OZ6B
027B
0268
03IA
034A
035B
036B
0378
039B
04 OB
04 IB
042B
05 EB
OS3B
054B
05SB
OS4B
OS7A
OSflA
059A
060A
062B
064A
0»SA
066B
06 OB
069B
07CB
07IB
07ZB
07 JB
074B
07IB
076B
077B
07BB
0790
oaoo
OBIB
ACENAPHTHEHE
BENZIDINE
1,2,4-IRICHLOROBEHZEHE
HEXACIILOROBEIIZENE
HEXACHLOROETHAME
BISI2-CHLOROETHYDETHER
2-CIUORONAPHTHALENE
2.4,6-TRlCHLOROFHEHOL
P-CHLORO-M-CRESOL
2-CHLOROFHEIIOL
I 2-OICIILOROBEMZEIIE
I 3-DICHLOROBEIIZEIIE
1 4-OICHLOROBEHZEHE
3 J'-OICHLOROBEMZIOIHE
2 4-DICHLOROP1IEIIOL
t 4-OIMETHYLPHEIIOL
2 4-DIHITROTOLUEME
2 6-DIH1TROTOLUEHE
I 2-DIPHEMYLHYDRAZINE
FLUORAHTHENE
4-CMLOROPHEMYL PIIEHTL ETH
4-BROMOPHENYL PHEMYl ETHE
BIS 12-CHLOROISOPROPYL) E
NEXACHLOROBUUOIEHE
HEXACHLOROCYCLOPEMTAOIEUE
ISOPHOROHE
HAPHTHALEME
HITROBEMZEIIE
2-NITROFIIEIIOL
4-NITROPHEHOL
2,4-01111 TROPHEMOL
4r6-DJIIItnO-0-CRE90l
H-NITROSOOIPMEMYLAIUNE
PEMTACMLOROPHEKOL
PHENOL
BIS (2-ETHYLHEXUI PHTHAL
OI-H BUTYL PMIHALATE
OI-N-OCTYL PIUIIALATE
OIETHVL PIITHALATE
DIMETHYL PHTHALATE
BEMIOIAIAHIHRAIICENE
BEIIZOUIPIREHE
BEIIZOIBirtUORAmilEME
BEIirOIKiriUORANTIKKE
CHRY9EMI
ACEMAPMTHYLEMI
AMTMRACENI
BEMZOIGIIIIPERYLEME
tllAHdlRIIIC
27
24
27
27
23
26
22
26
21
26
27
27
25
20
27
27
26
27
25
27
26
14
22
26
24
27
27
II
24
23
20
26
13
27
26
27
27
27
26
27
26
27
26
25
27
24
27
27
>7
27
(i
20.
97.
31.
41.
19.
31.
10.
26.
26.
27.
32.
32.
33.
101.
20.
27.
45.
30.
25.
50.
33.
31.
55.
33.
32.
57.
27.
20.
29.
50.
100.
44.
II.
46.
29.
67.
47.
100.
35.
32.
65.
122.
106.
09.
93.
24.
34.
109.
29.
3S.I
*S:t
30.
102.
32.
43.
20.
32.
10.
27.
27.
20.
33.
33.
35.
105.
30.
20.
47.
40.
27.
60.
35.
32.
SO.
35.
33.
59.
20.
20.
30.
61.
112.
45.
12.
40.
30.
70.
49.
112.
37.
34.
67.
127.
no
93
97
25
36
114
30
32.1
100.4
34.7
45.9
21.5
34.9
20.1
29.3
29.1
30.2
35.9
35.5
37.2
112.3
32.0
30.1
St. 3
42.7
20.7
64.4
37.5
34.1
61.8
37.2
35.4
63.2
30.2
21.9
32.3
65.0
119.9
49.9
12.9
51.4
32.1
74.6
52.7
119.8
39.7
36.4
72.2
136.0
117.4
99.2
103.5
26.9
38.6
121.4
32.6
10.9
• .289
1.007
0.324
0.418
0.260
0.351
0.499
0.322
0.356
8.311
0.349
0.337
8.342
0.944
0.312
8.345
8.447
0.414
0.297
0.531
0.352
8.340
8.484
8.354
8.341
0.738
0.301
8.216
8.323
0.587
0.831
0.459
0.134
0.436
0.331
0.603
8.446
0.923
0.366
0.368
8.697
1.235
1.002
0.940
0.901
0.296
0.352
1.541
0.324
0.352
387
071
345
445
.276
.373
.531
.342
.379
.331
.371
.359
.363
.005
.332
.367
.475
.440
.316
.545
.375
.359
.514
.377
.363
.786
.320
.228
.343
.624
.885
.409
.141
.464
.352
.641
.475
.903
.390
.392
.742
.314
.152
.008
.959
.315
.374
.641
.3«
.375
344
198
307
490
309
.418
.592
.393
.423
.371
.416
.402
.407
.127
.372
.412
.532
.494
.353
.631
.420
.398
.575
.422
.406
.890
.359
.251
.304
.698
.991
.546
.156
.520
.394
.719
.532
.101
.436
.439
.031
.472
.290
.129
.074
.352
.419
.838
.386
.420
till
-------
Table III-l (Continued)
ro
oo
COMPOUND
201B ACENAPHTHENE-D10
205B BENZIDINE-08 IRINGS-D8)
208B 1,2,4-TRICHLOROBEMZENE-D3
209B HEXACHLOROBENZENE-13C6
2I2B HEXACHLOROETIIAIIE-1-13C
216B BIS(2-CHLOROETHYL)-D8 ETH
220B 2-CHLORONAPHTHALENE-D7
221A 2,4,6-TRICIILOnOFHEK'OL-3,5
222A 4-CHLORO-3-METHYLPHEMOL-2
224A 2-CHLOROFHENOL-3,4,5,6-04
225B I,2-DICIILOROBENZENE-D4
226B 1,3-DICHLOROBENZENE-D4
227B 1,4-DICHLCROBENZEME-D4
226B 3,3'-DICMLOROBEMZIDItlE-D6
231A 2,4-DICHLOROPHENOL-3,5,6-
234A 2,4-DIMETHYLPHEHOL-3,5,6-
235B 2,4-DIMITROTOLUEME-3,5,6-
236B 2.6-DIIIITROTOLUEHE-D3
237B 1,2-DIPHENYL-DIO-HYDRAZIH
239B FLUOPANTHEHE-D10
240B 4-CHLCROFHENYL PIIENYL-D5
242B BIS(2-CHLOROISOPnOPYL)ETH
252B HEXACHLORO-1.3-BUTAOIENE-
253B HEXACHLOROCYCLOPENTAOIENE
254B ISOPHOROME-08
255B IIAPHTHALEME-D8
256B HITROBENZENE-05
257* 2-HITROFIIEIIOL-3,4,5,6-04
258* 4-NITROFHENOL-2,3,5,6-04
259A 2,4-DINITROPHE>IOL-3,5,6-D
260A 4.6-DINITRO-0-CRESOL-D2
262B M-NITROSODIPHENYLAMIME-06
264A PENTACHLOROPHEI'OL-13C6
265A PHEIIOL-2,3,4,5,6-D5
266B BISI2-ETHYLHEXYLIFHTHALAT
268B OI-H-BUTYL PHTHALATE-D4
269B OI-H-OCTYL PHTHALATE-04
270B OIETHYL FHTHALATE-3,4,5,6
271B DIMETHYL PHTHALATE-3,4,5,
272B BEMZO(A>ANTHRACEHE-D12
273B BEMZO(A)PYREME-D12
274B BEIIZO(B)FLUORANTHENE-D12
275B BENZO(K)FLl<03ANTHENE-D12
276B CIIRYSENE-D12
277B ACENAFIITHYLENE-D8
278B AIITHRACEIIE-D10
279B BENZO(GHI)PERYLENE-D12
28CB FLUOREHE-D10
281B PHEIIAHTHPEIIE-DIO
284B PYREME-D10
HAFHTHE
ZIDIIIE
ACEHAFHTHEIIE
Benz J
DEHOI1 DEGR
OF FREEDOM
24
23
23
23
20
21
27
24
25
25
24
24
25
26
27
27
24
16
26
27
27
21
24
22
26
27
11
27
22
27
27
19
26
27
26
25
27
26
27
24
27
26
26
27
27
25
27
27
26
25
2*
CV LIMIT
(5 POINTS)
15.1
155.5
27.4
38.5
25.7
29.2
31.9
23.1
20.4
27.4
34.0
26.0
24.3
142.9
29.3
27.4
60. 7
43.7
20.9
79.6
29.7
30.4
28.2
94.3
36.7
23.9
20.7
19.0
76.4
49.3
42.7
26.5
41.5
58.5
70.8
50.1
148.9
29.8
59.1
94.2
152.6
132.9
108.4
107.4
25.2
31.9
119.6
38.3
28.5
95.7
,16:1
CV LIMIT
(4 POINTS)
15.8
161.8
28.6
40.1
26.7
30.4
33.2
24.0
21.2
28.5
35.4
27.1
25.3
148.8
30.5
28.6
84.0
45.3
21.8
83.1
30.9
31.6
29.4
98.2
38.3
24.9
21.4
19.8
79.5
51.3
44.5
27.6
43.2
60.9
73.7
52.1
155.1
31.1
61.6
98.0
159.0
138.5
112.9
111.9
26.2
33.3
124.6
39.9
29.7
99.7
.l*:!
CV LIMIT
13 POINTS)
16.8
172.0
30.4
42.6
28.3
32.3
35.4
25.6
22.6
30.3
37.7
28.8
27.0
158.4
32.5
30.4
89.3
48.0
23.2
88.5
32.9
33.6
31.2
104.3
40.7
26.5
22.6
21.1
84.5
54.7
47.3
29.3
46.0
64.8
78.5
55.5
165.1
33.1
65.6
104.3
169.2
147.3
120.1
119.1
27.9
35.4
132.7
42.5
31.6
106.0
,19:?
LOG LIMIT
15 POINTS)
0.173
1.117
0.266
0.379
0.255
0.31S
0.543
0.260
0.225
0.272
0.349
0.288
0.268
1.057
0.279
0.264
1.068
0.523
0.238
0.636
0.305
0.298
0.264
0.614
0.336
0.240
0.236
0.202
0.693
0.455
0.402
0.326
0.375
0.454
0.610
0.506
1.071
0.304
0.479
0.782
1.305
1.096
0.961
0.869
0.250
0.325
1.559
0.569
0.304
0.692
8:m
LOG LIMIT
(4 POINTS)
0.184
1.188
0.282
0.403
0.271
0.335
0.578
0.277
0.240
0.290
0.371
0.307
0.285
1.125
0.297
0.281
1.136
0.554
0.253
0.677
0.325
0.316
0.280
0.652
0.357
0.256
0.248
0.215
0.737
0.484
0.428
0.345
0.399
0.483
0.649
0.538
1.140
0.324
0.510
0.831
1.389
1.166
1.023
0.926
0.266
0.345
1.659
0.605
0.324
0.949
?:«*
LOG LIMIT
(3 POINTS)
0.206
1.328
0.316
0.451
0.302
0.374
0.648
0.310
0.268
0.324
0.415
0.343
0.319
1.260
0.332
0.315
1.271
0.616
0.284
0.759
0.364
0.353
0.314
0.729
0.400
0.287
0.274
0.241
0.823
0.543
0.480
0.385
0.447
0.541
0.727
0.602
1.277
0.3S3
0.571
0.930
1.556
1.306
1.145
1.037
0.298
0.386
1.859
0.670
0.363
1.062
f:ff«
-------
COMPOUND
DEMON DECK
OF FREEDOM
Table III-1 (Continued)
CV LIMIT
15 POIUtSI
CV UNIT
14 POINTS I
CV LIMIT
13 POINTS I
106 LIMIT
IS POINTS I
LOG LIMIT
14 ronnsi
LOG LIMIT
IS POINTSI
ro
1X5
306B
309B
31 ZB
1I6B
320B
321*
3Z2A
324 A
32SB
326B
327B
326B
331 A
334A
33SB
3J6B
337B
339B
3'(OD
3HZB
3S2B
3S3B
354B
3S3B
356B
357A
359A
359A
360A
36ZB
364A
36SA
3666
I68B
J69B
J/00
1710
1UB
37SB
374B
37IB
376B
177B
170D
1790
iaoB
IBIB
ID4B
loin
1.2»4-TRICHLOROBEHZENE
HEXACHLOROBEIIZENE
HEXACHLOROETHAHE
BISI2-CHLOROETHYLIETHER
2-CHLORCIIAPHTHALEME
2.4.6-TRieilLOROPHENOL
P-CHIORO-M-CRESOL
2-CIILOROPMENOL
1,2-OICIUOROBEMZEME
1,3-OICIIlOROBEMZENE
I .4-DICHLOROBENZENE
3,3'-DICHLOROBENZIDINE
2>4-DICHLOROPMENOL
2,4-DlMETHYLPIIEIIOL
2,4-DXMITROTOLUENE
2.6-OINITROTOLUENE
1.2'DIPIIEHYIIIYDRAZINE
HUORANTHEHE
4-CHlOROrHEHYl PIIENYL ETH
BIS 12-CHLOROISOPROPYLI E
HEXACHLORODUTAOIENE
HEXACIILOROCYCLOPEIITADIENE
ISOPIIOROHE
NAPHTHALENE
miHODEIIZEIIE
2-HITROPIIEItOL
4-NITROPHENOl
2,4-OIIIITROPHENOL
4,6-OIIUTRO-0-CRE30l
N'MITROSOOIPHEHYLAMINE
PEMTACIILOROPIIENOL
PHEIIOL
BIS II-ITNYUKXYL) PHTHAL
OI-H-DUTYl PMTMAIATE
DI-N-OCTYL PIUIUIATE
DIE1HVL PIUHAIA1E
DIMtTHVL PMTHALATE
BENZOIAIANTIIRAIICENE
BENZOtAIPtRENE
DdlZOIOIFLUDRANTMrNE
DKIIZOIKirLUORAHIIItNE
CMRY9IIII
ACENAPIHIIVLtllE
AWHRKlllt
BIII/IxnilllPIRYlEME
niriiMiiimriii
I'TRCIIE
an A IIM'IUHYLAMINE
26
24
20
22
It
26
2t
26
26
26
27
26
27
27
26
16
26
26
28
22
26
22
26
26
12
26
23
26
27
IS
28
28
27
27
26
28
26
25
27
26
24
26
26
27
26
26
28
26
27
25
23.
20.
26.
21.
10.
26.
19.
19.
34.
22.
22.
32.
21.
19.
79.
64.
19.
21.
21.
23.
16.
20.
34.
IS.
22.
20.
33.
25.
44.
26.
22.
29.
15.
14.
22.
16.
25.
25.
35.
ttt.
59.
22.
23.
19.
44.
79.
16.
61.1
53.0
it:t
24.
20.
27.
22.
II.
27.
20.
20.
36.
23.
23.
33.
22.
19.
62.
66.
20.
22.
21.
24.
19.
20.
35.
16.
23.
21.
35.
26.
46.
27.
23.
30.
16.
15.
23.
18.
26.
27.
36.
29.
61.
23.
24.
20.
46.
83.
17.
35.4
43.7
26.0
22.1
29.0
13.9
11.9
(9.6
21.3
21.6
38.5
25.2
25.0
35.4
23.4
21.0
87.5
70.7
2S.O
23.8
23.4
25.5
20.9
22.1
38.1
17.1
24.6
22.8
37.4
28.7
49.1
29.3
24.6
32.
17.
16.
25.
20.
28.
26.
39.
31.
65.6
24.6
25.4
22.0
49.1
66.4
16.3
37.7
67.6
56.7
.275
.250
.594
.222
.175
.341
.239
6.246
8.345
6.279
6.262
6.343
0.262
6.256
0.610
6.651
0.242
0.260
6.259
6.292
6.244
6.269
0.574
6.192
8.166
0.256
0.496
0.396
0.461
0.259
0.261
0.572
0.251
0.210
0.261
6.215
6.451
6.334
6.541
6.290
6.627
6.276
6.262
0.240
0.380
0.572
0.200
0.371
0.819
0.494
6.292
8.266
6.631
6.236
0.186
6.363
0.254
8.264
0.367
6.297
6.276
0.365
6.279
6.272
6.862
6.903
6.258
6.276
6.275
6.311
6.266
0.266
0.611
0.205
8.196
6.273
6.536
6.422
6.427
6.274
6.276
6.609
0.268
0.224
0.299
6.229
0.466
6.355
0.576
0.309
0.666
0.296
0.279
0.2S6
0.405
6.609
0.213
6.394
0.672
P.526
t.m
327
298
704
264
208
467
264
.295
411
.333
.312
.409
.312
.305
.965
.006
.269
.310
.309
.347
.291
.326
.665
.230
.217
.306
.592
.473
.478
.304
.311
.662
.300
.250
.335
.256
.538
.397
.645
.346
.746
.331
.312
.267
.453
.683
.238
.442
.977
.569
-------
COMPOUND
DEMOH DEGR
OF FREEOOH
Table III-l (Concluded)
CV LIMIT
15 POINTS)
CV LIMIT
14 POINTS!
CV LIMIT
(3 POINTS)
LOG LIMIT
15 POINTS)
LOG LIMIT
14 POINTS)
105 LIMIT
(3 POINTS)
S06B N-OODECANE 24
507B OIPIIENTLAHINE 20
508B DIPHEMYLETHER 25
S09B ALPHA TERPINEOL 25
5ICB STYRENE 24
SUB DI-M-BUTYL AMIHE II
5I2B BIPHENYL 25
513B P-CYMENE 26
5I7B M-OECANE CIO 26
5I9B N-HEXADECANE CI6 27
52IB N-EICOS/.NE C20 27
523B N-TETRACOSAME C24 26
526B N-TRIACCNTANE C30 26
602B 2-HAPHTHYL-07-AMINE 27
603B 2-HETHYLPYRIOINE-07 23
604B OIBENZOTHIOPHENE-06 22
60SB DIBEHZOFURAN-06 26
606B N-OODECMIE-D26 28
607B OIPHENYL-DIO-AMINE 18
606B OIPHENYL-OIO ETHER 23
6098 ALPHA-TERPIHEOL-03 24
6IOB STYREHE-2,3,4,5,6-D5 24
61 IB DI-H-DUTYL-018-AM1IIE 8
6I2B OIPHENYL-OIO 22
613B P-CYIIENE-D14 24
6I7B N-DECAIIE-D22 25
6I9B N-HEXAOECAHE-D34 27
62IB N-EICOSAHE-042 26
623B N-TETRACOSAHE-D50 28
626B H-TRIACONTANE-D62 26
702B BETA IIAFIITHYLAMIHE 27
703B ALPHA PICOLIIIE 24
704B OIBEIIZOTHIOPHENE 25
705B DIBEHZOFURAN 28
706B N-DODECANE CI2 26
707B OIPIIEMVLAMINE 20
706B DIPHEMYLETHER 24
709B ALPHA TERPINEOL 23
71CB STYRENE 26
7118 DI-N-BUTYL AMIME 8
712B BIPHENYL 22
7I3B P-CYI1EME 24
717B N-DECANE CIO 25
719B N-HEXADECANE CI6 28
72IB N-EICOSANE C20 28
723B N-TETRACOSANE C24 28
726B N-TRIACONTANE C30 28
29.6
26.9
31.
32.
32.
101.
20.
29.6
42.1
29.3
38.3
56.5
114.1
116.0
47.7
26.4
17.6
33.1
22.5
13.5
55.9
28.1
91.8
10.8
29.0
32.8
24.4
21.4
62.5
154.1
29.2
19.7
17.7
15.0
19.5
15.9
19.1
21.6
19.8
41.
18,
16.
28.9
19.4
24.8
26.5
32.9
30
28
32
33
34
104
21
30
43
30
39
58
lie
120
49
27.5
18.3
34.5
32.8
29,
34.
23.4
14.1
58.2
29,
94.
11.
30.
34.
25.5
22.
65.
160.
30.4
20.
IB.
15.
20.
16.
19.
22.
20.
42.7
19.3
17.0
30.1
20.2
25.9
27.6
34.3
35.6
.2
.3
.7
.8
.6
.5
.5
.7
.5
36
110
22
32
46
32
42
62
126
128.
52.
29.
19.
36.
24.
14.
61.
31.
99.
11.
32.
3&.
27.
23.7
69.3
170.7
32.4
21.8
19.6
16
21
17.6
21.2
23.9
21.9
44.7
20.5
18.1
32.0
21.5
27.6
29.4
36.5
0.310
0.270
0.337
0.368
0.352
1.004
0.265
0.320
0.436
0.339
0.404
0.527
0.964
0.959
0.441
0.296
0.203
0.319
0.259
0.140
0.572
292
101
119
272
302
254
233
539
111
369
225
217
180
227
176
241
267
0.261
1.309
0.224
0.166
0.365
0.241
0.271
0.266
0.411
0.329
0.286
0.359
0.391
0.374
1.058
0.282
0.340
0.464
0.360
0.430
0.561
1.026
1.021
0.468
0.315
0.216
0.339
0.275
0.149
0.609
0.311
1.153
0.126
0.290
0.321
0.270
0.248
0.573
1.183
0.393
0.240
0.230
0.191
0.241
0.187
0.256
0.284
0.277
1.371
0.238
0.178
0.389
0.256
0.289
0.283
0.437
1
0.369
0.320
.402
.438
.418
.167
.316
.381
.520
.404
.482
.629
1.149
1.144
0.524
0.352
0.241
0.380
0.3C6
0.167
0.681
0.348
259
0.141
0.324
0.360
0.303
0.277
0.643
1.324
0.440
0.268
0.258
0.215
0.270
0.209
0.287
0.318
0.310
1.497
0.266
0.199
0.435
0.287
0.324
0.318
0.490
-------
Table III-2
CALIBRATION LIMITS — EXTERNAL STANDARD
COMPOUND
001B ACENAPHTHEHE
005B BEHZIOIHE
008B 1,2.4-TRICHLOROBEHZEHE
009B HEXACHLOROBEHZENE
012B HEXACHLOROETHANE
016B BISI2-CHLOROETHYL1ETHER
020B 2-CHLORONAPHTHALENE
021A 2,4,4-TRICHLOROPHEHOL
022A P-CHLORO-M-CRESOL
024A 2-CHLOROFHENOL
0258 1.2-DICHLOROBENZENE
0268 1,3-OICHLOROBEHZENE
027B 1,4-OICHLCROBENZENE
028B 3.3'-DICHLCROBEHZIDINE
031A 2.4-DICHLOROPHENOL
034* 2,4-OIHETHYLPHENOL
0358 2,4-OIMITROTOLUENE
03SB 2.6-DIHITROTOLUENE
0378 1,2-DIPHEHYLHYORAZINE
039B FLUORANTHENE
0408 4-CHLOROPHENYL PHENYL ETH
0418 4-BROI10PHENYL PHENYL ETHE
0428 BIS (2-CHLOROISOFROPYL) E
0528 HEXACHLOROBUTAOIENE
053B HEXACHLOP.OCYCLOPENTAOIENE
0548 ISOFHOROHE
055B NAPHTHALENE
0568 NITROBENZENE
057* 2-NITROPHENOL
058* 4-NITROPHENOL
059* 2.4-OINITROPHENOL
060* 4,6-OIHITRO-O-CRESOL
062B N-NITROSODIPHENYLAMINE
064A PENTACHLOROPHENOL
065A PHENOL
066B BIS 12-ETHYLHEXYL) PHTHAL
0688 DI-N-BUTYL PHTHALATE
0698 DI-N-OCTYL PHTHALATE
070B OIETHYL PHTHALATE
0718 DIMETHYL PHTHALATE
0728 BENZOIA lANTHRAMCENE
073B BENZOfAIPYREHE
074B BENZOCBIFLUORANTHENE
075B BENZOdUFLUORANTHENE
0768 CHRYSENE
077B ACEIIAPHTHYLENE
078B ANTHRACENE
079B BENZO(6HI)PERYLENE
080B FLUORENE
0818 PHENANTHRENE
0841
1641
OEHOtl DEGR
OF FREEDOM
29
25
29
29
25
30
24
29
23
30
29
30
27
28
29
29
29
29
30
30
30
16
24
27
29
30
29
14
30
24
28
27
17
29
29
29
30
29
30
29
28
27
25
27
29
27
30
27
29
30
28
CV LIMIT
(5 POINTS I
49.1
101.8
58.5
52.4
41.1
63.5
37.1
57.5
52.4
61.3
53.7
55.1
54.2
95.1
55.4
52.6
61.1
58.5
49.0
59.
51.
87.
67.
51.
54.
68.4
43.3
48.6
62.2
69.2
79.7
60.5
49.4
70.6
60.5
77.9
56.4
92.4
56.2
52.0
65.8
108.3
94.2
66.0
91.7
46.2
42.7
120.4
50.4
52.1
it:i
CV LIMIT
(4 POINTS)
51.1
106.0
61.0
54.7
42.8
66.2
38.6
59.9
54.6
63.9
56.0
57.5
56.4
99.1
57.7
54.8
63.6
60.9
51.1
61.6
54.0
91.2
70.6
53.7
56.9
71.3
45.2
50.3
64.8
72.1
83.0
63.0
51.3
73.6
63.1
81.2
58.7
96.3
58.6
54.2
68.6
112.8
98.1
89.6
95.5
48.1
44.5
125.5
52.5
54.3
l?:o3
CV LIMIT
(3 POINTS!
54.4
112.7
65.0
58.2
45.5
70.5
41.0
63.8
58.0
68.1
59.6
61.2
60.1
105.5
61.5
58.4
67.8
64.9
• 54.4
65.6
57.5
96.6
75.1
57.2
60.6
75.9
48.1
53.2
69.0
76.6
68.4
67.1
54.4
78.4
67.2
66.4
62.6
102.6
62.4
57.7
73.0
120.0
104.3
95.3
101.7
51.2
47.4
133.6
55.9
57.9
73.8
54.3
31
-------
Table III-2 (Continued)
COMPOUND
DENOM OEGR
OF FREEDOM
CV LIMIT
(5 POINTS)
CV LIMIT
(4 POINTS)
CV LIMIT
13 POINTS)
201B ACENAPHTHENE-010 26
205B BENZIOINE-08 (RINGS-OS) 23
2088 1.2i4-TRICHLOROBENZEME-03 23
209B HEXACHLOROBENZENE-13C6 23
2I2B HEXACHLOROETHANE-1-13C 20
210B BISI2-CHLOROETHYL)-D8 ETH 22
220B 2-CHLORONAPHTHALENE-D7 28
221A 2,4,6-TRICHLOROPHENOL-3.5 25
222A 4-CHLORO-3-I1ETHYLPHENOL-2 27
224A 2-CHLOROFIIENOL-3,4,5,6-04 25
22SB l,2-DICHLOROBENZENE-D4 26
226B 1.3-OICHLOROBENZEME-D4 26
227B 1.4-OICHLOROBENZEHE-D4 27
2269 3.3'-OICHLOROBENZIOINE-06 25
231A 2,4-DICHLOROPHEMOL-3.5i6- 27
234A 2f4-DIMETHYLPHENOL-3t5t6- 27
235B 2.4-OINITROTOLUENE-3i5,6- 25
236B 2.6-DINITROTOLUENE-03 16
237B 1,2-DIPHENYL-D10-HYDRAZIN 27
239B FLUORANTHENE-010 20
240B 4-CHLOROFIIENYL PHENYL-05 26
242B BISC2-CHLOROIS3PROPYDETH 22
252B HEXACHLORO-li3-BUTAOIENE- 25
253B HEXACHLOROCYCLOPEHTAOIENE 22
2S4B ISOPHORONE-08 26
255B HAPHTHALENE-OB 27
256B NITRCBENZEME-05 12
257A 2-NITROFIIENOL-3,4,5,6-04 27
2S5A 4-NITROFHENOL-2,3,5.6-04 23
259A 2,4-OIMITROFHEIIOL-3.5i6-D 26
260A 4,6-DINITRO-0-CRESOL-02 27
262B N-IUTROSOOIPHENYLAMINE-06 20
264A PENTACHLCROPHENOL-13C6 28
265A PHEMOL-2>3i4,5,6-D5 27
266B BISI2-ETHYLHEXYDPHTHALAT 26
268B OI-N-BUTYL PHTHALATE-04 25
269B OI-N-OCTYL PHTHALATE-04 27
270B DIETHYL PHTHALATE-3,4,5,6 26
271B DIMETHYL PHTHALATE-3.4,5. 28
272B BENZOIAIANTHRACENE-012 25
273B BEMZO(A)PYRENE-012 26
274B BENZO(B)FLUORANTHENE-D12 26
275B BEMZOCK)FLUORAHTHENE-D12 26
276B CHRYSENE-012 27
277B ACEHAPHTHYLENE-D8 26
278B ANTHRACENE-010 25
279B BEIIZO(GtU)PERYLENE-012 26
280B FLUORENE-010 27
281B PHEHAHTHRENE-D10 28
284B PYRENE-D10 25
43.2
160.0
56.5
49.3
48.2
62.2
57.2
52.9
56.5
54.6
62.3
62.3
59.6
128.9
57.0
57
94
44
49
79
51
63
53
57
50
47
43
61
81
81
65
55
72.5
55.5
90.1
59.0
133.2
49.6
87.3
91.2
143.9
124.8
94.0
103.2
45.3
47.6
126.1
53.4
50.6
95.2
45.0
166.6
58.
51.
50.
64.
59.
55.
58.
56.
64.
64.
62.
134.
59.
60.
98.
45.
51.
82.
53.
65.
56.1
59.3
52.7
49.8
45.3
64.2
84.3
85.0
68
58
75
57
93
61
138
51.7
91.0
95.0
149.9
130.0
97.9
107.5
47.2
49.5
131.3
55.6
52.7
99.2
47.9
177.1
62.5
54.5
53.2
68.7
63.5
58.6
62.7
60.5
69.0
69.0
66.0
142.6
63.2
64.2
104.8
48.5
54.8
88.3
57.2
70.0
59.7
63.0
56.1
53.1
47.8
68.4
89.7
90.5
73.1
61.
80.
61.
99.9
65.3
147.7
55.0
96.9
101.1
159.5
138.4
104.1
114.5
50.2
52.7
139.7
59.2
56.2
105.5
.5
.5
.6
32
-------
Table III-2 (Concluded)
COMPOUND
506B N-DODECANE
507B OIPHEHYLAHINE
508B OmiEMYLETHER
509B ALPHA TERPIHEOL
51 OB STYP.EHE
SUB OI-H-BUTYL AHINE
SUB BIPHENYL
513B P-CYMEHE
517B N-DECANE CIO
519B H-HEXADECAHE C16
521B N-EICOSANE C20
523B N-TETRACOSAME C24
526B N-TRIACONTAHE C30
602B Z-NAPHTHYL-07-AMINE
603B 2-METHYLPYRIOINE-07
604B DIBEHZOTHIOPHENE-D8
605B OIBENZOFURAtl-08
606B M-OODECANE-026
607B DXPHEHYL-D10-AMINE
608B DIPHEMYL-010 ETHER
609B ALPHA-TERPIHEOL-D3
610B STYRENE-2,3.4,5>6-05
61 IB OI-ll-BUTYL-018-AMINE
6UB DIPHENYL-010
613B P-CYMENE-D14
617B N-OECANE-022
619B N-HEXADECAHE-034
621B N-EICOSANE-D42
6238 N-TETRACOSAHE-050
626B N-TRIACOHTANE-062
DEMON OEGR
OF FREEDOM
27
24
27
28
27
13
27
29
27
30
30
30
29
27
22
24
28
25
19
25
24
23
7
22
24
26
27
27
27
26
CV LIMIT
(5 POINTS)
54.2
38.5
53.6
63.5
65.0
63.6
49.2
57.0
63.5
54.2
56.4
70.0
92.1
74.2
48.0
53.4
47.6
50.4
44.0
45.0
71.4
50.8
101. 1
48.5
41.0
48.4
47.8
49.9
74.0
136.0
CV LIMIT
<4 POINTS 1
56.5
40.1
55.8
66.2
67.7
65.8
51.2
59.4
66.2
56.5
58.7
73.0
96.0
77.3
49.9
55.5
49.6
52.4
45.8
46.8
74.3
52.8
103.8
50.4
42.7
50.4
49.8
52.0
77.1
141.7
CV LIMIT
•3 POINTS)
60.1
42.7
59.4
70.5
72.1
69.6
54.5
63.3
70.5
60.2
62.6
77.7
102.3
82.3
53.0
59.1
52.8
55.8
48.6
49.8
79.1
56.2
108.4
53.6
45.4
53.6
53.0
55.3
82.1
150.8
33
-------
calibration curve was returned, as area ratio decreasing with increasing
input ratio was considered to be unacceptable. The goodness of fit of the
log-log calibration curve was then tested by comparing the residual root
mean sum of squares from the regression with
/ 9 \
Log Limit
=("LFN-2,DF<-95>)
2
where o[ Is the weighted average variance of the logarithms of the response
factors for CAL 100, PRR, and VER across all labs In the study; DF 1s the
2
number of degrees of freedom In the estimate of
-------
Table III-3
FREQUENCIES OF CALIBRATION RESULTS
LABCODE MESSAGE
FREQUENCY! o CALII i CALII 2 CALII 3 CALI|CURVATUR|CURVATUR|LIN CAL (LINEAR cI LOG-LOS (LOG-LOG I
IBRATION IBRATION IBRATIOH IBRATIOH |E < 1/4 IE <= 0 IREJ-LBL lALIBRATIlCALIBRATlFIT REJEl TOTAL
201
200
190
193
199
198
197
164
194
Ol
197
200
203
203
134
192
2693
A
B
C
D
E
F
G
H
I
J
K
L
H
N
0
TOTAL
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3 1
1 1
6 1
5 1
6 1
13 1
10 1
17 1
16 1
12 1
1 1
2 1
6 1
134 1
8 1
244
0 1
0 1
2 1
0 1
3 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
6 1
0 1
0 1
11
0 1
0 1
3 1
0 1
7 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
10
0 1
0 1
9 1
0 1
1 1
0 1
0 1
0 1
4 1
0 1
0 1
4 1
0 1
0 1
0 1
18
0 1
0 1
0 1
2 1
3 1
1 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
1 1
7
0 1
2 1
0 1
1 1
0 1
0 1
0 1
0 1
0 1
0 1
0 1
1 1
0 1
0 1
0 1
4
1 1
2 1
2 1
2 1
14 1
4 1
1 1
1 1
0 1
0 1
0 1
1 1
21 1
0 1
0 1
49
182 1
179 1
134 1
162 1
80 1
120 1
177 1
156 1
166 1
171 1
192 1
176 1
132 1
0 1
175 1
2204
13 1
12 1
37 1
18 I
41 1
55 1
6 1
10 1
6 1
12 I
4 1
16 1
18 1
0 1
5 1
255
2 1
4 1
3 1
3 1
44 1
5 1
1 1
0 1
0 1
2 1
3 1
1 1
20 1
0 1
3 1
91
-------
laboratory experiencing the particular calibration outcome. Overall, among
those situations for which sufficient data was available (I.e. four or five
calibration points), 84 percent were acceptable for linear calibration,
10 percent were rejected for linearity but had an acceptable log-log fit,
4 percent had unacceptable linear and log-log fits, and 2 percent were
labeled compounds rejected for linear fit (no log-log fit could be performed
because the Input ratio Is 1 on all samples).
The calibration results were then applied to all samples In the study,
with
Amount • Area Rat1° x Input Concentration (Reference)
W
for linear calibrations, and
Amount . (AreabRat1°) Y x Input Concentration (Reference)
for log-log calibrations. According to the study design, entries were
calculated for compounds by Internal standard, labeled analogues by Internal
standard, and compounds by Isotope dilution. Amount values were not
calculated by external standard methods.
Linearity Limits for Calibration
Across-compound summary percentlle statistics on the CV limits for
testing calibration linearity for each compound series are presented In
Table II1-4. The median number across compounds should be an acceptable
number to use for deciding whether to assume the proportional calibration
based on the average response factor or use a more detailed representation
of the response curve. This has been done both for 3 and 5 calibration
points, for each compound series.
36
-------
Table III-4
SUMMARY OF COEFFICIENT OF VARIATION LIMITS
FOR CALIBRATION LINEARITY
3 Calibration Points
5 Calibration Points
Methods/
Series
External Standard
External Std. (L.A.)
Internal Standard
Internal Std. (L.A.)
Isotope Dilution
zsth
X1le
57.7
54.8
32.1
28.8
21.5
Median
64.3
63.0
37.2
36.4
24.8
75th
*1le
74.8
89.7
64.1
84.5
32.4
Z5th
H!l
52.0
49.4
29.0
26.0
19.4
Median
58.0
57.0
33.6
32.8
22.5
75th
Jill
67.5
81.0
• 57.8
76.4
29.2
Note: L.A. » Labeled analogs.
37
-------
IV DATA SCREENING
After the amounts were calculated, they were screened for outliers,
both on a laboratory and Individual-point basis. First, the laboratories
were ranked and screened according to Youden's extreme rank method (see
Appendix 6) 1n order to Identify laboratories with significantly poorer
results than the majority of the study laboratories. For each compound, the
absolute deviations of each laboratory's amount from the median amount
across all laboratories for that sample were used for ranking. The rank
sums were taken across all eleven samples for the labeled compounds, and
across all samples except the BLK and EPA for unlabeled compounds. Each
compound was tested separately, and laboratories that were unable to report
one or more of the measurements were not evaluated for that compound.*
Table IV-1 presents the results by compound and laboratory. Laboratory
codes are listed for each column. A "." indicates that not all sample
values were reported or quantifiable for that compound at that laboratory.
A "+" indicates all data was present and the laboratory ranking results were
acceptable for that laboratory. "HI" Indicates the occurrence of an
unacceptably high proportion of extreme values reported by that laboratory
for that compound. The binomial probability at p = .05 of seeing the
observed number of compound rejections or greater for each laboratory was
computed. Laboratories with a binomial probability of less than .05 of that
many rejections or more were rejected overall and removed from the study.
Lab E, with 29 out of 89 rejections, was removed on this basis. Table IV-2
presents totals of the numbers of compounds, number of rejections, and
overall results.
One laboratory did not report CAL 200 and another did not report APS, EPA,
and BLK. These two laboratories, B and I, could not be screened in this
protocol. However, preliminary examinations excluding the missing samples
from the calculation indicated no problems with these laboratories.
39
-------
Second, the amount values were then screened Individually for
outliers. Two methods were applied: (1) a robust quantlle method based on
the median and Interquantlle distance (QSCREEN), and (2) Ferguson's method,
based on the sample kurtosls (FSCREEN). These methods are described In
Appendix H. Both screening methods were applied to each sample, across
laboratories on the logarithms of the amounts. QSCREEN was applied at level
.001 and FSCREEN at level .01 for reasons described In Appendix H. If fewer
than five laboratories reported detectable amounts of a compound, neither
screening procedure could be applied. A total of 501 points were Identified
as outliers by the quantlle method, and 251 points by Ferguson's method.
Out of 26,195 points screened, 508 points were Identified by at least one
method (approximately 2 percent). Amounts for which either method rejected
were set to missing. Details are given 1n Appendix H.
40
-------
Table IV-1
LABORATORY RANKING RESULTS
CMPD_NO A
00IB ACENAPHTIIENE 4
OOSB BENZIDINE 4
008B 1,2,4-TRICHLOROBENZENE 4
009B HEXACHLOROBENZEHE 4
012B HEXACHLOROETHANE 4
018B BIS(2-CHLOROETHYL)ETHER 4
020B 2-CHLOROHAPHTHALEHE 4
021A 2,4,6-TRICHLOROPHENOL 4
022A P-CHLORO-H-CRESOL 4
024A 2-CHLOROPHENOL 4
025B 1,2-DICHLOROBENZENE 4
026B 1,3-DICHLOROBENZENE 4
027B 1,4-DICHLOROBENZENE 4
028B 3>3'-DICHLOROBENZIDINE 4
031A 2,4-DICHLOROPHEMOL 4
034A 2,<*-DIMETHYLPHENOL 4
035B 2>4-OINITROTOLUENE 4
036B 2,6-DINITROTOLUENE 4
037B 1,2-DIPHENYLHYDRAZINE
039B FLUORAtlTHEME • 4
040B 4-CHLOROPHENYL PHENYL ETH 4
04IB 4-BROMOPHEHYL PHENYL ETHE 4
042B BIS (2-CHLOROISOPROPYL) E 4
052B HEXACHLOROBUTAOIENE *
053B HEXACHLOROCYCLOPENTADIENE 4
OS4B ISOPHDROME 4
055B NAPHTHALENE »
056B NITROBENZENE 4
057A 2-NITROPHENOL
058A 4-NITROPHENOL 4
059A 2,4-OINITROPHENOL 4
060A 4,6-DINITRO-O-CRESOL 4
062B N-NITROSODIPHENYLAMIHE
064A PEIITACHLOROPHEHOL 4
065A PHENOL 4
066B BIS (2-ETHYLHEXYL) PHTHAL 4
060B 0I-N-BUTYL PHTHALATE 4
069B DI-N-OCTYL PHTHALATE 4
070B DIETHYL PHTHALATE 4
071B DIMETHYL PHTHALATE *
072B BENZOIAIANTHRANCENE 4
0730 BENZOUIPYREIIE 4
074B BENZO(B)FLUORANTHEHE 4
075B BENZO(K)FLUORANTHENE 4
076B CHRYSENE 4
077B ACENAPHTHYLENE
0788 ANTHRACENE 4
0790 BEtlZOlGHIlPERYLENE 4
060B FLUOREME 4
081B PHENANTHRENE 4
00'
-------
Table IV-1 (Continued)
CMPD_MO A BC DE F 6 HIJKLN O
209B HEXACHLOROBENZENE-13C6 4 .4 44 4. ..4.44 4
212B HEXACHLOROETHAHE-1-13C 4 .4 4. .. 4.4.44
218B BIS(2-CHLOROETHYL)-08 ETH 4 . . 4 . 4 HI 4 ... 4 4
220B 2-CHLOROHAPHTHALEHE-D7 4 .4 4. 4. 4.4.44 HI
221A 2,4,6-TRICHLOROPHEHOL-3,5 4 .4 .. .4 4.4.4.
222A 4-CIILORO-3-METHYLPHEHOL-2 . .4 4. 44 4.4.44
224A 2-CHLOROPHENOL-3,4,5,6-D4 4 .4 4. 44 ..4.44
225B 1,2-DICHLOROBEHZEHE-D4 4 .. 4. 44 4.4.44 4
226B 1,3-DICHLOROBEHZEIIE-D4 4 .4 4. 44 ..4.44
227B 1.4-DICHLOROBEHZEME-D4 4 .4 4. .4 4.4.44
228B 3,3'-DICHLOROBEHZIDIHE-D6 HI . HI . HI 4 4 4.444. 4
231A 2,4-DICHLOROPHEHOL-3,5,6- 4 .4 4. 44 4.4..4
234A ?,4-DIMETHYLPHENOL-3,5,6- 4 .. 4. 44 4.4.44
235B 2,4-OINITROTOLUEHE-3,5,6- 4 .4 .. .4 4...4HI.
236B 2.6-DIHITROTOLUEHE-D3 4 .4 .. .4 ....4.
237B 1,2-OIPHEHYL-ClO-HYDRAZIN 4 .4 4. 44 4.4.4.
239B FLU03AMTHEHE-D10 4 .4 4 HI 44 4.4.44 4
240B 4-CHLOROPHEHYL PMENYL-D5 4 .4 4. 4* 4.4.44 4
2
-------
Table IV-1 (Continued)
CMPD_NO
321A
322A
324A
325B
3268
327B
32SB
331A
334A
335B
336B
337B
339B
340B
342B
352B
353B
354B
35SB
356B
357A
358A
359A
360A
36JB
364A
365A
366B
36 OB
36
-------
TabU IV-1 (Concluded)
CMPD.MO A BCDE FGHIJ KLH 0
5I3B P-CYMEHE » . 4 4 HI 4 4 4 . 4 ..» *
517B N-DECAHE CIO 4 .»«» 444.4 4 * * »
S19Q H-HEXAOECANE C16 « . * * HI * » * . » « «
52IB H-EICOSAME C20 4 .444 444.4 .«* 4
523B H-TETRACOSANE C24 » . 4 4 HI 4 4 4 . 4 »». «
526B H-TRIACOHTAIIE C30 * .44. 4*4.* . * .
602B 2-HAPHTHrL-07-AMINE 4 .44. ..*.» 4 . *
603B 2-METHYLPYRIOIHE-D7 . . 4 * . 44..* *** «
60^6 OIBEHZOTMIOPIIEIIE-D6 » ..». ».».. .t.
605B DIBEHZOFURAH-00 + .»». *»».» .*.
606B N-DODECAIIE-026 * .f4. « » » . HI » « + «
607B DIPIIEMYL-OIO-AMIIIE 4 ..4. .4..* .4.
608B DIPHEMYL-010 ETHER 4 .44. .44.4 .44
609B ALPHA-TERPIHEOL-03 4 .44. 44..4 4.4 HI
610B STYREME-2,3.4,5,6-05 + .44. 4*4.» .4*
61 IB DI-H-BUTYL-D18-AMIHE . ..4. ....4 4..
612B OirilEMYL-OIO . . « * ...
613B P-CYMEME-D14 + ..4. 44*.* .4
617B H-OECAME-022 4 .4.4 444.* .4
6190 H-HEXAOECAIIE-D34 « .44. 444.4 .4
62 IB H-EICOSAME-042 4 .44. 444.* .4.
623B N-TETRACOSAME-D50 » .44 HI 444.* «». 4
626B N-TRIACOHTAIIE-062 HI . » » HI 4 4 4 . 4 .
70CB BETA HAPHTHYLAMIHE » . . . 4 • . . 4 . « 4.«
703B ALPHA PICOLIHE 4 ..4. 44..* .*. 4
70<»B DIBENZOrHIOPIIEHE 4 ..4. 444.. 4.4*4
70SB DIBEHZOFURAN * .44. .44.4 44. 4
706B N-OODECAUE CI2* .44. .44.4 »4* 4
707B DIPHEMYUMIME t ..4. .»..4 #4. 4
708B DIPIIENYLETHER 4 .44. .4. .4 44* *
709B ALPHA TERPINEOL . * HI * *
710B STYRENE + .44. +* + .» *.* *
71 IB DI-H-BUTYL AMINE « *
712B BIPIIEHYL 4 .44. .44.4 .4..
713B P-CYI1EME + .44. 444.4 4.. 4
7I7B N-DECAtlE CIO* .44. ***.« *««
719B H-HEXADECAHE C16 * . * * . * * * . * * . HI «
72 IB M-EICOSAME C20 4 .44. **4.* «.* *
723B H-TETRACOSANE C244 .44. .44.4 44* *
726B M-TRIACOMTAME C30 4 4 * * * * 4 .
-------
Table IV-2
SUMMARY OF LABORATORY RANKING RESULTS
LAB
A
B
C
0
E
F
6
H
I
J
K
L
M
0
NUMBER
OP
CMPDS
185
0
153
167
69
151
17*
157
0
164
94
166
127
NUMBER
or
REJECTS
5
2
29
7
2
0
3
0
0
9
REJECT
LAB
*
HI
45
-------
V METHOD PRECISION AND ACCURACY
After the data set was recomputed and screened as described In the
preceding chapters, a number of statistical analyses were performed to
evaluate the performance of the proposed analytical method In relation to
current analytical methods. The method precision and accuracy were
calculated from the analyses of the aqueous performance standard (APS)
sample. This water sample, containing 100 ug/L of each of the compounds In
the study, was subjected to the complete method: extraction, Injection, and
calibration. Three measures of method performance were calculated with
respect to the analysis for each compound by Internal standard methods, the
corresponding labeled analogue by Internal standard, and the compound by
Isotope dilution:
(1) Percentage of cases with "not detected" or unquantlflable results.
(2) Method precision, calculated as the coefficient of variation of the
reported results:
100 Sn/5T (percent)
(3) Method accuracy, calculated as the relative absolute deviation of
the average measured concentration from the true value (100 ug/L):
100 [ * i0Q°° I (percent)
Here 7 and $n are the sample mean and standard deviation of the reported
analyses across laboratories (excluding "not detected" results). These
values are tabulated in Table V-l by compound. Figures V-l and V-2 show the
method precision and accuracy plotted versus compound number.
The median accuracy across all compounds Is 22.3 percent for Internal
standard, 26.1 percent for labeled compounds by Internal standard, and
7.6 percent for compounds by Isotope dilution. This considerable
47
-------
Improvement 1n the accuracy (bias) of the Isotope dilution method Is due to
the addition of the reference compounds (labeled analogues) prior to the
extraction process. This corrects for recovery problems during the
extraction, since both the compound and Its labeled analogue should be
extracted with similar efficiency.
The median precision across all compounds 1s 29.8 percent for Internal
standard, 33.4 percent for analogues by Internal standard, and 14.3 percent
by Isotope dilution. This Improvement presumably Is due to the closer match
between the response sensitivities of the compound and the analogue than
between those of the compound and the general reference standard.
Thus, the Isotope dilution methodology can be seen to be noticeably
more precise and more accurate than the Internal standard method. However,
there 1s also some Indication that Isotope dilution requires more care 1n
Its application, since the median proportion of laboratories that could not
quantify or detect compounds Is 15.4 percent by Internal standard,
8.3 percent for analogues by Internal standard, but 23.1 percent by Isotope
dilution. These problems may be expected to diminish as the laboratories
gain experience with the Isotope dilution method, and with Increased use of
direct computer submission of data on magnetic media, which should eliminate
transcription and coding as a source of error. Also, In practice,
Method 1625 specifies that If a laboratory 1s unable to quantify a compound
by Isotope dilution, then the laboratory should report the quantification by
Internal standard methods, thus limiting the nonquantltatlon to a minimum.
48
-------
Table V-l
PRECISION AND ACCURACY EVALUATION
AQUEOUS PERFORMANCE STANDARD
VO
COMPOUND BY INTERNAL
STANDARO
MEASUREMENT
LABELLED ANALOG BY INTERNAL
STANDARD
COMPOUND BY ISOTOPE
DILUTION
NOT NOT NOT
N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR-
LABS /QUANT SION ACY LABS /QUANT SION ACY LABS /QUANT SION ACY
7.
7.
7.
7.
7.
COMPOUND
001B ACENAPHTHENE
005B BENZIOINE
OOSB 1,2,4-TRICHLOROBENZENE
009B HEXACHLOROBENZENE
012B HEXACHLOROETHANE
016B BISI2-CHLOROETHYDETHER
020B 2-CHLORONAPHTHALENE
021A 2,4.6-TRICHLOROPHENOL
022A P-CHLORO-H-CRESOL
C24A 2-CHLOROPHENOL
02£.n 1,2-DICHLOROBENZENE
Oi'6B 1,3-OICHLOROBENZENE
027B 1,4-DICHLOROBENZENE
028B 3,3'-DICHLOROBENZIDINE
031A 2,4-OICHLOROPHENOL
034A 2,4-DIMETHYLPHENOL
0358 2,4-DINITROTOLUEHE
036B 2,6-OINITROTOLUENE
0370 1,2-DIPIIENYLHYORAZINE
039B FLUOR ANTHEHE
13
13
13
13
11
13
11
13
11
13
13
13
13
13
13
13
13
13
13
13
7.7
38.5
15.4
7.7
9.1
7.7
16.2
23.1
9.1
7.7
15.4
7.7
7.7
30.8
7.7
15.4
7.7
7.7
23.1
23.1
18.1
75.3
39.0
23.9
68.6
24.7
61.3
15.. 7
31.3
26.2
32.4
41.4
39.8
51.7
21.6
42.9
21.2
23.1
30.0
23.8
26.3
67.4
17.8
14.3
55.4
17.0
50.3
10.7
19.6
17.2
40.7
46.4
45.2
43.5
13.4
43.3
10.1
10.9
14.4
24.0
12
12
11
11
9
10
12
11
12
11
12
12
12
12
12
12
11
10
12
12
6.3
33.3
0.0
9.1
0.0
0.0
0.0
18.2
6.3
0.0
6.3
6.3
0.0
16.7
0.0
0.0
9.1
£0.0
6.3
6.3
26.9
76.2
51.3
36.6
71.7
32.0
34.4
42.6
16.1
23.9
44.0
50.7
46.5
61.6
25.4
36.0
36.0
21.4
26.2
20.6
27.5
56.2
46.0
19.5
53.9
26.1
31.1
2.1
14.0
22.6
44.4
53.5
48.9
36.4
17.6
36.2
19.4
12. b
24.0
23.1
13
13
13
13
11
13
11
13
11
13
13
13
13
13
13
13
13
13
13
13
23.1
36.5
30.6
30.8
27.3
30.8
18.2
30.6
18.2
23.1
23.1
23.1
15.4
23.1
7.7
23.1
36.5
33.5
15.4
15.4
10.3
54.2
6.8
6.3
66.4
20.5
37.2
26.6
14.1
9.0
10.6
21.7
24.1
16.1
7.7
14.3
11.8
11.2
39.0
18.6
2.7
1.4
5.7
6.1
62.3
5.3
32.4
11.3
0.0
3.1
3.7
13.9
10.3
9.6
6.0
2.2
9.0
6.1
27.1
13.0
(CONTINUED)
-------
Table V-l (Continued)
MEASUREMENT
COMPOUND BY INTERNAL LABELLED ANALOG BY INTERNAL COMPOUND BY ISOTOPE
STANDARD STANDARD DILUTION
NOT NOT NOT
N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR-
LABS /QUANT SION ACY .LABS /QUANT SION ACY LABS /QUANT SION ACY
a •/.•/.•/. 9 •/.•/.•/. 9 •/.•/.•/.
COMPOUND
040B 4-CHLOROPHENYL PHENYL tTH 13 7.7 24.5 20.2 12 0.0 30.9 26.7 13 7.7 19.4 12.5
041B 4-BROHOPHENYL PHENYL ETHE 13 7.7 20.2 16.0 ........
042B BIS (2-CHLOROISOPROPYL) E 10 10.0 16.1 25.0 10 10.0 17.0 29.9 10 10.0 9.3 5.7
052B HEXACHLOROBUTADIEME 13 7.7 53.4 44.8 11 0.0 61.4 50.9 13 15.4 31.5 15.9
053B HEXACHLOROCYCLOPENTADIENE 13 23.1 108.7 75.7 9 11.1 134.1 74.5 13 61.5 7.8 0.1
054B ISOPHOROME 13 15.4 23.8 16.8 12 8.3 14.6 19.2 13 15.4 13.8 9.7
-------
Table V-l (Continued)
COMPOUND
072B BEHZO(A)ANTHRANCENE
073B BENZOCAIPYRENE
074B BENZO(B)FLUORANTHENE
075B BENZOIKIFLUORANTHENE
076B CMRYSEHE
077B ACEHAPHTHYLENE
076B ANTHRACENE
079B BENZOIGHDPERYLENE
060B FLUORENE
081B PHENANTHRENE
084B PYRENE
502B BETA MAPHTHYLAHINE
503B ALPHA PICOLINE
504B DIBEIIZOTHIOPHENE
505B DIBENZOFURAN
506B N-DODECANE
507B DIPIIEHYLAMIME
508B DIPHENYLETHER
509B ALPHA TERPIHEOL
510B 5TYRENE
COMPOUND BY INTERNAL
STANDARD
MEASUREMENT
LABELLED ANALOG BY INTERNAL
STANDARD
COMPOUND BY ISOTOPE
DILUTION
NOT NOT NOT
N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR-
LABS /QUANT SION ACY LABS /QUANT SION ACY LABS /QUANT SION ACY
X
X
X
X
X
X
X
13
13
13
13
13
12
13
13
13
13
12
13
13
13
13
12
13
12
13
13
30.6
23.1
23.1
15.4
23.1
1'>.7
7.7
30. B
7.7
15.4
16.7
30. 0
30. 8
15.4
7.7
a. 3
23.1
a. 3
15.4
15.4
24.7
29.6
59.7
72.4
23.9
17.2
25.7
43.0
19.0
20.0
33.9
68.7
41.6
19.8
23.5
86.6
28. 8
17.8
14.7
46.9
18.6
16.1
28.2
37.1
21.9
22.3
28.2
13.0
18.7
25.0
28.7
36.5
33.2
23. 8
19.4
47.3
21.4
30.4
17.5
52.3
12
12
12
12
12
12
12
12
12
12
11
11
12
12
12
12
11
11
11
12
16.7
16.7
25.0
16.7
16.7
0.0
16.7
16.7
0.0
a. 3
9.1
27.3
16:7
16.7
a. 3
0.0
27.3
0.0
9.1
8.3
27.4
28.1
58.3
53.3
36.6
23.4
23. a
42.0
22.0
22.0
22.2
49.8
49.7
22.5
19.6
62.4
30.3
29.5
33.2
59.3
14.0
16.6
38.6
31.1
26.5
29.3
21.9
10.8
23.3
23.3
22.8
24.5
27.7
24.2
24. a
51.9
25.2
31.3
8.3
53.1
13
13
13
13
13
12
13
13
13
13
12
13
13
13
13
12
13
12
13
13
30.8
15.4
30. a
30. a
7.7
8.3
15.4
30. a
7.7
23.1
16.7
53.8
30.8
23.1
23.1
a. 3
38.5
25.0
53. 6
23.1
13.8
20.5
65.1
14.3
22.6
19.3
20.2
12.5
11.3
5.3
12.1
71.2
16.8
13.3
9.2
52.2
20.7
8.9
23.0
25.4
5.5
11.9
43.1
8.0
5.9
14.7
2.0
7.6
3.4
5.0
7.6
26.6
5.2
9.2
7.6
21.4
10.5
5.6
0.6
10.7
I CONTINUED I
-------
Table V-l (Concluded)
in
r\>
COMPOUND
51 IB DI-N-BUTYL AHINE
SUB BIPHENYL
513B P-CYMENE
517B N-DECANE CIO
519B N-HEXAOECANE C16
521B N-EICOSANE C20
5Z3B N-TETRACOSANE C24
526B N-TRIACONTANE C30
COMPOUND BY INTERNAL
STANDARD
MEASUREMENT
LABELLED ANALOG BY INTERNAL
STANDARD
COMPOUND BY ISOTOPE
DILUTION
NOT NOT NOT
N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR- N OF DETECT PRECI- ACCUR-
LABS /QUANT SION ACY LABS /QUANT SIGN ACY UBS /QUANT SION ACY
•/.•/. x
i
13 84.6 68.6 95.1
13 15.4 27.9 26.9
13 15.4 45.4 48.5
12 8.3 80.1 64.0
13 23.1 27.5 22.0
13 7.7 24.0 16.1
13 23.1 25.0 11.0
13 23.1 28.1 15.5
7.
7.
7.
11 72.7 126.1 73.9
11 63.6 14.4 41.7
12 0.0 67.5 53.6
12 6.3 38.2 39.4
12 0.0 38.0 28.7
12 8.3 25.8 23.4
12 25.0 23.3 20.5
12 16.7 22.5 21.8
X 7. 7.
13 84.6 137.0 27.8
13 46.2 12.3 5.2
13 30.8 9.9 3.3
12 25.0 28.5 29.4
13 15.4 14.6 14.5
13 7.7 33.6 22.1
13 30.8 8.6 5.6
13 7.7 20.5 12.3
-------
Figure V-l
METHOD PRECISION, APS SAMPLE
Compound by Internal Standard
Labelled Analog by Internal Standard
Compound by Isotope Dilution
in
CO „
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M«tll»ttlt»UlUlMSSS5I»SM«M4*>»»r?»7eMHMIMIIIIIII>tt
-------
.Figure V-2
METHOD ACCURACY, APS SAMPLE
Compound by Internal Standard
Labelled Analog by Internal Standard
Compound by Isotope Dilution
•
•
• •
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• *
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-------
VI QUALITY CONTROL LIMITS
Another Important use of the data developed in the study 1s the
calculation of quality control limits for testing and screening of priority
pollutant analyses submitted to EPA for use 1n future analytical programs.
These quality control limits were calculated by constructing statistical
prediction Intervals for future observations of a quantity of Interest using
statistical estimates determined In this study.
To help ensure the Initial and ongoing quality of analytical
measurement by Isotope dilution and Internal standard methods, a number of
quality control limits are provided In this section. These limit values
were developed for application In the quality control procedures being
developed by EPA for final specifications of these methods. The limits are
calculated using the results of a variance components analysis of the
measured amounts on two subsets of the data: the calibration-type samples
(CAL 100, VER, and PRR) and the extracted samples (BLK, APS, and EPA). The
Inter- and Intralaboratory variance components of the logarithms of the
amounts were estimated (s| and S?) along with the logarithmic mean response
(M) by maximum-likelihood techniques. Details of the variance components
procedure are given In Appendix I.
The measured concentrations of these compounds have been assumed to
follow a lognormal distribution throughout the analysis described 1n this
section, as well as In other sections of this report. The lognormal
distribution has been frequently and effectively applied to model pollutant
concentrations, Including other effluent guidelines priority pollutant data,
and agrees with the physical Interpretation of nonnegative concentration
values. Limits derived from this assumption are always nonnegative.
Descriptive and summary statistics calculated for this data support the
assumption of lognormal1ty.
In other EPA method validation studies the compound-specific
performance specifications have usually been determined at individual test
55
-------
levels of p « .05 (I.e. based on 95 percent confidence limits for a single
future observation). Using such specifications, each compound measured
would have a 5 percent chance of falling outside Its QC limit.
Because of the large number of compounds (154, Including labeled
analogues) Involved 1n the quality tests for Method 1625A, It would be
extremely likely that one or more Items on each test would be failed simply
by random chance If the tests were all performed at Individual test levels
of p - .05. It was deemed desirable, Instead, to specify test limits such
that the global test level (I.e. the chance of falling on one or more of the
compounds out of the whole list) was held to 5 percent. Two approaches were
suggested: (1) reduce the Individual test level, and (2) allow retesting of
those Items that failed and only Indicate an out-of-control process If the
same Item falls twice. These remedies can be applied In conjunction. For
Instance, the start-up test, described below, Involves both precision and
accuracy testing for a total of 308 Items on the test. Testing at an
Individual level of .01 and allowing one retest of the failed Items will
achieve an overall level of 5 percent. Details of the binomial calculations
for these considerations are given In Appendix J.
Start-up Test Limits
When a laboratory begins operation, It 1s required to perform four
replicate extracts and analyses of prepared samples containing 100 ng/L of
all compounds. The arithmetic average and standard deviation of the four
values given by
4
* 1=1 j
4
S = ^ E (Xi - 7)2 ,
are then cooputed for each compound.
56
-------
ELEMENT NAMEt CONCENTRATION/DILUTION FACTOR
Definition: The concentration or dilution ratio of the sample fraction or spike before
analysis.
Input Type/Length
Quantitatlon Report X( 11)
As Stored Internally 9O)V9(3)
Uhltof MMSUT*
Pure number.
Edit Criteria:
Format: two numbers separated by a colon, the first is the pre-ex tract ion/dilution
amount; the second is the post extraction/dilution amount, ie XXXXX:XXXXX;
Example: 1000:1 means that an initial 1000 mL volume of sample was concentrated to
1 mL extract; 1:100 means that an inital volume of sample was diluted with 99 parts
reagent water.
Acceptable range: 10000:1 to 1:10000.
NAiNA - used for calibration standards
Use: When a semi-volatiles fraction (acid or base/neutral) is extracted, the normal
volume of sample is 1 liter (1000 mL). The extract is normally concentrated to a
volume of 1 mL. The units on the quantitation report for semi-volatiles is UG/ML.
Multiplying these units by 1000 mL/L, and dividing by the concentration ratio (1000/1)
yields the final volume in ug/L. Mathematically, the concentration factor (CF) can be
expressed in the following equation:
Csamp (ug/L) = Cext (ug/mL) x iOOC (mL/L) / CF
for our example,
-------
ELEMENT NAME: CONCENTRATION/DILUTION FACTOR (Continued)
•
Edit Criteria (continued):
Csamp (ug/L) = Cext (ug/mL) x 1000 (mL/L) / 1000
Similarly, for volatiles,
Csamp (ug/L) = Cdil samp (ug/L) / DF
For a dilution factor of 1:10,
Csamp (ug/L) = Cdil samp (ug/L) / (1/10)
and C samp (ug/L) = 10 x Cdil samp (ug/L)
As can be seen, the concentration and dilution factors are critical to computation of
the correct concentrations in water.
-------
Limits for 7 required to ensure method accuracy are given In
Table VI-1. The limits for 7 were calculated by
exp[(M + \ S* - | nj) * td(l - £) sf * "A/4 * SE/L * SA/N + 3Z S*/(M-L) ] ,
22 22
where M, SjJ, and S£ are the variance components results; nA - exp(SA) -1;
L Is the number of laboratories 1n this study; N Is the total number of
observations of the compound In the set of samples for this study; td Is
the Inverse cumulative t distribution with d = m1n (N-L, L-l) degrees of
freedom; and p Is the Individual test level. The derivation of this formula
Is given In Appendix K. Values are given for p levels of .05 and .01 for
labeled compounds by Internal standard and for compounds by 'Isotope
dilution. In order to achieve an overall significance level of 5 percent on
the precision (described below) and accuracy tests, the Individual compound
limits would be based on an Individual significance level of .01, and one
retest of those compounds that failed the first round would be allowed (for
discussion of multi-round testing see Appendix J).
Table VI-1 also gives upper limits for S to ensure method precision.
The limits for S were calculated by
exp(M) QU-p. SA) K(l-p.d) ,
where Q(q,s) is the qth quantile of the distribution of the standard
deviation of four lognormal variates with logarithmic mean 0 and logarithmic
standard deviation s, and K(q,d) is
C3(q)/3
where F 1s the Inverse cumulative of an F distribution, C is the inverse
cumulative of a chi -squared distribution, and d is the degrees of freedom in
the estimate of SA, e.g., N-L. The derivation of this formula and the
details of the computer simulation used to evaluate Q are given in
Appendix L. Values are given at individual test levels of .05 and .01. To
obtain an overall 5 percent level over all compounds, In conjunction with
the start-up accuracy test, the .01 individual levels would be used with one
retest allowed for compounds that fail the first round.
57
-------
Table VI-1
START-UP LIMITS FOR ACCURACY AND PRECISION
... ....———„ SEKI:S»LI
CON POUND
231 B ACENAPHTHENE-010
233 B BENZXOXNE-08 (RXN6S-08)
2381 1*Z*4-TRXCHLOROBENZENE-03
209 B HEX*CHLOROBENZENE-13C6
21 2 B MEX*CNLOROETM»NE-1-13C
21 SB 6XSC2-CHLOROETNVO-08 CTN
220 B 2-CHLORON*PHTH*LENE-07
221 » 2»4«6-TRZCMLOROPHEmL-3«3
222* 4-CMLORO-3-NETHYLPNENOL-2
223 B 1*2-OXCNLOROBENZENS-D4
226 B 1»3-OXCMLORORENZENE-04
227 B 1*4-DICHLOR08ENZENE-D4
228 B 3»3*-DtCHLOROBtNZIOIN(-0<
231 * 2»4-DXCMLOROPHENOL-3«S«6-
234* 2»4-DXNETHTLPHENOL-3«5«4-
2338 2s4-DINXTROTOLUENE-3«S«4-
23« B 2«6-OXNXTROTOLUENE-D3.
2378 1s2-OXPMENVL-010-HTDRAZZN
2398 PLUOttNTHENE-OlO
2408 4-CHLOROPNENTL PNENTL-05
2428 BXSC2-Cm.OROXSOPROPTL)ETM
2328 NeX*CHLORO-1»3-BUT»OlE»E-
2S3B HEX*CMLOROCTCLOPENT*OXENE
2348 XSOPMORONE-08
233 B N«PMTM*LENE-08
216 B NXTROBENZENE-03
237* 2-NITROPMENOL-3,4*5«4-04
238* 4-NXTROPHENOL-2«3»5«4-04
239* 2«4-OXNXTROPHENOL-3»S*4-0
260* 4«6-OXNXTRO-0-CRESOL-02
212 B N-NXTROSODXPHENTL*NINE-06
264* PENTKHLOROPNENOL-13C6
263* »MENOL-2s3*4«5«6-05
2641 BXS(2-ETNTLHEXTL)PHTH*L«T
2188 OI-N-BUTTL PNTN*L*TB-04
269 B OX-N-OCTT1 PHTH*L*TE-04
2708 OZETHTL PHTN«L*TE-3»4*5«4
271 B DIMETHYL PMTM«L«TE-3»4,3»
2728 8ENZO(*>*NTNR*CCNE-012
2738 BENZO(A>PTRENE-012
274B 8ENZO(B)FLUORANTHENE-012
273 B BENZOCK>PLUOR*NTMENE-D12
2768 CHRTSENC-D12
2778 *CEN«PHTHTLENE-08
278 B ANTMRICENE-010
2798 BENZOCCHZ)PERTLENE-012
2BOS FLUORENE-010
281 B PHENANTNRENE-010
2S4B PTRENE-010
6328 2-HAPNTHTL-07-4NINE
633 B 2-NETHT1.PTIIIOXKE-07
6041 OIBE1ZOTMXOPHENE-OS
603 B OXJENZOFUR*N-08
6068 N-OOOECANE-026
6071 OIPHENTL-010-AHINE
638 B OIPHENTL-010 EThER
639 B *L»ttl-TERPINEOL-03
6108 STTRENE-2*3«4*3«6-03
611 B OI-N-BUTTL -018-»NINE
' 61 28 OZPMENYL-010
613 B P-CTNEME-014
61 7 B N-OECANE-022
619B »-NEZ«OEC«NE-034
621 3 N-«ICOS*NE-042
6238 H-TET««COS»»e-050
6268 tt-TRI*CONT«NE-962
•CLLEU •••
*CCUR.
P .OS
LOME*
44
I-
22
47
10
38
39
34
38
4j
21
If
22
13
47
22
32
94
40
44
49
44
13
0
37
36
33
49
23
33
48
62
48
29
42
32
20
13
4
34
43
19
23
43
47
41
41
38
33
41
2
18
56
33
12
37
43
33
• 14
1
42
11
13
46
43
37
37
lot* »T mi
•CCUR.
P .05
UPPER
ISO
1034
143
172
202
144
131
144
134
130
141
133
133
284
133
133
170
144
134
129
131
119
182
601
114
122
144
121
240
208
184
109
163
130 -
153
T43
231
159
265
204
142
314
303
145
120
147
193
114
111
137
969
224
112
114
187
148
123
1*8
T66
1472
110
200
174
130
135
156
174
ennui. IT*
ACCUR.
P .01
LOWER
38
0
13
34
5
29
30
43
30
34
14
13
13
r
38
13
22
44
31
34
40
33
8
0
49
28
18
41
14
22
34
34
37
21
32
a
12
9
2
25
35
11
15
33
39
31
29
51
45
32
0
11
48
47
7
27
34
22
8
0
28
4
8
37
34
27
27
HDIWD — —
»CCUR.
P .01
UPPER
147
4987
212
228
400
194
148
183
174
142
212
203
193
342
144
228
243
184
173
141
141
149
314
3458
133
137
245
143
398
308
247
124
212
210
205
193
383
240
640
298
181
577
514
219
144
194
268
131
130
174
3891
380
130
136
331
206
135
292
281
166102
165
359
298
162
172
211
242
PREC.
P .03
29
139
41
39
51
26
31
34
74
18
27
35
33
34
22
17
28
44
27
27
40
21
44
33
18
30
20
18
117
48
48
28
38
101
22
18
33
53
44
31
19
107
79
SO
24
37
34
33
31
23
24
88
24
25
37
32
28
34
33
197
30
47
48
35
24
22
31
PREC.
P .01
38
249
37
81
77
33
41
47
111
24
33
48
48
80
28
22
37
59
33
33
32
27
43
40
23
39
28
23
188
44
44
37
49
141
29
23
44
78
108
41
24
168
114
69
31
49
45
43
40
29
33
138
31
31
53
42
37
48
49
456
43
67
70
46
34
28
41
58
-------
Table VI-1 (Concluded)
COM FOUND
3318 ACENAPHTNENE
30$S BCM2IOINE
308» 1*2*4-TRXCHLOROBENZENE
3098 HEXACHLOROBENZENE
3128 HEXACHLOROETHANE
3188 BXSC2-CHLOROETHTDETHER
3208 2-CHLORONAPHTHALENE
321* 2«4*6-TRXCHLOROPHENOL
322* P-CHLORO-H-CRESOL
324* 2-CHLOROPHtNOL
3218 1,2-DXCHLOROBENZENE
3268 1«3-OXCHLOROBENZENE
3271 1,4-OXCHLOROBENZENE
3288 3*3*-DICHLOROBENZXOXNE
331 * 2«4-DXCHLOROPHENOL
334* 2«4-OXNETHYLPHENOL
333B 2*4-OXNXTROTOLUENE
33A8 2«6-OXNXTROTOLUENE
337B 1«2-DXPHENTLHTORAZX1IE
339B PLUORANTHENE
340B 4-CHLOROPHENYL PHENTL ETH
3*2B BIS C2-CHLOROXSOPROPTL) E
352B MEXACHLOR08UTAOXENE
3S3B HEXACNLOROCVCLOPENTAOXENE
354 B XSOPHORONE
3SSB NAPHTHALENE
3S«B MXTROBEHZENE
317* 2-NXTROPHENOL
318* 4-NXTROPHENOL
359* 2»4-OXNXTROPHENOL
360 A 4«6-OXNXTRO-0-CRESOL
362B N-NXTROSODXPHENYLANXNE
364* PENTACHLOROPHENOL
345* PHENOL
366B BIS (2-ETHYLHEXYL) PHTH*L
36BB OX-N-BUTTl PHTN*L«TE
389B OX-N-OCTYL PHTHALATE
370B OXETHTL PHTHALATE
371 B OXNETHTL PHTHALATE
3728 BENZO(A)ANTHRANCENE
373B BENZO<*>PTRENE
3748 BEHZOCB)PLUORANTHENE
3758 BENZOdOPLUORANTHENE
3768 CHRTSENE
3778 ACENAPHTHTLENE
378B ANTHRACENE
3798 BENZO(CHX)PERTLENE
3SOB PLUORENE
381B PHENANTHRENE
3848 PTRENE
7028 SETA NAPHTHTLANXNE
7338 ALPHA PICOLXNE
7348 OX8EMZQTHX3PHENE
7058 OX8ENZOPURAN
7068 N-OCOEC«NE C12
7978 OXPNENTL«NINE
7088 OXPHENTLETHER
7098 *LPHt TERPINEOL
71 OB STTRENE
7118 OX-N-BUTTL «HINE
7128 8XPHENTL
7138 P-CTHENE
7178 N-OECANE C10
7198 N-HEXAOECANE C16
7219 N-EXCOSANE C20
7238 N-TETRACOSANE C24
7268 N-TRIACONTANE C30
'COHFOUNC
ACCUR.
P .05
LOME*
85
28
89
95
38
67
63
71
83
85
81
75
72
78
91
71
84
87
64
81
84
88
64
80
85
87
83
85
72
79
84
76
83
82
81
86
86
86
85
76
74
50
67
70
80
69
81
87
96
84
23
69
87
91
50
-71
89
57
66
84
84
34
89
67
87
73
IS BT I3DTO
ACCUR.
P .03
UPPER
123
295
125
118
515
161
259
169
121
124
131
168
164
131
123
133
140
129
234
134
148
127
198
124
140
128
132
128
127
122
122
122
128
118
185 '
146
145
170
164
145
165
350
124
157
161
148
141
123
115
137
513
129
"136
126
260
167
125
172
178
131
' 127
141
146
20«
127
168
FE UILUTIO
ACCUR.
P .01
LOHER
79
16
82
90
21
53
46
39
76
79
73
63
61
68
85
42
75
80
49
71
75
81
51
49
76
80
69
78
62
72
77
65
76
77
69
74
77
75
74
65
62
32
39
59
69
58
72
81
93
76
10
59
?9
85
35
SJ
82
42
33
73
76
24
80
S3
80
61
ACCUR.
P .01
UPPER
134
518
13*
124
960
196
337
205
131
135
146
201
194
174
131
153
138
141
• 308
177
166
138
231
144
136
139
161
140
146
134
133
142
140
127
220
165
161
196
188
168
195
545
143
186
186
174
160
132
119
152
1236
149
•fso
136
369
205
136
234
221
148
140
193
162
263
139
200
PR EC.
P .05
16
77
14
11
144
25
70
41
27
9
13
31
31
20
9
10
13
21
53
23
32
12
41
10
19
15
14
12
30
13
14
28
16
27
23
11
12
33
27
15
20
120
19
38
28
30
15
22
10
14
32
27
23
15
53
32
14
29
31
29
13
36
24
44
a
24
PR EC.
P .01
21
119
19
16
227
34
100
57
37
13
17
43
42
26
12
13
18
30
73
33
42
17
56
13
25
20 ,
25
15
42
18
19
45
21
36
31
13
16
44
36
20
26
183
26
51
38
41
21
29
13
19
49
38
31
20
.74
45
19
44
42
41
13
51
33
59
11
32
59
-------
Ongoing Calibration-Verification Limits
During each shift, a standard calibration sample containing 100 ug/mL
of all compounds, Is analyzed to check the method calibration. Limits for
the results of this check are given 1n Table VI-2 for compounds by Internal
standard (which would be appropriate for Method 625), labeled compounds by
Internal standard, and compounds by Isotope dilution. The limits are
obtained from the variance components analysis of the calibration- type
samples as
expCln(lOO) * td(l - £) SA] ,
where td 1s again the Inverse cumulative t distribution, and d 1s the
degrees of freedom 1n the estimate of SA, e.g. N-L. The derivation of
this formula Is given 1n Appendix K. The maximum-minimum and minimum-
maximum limits were set at 85 and 115, respectively for calibration
verification of all compounds; I.e., for the 100 ug/mL calibration
verification standard, no specification falls 1n the range of 85 to
115 ug/mL. These limits were chosen because Isotope dilution has the
potential of being too precise, and 1n the same way that some probability
exists that wide limits can be developed, there is a remote probability that
narrow limits can be developed, also. Since calibration is verified with a
single analysis for all compounds, it was felt that an additional allowance
for those compounds which fall in the range of 85 to 115 would not render
the analysis for any given compound too imprecise.
Limits are given in Table VI-2 for individual test levels of .05, .01,
.001, and .0001. To achieve an overall 5 percent level on this test for
Method 625* (compounds by internal standard), either the .01 values from the
first section of Table VI-2 could be used with one retest allowed for
failing compounds, or a single- round test at individual level .001 could be
used. To achieve an overall 5 percent level for Method 1625A, the .01 level
*
For Method 625, acid (A) and base/neutral (B) compounds are tested
separately, for a total of 12 and 48 compounds tested.
60
-------
Table VI-2
ONGOING CALIBRATION VERIFICATION LIMITS
er>
COMPOUND
001B ACENAPHTHENE
005B BENZIDINE
008B 1,2,4-TRICHLOROBENZENE
009B HEXACHLOROBENZENE
OI2B HEXACHLOROETHANE
018B BIS(2-CHLOROETHYL)ETHER
020B 2-CHLORONAPHTHALENE
021A 2,4,6-TRICHLOROPHENOL
022A P-CHLORO-M-CRESOL
024A 2-CHLOROFHENOL
025B 1,2-DICHLOROBEMZENE
026B 1,3-DICHLOROBENZENE
027B 1,4-DICHLOROBENZENE
026B 3.3'-DICHLOROBEMZIDINE
031A 2,4-DICHLOROPHENOL
034A 2,4-DIMETHYLPHENOL
035B 2,4-DINITROTOLUENE
036B 2,6-DINITROTOLUENE
037B 1,2-DIPHENYLHYDRAZINE
039B FLUOPANTHENE
040B 4-CHLOROPHENYL PHENYL ETH
041B 4-BROMOFHENYL PHENYL ETHE
042B BIS (2-CHLOROISOPROPYLI E
052B HEXACHLOROBUTADIENE
053B HEXACHLOROCYCLOPENTADIENE
054B ISOPHORONE
055B NAPHTHALENE
056B NITROBENZENE
057A 2-NITROPHENOL
058A 4-NITROPHENOL
059A 2,4-DINITROPHENOL
060A 4,6-DINITRO-O-CRESOL
062B N-NITROSOOIPHENYLAHINE
064A PENTACHLOROPHENOL
065A PHENOL
066B BI3 (2-ETHYLHEXYL) PHTHAL
066B DI-N-BUTYL PHTHALATE
069B DI-H-OCTYL PHTHALATE
070B DIETHYL PHTHALATE
071B DIMETHYL FHTHALATE
072B BENZO(A)ANTHRANCENE
073B BENZOIAIPYREHE
074B BENZOIBIFLUORANTHENE
075B BENZOIKIFLUORANTHENE
076B CHRYSENE
077B ACENAPHTHYLENE
078B ANTHRACENE
079B BEMZOIGHDPERYLENE
080B FLUORENE
081B PHEIIANTHRENE
084B PYREIIE
502B BETA IIAPHTHYLAMINE
503B ALPHA PICOLINE
9CK1C:
P .05
LOWER
85
39
80
65
72
69
74
78
85
77
70
78
77
57
76
84
67
66
77
69
75
75
70
80
75
73
74
78
78
56
64
67
76
63
74
61
73
52
69
69
57
36
43
39
42
85
66
42
71
66
67
u
t-iunruuroj:
P .05
UPPER
118
254
125
153
140
145
135
128
115
131
143
129
129
177
131
119
150
151
130
145
134
133
142
126
133
137
134
129
127
178
155
149
131
158
136
164
137
194
144
144
175
277
235
254
237
117
151
240
141
151
148
12*
i Hi imcKr
P .01
LOWER
80
28
74
56
63
61
67
71
85
70
62
71
70
46
69
79
58
57
70
60
67
67
62
73
68
65
67
70
72
45
55
58
67
54
66
51
65
41
61
61
47
25
31
28
31
80
57
30
63
57
58
5i
IAL 3IAMUAI
P .01
UPPER
126
356
136
178
158
165
150
141
118
144
162
141
142
217
144
127
174
175
143
166
148
149
162
136
148
153
149
143
139
221
181
173
150
186
151
195
153
246
164
164
214
400
320
354
322
125
175
330
159
175
171
m
KU -------
P .001
LOWER
74
18
66
46
54
51
57
63
80
62
52
63
62
35
61
72
48
47
62
51
59
57
52
66
59
56
59
60
64
34
45
48
53
43
57
41
57
30
52
51
36
15
21
18
21
74
47
20
54
47
48
11
P .001
UPPER
136
552
151
217
185
196
175
159
125
163
191
158
160
284
163
138
210
212
163
197
169
176
192
152
169
178
171
166
156
295
222
209
187
230
174
245
177
335
194
194
279
646
483
546
480
135
211
503
186
211
207
271
225
P .0001
LOWER
68
12
60
38
46
43
49
56
75
55
45
56
55
27
55
67
40
39
54
43
52
47
44
59
52
49
51
51
57
25
37
40
40
35
50
33
49
22
44
44
28
10
14
12
14
68
40
13
46
40
40
28
36
P .0001
UPPER
146
844
167
262
217
231
203
180
133
183
223
177
180
370
183
150
252
253
185
234
193
211
228
169
193
205
194
197
174
393
270
251
249
283
199
306
204
450
229
228
360
1027
723
.828
705
147
252
761
216
252
249
I"
-------
Table VI-2 (Continued)
COMPOUND
504B DIBENZOTHIOPHEHE
505B DIBENZOFURAN
506B N-DODECAME
507B DIPHEHYLAMINE
5083 DIPHEHYLETMER
509B ALPHA TERPINEOL
510B STYRENE
51 IB DI-H-BUTYL AM I HE
51ZB BIPHEMYL
513B P-CYMEHE
517B N-DECANE CIO
519B N-HEXAOECANE C16
52 IB H-EICOSAIIE CIO
523B N-TETRACOSAHE CZ4
526B N-TRIACONTAHE C30
stKit:
P .05
LOWER
71
73
65
70
70
71
69
30
60
72
59
67
67
67
55
t-umruurtti:
P .05
UPPER
140
137
154
142
143
140
144
328
125
138
169
149
150
148
160
I Ul INItKt
P .01
LOWER
63
65
56
62
62
63
61
15
73
64
49
58
58
59
45
Ml 9IANUW
P .01
UPPER
158
153
180
162
162
158
165
646
136
155
204
172
173
171
223
KU
P .001
LOWER
54
57
45
52
52
54
51
4
66
55
39
49
48
49
34
P .001
UPPER
185
176
220
192
192
185
196
2397
151
181
260
206
209
204
296
P .0001
LOWER
46
49
37
44
44
46
43
1
60
48
31
41
40
41
26
P .0001
UPPER
216
202
26ft
227
226
216
232
17589
168
209
327
245
249
243
392
CTl
ro
-------
Table VI-2 (Continued)
01
CO
COMPOUND
20IB ACEHAPHTHEHE-D10
205B BENZIOIUE-D8 (RIHGS-DBI
208B 1,2,4-TRICHLOROBENZENE-03
209B HEXACHLOROBENZEME-13C6
212B HEXACHLOROETHAIIE-1-13C
2I8B BIS(2-CHLOROETHYL)-D8 ETH
220B 2-CHLOROHAPHTHALENE-D7
221A 2,4,6-TRICHLOROPHEIJOL-3,5
222A 4-CHLORO-3-METHYLPHEMOL-2
224A 2-CHLOROFHEHOL-3,4,5,6-D4
225B 1,2-DICHLOROBEIIZEHE-D4
226B 1.3-OICHLOROBEIIZENE-D4
227B 1.4-DICHLOROBENZEHE-D4
228B 3,3'-DICHLOROBENZIDIHE-D6
231A 2,4-DICHLOROPHEHOL-3,5,6-
234A 2,4-DII1ETHYLPHENOL-3,5.6-
235B 2,4-OINITROTOLUEIIE-3,5,6-
236B 2.6-OIIIITROTOIUEME-D3
237B 1,2-DIFHENYL-D10-HYDRAZIN
2398 FLUORAHTHEHE-010
240B 4-CHLOROFHEHYL PHENYL-D5
242B BIS(2-CHLOROISOPROPYLIETH
252B HEXACHLORO-1.3-BUTAOIENE-
253B HEXACHLOP.OCYCLOPEHTAOIENE
254B ISOPHOROME-D8
255B MAPHTHALENE-D8
256B HITROBEHZEHE-D5
257A 2-NITROPHEHOL-3,4,5,6-D4
258A 4-NITROPHEMOL-2, 3, 5,6-04
259A 2,4-DIHITROFHEMOL-3,5.6-D
260A 4.6-DIHITRO-0-CRESOL-02
262B N-NITROSODIPHEHYLAHIHE-D6
264 A PENTACHLOROPHEHOL-13C6
265A PHEHOL-2,3,4,5,6-05
266B BIS(2-ETHYIHEXYL)PHTHALAT
266B OI-M-BUTYL PHTHALATE-04
269B OI-H-OCTYL PHTHALATE-04
270B OIETHYL PHTHALATE-3,4,5,6
271B DIMETHYL PHTHALATE-3,4,5i
272B BEMZO(A)AHTHRACENE-D12
273B BEHZO(AIPYREHE-D12
274B BEHZO
-------
Table VI-2 (Continued)
COMPOUND
605B DIBENZOFURAN-OB
606B N-DODECANE-026
607B OIPHEMYL-D10-AMINE
608B OIPHEHTL-010 ETHER
609B ALPHA-TERPIHEOL-D3
610B STYBEHE-Z. 3,4, 5,6-05
61 IB DI-H-BUTYL-Oia-AMINE
612B OIPHEHYL-D10
613B P-CYHEME-D14
617B M-OECAME-D22
619B N-HEXAOECANE-D34
621B H-EICOSAHE-042
623B N-TETRACOSAHE-050
626B N-TRIACONTANE-D62
5EKIE9SLA
P .05
LOWER
64
67
61
85
49
70
30
61
63
70
76
Bl
74
53
BELLED AM
P .05
UPPER
119
149
124
115
203
143
337
124
120
143
132
123
136
167
iLoes BI ir
P .01
LOMER
79
59
74
65
36
61
17
74
76
61
69
75
66
43
IIEKNAL 31.
P .01
UPPER
127
171
135
116
261
163
565
136
128
163
145
133
151
235
P .001
LOWER
72
49
66
62
27
52
7
63
72
52
61
66
57
32
P .001
UPPER
139
204
151
123
364
193
1420
159
140
193
165
147
174
316
P .0001
LOMER
66
41
59
77
20
44
2
52
66
44
54
62
50
24
P .0001
UPPER
150
242
169
129
502
226
4236
192
152
227
166
162
199
423
-------
Table VI-2 (Continued)
COMPOUND
30 IB ACEHAPHTHENE
305B BENZIDIHE
30SB 1,2,4-TRICHLOROBENZENE
3098 HEXACHLOROBENZENE
31ZB HEXACHLOROETHAME
316B BISCZ-CHLOROETHYL1ETHER
3ZOB Z-CHLORONAPHTHALEME
321A 2,4,6-TRICHLOKOPHENOL
322A P-CHLORO-H-CRESOL
324A Z-CHLOROPHEHOL
325B l.Z-OICHLOROBEIIZENE
326B 1,3-OICHLOROBEMZEIIE
3Z7B 1,4-DICHLOROBENZENE
328B S.S'-DICHLORODENZIDINE
331 A 2,4-DICHLOROPHENOL
334A 2,4-DIHETHYLPHENOL
335B 2,4-OINITROTOLUENE
336B 2,6-DINITROTOLUENE
337B 1,2-DIFHEHYLHYDRAZINE
339B FLUORANTHENE
340B 4-CHLOROPHENYL PHENYL ETH
34JB BIS (2-CHLOROISOFROPYL) E
352B HEXACHIOROBUTADIEIIE
353B HEXACHLOROCYCLOPEHTADIENE
354B ISOPHOROME
355B NAPHTHALENE
356B NITROBENZENE
357A 2-HITROPHEIIOL
358A 4-NITROFHENOL
359A 2,4-DINITROPHENOL
360A 4,6-DINITRO-O-CRESOL
36ZB N-NITROSODIPHENYLAMINE
364A PENTACHLOROPHENOL
365A PHENOL
366B BIS (2-ETHYLHEXYLI PHTHAL
368B DI-H-BUTYL PHTHALATE
369B OI-H-OCTYL PHTHALATE
370B DIETHYL PHTHALATE
3718 DIMETHYL PHTHALATE
372B BEMZOIAIANTHRANCENE
373B BENZO(A)PYREI1E
374B BENZOCBIFLUORANTHENE
375B BENZO(K)FLUORAHTHENE
3768 CHRYSENE
377B ACENAPHTHYLENE
378B ANTHRACENE
379B BENZOIGHDPERYLENE
3SOB FLUORENE
381B PHENANTHRENE
38AB PYRENE
702B BETA IIAPHTHYLAMIHE
703B AlPHA PICOLIIIE
704B DIBENZOIHIOPHENE
acHita
P .05
LOWER
85
63
65
65
65
61
60
85
85
85
85
83
81
65
84
84
65
78
85
64
65
64
65
65
65
65
85
85
76
85
65
65
85
ez
65
65
65
65
65
65
65
61
4Z
85
80
60
85
85
65
65
67
81
i=tUnKUUND3
P .05
UPPER
US
160
115
115
115
124
125
115
115
115
115
121
124
115
119
120
115
128
115
120
117
118
US
115
117
115
115
115
129
US
118
116
115
122
115
117
116
115
US
116
115
124
239
117
125
126
117
115
115
115
150
m
BT I3UIUF
P .01
LOWER
65
53
85
65
82
75
73
85
85
65
64
77
75
65
79
76
65
71
64
76
61
79
84
65
81
63
85
65
71
64
60
61
85
77
65
61
82
63
63
61
65
75
30
81
74
73
61
64
84
65
57
K
'6 DILUTION
P .01
UPPER
115
189
116
116
122
134
136
US
115
116
119
1Z9
133
117
1Z7
127
115
140
119
127
123
126
119
116
123
121
115
117
142
119
125
123
117
130
116
123
123
120
121
123
116
134
329
123
135
136
124
120
119
118
174
izi
P .001
LOWER
63
42
62
62
76
67
65
85
85
82
79
71
66
61
73
72
63
63
79
72
76
73
79
62
75
77
65
61
62
79
74
74
61
70
80
76
76
76
77
76
ez
67
20
75
67
66
75
79
79
80
47
7?
P .001 f
UPPER I
120
237
122
122
131
148
153
118
US
123
127
141
147
123
136
139
121
160
126
138
132
137
127
123
133
129
115
123
161
126
135
134
124
142
125
132
131
128
129
132
122
148
500
133
150
152
134
127
126
125
212
11?
1 .0001 1
.OMER 1
60
34
76
76
71
61
58
61
65
78
74
65
62
77
67
67
79
55
75
67
71
67
74
77
70
73
65
77
55
75
69
68
77
65
76
71
71
74
73
70
76
61
13
70
60
60
69
74
75
76
39
7?
P .0001
JPPER
125
296
128
128
141
164
171
123
US
129
135
154
161
130
149
150
127
163
134
149
142
148
135
129
142
137
US
129
163
133
145
146
130
155
131
142
140
135
137
142
129
164
756
142
166
168
145
135
133
132
256
165
140
-------
Table VI-2 (Concluded)
COHPC
705B
706B
70 7B
706B
7098
710D
71 IB
7126
7 138
717B
71 98
721B
7238
726B
XJNO
DIBEHZOFURAN
N-DODECANE
DIPHENYLAMINE
DIPHENYLETHER
ALPHA TERPIMEOL
STYRENE
DI-N-BUTYL AMINE
BIPHENYL
P-CYtlEUE
H-DECAHE
H-HEXADECANE
H-EICOSAHE
N-TETRACOSANE
N-TRIACONTANE
C12
CIO
C16
CZO
C24
C30
----- 3tK.it;
P .05
LOWER
as
60
79
85
76
63
.
60
65
69
65
76
62
63
)-Luni*uunu9
P .05
UPPER
115
125
127
115
126
120
,
125
115
145
116
131
121
120
HI J3UIUF
P .01
LOHER
63
74
72
65
71
76
.
74
65
60
82
69
77
78
'C uiLuitun
P .01
UPPER
120
136
139
115
140
129
.
136
115
166
122
144
130
129
P .001
LOWER
76
66
64
65
62
71
•
66
63
50
77
61
71
71
P .001 f
UPPER 1
128
150
156
116
161
141
•
152
121
196
130
163
142
140
' .0001
.OHER 1
73
60
57
63
54
65
.
58
79
42
72
54
65
66
P .0001
UPPER
136
166
176
120
186
153
.
171
127
235
138
184
154
152
-------
specifications (in the second and third sections of Table VI-2, for the
series labeled compounds by internal standard and compounds by isotope
dilution) could be used, allowing one retest for failing compounds, or the
.0001 level specifications could be used for a single-round test.
Ongoing Quality Assurance Tests
In each batch of samples processed by the laboratory, one water sample
with known composition of 100 ug/L of all compounds is extracted and
analyzed. Limits for the recovery of each compound and labeled compounds
are given in Table VI-3. The limits are computed from the variance
components analysis of extracted samples as
exp[M * t(d, 1 - $) ys* + SJ; + S*/L + SJ;/N ] ,
where t is as above, and d is the appropriate degrees of freedom, e.g.,
min (N-L, L-l). The derivation of this formula 1s given 1n Appendix K.
The limits are given at individual test levels of p = .05, .01, and
.001. For the ongoing quality assurance test of all 154 compounds, the .01
level would be used to achieve an overall 5 percent significance level,
assuming one retest 1s allowed for compounds which fail the first round.
In addition to the one QA sample in each batch, the recovery of labeled
compounds is checked for every sample which is analyzed. Limits on the
recovery of the labeled compounds in these samples are also obtainable from
Table VI-3. Because the analysis of wastewater samples 1s not necessarily
repeatable, an individual test level of p = .001 would be used to give an
approximate overall 5 percent level test, with no allowance for retesting of
failed compounds.
67
-------
Table VI-3
ONGOING QUALITY ASSURANCE LIMITS
COMPOUND
2018 ACENAPHTHENE-D10
205B BENZIOINE-06 (RINGS-OS)
2088 1,2,4-TRICHLOROBENZENE-D3
209B HEXACHLOROBENZENE-13C6
212B HEXACHLOROETHANE-I-13C
218B BIS(2-CHIOROETHYL)-DS ETH
220B 2-CHLORONAPHTHALENE-D7
221A 2,4,6-TRICHLOROPHENOL-3,5
222A 4-CHLORO-3-METHYLPHENOL-2
224A 2-CHLOROPHENOL-3t4,5,6-04
2258 1.2-DICHLOROBEHZENE-D4
226B 1.3-OICHLOROBENZENE-04
2278 1,4-DXCHLOROBENZENE-D4
2288 3,3'-OICHLOROBENZIDINE-D6
231A 2.4-OICHLOROPHEHOL-3.5,6-
234A 2.4-OIMETHYLPHENOL-3t5.6-
235B 2,4-DINITROTOLUENE-3,5.6-
236B 2.6-DINITROTOLUENE-03
237B 1,2-DIPHENYL-010-HYORAZIN
2398 FLUORANTHENE-D10
240B 4-CHLOROFHENYL PHENYL-D5
2428 BIS(2-CHLOROISOPROPYL)ETH
2528 HEXACHLORO-1.3-BUTAOIENE-
253B HEXACHLOROCYCLOPENTAOIENE
2548 ISOPHOROME-D6
2558 NAPHTHALEHE-D8
256B NITROBENZENE-05
257A 2-NITROPUEHOL-3t4,5,6-04
258A 4-NITROPHENOL-2i3,5.6-D4
259A 2.4-OINXTROPHENOL-3.5.6-0
260A 4,6-OINITRO-0-CRESOL-02
262B N-NITROSODIPHENYLAMINE-D6
264A PENTACHLOROPHENOL-13C6
265A PHENOL-2,3,4,5,6-DS
266B BIS(2-ETHYLHEXYI)PHTHAIAT
268B DI-M-BUTYL PHTHALATE-D4
2698 OI-N-OCTYL PHTHALATE-04
270B OIETHYL PHTHALATE-3i4,5>6
271B DIMETHYL PHTHALATE-3,4,5,
2728 BEHZO
-------
Table VI-3 (Concluded)
SERIES=<
COMPOUND
30IB ACENAPHTHEHE
305B BENZIDINE
308B 1,2,4-TRICHLOROBENZENE
309B HEXACHLOROBENZENE
312B HEXACHLOROETHANE
318B BIS(2-CHLOROETHYL)ETHER
32OB 2-CHLORONAPHTHALENE
321A 2,4,6-TRICHLOROPHENOL
322A P-CHLORO-M-CRESOL
324A 2-CHLOROPHENOL
325B 1,2-DICHLOROBENZENE
326B 1,3-DICHLOROBENZENE
327B 1.4-DICHLOROBENZENE
32BB 3t3'-DICHLOROBENZIDINE
331A 2.4-OICHLOROPHENOL
334A 2.4-DIMETHYLPHENOL
335B 2.4-DINITROTOLUEME
336B 2.6-0INITROTOLUENE
337B 1.2-OIPHENYLHYDRAZINE
339B FLUORAMTHENE
340B 4-CHLOROPHENYL PHENYL ETH
342B BIS (2-CHLOROISOPROPYL) E
352B HEXACHLOROBUTADIENE
353B HEXACHLOROCYCLOPENTADIENE
354B ISOFHORONE
355B NAPHTHALENE
3S6B NITROBENZENE
3S7A 2-NITROPHENOL
358A 4-NITROFHENOL
359A 2.4-DIHITROPHENOL
360A 4,6-DIHITRO-O-CRESOL
362B N-NITROSOOIPHENYLAHINE
364A PEHTACHLOROPHENOL
365A PHEHOL
366B BIS (2-ETHYLHEXYU PHTHAL
368B OI-N-BUTYL PHTHALATE
369B DI-N-OCTYL PHTHALATE
370B DIETHYL PHTHALATE
371B DIMETHYL PHTHALATE
372B BEHZO(A)ANTHRANCENE
373B BENZOIAtPYRENE
374B BENZO(B)FLUORANTHENE
375B BENZO(K)FLUORANTHENE
376B CHRYSENE
377B ACEHAPHTHYLENE
378B ANTHRACENE
379B BENZOtGHDPERYLENE
380B FLUOREME
3818 PHENANTHRENE
384B PYRENE
702B BETA NAPHTHYLAMINE
7038 ALPHA PICOLINE
704B OIBENZOTHIOPHENE
705B DIBENZOFURAN
706B N-OOOECANE CI2
707B DIPHENYLAMINE
708B OIPHENYLETHER
709B ALPHA TERPINEOL
71OB STYRENE
71IB DI-N-BUTYL AHINE
712B BIPHENYL
713B P-CYMEHE
717B N-DECANE CIO
719B N-HEXADECANE C16
721B N-EICOSANE C20
723B N-TETRACOSANE C24
726B N-TRIACONTANE C30
unruuNu:
P .05
LOWER
60
22
85
91
28
63
52
62
72
63
79
69
66
75
89
70
82
80
56
75
74
85
57
79
80
83
81
83
63
76
80
67
79
71
78
84
84
78
79
73
71
36
63
60
74
62
78
78
92
81
22
80
87
43
65
85
53
61
74
81
28
82
60
86
69
t 01 isuiur
P .05
UPPER
130
346
130
123
620
170
298
189
137
126
135
182
177
157
126
135
143
139
260
165
165
131
216
127
148
134
136
132
143
127
128
137
134
135
192
149
148
186
175
149
171
432
131
177
173
162
146
135
119
141
523
!»
133
285
181
131
182
190
147
131
160
158
229
129
177
•e uiiuixur
P .01
LOWER
7Z
11
77
85
13
50
35
48
62
76
70
55
53
64
83
60
72
70
40
64
63
77
43
67
70
75
65
75
51
68
72
53
71
62
64
74
74
65
67
62
59
20
53
48
61
50
68
70
87
72
9
?8
79
29
51
77
38
48
62
72
19
71
46
78
56
P .01
UPPER
144
672
144
132
1303
213
442
244
159
138
152
225
219
185
135
156
164
159
360
194
194
145
287
148
168
149
169
145
175
141
142
173
150
154
232
169
166
222
207
176
206
761
155
221
207
199
168
151
126
159
1278
174
168
146
424
231
144
258
244
176
147
237
181
301
142
215
P .001
LOWER
62
4
66
76
4
35
19
32
49
66
58
40
39
49
75
48
57
56
25
50
50
65
28
48
58
64
36
65
37
58
61
31
60
51
48
60
63
50
52
48
44
8
41
35
47
37
54
59
eo
60
2
68
16
34
66
19
32
45
60
10
58
30
67
42
P .001
UPPER
170
2051
168
148
4546
306
833
367
201
159
182
313
300
238
150
195
206
198
587
248
247
170
437
209
204
174
302
168
244
167
168
292
178
188
310
208
197
288
266
228
272
1886
203
306
272
271
210
178
138
191
7248
237
507
168
772
349
169
509
358
241
175
447
223
451
165
286
69
-------
Retention Time
Limits are also needed for the retention time and relative retention
time for each compound. These limits were obtained from the analysis of
retention times for compounds from all 11 study, samples. Relative retention
time was computed as the ratio of the retention time for each compound to
the retention time of the reference compound CflE?PPF**for Internal standard,
the corresponding labeled compound for Isotope /dilution).
Retention time data received from the laboratories was less
reproducible than expected. Past experience with analyses of this type has
revealed that laboratories may eliminate the Initial Isothermal hold,
Increase the temperature program rate, Increase the final temperature or use
some combination of these techniques to save analysis time. Although these
techniques may work when standard and blanks are being analyzed, separation
of complex mixtures often found in samples may be Incomplete when they are
employed. Because these methods are to be applied to such complex samples,
an Investigation was made Into the actual analytical conditions employed by
each laboratory.
When a gas chromatograph Is operated Isothermal ly, the retention time
of a given compound Is an Indication of the column temperature, and when a
gas chromatograph 1s operated under temperature programmed conditions, the
compounds will elute at predictable Intervals. By comparing the retention
times of the compounds which elute prior to the end of the initial
isothermal hold, and by comparing the intervals at which the conpounds elute
during the ramp phase of the temperature program, the actual temperature
program employed for a given analysis can be deduced.
Figure VI-1 shows the actual temperature programs used by laboratories
in this study. As can be seen, many of the laboratories used programs other
than those specified in the method and reinforced in the instructions
{superimposed programs have been eliminated to provide clarity).
Laboratories A, C, J, K, and 0 used the proper temperature program. As a
result, these data only were used for generation of retention time
specifications.
70
-------
300
TEMPERATURE PROGRAMS USED IN INTER-LAB STUDY
to
to
£200
to
m
LLI
DC
o
LLI
Q^
LU
§100
I-
cc
LU
Q.
LLI
0
10
I
I
C/MIN
I
I
1
I
10 20 30 40
RETENTION TIME (MINUTES)
Figure VI-1 COLUMN TEMPERATURE PROGRAMS USED
50
-------
Before analysis, the relative retention time values were subjected to
an outlier analysis similar to that used on the amount values. A QSCREEN at
level .001 was used as described 1n Section IV and Appendix H. Flagged
cases had both their retention time and relative retention times set to
missing for this analysis. Also only retention times from detected
compounds were used. Therefore, for the unlabeled compounds, the BLK
entries and most of the EPA entries were missing.
Given 1n Tables VI-4 and VI-5 are the results for retention times and
relative retention times. Nominal-scale analyses were used for these
calculations. For these analyses, the mean, standard deviation, coefficient
of variation, minimum, and maximum are computed with the standard formulas.
The 95 percent confidence Hm1t for the mean of the quantity 1s computed as
7 * tn-l('975) V n '
n
where I = £ X./n ,
1=1 1
l/2
Sn = L (X. - 7)*/(n-l)
" \1=1 1 /
and t. 1s the Inverse cumulative distribution function of the t distribution
with d degrees of freedom. The prediction limits are given by
This 1s derived analogously to the regression prediction formulas (see, for
instance, Draper and Smith, Applied Regression Analysis, p. 30). Also given
are the percentage of times the observation fell outside the calculated
95 percent prediction limits.
72
-------
Table VI-4
RETENTION TIME
COMPOUND
001B ACENAPHTHENE
OOSB BEHZIDINE
OOSB 1,2>4-TRICHLOROBENZENE
009B HEXACHLOROBEMZENE
012B HEXACHLOROETHAHE
018B BISt2-CHLOROETHYL)ETHER
020B 2-CHLORONAPHTHALENE
02U 2,4,6-TRICHLOROPHEMOL
022A P-CHLORO-M-CPESOL
024/k 2-CHLOROFHENOL
0258 1,2-DICHLOROBEHZENE
026B 1,3-DICHLORDBENZEHE
027B 1,4-DICHLOROBEHZEHE
026B 3,3'-OICHLOROBENZIDINE
031A 2,4-DICHLOROPHENOL
034A 2,4-DIHETHYLPHEMOL
035B 2,4-OIHITROTOLUENE
036B 2,6-OINITROTOLUEHE
037B 1,2-DIPH£HYLHYDRAZIHE
039B FLUORANTHENE
040B 4-CHLOROPHENYL PHENYL ETH
041B 4-BROMOPHENYL PHEHYL ETHE
0428 BIS U-CHLOROISOPROPYU E
OS2B HEXACHLOROBUTAOIEHE
053B HEXACHLOROCYCLOPEMTADIENE
054B ISOPHOROME
055B HAPHTHALEHE
056B NITROBENZENE
057A 2-NITROPHEHOL
058A 4-NITROPHENOL
X)59A ,2,4-OIUITROPHENOL
060A \.6-DINITRO-0-CRESOL
062B N^MITROSODIPHEtlYLAMINE
064A PtHTACHLOROPHENOL
065A PHEHOL
066B BIS (2-ETHYLHEXYL) PHTHAL
068B DI-N-BUTYL PHTHALATE
069B DI-N-OCTYL FHTHALATE
070B OIETHYL PHTHALATE
071B DIMETHYL PHTHALATE
072B BEHZOU)AHTHRAHCEHE
07JB BEMZO(A>PYREIIE
074B BENZOIBIFLUORAMTHEME
07SB BEHZOIKlFLUCRAIITHEtlE
076B CHRYSEIIE
077B ACEIIAFIITHYLENE
078B ANTHRACEIIE
079B BEHZO(GHI)PERYLENE
OflOB FLUORENE
08IB PHEHANTHREHE
OC^B PVREIJE
1640 2,2'-OIFLUOnOBIPHEKYL
N OF
CASES
MEASRD
40
30
40
39
32
39
30
39
39
36
40
39
10
39
39
39
40
39
39
39
37
37
40
39
37
40
40
16
39
39
39
39
16
39
40
39
39
38
39
40
39
40
40
37
39
32
39
40
40
40
32
54
HE AH
1304
1856
958
1522
820
704
1201
1165
1090
705
760
723
740
2090
947
923
1344
1297
1440
1818
1411
1498
799
1006
1143
889
967
849
899
1354
1327
1437
1464
1561
700
2125
1723
2242
1413
1273
2088
2353
2291
2291
2085
1247
1592
2752
1401
'.583
1649
1163
STANDARD
DEVIATION
46
64
37
51
36
28
41
42
40
27
33
28
31
63
37
36
59
50
49
56
49
49
32
39
43
35
37
52
34
45
46
49
71
52
27
64
55
75
48
44
66
91
79
78
62
15
53
169
48
52
72
42
COEF
OF
VARN
3.5
3.4
3.9
3.4
4.4
3.9
3.4
3.6
3.7
3.6
4.3
3.9
4.2
3.0
3.9
3.9
4.4
3.6
3.4
3.1
3.4
3.3
4.0
3.6
3.6
3.9
3.6
6.1
3.8
3.3
3.4
3.4
4.6
3.3
3.9
3.0
3.2
3.3
3.4
3.5
3.2
3.9
3.5
3.4
3.0
1.2
3.3
6.1
3.4
3.3
3-9
3.6
MINIMUM
1253
1805
906
1472
771
660
1167
1111
1037
661
720
680
690
2049
895
670
1265
1232
1389
1765
1359
1450
750
953
1090
640
915
793
849
1301
1275
1384
1389
1512
654
2077
1678
2192
1363
1222
2042
2240
2230
2234
2044
1216
1534
2572
1350
1534
1773
1112
MAXIMUM
1397
1967
1031
1626
882
757
1275
1247
1169
754
825
779
790
2221
1017
992
1452
1374
1539
1929
1507
1602
659
1082
1227
957
1040
906
969
1443
1410
1534
1537
1666
750
2258
1837
2396
1510
1363
2223
2544
2458
2463
2214
1261
1699
3095
1499
1690
1972
1245
LOWER
95PCT
CONF_LMT
1289
1632
946
1506
807
695
1186
1151
1077
696
750
714
730
2070
935
911
1325
1281
1424
1800
1395
1482
769
993
1126
678
955
621
888
1339
1313
1421
1426
1544
691
2104
1705
2218
1398
1259
2066
2324
2265
2265
2065
1242
1574
2698
1386
1566
Hli
UPPER
95PCT
CONF_LMT
1319
I860
970
1539
833
713
1217
1176
1103
713
771
732
750
2111
959
935
1363
1314
1456
1836
1428
1514
609
1018
1157
900
979
876
910
1368
1342
1452
1502
1578
708
2146
1741
2267
1429
1287
2109
2382
2316
2317
2106
1253
1609
2806
1417
1599
m
LOMER
95PCT
PRED_LHT
1211
1724
883
1416
746
647
1115
1078
1007
649
693
666
676
1960
871
849
1222
1195
1339
1704
1311
1397
734
927
1054
816
891
735
628
1262
1234
1336
1309
1455
644
1993
1609
2089
1314
1182
1952
2167
2128
2131
1958
1216
1483
2406
1303
1476
1699
1078
UPPER
95PCT
PREO_LMT
1398
1988
1034
1627
695
761
1267
1251
1173
760
628
760
804
2220
1023
998
1465
1400
1540
1932
1511
1599
864
1065
1231
959
1043
963
969
1446
1421
1537
1619
1667
755
2257
1636
2396
1513
1363
2223
2539
2453
2452
2213
1278
1701
3097
1499
1689
1996
1248
'/. OUT
OF
PREDJJIT
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
5.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.6
2.6
2.6
0.0
0.0
0.0
2.5
2.5
5.4
2.6
3.1
0.0
0.0
0.0
2.5
0.0
1.9
-------
Table VI-4 (Continued)
COMPOL'HD
N OF MEAN STANDARD COEF MINIMUM MAXIMUM LOWER UPPER LOWER UPPER 7. OUT
CASES DEVIATION OF 95PCT 9SPCT 95PCT 95PCT OF
MEASRD VARN CONF LMT CONF LMT PREO_LMT PRED_LMT PREO HIT
201B ACENfPHT!IENE-010
205B BENZIPINE-D8 (RINGS-OS)
206B 1,2>4-7RICHLOROBENZEHE-D3
209B HEXACHIOROBENZENE-13C6
212B HEXACHLOROETHAME-1-13C
218B BIS(2-CHLOROETHYLJ-08 ETH
220B 2-CHLORONAPHTHALENE-D7
221A 2,4,6-TRICHLOROPHEHOL-3,S
222A 4-CHLORO-3-METHYLPHENOL-2
224A 2-CHLOROPHEHOL-3, 4, 5.6-D4
225B 1.2-DICHLOROBEHZEUE-04
226B 1.3-DICHLOROBENZENE-D4
227B 1 .4-DICHLOROBENZEHE-D4
228B 3,3'-DICHLOROBEHZIOINE-06
231A 2,4-DICHLOROPHENOL-3,5,6-
234A 2,4-DIMETHYLPHEHOL-3,5,6-
235B 2,4-DIHITROTOLUENE-3,5,6-
236B 2.6-DIHITROTOLUEHE-D3
237B I.2-DIPHENYL-D10-HYDRAZIN
239B FLUORANTHENE-D10
240B 4-CHLOROPHEHYL PHENYL-D5
242B BIS(2-CHLOROISOPROPYL)ETH
252B HEXACHLORO-1.3-BUTAOIEME-
253B HEXACHLOROCYCLOPENTADIENE
254B ISOPHOROtlE-08
255B HAPHTHALEHE-DS
2S6B HITROBENZENE-D5
.257A 2-NITROPIIENOL-3,4,5,6-D4
258A 4-NITROPHEMOL-2, 3,5,6-04
2S9A 2,4-OIHITROPHEHOL-3,5,6-D
260A 4.6-DIHITRO-0-CRESOL-D2
262B N-HITROSODIPHENYLAMIIJE-D6
264A PENTACHLOROPHEUOL-13C6
265A PHENOL-2,3,4,5,6-05
266B BIS(2-ETHYLHEXYL)PHTHALAT
266B DI-N-BUTYL PHTHALATE-D4
269B DI-N-OCTYL PHTHALATE-04
270B DIETHYL PHTHALATE-3,4,5,6
271B DIMETHYL PHTHALATE-3,4,5,
272B BEHZO
-------
Table VI-4 (Continued)
COMPOUND
308B li2,4-TRICHLOROBENZENE
30SB HEXACHLOROBENZENE
312B HEXACHLOROETHANE
316B BIS12-CHLOROETHYDETHER
3208 2-CHLORONAPHTHALENE
321A 2,4,6-TRICHLOROPHENOL
322A P-CHLORO-M-CRESOL
324A 2-CHLOROPHEHOL
3258 1,2-DICHLOROBENZENE
326B 1,3-DICHLOROBENZENE
327B 1.4-OICHLOROBENZENE
3288 3,3'-DICHLOROBEHZIDINE
331A 2,4-DICHLOROPHEHOL
334A 2,4-OIMETHYLPHENOL
3358 2,4-DINITROTOLUENE
3368 2,6-OIHITROTOLUENE
337B li2-OIPHENYLHYDRAZINE
3398 FLUORANTHENE
3408 4-CHLOROPHEHYL PHENYL ETH
342B BIS (2-CHLOROISOPROPYL) E
3S2B HEXACHLOROBUTADIENE
353B HEXACHLOROCYCLOPEMTADIENE
354B ISOPHORONE
3558 NAPHTHALENE
356B NITRCBEMZENE
3S/A 2-HITROPHENOL
358A 4-NITROPHEHOL
359A 2.4-DINITROPHENOL
360A 4,i-DINITRO-0-CRESOL
362B N-NITROSODIPHENYLAMINE
364A PJNTACHLOROPHEHOL
365A PHPHOl
3668 BIS (2-ETHYLHEXYL) PHTHAL
368B DI-H-eUTYt PHTHALATE
3698 DI-N-OCTYL PHTHALATE
3708 DIETHYL PHTHALATE
37JB DIMETHYL PHTHALATE
3728 BEIIZO(A)ANTHRANCENE
3738 BEHZOIAIPYREHE
3748 BENZOtBlFLUORANTHENE
3758 BEMZOfKlFLUORANTHEHE
3768 CHRYSENE
377B ACENAPHTHYLEHE
378B ANTHRACENE
3790 EENZO(GHI)PERYLENE
3808 FLUORENE
3818 PHENANTHRENE
3848 PYREUE
5028 BETA NAPHTHYLAMINE
503B ALPHA PICOLIHE
504B DIBENZOTHIOFIIENE
505U OIBtllZOFURA.il
N OF
CASES
MEASRD
39
40
28
39
31
37
35
39
40
40
40
39
40
35
40
39
40
40
40
40
40
38
40
39
16
40
38
38
36
16
40
40
36
39
36
40
39
37
38
38
38
37
31
39
36
40
40
30
38
38
tt
MEAN
958
1522
823
704
1200
1165
1091
705
760
724
740
2086
947
924
1344
1300
1439
1817
1409
799
1006
1142
889
967
849
900
1354
1325
1435
1464
1561
700
2124
1723
2240
1414
1273
2090
2350
2293
2296
2083
1247
1592
2750
1401
1583
1852
1371
427
Hil
STANDARD
DEVIATION
37
50
37
28
41
43
40
27
33
28
31
61
36
38
59
52
49
55
48
32
38
43
35
38
52
35
46
44
48
71
51
27
63
55
81
48
45
67
88
81
81
60
15
53
166
48
52
72
48
8
57
46
COEF
OF
VARN
3.9
3.3
4.4
3.9
3.4
3.7
3.6
3.8
4.3
3.9
4.2
2.9
3.8
4.2
4.4
4.0
3.4
3.0
3.4
4.0
3.8
3.7
3.9
3.9
6.1
3.9
3.4
3.3
3.3
4.8
3.3
3.9
3.0
3.2
3.6
3.4
3.5
3.2
3.7
3.5
3.5
2.9
1.2
3.3
6.0
3;4
3.3
3.9
3.5
1.9
u
MINIMUM
906
1472
771
660
1167
1111
1037
661
720
680
690
2049
895
870
1265
1232
1389
1765
1359
750
953
1090
840
915
793
849
1301
1275
1384
1398
1512
654
2085
1678
2092
1363
1222
2042
2240
2230
2234
2044
1216
1534
2572
1350
1534
1775
1320
415
1509
[284
MAXIMUM
1031
1626
882
757
1275
1247
1169
754
825
779
790
2221
1017
992
1452
1388
1539
1929
1507
859
1082
1227
957
1040
906
969
1443
1418
1534
1537
1666
750
2258
1837
2396
1510
1363
2223
2544
2458
2463
2214
1261
1699
3095
1499
1690
1972
1466
446
1665
1430
LOWER
95PCT
CONF_LMT
946
1506
809
695
lies
1151
1078
696
750
715
730
2067
935
911
1325
1284
1424
1800
1393
789
994
1128
878
955
821
889
1339
1311
1419
1426
1544
691
2102
1705
2213
1398
1259
2068
2322
2266
2269
2063
1241
1574
2694
1386
1566
1826
1355
425
1543
1320
UPPER
95PCT
CONF_LMT
971
1538
837
713
1215
1180
1105
713
771
733
750
2106
959
937
1363
1317
1455
1835
1424
809
1018
1156
900
980
676
911
1369
1340
1451
1502
1577
708
2145
1740
2267
1429
1288
2113
2379
2319
2322
2104
1253
1609
2806
1417
1599
1879
1387
430
m*
LOWER
95PCT
PRED_LMT
882
1418
747
647
1115
1077
1009
650
693
667
676
1962
872
844
1222
1195
1340
1704
1311
734
928
1055
818
890
735
828
1261
1234
1336
1309
1456
644
1994
- 1609
2074
1316
1181
1952
2171
2126
2128
1960
1215
1483
2408
1303
1476
1704
1272
411
1446
1240
UPPER
95PCT
PRED_LMT
1035
1625
899
761
1285
1254
1173
759
628
782
804
2211
1021
1003
1465
1406
1539
1930
1507
664
1084
1230
959
1044
963
972
1448
1416
1534
1619
1665
755
2254
1836
2406
1511
1365
2228
2530
2459
2463
2207
1279
1701
3092
1499
1689
2001
1470
444
1633
1430
'/. OUT
OF
PRED_LMT
0.0
2.5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
15.4
0.0
0.0
0.0
0.0
2.5
0.0
2.5
0.0
D.O
0.0
0.0
0.0
0.0
0.0
0.0
5.3
2.8
0.0
2.5
0.0
2.8
2.6
0.0
0.0
0.0
0.0
7.9
0.0
2.6
5.4
0.0
0.0
2.8
0.0
2.5
0.0
0.0
2.6
0.0
0.0
-------
Table VI-4 (Concluded)
COMPOUND
506B N-DOOECANE
507B DIPHEHYLAMINE
508B DIPHEHYLETHER
509B ALPHA TERPINEOL
51QB STYRENE
51 IB DI-N-BUTYL AhIHE
512B BIPHENYL
513B P-CYMENE
517B H-DECAME
519B H-HEXADECAHE
52IB N-EICOSANE
52JB N-TETRACOSANE
526B N-TRIACOMTANE
602B 2-MAPHTHYL-D7-AMINE
603B 2-METHYLPYRIOIHE-D7
604B OIBENZOTHIOPHENE-D8
605B OIBEHZOFURAH-D8
606B N-DODECANE-D26
607B DIPHENYL-D10-AMINE
60BB DIPHEHYL-D10 ETHER
609B ALPHA-TERPINEOL-D3
610B STYREHE-2.3,4,5.6-D5
61 IB DI-N-BUTYL-D18-AMIHE
612B DIPHEHYL-D10
613B P-CYMENE-D14
617B N-DECAHE-D22
619B N-HEXADECAHE-D34
62IB N-E1COSAHE-D42
623B H-TETRACOSANE-050
626B N-TRIACOHTANE-D62
702B BETA NAPHTHYLAMINE
703B ALPHA PICOLIHE
704B OIBEHZOTHIOPHENE
705B DIBEHZOFUHAN
706B N-DODECAIIE
707B DIPHEMYLAMINE
708B DIPHEHYLETHER
709B ALPHA TERPIHEOL
710B STYREHE
71 IB DI-H-BUTYL AMIME
712B BIPHEHYL
7138 P-CYHEME
717B H-DECAHE
719B H-HEXAOECAME
721B H-EICOSAME
723B H-TE7RACOSAHE
726B N-TRIACOHTANE
CIO
C16
C20
C24
C30
IE
17
18
I
\
•05
[HE
C12
CIO
C16
C20
C24
C30
N OF
CASES
MEASRD
39
40
39
39
40
30
32
38
39
39
39
39
39
48
49
39
49
50
40
50
50
49
20
30
50
50
49
48
49
49
39
39
32
40
40
40
40
39
37
30
31
40
40
40
40
33
37
MEAN
979
1439
1216
977
550
733
1195
754
719
1471
1676
2024
2433
1364
417
1559
1331
953
1437
1211
973
546
742
1205
742
698
1447
1655
1997
2384
1371
426
1564
1335
981
1439
1216
975
549
733
1195
755
720
1469
1677
2025
2429
STANDARD
DEVIATION
37
48
44
38
16
66
48
30
28
135
156
62
109
47
9
57
46
63
52
43
37
16
60
45
29
27
135
151
61
9ft
48
10
56
46
3d
48
43
36
17
66
49
30
28
134
154
62
106
COEF
OF
YARN
3.8
3.4
3.6
3.9
3.0
9.0
4.0
3.9
3.9
9.2
9.3
3.1
4.5
3.4
2.3
3.6
3.5
6.6
3.6
3.5
3.6
2.6
10.6
3.7
3.9
3.9
9.3
9.1
3.1
4.1
3.5
2.3
3.6
3.5
3.9
3.4
3.6
3.7
3.0
9.0
4.1
3.9
3.9
9.1
9.2
3.1
4.4
MINIMUM
928
1388
1164
924
521
651
1139
708
673
1354
1389
1962
2340
1319
386
1507
1281
707
1385
1160
923
519
659
1163
697
654
1331
1360
1960
2308
1320
392
1509
1284
928
1386
1164
924
521
651
1139
708
673
1354
1389
1964
2340
MAXIMUM
1055
1537
1304
1050
580
622
1279
811
773
1720
1857
2151
2662
1464
442
1662
1426
1034
1534
1300
1048
578
632
1275
799
751
1697
1632
2125
2597
1466
446
1665
1430
1055
1537
1304
1050
580
822
1279
611
773
1720
1857
2151
2662
LOWER
95PCT
COHF_U1T
967
1424
1202
964
545
708
1177
744
710
1427
1625
2003
2397
1355
415
1540
1316
935
1420
1199
962
541
705
1169
734
690
1408
1612
1979
2356
1355
423
1543
1320
969
1424
1202
963
544
706
1177
745
711
1426
1627
2005
2393
UPPER
95PCT
CONF_LHT
991
1455
1230
989
555
758
1212
763
726
1515
1726
2044
2466
1362
420
1577
1345
971
1454
1224
983
550
780
1222
750
705
1465
1699
2014
2412
1386
430
1564
1350
993
1455
1230
987
555
756
1213
764
729
1512
1726
2046
2464
LOWER
95PCT
PREO_U1T
903
1340
1126
699
517
595
1096
693
661
1194
1356
1896
2209
1272
398
1442
1237
624
1330
1125
698
514
570
1112
664
643
1172
1348
1873
2164
1273
406
1447
1240
903
1340
1127
900
515
595
1094
694
662
1195
1361
1897
2210
UPPER
95PCT
PRED_U1T
1055
1538
1306
1055
584
671
1294
614
777
1746
1995
2151
2657
1464
437
1675
1425
1081
1545
1296
1048
577
915
1296
801
752
1721
1962
2121
2584
1469
446
1680
1430
10S6
1538
1305
1050
584
871
1296
615
776
1744
1992
2153
2647
•/. OUT
OF
PRED_LHT
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.6
0.0
6.1
0.0
2.0
4.0
0.0
2.0
0.0
2.0
0.0
0.0
0.0
0.0
0.0
0.0
2.0
2.0
0.0
2.6
0.0
0.0
0.0
0.0
0.0
2.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.7
-------
Table VI-5
RELATIVE RETENTION TIME
COMPOUND
001B
005B
008B
009B
012B
016B
020B
021A
022A
024A
025B
026B
027B
028B
031 A
034A
035B
036B
037B
039B
040B
041B
042B
0523
053B
054B
055B
056B
057A
058A
059A
060A
062B
064A
065A
066B
068B
0698
070B
0718
072B
073B
0748
075B
076B
077B
078B
079B
060B
081B
0648
ACENAPHTHENE
8ENZIDINE
1.2,4-TRICHLOROBENZENE
HEXACHLOROBENZENE
HEXACHLOROETHANE
BIS(2-CHLOROETHYL)ETHER
2-CHLORONAPHTHALENE
2,4,6-TRICHLOROPHENOL
P-CHLORO-M-CRESOL
2-CHLOROPHEIIOL
1,2-OICHLOROBENZENE
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
3,3'-DICHLOROBENZIDINE
2,4-OICHLOROPHEHOL
2,4-DIHETHYLPHENOL
2,4-DINITROTOLUEHE
2)6-OINITROTOLUEHE
1.2-DIPHENYLHYDRAZINE
FLUOR ANTHEHE
4-CHLOROPHEHYL PHENYL ETH
4-BROMOPHENYL PHENYL ETHE
BIS C2-CHLOROISOPROPYL) E
HEXACHLOROBUTADIENE
HEXACHLOROCYCLOPENTADIENE
130PHORONE
NAPHTHALENE
NITROBENZENE
2-Mr.?OPHEHOL
4-h'ITf.TJPHENOL
2,4-DIIiITROPHENOL
4,6-l'IHITRO-O-CRESOL
N-NI1ROSODIPHENYLAMINE
PENTACHLOROPHEHOL
PHENOL
BIS 12-ETHYLHEXYL) PHTHAL
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BEMZO(A)ANTHRANCENE
BENZOIAIPYREME
BENZO(B)FLUORANTHENE
DEHZOtK)FlUORANTHEH£
CHRYSENE
ACENAPHTHYLENE
ANTHRACENE
BEHZOIGHDPERYLENE
FLUOREUE
PHEHAHTHRENE
PYRENE
2,2'-0:FLUOROBIFHENYL
N OF MEAN
CASES
MEASRO
40 1.121
30 1.590
40 0.623
39 1.308
32 0.704
39 0.60S
30 1.021
39 1.001
39 0.937
38 0.606
40 0.653
39 0.623
40 0.636
39 1.797
39 0.814
39 0.793
40 .155
39 .115
39 .237
39 .563
37 .211
37 .269
40 0.687
39 0.864
37 0.982
40 0.764
40 0.831
16 0.719
39 0.773
39 1.162
39
39
16
39
40
39
39
38
39
40
39
40
40
37
39
32
39
40
40
40
32
54
.141
.234
.242
.342
.601
.827
.481
.925
.214
.094
.795
.023
.969
.973
.793
.090
.368
.363
.204
.360
:*8ft
STANDARD
DEVIATION
0.005
0.021
0.004
0.009
0.007
0.005
0.003
0.003
0.003
0.007
0.010
0.008
0.015
0.026
0.004
0.005
0.028
0.024
0.008
0.017
0.006
0.009
0.006
0.004
0.002
0.005
0.004
0.005
0.005
0.007
0.005
0.008
0.008
0.011
0.007
0.027
0.015
0.028
0.008
0.005
0.028
0.037
0.031
0.031
0.024
0.004
0.011
0.066
0.007
0.012
0.030
0.000
COEF
OF
VARN
0.5
1.3
0.5
0.7
1.0
0.9
0.3
0.3
0.4
1.1
1.5
1.2
2.3
1.4
0.5
0.7
2.4
2.1
0.7
1.1
0.5
0.7
0.9
0.4
0.2
0.7
0.5
0.7
0.6
0.6
0.5
0.7
0.6
0.8
1.1
1.5
1.0
1.4
0.7
0.4
1.5
1.8
1.6
1.6
1.3
0.4
o.a
3.6
0.6
0.9
1-9
0.0
MINIMUM MAXIMUM LOWER UPPER LOWER
95PCT 95PCT 95PCT
CONF_LHT CONF_LMT PRED_LMT
1.106 1
1.553 1
.129 1
.626 1
.119 1.122 1.110
.562 1.596 1.546
0.615 0.832 0.822 0.825 0.814
1.296 1
.326 1
.305 1.311 1.289
0.693 0.714 0.702 0.706 0.690
0.594 0.614 0.603 0.607 0.594
1.011 1
.025 1
0.995 1.008
.020 1.022 1.015
.000 1.002 0.996
0.930 0.945 0.936 0.938 0.930
0.594 0.620 0.603 0.608 0.592
0.632 0.665 0.650 0.657 0.633
0.608 0.635 0.620 0.625 0.607
0.620 0.670 0.631 0.641 0.605
1.772
1.849
1.789 1.805 1.745
0.805 0.621 0.612 0.815 0.805
0.782 0.805 0.792 0.795 0.783
1.093
1.090
1.218
1.538
1.202
1.277
.180
.177
.253
.591
.223
.307
.146 .164 .097
.107 .123 .066
.235 .240 .220
.558 .569 .528
.208 .213 .198
.286 .292 .271
0.674 0.697 0.665 0.689 0.674
0.857 0.672 0.663 0.866 0.857
0.978 0.987 0.981 0.982 0.977
(1.753 0.775 0.762 0.765 0.753
0.821 0.840 0.630 0.832 0.822
0.713 0.725 0.717 0.722 0.708
0.763 0.784 0.772 0.775 0.764
.145
.132
.215
.231
.329
.588
.602
.465
.895
1.196
1.079
1.765
.174
.151
.250
.252
.363
1.160
1.139
1.232
1.237
1.338
.616 0.599
.881
.511
1.984
1.230
1.101
1.851
1.816
1.476
1.916
1.212
1.092
1.786
.944 2.092 2.011
.926 2.031
.935 2.035
.770
.076
1.353
1.841
1.095
L.391
1.959
1.962
1.785
1.088
1.365
2.236 2.488 2.336
1.185
1.335
Lilt
1.218
.383
.628
.000
1.202
1.356
.164
.143
.237
.246
.345
.603
.636
.486
.934
.217
.095
.604
.034
.979
.983
.800
.091
.372
.391
.207
.364
•Ml \:IU
.148
.130
.217
.224
.320
.587
.772
.451
.868
.198
.084
.738
.948
.905
.909
.744
.081
.346
.187
.189
.336
•m
UPPER
95PCT
PRED_LMT
1.132
1.634
0.633
1.327
0.716
0.616
1.026
1.006
0.944
0.619
0.674
0.638
0.666
1.649
0.623
0.604
1.212
1.164
1.255
1.598
1.224
1.307
0.700
0.872
0.986
0.774
0.840
0.731
0.783
.176
.152
.251
.259
.363
.615
.882
.511
.962
.231
.104
.652
2.097
2.032
2.037
.841
.099
.390
.540
.219
.384
1.649
1.000
7. OUT
OF
PREO_LMT
2.5
0.0
0.0
0.0
0.0
5.1
6.7
7.7
2.6
2.6
5.0
0.0
2.5
0.0
2.6
5.1
2.5
5.1
2.6
0.0
0.0
0.0
0.0
2.6
2.7
7.5
5.0
0.0
5.1
2.6
0.0
2.6
0.0
0.0
2.5
0.0
0.0
5.3
2.6
5.0
0.0
2.5
0.0
0.0
0.0
3.1
2.6
0.0
2.5
2.5
8.0
.0
-------
Table VI-5 (Continued)
00
COMPOUND
201B ACENAPHTHENE-D10
205B BENZIOINE-D8 (RINGS-D8)
206B 1.2.4-TRICHLOROBENZENE-D3
209B HEXACHLOROBENZENE-13C6
212B HEXACHLOROETHAHE-1-13C
218B BIS(2-CHLOROET;iYL)-D8 ETH
220B 2-CHLORONAPHTHALENt-D7
221A 2,4,6-TRICHLOROPHENOL-3,5
222* 4-CHLORO-3-HETHYLPHENOL-2
224A 2-CHLOROPHENOL-3,4,5,6-04
225B 1.2-DICHLOROBEHZENE-D4
226B 1.3-DICHLOROBENZENE-D4
227B 1.4-DICHLOROBENZENE-D4
226B 3,3'-DICHLOROBEIIZIOIUE--06
231A 2,4-OICHLOROPHENOL-3.5,6-
234A 2,4-DIHETHYLPHEIIOL-3,5,6-
235B 2,4-DINITROTOLUENE-3,5,6-
236B 2.6-OINITROTOLUENE-03
237B 1,2-OIPHENYL-DlO-HYDRAZIN
239B FLUORANTHENE-010
240B 4-CHLOROPHENYL PHENYL-D5
242B BIS(2-CHLOROISOPROPYL)ETH
252B HEXACHLORO-1.3-BUTAOIEME-
253B HEXACHLOROCYCLOPENTADIENE
254B ISOPHOROME-08
255B NAPHTHALEHE-D8
256B NITROBENZENE-DS
257A 2-NITROPHEHOL-3,4,5,6-04
2S8A 4-NITROPHENOL-2,3,5,6-04
259A 2,4-DINITROPHEHOL-3,5,6-D
260A 4,6-OINITRO-0-CRESOL-D2
2626 N-HITROSODIPHEHYLAMIHE-D6
264A PENTACHLOROPHENOL-13C6
265A PHEIIOL-2,3,4,5,6-D5
266B BIS(2-ETHYLHEXYL)PHTHALAT
266B DI-N-BUTYL PHTHALATE-D4
269B DI-N-OCTYL PHTHALATE-04
270B DIETHYL PHTHALATE-3,4,5,6
271B DIMETHYL PHTHALATE-3,4,5,
272B EEHZOIA1AUTHRACEME-012
273B BENZ01AIPYRENE-D12
274B BEHZO(B)FLUORANTHEIIE-D12
275B BENZO(K)FLUORANTHEME-D12
276B CMRYSENE-D12
277B ACEIIAPHTHYLENE-08
278B ANTHRACEME-010
279B BENZO(GHI)PERYLEME-D12
280B FLUOREME-D10
261B PHENAMTHREHE-D10
284B PYRENE-D10
30IB ACEIIAPHTHENE
iOSB BEIIZIOIHE
N OF
CASES
MEASRD
50
37
49
49
40
30
49
48
46
47
40
50
50
49
48
49
40
39
49
50
49
50
49
31
50
50
20
49
46
48
49
30
49
50
49
50
46
49
48
49
49
49
47
49
50
49
49
50
50
40
18
MEAN
1.116
1.590
0.821
1.308
0.703
0.596
1.019
1.000
0.937
0.602
0.649
0.620
0.634
1.796
0.812
0.792
1.166
1.101
1.232
1.559
1.209
0.678
0.864
0.981
0.757
0.828
0.716
0.772
1.161
1.138
1.233
1.239
1.341
0.599
1.826
1.478
1.924
1.213
1.092
1.790
2.021
1.964
1.970
1.790
1.087
1.365
1.355
1.200
1.357
1.564
1:88?
STANDARD
DEVIATION
0.005
0.020
0.004
0.010
0.006
0.006
0.002
0.003
0.003
0.008
0.009
0.008
0.016
0.025
0.005
0.005
0.007
0.005
0.008
0.018
0.007
0.007
0.004
0.002
0.005
0.004
0.005
0.005
0.007
0.005
0.008
0.007
0.011
0.007
0.027
0.016
0.028
0.008
0.005
0.027
0.033
0.030
0.031
0.023
0.004
0.011
0.083
0.007
0.011
0.030
8:888
COEF
OF
VARN
0.4
1.3
0.5
0.7
0.9
1.0
0.2
0.3
0.3
1.3
1.3
1.2
2.5
1.4
0.6
0.7
0.6
0.5
0.6
1.2
0.6
1.0
0.4
0.2
0.6
0.5
0.7
0.7
0.6
0.5
0.7
0.5
0.8
1.2
1.5
1.1
1.5
0.7
0.4
1.5
1.6
1.5
1.6
1.3
0.3
0.8
3.5
0.6
0.8
1.9
8:8
MINIMUM
1.101
1.553
0.813
1.285
0.692
0.587
1.010
0.995
0.932
0.587
0.631
0.607
0.617
1.770
0.800
0.782
1.150
1.035
1.216
1.521
1.189
0.665
0.857
0.978
0.747
0.820
0.710
0.762
1.152
1.130
1.213
1.229
1.317
0.586
1.797
1.447
1.895
1.194
1.076
1.761
1.976
1.924
1.933
1.767
1.074
1.349
2.230
1.180
1.332
1.535
MSI
MAXIMUM
1.123
1.625
0.830
1.326
0.714
0.605
1.023
1.008
0.945
0.618
0.662
0.633
0.668
1.848
0.823
0.805
1.179
1.109
1.247
1.587
1.222
0.688
0.871
0.987
0.769
0.837
0.723
0.782
1.176
1.149
1.248
1.251
1.362
0.615
1.880
1.510
1.983
1.228
1.100
1.845
2.085
2.026
2.031
1.837
1.093
1.387
2.472
1.212
1.379
1.624
1:881
LOWER
95PCT
CONF_LMT
1.115
1.583
0.820
1.305
0.701
0.593
1.018
0.999
0.936
0.600
0.647
0.618
0.629
1.789
0.811
0.791
1.164
1.099
1.230
1.554
1.207
0.676
0.863
0.980
0.756
0.827
0.714
0.771
1.159
1.136
1.230
1.236
1.338
0.597
1.818
1.474
1.916
1.211
1.091
1.783
2.011
1.955
1.960
1.783
1.086
1.362
2.332
1.198
1.353
1.574
i:»i
UPPER
95PCT
CONF_LMT
1.117
1.597
0.823
1.310
0.705
0.598
1.020
1.000
0.938
0.605
0.652
0.623.
0.638
1.803
0.814
0.794
1.169
1.103
1.234
1.564
'1.211
0.679
0.865
0.982
0.758
0.829
0.719
0.774
1.163
1.140
1.235
1.241
1.344
0.601
1.834
1.483
1.932
1.215
1.094
1.798
2.030
1.973
1.979
1.796
1.088
1.369
2.379
1.202
1.360
1.593
1:88!
LOWER
95PCT
PREO_LMT
1.107
1.549
0.813
1.288
0.690
0.584
1.014
0.994
0.930
0.587
0.632
0.605
0.601
1.744
0.802
0.781
1.152
1.090
1.216
1.522
1.194
0.664
0.856
0.976
0.747
0.819
0.706
0.761
1.147
1.127
1.216
1.225
1.320
0.584
1.771
1.446
1.867
1.197
1.083
1.735
1.954
1.902
1.906
1.743
1.080
1.342
2.187
1.185
1.334
1.523
6.999
1. 000
UPPER
95PCT
PRED_LMT
1.125
1.632
0.630
1.327
0.717
0.607
1.024
1.005
0.943
0.618
0.667
0.636
0.666
1.848
0.822
0.803
1.181
1.112
1.248
1.596
1.223
0.691
0.871
0.986
0.767
0.836
0.727
0.783
1.175
1.149
1.249
1.252
1.363
0.613
1.880
1.510
1.932
1.229
1.102
1.846
2.088
2.025
2.033
1.837
1.095
1.388
2.524
1.214
1.380
1.644
1:88!
X OUT
OF
PRED_LMT
4.0
0.0
0.0
2.0
0.0
0.0
6.1
8.3
6.5
0.0
2.5
0.0
6.0
2.0
4.2
2.0
2.5
5.1
2.0
2.0
2.0
0.0
2.0
3.2
6.0
2.0
0.0
0.0
2.1
2.1
2.0
0.0
2.0
2.0
2.0
0.0
4.2
2.0
2.1
0.0
0.0
2.0
0.0
2.0
4.0
0.0
0.0
2.0
2.0
0.0
3:8
-------
Table VI-5 (Continued)
COMPOUND
308B 1,2,4-TRICHLOROBENZENE
309B HEXACHLOROBENZENE
31 SB HEXACHLOROETHANE
318B BIS(2-C!ILOROETHYL)ETHER
320B 2-CHLOROHAPHTHALENE
321A 2,4,6-TRICHLOROPHENOL
322A P-CHLORO-M-CRESOL
324A 2-CHLOROPHENOL
3258 1.2-DICHLOROBENZEME
326B 1,3-OICHLOROBEMZEME
327B 1,4-DICHLORODENZENE
328B 3,3'-OICHLOROBENZIDINE
331A 2,4-DICHLOROPHENOL
334A 2,4-DIMETHYLPHEHOL
335B 2,4-DINITROTOLUENE
336B 2,6-DINITROTOLUENE
337B 1,2-DIPHENYLHYORAZIKE
339B FLUORANTHENE
340B 4-CHLOROPHENYL PHENYL ETH
342B BIS (2-CHLOROISOPROPYL) E
352B HEXACHLOROBUTADIENE
353B HEXACHLOROCYCLOPENTAOIENE
354B ISOPHORONE
355B NAPHTHALENE
356B NITROBENZENE
357A 2-NITROPHENOL
3SBA 4-NITROPHEHOL
359A 2,4-DIHITROPHENOL
360A 4,6-DINITRO-O-CRESOL
362B N-HITRQSOOIPHENYLAttlNE
364A PENTACHLOROPHENOL
36SA PHENOL
366B BIS (2-ETHYLHEXYL) PHTHAL
368B OI-N-BUTYL PHTHALATE
36<3B DI-H-OCTYL PHTHALATE
370B DIETHYL PHTHALATE
371B DIMETHYL PHTHALATE
372B BENZOIAIANTHRANCENE
373B BENZO(A)PYSEME
374B BENZOIBjFLUORAHTHEHE
37SB BENZO(K)FLUORANTHENE
376B CHRYSENE
377B ACEHAPHTHYLENE
37GB ANTHRACENE
379B BENZO(GHI)PERYLENE
3808 FLUOREME
381B PHENANTHRENE
30'iB PYREIIE
502B BETA NAPHTHYLAMINE
503B ALPHA PICOLINE
504B DICENZnTMIOFHENE
5050 DILtlli-OFURAN
N OF MEAN STANDARD COEF MINIMUM MAXIMUM LOWER UPPER LOWER UPPER '/. OUT
CASES DEVIATION OF
MEASRO VARN
39
40
28
23
31
37
35
39
32
40
40
39
40
35
32
31
40
40
40
40
40
30
40
.002 0.001 0.1 0
.000 0.000 0.0 1
.000 C.OOO 0.0 1
.012 0.002 0.2 1
.002 0.002 0.2 0
.001 0.002 0.2 0
.000 0.001 0.1 0
.004 0.003 0.3 0
.001 0.003 0.3 0
.003 0.002 0.2 0
95PCT 95PCT 95PCT 95PCT OF
CONF.LMT CONF_LMT PRED_U1T PRED_LMT PREO_LMT
.990
.000
.000
.008
.994
.995
.998
.992
.993
.994
.003 0.003 0.3 0.993
.001 0.000 0.0 1
.000
.001 0.002 0.2 0.991
.001 0.001 0.1 1
.001 0.001 0.1 1
.003 0.001 0.1 1
.000
.001
.001
.004 0.002 0.2 0.994
.002 0.001 0.1 C.998
.002 0.006 0.6 0.998
.013 0.001 0.1 1
.011
.000 0.001 0.1 0.999
.000 0.000 0.0 1
.000
.008 0.004 0.4 0.995
39 1.004 0.001 0.1 1
16 1.004 0.001 0.1 1
.002
.002
40 1.001 0.004 0.4 0.992.
38
38
36
16
40
40
36
39
36
40
39
37
38
38
38
37
31
39
36
40
40
30
38
.001 0.002 0.2 0.997
.002 0.001 0.1
.001 0.000 0.0
.001 0.000 0.0
.000 0.001 0.1
.003 0.004 0.4
.001 0.000 0.0
.001 0.001 0.1
.001 0.000 0.0
.001
.001
.001
.995
.990
.000
.001
.000
.001 0.002 0.2 0.996
.001 0.002 0.2 0.994
.003 0.002 0.2 0.998
.002 0.001 0.1 0.998
.003 0.001 0.1 1.000
.002 0.001 0.1 0.999
.002 0.001 0.1 1
.002 0.001 0.1 1
.001
.000
.002 0.002 0.2 0.996
.004 0.001 0.1 1.000
.004 0.002 0.2 0.994
.003 0.001 0.1 0.998
.002 0.001 0.1
.178 0.007 0.6
1.001
.005
.001
.001
.018
.007
.003
.003
.007
.005
.008
.006
.001
.003
.003
.003
.004
.009
.004
.040
.016
.002
.002
.018
.007
.006
.005
.010
.008
.001
.002
.001
.010
.002
.003
.001
.010
.003
.009
.004
.006
.005
.006
.004
.004
.006
.010
.005
.004
,165 1.192
.002
.000
.000
.011
.001
.000
.000
.002
.000
.002
.002
.000
.001
.001
.001
.002
.003
.002
.001
.013
.000
.000
.006
.003
.004
.000
.001
.002
.001
.001
.000
.001
.000
.001
.001
.000
.001
.002
.002
.002
.001
.002
.002
.001
.003
.003
.002
.002
.176
.003 1.000
.000 0.999
,000 1.000
.013 1.007
.003 0.997
.002 0.998
.001 0.998
.005 0.997
.003 0.995
.004 0.998
.004 0.997
.001 1.000
.002 0.997
.001 0.999
.001 1.000
.003 1.001
.005 0.999
.002 1.000
.004 0.990
.013 1.010
.001 0.999
.000 0.999
.009 0.999
.004 1.001
.005 1.002
.002 0.994
.002 0.997
.003 1.000
.001 1.000
.001 1.000
.000 0.998
.004 0.995
.001 1.000
.002 1.000
.001 1.000
.002 0.996
.002 0.998
.003 0.999
.002 1.000
.003 1.000
.002 1.000
.002 1.000
.002 1.000
.002 0.998
.004 1.001
.004 0.999
.003 1.000
.002 1.001
.181 1.163
.005 7.7
.001 10.0
.000 3.6
.016 4.3
.007 3.2
.004 5.4
.003 11.4
.010 7.7
.008 12.5
.008 7.5
.009 10.0
.001 5.1
.006 5.0
.003 8.6
.002 3.1
.005 3.2
.009 2.5
.004 5.0
.015 2.5
.016 2.5
.002 5.0
.001 3.3
,017 10.0
.006 7.7
.007 0.0
.009 12.5
.006 5.3
.005 5.3
.002 0.0
.002 6.3
.002 2.5
.010 7.5
.002 5.6
.003 0.0
.002 0.0
.006 10.0
.005 5.1
.007 5.4
.004 2.6
.005 7.9
.004 10.5
.004 5.4
.004 9.7
.006 10.3
.006 5.6
.008 7.5
.005 5.0
.003 6.7
.193 0.0
38 0.368 0.015 4.0 0.337 0.387 0.363 0.373 0.338 0.398 5.3
31 1.342 0.011 0.8
40 1.147 0.006 0.5
:?!! I:?!? \:lll r.i49 r.ill r.uo l\s
-------
Table VI-5 (Concluded)
COMPOUND
506B N-DODECAHE
507B OIPHENYLAHINE
508B DIPHEHYLETHER
509B ALPHA TERPINEOL
510B STYRENE
51 IB DI-H-BUTYL AMINE
512B BIPHENYL
5I38 P-CYMEHE
517B H-DECAHE CIO
S19B N-HEXADECANE C16
521B N-EICOSANE C20
523B N-TETRACOSANE C24
526B N-TRIACONTANE C30
602B 2-HAPHTHYL-D7-AMINE
603B 2-METHYLPYRIDIHE-D7
604B DIBENZOTHIOPHENE-D8
605B OIBEHZOFURAN-D8
606B N-DODECANE-D26
607B DIPHENYL-D10-AMINE
606B DIPHENYL-D10 ETHER
609B ALPHA-TERPINEOL-D3
410B STYRENE-2,3,*,5,6-05
6UB OI-H-BUTYL-D16-AMINE
61CB DIPHENYL-D10
6i;B P-CYMENE-014
61/B II-DECANE-D22
61 SB N-HEXAOECAHE-034
62IB M-fcJCCOSANE-D42
623B K-TETRACOSANE-D50
626B N-fR]ACONTANE-D62
702B BETA MAPHTHYLAMINE
703B ALPHA PICOLIHE
704B DIBEHZOTHIOPHENE
705B DIBEiJZOFURAH
706B N-DODECAHE C12
707B DIPHENYLAMINE
70SB DIPHEHYLETHER
709B ALPHA TERPINEOL
710B STYRENE
71IB DI-H-BUTYL AMIHE
712B BIPHENYL
713B P-CYMENE
717B H-DECANE CIO
71?B N-HEXADECANE C16
72IB N-EICOSAKE C20
7238 H-TETRACOSAHE C24
726B N-TRIACONTANE C30
N OF f
CASES
HEASRO
39 C
40 1
39 1
39 C
40 C
30 C
32 1
38 (
39 (
39 1
39 1
39 1
39 !
46 1
49 (
39
49
50 (
40
50
50 (
49 (
20 I
30
50 I
50
49
43
49
49
39
39
32
40
40
32
40
39
37
16
23
40
40
40
40
38
37
EAN
.843
.237
.045
.839
1.473
1.641
.025
1.649
1.619
.265
.440
.740
1.091
.176
1.359
.337
.145
>.819
1.231
.042
).636
t.469
>.653
1.021
).638
1.600
L.244
.423
.717
.050
.001
.017
.003
.003
.018
.004
.003
.003
.005
.005.
.003
.015
.030
.016
.016
.013
.019
STANDARD
DEVIATION
0.004
0.008
0.003
0.004
0.009
0.052
0.002
0.007
0.008
0.115
0.121
0.025
0.044
0.007
0.016
0.011
0.005
0.044
0.009
0.003
0.004
0.009
0.060
0.003
0.007
0.007
0.115
0.117
0.023
0.038
0.003
0.006
0.001
0.002
0.016
0.002
0.003
0.003
0.002
0.013
0.001
0.004
0.004
0.002
0.003
0.001
0.004
COEF
OF
VARH
0.5
0.7
0.3
0.5
1.9
8.2
0.2
1.0
1.2
9.1
8.4
1.4
2.1
0.6
4.6
0.8
0.5
5.4
0.7
0.2
0.4
2.0
9.2
0.2
.1
.2
.2
.2
.3
:9
0.3
0.5
0.1
0.2
1.6
6.2
0.3
0.3
0.2
1.3
0.1
0.4
0.4
0.2
0.3
0.1
0.4
MINIMUM
0.835
1.216
1.035
0.831
0.447
0.584
1.022
0.637
0.605
1.198
1.201
1.696
2.042
1.156
0.312
1.312
1.134
0.614
1.211
1.031
0.828
0.443
0.591
1.013
0.626
0.588
1.167
1.175
1.696
1.998
0.994
1.007
1.001
0.995
0.963
0.997
0.993
0.998
1.002
0.9BO
1.002
0.993
.021
.011
.007
.011
.012
MAXIMUM
0.851
1.252
1.049
0.648
0.491
0.714
1.030
0.660
0.632
1.493
1.529
1.790
2.160
1.188
0.384
1.357
1.154
0.878
1.246
1.046
0.844
0.488
0.720
1.026
0.651
0.617
1.473
1.506
1.763
2.116
1.005
1.033
1.010
1.005
1.026
1.006
1.005
1.016
1.009
1.021
1.009
1.018
1.045
1.019
1.023
1.015
1.026
LOHER
95PCT
CONF_LHT
0.841
1.234
1.044
0.638
0.470
0.621
1.025
0.646
0.616
1.226
1.401
1.732
2.076
1.174
0.354
1.334
1.143
0.806
1.228
1.041
0.835
0.466
0.625
1.020
0.636
0.598
1.211
1.389
1.711
2.039
1.001
1.015
1.002
1.002
1.013
1.003
1.002
1.002
1.005
0.999
1.003
1.014
1.029
1.016
1.015
1.013
1.018
UPPER
95PCT
CONF_LHT
0.644
1.240
1.046
0.841
0.476
0.660
1.026
0.651
0.621
1.302
1.479
1.748
2.105
1.176
0.364
1.341
1.146
0.831
1.234
1.042
0.837
0.472
0.681
1.022
0.640
0.602
1.277
1.457
1.724
2.060
1.002
1.019
1.003
1.003
1.023
1.004
1.004
1.004
1.006
1.012
1.004
1.016
1.031
1.017
1.016
1.014
1.021
LOWER
95PCT
PRED_LMT
0.834
1.220
1.038
0.831
0.454
0.532
1.022
0.635
0.603
1.029
1.192
1.689
2.001
1.163
0.326
1.314
1.134
0.730
1.213
1.036
0.829
0.450
0.524
1.016
0.624
0.565
1.010
1.184
1.671
1.972
0.996
1.006
1.000
0.996
0.966
1.000
0.997
0.998
1.002
0.978
1.001
1.008
1.022
1.013
1.010
1.012
1.011
UPPER
95PCT
PRED_LMT
0.651
1.254
1.052
0.648
0.492
0.749
1.029
0.662
0.634
1.502
1.688
1.790
2.180
1.169
0.393
1.361
1.155
0.906
1.249
1.047
0.644
0.488
0.763
1.027
0.652
0.615
1.478
1.662
1.764
2.127
1.007
1.028
1.006
1.007
1.051
1.007
1.009
1.008
1.009
1.033
1.006
1.023
1.038
1.020
1.021
1.015
1.026
7. OUT
OF
PRED_LHT
0.0
2.5
7.7
5.1
2.5
0.0
9.4
0.0
0.0
0.0
0.0
0.0
0.0
2.1
4.1
2.6
2.0
4.0
2.5
4.0
2.0
6.1
0.0
6.7
0.0
2.0
0.0
12.5
0.0
0.0
10.3
7.7
3.1
7.5
7.5
3.1
10.0
5.1
10.6
0.0
4.3
2.5
7.5
2.5'
10.0
5.3
0.0
-------
VII CONCLUSIONS AND FURTHER WORK
From this study, the conclusion can be drawn that Isotope dilution GCMS
1s the most accurate and precise analytical technique available for the
analysis of semi-volatile organic compounds 1n environmental samples. On
average, the precision of analysis 1s Improved by approximately a factor of
two, and the accuracy 1s Improved by approximately a factor of three over
Internal standard techniques.
The Inter!aboratory validation of Method 1625A represents the most
comprehensive evaluation of an Isotope dilution GCMS method to date. More
than 250,000 pieces of Information were collected and evaluated. As a
result, the specifications developed should well represent the performance
of the method In water and wastewater laboratories. For the most part, the
method was tested 1n laboratories with little or no experience with Isotope
dilution; the fact that nearly all of these laboratories performed the
method with reasonable accuracy and predson Is a tribute to the
laboratories and to the Isotope dilution technique. The current draft of
Method 1625B 1s given 1n Appendix M of this report, Including the limits
generated 1n this study. In a few cases, the limits obtained from the
statistical analysis were not found to be practically useful, and no limit
was set 1n those cases.
The limits set 1n Revision B of Method 1625 reflect all sources of
variability, Including variability attributable to the number of compounds
being tested simultaneously. The specifications are realistic and reflect a
95 percent confidence limit for all tests. With reasonable care, any
laboratory practicing these methods should be able to meet every
specification in the Method.
81
-------
A flaw in the study design which should be avoided 1n subsequent
studies was the lack of replicate analyses of the pollutants 1n water
samples. The derivation of quality control limits requires both an
1nterlaboratory component and an intralaboratory component. In this study,
the relationship between these components was Inferred from labeled
compounds data, and assumed to be Identical for the pollutants. Although
this Inference Is true within the limits of the measurement technique, a
direct measurement of these components would have been more correct.
If funding and time permit, the data collected In this study may be
further analyzed to determine If alternate statistical techniques are more
appropriate to generation of specifications for retention time, calibration
linearity, and other parameters. The response ratio data from the PRR
sample could be analyzed to evaluate the use of standardized calibration
curves In place of Individual laboratory calibrations. The mass spectral
data collected need analysis to determine specifications for compound
identification, and spectral data from the analysis of
decaf luorotHphenlyphosphine can be used to determine an 1 nterl aboratory
spectrum for this reference compound.
82
-------
Appendix A
31 March 1983 Draft
Method 1625 Revision A
Semivolatile Organic Compounds by Isotope Dilution GCMS
1 Scope and application—this method is designed to determine
the semivolatile toxic organic pollutants associated with the
1976 Consent Decree and additional compounds amenable to extrac-
tion and analysis by capillary column gas chromatography-mass
spectrometry (GCMS).
1.1 The chemical compounds listed in tables 1 and 2 may be
determined in municipal and industrial discharges by this method.
The method is designed to meet the survey requirements of Ef-
fluent Guidelines Division (EGD) and the National Pollutants
Discharge Elimination System (NPDES) under 40 CFR 136.1. Any
modifications of this method, beyond those expressly permitted,
shall be considered as major modifications subject to applica-
tion and approval of alternate test procedures under 40 CFR
136.4 and 136.5.
1.2 The detection limit of this method is usually dependent
on the level of interferences rather than instrumental limita-
tions. The limits listed in tables 3 and 4 represent the minimum
quantity that can be detected with no interferences present.
1.3 The GCMS portions of this method are for use only by an-*
anlysts experienced with GCMS or under the close supervision of
such qualified persons. Laboratories unfamiliar with analyses
of environmental samples by GCMS should run the performance
tests in reference 1 before beginning.
2 Summary of method
2.1 Stable isotopically labeled analogs of the compounds of
interest are added to a one liter wastewater sample. The sam-
ple is extracted at pH 12-13, then at pH <2 with methylene
chloride using continuous extraction techniques. The extract
is dried over sodium sulfate and concentrated to a volume of
one mL. An internal standard is added to the extract, and
the extract is injected into the gas chromatograph (GC). The
compounds are separated by GC and detected by mass spectrometry.
The labeled compounds serve to correct the variability of the
analytical technique.
1
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2.2 Identification of a compound (qualitative analysis) is
performed by comparing the GC retention time and background
corrected characteristic spectral masses with those of authentic
standards.
2.3 Quantitative analysis is performed by GCMS using extracted
ion current profile (EICP) areas. Isotope dilution is used
when labeled compounds are available; otherwise, an internal
or external standard method is used.
2.4 Quality is assured through reproducible calibration and
testing of the extraction and GCMS systems.
3 Contamination and interferences
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield artifacts and/or elevated baselines causing
misinterpretation of chromatograms and spectra. All materials
shall be demonstrated to be free from interferences under the
conditions of analysis by running method blanks initially and
with each sample lot (samples started through the extraction
process on a given 8 hr shift, to a maximum of 20). Specific
selection of reagents and purification of solvents by distil-
lation in all-glass systems may be required. Glassware and,
where possible, reagents are cleaned by solvent rinse and
baking at 450°C for one hour minimum.
3.2 Interferences coextracted from samples will vary consider-
ably from source to source, depending on the diversity of the
industrial complex or municipality being sampled.
4 Safety
4.1 The toxicity or carcinogenicity of each compound or reagent
used in this method has not been precisely determined; however;
each chemical compound should be treated as a potential health
hazard. Exposure to these compounds should be reduced to the
lowest possible level. The laboratory is responsible for main-
taining a current awareness file of OSHA regulations regarding
the safe handling of the chemicals specified in this method.
A reference file of data handling sheets should also be made
available to all personnel involved in these analyses. Addi-
tional information on laboratory safety can be found in refer-
ences 2-4.
2
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4.2 The following compounds covered by this method have been
tentatively classified as tcnow or suspected human or mammalian
carcinogensi benzo(a)anthracene, benzidine, 3,3'-dichlorobenzi-
dine, benzo(a)pyrene, dibenzo(a,h)anthracene, N-nitrosodimethyl-
amine, and 3-naphthylamine. Primary standards of these toxic
compounds shall be prepared in a hood, and a NIOSH/MESA approved
toxic gas respirator should be worn when high concentrations
are handled.
5 Apparatus and materials
5.1 Sampling equipment for discrete or composite sampling
5.1.1 Sample bottle, amber glass, 1.1 liters minimum. If amber
bottles are not available, samples shall be protected from
light. Bottles are detergent water washed, then solvent rinsed
or baked at 450°C for one hour minimum before use.
5.1.2 Bottle caps—threaded to fit sample bottles. Caps are
lined with Teflon. Aluminum foil may be substituted if the
sample is not corrosive.
5.1.3 Compositing equipment—automatic or manual compositing
system incorporating glass containers for collection of a mini-
mum 1.1 liters. Sample containers are Icept at 0 to 4°C during
sampling. Glass or Teflon tubing only shall be used. If the
sampler uses a peristaltic pump, a minimum length of compressible
silicone rubber tubing may be used in the pump only. Before use,
the tubing is thoroughly rinsed with methanol, followed by
repeated rinsings with reagent water (6.5) to minimize sample
contamination. An integrating flow meter is used to collect
proportional composite samples.
5.2 Continuous liquid-liquid extractor—Teflon or glass con-
necting joints and stopcoctcs without lubrication (Hershberg-Wolf
Extractor) one liter capacity,. Ace Glass 6841-10 or equivalent.
5.3 Drying column—15 to 20 mm i.d. Pyrex chromatographic
column equipped with coarse glass frit or glass wool plug.
5.4 Kuderna-Danish (K-D) apparatus
5.4.1 Concentrator tube—10 mL, graduated (Kontes K-570050-
1025 or equivalent) with calibration verified. Ground glass
stopper (size 19/22 joint) is used to prevent evaporation of
extracts.
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5.4.2 Evaporative flask—500 mL (Kontes K-570001-0500 or
equivalent), attached to concentrator tube with springs (Kon-
tes K-662750-0012).
5.4.3 Snyder column—three-ball macro (Kontes K-503000-0232
or equivalent).
5.4.4 Snyder column—two ball micro (Kontes K-469002-0219 or
equivalent).
5.4.5 Boiling chips—approx 10/40 mesh, extracted with methylene
chloride and baked at 450°C for one hr minimum.
5.5 Water bath—heated, with concentric ring cover.- capable .
of temperature control (± 2°C), installed in a fume hood.
5.6 Sample vials—amber glass, 2-5 mL with Teflon-lined screw
cap.
5.7 Analytical balance—capable of weighing 0.1 mg.
5.8 Gas chromatograph—shall have splitless or on-column injec-
tion port; temperature program with 30 C hold; and shall meet
all of the performance specifications in section 12.
5.8.1 Column—30 ± 5 m x 0.25 ± 0.02 mm i.d. 5 % phenyl, 95 %
methyl silicone bonded phase fused silica capillary column (J & W
DB-5 or equivalent).
5.9 Mass spectrometer—electron impact ionization, shall repe-
titively scan from 35 to 450 amu in one second or less, and
shall produce a 70 eV, unit resolution (valleys between m/z
441-443 less than 10 percent of the height of the 441 peak) ,
background corrected mass spectrum from 50 ng decafluorotri-
phenylphosphine (DFTPP) introduced through the GC inlet. The
spectrum shall meet the mass-intensity criteria in table 5
(reference 5). The mass spectrometer shall be interfaced to
the GC such that the end of the capillary column terminates
within one centimeter of the ion source but does not intercept
the electron or ion beams. All portions of the column which
connect the GC to the ion source shall remain at or above the
column temperature during analysis to preclude condensation
of less volatile compounds.
5.10 Data system—shall collect and record MS data, store mass-
intensity data in spectral libraries, process GCMS data, generate
reports, and shall calculate.and record response factors.
4
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5.10.1 Data acquisition—mass spectra shall be collected
continuously throughout the analysis and stored on a mass storage
device.
5.10.2 Mass spectral libraries—user created libraries contain-
ing mass spectra obtained from analysis of authentic standards
shall be employed to reverse search GCMS runs for the compounds
of interest (7.3).
5.10.3 Data processing—the data system shall be used to search,
locate, identify, and quantify the compounds of interest in each
GCMS analysis. Software routines shall be employed to compute
retention times and peak areas. Displays of spectra, mass chroma-
tograms, and library comparisons are required to verify results.
5.10,4 Response factors and multipoint calibrations—the data
system shall be used to record and maintain lists of response
factors (response ratios for isotope dilution) and multi-point
calibration curves (section 7). Computations of relative stan-
dard deviation (coefficient of variation) are useful for testing
calibration linearity. Statistics on initial and on-going per
formance shall be computed and maintained (7.-8 and 12.8).
6 Reagents and standards
6.1 Sodium hydroxide—reagent grade, 6N in reagent water.
6.2 Sulfuric acid—reagent grade, 6N in reagent water.
6.3 Sodium sulfate—reagent grade, granular anhydrous, rinsed
with methylene chloride (20 mL/g) and conditioned at 450°C for
one hour minimum.
6.5 Methylene chloride—distilled in glass (Burdick and Jack-
son or equivalent).
6.5 Reagent water—water in which the compounds of interest
and interfering compounds are not detected by this method.
6.6 Standard solutions—purchased as solutions or mixtures with
certification to their purity, concentration, and authenticity,
or prepared from materials of known purity and composition. If
compound purity is 96 percent or greater, the weight may be used
without correction to calculate the concentration of the standard.
When not being used, all standards are stored in the dark at
-20 to -10°C in screw capped vials with Teflon-lined lids. A
mark is placed on the vial at the level of the solution so that
5
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any solvent evaporation loss can be detected. The vials are
brought to room temperature prior to use. Any precipitate is
redissolved and solvent is added if solvent loss has occurred.
6.7 Preparation of stock solutions—prepare in methylene
chloride, benzene, p-dioxane, or a mixture of these solvents
per the steps below. Observe the safety precautions in section
4. The large number of labeled and unlabeled acid, base/neutral,
and Appendix C compounds used for combined calibration (section
7) and calibration verification (12.5) require high concentra-
tions (approx 40 p.g/mL) when individual stock solutions are
prepared so that dilutions of mixtures will permit calibration
with all compounds in a single set of solutions. The working
range for most compounds is 10-200 iig/mL. "Compounds with a
reduced MS' response are prepared at higher concentration.
6.7.1 Dissolve an appropriate amount of assayed reference
material in a suitable solvent. For example, weigh 40 mg naph-
thalene in a 10 mL ground glass stoppered volumetric flask and
fill to the mark with benzene. After the naphthalene is com-
pletely dissolved, transfer the solution to a 15 mL Teflon-
lined vial.
6.7.2 Stock standard solutions should be checked for signs of
degradation prior to the preparation of calibration or perfor-
mance test standards. Quality control check samples that can
be used to determine the accuracy of calibration standards are
available from the US Environmental Protection Agency, Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
6.7.3 Stock standard solutions shall be replaced after six months,
or sooner if comparison with quality control check samples indi-
cate a change in concentration.
6.8 Labeled compound spiking solution—from stock standard solu-
tions prepared as above, or from mixtures, prepare the spiking
solution at a concentration of 200 |ig/mL, or at a concentration
appropriate to the MS response of each compound.
6.9 Secondary standard—using stock solutions (6.7), prepare
a secondary standard containing all of the compounds in tables
1 and 2 at a concentration of 400 |ig/mL, or higher concentration
appropriate to the MS response of the compound.
6
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6.10 Internal standard solution—prepare 2,2'-difluorobiphenyl
at a concentration of 10 mg/mL in benzene.
6.11 DFTPP solution—prepare at 50 p.g/mL in acetone.
6.12 Solutions for obtaining authentic mass spectra (7.3)—
prepare mixtures of compounds at concentrations which will
assure authentic spectra are obtained for storage in.,libraries.
6.13 Calibration solutions—combine 0.5 mL of the solution
in 6.8 with 25, 50, 125, 250, and 500 p,L of the solution in
6.9 and bring to 1.00 mL total volume each. This will produce
calibration solutions of nominal 10, 20, 50, 100 and 200 \ig/mL
of the pollutants and a constant nominal 100 ng/mL of the labeled
compounds. Splice each solution with 10 pL of the internal
standard solution (6.10). These solutions permit the relative
response (labeled to unlabeled) to be measured as a function
of concentration (7.5).
6.14 Performance standard—used for initial (7.10) and on-going
(12.8) performance verifications. This solution shall contain
the pollutants and labeled compounds at a nominal concentration
of 100 |ig/mL.
6.15 Stability of solutions—all standard solutions (6.8-6.13)
shall be analyzed within 48 hours of preparation and on a monthly
basis thereafter for signs of degradation. Standards will remaiji
acceptable if the peak area at the quantitation mass relative
to the DFB internal standard remains within ± 15 percent of
the area obtained in the initial analysis of the standard.
7 Calibration
7.1 v Using the procedure in section 10, extract and concentrate
four 1.0 liter aliquots of reagent water containing one mL each
of the performance standard (6.14), and extract and concentrate
a one liter aliquot of reagent water containing 0.5 mL of the
labeled compound spiking solution (6.8).
7.2 Assemble the GCMS and establish the operating conditions
in table 3. Analyze standards per the procedure in section 11
to demonstrate that the analytical system meets the detection
limits in tables 3 and 4, and the mass-intensity criteria in
table 5 for 50 ng DFTPP.
7
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7.3 Mass spectral libraries—detection and identification of
compounds of interest are dependent upon the spectra stored in
user created libraries.
7.3.1 Obtain a mass spectrum of each labeled and unlabeled
compound and of the internal standard by analyzing an authentic
standard either singly or as part of a mixture in which there
is no interference between closely eluted components. That
only a single compound is present is determined by examination
of the spectrum. Fragments not attributable to the compound
under study indicate the presence of an interfering compound.
7.3.2 Adjust the analytical conditions and scan rate (for
this test only) to produce an undistorted spectrum at the GC
peak maximum. An undistorted spectrum will usually be obtained
if five complete spectra are collected across the upper half
of the GC peak. Software algorithms designed to "enhance" the
spectrum may eliminate distortion, but may also eliminate
authentic masses or introduce other distortion.
7.3.3 The authentic reference spectrum is obtained under DFTFP
tuning conditions (7.2 and table 5) to normalize it to spectra
from other instruments.
7.3.4 The spectrum is edited by saving the 5 most intense
mass peatcs and all other peaks greater than 10 percent of the
base peak. This edited spectrum is stored for reverse search
and for compound confirmation.
7.4 Demonstrate that the 20 ng anthracene-d-_ or phenanthrene-
d1Q produces an area at m/z 188 approx one-tenth that required
to exceed the linear range of the system. For a typical instru-
ment, an area of 20,000 to 50,000 is appropriate. The exact
value must be determined by experience for each instrument.
7.5 Calibration with isotope dilution—isotope dilution is
used when 1) labeled compounds are available, 2) interferences
do not preclude its use, and 3) the quantitation mass extracted
ion current profile (EICP) area for the compound is in the cali-
bration range. If any of these conditions preclude isotope dilu-
tion, internal or external standard methods (7.6 or 7.7) are used.
7.5.1 A calibration curve encompassing the concentration range
is prepared for each compound to be determined. The relative
response vs weight ratio (labeled to unlabeled) of the compound
8
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in standard solutions is computed using a linear regression.
The example in Figure 1 shows a calibration curve for phenol
using phenol-d- as the isotbpic diluent. Also shown are the
±10 percent error limits (dotted lines). Relative Response (RR)
is determined according to the procedures described below. Five
data points are employed for calibration.
7.5.2 The relative response of an unlabeled compound to its
labeled analog is determined from isotope ratio values cal-
culated from acquired data. Three isotope ratios are used in
this process:
R * the isotope ratio measured for the pure unlabeled compound
R = the isotope ratio measured for the labeled compound
R = the isotope ratio of an analytical mixture of unlabeled
and labeled compounds
The m/z's are selected such that R > R . If R is not between
x y m
2R and 0.5R , the method does not apply and the sample is analyzed
y x
by internal or external standard methods.
7.5.3 Capillary columns usually separate the labeled-unlabeled
pair, with the labeled compound eluted first (figure 2). For
this case,
R = area m./z, at the retention time of the unlabeled com-
pound (RT_)
R = area m /z» at tne retention time of the labeled compound (RT-)
area at m./z (at RT-)
R_ = __-, a<- m /* (a<- PT \> as measured in the mixture of the
m area at m_/z vat KL.)
labeled and unlabeled compounds (figure 2)
and RR = R .
m
7.4.4 Special precautions are taken when the labeled-unlabeled
pair is not separated, or when another labeled compound with
interfering spectral masses overlaps the unlabeled compound
(a case which can occur with isomeric compounds). In this case,
it is necessary to determine the respective contributions of
the labeled and unlabeled compounds to the respective EICP areas.
If the peaks are separated well enough to permit the data system
9
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or operator to remove the contributions of the compounds to each
other, the equations in 7.5.3 apply. This usually occurs when
the height of the valley between the two GC peatcs at the the
same m/z is less then 10 percent of the height of the shorter
of the two peafcs. If significant GC and spectral overlap
occur, RR is calculated using the following equations
„. '
m - V(Ey * »
R is measured as shown in figure 3A
J\
R is measured as shown in figure 36
R is measured as shown in figure 3c
m
For the example, RX - 4^g° = 9.64
p _ 2650 Q n,nfl
Ry * 43600 = °-0608
_ 49200 _ oig
Rm = 48300 ~ l'019
RR = 1.107
7.5.5 To calibrate the analytical system by isotope dilution,
analyze a 1.0 (iL aliquot of each of the calibration standards
(6.13) using the procedure in section 11.
7.5.6 Linearity — if the ratio of relative response to concen-
tration for any compound agrees within 5 percent relative stan-
dard deviation over the 5 point calibration range, an averaged
relative response/concentration ratio may be used for that com-
pound; otherwise, a complete calibration curve shall be used
for that compound.
7.6 Internal standard calibration — used when criteria for
isotope dilution (7.5) cannot be met. The internal standard
to be used for both acid and base/neutral analyses is 2,2'-
dif luorobiphenyl. The internal standard method is also applied
to determination of compounds having no labeled analog, and to
measurement of labeled compounds for intra-laboratory statistics
(7.10 and 12.8) .
7.6.1 Response factors — calibration requires the determination
of a response factor (RF) which is defined by the following
equation:
RF = (AsC.s)/(AisCs)
10
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A is the area of the characteristic mass for the compound in
s
the daily standard
A., is the area of the characteristic mass for the internal
i S
standard
C. is the concentration of the'internal standard (jig/mL)
C is the concentration of the compound in the daily standard
(jig/mL)
7.6.1.1 The response factor is determined for at least five
concentrations appropriate to the response of each compound
(6.13); nominally, 10, 20, 50, 100, and 200 jig/mL. The amount
of internal standard added to each extract is the same (100
so that C. remains constant. The RF is plotted vs concentration
for each compound in the standard (C ) to produce a calibration
curve.
7.6.1.2 Linearity—if the response factor (RF) for any compound
agrees within 10 percent relative standard deviation over the
5 point calibration range, an averaged response factor may be
used for that compound; otherwise, the complete calibration
curve for that compound shall be used over the 5 point calibra-
tion range.
7.7 External standard calibration—used when interferences
preclude use of the isotope dilution and internal standard
methods. A master calibration curve is prepared by analyzing
a minimum of five concentrations of standards (6.13). Concentra-
tion vs peak area is plotted for each compound.
7-7-1 Linearity—if the ratio of response to concentration
for any compound agrees within 10 percent relative standard
deviation over the 5 point calibration range, an averaged
response to concentration ratio may be used for that compound
otherwise, the complete calibration curve for that compound
shall be used over the 5 point calibration range.
7.8 Combined calibration—by using calibration solutions con-
taining the labeled and unlabeled compounds and the internal
standard (6.13), a single set of analyses can be used to pro-
duce calibration curves for the isotope dilution, internal
standard, and external standard methods. These curves are
11
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verified each shift (12.5) by analyzing the performance standard
(6.14). Recalibration is required only if calibration (12.5)
and on-going performance (12.8) criteria cannot be met.
7.9 Polar compound detection—unlabeled benzidine and penta-
chlorophenol shall be detectable at the 50 jig/mL level (per
all criteria in section 13). The 50 (ig/mL calibration stan-
dard (6.13) can be used to demonstrate this performance.
7.10 Initial intra-laboratory precision and accuracy—as a
final step in the calibration procedure, the laboratory shall
demonstrate the ability to perform replicate analyses of the
compounds to be determined by this method within limits con-
sidered normal for these analyses using reagent water as the
matrix.
7.10.1 Analyze the four extracts of standards, and the extract
of the blank (7.1), adding 10 ^L of the internal standard solu-
tion (6.10) immediately prior to injection, using the procedure
in section 11. Compute the concentration of the unlabeled com-
pounds (tables 1 and 2) by isotope dilution for those compounds
which have labeled analogs. Compute the concentration of the
unlabeled compounds which have no labeled analogs, and of the
labeled compounds, by the internal standard method (7.6). Com-
pute the average percent recovery and the relative standard
deviation (coefficient of variation) of percent recovery for
all compounds. The average percent recovery shall be 85-115
and the relative standard deviation shall be less than 10 for
all compounds by isotope dilution, and the average percent
recovery shall be 50-130 and the relative standard deviation
shall be less than 35 for all compounds measured by the internal
standard method; otherwise, the system variables need to be
better controlled and the test repeated until these specifi-
cations are met.
8 Quality assurance/quality control (QA/QC)
8.1 Each laboratory that uses this method is required to operate
a formal quality assurance program. Minimum program requirements
consist of an initial demonstration of laboratory performance
and analysis of standards and blanfcs as tests of continued
12
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performance. Specific QA/QC can vary depending on program
requirements, but the principles remain the same. Quality is
controlled, in part, by restricting the allowable range of a
given variable (e.g., GC column temperature) to the limits
shown to yield the reproducibility required. Quality is assured
by comparing results of analysis of blanlcs and standards to
specifications based on Known inter- and intra-laboratory
variability for analysis of the compounds of interest or of
similar compounds (reference 6).
8.1.1 Intra-laboratory variability of this method is measured
using results of four initial analyses of standards in reagent
water (7.10.1), and updated with every sample lot. Control
limits of ± 3 standard deviations from cumulative data deter-
mine acceptable performance. Figure 4 shows an example of
such' a quality control chart. Th'e laboratory shall maintain
these charts to demonstrate the ability to perform acceptable
analyses.
8.1.2 Matrix effects are evaluated by comparing the results
of analyses of labeled compounds in reagent water to results
of analyses of the compounds in samples. Differences in re-
coveries are attributed to the sample matrix.
8.2 Blanlcs—before processing samples, a reagent water blank
shall be analyzed to demonstrate that the analytical system
is interference free. With each sample lot, a blank shall be
analyzed to demonstrate freedom from contamination.
8.3 Documentation—laboratory activities shall be documented
in log books or on magnetic media. Sample logs connect samples
and results; instrument logs record changes which may alter
instrument performance; standards logs document preparation
and traceability of analytical standards; extraction logs
record times, rates, and volumes; QA/QC logs monitor ongoing
laboratory performance.
8.4 The specifications contained in this method can be met if
the apparatus used is calibrated properly, then maintained in
a calibrated state. The GCMS instrument in particular will
provide the most reproducible results if dedicated to the set-
tings and conditions required for the analysis of semivolatiles
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by this method.
8.5 Depending on specific program requirements, field repli-
cates may be collected to determine the precision of the sam-
pling technique, and spiked samples may be required to deter-
mine the accuracy of the analysis when internal or external
standard methods are used.
9 Sample collection, preservation, and handling
9.1 Collect samples in glass containers following conventional
sampling practices (reference 7). Composite samples are col-
lected in refrigerated glass containers (5.1.3) in accordance
with the requirements of the sampling program.
9.2 Maintain samples at 0-4°C from the time of collection
until extraction. If residual chlorine is present, add 80 mg
sodium thiosulfate per liter of water. EPA methods 330.4 and
330.5 may be used to measure residual chlorine (reference 8).
9.3 Begin sample extraction within seven days of collection,
and analyze all extracts within 40 days of extraction.
10 Sample extraction and concentration
10.1 Labeled compound spiking—measure 1.00 ± 0.01 liter of
sample into a glass container. For untreated effluents, and
samples which are expected to be difficult to extract and/or
concentrate, measure an additional 10.0 ± 0.1 mL and dilute
to a final volume of 1.00 ± 0.01 liter with reagent water in
a glass container.
10.1.1 For each sample or sample lot (to a maximum of 20) to
be extracted at the same time, place two 1.00 ± 0.01 liter
aliquots of reagent water in glass containers.
10.1.2 Spike 0.5 mL of the labeled compound spiking solution
(6.8) into all samples and one reagent water aliquot.
10.1.3 Spike 1.0 mL of the performance standard (6.14) intp
the remaining reagent water aliquot.
10.1.4 Stir and equilibrate all solutions for 1-2 hr.
10.2 Base/neutral extraction—place 100-150 mL methylene chloride
in each continuous extractor and 200-300 in each distilling
flask.
10.2.1 Pour the sample(s), blank, and standard aliquots into
the extractors. Rinse the glass containers with 50-100 mL
14
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methylene chloride and add to the respective extractor.
10.2.2 Adjust the pH of the waters in the extractors to 12-13
with 6N NaOH while monitoring with a pH meter. Begin the
.extraction by heating the flask until the methylene chloride
is boiling. When properly adjusted, 1-2 drops of methylene
chloride per second will fall from the condenser tip into
the water. After 1-2 hours of extraction, test the pH and
readjust to 12-13 if required. Extract for 18-24 hours.
10.2.3 Remove the distilling flask, estimate and record the
volume of extract (to the nearest 100 mL), and pour the con-
tents through a drying column containing 7 to 10 cm anhydrous
sodium sulfate. Rinse the distilling flask with 30-50 mL
methylene chloride and pour through the drying column. Col-
lect the solution in a 500 mL K-D evaporator flask equipped
with a 10 mL concentrator tube. Seal, label as the base/
neutral fraction and concentrate per sections 10.4 to 10.6.
10.3 Acid extraction—adjust the pH of the waters in the
extractors to 2 or less using 6N sulfuric acid. Charge clean
distilling flasks with 300-400 mL methylene chloride. Test and
adjust the pH of the waters after the first 1-2 hr of extrac-
tion. Extract for 18-24 hours.
10.3.1 Repeat 10.2.3, except label as the acid fraction.
10.4 Concentration—concentrate the extracts in separate 500
mL K-D flasks equipped with 10 mL concentrator tubes.
10.4.1 Add 1 to 2 clean boiling chips to the flask and attach
a three-ball macro Snyder column. Prewet the column by adding
approx 1 mL methylene chloride through the top. Place the K-D
apparatus in a hot water bath so that the entire lower rounded
surface of the flask is bathed with steam. Adjust the vertical
position of the apparatus and the water temperature as required
to complete the concentration in 15 to 20 minutes. At the pro-
per rate of distillation, the balls of the column will actively
chatter but the chambers will not flood. When the liquid has
reached an apparent volume of 1 mLf remove the K-D apparatus
from the bath and allow the solvent to drain and cool for at
least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with 1-2 mL
methylene chloride. A 5 mL syringe is recommended for this
15
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operation.
10.4.2 For performance standards (7.1 and 12.8) and for
blanks (7.1 and 12.7), combine the acid and base/neutral
extracts for each at this point. Do not combine the acid
and base/neutral extracts for samples.
10.5 Add a clean boiling chip and attach a two ball micro
Snyder column to the concentrator tube. Prewet the column
by adding approx 0.5 mL methylene chloride through the top.
Place the apparatus in the hot water bath. Adjust the ver-
tical position and the water temperature as required to com-
plete the concentration in 5-10 minutes. At the proper rate
of distillation, the balls of the column will actively chatter
but the chambers will not flood. When the liquid reaches an
apparent volume of approx 0.5 mL, remove the apparatus from
the water bath and allow to drain and cool for at least 10
minutes. Remove the micro Snyder column and rinse its lower
joint into the concentrator tube with approx 0.2 mL methylene
chloride. Adjust the final volume to 1.0 mL.
10.6 Transfer the concentrated extract to a clean screw cap
vial. Seal the vial with a Teflon-lined septum, and mark the
level on the vial. Label with the sample number and fraction,
and store in the dark at -20 to -10°C until ready for analysis.
11 GCMS analysis
11.1 Establish the operating conditions given in tables 3 or
4 for analysis of the base/neutral or acid extracts, respectively.
For analysis of combined extracts (10.4.2), use the operating
conditions in table 3.
11.2 Bring the concentrated extract (10.6) or performance
standard (6.14) to room temperature and verify that any pre-
cipitate has redissolved. Verify the level on the extract (10.6)
and bring to the mark with solvent if required.
11.3 Add 10 U.L of the internal standard solution (6.10) to the
extract immediately prior to analysis to minimize the possibility
of loss by evaporation, adsorption, or reaction. Mix thoroughly.
11.4 Inject 1.0 |j.L of the standard solution or extract using
on-column or splitless injection. Start the GC•column initial
16
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isothermal hold upon injection. Start MS data collection after
the solvent peak elutes. Stop data collection after the benzo-
(ghi)perylene or pentachlorophenol peak elutes for the base/neu-
tral or acid fraction, respectively. Return the column to the
initial temperature for analysis of the next sample.
12 System performance
12.1 At the beginning of each 8 hr shift during which analyses
are performed, system performance and calibration shall be veri-
fied. For these tests, analysis of the performance standard (6.14)
shall be used to verify all performance criteria with a single
analysis. Adjustment and/or recalibration (per section 7 ) shall
be performed until all performance criteria are met. Only after
all performance criteria are met may samples and blanks be analyzed.
12.2 DFTPP spectrum validity—inject 1 ^L of the DFTPP solution
(6.11) either separately or within a few seconds of injection of
the standard analyzed at the beginning of each shift. The cri-
teria in table 5 shall be met.
12.3 Early and late eluted components
12.3.1 Base/nuetral—N-nitrosodimethylamine shall be sufficiently
resolved from the solvent peak to permit detection, and benzo(ghi)-
perylene shall give a mass spectrum which permits detection, both
per all criteria in section 13. The retention time of benzo(ghi)-
perylene shall be 40-45 minutes.
12.3.2 Acid—phenol shall be sufficiently resolved from the sol-
vent peak to permit detection, and pentachlorophenol shall give
a mass spectrum which permits detection, both per all criteria
in section 13. The retention time of pentachlorophenol shall be
20-25 minutes.
12.4 GC resolution—the valley height' between anthracene and
phenanthrene at m/z 178 (or the analogs at m/z 188) shall not
exceed 10 percent of the taller of the two peaks.
12.5 Verification of calibration—the response ratios of the
labeled/unlabeled pairs shall be within ± 10 percent of their
respective points on the original calibration curves (7.5.5).
The response factors for the labeled compounds and for the unlabeled
compounds having no labeled analog shall be within ± 20 percent of
their respective points on the original calibration curves (7.2.1).
17
-------
12.6 Multiple peaks—each component injected shall give a
single, distinct GC peak.
12.7 Laboratory blanks—if any compound of interest (table
1 and 2) or any potentially interfering compound is found in
a blank at greater than 10 jig/L (assuming a response factor
of 1 relative to the internal standard for compounds not listed
in tables 1 and 2), analysis of samples is halted until the
source of contamination is eliminated and a blank shows no
evidence of contamination at this level.
12.8 On-going intra-laboratory precision and accuracy
12.8.1 Analyze the extracted performance standard (10.1.3)
prior to analysis of samples from the same lot.
12.8.2 The percent recovery for the unlabeled/labeled pairs
shall be 80-120 by isotope dilution. The percent recovery
for the labeled compounds and the unlabeled compounds having
no labeled analog shall be 40-130 percent by the internal
standard method. The result for each compound, measured and
recorded as in section 7.8, shall be within ± 3 standard
deviations of the result for initial (7.8) and previous on-
going data.
12.8.3 Add results which pass the specification in 12.8.2
to initial and previous on-going data. Update QC charts to
form a graphic representation of continued laboratory perfor-
mance (Figure 4).
13 Qualititative determination—accomplished by comparison
of data from analysis of a sample or blank with data from
analysis of the shift standard (12.1). Identification is con-
firmed when spectra and retention times agree per the follow-
ing criteria:
13.1 Labeled compounds and unlabeled compounds having no
labeled analog t
13.1.1 The signals for all characteristic masses stored in
the spectral library (7.3.4) shall be present and shall maxi-
mize within the same two consecutive scans.
13.1.2 Either 1) the background corrected EICP areas, or
2) the corrected relative intensities of the mass spectral
peaks at the GC peak maximum shall agree within a factor of
two for all masses stored in the library.
18
-------
13.1.3 The relative retention time of the compound shall agree
within ± 15 scans or ± 15 seconds (whichever is greater) of
the relative retention time in the shift standard (12.1).
13.2 Unlabeled compounds having a labeled analogi
13.2.1 The signals for all characteristic masses stored in
the spectral library (7.3.4) shall be present and shall maxi-
mize within the same two consecutive scans.
13.2.2 Either 1) the background corrected EICP areas, or
2) the corrected relative intensities of the mass spectral
peaks at the GC peak maximum shall agree within a factor of
two for all masses stored in the library.
13.2.3 The retention time difference between the labeled/
unlabeled pair shall agree within ± 2 scans or ± 2 -seconds
(whichever is greater) of this difference in the shift stan-
dard (12.1).
13.3 Masses present in the experimental mass spectrum that
are not present in the reference mass spectrum shall be ac-
counted for by contaminant or background ions. If the ex-
perimental mass spectrum is contaminated, an experienced spec-
trometrist is to determine the presence or absence of the com-
pound.
14 Quantitative Determination
14.1 Isotope dilution—by adding a known amount of each
labeled compound to every sample prior to extraction, auto-
matic correction for component recovery is accomplished. This
is because the unlabeled compound and its labeled analog ex-
hibit the same effects during extraction, concentration,
and gas chromatography. Relative response (RR) values for the
sample mixtures are used in conjunction with calibration curves
(7.5) to determine concentrations directly, so long as the la-
beled compound spiking levels are constant. For the phenol
example given in figure 1, RR would be equal to 1.180. For
this RR value, the calibration curve given in figure 1 indi-
cates a concentration of 108 ng/L.
14.2 Internal standard—by adding a constant known amount of
internal standard (C. ) to every sample extract, the concentra-
tion of pollutant (C ) in the sample is calculated using the
19
-------
following equation:
Co = 1000 p,g/L) of the compounds of interest, inter-
fering compounds, and/or polymeric materials. Some samples
will not concentrate to one mL (10.5); others will overload
the GC column and/or mass spectrometer.
15.2 Analyze the dilute aliquot (10.1) when the sample will
not concentrate to 1.0 mL.
15.3 Recovery of internal standard — the EICP area of the in-
ternal standard should be within a factor of two of the area
in the shift standard (12.1). If the absolute areas of the
labeled compounds are within a factor of two of the respective
areas in the shift standard, and the internal standard area
is less than one-half of its respective area, then internal
standard loss in the extract has occurred. In this case,
use one of the labeled compounds (preferably a polynuclear
aromatic hydrocarbon) to compute the concentration of an un-
labeled compound with no labeled analog.
20
-------
15.4 Recovery of labeled compounds—in most samples, labeled
compound recoveries should be similar to those from reagent
water (12.8). If the recovery of any labeled compound is
less than 10 percent of the average, on-going recovery (12.8),
the dilute extract (10.1) is analyzed by isotope dilution;
otherwise, the extract is diluted and analyzed as in section 14.4.
If the recoveries of all labeled compounds and the internal
standard are low (per the criteria above), then a loss in in-
strument sensitivity is the most likely cause. In this case,
the performance standard (12.1) shall be analyzed and calibra-
tion verified (12.5). If a loss in sensitivity has occurred,
the instrument shall be repaired, the performance specifications
in section 12 shall be met, and the extract reanalyzed. If
a loss in instrument sensitivity has not occurred, the extract
is handled as in section 14.4.
16 Method performance
16.1 Preliminary method performance data can be found in refer-
ence 9.
21
-------
References
1. "Performance Tests for the Evaluation of Computerized Gas
Chromatography/Mass Spectrometry Equipment and Laboratories"
USEPA, EMSL Cincinnati, Ohio 45268, EFA-600/4-80-025 (April 1980).
2. "Woricing with Carcinogens," DHEW, PHS, CDC, NIOSH, Publication
77-206, (Aug 1977).
3. "OSHA Safety and Health Standards, General Industry" OSHA 2206,
29 CFR 1910 (Jan 1976).
4. "Safety in Acedemic Chemistry Laboratories," ACS Committee on
Chemical Safety (1979).
5. "Reference Compound to Calibrate Ion Abundance Measurement in
Gas Chromatography-Mass Spectrometry Systems," J.W. Eichelberger,
L.E. Harris, and W.L. Budde, Anal. Chem., 47. 995 (1975).
6. "Handbook of Analytical Quality Control in Water and Waste-
water Laboratories," USEPA, EMSL, Cincinnati, OH 45268, .EPA-600/
4-79-019 (March 1979).
7. "Standard Practice for Sampling Water," ASTM Annual BOOK of
Standards, ASTM, Philadelphia, PA, 76 (1980).
8. "Methods 330.4 and 330.5 for Total Residual Chlorine," USEPA,
E?I3L, Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979).
9. Colby, B. N. , Beimer, R. G. , Rushneck, D. R., and Telliard,
W. A., "Isotope Dilution Gas Chromatography-Mass Spectrometry
for the Determination of Priority Pollutants in Industrial
Effluents." USEPA, Effluent Guidelines Division, Washington
DC 20460 (1980).
22
-------
Table 1
Base/neutral Extractable Compounds
Compound Storet
CAS Registry
acenaphthene
acenaphthylene
anthracene
benzidine
benzo ( a ) anthracene
benz o ( b ) f luor ant hene
benzo ( Ic ) f luoranthene
benzo ( a ) pyrene
benzo ( ghi ) perylene
biphenyl (Appendix C)
bis(2-chloroethyl) ether
bis ( 2-chloroethcncy) methane
bis ( 2-chloroisopr opyl ) ether
bis(2-ethylhexyl) phthalate
4-bromophenyl phenyl ether
butyl benzyl phthalate
n-CIO (Appendix C)
n-C12
n-C14
n-C16
n-C18
n-C20
n-C22
n-C24
n-C26
n-C28
n-C30
34205
34200
34220
39120
34526
34230
34242
34247
34521
81513
34273
34278
34283
39100
34636
34292
77427
77588
77691
77757
77804
77830
77859
77886
77901
83-32-9
208-96-8
120-12-7
92-87-5
56-55-3
205-99-2
207-08-9
50-32-8
191-24-2
92-52-4
111-44-4
111-91-1
108-60-1
117-81-7
101-55-3
85-68-7
124-18-5
112-40-3
629-59-4
544-76-3
593-45-3
112-95-8
629-97-0
646-31-1
630-01-3
630-02-4
638-68-6
001 B
077 B
078 B
005 B
072 B
074 B
075 B
073 B
079 B
512 B
018 B
043 B
042 B
066 B
041 B
067 B
sn 3
506 B
>"1 1 5
^\<-{ "&
SsT'i- &
•52-i 5
52-1- ^
^l 3
•rz-H- ^
•T2>> t?
•S"z-t ^
001 B
002 B
003 B
004 B
005 B
007 B
009 B
006 B
008 B
Oil B
010 B
012 B
013 B
014 B
015 B
2-chloronaphthalene 34581 91-58-7 020 B 016 B
4-chlorophenyl phenyl ether 34641 7005-72-3 040 B 017 B
chrysene 34320 218-01-9 076 B 018 B
p-cymene (Appendix C) 77356 99-87-6 513 B
dibenzo(a,h)anthracene 34556 53-70-3 082 B 019 B
dibenzofuran (Appendix C) 81302 132-64-9 505 B
dibenzothiophene (Synfuel) 77639 132-65-0 504 B
di-n-butylamine (Appendix C) 77300 111-92-2 511 B
di-n-butyl phthalate 39110 84-74-2 068 B 026 B
1,2-dichlorobenzene 34536 95-50-1 025 B 020 B
1,3-dichlorobenzene 34556 541-73-1 026 B 021 B
1,4-dichlorobenzene 34571 106-46-7 Q27 B 022 B
3,3'-dichlorobenzidine 34631 91-94-1 028 B 023 B
diethyl phthalate 34336 84-66-2 070 B 024 B
2,4-dimethylphenol 34606 105-67-9 034 A 003 A
dimethyl phthalate 34341 131-11-3 07i B 025 B
2,4-dinitrotoluene 34611 121-14-2 035 B 027 B
2,6-dinitrotoluene 34626 606-20-2 026 B 028 3
dioctyl phthalate 34596 117-84-0 069 B 029 3
diphenylamine (Appendix C) 77579 122-39-4 507 3
diphenyl ether (Appendix C) 77587 101-84-8 508 B
23
-------
Table 1 (continued)
Compound
. 1,2-diphenylhydrazine
fluoranthene
fluorene
hexachlorobenzene
hexachlorobutadiene
hexachloroethane
hexachlorocyclopentadiene
indeno(1,2,3-cd)pyr ene
isophorone
naphthalene
0-naphthylamina (Appendix C)
nitrobenzene
N-nitrosodimethylamine
N-nitrosodi-n-proplyamine
N-nitrosodiphenylamina
phenanthrena
phenol
a-picoline (Synfuel)
pyrene
styrene (Appendix C)
a-terpineol (Appendix C)
1,2,4-trichlorobenzene
Storet
34346
34376
34381
39700
34391
34396
34386
34403
34408
34696
82553
34447
34438
34428
34433
34461
34694
77088
34469
77128
77493
34551
CAS Reaistrr
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
67-72-1
77.47-4
193-39-5
78-59-1
91-20-3
91-59-8
98-95-3
62-75-9
621-64-7
86-30-3
85r01-8
108-95-2
109-06-8
129-00-0
100-42-5
98-55-5
120-82-1
EPA-EGD
037 B
039 B
080 B
009 B
052 3
012 B
053 3
083 B
054 B
055 B
502 B
056 B
061 B
063 B
062 B
081 B
065 A
503 B
084 B
510 B
509 B
008 B
NPDE5
030 B
031 B
032 B
033 B
034 B
036 B
035 B
037 B
038 B
039 B
040 B
041 B
042 B
043 B
044 B
010 A
045 B
046 B
Table 2
Acid Extractable Compounds
Compound
benzoic acid (Synfuel)
4-chloro-3-methylphenol
2-chlorophenol
2,4-dichlorophenol
2,4-dinitrophenol
hexanoic acid (Synfuel)
2-methyl-4,6-dinitrophenol
2-nitrophenol
4-nitrophenol
pentachlorophenol
2,4,6-trichlorophenol
Storet
77247
34452
34586
34601
34616
77190
34657
34591
34646
39032
34621
CAS Reaistarv
65-85-0
59-50-7
95-57-8
120-83-2
51-28-5
142-62-1
534-52-1
88-75-5
100-02-7
87-86-5
88-06-2
EPA-EGD
500 A
022 A
024 A
031 A
059 A
501 A
060 A
057 A
058 A
064 A
021 A
NPDES
008 A
001 A
002 A
005 A
004 A
006 A
007 A
009 A
Oil A
24
-------
Table 3
Gas Chromatography of Base/Neutral Extractable Compounds (1)
Relative Limit of Detection
(3)
C omoound
N-nitrosodimethy lamine
a-picoline
styrene
p— cymene
d i -nf-buty lamine
phenol
bis ( 2-chlor oethyl) ether
1 , 3-dichlorobenzene
1 , 4-dichlorobenzene
1 , 2— <^ichlorr>*?*pnz*T10
bis ( 2-chlor oisopropy 1 ) ether
hexachlor oet hane
N-nitroso— di-n-propyl amine
nitrobenzene
isophorone
2 , 4-dimethy Iphenol
bis ( 2-chlor oethoxy ) methane
1 ? 4— tri pti lor rth*»yi^«*p*>
naphthalene
dodecane
huPHicnlorobuta'ii ipnf
hexachlor ocyclopentad i ene
' i ? * — ^ifl iir)T*f?fc?inh— Tiyl (in^*r"nTiT s^und?
2-chlor onaphtfaalene
biphenyl
acenapfat ha lene
dimethyl phthalate
acenaphthene
d ibenzof uran
diphenylether
2 ,6-dinitrotoluene
0 -naphthy lamine
f luorene
diethyl phthalate
4-chlor opheny Ipheny lather
2 ,4-dinitrotoluene
1 , 2-diphenylhydrazine ( 3 )
N-nitrosodipheny lamine (4)
4-bromopheny Ipheny lether
hexachlor obenz ene
phenanthrene
anthracene
d ibenzo thi ophene
di-n-butylphthalate
f luoranthene
pyrene
benzidine
2,3,7, 8-tetrachlor odibenzo-p-dioxin
butylbenzylphthalate
chrysene
benzo ( a ) anthracene
3,3' -dichlorobenzidine
bis ( 2-ethlyhexy 1 ) phthalate
di-n-octyiphthalate
25
Retention
Time (2)
.26
.28
.40
.46
.51
.58
.59
.61
.61
.64^
.67
.69
.69
.70
.74
.77
.78
.80
.81
.82
.84
.95
ird)1.00
1.01
1.03
1.05
1.05
1.15
1.18
1.06
1.19
1.20
1.23
1.23
1.24
1.26
1.27
1.26
1.31
1.33
1.39
1.39
1.40
1.51
1.59
1.62
1.62
_
1.77
1.87
1.87
1.87
1.92
2.13
ng
in-iected
50
20
20
20
200
20
20
20
20
20
20
20
20
20
50
20
20
20
20
20
20
2O
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
-------
Table 3 (continued)
Compound SS2L—— na
benzo(b)£luoranthene 2.21 20
benzo (Ic) f luoranthene 2.21 20
benzo(a)pyrene 2.34 20
indeno(l,2,3-cd)pyrene 3.05 50
dibenzo( a, h) anthracene 3.10 50
benzo(g,h,i)perylene 3.26 50
Notesi bonded phase
(1)30 m SE54Afused silica capillary column. .. conditions»
gas velocity 30 cm/sec; temperature program* 5 min at. 30 C; 30 -280
at 8°C per min, iso at 280°C until benzo(ghi)perylene elutes
(2) To 2,2t-difluorobipnenyl
(3) This is a minimum level at which the entire analytical
system must give recognizable mass spectra (baclcground corrected)
and acceptable calibration points.
(4) detected as diphenylamine. If rigorous differentiation
betveen N-nitrosodiphenylamine and diphenylamine is required,
EPA Method 607 is to be used.
(5) detected as azobenzene
Table 4
Gas Chromatography of Acid Extractable Compounds (1)
Relative Limit of Detection
Retention ng (3)
Compound Time .(2) injected
2-chlorophenol .59 50
hexanoic acid .63 200
2-nitrophenol .75 50
benzole acid ,83 50
2,4-dichlorophenol .79 50
2,4,6-trichlorophenol .97 50
4-chloro-3-methylphenol .90 50
2,2'-difluorobiphenyl 1.00 20
4-nitrophenol 1.07 50
2,4-dinitrophenol 1.16 200
2-methy 1-4,6-dini tr ophenol 1.25 200
pentacfalorophenol 1.37 100
Motes: bonded phase
(I) 30 m SE54Afused silica capillary column. conditions:
gas velocity 30 cm/sec; temperature program: 5 min at 30 C; 30-250 C
or until pentachlorophenol elutes
(2) to 2,2t-difluorobiphenyl
(3) This is a minimum level at vhich the entire analytical
system must give recognizable mass spectra (baclcground cor-
rected) and acceptable calibration points.
26
-------
Table 5
DFTPP Mass-intensity Specifications
Mass Intensity required
51 30-80% of mass 198
68 <2% of mass 69
70 <2% of mass 69
127 40-60% of mass 198
197 <1% of mass 198
198 base peak, 100%
199 5-9% of mass 198
275 10-30% of mass 198
441 < mass 443
442 >40% of mass 198
443 17-23% of mass 442
27
-------
Table 6
Base/Neutral Extractable Compound Characteristic Ions
Compound
labeled
analoa
acenaphthene dlO
acenaphthylene d8
anthracene dlO
benzidine d8
benzo(a)anthracene d12
benzo(b)fluoranthene d!2
benzo (tc) t luoranthene d 12
benzo.( a) pyr ene d 12
benzo(g,h,i)perylene €12
biphenyl dip
bis(2-chloroethyl) ether d3
bis(2-chloroethoxy)methane (1)
bis(2-chloroisopropyl) ether d!2
bis(2-ethylhexyl) phthalate d4
4-bromophenyl phenyl ether (1)
butyl benzyl phthalate (1)
n-C12 d22
2-chloronaphthalene d7
4-chlorophenyl phenyl ether d5
chrysene d!2
dibenzo(a,h)anthracene (1)
dibenzofuran d8
dibenzothiophene d8
di-n-butylamine d!8
di-n-butyl phthalate d4
1,2-dichlorobenzene d4
1,3-dichlorobenzene d4
1,4-dichlorobenzene d4
3,3'-dichlorobenzidine d*
diethyl phthalate d4
2,4-dimethylphenol dJ
2,4-dinitrotoluene d3
2,6-dinitrotoluene d3
di-n-octyl phthalate d4
dimethyl phthalate d4
diphenylamine d6
diphenyl ether dlO
1,2-diphenylhydrazine* dlO
fluoranthene dlO
Primary m/z
154/164
152/160
178/188
184/192
228/240
252/264
252/264
252/264
276/288
154/164
93/99
121/131
149/153
57/66
162/169
204/209
228/240
168/176
184/192
86/96
149/153
146/152
146/152
146/152
252/258
149/153
122/125
165/167
165/167
149/153
163/167
169/175
170/180
77/82
202/212
28
-------
Table 6 (continued)
Compound
labeled
analog
fluorene dlO
hexachlorobenzene 13C6
hexachlorobutadiene 13C4
hexa chloroethane 13C1
hexachlorocyclopentadiene 13C1
indeno(1,2,3-cd)pyrene (1)
isophorone d8
naphthalene d8
B-naphthylamine d7
nitrobenzene d5
N-nitrosodimethylamine (1)
N-nitrosodi-n-propylamine (1)
N-nitrosodiphenylamine** d6
phenanthrene d10
phenol d5
a-picoline d7
pyrene dlO
styrene d5
a-terpineol d3
1,2,4-trichlorobenzene d3
Primary m/z
166/176
284/292
225/231
201/204
237/240
82/88
128/136
143/150
77/82
169/175
178/188
94/99
93/100
202/212
104/109
59/62
180/183
*Detected as azobenzene
**Detected as diphenylamine
(1) Compound not available at time of writing
Table 7
£cid Extractable Compound
Compound
benzole acid
4-chloro-3-methylphenol
2-chlorophenol
2,4-dichlorophenol
2 ,4-dini trophenol
hexanoic acid
2-methyl-4 , 6-dini trophenol
2-ni trophenol
4-ni trophenol
pentachlorophenol
2,4,6-trichlorophenol
Characteristic Ions
labeled
analog
d5
d2
d4
d3
d3
dll
d2
d4
d4
13C6
d2
Primary m/z
122/127
107/109
128/132
162/167
184/187
60/63
198/200
139/143
139/143
266/272
196/202
29
-------
too *
10-
ai-
aot.
.01 .1 1.0 10.0
WEIGHT RATIO (UNLABELED/LABELED)
RGUM4
30
-------
area at
area at
Figure 2 Extracted Ion Current Profiles for Chromatographically
Resolved Labeled (m^/z) and Unlabeled (m-/z) Pairs
31
-------
area=4780
area=2560
area=43600
area=48300
area=49200
Figure 3 Extracted Ion Current Profiles for (3A) Unlabeled
Compound, (3B) Labeled Compound, and (3C) Equal Mixture of
Unlabled and Labeled Compounds
32
-------
Appendix B
Instructions for Preparation and Analysis of Performance Evaluation
Samples
1 Overview
In these instructions, numbers in brackets [_] refer to para-
graph numbers in Method 1625A (March 1983 draft). This Method is
the only Method to be used in this performance evaluation.
Performance evaluation consists of three (3) extractions/con-
centrations and eleven (11) im'ections. A one liter water sample,
a one liter reagent water (method) blank, and a one liter aliquot
of reagent water containing a standard (the aqueous standard) are
to be extracted and concentrated [lO]. The eleven injections are
for calibration [7.5], determination of inter-laboratory response
ratios (not in the Method), calibration, verification [12.5], and
analyses of extracts of the blank, aqueous standard, and sample
[ll], as detailed in table 1.
2 Materials provided—all standards and the water sample have been
provided; you are to provide the reagent water for the blank and
aqueous standard [lO], and decafluorotriphenylphosphine (DFTPP).
The five solutions provided arei
Solution Total Method
identification volume Purpose Reference
200 ng/mL 4.3 ± 0.2 mL calibration (2.5 mL) [6.8, 6.13J
isotopes spiking into waters [lO.l]
blank (0.5 mL)
standard (0.5 mL)
sample (0.5 mL)
400 ng/mL PP 2.0 ± 0.1 mL calibration (0.95 mL) [6.9, 6.13]
standards spiking into water [10*l]
standard (0.25 mL)
100 ng/mL mixed 1.0 ± 0.1 mL inter-lab response
standards ratios (0.5 mL)
10 mg/mL inter- 1.0 ± 0.1 mL spiking into extracts [11.3]
nal standard +01
sample 1.0 _ Q* L performance evaluation
The first four solutions listed above are packaged in sealed
glass ampuls. Notice that several solutions are used for multiple
purposes and that there is little excess. Once an ampul is opened,
the solution should be aliquotted as required by these instructions
and the Method to preclude changes in concentration caused by eva-
poration of the solvent. The sample is to be refrigerated (0-4 C)
until ready for extraction. The solutions of standards are to be
kept in the dark at -20 to -10 C when not in use.
3 Preparations for analysis of performance evaluation samples—
in order to successfully analyze the solutions and extracts, it is
necessary to obtain a valid spectrum for DFTPP [7.3.3, 12.2, arid
table 5] and authentic spectra for all labeled (isotopes) and up-
labeled (PP standards) compounds. To obtain these authentic spectra,
separately inject approx 0.5 |iL of the "200 ng/mL isotopes" and
approx 0.25 pL of the "400 \iq/mL PP standards" [7.3]. Reporting
of edited spectra [7.3.4] is required for this performance evalua-
tion (see section 8.1.4 of these instructions). If two compounds co-
elute, a qualified spectrometrist is to deduce the correct spectrum
and/or alternate quantitation mass for each compound.
4 Preparation of standard solutions for calibration and inter-lab-
oratory response ratios.
4.1 Calibration solutions—in each of five (5) cleaned 1.5-3.0 mL
-------
glass vials with Teflon-lined screw caps, place 500 \iL, of the "200
tig/mL isotopes" and separately add 25, 50, 125, 250 and 500 \iL of
the "400 p.g/mL PP standards." Bring each solution to 1.0 mL total
volume with methylene chloride [6.13]. Add 10 fiL of the "10 mg/mL
internal standard" [6.10] to each vial immediately prior to injec-
tion.
4.2 Inter-laboratory response ratio solution—in a cleaned 0.8-
3.0 mL glass vial with Teflon-lined screw cap, place 500 uL of the
"100 (ig/mL mixed standards." Add 5.0 p.L of the "10 mg/mL internal
standard" immediately prior to injection.
5 Extraction of waters—the flow chart in figure 1 shows the ex-
tractions required. Some steps have been omitted from this chart
but are detailed in the Method [10]. Continuous extraction only
is to be used.
6. Method specifications—all specifications in the Method shall
be met with the following exceptionsi
6.1 preparation of solutions of standards [6.7-6.9] is not required.
All pollutant and labeled standards have been provided and are the
only standards to be used.
6.2 determination of initial and on-going recovery and precision
[7.1, 7.10, and 12.8] is not to be performed.
6.3 the sample is not "complex" and the section on "Analysis of
complex samples" [15] does not apply.
6.4 the specifications, for verification of calibration [12.5] need
not be met for the "B" shift (injection number 7, table 1); however-,
differences between the results of this injection and injection num-
ber 4 indicate an instability problem with the instrument and can
affect the results obtained in injections 8-10. You will be eval-
uated on all of these results (see section 9 of these instructions).
6.5 the chromatographic conditions [tables 3 and 4] shall super-
cede the elution time specifications [12.3.1 and 12.3.2]. The col-
umn to be used is a 30 meter, 0.25 mm i.d., J & W DB-5, or equiva-
lent. Equivalent means a 30 meter, 0.25 mm i.d., bonded phase
fused silica capillary containing 94 percent methyl, 4 percent
phenyl, and 1 percent vinyl silicone.
7 Corrections to Method 1625—the additions and corrections in
table 2 supercede data in the Method [tables 6 and 7].
8 Reporting
8.1 Data to be reported
8.1.1 hardcopy of mass spectra and mass-intensity lists of DFTPP.
8.1.2 hardcopy of RIC chroma tog rams from the 11 injections (table
1) normalized on the largest non-solvent peak.
8.1.3 technical data from analysis of the 11 injections as detailed
in TAB 1 of "Appendix A Quantitation Reports on Magnetic Tape," and
given on the "Performance Evaluation Data Sheet" in figure 2.
8.1.4 hardcopy of library mass-intensity data [7.3.4].
8.2 Formats—data may be reported in one or more of the following
formatsi
8.2.1 quantitation reports on magnetic tape per the specifications
in "Appendix A Quantitation Reports on Magnetic Tape."
8.2.2 hardcopy quantitation reports as given by example in TAB 1
of "Appendix A Quantitation Reports on Magnetic Tape."
8.2.3 "Performance Evaluation Data Sheets" as given in figure 2.
The most desirable forms for data reporting are both magnetic
tape and hardcopy quantitation reports. If magnetic tape reporting
-------
only is employed, you assume all risk for illegible and/or non-
readable tape. Extensions of time for regeneration of tape shall
not be granted. If more than one form of data submission is used,
the order of precedence (8.2.1-8.2.3 above) shall be employed for
data evaluation; i.e., the magnetic tape data shall be assumed cor-
rect; in its absence, the hardcopy shall be assumed correct; in its
absence, data sheets (figure 2). shall be assumed correct.
8.3 The compound numbering system given in TAB 2 of "Appendix A
Quantitation Reports on Magnetic Tape" is required for all forms
of reporting. For data evaluation, compound names shall be ig-
nored. The compound numbering system shall be used as follows«
8.3.1 pollutants with no labeled analog are quantitated by inter-
nal or external standard methods [7.6 or 7.7] and reported as three
digit numbers with a zero (0) as the first digit for the priority
pollutants, and a five (5)-as the first digit for the Appendix C
and synfuel pollutants.
8.3.2 labeled compounds are quantitated by internal or external
standard methods [7.6 or 7.7] and reported as three digit numbers
with a two (2) as the first digit for the priority pollutants,
and a six (6) as the first digit for the Appendix C and synfuel
pollutants.
8.3.3 pollutants quantitated by isotope dilution [7.5] are re-
ported as three digit numbers with a three (3) as the first digit
for the priority pollutants, and a seven (7) as the first digit
for the Appendix C and synfuel pollutants.
Examples of reporting using these numbers are given in fig-
ure 2 and in TAB 1 of "Appendix A Quantitation Reports on Magne-
tic Tape."
8.4 Deadline— all data shall be received at the EPA Sample Con-
trol Center address given in Section 4 of "Appendix A Quantita-
tion Reports on Magnetic Tape" by 1700 EDST, 22 June 1983. Data
received after that hour may result in disqualification of the
submitting laboratory.
9 Data evaluation—you are responsible for analyses of only those
compounds for which standards have been provided (as given on the
data sheets supplied with the standards and sample). Scoring
shall be based on the followingi
9.1 Completeness—all results for all compounds from all 1J injec-
tions, plus RIC chromatograms, DFTPP spectra and lists, and lib-
rary mass-intensity data.
9.2 Method specifications—all specifications in the Method (other
than those specifically excepted in section 6 of these instructions)
shall be met.
9.3 Mean concentrations—the compounds (labeled and/or unlabeled)
found in the blank, aqueous standard, and sample shall be evaluated
as closest to the mean of all submitting laboratories, based on
an arithmetic or log-normal distribution (whichever is most appro-
priate) after removal of outliers. Scoring will be on a compound
by compound basis.
10 Questions—concerning these instructions and/or the Method
and/or solutions should be addressed to Susan Hancock or Deborah
Danforth-Miller at the EPA Sample Control Center (703-557-5040).
-------
Table 1 Injections to be Performed for Performance Evaluation
Injection
number (2)
1
2
3
4
5
6
7
8
9
10
11
Solution injected
DFTPP (4)
10 ng/mL calibration
20 ng/mL calibration
50 ng/mL calibration
100 |ig/mL calibration
200 ng/mL calibration
100 ng/mL mixed standards
DFTPP (4)
100 jig/mL calibration
extract of blank
extract of aqueous standard
extract of sample (acid)
extract of sample (b/n)
Report identifier (3)
(5),(6),CAL,00010,00,C,NAiNA,NA$
(5),(6),CAL,00020,00,C,NAiNA,NA$
(5),(6),CAL,00050,00,C,NAiNA,NA$
(5),(6),CAL,00100,00,C,NAiNA,NA$
(5),(6),CAL,00200.00,C,NAiNA,NA$
(5),(6),PRR.00100,OO.C,NAiNA,NA$
(5),(6),VER,00100,00,C,NAiNA,NA$
(5),(6),BLK,00000,00,C,1000il,MM/DD/YY-(7)
(5),(6),APS,00000,00,C,1000il,MM/DD/YY-(7)
(5),(6),EPA,00000,00,A,1000il,MM/DD/YY-(7)
(5),(6),EPA,00000,00,B,100011,MM/DD/YY-(7)
Notes«
(1) All 11 injections must be performed in the order given. The first six injections must
be performed within a given eight (8) hour period! the seventh through eleventh injections
must be performed within a given eight (8) hour period. The periods can' overlap.
(2) All injections must be 1.0 ± 0.2 jiL as measured by difference between amount in the
syringe before and after injection.
(3) To be used in the "SAMPLE" field in the header of the data file, and on all magnetic
tapes, quantitation reports, data sheets, chromatograms, and spectra and lists.
(4) Can be co-injected with the first injection on a given shift if you wish to take the
risk that the specifications [table 5] will be met.
(5) Instrument identifier. See section 3.1.3 of Appendix A
(6) Shift on which analysis is performed. See section 3.1.3 of Appendix A
(7) Shift on which extraction is performed. See section 3.1.3 of Appendix A
-------
Table 2
Base/neutral and Acid Extractable Compound Characteristic Masses
Labeled
Compound analog Primary m/z
bis(2-chloroethoxy)methane 93
bis(2-chloroethyl) ether d8 93/101
4-bromophenylphenyl ether 248
butylbenzyl phthalate 149
n-CIO d22 57/66
n-C14 57
n-C16 d34 57/66
n-C18 57
n-C20 d42 57/66
n-C22 57
n-C24 d50 57/66
n-C26 57
n-C28 x 57
n-C30 d62 57/66
p-cymene d!4 114/130
dibenzo(a,h)anthracene 278
2,4-dinitrotoluene d3 165/168
diphenylamine dlO 169/179
hexachlorocyclopentadiene 13C4 237/241
indeno(1,2,3-cd)pyrene 276
nitrobenzene d5 123/128
N-nitrosodimethylamine 74
N-nitrosodi-n-propylamine 70
2,4,6-trichlorophenol d2 196/200
-------
STANDARD
BLANK
SAMPLE
[10.1.1]
[10.1.2]
1 L reagent
water
1 L reagent
water
T
splice 500 |iL
of "200 (ig/mL
isotopes"
[10.1.3]
[10.1.4]
spike 500 p.L
of "200 jig/mL
isotopes"
spike 250 \i"L
of "400 jig/mL
PP standards"
stir and
equilibrate
stir and
equilibrate
STANDARD OR BLANK
[10.2]
extract base/
neutral
concentrate
to 2-4 mL
concentrate
to 2-4 mL
[10.4,10.5]
[11.3]
[11.4]
concentrate
to 1.0 mL
add internal
standard
inject
organic
1 L aliquot
spike 500 \iL
of "200 (j,g/mL
isotopes"
stir and
equilibrate
concentrate
to 1.0 mL
concentrate
to 1.0 mL
add internal
standard
add internal
standard
inject
inject
Figure 1 Flow Chart for Extraction/Concentration of Standard,
Blank, and Sample for Performance Evaluation by Method 1625A.
Numbers in brackets [] refer to section numbers in the Method.
6
-------
Performance ^valuation Data Sheet Lab
1
Identifier Al, V>, v<1 ' ^,f
EGO Number
Data Ref
scan
Retention time
Data
Library
Rel Ret time
Data Library
peak
area
COO
Amount (nq/mL)
Data Library
Response factor-
Data Library
(,00
note
IfcH-
-74
10 COO
100
164-
66000
(1)
l IT.
'. 11
I-D*.?
\OO
U IO
MO
(2)
(3)
(4)
(5)
(6) (7)
(8)
(9)
(10) I (11)
(12)
(13)
(14)
SAMPLE
Explanation of notes for data fields i
(1) Compound number from Appendix A "Quantitation Reports on Magnetic Tape"
(2) Compound used for quantitation and retention time reference. Compound 164 is 2,2*-difluoro-
biphenyl.
(3) Quantitation m/z specified in tables 6 and 7 of Method and/or table 2 of these instructions;
alternate primary m/z if an interference occurs at primary m/z (see paragraph 3 of the in-
structions) .
(4) Scan number at which the compound elutes in this analysis.
(5) The retention time of the compound in this analysis in either seconds (an integer) or in
minutestseconds, with the colon separating the minutes and seconds.
(6) The reference retention time in the library in seconds or minutest seconds.
(7) The retention time of the compound divided by the retention time of the reference compound.
(8) The relative retention time (7 above) stored in the library.
(9) The peek area at the quantitation m/z (2 above).
(10) The concentration of the compound detected as computed by internal standard [7.6] or iso-
tope dilution [7.5].
(11) The Deference amount in the library.
(12) The response factor for quantitation by the internal standard method [7.6], or the rela-
tive response (RR) divided by the concentration for the isotope dilution method [7.5.6].
(13) The response factor or RR/concentration (12 above) stored in the library.
(14) Reference to any notes you may wish to addj e.g., "alternate quantitation mass used."
Figure 2 Sample of Performance Evaluation Data Sheet
A blank Performance Evaluation Data Sheet is also provided; make as many copies of this sheet
as you feel you will need. Save the original in case more copies are needed.
-------
Performance ^'valuation Data Sheet Lab
Identifier
EGD Number
Data
—
.
Ref
--
m/z
...
...
scan
Retention time
Data
•-
Library
Rel Ret time
Data
• - —
...
Library
--•-
-
peak
area
- -
Amount (ud/mL)
Data
Library
••
-
• - •--
—
• -••
"•"';,_ ..
Response factor
Data
...
Library
- . -
_ — —
note •
... . .
....
, ,
-------
Appendix C
fc Order for Preparation of Performance Evaluation Samples
1 Objective—to prepare and certify priority pollutant calibra-
tion standards and samples for performance evaluation of analy-
tical laboratories which respond to EPA's solicitation for
priority pollutant analyses .using the latest gas chromatography
mass spectrometry (GCMS) methods.
2 Standards to be provided—using stable isotopically labeled
(labeled) compounds furnished by EPA's Effluent Guidelines
Division (EGD) Sample Control Center at Viar & Co (listed in
Appendix A, attached), and procured standards from commercial
suppliers, prepare solutions of standards to be used by the
laboratories for calibration of GCMS instruments.
2.1 Labeled standards
2.1.1 Concentration—nominal concentrations of 200 micrograms
per milliliter (p.g/mL) in methylene chloride-d- and/or benzene-d,.
Prepared by mixing and diluting the government furnished five
milligram per milliliter (mg/mL) labeled standards.
2.1.2 Quantity—180-200 mL total, divided into forty (40) each
4.3 ± 0.2 mL aliquots.
2.2 Priority pollutant standards (unlabeled analogs of the
compounds in Appendix A, attached)
2.2.1 Concentration—nominal concentrations of 400 |ig/mL
in methylene chloride and/or benzene. Prepared by mixing and
diluting priority pollutant standards.
2.2.2 Quantity—84-90 mL total, divided into forty (40) each
two ± 0.1 mL aliquots.
2.3 Mixed labeled and priority pollutant standard
2.3.1 Concentration—nominal concentrations of 100 p.g/mL by mixing
appropriate volumes of standards in 2.1 and 2.2 and diluting.
2.3.2 Quantity—44-50 mL total, divided into forty (40) each
0.9 ± 0.1 mL aliquots.
2.4 Single lot—sufficient quantities of the solutions in 2.1
and 2.2 shall be prepared to produce all aliquots required in
2.1 through 2.3 from a single lot.
2.4 Internal standard spiking solution—2,2'-difluorobiphenyl
2.4.1 Concentration—ten milligrams per milliliter (mg/mL) in
-------
methylene chloride and/or benzene.
2.4.2 Quantity—fourty (40) each one ± 0.1 mL aliquots
2.5 Packaging
2.5.1 Ampuls—each of the aliquots irt 2.1 through 2.4 shall
be packaged in a flame sealed, snap top, amber glass ampul.
2.5.2 Sets—a set consisting of one each of the ampuls (2.5.1)
of the aliquots in 2.1 through 2.4 (making a total of four
per set) shall be packaged in styrofoam (or equivalent) packing
material so that shipment by Federal Express (or equivalent
air carrier) shall not result in breakage of any ampul.
2.6 Labeling—each of the ampuls (2.5.1) shall be labeled
with a unique lot number, and with text as follows»
2.6.1 "200 (ig/mL isotopes" to designate the labeled standards
(2.1).
2.6.2 "400 ng/mL PP standards" to designate the priority
pollutant standards (2.2).
2.6.3 "100 p.g/mL mixed standards" to designate the mixed
labeled and priority pollutant standard (2.3).
2.6.4 "10 mg/mL internal standard" to designate the internal
standard spiking solution (2.4).
2.7 Composition—the true value of the concentrations of the
solutions in 2.1 through 2.4 shall be known within ± 5 percent
of true value by traceability to source, and verified by
analysis.
3 Sample
3.1 Compounds—to be selected from unlabeled analogs of the
compounds in Exhibit A, attached. Distribution of these com-
pounds shall be as follows>
3.1.1 Acid—3-4 including phenol and pentachlorophenol
3.1.2 Base/neutral and Appendix C—20-25 including naphthalene,
one of the dichlorobenzenes, bis (2-chloroisopropyl) ether,
hexachlorobutadiene, diethyl phthalate, 3,3'-dichlorobenzidine,
benzo(a)anthracene, chrysene, one of the dinitrotoluenes,
styrene, n-triacontane, and dibenzothiophene; and excluding
di^n-butyl-, bis(2-ethylhexyl)-. and di-n-octyl phthalates,
one of the diphenylamines, and anthracene.
-------
3.1 Concentrations—approximately evenly distributed in the
range of 10-200 ng/L in reagent water.
3.2 Quantity—40-50 liters total, divided into 40 each one
+0.1, -0 liter aliquots
3.3 Labeling—"water sample" plus a unique lot and serial
number.
3.4 Packaging—in cleaned sample bottles with Teflon lined
screw cap lids. Leak tested by inverting for one hour minimum
with no trace of sample present on lid. Packed in sets as
appropriate to fit into containers for shipment to the Sample
Control Center or other location as designated by EPA.
4 Documentation
4.1 Deliverables
4.1.1 Two each data sheets listing lot numbers, compounds,
concentrations, and solvents for solutions in 2.1 through 2.4,
to be shipped with solutions.
4.1.2 One each data sheet listing compounds and concentrations
for the sample in section 3, to be held for disposition upon
instructions from W A Telliard only.
4.2 In-house records
4.2.1 Traceability—source traceability through documentation
shall be maintained for all compounds, mixtures, solutions,
lot numbers, and other information for all items in sections
1 through 3..
4.2.2 Preparation—all weights, volumes, dilutions, and other
information necessary to prove the final concentrations of the
solutions in sections 2 through 3 shall be documented in log-
books, on data sheets, or on other forms in an easily understood
format.
5 Confidentiality—records of the concentrations and the com-
pounds in the water sample in section 3 shall be maintained
in strictest confidence by the contractor and its employees,
and/or by anyone else who may gain knowledge of the compounds
and/or concentrations from the contractor. If necessary, the
contractor shall require signed confidentiality agreements
from each of its employees, or others who shall have know-
ledge of the compounds and concentrations as a result of the
-------
contractor's Knowledge. Because release of this information
would compromise EPA's objective evaluation of laboratories,
the government shall have rights of full restitution for all
costs and delays resulting from disclosure of the composition
of the performance standard in section 3.
6 Anonymity—the contractor shall not disclose, or make any
mark on any ampul (section 2) or sample (section 3) which
would identify the contractor as the source of these materials.
7 Automatic qualification of contractor—EPA has selected
this contractor based on the contractor's history and perfor-
mance for the work described herein. Recognizing that this
contractor would be one of the laboratories seeking qualifica-
tion under solicitations requiring analysis of the performance
evaluation sample in section 3, and that the contractor will
have knowledge of the true values of all solutions and samples
in sections 2 through 3, and further that the contractor will
certify all solutions and samples by chemical analysis, EPA
will deem this contractor to be qualified for work under soli-
citations associated with analysis of the solutions and samples
in sections 2 through 3.
7 Certifications of analysis—as required by EPA, contractor
shall submit appropriate certifications for analysis of the
standards in section 2, and the sample in section 3.
8 Standards use—to assist the contractor in understanding
the concentrations and amounts in section 2, the use of these
standards is described below.
8.1 Obtaining authentic mass spectra—the solutions in 2.1
and 2.2 can be used to obtain authentic mass spectra of the
labeled compounds and priority pollutants.
8.2 Five point calibration—by combining 0.50 mL of the solu-
tion in 2.1 with 25, 50, 125, 250, and 500 \iL of the solution
in 2.2 and bringing to 1.00 mL total volume, calibration solu-
tions of 1C, 20, 50, 100, and 200 fig/mL will be produced.
8.3 The solution in 2.3 is to be used for determination of
response ratios.
8.4 Labeled compound spiking—three each 0.5 mL aliquots of
the solution in 2.1 will be spiked into a blank, reagent water,
and the sample in section 3 to determine contamination, recovery,
and ability to analyze samples, respectively.
-------
Appendix A
PURGEABLES/VOLATILES - A
50 |j.g oach component/1 mL mothanol-d., solution
Components
EPA 3V MD— 1455 Acrylonitrile-d,
6V MS— 1312 Carbon-'^C Tetrachloride
7V MD — 736 Chlorobenzene-dj
23V MS— 1318 Chloroform-"C
13V MD— 1152 1.1-Dichloroethane-2,2.2-d3
29V MD— 2201 1,1-Dichloroethylene-d2
44V MD — 53 Dichlpromethane-d2
32V MD— 2363 1 ,2-Dichlcropropane-d«
14V MS— 2346 1,1,2-Trichloroethane-1. 2-^02
PURGEABLES/VOLATILES - B
50 |ig each component/ 1 mL rrethanol-d* solution
Components
EPA 4V MD— 6 Benzene-d9
47V MS— 2313 Bromcform-13C
10V MD— 103 1,2-Dichloroethane-d4
38V MD— 17r36 Ethylbenzene-d,0
15V MD— 1416 1,1,2.2-Tetrachlproethane-d2
86V MD— 351 Toluene-2.3,4,5.6-d5
11V MD— 1150 1,1.1-Trichloroethane-d3
PURGEABLES/VOLATILES - C
50 ng each component/1 mL methanol-d4 solution
Components
EPA 46V MD—23 Bromomethane-d3
16V MD—334 Chloroethane-d5
45V MD—324 Chloromethane-dj
88V MD—965 Vinyl-d3 Chloride
PURGEABLES/VOLATILES - D
50 fjg each component'1 mL methanol-d4 solution
Components
EPA 516V MD—2 Acetone-d6
48V MS—2368 Bromodichloromethane-13C
SUV MD—2402 2-Butanone-4,4.4-d3
51V MS—2364 Chlorodibromometl-iane-13C
30V MD—2526 1,2-Dichloroethylene-1,2-d2 (cis/trans mixture)
33V MD—2669 1,3-Dichloropropene-d4 (cis/trans mixture)
515V MD—267 Diethyl-d,0 Ether
85V MS—2411 Tetrachloroethylene-1,2-13Cj
87V MS—2410 1,1.2-Trichloroethylene-1,2-'3C2
Ta.ble ?. Volatiles
A-l
-------
ACID EXTRACTABLES- 2
5 mg each component/1 mL benzene-dg solution
Components
EPA 22A
24A
31A
34A
60A
59A
57A
58A
64A
65A
21A
MD— 2355
MD— 2280
MD— 2281
MD— 2284
MD— 2357
MD— 2285
MD— 2290
MO— 2356
MS— 2293
MD— 1502
MD— 2279
4-Chlpro-3-methylphenol-2.6-d2
2-Chlorophenol-3.4.5.6-d4
2.4-Oichlorophenol-3.5.6-d3
2.4-Dimethylphenol-3.5.6-d3
4.6-Dinitro-2-methylphenol-3.5-d2
2.4-Dinitrophenol-3.5.6-d3
2-Nitrophenol-3.4.5.6-d4
4rNitrophenol-2.3.5.6-d4
Pentachlorophenol-13C«
Phenol-2.3.4.5.6-d,
2.4,6-Trichlorophenol-3.5-d2
Table 2 Acids
BASE NEUTRALS - 4.1
5 mg each component/1 mL benzene-d8 solution
Components
EPA 778 MD—128 Acenaphthylene-ds
74B MD—2360 Benzo(b)fluoranthene-d,?
79B MD—830 Benzo(ghi)perylene-d,2
73B MD—1956 Benzo(a)pyrene-d,2
42B MD—2702 Bis(2-chloroisopropyl)-d,2 Ether
26B MD—2405 1.3-Dichlorobenzene-d4
35 B MD—2407 2.4-Dinitrotoluene-3.5.6-d3
39B MD—2361 Flupranthene-d,0
52B MS—2408 Hexachloro-1.3-butadiene-'3C4
53B MS—2710 Hexachlorocyclopentadiene-l.2.3.4-'3C4
81B MD—120 Phenanthrene-d,0
BASE NEUTRALS - 4.2
5 mg each component/1 mL benzene-d6 solution
Components
EPA 20B MD—2462 2-Chloronaphthalene-d7
408 MD—2312 4-Chlorophenyl Phenyl-ds Ether
68B MD—2310 Di-n-butyl Phthalate-3.4,5,6-d4
70B MD—2726 Diethyl Phthalate-3,4.5.6-
-------
BASE NEUTRALS-6.1
5 mg each component/1 ml benzene-d6 solution
Components
EPA 72B MD—364 Benz(a)anthracene-d,2
66B MD—2306 Bis(2-ethylhexyl) Phthalate-3,4,5.6-d4
25B MD—1191 1,2-Dichlorobenzene-d4
27B MD—1034 1,4-Dichlorobenzene-d4
718 MD—2305 Dimethyl Phthalate-3,4,5.6-d*
36B MD—2359 2,6-Dinitrotoluene-ff,a,a-d3
56B MD—27 Nitrobenzene-ds
BASE NEUTRALS - 6.2
5 mg each component/1 mL benzene-d« solution
Components
EPA 18 MD—42 Acenaphthene-d,0
788 MD—46 Anthracene-d,0
758 MD—2362 Benzo(k)fluoranthene-d,2
188 MD—2479 Bis(2-chloroethyl)-d8 Ether
768 MD—402 Chrysene-d,2
808 MD—1298 Fluorene-d10
55B MD—26 Naphthalene-d9
848 MD—363 Pyrene-d,0
BASE rJEUTRALS - 5
5 mg ench component/1 mL t~ TV** np-ri,. solution
Components
EPA 5B
SUB
28B
507B
37B
503 B
502B
62B
MD— 2330
MD— 2401
MD— 2703
MD— 2704
MD— 2705
MD-2320
MD— 191
MD— 2311
Benzidme-dr, (rmgs-dR)
Di-n-hutyl-d ,B-amme
3.3'-Dichlorobenzidine-d, (rings-d6)
Diphenyl-d ,0-amine
1,2-Diphenyl-d10-hydrazine
2-Methylpyridine-d7 (a-Picoline)
2-Naphthyl-dv-amine
N-Nitroso'diphenyl-2.2'.4.4',6.6'-d6-amihe
Table 3 (continued^
A-3
Base/neutrals
-------
SEMI-VOLATILES- 1 / APPENDIX C
5 mg each component/1 mL benzene-ds solution
Components
EPA 513B
S17B
505 B
504B
S12B
508B
506B
521 B
519B
510B
509B
523B
526B
MD— 2709
MO— 960
MD— 2316
MD— 2315
MD— 208
MD— 373
MD— 882
MD— 1532
MD— 821
MD— 126
MD— 2707
MD— 883
MD— 2708
p-Cymene-d14
n-Decane-d22
Dibenzofuran-d8
Dibenzothiophene-dg
Oiphenyl-dio
Oiphenyl-dto Ether
n-Opdecane-dja
n-Eicosane-d42
n-Hexadecane-d^
Styrene-2.3.4.5.6-ds
-------
14 Apr 83
Changes to "Task Order for Preparation of Performance Evalua-
tion Samples."
Change #1» Section 2.6.2: change "200 ^ig/mL..." to "400
jig/mL..."
change #2i In order to differentiate betveen (1) results of
analysis of the "Mixed labeled and priority pollutant standard"
(section 2.3 of the task), and (2) the 100 jig/mL calibration
solution prepared by mixing appropriate volumes of the "Lab-
eled standards" (section 2.1) and the "Priority pollutant
standards" (section 2.2) using the procedure in section 8.2,
the contractor shall add one to three of the compounds below
to the "Priority pollutant standards" (section 2.2) at a con-
centration of approximately 100 (ig/mL after the appropriate
volume of the "Priority pollutant standards" (section 2.2)
has been withdrawn for mixing to form the "Mixed labeled and
priority pollutant standards" (section 2.3)t
-------
Appendix D
Appendix A Quantitation Reports on Magnetic Tape
1. Tape Characteristics
a. Tape - 9 Track; 800/1600 BPI; 600, 1200, or 2400 foot reels
b. Code - ASCII
c. Lab^fc - no internal labels
d, Blodcsize - 800 decimal words/block or bytes/block
2. File Characteristics
a. Each quantitation report represents a file on the submitted tape. A tape
will contain multiple files. Each of these files must end with a tape mark.
The last file on the tape will end with two tape marks.
b. Each line of the quantitation report constitutes a record. Records/lines
can be variable in length from one to 80 characters. Each record/line must
end with a carriage return (Octal 15 or Hexidecimal OD). A blank line is
interpreted as two consecutive carriage returns. A form feed character
(Octal 1* or Hexidecimal OC) must be used after the last record in the file
to signify the end of all records.
c. Records/lines must be combined into fixed length blocks of 800 bytes in
length. Blocks should not include any prefixes or postfixes. Records may
span blocks. A file will consist of multiple blocks. Blocks are separated on
the tape by inter-record gaps.
3. Data Format
The quantitation report is divided into four basic sections for information
reporting. The sections in the order in which they appear within the quantitation
report are called:
-------
o Header Section
o Compound List Section
o Techincal Data Section
o Reference Data Section
Each of these sections must be present in each quantitation report submitted on
tape. The absence of any one of these sections from a quantitation report is cause for
the non acceptance of the quantitation report. TAB 1 provides a sample quantitation
report showing these basic sections.
3.1 Header Section
The header section provides descriptive information about the analysis and
the conditions under which it was performed. This section at a minimum must
contain at least four lines of descriptive information. The four lines that must
be present are identified as follows.
o Title Line
o Date/Time Analyzed Line
o Sample Line
o Condition Line
*
Although the above four lines of information must be present in each
header section, there is no actual limit as to the total number of lines that may
be present. Laboratories are permitted to use this section to record any
additional information deemed necessary to properly identify the analysis. The
four lines however must appear in the order specified above, but additional lines
may be interspersed between them. The complete specifications for each of
these four lines is provided in subsequent paragraphs.
-------
3.1.1 Title Lines
This must be the first line within the header section and as such
represents the first line of each quantitation report submitted. Only one
title line is permitted within the Header Section. The line must contain
the value QUANTITATION REPORT starting in position one (left most
position) of the line. Other information may appear after this value on the
line but must be separated from the value by at least one space (blank).
3.L2 Date/Time Analyzed Line
This line must contain the date and time that the analysis was
performed. This line must preceed any other date lines within the header
section. The format of this line is as follows:
Line Position Data Element Format
1-S Date Analyzed MM/DD/YY
MM = month; 01-12
DO = day; 01-31
YY = year; 83-99
9 Field Delimiter Space
10-17 Time Analyzed HH:MM:SS
HH = hour; 00-2V
MM = minute; 00-59
SS = second; 01-59
3.1.3 Sample Line
The Sample line contains the following data elements. Data elements
are recorded on the line in the order specified. Data elements are separate
from each other by means of a comma (,}. The end of the data element list
is signified by a dollar sign ($). The specifications for the sample line are:
-------
Line Position
Data Element
Format
1-7
S
9
Literal Value
Field Delimiter
Instrument1
Field Delimiter
Shift
Field Delimiter
Quan Report Type
Field Delimiter
Sample Number
Field Delimiter
Bottle Number
Field Delimiter
Fraction
SAMPLE:
Space
2 positions; alphanumeric
Comma (t)
1 position; alpha
Code Meaning
G Graveyard
D Day
S Swing
Comma (,)
3 positions; alphanumeric
Code Meaning
Calibration
Precision
and Recovery
Calibration
Verification
Aqueous
Performance
Standard
EPA Sample
Standard
Blank
Comma (,)
5 positions; alphanumeric
Comma (,)
2 positions; numeric
For EPA Samples -
Range: 01-99
All others: 00
Comma (,)
1 position; alphanumeric
Code Meaning
Acid
Base
Combined acid base/
neutral
Pesticide
Volatile
PAR
VER
APS
EPA
STD
BLK
B
C
P
V
1. All calibration, precision and recovery, standards and blank quantitation files
will be tracked by this instrument number within laboratory. Changing of this
instrument number by the laboratory would necessitate the submittal of new
calibration and other initial quantitation files by the laboratory.
-------
Line Position Data Element Format
Field Delimiter Comma (,)
Cone/Dilution Factor 11 positions maximum;
numeric with colon (:)
separating initial and final
sample volume
NA:NA - used for calibration
standards and other runs
that are not extracted
Field Delimiter Comma (,)
Date Extracted MM/DD/YY . X; 10 positions
MM • month; 01-12
DD - day; 01-31
YY - year; 83-99
X - shift; G (graveyard)
D (day), S (swing)
NA - used for calibration
standards and other runs
that are not extracted
Dollar Sign ($) End of data delimiter
-------
3.1.* Condition Line
The Condition line contains the following data elements. As with the
sample line, data elements are recorded on the line in the order indicated.
Data elements are separated from each other by means of a comma Q.
The end of the data element list is signified by a dollar sign ($X The
specifications for this type of line are:
Line Position
Data Element
Format
1-7
8
9
Literal Value
Field Delimiter
Method
Field Delimiter
Column Length
Field Delimiter
Column Inside Diameter
COND&;
Field Delimiter
Column Initial
Temperature
Field Delimiter
Column Temperature
Program
5 positions; alphanumeric
1624A or 1625 A
Comma (,)
6 positions; alphanumeric
expressed in meters ie.
2.5 M or 35 M;
Volatile Range 2.S-3.1 M
Semi Volatile Range 25-35 M
Comma (,)
6 positions; alphanumeric
expressed in millimeters
ie. 2 mm or .3 mm;
Volatile Range: 1-3 mm
Semi Volatile Range:
- 0.2 - 0.35 mm
Comma (,)
7 positions; numeric
an at sign ((§) is
used to separate
Hold and Temperature
ie Hold 0 Temp
VoiatileTempRange: 25-50°C
Semi Voi Temp Range: 25-3 5°C
Comma (,)
10 positions; numeric
with a dash (-) separating
initial and final
temperatures and with
an at sign ((§) separating
temperature program rate
ie. * 5-250@ *
-------
Line Position Data Element Format
Field Delimiter Comma (,)
Column Final 7 positions; numeric with
Temperature an at sign (@) separating
hold and temperature ie.
Hold @ Temp
Field Delimiter Comma (,)
Carrier Gas Flow Rate 9 positions; alphanumeric
Format: 30ML/M or
30 CM/S;
Volatile range: 20-40 ml/min
Semi Volatile range: 20-60 cm/sec
End of Data Delimiter Dollar sign ($)
-------
12 Compound List Section
The compound list section is the second basic section of information
appearing on the quantitation report. It identifies the actual compounds that
were determined during analysis. This section is made up of two types of lines:
o Title Line
o Compound Identification Line
12,1 Title Line
The title line must appear first within the Compound List Section.
Only one title line may be present in the section. This line is formatted as
follows:
Line Position Data Element Format
1 Field Delimiter Space
2-3 Literal Value NO
Field Delimiter Spaces (At Least 2)
Literal Value NAME
-------
Compound Identification Line
A compound identification line is included in this section for each
compound that was determined during analysis. Compound lines should be
shown in the order in which they were determined. Each compound
identification line is made up of three data elements specified in the
following order within the line:
o Compound Reference Number
o EGO Compound Number
o Compound Name
The compound reference number b a numerical code that establishes
the order of compound determination by the GC/MS. The code is used on
the Quantltatlon Report to match up compound identification with com-
pound analysis and reference data appearing in subsequent sections of the
report. On each quantitation report this number always starts with 1. The
number 1 is always assigned to the first compound that is determined, the
number 2 to the second compound is determined and so on.
Each compound identification line will appear in the following
format:
Line Position Data Element Format
1-3 Compound Reference 1 to 3 character
Number number; right justified
in field; range
1-250
»-5 Field Delimiter Spaces (At Least 2)
EGD Compound 3 positions; numeric
Number Range Meaning
001-129 Quantitated by internal
or external standard
130-199 Misc., internal standard
and surrogate compound
201-299 Labeled Compound (isotope)
Quantitated by internal or
external standard
-------
Line Position
Data Element
Format
Range Meaning
301-399 Quantitated by
isotope dilution
501-599 Synfuel specific and
Appendix C Comp.
quantitated by internal
or external standard
Synfuel specific and
Appendix C labeled com-
pounds (isotopes) quan-
titated by internal
or external standard
Synfuel specif ic and
Appendix C
Field Delimiter
Compound Name
601-699
701-799
quantitated by isotope
dilution.
Spaces (At Least 2)
70 positions; alphanumeric
-------
Technical Data Section
The technical data section provides measurement data for each compound
that is determined. It is the third section within the quantitation report. This
section is made up of two types of lines:
o Title Line
o Compound Technical Data Line
3J.1 Title Line
The title line must appear first within the Technical Data Section.
Only one title line may be present in the section. This line is formatted as
follows:
Line Position Data Element Format
1 Field Delimiter Space
2-3 Literal Value NO
Field Delimiter Spaces (At Least 2)
Literal Value M/E
Field Delimiter Spaces (At Least 2)
Literal Value SCAN
Field Delimiter Spaces (At Least 2)
Literal Value TIME
Field Delimiter Spaces (At Least 2)
Literal Value REF
Field Delimiter Spaces (At Least 2)
Literal Value RRT
Free Area Spaces or other
literal values
First non-blank Literal Value AREA
character at or past
position 41.
Field Delimiter Spaces (At Least 2)
Literal Value AMOUNT
Free Area Spaces or other
literal values
-------
Compound Technical Data Line
A compound technical data line is included in this section for each
compound that is determined. Compound technical data lines are ordered
the same as the compound identification lines in the compound list section.
The compound reference number is used for this purpose and serves to
connect compound identification with the technical data. The compound
technical data line at a minimum must contain the following data ele-
ments.
o Compound Reference Number
o Mass to Charge Ratio
o Scan Number
o Retention Time
o Reference Compound
o Relative Retention Time
o Peak Area
o Amount
o Unit of Measure
The specific format for this line is as follows:
Line Position Data Element Format
1-3 Compound Reference 3 positions; numeric; right-justified
Number Range 1-250
Field Delimiter Spaces (At Least 1)
Mass to Charge Ratio * positions; numeric;
(M/2) Volatile range: 20-250;
Semi Volatile range: 35-450
Field Delimiter Spaces (At Least 1)
Scan Number 5 positions; numeric;
range 1-9999
Field Delimiter Spaces (At Least 1)
Retention Time 6 positions; numeric
with colon; format;
MM:SS
Field Delimiter Spaces (At Least 1)
Reference Compound 3 positions; numeric;
range 1-250
-------
Line Position
Data Element
Format
First non-blank
character at or
past position
Field Delimiter
Relative Retention Time
Field Delimiter
Open Field
Peak Area
Field Delimiter
Amount
Field Delimiter
Unit of Measure
Field Delimiter
Open Area
Spaces (At Least 1)
5 positions; numeric
with decimal point and
3 decimal places
Spaces (At Least 1)
Spaces or other
field value
10 positions; numeric
Spaces (At Least 1)
10 positions; numeric
with decimal point
and 3 decimal
places
Spaces (At Least 1)
5 positions; alphanumeric
Valid codes: uC/L or uG/ml
Spaces (At Least 1)
Spaces or other
field values.
-------
3.4 Reference Data Section
The reference data section is the fourth section that must appear on each
Quantitation Report. It provides reference and library data about the analysis
that was performed. It is made up of two types of lines:
o Title Line
o Compound Reference Data Line
3.4.1 Title Line
The title line must appear first within this section. Only one title
line is permitted within the section. Subsequent title lines will be deleted
if present. The line is formatted as follows:
Line Position Data Element Format
1 Field Delimiter Space
2-3 • Literal Value NO
Field Delimiter Spaces (At Least 1)
Literal Value RET (L)
Field Delimiter Spaces (At Least 1)
< Open Area Spaces or other
literal values
First non-blank Spaces (At Least 1)
character at or past Literal Value RRT (L)
position 19.
Field Delimiter Spaces (At Least 1)
Open Area Spaces or other
literal values
First non-blank Literal Vaiue ' AMNT (L)
character at or
past position 43.
Field Delimiter Spaces (At Least I)
Literal Vaiue R.FAC
Field Delimiter Spaces (At Least 1)
Literal Value R.FAC (L)
Open Area Spaces or other
literal values
-------
3.4.2 Compound Reference Data Line
A compound reference data line is included in this section for each
compound that is determined. These lines are ordered the same as the
compound identification lines in the compound list section. The compound
reference number is used for this purpose and serves to connect the
compound identification with the reference data. This means that there is
a one to one correspondence between the compound identification lines and
the* reference data lines. The reference data line at a minimum must
contain the following data elements.
o Compound Reference Number
o Library Retention Time
o Library Relative Retention Time
o Library Amount
o Response Factor
o Library Response Factor
The specific format for this line is as follows:
Line Position Data Element Format
1-3 . Compound Reference 3 positions; numeric;
Number Range 1-250
Field Delimiter Spaces (At Least 1)
Library Retention Time 6 positions; numeric
with colon; format -
MM:SS
Field Delimiter Spaces (At Least 1)
Open Area Spaces or other
data values
First non-blank Library Relative Retention 5 positions
character starting Time
at or past
position IS.
-------
Line Position
Data Element
Format
Pint non-blank
character starting
at or past
position *1.
Field Delimiter
Open
Library Amount
Field Delimiter
Response Factor
Field Delimiter
Library Response Factor
Field Delimiter
Open Area
Spaces (At Least 1)
Spaces or other
data values
9 positions; numeric
with decimal
point and 2 decimal
places
Spaces (At Least 1)
7 positions; numeric
with decimal point
and 3 decimal
places
Spaces (At Least 1)
7 positions; numeric
with decimal point
and 3 decimal
places.
Spaces (At Least 1)
Spaces or other
data values.
-------
*. Packaging and Shipping Instructions
Format Requirements:
o Tapes shall be industry standard 9-Tradc, 800 or 1600 bits per inch
with no internal labels.
o Tapes shall contain one or more files. Each file shall end with a tape
mark. The last file shall end with two tapemarks. The first file may
be preceded with one tapemark.
See paragraph 2 for Record and Block format descriptions.
Packaging Requirements:
o Each tape reel shall bear a SCC supplied external tape label
containing the external tape number, the laboratory name, the tape
density, the block size, and the number of files.
o Each tape package shall contain in addition to the tape reel(s) at
least one Quantitation Report Magnetic Tape Trans mittal Form for
each tape reel (see Tab 3 for a sample trans mittal form and
transmittal form description), all Lab Chronicle Reports associated
with the reported samples, and BFB or DFTPP spectra analysis
required per shift per machine.
o Tape reels with their associated transmittaJ forms and chronicle
reports shall be packaged in such a way to ensure their safety and
integrity. The outside of all packages should be marked with a *DO
NOT X-RAY' label. It will be the laboratory's responsibility to
replace any tape, quantitation report data, and accompanying docu-
ments damaged during shipping to the Sample Control Center.
-------
Shipping Requirements:
Tape packages shall be shipped either by the U.S. Postal Service or by any
carrier with direct delivery.
Shipping address by U.S. Postal Services
USEPA
Effluent Guidelines Division
Sample Control Center
P.O. Box 1407
Alexandria, VA 22313
Shipping address by other carriers:
USEPA
Effluent Guidelines Division
Sample Control Center
Suite 200
300 N. Lee St.
Alexandria, VA 22313
-------
TAfc J.
%
P'lANTTTATION PFPORT FILE: 1
>
DATA: 12045<;TO.TI
os/31/93 lo:o«:oo
1625a » 30*, o.?5MM.5*»30. 10-280*8, 16*280.
INSTRUMENT: AI WFIGHT: o.ooo
5UPMTTTED RY: ANALYST: JLP ACCT.NO.:
AMOUNT*ARFA « t»EF.A*NT/(REF.AR£A)* HE5P.FACT)
NO NA«E
1 1ft* ?.2'-DTFLUOPO*IP*PNYL
? Ofcl N-*TT*-OSOOT"PTHYLft*INE
1 603 (07) A-PICOLINE
* 703 A-BTCOLINE
« 610 (0^) STYPENE
* 710 STYOPNF
7 265 (H6;) PHENOL
P 365 ouCNOL
9 617 (022) N-OECANE
1" 218 (08) RIS(2-OLOROETHYL)ETHEP
11 224 (OA) 2-OLORrPHENOL
12 324 P-CHLOPOOHENPL
13 318 RIS(?-CHLOPOETHYL) ETHER
14 7J7 N-DECA»IE
1? 226 (04) 1,3 OIC^LOPOaENZENE
16 326 1.3 OICHLOOO°ENZENF
17 227 (04) 1.4 DIOLOROPENZENE
18 327 1,4 OICHL030PENZENE
19 613 (014) 0-CY«ENE
20 713 O-CYMFNE
21 225 (04) 1,2 DTOLORO«ENZENE
22 711 OI-N-P.HTYI_A*TNE
21 325 1,2 OIChLOPOOFNZENE
24 611 (01«) OI-N-9IJTYLA*INE
2«5 242 (012) ai«:(?-CMLOPOISOPROPYL
26 342 oi«;(?-CHLOPOTSOP90PYL)ETHER
27 312 HFXACHLOPOTTi-ANF.
2P 212
-------
47
Vfl '
49
50
51
59
51
5*
5?
5ft
57
5*
59
60
61
62
63
64
65
6*
67
6HENOL
i-NlT^Of'WENOl.
(03) 2.4 OTNTTPOTOLUENE
9.4 OINITPOTCLUENE
f07) P-N/»OHT^YLA^INE
Q-NAOHTHYLAMJNE
SCAN
1190
367
4A3
4«q
5fl*
591
733
735
735
715
739
742
742
756
760
762
769
772
779
791
QOI
304
«04
«04
"22
TTrtF
?o:4fl
6:2e
ft: Oft
»:i?
10:17
10:21
12:^o
12:52
12:52
12:52
12:56
12:*«
12:59
13:14
13:i«»
13:20
13:27
13:31
13:3«
13:51
14:01
14:04
14:04
14:04
14:21
PEF
1
1
1
3
1
5
1
7
1
1
1
11
10
9
1
IS
1
17
1
19
1
24
?1
1
1
POT
1 .DUO
0.3U8
n.3H9
1 . 01 3
n.. A.94
1.005
0.616
1.003
0.618
n.619
0.621
1.004
1.010
1 .029
0.639
1.003
n.646
1.004
".655
1.015
0.673
1.000
1.00*
1.&76
O.nwl
METH
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
SB
RV
ev
88
BB
V8
PV
8V
VV
8V
88
38
VB
VV
P8
BB
68
88
88
88
88
8V
SB
PB
RV
AOEA(HGHT) AMOUNT
132330.
70180.
B5539.
Q5317.
119666.
14434Q.
191732.
136305.
245693.
?9087.
74696.
95399.'
11*471.
126009.
SOQ05.
91219.
52591.
9«554.
206174.
214925.
50244.
11385.
92511.
1099.
^SMbs.
100.000
99.500
100.000
100.000
100.000
102.500
100.000
100.100
100.000
100.000
100.000
100.200
99.750
100.500
100.000
100.750
100.000
99.250
100.000
99.750
100.000
100.250
100.000
100.000
100.000
UG/Mt.
UG/ML
UG/ML
US/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
5TOT
1.61
1.60
1.61
1.61
1.61
1.65
1.61
1.61
1.25
1.25
1.61
1.61
1.24
1.25
1.25
1.25
1.25
1.24
1.25
1.24
1.25
1.25
1.25
1.25
1.25
-------
2>
27
2*
29
30
31
32
33
34
3«
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
NO
01
02
01
04
' l2l
201
204
70
128
123
88
82
143
139
125
122
93
167
1*2
133
100
66
136
129
62
59
57
231
225
107
109
241
237
200
196
169
162
164
154
180
170
160
152
167
163
167
165
164-
154
1ST
184-
176
168
143
139
168
165
150
143
Q12
354
^54
«61
373
«»77
919
«26
931
934
955
956
971
979
qaj
9««,
900
990
997
\ooo
1006
1009
1012
?037
1037
1117
1117
1171
1171
1190
1191
5214
1217
1217
1221
1238
V244
1293
1296
1296
1298
1308
1311
1326
1332
1352
1354
1359
T363
1378
1379
1385
13R7
1396
1400
14
14
14
15
IS
15
16
16
16
16
16
16
17
17
17
17
17
17
17
17
17
17
17
18
18
19
19
20
20
20
20
21
21
21
21
21
21
22
22
22
22
22
22
23
23
23
23
23
23
24
24
24
24
24
24
PET(L) PATIO
20:4Q
6:25
8:06
8:12
1.
1.
1.
1.
00
no
oo
00
:34 25
:57 2*
:57 1
: 04 i
• 17 1
:21 30
:0«> I
:12 32
: 18 1
:21 34
:43 1
:44 36
:00 1
:08 1
:10 39
: 17 1
:19 41
: 19 1
:27 1
:30 44
:36 1
:39 46
:43 43
:09 l
:09 49
:33 52
:33 1
:30 1
:30 53
:49 1
:51 55
: 15 1
:18 57
: 18 1
:22 59
:40 1
:46 61
:38 1
:4l 63
:41 1
:43 65
:53 1
:57 67
: 12 1
:19 69
:40 1
:42 71
:47 1
:51 73
:o7 1
:08 75
: 14 1
:16 77
:26 1
:30 79
PPT(L)
1.000
0.30B
0.389
0.395
1.012 A PV
1.000
n.718
0.7?4
0.734
1.005
0.772
1.008
n.782
1.003
O.HP3
1.001
0.416
0.823
1.002
0.830
1.002
O.H3?
0.838
1.003
O.H45
1.003
1.022
0.871
1.000
1.000
0.939
0.984
1.000
1.000
1.001
1.020
1.002
1.023
1.003
1.040
1.005
1.087
1.002
1.089
1.002
1.099
1.002
1.114
1.005
1.136
1.001
1.142
1.003
9H
R*3
VV
RR
RB
VR
VV
R«
RV
P3
PV
RV
°.d
RV
r"R
Bd
VV
PS
eg
VR
RB
VV
BB
BB
BV
ev
R9
Bo
R.B
RB
BB
B9
RH
SB
BB
RR
BP
BB '
VV
VV
VB
BB
BB
BB
RB
BB
RB
P.V
1.158 A VB
1.001 A PV
1.164 A P.B
1.001 A VB
1.173 A BV
1.003 A RV
RATIO AMNT
1.00 100.00
1.00 99.50
1.00 100.00
2.5R 100.00
24739.
2744 f .
12/?dl .
90102.
33737.
41919.
ll«964.
Q26b4.
2M77.
3P114.
S2780.
99027.
1.10312.
3M65.
70600.
6*197.
69057.
173929.
23P175.
280748.
60136.
100849.
15*423.
P2S26.
17916.
129831.
99414.
?3908.
?R030.
17779.
30623.
114393.
215477.
214588.
208044.
30639.
104115.
166440.
2P5824.
161184.
l«c-673.
27562.
33165.
117288.
160368.
8463%
9632.
176268.
213270.
?7783.
15052.
42897.
47189.
R2896.
170206.
AMNT(L)
100.00
09.50
100.00
100.00
90
100
100
QQ
100
102
100
QQ
100
100
100
100
Q9
100
99.
100
QQ
LOO
100
100
100
99
99
100
101
100
100
100
101
100
100
100
100
100
101
100
101
100
99
100
99
100
100
100
101
100
99
100
100
100
99
100
90
100
09
R.FAC
1.000
0.533
0.64-6
1.114
.250
.000
.000
.500
.000
.000
.000
.000
.000
.200
.000
.000
.250
.000
.600
.000
.000
.000
.000
.500
.000
.500
.750
.000
.000
.300
.000
.000
.000
.000
.100
.000
.750
.000
.500
.000
.000
.000
.500
.000
.750
.000
.250
.000
.000
.000
.900
.000
.750
.000
.900
.000
.500
.000
.000
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
R.FAC(L)
1
0
0
1
.000
.533
.646
.114
1.24
l.M
1.61
1.60
1.61
1.64
1.61
1.59
1.61
1.61
1.25
1.25
1.24
1.61
1.60
1.61
1.59
1.25
1.61
1.61
1.61
1.60
1.24
1.61
1.62
1.61
1.61
1.61
1.62
1.61
1.61
1.25
1.25
1.25
1.26
1.61
1.62
1.25
1.24
1.25
1.24
1.25
1.25
1.25
1.26
1.61
1.60
1.25
1.25
1.61
1.60
1.25
1.24
1.61
1.59
PATIO
1.00
1.00
1.00
1.00
-------
05 .
06
07
Qfl
09
10
11
12
13
14
15
16
17
!>>
19
20
21
2?
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
3*
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
*,?
63
64
65
10:17
10:21
12: = o
12:52
12:52
12:*?
12:56
12:50
12:59
13:14
13: ifl
13:20
13:27
13:31
13:3*
13:51
14:oi
14:04
I*.:n4
14:04
14:23
14:34
14:57
14:57
15:04
15:17
15:21
16:05
16:12
16:18
16:?i
16:43
16:44
17:00
17:na
17:io
17:17
17:io
17:19
17:27
17:30
17:36
17:39
17:43
18:09
18:09
19:33
19:33
?o:30
20:30
20 : *9
20:*l
21:15
21:18
21:18
21 :2?
21 :*n
21:4^
?25 ?q
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22s M
1.00
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i .no
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.no
l.no
l.oo
l.no
l.no
l.oo
1 .00
1 .no
l.no
l.oo
l.no
l.oo
l.no
l.no
l.no
l.oo
l.oo
l.no
l.oo
l.no
.00
.00
• no
.00
• no
.00
.00
l.no
l.oo
l.oo
l.no
l.no
l.no
l.no
1.00
1*00
l.oo
l.no
l.oo
1.00
i.oo
1.00
1.00
l.oo
I .00
1 .00
l.no
1.00
l.no
1 .no
1 .00
l .no
1 .no
1 .00
l.no
0.494
0.497
0.61*
n.Mq
0.61*
0.61"
O.*21
0.621
0.624
0.635
0.639
O.A40
0.64*
O.A49
0.65=
0.66=
0.673
0.676
0.676
0.67*
n.691
ft. 699
0.71*
0.71"
0.724
0.734
0.737
0.77?
0.77P
0.78?
0.79?
0.803
0.803
O.P1*.
0.823
0.823
O.S30
0.«3?
O.P3?
O.a3fl
O.A40
0.84=
0.849
0.850
0.871
0.871
0.935
0.939
0.984
0.984
l.OOQ
1.001
1.02n
1.023
1.023
1.025
1 .040
1 .04=
1.0H7
1 .087
1.085
1.00
2.02
1.00
1.62
1.00
1.00
1.00
1.61
1.62
I.*?
1.00
1.57
1.00
1.55
l.no
1.53
1.00
1.48
1.48
1.00
l.no
1.45
1.39
1.00
1.00
1.00
1.36
1.00
1.30
l.no
1.28
1.00
1.25
1.00
1.00
1.22
1.00
1.20
1.00
1.00
1.19
1.00
1.18
1.20
1.00
1.15
1.07
1.00
1.00
1.02
1.00
1.00
1.00
0.98
1.00
0.9fl
1.00
0.96
1.00
0.92
1.00
100.00
102.50
100.00
100.10
100.00
100.00
100.00
100.20
99.75
100.50
100.00
100.75
100.00
99.25
100.00
99.75
100.00
100.25
100.00
100.00
100.00
99.25
100.00
100.00
99.50
100.00
102.00
100.00
99.00
100.00
100.20
100.00
100.00
99.25
100.00
99.80
100.00
99.00
100.00
100.00
100.50
100.00
99.50
99.75
100.00
101.00
100.30
100.00
100.00
101.00
100.00
100.10
100.00
100.75
100.00
101.50
100.00
101.00
100.00
99.50
100.00
100.00
10?. 50
100.00
100.10
inn. oo
100.00
ion. oo
100.20
99.75
100.50
100.00
100.75
100.00
99.25
100.00
99.75
100.00
100.25
100.00
100.00
100.00
99.25
100.00
100.00
99.50
100.00
102.00
100.00
99.00
100.00
100.20
100.00
100.00
99.25
100.00
09.80
100.00.
99.00
100.00
100.00
100.50
100.00
99.50
99.75
100.00
101.00
100. 30,
100.00
100.00
101.00
100.00
100.10
100.00
100.75
100.00
101.50
100.00
101.00
100.00
09.50
ino.00
0.904
1.177
1.449
0.710
1.957
0.220
0.564
1.275
3.945
0.510
0.385
1.779
0.397
1.888
1.558
1.045-
0.380
10.333
1.841
0.008
0.195
0.964
2.235
0.093
0.6A4
0.255
1.276
0.907
0.780
0.198
1.453
0.309
1.876
0.992
0.266
2.012
0.500
1.054
1.314
1.755
1.203
0.522
1.466
0.913
0.172
1.645
1.302
0.751
0.181
1.161
0.285
O.RIO
0.864
1.870
1.622
0.955
0.609
1.278
1.258
1.164
1.218
0.904
1.177
1.449
0.710
1.857
0.220
0.564
l.?75
3.945
0.510
0.385
1.779
0.397
1.888
1.558
1.045
0.180
10.333
1.841
0.00ft
0.195
0.964
2.235
0.093
0.684
0.255
1.276
0.907
0.780
0.198
1.453
0.399
1.876
0.992
0.266
2.012
0.500
1.054
1.314
1.755
1.203
0.522
1.466
0.913
0.172
1.645
1.302
0.751
0.181
1.161
0.285
0.810
0.864
1.870
1.622
0.955
0.609
1.278
1.258
1.364
1.21ft
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
-------
6*
67
6«
60
70
71
7?
73
7*
75
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77
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79
80
2?:43
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23:42
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24:14
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24:26
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l.oo
1 .00
1 .00
l.oo
l.oo
l.oo
l.oo
1 .00
l.oo
1 .00
1 .00
l.nn
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1.00
1.091
1 .095
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1.114
1.11C
1.13*
1.13°
1.14?
1.1*5-
1.159
1.15S-
1.164
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1.17?
1.17*
0.92
1.00
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0.90
1.00
0.88
1.00
0.*3
1.00
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1.00
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0.85
99.75
100.00
100.25
100.00
101.00
100.00
99.90
100.00
100.75
100.00
99.90
100.00
99.50
100.00
99.00
Q9.75
100.00
100.25
100.00
101.00
100.00
99.90
100.00
100.75
100.00
99.90
100.00
99.50
100.00
99.00
1.155
0.208
1.200
O.A86
1.35*
0.064
1.139
1.332
1.201
0.210
1.263
0.32*
1.106.
0.626
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1.155 ]
0.208 ]
1.200 ]
O.A86 1
1.354 ]
0.064 ]
1.139 ]
1.332 :
1.201 ]
0.210 ]
1.263 ]
0.324 ]
1.106 ]
0.626 ]
2.074 ]
1.00
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
L.OO
-------
I
^UANTITATIO* BPPORT FTI.F.: 1P045STD
*
DATA: !2045<;Tn.Ti
"5/31/83 in:o*:oo
SAMPLE: Ai,o,CAL«loo»on,c»wA:NA,NA$
CONOS.: 1625A»30M,n.P3MM,6*30»30-280*8,160280
KOPMULA: INSTRUMENT: AI WFIGHT: o.ooo
SUBMITTED BY: ANALYST: JLP ACCT.NO.:
AMOUNT*Aft£A * PEF. AMNT/(»F.F. AREA) * RESP.FACT)
NO NAMF
1 16* ?,?»-OTFLUOPr*IP-«F>NYL
2 M9 (034) w-HEXAPPCAME
3 280 (010)F1.UORF.NP
* 3*0 rU'OBENE
5 719 N-HE*Ar)ECA^£
6 240 (05)4-CHLOPQPHENrLPHFNYLETH£R
7 340 4-rHLOPOPHENVLPHF.MYLETHER
S 270 f04) OIETHYLPMTMALATE
9 370 nifTHYLPHTHALATE
10 607 f010)OTPH£NYLAMlNE
11 237 (010) OIPHENYLbYOOAZINE
12 260 (02) 4,6 OTNTTPOCPESOL
13 360 4,6 niNITRO-C-CPFSOL
14 262 (06) N-NITROSOOIPHENYLAMINE
15 362 N-NITROSOOIPHENYLAMINE
16 707 "IPHENYLAMINE
17 337 1,2 OIPHENYLHYOPA7INE
18 041 4-PPQMOPHENYLPHENYLETHER
19 309 HEXACHLORORENZENE
20 209 (13C6) HEXACHLOR03.ENZENE
21 604 (08) DIBENZOTHIOPHENE
22 704 OTBENZOTWIOPHENE
23 364 e»ENTACHLOflOP*-ENOL
2* 264 (13C6) PFNTACHLOPOPHFNOL
25 281 010 PHENANTHBENE
26 381 PHENANTHRENE
27 278 (010) ANTHRACENE
28 378 fNTHRACENE
29 621 (042) N-EICOSANE
30 268 (04) OI-N-BOTYL PHTHALATE
31 368 OI-N-BUTYL PHTHALATE
32 721 N-EICOSANE
33 239 (P10) FLUOPANTHENE
34 339 FLUOPANTHENE
35 205 (Ofl) BENZIOINE
36 305 9ENZTDINF
37 2B4 (010) PYPENE
3* 384 PYRENE
39 623 (050) N-TETP«COSANE
40 067 9UTYLBENZYLPHTHALATE
41 723 N-TETRACOSANP
42 276 (012) CHQYSE*E
43 272 (012)8EN70(A)ANTHPACENE
44 376 CWRY«?ENE
45 372 RFN?0
-------
47
4P
4Q
SO
51
52
53
54
55
56
57
5P
59
60
61
62
63
NO
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
3«
39
40
41
42
32fl
266
366
2*9
369
?74
374
275
375
273
373
626
726
083
082
279
379
M/E
190
66
176
166
57
209
204
153
1*9
179
82
200
198
175
169
169
77
248
284
292
192
184
266
272
188
178
188
178
66
153
149
57
212
202
192
1P4
212
202
66
149
S7
?40
1.V DICHLORCPENZIDINE
CU) BTS(2-£THYLHF,XYL)PHTHALATE
qTS(?-.FTWYLHPXYL)°HTHALATE
(04) Ol-*-OCTYLPHTHALATE
nj-N-OCTYLPHTHALATE
(012) i=IENZO(P)FLUORANTHFNE
qFN7r){PJFLUOOANTHENE
(012) RENZO(K)FLUnRANTHENE
RENZO (K ) FLUOC ANTMPNE
(012) R£NZOm?Y3FNE
qENZOUlPYOEKE
(0^?) N-TRIACONTANE
M-T5TACONTANE
TNnPNOPYPENE
OTPFMZO(A.H) BNTHPACENE
(01 2) BFN70 (GtHt I r«»ERYLENE
OFNZO (G«H, I ) PERYLENE
e;CAN
1190
1404
1422
1428
14?8
1431
1434
1437
1439
1*57
1459
1461
1463
1464
1465
1465
1465
1523
1546
1*46
1579
1583
1585
1585
1602
1607
IMZ
1616
7735
1738
1740
1759
1B25
Ifi29
1>62
1362
1*65
ie*9
210«
?0]3
P034
POflfl
TI*E
20:49
24:34
?4:53
24:59
24:59
25: 03
25:06
25:09
25: 11
25:30
25:32
25:34
25:36
25:37
25:38
25:38
25:38
26:39
27: 03
27:03
27:38
27:42
27:44
27:44
28: 02
28: 07
28:13
28:17
30:22
30:25
30:27
30:47
31:56
32:00
32:35
32t 35
32:38
32:42
15:03
35:14
15:36
36:32
PEF
1
1
1
3
2
1
6
1
8
1
1
1
12
1
14
10
11
1
20
1
1
21
24
1
1
25
1
27
1
1
30
29
1
33
1
35
1
37
1
1
39
1
RPT METH
1.000
1.180
1.195
1.004
1.017
.203
.002
.208
.001
.22*
1.226
1.228
1.001
1.230
1.001
1.005
1.004
1.280
1.000
1.299
1.327
1.003
1.000
1.332
1.3*6
1.003
1.355
1.002
1.458
1.461
1.001
1.014
1.534
1.002
1.565
1.000
1.567
1.002
1.6B7
1.692
1..013
R8
PV
BV
ee
8V
V8
Vfi
vv
vv
vv
BB
BB
VB
VV
VV
VV
VV
BB
VB
BB
9V
SB
BB
SB
VV
VV
VV
VB
VV
VV
VB
VV
VB
VV
BB
BV
VV
VV
VV
SB
VB
1.755 A BV
APF-A(HGHT) AMOUNT
1??330.
174336.
128723.
101185.
2175.37.
59235.
57010.
202942.
237539.
12*214.
380511,
12760.
16713.
151118.
294521.
294061.
466838.
41779.
39699.
2<>095.
183008.
211801.
22404.
18341.
196845.
245017.
192533;
243085.
169601.
270559.
376900*
225089.
135111.
147718.
36193.
32639.
121888.
1*8070.
126632.
12593.
141715.
S2320.
100.
100.
100.
100.
100.
100.
102.
100.
100.
100.
100.
100.
100.
100.
101.
100.
100.
100.
100.
100.
100.
100.
100.
100.
100.
105.
100.
101.
100.
100.
99.
100.
100.
99.
100.
100.
100.
101.
100.
100.
100.
100.
000
000
000
ooo
250
000
000
000
000
000
000
000
100
000
000
000
000
500
000
000
000
000
400
000
000
000
000
500
000
000
000
000
000
500
000
000
000
000
000
250
250
000
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
STOT
1.25
1.25
1.61
1.61
1.25
1.25
1.27
1.25
1.25
1.61
1.61
1.61
1.61
1.61
1.62
1.61
1.61
1.25
1.61
1.61
1.25
1.25
1.61
1.61
1.25
1.31
1.25
1.26
1.25
1.25
1.23
1.25
1.61
1.60
1.25
1.25
1.61
1.62
1.25
1.25
1.25
1.25
-------
41
44
45
46
47
4*
44
50
51
52
53
54
55
5*
57
58
59
on
61
62
63
NO
1
2
3
4
5
6
7
9
9
10
n
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
2"
29
30
31
32
33
34
35
36
37
3»
2^0
' 228
226
2S8
252
153
149
153
149
264
252
264
252
264
252
66
57
276
278
2*8
276
PFT
20:
24:
24:
24:
24:
25:
25:
25:
25:
25:
25:
25:
25:
25:
25:
25:
25:
26:
27:
27:
27:
27:
27:
27:
28:
2fl:
28:
28:
30:
30:
30:
3o:
31:
32:
32:
32:
32:
32:
?ofla
?OP3
?n93
?097
?09«
2111
?J33
2265
2267
?321
5?31«
??31
2336
?4Q«
?415
?4Afl
?526
?«11
?3B<1
2935
2953
36
36
36
36
16
37
37
39
39
40
40
40
:32 1
:38 42
:3* 43
:42 1
:43 46
:18 1
:20 48
:38 1
:40 50
:37 l
:46 52
:48 1
40:53 54
&2
42
43
44
49
49
51
51
(U PATIO
49 1.
34 1.
53 1.
59 1.
59 1.
03 1.
06 1.
09 1.
11 1.
30 1.
32 1.
34 1.
36 1.
37 1.
38 1.
3* 1.
39 1.
39 1.
03 1.
03 1.
38 1.
42 1.
44 1.
44 1.
02 1.
07 1.
13 1.
17 1.
22 1.
25 1.
27 1.
*7 1.
56 1.
00 1.
35 1.
35 1.
13 1 .
4? 1.
no
00
00
00
no
00
00
no
no
00
00
no
no
00
no
00
00
no
00
00
no
00
00
00
no
00
00
00
no
00
00
00
no
no
no
no
00
00
:o8 1
:16 56
:03 1
:12 58
:33 1
:54 1
:22 1
:41 62
PPT(L>
1.000
1.180
1.195
1.200
1.200
1.203
1.205
1.208
1.20ft
1.224
1.22ft
1.239
1.229
1.230
1.231
1.234
1.231
1.280
1.299
1.299
1.327
1.330
1.332
1.33?
1.346
1.350
1.35«
1.359
1.45S
1.461
1.462
1.47*
1.534
1.534
1 .565
t.561
1.567
1.571
1.755
1.002
1.002
1.762
1.000
1.791
1.001
1.903
1.001
1.950
1.004
1.959
1.002
2.024
1.003
2.067
1.027
P.379
2.396
2.466
1.006
PATIO
1.00
1.00
1.00
O.R4
O.P5
1.00
0.83
1.00
0.83
1.00
1.00
1.00
0.81
1.00
0.81
0.81
O.P2
1.00
0.77
l.no
1.00
0.75
0.75
1.00
l.on
0.74
l.on
0.74
l.no
l.on
0.68
0.69
l.on
0.65
1.00
0.64
l.nr>
0.64
A RV
BV
ev
ee
ev
B8
ev
ev
R9
RV
ev
vv
vv
ev
vv
RV
BV
vv
RV
Of-OT
A ev
AMNT
100.00
100.00
100.00
100.00
100.25
100.00
102.00
100.00
100.00
100.00
100.00
100.00
100.10
100.00
101.00
100.00
100.00
100.50
100.00
100.00
100.00
100.00
100.40
100.00
100.00
105.00
100.00
101.50
100.00
100.00
99.00
100.00
100.00
99.50
100.00
100.00
100.00
loi.no
52380.
64084.
65018.
11593.
9796.
48827.
111563.
57834.
31503.
34614.
40668.
3943*.
44592.
P62SO.
34427.
42364.
45153.
17673.
19679.
12284.
18144.
AMNT(L)
100.00
ion. oo
100.00
100.00
100.25
100.00
102.00
100.00
100.00
100.00
100.00
100.00
100.10
100.00
101.00
100.00
100.00
100.50
100.00
100.00
100.00
100.00
100.40
100.00
100.00 '
105.00
100.00
101.50
100.00
100.00
99.00
100.00
100.00
99.50
ion. oo
100.00
ion. oo
101.00
100.000
99
100
100
99
100
200
100
100
100
100
100
.500
.700
.000
.500
.000
.000
.000
.000
.000
.000
.000
100.750
100
99
100
100
100
100
100
100
P.FAC
1.000
1.317
0.973
1.485
1.245
0.448
0.944
1.534
1.170
0.939
2.675
0.096
1.308
1.142
1.930
2.367
1.227
0.314
1.364
0.2PO
1.3R3
1.157
1.217
0.139
1.488
1.185
1.455
1.244
1.283
2.045
1.407
1.326
1.021
1.099
0.274
0.902
0.921
1.203
.000
.750
.000
.000
.000
.750
.000
.000
US/ML
UG/.ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
•JG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
UG/ML
.25
.24
.25
.25
.24
1.25
2.49
1.61
1.61
1.25
1.25
1.25
1.25
1.25
1.24
1.25
1.25
1.25
1.25
1.25
1.25
K.FAC(L) RATIO
1.
1.
0.
1.
1.
0.
0.
1.
1.
0.
2.
0.
1.
1.
1.
2.
1.
0.
U
0.
1.
1.
1.
0.
1.
1.
1.
1.
1.
2.
1.
1.
1.
1.
0.
0.
0.
1.
000
317
973
485
245
448
944
534
170
939
875
096
308
142
930
367
227
314
364
220
383
157
217
139
488
185
455
244
283
045
407
326
021
099
274
902
921
203
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
-------
39
40
41
42
43
44
4«5
46
47
44
49
50
51
5?
53
54
55-
56
57
5fi
59
60
61
62
63
35:09
35:14
35:36
36': 32
36:32
36:38
36:38
36:4?
36:43
37:19
37:20
39:38
39:40
40:37
40:46
40:43
40:53
42:08
42:16
43:03
44:12
49:33
49:54
51:22
51:41
ll.oo
1 .00
1.00
1.00
1.00
l.oo
1.00
1.00
1.00
1.00
1.00
1.00
1.00
l.oo
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.687
1.69?
1.709
1.752
1.75«
1.75?
1.75?
1.76?
1.763
1.791
1.79?
1.903
1.905
1.950
1.950
1.959
1.963
2.024
2.029
2.067
2.123
2.379
2.39*
2.46«
2.481
l.oo
l.oo
O.ci9
l.oo
1.00
0.57
0.57
1.00
0.57
1.00
0.56
1.00
0.53
l.on
0.51
1.00
0.51
1.00
0.49
l.OQ
0.48
1.00 t
1.00
1.00
0.41
100.00
100.25
100.25
100.00
100.00
99.50
100.70
100.00
99.50
100.00
200.00
100.00
100.00
100.00
100.00
. 100.00
100.75
100.00
99.75
100.00
100.00
100.00
100.75
100.00
100.00
100.00
100.25
100.25
100.00
100.00
90.50
100.70
100.00
99.50
100.00
200.00
100.00
100.00
100.00
100.00
ion. oo
100.75
100.00
90.75
100.00
100.00
100.00
100.75
100.00
100.00
0.957
0.095
1.116
0.395
0.396
1.246
1.233
0.088
0.849
0.369
1.142
0.437
1.409
0.262
1.176
0.298
1.122
0.198
1.315
0.320
1.066
0.134
0.148
0.093
1.477
0.957
0.095
1.116
0.395
0.396
1.246
1.233
0.088
0.849
0.369
1.142
0.437
1.409
0.362
1.176
0.298
1.122
0.198
1.315
0.320
1.066
0.134
0.148
0.093
1.477
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
-------
5X24,/ai PAGE
FFFLUE'V'T GLinELI^ES nivISION
CODE L
EGLD COMPOUND COMPOUND
FPftCTTON COwwOUM1 TYPF
ooi B ATE^APHTHFNE p
002 v «rRoi_F.lN °
003 V ArRVLONTT'ilLE P
004 v aFNTENE P
005 a PF.N7ini*E P
006 V CARBON TFTRaCHLORIOE P
007 V CWLO*n*FM7ENF " P
008 9 1.2.4-T6ICHLnu-«. OR^PTHANE " P
Oil V l.l.l-T5ICHL030PTM4riE P
012 R HPXACWL^OETMV^F P
013 V 1,1-OTOLOPOFTH*NE P
014 V 1.1.2-TSICHLOP06THAME P
015 V 1^1.2.2-TETRftCMl.OROETHANE P
016 V CWLOROETHANE P
017 V BTS (CHLOPOMFTHYL) ETHER (NM> P
019 P aTS(2-OLOPOETrtYUF.THEP P
019 V 2-CHLOROFTHYLVU'YL FTHES P
020 « 2-CHLOPCNAPHTHALENF, P
021 A 2.4.6-TPICHLOROPMENOL P
022 A P-CHLORC-M-C"ESOL P
023 V CHLOROFORM P
024 A 2-OLOPCPwENOL P
025 B 1.2-OIC*-LnROPEN7PME P
026 R 1.3-QIOLOROBEN7ENE P
027 B 1.4-OTCHLOROaFN7£NE P
028 R 3.3»-OICHLQOOaEf-!ZTDINE P
029 V 1,1-OTOl.OROFTHYLENE P
030 V LZ-TPft'-S-niCHLOPOETHYLENE P
031 A 2.4-OTC!-lOP"OHeNOL P
032 V 1.2-OTOLOPOOPOPANE P
033 V 1»3-QTOLOPOP90PYLEN£ P
034 A 2t4-r)TMFTHYI.OHENOL P
035 B 2.4-DINITROTOLUENE P
036 R 2,6-OTNTTROTOLU£NE P
037 R lt2-OTP^FNYLMYDPAZI-ME P
038 V ETHYL3F.NZF.NE ' P
039 B FI_OOANT»-FNE p
040 B 4-CMLnPCPHENYL PHFNYL ETHER P
0*1 B 4-H90MQPHENYL PHENYL FTH£R P
0*2 B BTS (2-rMLO«OISOO&nPYL) ETHPP P
043 R mS (?-rHLOPOETHOXY) ETHANE P
044 V MFTHYLE^E OLO^IDE P
045 V vPTHYL THLOBIDE P
046 V MFTMYL BI?OMinF p
047 V ijoovtOFQCM p
048 V OTC-LORP030Mn*ETHANE P
049 V T&irrtLOeoFLUOOOMETHfiME (Nrt) p
-------
5/P4/B3
FFFU'E*IT Fl'T'Fl INEOMOwtTHfl*4E P
052 R HFjoCHLCP'^UTAiJlENF. P
053 R MFlOL -P
05« ft *-r-OfcSOL P
061 R N—:NT-nocnoi'-CT-YLAMTNE P
062 R N-NTTOO«:OulK-F.i-.irLAMINE P
063 R Ni-NTTcoeO'')T-'-<-D0OPYL*MINE P
06* A PFNTiOl O-0»HFi'MOL P
065 A P«FN!OI. P
066 R PTS (P-PTHYLMFxYL) PHTHALATE P
067 R QilTYL 8PN7Y1. PMATHAL4TE P
068 R OT-N-otjTYL "MThALATE P
069 R OT-K--OCTYL PHTHALATE P
070 R OTETHYL PHTMALATE P
071 R OTVF.TMYL =>HTHAL4TE P
072 R OFN70 ( A) ANTHPA-xCENE P
073 8 RFN7Q(A)PY^FMF P
074 R PFN70(P)FLUORANTHFNE P
075 P PFNTOdOFUJOCANTHENE P
07ft R CWYSPNP P
077 ° ACE^APHTr'YL^^F. P
078 B ANTMSSC^NE P
079 R OFN?O (G>-i JPF^YLE^E p
080 R FLUO^FNF P
081 B PME^AWTK»»ENF P
082 R OIRPN^O(A,H)ANTHRACENE P
083 ° INDPNO(l,?.3-ri)»PYPENE P
084 B PYRf-^F P
085 v TPTOftCHi O^OP.TMYLENE P
086 V TOLUEVF, r P
087 V T°irHLOcnFTHYt.£NE P
088 V VTNYL rt-LO^inF P
089 P AI..09TN P
090 P OTELOPIN P
091 P 0*1.1*0.^ £ P
092 P 4.4»-prjT p
093 P 4.4«-nOF P
094 P 4.4»-nnn p
095 P 4i_Puft-EKDnS 'LP*N P
096 P RFTa-ENPO^i.n.FaN P
097 P f'QrlSULrafM ^HLFtTF P
098 P FLORIN P
-------
•S/-?W83
PAGE
USFB* FFFLUENT Gl!IoeLI'"fS DIVISION
rOMPQIINO rOOE LIST
EGLO COMPOUND
NUMBER FRACTION
099
100
101
102
103
cn*4°nuNO
105
106
107
108
109
110
111
112
113
129
130
ISO
151
152
153
15*
155
156
157
158
159
160
161
162
163
16*
165
166
167
168
169
170
172
173
17*
175
176
177
178
179
IflO
181
132
P
P
P
R
V
A
A
V
A
V
P
R
A
R
B
V
V
V
V
V
V
V
V
P
R
B
A
P
9
V
V
ENO°IN
HFPTACHI.OR
HFPTACHLOP
ALPHA-8HC
TYPE
P
PCB--12*?
PC9-125*
PCB-1P21
PCS-1232
PC9-101*
TOXAPHE^E
2.3.7.8-TCDD
XVLFNFS
PHENOL-n6
PPNTaFLUOROPHENOL
TPIFLUO»0-M-C*ESOL
2.2-OIFHJOROTETRACHLOROETHANE
2-FLUORCflIPHFNYL
I-FLUOBONAPHTHALENE
2-FLOURQPHENOL
2-FLUOPCNAPHTHALENE
PYRTDTNF-05
ANILINE-05
NAPHTHALENE-OS
TOLUENE-08
NTTPOOF;MZEN£-D5
2t2»-niFLUOROPIPHENYL
9ENZENE-06
DECAFLUrPQBIPWENYL
M-OIFLUOROflENZENE
METHYLENE C^LORIDE-02
l»lt2«2-TETRACMLOPOETHANE-D2
ETHYLBEK'ZENE-010
1.2 DTCHLOROETMANE-0*
2.2 OTOLOP30PANE-06
CHLOR09PNZENE-05
1.2 DIOLOROPENZENE-D4
CMPYSENE 012
FLUORPNE 010
2-NITRQBHENOL D*
OI-M.BUTYL-PHTHALATP-O*
4-FI.UOPHANILINE
P
P
P
P
P
P
P
P
P
P
S
S
S
S
5
S
s
S
S
S
S
S
S
5
I
S
S
S
S
S
s
S
S
S
S
5
s
-------
?FFi.nF>.iT ^i. IOFI r'-'i-? f«T
p i_TSTJ'jfi
EfiLD COMPOUM3 CO
NUM8ER FPflCTTDM CVViiUfM TY-F
V \ .4-DTOl OW-^uTi'.- T
201 P a.rF.\APi..TWFMF-010 0
202 V O
203 V f.rov(_nNTTwu F-03 0
204 v *F'j7E'-'E-ri* n
B KF
V Cii 0
20« P 1 .2.*-T=tCHI ru'jnk.F.g7FNF-f»3 0
209 Q -c» ^CwLro(''':ic."7E-F-l3C6 ' 0
210 V 1 .ir-nTOt 0*!»eT-*.-4F-04 0
211 V Ulil-TCTCHl.^wftFT^ANF-03 n
212 a ^FXAC^Lf!POEm^*ih-]-i3C 0
213 V 1 . l-OTOLOPMFT-iaivE-?, 2,2-03 D
214 V ] , l.^-TBTTHi nooFTHft«jF-}3C2 u
21S V 1. 1.2.2-TET--aCHl OOOFTH4NE-02 0
216 V C'-'t.^OF.THftMF-OS 0
217 V .0
218 P HlS(?-Ci-LnP'iFTHYL)-Oa fTH«i^ D
219 V 0
220 B ?-OLT:»r'"APHTHALF.'"E-07 0
221 « ?.4,6-TciCHLOPOPHFNOL-3.5-02 U
222 A 4-CMLOflr-3-MF.THYL:'HFNOL-2»6-n5! 0
223 V CHLnROFr«M-13C 0
224 A 2-CMLnqrPi-ENOL-3, 4. 5,6-04 D
225 R l,^-OTCuI.DRnQEN7ENF-04 0
226 R t O-OIC»-l.OHnafN7E'-iE-04 U
227 P 1,4-OTCHI.OROOFNZFMF-04 0
223 P 3.3'-nTrH.:1-'naE'"ZIOTN(:-r>6 D
229 V 1. l-OTCt-LC'J^FTHYLfNF-^2 D
230 V 1.2-OTCM .'V' )FTHYLFNF-r.2 0
231 A ?.4-JTOLf>«)PHENOI.-3,(?»r— C3 0
232 v 1.2-OTOU1300POPANE-P* 0
233 V 1.3-')TOL090000PYLFME-1»2-02 D
234 a 2.4-nTMFTHYi »Hf(vjni.-3,5,(S-03 0
235 P ?.4
236 R ^.e
237 P i,2-nrowFNri.-nii.-r'YnHfl7iNe o
23B V ETWYLBFK7ENF.-nio 0
239 B Fl un^ANTMF-IF-nif) 0
240 P 4.-rHi_norP"F:'iYL I^HENYI.-OS ETrEP D
241 P D
242 o PIS<2-Cl-l.^JfiI';n»-pnPYL)ETMEPl'l? D
?43 R D
244 V "FTHrLE'^E C-»I.OHTDF.-n2 D
245 v cut_npnMCTHa:jF-03 D
246 V MOO*0*FTifl-NF-03 0
247 V .-oo^OFO = --13C 0
V wDQ-MjD JTMI •)'-)
-------
OtVlSTON
rni)E LISTING
EGLD COMPOUND COMPOUND
COMPOUND TYPF.
249 »/ 0
250 w D
252 *? WF*AC^LfOi-l•3-BUTADIENE-13C4 0
253 q HP x*Cp4L''or>CYrLOPENTfiQ IEN£"-13C 0
?54 Q jcQpwoopKif;—op Q
255 H Mit'MTHAi.F/jF.—08 0
256 » -N T fOOF.* 7FNF-05 0
257 A y—\T r50CHFiMOL-3»*»5t6-04 . 0
258 A «»—', T raOCM|-NOL—£• 3»5»6—04 0
259 A P. 4-0 TNTTJOPHF.NOL—i«5«6—03 u
260 A *.iS-OTNT1>0-0-C«F<;OL-n2 0
261 n D
263 a ' 0
?64. A PP\TACHI OPOPHFfv'OL-13C6 0
265 A PMP'^OL-5.3«4«S»6—05 D
267 P 0
268 B r.T-N-qtJTYL PMTHALATF-04 D
?69 « OT-M-1CTYL PHTHALATE-04 0
270 R OTETHYL PHTHALATE-3«4»5»6-04 U
271 P oTi-FTHYt PHTHALATE-3»4»5»6-04 0
272 P qpN^o*A)ANTnOACENE-012 D
273 »3 »FN70(A)PYRFNE-012 0
276 P C^'YSFNP—Ol? n
277 B ^^f:^•A?HTHYI.ENF-08 D
278 P 4K.F\'F-010 0
281 P PMi-^^NT'-PENE—OlO 0
282 P " D
293 P. 0
284 P PYWF'4F.-P10 0
285 V TFTPArm QPOETHYLENF.-13C2 D
286 V TOLM£vE-2.3.4.?.6-05 0
288 V VTNYL-O? CHLOPIOE " 0
289 P 0
290 P 0
291 P 0
292 P 0
293 P 0
294 P D
295 P 0
296 P D
297 o Q
-------
USFP4 FFFL'lEM GMMELINES OIVISION
fOOE LISTING
PAGE
EGLD COMPOUND
NUMBER FRACTION
298
299
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
P
p
B
V
V
V
P
V
v
P,
B
V
V
p.
V
V
V
V
V
p
V
9
A
A
V
A
B
B
R
P,
V
V
A
V
V
&
B
B
B
V
B
B
P
B
R
V
V
V
V
aCRYLONTTPILE
CAPRQN TFTRACHLOfrTDF
1.1. 1-TO ICHLOROETHANE
1.1-OICHLOPOETHANE
1 ^ 1 .2-TB ICHLOROETHANE
1.1.2. 2-TETRACHLOROETHANE
CHLOROETHANE
BIS (2-C^LOROETHYL) ETHER
2-CHLORONAPHTHALENE
2.4,6-TGlCHLOROPHENOL
P-CHLORO-M-CRESOL
CHLOROFORM
2-C«LOROPHENOL
1.2-DTCULOROOENZENE
1 . 3-0 TC^LOWOBENZENE
1 .4-0 T CHLOROBENZENE
3»3'-niCHLOPOBENZIDTNE
1.2-OTCHLOROETHYLENE
2 . 4-0 T CHLOPOPHENOL
1 « 2-0 ICHLOROPROP ANE
1.3-DICHLOROOROPYLENE
2.4-OIMPTHYLPHENOL
2.4-D IN ITROTOLUENE
2 » 6-0 1 N I TROTOLUENE
1 .2-OTPHENYLHYDRAZINE
4-CuLOPOPHEN'YL PHENYL ETHER
BIS (P-CHLOPQISOPROPYL) ETHEP
E CHLORIDE
METHYL CHLOWIDE
METHYL
COMPOUND
TYPE
0
0
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
p
P
P
P
P
P
-------
5/24/33
PAGE
USE"»A AFFLUENT GUIDELINE* DIVISION
COMPOUNO rOPE
E6LO COMPOUND
NUMBER FRACTION
COMPOUND
COMPOUND
TYPE
3*8
349
350
351
352
353
354
355
356
357
356
359
360
361
362
363
364
365
366
367
36S
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
.394
395
396
V
V
V
V
fl
R
P
q
R
A
A
A
A
R
8
R
A
A
B
P
R
R
B
R
B
R
B
P
R
R
B
R
R
R
R
a
R
V
V
V
V
P
P
P
P
P
P
P
o
HFXACHL>POCYCLOPENTADIEN£
ISOPMOPOF
NAPHTHALFNI-
P
P
4-NITOOPHPNOL
2«4-OINTTMOWH
4,6-OTNlTPO-O-CRESOL
N-NTTPO«?OOIPHF,NYLAMINE
PENT ACHI. OPOPHPNOL
PHENOL
RIS (P
PHTHALATf
DI-N-PUTYL PHTHALATF
OI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
OTMFTHYL PHTHALATE
RFN70(A) ANTMS4NCENE
BFN?0(A)PYRENI-
9FN70(8)FLUORANTHENE
BFN7Q (K ) FLUOO ANTHENE
ACENAPHTHYLENE
BFN70(Q»-I)PERYLENE
FLUORENF
PHENANTHPENE
P
P
P
P
P
P
TFTPACHLOROETHrLENE
TOLUF.NE
TBICHLOOOETHYLENE
VINYL C'-LORIHE
P
P
P-
P
P
P
P
P
P
P
P
-------
5/24/83
AFFLUENT GLIOELINF-S DIVISION
LISTING
PAGE
EGLD COMPOIJNC
NUMPFP
COMPOUND
397
393
399
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
518
519
520
521
522
523
524
525
526
600
601
602
603
604
605
606
607
608
609
610
611
612
613
614
615
616
M7
618
D
D
.P
A
A
P
R
a
p
p
p
p
p
p
a
p
p
V
V
V
p
B
P.
p
P
p
P
P
p
p
A
A
P
P
P
P
P
R
B
P
R
P
P
P
V
V
V
R
R
«F%7QTC ACID
HFXANOIC ACID
ALPHA
. Ai-I'MF
0
AI.PHA TF.PPINFOL
. AMTNE
P-CYWF.NP
MFTHYL PTMYL
-------
5/24/83
°AGE
3UIOEI.TNES DIVISION
CODE LlSTIWfi
E6LO COMPOUND .
NUMBER FRACTION
619
620
621
622
623
62*
625
626
700
701
702
703
70*
705
706
707
708
709
710
7u
712
713
714
715-
717
718
719
720
721
722
723
72*
725
726
P
P
8
«
P
P
B
P
A
A
P
8
"3
B
8
8
B
8
8
P
fl
8
V
V
V
8
8
8
8
8
8
8
8
8
8
COMPOUND
N-wF,XAO?CANE-034
N-ETCOSANE-D42
W-TFTRACOSAME-D50
N-T01ACCNTANE-D62
RFi^OTC ACID
HFXANOIC ACID
8?TA NAPHTHYLAMINE
ALPHA PTCOLINE
DIBENZOTHIOPHENE
DI9EN70PUPAN
N-OOOEONE C12
DTPHENYLAMINE
DIPHENYLETHER -
ALPHA TPRPINEOL
STYOENE
DT-N-BUTYL AMTNE
8IPHENYL
P-CYMENE
MFTHYL FTHYL KETONE
OIETHYL ETHER
ACETONE
N-OECANE CIO
,
N-HEXAOECANE C16
N-EICOSANE C2Q
N-TETRACOSANE C24
N-TRtAGCNTANE
C30
COMPOUND
TY»-E
0
0
0
0
0
0
0
0
P
p
P
P
P
P
P
P
P
p
P
P
P
P
P
P
P
P
p
P
P
P
427 RECORDS
-------
TAB 3 - Quantttation Report Magnetic Tape Trammittal Form Description
The main purpose of the tape transmittal form is to ensure the complete and
correct data processing of a tape volume (reel). Depending upon the number of files
per volume at least one tape transmittal form must accompany each tape volume sent
to the Sample Control Center. Field descriptions are as follows.
Laboratory
Return Tape To
External Tape t
Tape Density
Block Size
Number of Files
Contact Person and Phone Number
File Position
t The laboratory name.
t The address to which the tape volume is to be
returned after processing by the SCC,
t The tape number on the SCC supplied ex-
ternal tape labeL
t Either 800 or 1600 bpL
: The number of bytes per block.
: The number of Quantitation* report files on
the tape.
: Who to contact at the laboratory, regarding
any difficulties in the processing of the tape
volume, and their phone number including
area code.
: The relative file position of the Quantitation
Report File on the tape volume. The first
file on the tape has a relative file position of
1. The second file on the tape has a relative
file position of 2.
-------
EPA Sample Number : The 5 digit sample number assigned by the
SCC. N/A if not applicable.
Type : The 3 position EGLO code signifying the
sample type. Required.
Fraction : 1 position code:
A* Acid
B a Base/Neutral
C a Combined Acid Base/Neutral
V * Volatile
Ps Pesticide
N/A if not applicable.
Conc/Dilu t The concentration or dilution ratio of the
sample fraction before analysis. N/A if not
applicable.
%
Date Analyzed : The date of analysis.
-------
USEPA Effluent Guidelines Division Revision: A
Quantitation Report Magnetic Tape Transmittal Form Date: 5May83
Laboratory: External Tape #:
Return Tape To: Tape Density (BPIh
Block Size:
Number of Files:
Contact Person and Phone Number: ( )
File Position EPA Sample t Type Fraction Conc/DUu Date Analyzed
The data recorded on this tape have been verified and are true and complete.
Date: Analyst: QA:
-------
Quantitation Report Magnetic Tape Additional Files TransmittaJ Form
This form is only to be used when there are more than 14 quantitation report
files on a tape and It must be used with a Quantitation Report Magnetic Tape
TransmittaJ Form. As many Additional Files TransmittaJ Forms can be used to
accommodate all of the files on the tape. The field definitions are identical to those
on the Quantitation Report Magnetic Tape TransmittaJ Form.
-------
Appendix E
EGD Data Elements
Following is a brief description of each data element which is to be stored in the
EGD data base. The originating source for the data element is also given. The
complete specification for each data element and an example of its use are given on a
separate page following this summary.
Amount — The quantitative measurement of the compound determined by GC or
GC/MS analysis. The amount is computed for the compound using the referenced
internal standard or isotopic diluent and is multiplied by the concentration or
dilution factor to yield final solution concentrations in ug/L.
Amount (Library) — The reference amount in the standard and the amount on
which quantitation is based.
Bottle Number — A numeric code which uniquely identifies the bottles used for a
particular sample.
Carrier Gas Flow Rate — The volumetric (volume/time) rate of flow of the
carrier gas in the gas chromatograph, or the linear gas velocity (distance/time)
when a capillary column is used.
Column Final Hold — The final temperature of the gas chromatograph column
and the length of time that it was held.
Column Initial Hold — The initial temperature of the gas chromatograph column
and the length of time that it was held.
Column Inside Diameter — The internal diameter of the gas chromatograph
column.
-------
Column Length - The length of the gas chromatograph column.
Column Temperature Program — The change in column temperature with respect
to time giving the initial and final column temperatures.
Compound Comment Code — A coded value for any optional text that may be
associated with each compound.
Compound Name — The name of the compound determined. The compound name
corresponds to the EGD compound number, as given in the "U5EPA Effluent
Guidelines Division Compound Code Listing."
Compound Number — A numerical code which uniquely identifies each unique
chemical compound, as given in the "Effluent Guidelines Division Compound
Code Listing."
Compound Order Number — A numerical code that establishes the order of
compound determination by the GC/MS. The code is used on the Quantitation
Report to match segments of the compound data within the report.
Compound Type — A coded value which identifies a chemical compound as a
priority pollutant (P), or surrogate (S), internal standard (I), or isotopic dllutent
(D).
Concentration/Dilution Factor — The ratio of the volume of sample extracted or
diluted to the volume analyzed.
Date Analyzed — The date that the sample fraction was analyzed by the
laboratory.
Date Extracted — The date that the laboratory extracted the sample for analysis.
-------
Date Sampled — The date the sample was taken by the field sampler.
Episode Comment Code — A coded value for comments associated with an
episode.
Episode Number — The SCC assigned identification code with designates the
specific sampling trip.
Fraction — A coded value which designates the compound as either an acid,
base/neutral, volatile, pesticide or dioxin.
Fraction Comment Code — A coded value for any optional text that may be
associated with each fraction.
Industrial Category Code — The classification of the industrial processes per-
formed by the plant where a sample was taken.
Instrument — A coded value assigned by the laboratory that uniquely identifies
each GC/MS instrument within a laboratory. All Calibration, Precision and
Recovery, Standards and Blank Quantitation files will be tracked by this
instrument number within Laboratory. Changing of this instrument number by
the laboratory would necessitate the submittal of new calibration and other
initial QA runs by the laboratory.
Laboratory — A numerical code used to identify the specific laboratory where
the sample was analyzed.
Mass to Charge Ratio — Designates the quantitation ion. Abreviated as M/Z or
M/E.
Method — A coded value which uniquely identifies the method protocol that was
followed during analysis.
-------
Peak Area — The area beneath the peak of a mass chromatogram. The peak area
is proportional to the amount of the detected compound at an observed mass to
charge ratio. It is used to compute the concentration of the compound present in
the sample.
PH Level — The negative logarithm of the effective hydrogen ion concentration
as expressed in grain equivalents per liter.
Plant Code — A numerical code used to distinguish specific plants which have
been sampled.
Proprietary Indicator — A coded value which designates whether or not the
analysis data from a sample is' proprietary. Also indicates that confidentiality
papers have been signed.
Quantitation Report Type — A coded value that uniquely identifies the particular
type of quantitation report that is being submitted.
Reference Compound — A numeric code that is used as a pointer to the internal
standard or isotopic diluent within a quantitation report.
Relative Retention Time — The quotient of the retention time of a compound
divided by its internal standard or isotopic diluent.
Relative Retention Time (Library) — The relative retention time stored in the
library. The value is based on the analysis of a standard containing both
compounds.
Response Factor — The ratio between the response for the sample and a response
for a standard under identical analytical conditions.
Response Factor (Library) — The response factor stored in the library. The value
is determined from analysis of a standard.
-------
Retention Time — The time it takes the identified compound to elute from the
gas chromatograph.
Retention Time (Library) — The known time it takes an identified compound to
elute from the gas chromatograph. The time is determined from analysis of a
standard.
Sample Comment Code — A coded value for any optional text that may be
associated with each sample.
Sample Number — The SCC assigned identification code which identifies the indi-
vidual samples.
Sample Point (Site) — The specific point within an industrial wastestream where
a sample was taken.
Sample Point Flow — The flow rate at the point at which the sample was taken.
Value is recorded from a flow meter or other flow measuring device.
Sample Type — A coded value which describes the type of sample.
Scan Number — Gives the scan at which the compound was detected by the mass
spectrometer.
Shift — The scheduled period of operation of the GC/MS instrument. Operation
is divided into three shifts/day.
Time Analyzed — The time that the sample fraction was analyzed by the
laboratory.
Unit of Measure — The unit of measurement for the amount.
The following chart shows the source of each data element.
-------
SUMMARY OF DATA SOURCES FOR COLLECTION
OF ORGANIC PRIORITY POLLUTANT DATA
COLLECTION SOURCE
. TR2 LAB3
DATA FIELD SAMTRAC LC TAPE GENERATED
Amount X
Amount (Library) X
Bottle Number X
Carrier Gas Flow Rate X
Column Final Hold X
Column Initial Hold X
Column Inside Diameter X
Column Length X
Column Temperature Program X
Compound Comment Code X
Compound Name
Compound Number X
Compound Reference Number X
Compound Type
Concentration/Dilution Factor X
Date Analyzed X
Date Extracted X
Date Sampled X
Episode Comment Codes X
Episode Number X
Fraction X
Fraction Comment Code X
Industrial Category Code X
Instrument X
Laboratory X
(1) SAMTRAC - Computerized logistics system at the Sample Control Center.
(2) TR LC - Traffic Reports and Lab Chronicles.
(3) Quantitation Reports on magnetic tape received from analytical laboratories.
-------
SUMMARY OF DATA SOURCES FOR COLLECTION
OF ORGANIC PRIORITY POLLUTANT DATA
DATA FIELD
COLLECTION SOURCE
1
TR'
SAMTRAC LC
j3
TAPE
GENERATED
Mass to Charge Ratio
Method
Peak Area
PH Level
Plant Code
Proprietary Indicator
Quantitation Report Type
Reference Compound
Relative Retention Time
Relative Retention Time (Library)
Response Factor
Response Factor (Library)
Retention Time
Retention Time (Library)
Sample Comment Code
Sample Number
Sample Point (Site)
Sample Point Flow
Sample Type
Scan Number
Shift
Time Analyzed
Unit of Measure
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(1) SAMTRAC - Computerized logistics system at the Sample Control Center.
(2) TR LC - Traffic Reports and Lab Chronicles.
(3) Quantitation Reports on magnetic tape received from analytical laboratories.
-------
NOTES ON TYPE/LENGTH DESCRIPTION
The Type/Length Description for each EGD Data Element represents how each
data field is stored internally in the computer or how each data field is represented on
the quantitation report.
TYPES:
Z - Numeric data only - leading zeroes not printed.
9 - Numeric data only - zeroes printed.
X - Alpha numeric data.
V - Implied decimal point.
Explicit decimal point.
LENGTH;
(N) Where N is a positive integer value from 1 to 255, gives the number of data
positions allocated internally by the computer to store this portion of the
data field.
EXAMPLES;
Example 1. 9(7)V9(3)
9 - Numeric data.
(7)+(3) - 10 data positions allocated.
V - Implied decimal point after 3rd position from the right.
Can also be expressed as 9999999V999.
The number 1,130.31 would be stored internally under this Type/Length des-
cription as:
'0001130310'
-------
NOTES ON TYPE/LENGTH DESCRIPTION (CONT.)
The computer program would also know that there is a decimal point implied
between '0001130' and '310'.
Example 2. X(6)
X - Alphanumeric data.
(6) - 6 data positions allocated.
Can also be expressed as XXXX.
The field 'EPA1' would be stored internally or printed as:
•EPA1'
Example 3. ZZZ2ZZ9.999
Z - Numeric data - zeroes not printed.
9 - Numeric data - zeroes printed.
Explicit decimial point printed.
6 (Z's) + * (9's) + 1 (.) = 11 data positions allowed.
The field '0000023010' would be printed as:
' 23.010'
-------
ELEMENT NAME: AMOUNT
Definitions The quantitative measurement of the compound determined by GC or
GC/MS analysis. The amount is computed for the compound using the referenced
internal standard or isotopic diluent and is multiplied by the concentration or dilution
factor to yield final solution concentration in ug/L.
Input Type/Length
Quantitation Report ZZZZZ9.999
As Stored Internally 9(7)V9(3)
Unit of Measure
Ug/L
Edit Criteria:
Range: 10.000-999,999.999 ug/L
Examples:
Volatiles: Concentration (AMOUNT) is reported on quantitation report in ug/1; if
sample is diluted to bring a pollutant within the analytical range of the
instrument, the concentration is multiplied by the dilution factor. For example,
a concentration of 60 ug/1 from analysis of a sample which has been diluted 1:10
results in a final concentration of 600 ug/1.
Semi-volatiles: Concentration (AMOUNT) is reported on quantitation report in
ug/ml; sample is assumed concentrated by a factor of 1000 (concentration factor
1000:1), based on extraction of 1.00 liter of sample and a final extract volume of
1.0 ml. If extract is diluted to bring the concentration of a pollutant within
calibration range of the instrument, the concentration factor is reduced by the
amount of the dilution. For example, if the extract is diluted 1:10, the
concentration factor becomes 100:1 (1000:10 = 100:1).
-------
ELEMENT NAME: AMOUNT (LIBRARY)
Definition: The reference amount in the standard and the amount on which quanti-
tation is based.
Input Type/Length
Quantitation Report Z2ZZZ9.99
As Stored Internally . 9(7)V9(3)
Unit of Measure
The amount is reported as a pure number but must always be accompanied by a
UNIT. See UNIT.
Edit Criteria:
Range: 1.000 - 1000.000 ug/L
Examples: See AMOUNT.
-------
ELEMENT NAME: BOTTLE NUMBER
Definition: A numeric code which uniquely identifies the botties used for a particular
sample. Used as a suffix to the SAMPLE NUMBER.
Input Type/Length
Quantitation Report X(2)
As Stored Internally X(2)
Unit of Measure
Each.
Edit Criteria:
Range 01-99.
Example: See SAMPLE NUMBER.
-------
ELEMENT NAME: CARRIER GAS FLOW RATE
Definition: The volumetric (volume/time) rate of flow of the carrier gas in the gas
chromatograph for packed columns, or the linear gas velocity (distance/time) for
capillary columns.
Input Type/Length
Quantitation Report X(9)
As Stored Internally X(9)
Unit of Measure
Volatiles (packed column): ML/Min
Semi-volatiles (capillary column): CM/Sec
Edit Criteria:
Ranges: Volatiles: 20-40 mL/min; Semi Volatiles: 20-60 cm/sec;
Dioxin: 20-60 cm/sec
-------
ELEMENT NAME: COLUMN FINAL HOLD
Definition: The final temperature of the gas chromatograph column and the length of
time that it was held.
Input Type/Length
Quantitation Report X(7)
As Stored Internally X(7)
Unit of Measure
Time: minutes
Temperature: degrees Celsius
Units are understood and not reported.
Edit Criteria:
Format: Hold @ temperature ie XXX@XXX
Example: 15 (9 280 means that the column was held for 15 minutes.
-------
ELEMENT NAME: COLUMN INITIAL HOLD
Definition: The initial temperature of the gas chromatograph column and the length
of time that it was held.
Input Type/Length
Quantitation Report X(7)
As Stored Internally X(7)
Unit of Measure
Time: minutes
Temperature: degrees Celsius
Units are understood and not reported.
Edit Criteria:
1. Format: Hold @ Temp ie XXX@XXX
2. Temperature Ranges: Volatiles: 25-50°C; Semi Volatiles: 25-35°C
Example: See COLUMN FINAL HOLD.
-------
ELEMENT NAME: COLUMN INSIDE DIAMETER
Definition: The internal diameter of the gas chromatograph coiumn.
Input Type/Length
Quantitation Report X(6)
As Stored Internally X(6)
Unit of Measure
Millimeter (MM)
Edit Criteria:
Ranges: Volatiles: l-3mm; Semi-Volatiles: 0.2-0.35 mm;
Dioxin: 0.2-0.35 mm
-------
ELEMENT NAME: COLUMN LENGTH
Definition: The length of the gas chromatograph column.
Input Type/Length
Quantitation Report X(6)
As Stored Internally X(6)
Unit of Measure
Meters (M)
Edit Criteria:
Ranges: Volatiles: 2.8-3.1 m; Semi-Volatiles: 25-35 m;
Dioxin: 25-65 m
-------
ELEMENT NAME: COLUMN TEMPERATURE PROGRAM
Definition: The change in coiumn temperature with respect to time giving the initial
and final column temperatures.
Input Type/Length
Quantitation Report X(10)
As Stored Internally X(10)
Unit of Measure
Initial temperature: degrees Celsius
Final temperature: degrees Celsius
Rate: degrees Celsius per minute
Units are understood and not reported.
Edit Criteria:
1. Format: Initial Temp - Final Temp @ Temp Program rate ie XXX-XXX @ XX
2. Range: 1.5-8.5°C/min
Examples:
45-220 @ 8
30-280 @ 8
-------
ELEMENT NAME: COMPOUND COMMENT CODE
Definition: A coded value for any optional text that may be associated with each
compound.
Input Type/Length
Traffic Report X(<0
Laboratory Chronicles
As Stored Internally
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the compound comment code table. Range C001-C999.
See attached Compound Comment Code Table for valid codes.
-------
2/08/84
ISOTOPE DILUTION
COMPOUND LEVEL COMMENT CODE TABLE
PAGE
CODE
C001
C002
C003
C004
COOS
C006
C007
COOS
C009
C010
C011
C012
C013
C014
C015
C016
C017
C018
C019
C020
C021
C022
C023
C024
C025
C026
C027
C028
C029
C030
C031
C032
C033
C034
C035
C036
C037
C038
CO 39
C040
CO-41
C042
C043
C044
C045
C046
C047
C048
C049
C050
DESCRIPTION
COMBINATION OF 2 PCB'S
DATA FROM B/N FRACTION
BELOW VALID CALIBR . RANGE:NOTE CONC. FACTOR
ACID ANALYZED IN B/N FRACTION
NATURALLY OCCUR. CPD. INADVERT. SPIKED IN
QUANTITATED BY ISOTOPE DILUTION
1:5000 DILUTION
55.4 UG FOUND IN BLANK
5.92 UG FOUND IN BLANK
52.8 UG FOUND IN BLANK
33.0 UG FOUND IN BLANK
5.1 UG FOUND IN BLANK
11.8 UG FOUND IN BLANK
13.1 UG FOUND IN BLANK
SEVERE INTERFERENCES
INTERFERENCES
5.0 UG FOUND IN BLANK
3.02 UG FOUND IN BLANK
8.24 UG FOUND IN BLANK
COMMON LAB CONTAMINANT(METHYLENE CHLORIDE)
SLIGHT EMULSION PRESENT IN ACID CPDS.
UNCONFIRMED
4PPB FOUND IN BLANK
8PPB FOUND IN BLANK
5PPB FOUND IN BLANK
USED M/2 86
225,227 DATA COMBIN COMPLX INTEGRATION
DISC ERROR-DATA LOST FROM FILE
272,276 DATA AVG'D
273,281 DAT.A AVG'D
USED M/2 144
PEAK OVERLAP, USE 2ND ION
USED CUMM. RF AVG
ACTUALLY SPIKED AT 10 PPB; RESULTS NORMALIZED TO 20
ACTUAL SPIKE 50 PPB; RESULTS NORMALIZED TO 100
218,265 INTEGRATION PROBLEM-OVERLAP
16 PPM FOUND IN FIELD BLANK-11084 (EP 806)
POOR INTEGRATION IN REGION OF 218,225,227
29 PPH FOUND IN TRIP BLANK - EP 803
1/5000 DILUTIONS AFTER SUBTRACT 12 PCENT AS BKGD
BUTYL BENZYL PHTHALATE SEEN AT 13 PPB
BUTYL BENZYL PHTHALATE SEEN AT 11 PPB
BUTYL BENZYL PHTHALATE SEEN AT 8 PPB
2.5 PPB FOUND IN LAB BLANK
2.7 PPB FOUND IN LAB BLANK
2.1 PPB FOUND IN LAB BLANK
NOT MEASURED
BACKGROUND OVERLAP PREVENTS INTEGRATION
HIGH CONTAMINATION CAUSED POOR CHARACTERIZATION
NOT MEASURED DUE TO FILE ERROR
-------
2/08/84
ISOTOPE DILUTION
COMPOUND LEVEL COMMENT CODE TABLE
PAGE
CODE
C051
C052
C053
C054
C055
C056
C057
C058
C059
C060
C061
C062
C063
C06A
C065
C066
C067
DESCRIPTION
JUST AT DETECTION LIMIT
PEAK OVERLAP, POOR INTEGRATION
POOR COMPUTER INTEGRATION
PNA'S AT BKGD LEVEL, GEN. DET'N LIM. BETWN 2-3
RECOVERY NOT QUANTIFIABLE, HEAVY PHENOLIC OVERLAP
HEAVY OVERLAP MAY BE IN EFFECT
1/100 DILUTION
ISOTOPES COULDN'T BE USED FOR QUANTIFICATION
POOR INTEGRAT. OF LBLED COMDS CAUSED BY SATUR. PEAKS
POOR INTEGRATION IN REGION
ACTUAL SPIKE 80-NORMALIZED TO 100
AVERAGE OF COMPOUNDS 272 AND 276
AVERAGE OF COMPOUNDS 278 AND 281
SPIKED WITH TWO ACID SURROGATES
ACTUAL SPIKE 50-NORMALIZED TO 100
DETECTION LIMIT APPRO*. 50 UG/L
AVERAGE OF COMPOUNDS 225 AND 227
-------
ELEMENT NAME: COMPOUND NAME
Definition! The name of the compound determined. The compound name corresponds
to the EGD compound number.
Input Type/Length
Quantitation Report X(30)
As Stored Internally X(30)
Unit of Measure
N/A
Edit Criteria:
See attached EGLD Compound Table for valid names.
Examples:
BROMOFORM
1,2-DICHLORBENZENE-D4
-------
ELEMENT NAME: COMPOUND NUMBER
Definition: A numerical code which uniquely identifies each unique chemical com-
pound.
Input Type/Length
Quantitation Report 9(3)
As Stored Internally 9(3) .
Unit of Measure
N/A
Edit Criteria:
Must be one of the following codes:
001-129 = Priority Pollutants quantitated by internal or external stan-
dard.
130-199 = Miscellaneous surrogates and internal standards.
200-299 = Priority Pollutant labeled compounds (isotopes) quantitated by
internal or external standard.
300-399 = Priority Pollutants quantitated by isotope dilution.
400-429 = Labeled compounds (isotopes) quantitated by internal or ex-
ternal standard.
500-599 = Syn Fuel specific and Appendix C compounds quantitated by
internal or external standard.
600-699 = Syn Fuel specific and Appendix C labeled compounds (isotopes)
quantitated by internal or external standard.
700-799 = Syn Fuel specific and Appendix C compounds quantitated by
isotope dilution.
800-829 = Pollutants 100-129 quantitated by isotope dilution.
See attached EGLD Compount Table.
-------
2/09/84
PAGE
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND
NUMBER FRACTION
001
002
003
004
005
006
007
008
009
010
Oil
012
013
014
015
016
017
018
019
020
021
022
023
024
025
026
027
028
029
030
031
032
033
034
035
036
037
038
039
040
041
042
043
044
045
046
047
048
049
B
V
V
V
B
V
V
B
B
V
V
B
V
V
V
V
V
B
V
B
A
A
V
A
B
B
B
B
V
V
A
V
V
A
B
B
B
V
B
B
B
B
B
V
V
V
V
V
V
COMPOUND
ACENAPHTHENE
ACROLEIN
ACRYLONITRILE
BENZENE
BENZIDINE
CARBON TETRACHLORIDE
CHLOROBENZENE
1,2,4-TRICHLOROBENZENE
HEXACHLOROBENZENE
1,2-DICHLOROETHANE
1,1,1-T,RICHLOROETHANE
HEXACHLOROETHANE
1,1-DICHLOROETHANE
1,1,2-TRICHLOROETHANE
1,1,2,2-TETRACHLOROETHANE
CHLOROETHANE
BIS (CHLOROMETHYL) ETHER (NR)
BISC2-CHLOROETHYL)ETHER
2-CHLOROETHYLVINYL ETHER
2-CHLORONAPHTHALENE
2,4,6-TRICHLOROPHENOL
4-CHLORO-3-METHYLPHENOL
CHLOROFORM
2-CHLOROPHENOL
1,2-DICHLOROBENZENE
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
3,3'-DICHLOROBENZIDINE
1,1-DICHLOROETHENE
TRANS-1.2-DICHLOROETHENE
2,4-DICHLOROPHENOL
1,2-DICHLOROPROPANE
T-1.3-DICHLOROPROPENE
2,4-DIMETHYLPHENOL
2,4-DINITROTOLUENE
2,6-DINITROTOLUENE
1,2-DIPHENYLHYDRAZINE
ETHYLBENZENE
FLUORANTHENE
4-CHLOROPHENYL PHENYL ETHER
4-BROMOPHENYL PHENYL ETHER
BIS (2-CHLOROISOPROPYL) ETHER
BIS (2-CHLOROETHOXY) METHANE
METHYLENE CHLORIDE
CHLOROMETHANE
BROMOMETHANE
BROMOFORM
BROMODICHLOROMETHANE
TRICHLOROFLUOROMETHANE CNR)
COMPOUND
TYPE
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
-------
2/09/84 PAGE
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND COMPOUND
NUMBER FRACTION COMPOUND TYPE
099 P ENDRIN ALDEHYDE P
100 P HEPTACHLQR P
101 P HEPTACHLOR EPOXIDE P
102 P ALPHA-BHC P
103 P BETA-BHC P
104 P GAMMA-BHC P
105 P DELTA-BHC P
106 P PCB-1242 P
107 P PCB-1254 P
108 P PCB-1221 P
109 P PCB-1232 P
110 P PCB-1248 P
111 P PCB-1260 P
112 P PCB-1016 P
113 P TOXAPHENE P
129 D 2,3,7,8-TCDD P
130 V XYLENES P
150 A PHENOL-D6 S
151 A PENTAFLUOROPHENOL S
152 V PENTAFLOUROBENZENE S
153 A TRIFLUORO-M-CRESOL S
154 V 2,2-DIFLUOROTETRACHLOROETHANE S
155 B 2-FLUOROBIPHENYL S
156 B 1-FLUORONAPHTHALENE S
157 A 2-FLOUROPHENOL S
158 B 2-FLUORONAPHTHALENE S
159 B PYRIDINE-D5 S
160 B ANILINE-D5 S
161 B NAPHTHALENE-DS S
162 V TOLUENE-DS S
163 B NITROBENZENE-05 S
164 B 2,2'-DIFLUOROBIPHENYL I
165 V BENZENE-D6 S
166 B DECAFLUOROBIPHENYL S
167 V M-DIFLUOROBENZENE S
168 V METHYLENE CHLORIDE-D2 S
169 V 1 , 1,2,2-TETRACHLOROETHANE-D2 S
170 V ETHYLBENZENE-D10 S
172 V 1,2 DICHLOROETHANE-D4 S
173 V 2,2 DICHLOPROPANE-D6 S
174 V CHLOROBENZENE-D5 S
175 B 1,2 DICHLOROBENZENE-D4 S
176 B CHRYSENE D12 S
177 B FLUORENE D10 S
178 A 2-NITROPHENOL D4 S
179 B DI-N-BUTYL-PHTHALATE-D4 S
180 B 4-FLUOROANILINE S
181 V BROMOCHLOROMETHANE I
182 V 2-BROMO-l-CHLOROPROPANE I
-------
2/09/84
PAGE
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND
NUMBER FRACTION
050
051
052
053
055
056
057
058
059
060
061
062
063
064
065
066
067
068
069
070
071
072
073
074
075
076
077
078
079
080
081
082
083
084
085
086
087
088
089
090
091
092
093
094
095
096
097
098
V
V
B
B
B
B
B
A
A
A
A
B
B
B
A
A
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
V
V
V
V
P
P
P
P
P
P
P
P
P
P
COMPOUND
DICHLORODIFLUOROMETHANE (NR)
DIBROMOCHLOROMETHANE
HEXACHLORO-1,3-BUTADIENE
HEXACHLOROCYCLOPENTADIENE
ISOPHORONE
NAPHTHALENE
NITROBENZENE
2-NITROPHENOL
4-NITROPHENOL
2,4-DINITROPHENOL
2-METHYL-4,6-DINITROPHENOL
N-NITROSODIMETHYLAMINE
N-NITROSODIPHENYLAMINE
N-NITROSODI-N-PROPYLAMINE
PENTACHLOROPHENOL
PHENOL
BIS (2-ETHYLHEXYL) PHTHALATE
BUTYL BENZYL PHTHALATE
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BENZO(A)ANTHRACENE
BENZO(A)PYRENE
BENZO(B)FLUORANTHENE
BENZOdOFLUORANTHENE
CHRYSENE
ACENAPHTHYLENE
ANTHRACENE
BENZOCGHDPERYLENE
FLUORENE
PHENANTHRENE
DIBENZO(A,H)ANTHRACENE
INDENO(1,2,3-CD)PYRENE
PYRENE
TETRACHLOROETHENE
TOLUENE
TRICHLOROETHENE
VINYL CHLORIDE
ALDRIN
DIELDRIN
CHLORDANE
4,4'-DDT
4,4'-DDE
4,4'-DDD
ALPHA-ENDOSULFAN
BETA-ENDOSULFAN
ENDOSULFAN SULFATE
ENDRIN
COMPOUND
TYPE
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
-------
2/09/84 PAGE
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND COMPOUND
NUMBER FRACTION COMPOUND TYPE
248 V BROMODICHLOROMETHANE-13C D
249 V D
250 V D
251 V DIBROMOCHLOROMETHANE-13C D
252 B HEXACHLORO-1,3-BUTADIENE-13C4 D
253 B HEXACHLOROCYCLOPENTADIENE-13C4 D
254 B ' ISOPHORONE-D8 D
255 B NAPHTHALENE-08 D
256 B NITROBENZENE-05 D
257 A 2-NITROPHENOL-3,4,5,6-04 D
258 A 4-NITROPHENOL-2,3,5,6-D4 D
259 A 2,4-DINITROPHENOL-3,5,6-D3 D
260 A 2-METHYL-4.6-DINITROPHENOL-D2 D
261 B D
262 B N-NITROSODIPHENYLAMINE-D6 D
263 B D
264 A PENTACHLOROPHENOL-13C6 D
265 A PHENOL-2,3,4,5,6-D5 D
266 B BIS(2-ETHYLHEXYL)PHTHALATE-D4 D
267 B D
268 B DI-N-BUTYL PHTHALATE-D4 D
269 B DI-N-OCTYL PHTHALATE-D4 D
270 B DIETHYL PHTHALATE-3,4,5,6-D4 D
271 B DIMETHYL PHTHALATE-3,4,5,6-D4 D
272 B BEN20(A)ANTHRACENE-D12 D
273 B BENZO(A)PYRENE-D12 D
274 B BENZO(B)FLUORANTHENE-D12 D
275 B BENZO(K)FLUORANTHENE-D12 D
276 B CHRYSENE-D12 D
277 B ACENAPHTHYLENE-D8 D
278 B ANTHRACENE-DIO D
279 B BENZO(GHI)PERYLENE-D12 D
280 B FLUORENE-D10 D
281 B PHENANTHRENE-D10 D
282 B D
283 B D
284 B PYRENE-D10 D
285 V TETRACHLQROETHENE-1,2-13C2 D
286 V TOLUENE-2,3,4,5,6-D5 D
287 V TRICHLOROETHENE-13C2 D
288 V VINYL CHLORIDE-D3 D
289 P D
290 P D
291 P D
292 P D
293 P D
294 P D
295 P D
296 P D
-------
2/09/84
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND COMPOUND
NUMBER FRACTION COMPOUND TYPE
183 V 1,4-DICHLOROBUTANE I
184 D 2,3,7,8-TCDD-37CL4 I
201 B ACENAPHTHENE-D10 D
202 V D
203 V ACRYLONITRILE-D3 D
204 V BENZENE-D6 D
205 B BENZIDINE (RINGS-OS) D
206 V CARBON TETRACHLORIDE-13C D
207 V CHLOROBENZENE-D5 D
208 B 1,2,4-TRICHLOROBENZENE-D3 D
209 B HEXACHLOROBENZENE-13C6 D
210 V 1,2-DICHLOROETHANE-D4 D
211 V 1,1,1-TRICHLOROETHANE-D3 D
212 B HEXACHLOROETHANE-1-13C D
213 V l,l-DICHLOROETHANE-2,2,2-03 D
214 V 1,1,2-TRICHLOROETHANE-13C2 D
215 V 1,1,2,2-TETRACHLOROETHANE-D2 D
216 V CHLOROETHANE-D5 D
217 V D
218 B BISC2-CHLOROETHYD.ETHER-D8 D
219 V D
220 B 2-CHLORONAPHTHALENE-D7 D
221 A 2,4,6-TRICHLOROPHENOL-3,5-D2 D
222 A 4-CHLORO-3-METHYLPHENOL-2.6-D2 D
223 V CHLOROFORM-ISC D
224 A 2-CHLOROPHENOL-3,4,5,6-04 D
225 B 1,2-DICHLOROBENZENE-04 D
226 B l,-3-DICHLOROBENZENE-D4 D
227 B 1.4-DICHLOROBENZENE-D4 D
228 B 3,3'-DICHLOROBENZIDINE-D6 D
229 V 1,1-DICHLOROETHENE-D2 D
230 V TRANS-1.2-DICHLOROETHENE-D2 D
231 A 2,4-DICHLOROPHENOL-3,5,6-03 D
232 V 1,2-DICHLOROPROPANE-D6 D
233 V T-1,3-DICHLOROPROPENE-1,2-D2 D
234 A 2,4-DIMETHYLPHENOL-3,5,6-03 D
235 B 2,4-DINITROTOLUENE-3,5,6-03 D
236 B 2,6-DINITROTOLUENE-A,A,A-D3 D
237 B 1,2-DIPHENYL-D10-HYDRAZINE D
238 V ETHYLBENZENE-D10 D
239 B FLUORANTHENE-D10 D
240 B 4-CHLOROPHENYL PHENYL-D5 ETHER D
241 B D
242 B BIS(2-CHLOROISOPROPYL)ETHERD12 D
243 B D
244 V METHYLENE CHLORIDE-D2 D
245 V CHLOROMETHANE-D3 D
246 V BROMOMETHANE-D3 n
247 V BROMOFORM-13C 0
-------
2/09/84
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
PAGE
EGLD COMPOUND
NUMBER FRACTION
347
348
349
350
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
331
382
383
384
385
386
387
388
389
390
391
392
393
394
395
V
V
V
V
V
B
B
B
B
3
A
A
A
A
B
B
B
A
A
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
V
V
V
V
P
P
P
P
P
P
P
COMPOUND
BROMOFORM
BROMODICHLOROMETHANE
DIBROMOCHLOROMETHANE
HEXACHLORO-1.3-BUTADIENE
HEXACHLOROCYCLOPENTADIENE
ISQPHORONE
NAPHTHALENE
NITROBENZENE
2-NITROPHENOL
4-NITROPHENOL
2,4-DINITROPHENOL
2-METHYL-4,6-DINITROPHENOL
N-NITROSODIPHENYLAMINE
PENTACHLOROPHENOL
PHENOL
BIS (2-ETHYLHEXYL)
PHTHALATE
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BENZO(A)ANTHRACENE
BENZO(A)PYRENE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
CHRYSENE
ACENAPHTHYLENE
ANTHRACENE
BENZO(GHI)PERYLENE
FLUORENE
PHENANTHRENE
PYRENE
TETRACHLOROETHENE
TOLUENE
TRICHLOROETHENE
VINYL CHLORIDE
COMPOUND
TYPE
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
-------
2/09/84
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
PAGE
EGLD COMPOUND
NUMBER FRACTION
297
298
299
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
P
P
P
B
V
V
V
B
V
V
B
B
V
V
B
V
V
V
V
V
B
V
B
A
A
V
A
B
B
B
B
V
V
A
V
V
A
B
B
B
V
B
B
B
B
B
V
V
V
COMPOUND
ACENAPHTHENE
ACRYLONITRILE
BENZENE
BENZIDINE
CARBON TETRACHLORIDE
CHLOROBENZENE
1,2,4-TRICHLOROBENZENE
HEXACHLOROBENZENE
1,2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
HEXACHLOROETHANE
1,1-DICHLOROETHANE
1,1,2-TRICHLOROETHANE
1,1, 2 ,2-TETRACHLOROETHANE
CHLOROETHANE
BIS(2-CHLOROETHYL)ETHER
2-CHLORONAPHTHALENE
2,4,6-TRICHLOROPHENOL
4-CHLORO-3-METHYLPHENOL
CHLOROFORM
2-CHLOROPHENOL
1,2-DICHLOROBENZENE
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE '
3,3'-DICHLOROBENZlDINE
1,1-DICHLOROETHENE
TRANS-1.2-DICHLOROETHENE
2,4-DICHLOROPHENOL
1 ,2-DICHLOROPROPANE
T-1,3-DICHLOROPROPENE
2,4-DIMETHYLPHENOL
2,4-DINITROTOLUENE
2,6-DINITROTOLUENE
1,2-DIPHENYLHYDRAZINE
ETHYLBENZENE
FLUORANTHENE
4-CHLOROPHENYL PHENYL ETHER
BIS (2-CHLOROISOPROPYL) ETHER
METHYLENE CHLORIDE
CHLOROMETHANE
BROMOMETHANE
COMPOUND
TYPE
D
D
D
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
-------
2/09/84
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
PAGE
EGLD COMPOUND
NUMBER FRACTION
COMPOUND
396
397
398
399
500
501
502
503
504
505
506
507
508
509
510
511
512
513
514
515
516
517
518
519
520
521
522
523
524
525
526
600
601
602
603
604
605
606
607
608
609
610
611
612
613
614
615
616
P
P
P
P
D
A
A
B
B
B
B
B
B
B
B
B
B
B
B
V
V
V
B
B
B
B
B
B
B
B
B
B
A
A
B
B
B
B
B
B
B
B
B
B
B
B
V
V
V
2,3,7,8-TCDD-13C12
BENZOIC ACID
HEXANOIC ACID
2-NAPHTHYLAMINE
2-METHYLPYRIDINE
DIBENZOTHIOPHENE
DIBENZOFURAN
N-DODECANE (N-C12)
DIPHENYLAMINE
DIPHENYL ETHER
ALPHA-TERPINEOL
STYRENE
DI-N-BUTYL AMINE
BIPHENYL
P-CYMENE
2-BUTANONE (MEK)
DIETHYL ETHER
ACETONE
N-DECANE (N-C10)
N-TETRADECANE (N-C14)
N-HEXADECANE (N-C16)
N-OCTADECANE (N-C18)
N-EICOSANE (N-C20)
N-DOCOSANE (N-C22)
N-TETRACOSANE (N-C24)
N-HEXACOSANE (N-C26)
N-OCTACOSANE (N-C28)
N-TRIACONTANE (N-C30)
BENZOIC-D5 ACID
HEXANOIC ACID-D11
2-NAPHTHYLAMINE-D7
2-METHYLPYRIDINE-D7
DIBENZOTHIOPHENE-D8
DIBENZOFURAN-D8
N-DODECANE-D26 CN-C12)
DIPHENYLAMINE-D10
DIPHENYL ETHER-DID
ALPHA-TERPINEOL-D3
STYRENE-2,3,4,5,6-05
DI-N-BUTYL AMINE-D18
BIPHENYL-D10
P-CYMENE-D14
2-BUTANONE-4,4,4-03 (MEK)
DIETHYL ETHER-DID
ACETONE-D6
COMPOUND
TYPE
P
P
P
P
D
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
P
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
-------
2/09/84 PAGE
USEPA EFFLUENT GUIDELINES DIVISION
COMPOUND CODE LISTING
EGLD COMPOUND COMPOUND
NUMBER FRACTION COMPOUND TYPE
617 B N-DECANE-D22 (N-C10) D
618 B D
619 B N-HEXADECANE-D34 (N-C16) D
620 B D
621 B N-EICOSANE-D42 (N-C20) D
622 B D
623 B N-TETRACOSANE-D50 CN-C24) D
624 B D
625 B D
626 B N-TRIACONTANE-D62 (N-C30) D
700 A BENZOIC ACID P
701 A HEXANOIC ACID P
702 B 2-NAPHTHYLAMINE P
703 B 2-METHYLPYRIDINE P
704 B DIBENZOTHIOPHENE P
705 B DIBENZOFURAN P
706 B N-DODECANE (N-C12) P
707 B DIPHENYLAMINE P .
708 B DIPHENYL ETHER P
709 B ALPHA-TERPINEOL P
710 B STYRENE P
711 B DI-N-BUTYL AMINE P
712 B BIPHENYL P
713 B P-CYMENE P
714 V 2-BUTANONE (MEK) P
715 V DIETHYL ETHER P
716 V ACETONE P
717 B N-DECANE (N-C10) P
718 B P
719 B N-HEXADECANE (N-C16) P
720 B p
721 B N-EICOSANE (N-C20) P
722 > B P
723 B N-TETRACOSANE (N-C24) P
724 B p
725 B P
726 B N-TRIACONTANE (N-C30) P
829 D 2,3,7,8-TCDD p
430 RECORDS PRINTED
-------
ELEMENT NAME: COMPOUND ORDER NUMBER
Definition: A numerical code that establishes the order of compound determination
by the GC/MS. The code is used on the Quantitation Report to match the segments of
compound data within the report.
Input Type/Length
Quantitation Report 9(3)
As Stored Internally 9(3)
Unit of Measure
N/A
Edit Criteria:
Range: 001-250
-------
ELEMENT NAME; COMPOUND TYPE
Definition: A coded value which identifies a chemical compound as a priority
pollutant or surrogate.
Input Type/Length
Generated Based on Compound Number X(l)
As Stored Internally X(l)
Unit of Measure
N/A
Edit Criteria:
Must be one of the following codes:
CODE VALUE
D Isotopic Diluent
I Internal Standard
P Priority Pollutant
S Surrogate
-------
ELEMENT NAME: DATE EXTRACTED
Definition: The date that the laboratory extracted the sample for analysis.
Input Type/Length
Quantitation Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: MM/DD/YY, where MM is the month; DD is the day; and YY is the last
two digits of the Gregarian calendar year.
Example: 07/15/83 is July 15, 1983.
-------
ELEMENT NAME: DATE ANALYZED
Definition: The date that the sample fraction was analyzed by the laboratory.
Input Type/Length
Quantitation Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: MM/DD/YY, where MM is the month; DD is the day; and YY is the last
two digits of the Gregarian calendar year.
Example: 07/15/83 is July 15, 1983.
-------
ELEMENT NAME: DATE SAMPLED
Definition: The date the sample was taken by the field sampler.
Input Type/Length
Traffic Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: MM/DD/YY, where MM is the month; DD is the day; and YY is the last
two digits of the Gregarian calendar year.
Example: 07/15/83 is July 15, 1983.
-------
ELEMENT NAME: EPISODE COMMENT CODE
Definition: A coded value for comments associated with an episode.
Input Type/Length
Traffic Reports X(«)
Laboratory Chronicles
As Stored Internally . X(»)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Episode Comment Code Table. Range E001-E999.
See attached Episode Comment Code Table for a list of valid codes.
-------
ELEMENT NAME: EPISODE NUMBER
Definition: The SCC assigned identification code designating the sampling trip.
Input Type/Length
SAMTRAC 9(4)
As Stored Internally 9(4)
Unit of Measure
N/A
Edit Criteria:
1. Numeric
2. Greater than 0119.
-------
ELEMELBMEN&BiIAME: FRACTION
Definition: A coded value which designates the compound as either an acid,
base/neutral, volatile, pesticide or dioxin.
Input Type/Length
Priority Pollutant Data Sheet X(l)
QA/QC Sheet
As Stored Internally X(l)
Unit of Measure
N/A
Edit Criteria:
Must be one of the following codes:
CODE VALUE
A Acid Compound
B Base/Neutral Compound
C Combined Acid Base/Neutral
D Dioxin
P Pesticide Compound ,
V Volatile Compound
-------
ELEMENT NAME: FRACTION COMMENT CODE
Definition: A coded value for any optional text that may be associated with each
fraction.
Input Type/Length
Traffic Report/Lab Chronicles
Priority Pollutant Data Sheet
As Stored Internally X(<0
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Fraction Comment Code Table. Range F001-F999.
See attached Fraction Comment Code Table for a list of valid codes.
-------
2/08/84
ISOTOPE DILUTION
FRACTION LEVEL COMMENT CODE TABLE
PAGE
CODE
F001
F002
F003
F004
F005
F006
F007
F008
F009
F010
F011
F012
F013
F014
F015
F016
F017
F018
F019
F020
F021
F022
F023
F024
F025
F026
F027
F028
F029
F030
F031
F032
F033
F034
F035
F036
F037
F038
F039
F040
F041
F042
F043
F044
F045
F046
F047
F048
F049
F050
DESCRIPTION
ENTIRE FRACTION NOT DETECTED
ENTIRE FRACTION NOT REQUIRED
ENTIRE FRACTION NOT ANALYZED
BAD EMULSION-SPL. CENTRIFUGED AFTER EACH EXTRACT WASH.
SAMPLE CENTRIFUGED AFTER 3RD ORGANIC WASH
SAMPLE WASHES WERE CENTRIFUGED AFTER EACH WASH
BAD EMULSION DURING ORGANIC WASHES
BAD EMULSION
EMULSION PRESENT
SAMPLES RECEIVED AT 17 DEGREES CENTIGRADE
SAMPLE RECEIVED AT 19 DEGREES CENTIGRADE
SLIGHT EMULSION PRESENT
EMULSION PRESENT - SAMPLES CENTRIFUGED
SPL. SPIKED WITH 100UG B/N 4 A STABLE LABELLED CPDS.
1:50 DILUT. & 5UL. 12037 INT. STD.+5UL LBLD. VOA(SOPPM)
UNPRESERVED
1/50 DILUT. & 5UL. IN-
SPIKED WITH 5UL. EACH VOA INT.
DILUTED 10 TIMES FOR ANALYSIS
SPKD. 2/5UL. EACH VOA INT. STD
MATRIX DUPLICATE(REPLICATE)
DILUTED 1UOO
100 ML. OF SPL. SPKD. W/100UG.
STD.+5UL. LABELLED
STD. & LBLD
VOAC80 PPM)
VOA(SOPPM)
,+5UL LBLD. VOA +20UL.MTX,
SPKD. W/5UL.
MATRIX
DILUTED 1:10
DILUTED 1:50
DILUTED 1:20
SPKD. W/5UL.
LBLD., APPEND
DILUTED 1:40
DILUTED 1:25
DILUTED 1:500
DILUTED 1:1000
1L+100ML. EXT.
EACH VOA INT. STD
B/N&A STBL. LBLD.
, & LABELLED VOA
CPDS.
EA,
C,
VOA INT.STD.
& SYNFL SPKS
& LBLD. VOA+20UL. MTX DUP-
ADDEDC75ML. NAOH BASE REQ)
SPIKED W/100UG A&B/N STBL. LBLD CPDS
MATRIX SPKD. W/100UG STABLE L3LD. & UNLBLD
SPKD. W/20PPM VOA INT. STD.+80PPM LBLD. VOA,
SPKD. W/20PPM VOA INT. STD.+80PPM LBLD. VOA,
SPKD. W/20PPM VOA INT. STD.+80PPM LBLD. VOA
DILUTED 1/5
SPKD. W/5UL, VOA INT. STD.(20PPMULBLD(80PPM)
ACID ANALYZED IN B/N FRACTION
100 UG LABELLED B/N, A, PHTHALATE
500 UG UNLABELLED B/N, A, PHTHALATE
100 UG UNLABELLED B/N, A, PHTHALATE
24 HOUR COMPOSITE
REPLICATE
22 HOUR COMPOSITE
100 UG/L LABELLED B/N ADDED
100 UG/L LABELLED A ADDED
A&B/N CPDS.
DIL. 1:10
OIL. 1:5000
DIL. 1/10
-------
2/08/84
ISOTOPE DILUTION
FRACTION LEVEL COMMENT CODE TABLE
PAGE
CODE
F051
F052
F053
F054
F055
F056
F057
F058
F059
F060
F061
F062
F063
F064
F065
F066
F067
F068
F069
F070
F071
F072
F073
F074
F075
F076
F077
F078
F079
FOSO
F081
F082
F083
F084
DESCRIPTION
100 US/L UNLABELLED
100 UG/L UNLABELLED
MATRIX SPIKE
FINAL VOLUME
VOLUME
VOLUME
VOLUME
VOLUME
VOLUME
VOLUME
VOLUME
VOLUME
1
1
B/N ADDED
A ADDED
FINAL
FINAL
FINAL
FINAL
FINAL
FINAL
FINAL
FINAL
DILUTED
DILUTED
DILUTED 1
DILUTED 1
CONC 1000
4 ML, DILUTED 10.000X
2.8 ML, DILUTED 10,OOOX
95 ML, DILUTED 1000X
14.3 ML, DILUTED 1000X
13.8 ML, DILUTED 1000X
6.4 ML, DILUTED 10,OOOX
8.5 ML, DILUTED 10.000X
10.9 ML, DILUTED 1000X
10.2 ML, DILUTED 1000X
2000
4000
30
60
l; A & B/N INJEC ON CAP.
SAMPLES ORIG SPIKED W/ COCKTAILS
SAMPLE PARTIALLY SPKD W/ COCKTAILS
ANALYZED IN TRIPLICATE
MANUAL EXTRACTION
GOOD RECOVERY-SAMPLES NEUTRAL UPON RECEIPT
EMULSION PROBLEMS WITH EXTRCTABLES
SHAKE OUT USED FOR EXTRACTION
MODERATE EMULSION
ONE VIAL ARRIVED BROKEN, BUT HAD DUPLICATE
PRESERVED
PRESERVED WITH 3 DROPS SODIUM THIOSULFATE EACH BOTTLE
HEAVY EMULSION-B/N AND A EXTRAS W/CONT EXTR THEN XS SOLV
SAMPLE HAD TO BE DILUTED TWICE
LABLE SPIKE INCREASED FROM 50 TO 200 PPB
SAMPLE RERUN NOV. 4, 1982
EXTRACTS COMBINED FOR INJECTION
VGA'S NOT RUN SECOND TIME-NONE DETECTED
-------
ELEMENT NAME: INDUSTRIAL CATEGORY CODE
Definition: The classification of the industrial processes performed by the plant
where a sample was taken.
Input Type/Length
5AMTRAC 9(3)
As Stored Internally 9(3)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Industrial Category Code Table.
See attached Industrial Category Code Table for a list of codes.
-------
2/08/84 PASE
ISOTOPE DILUTION
INDUSTRIAL CATEGORY CODE TABLE
CODE DESCRIPTION
100 SOAPS + DETERS.
110 ADHESIVES
120 LEATHER TANNING
130 POTWS
200 TEXTILES
210 GUM + WOOD
220 PULP + PAPER
230 TIMBER
240 PRINTING + PUB
250 PAINT + INK
300 ORGANICS
310 PESTICIDES
320 PHARMACEUTICALS
330 CARBON BLACK
340 RUBBER
350 'PLASTICS + SYN
370 MINERAL MINING
400 COAL MINING
410 ' ORE MINING
420 PAVING + ROOF
430 STEAM EL'ECTRIC
440 PETROLEUM REF-
450 OIL + GAS
500 IRON + STEEL
510 FOUNDRIES
520 ELECTROPLATING
530 NONFERROUS MET.
531 NONFRS.MTL.PH1
532 NONFRS.MTL.PH2
540 BATTERIES
550 PLASTICS'
560 COIL COATING
570 COPPER
580 PORC + ENAMEL
590 ALUMINUM FORM
600 PHOTOGRAPHIC
700 INORGANIC CHEMS
701 INORG.CHEM.l
702 INORG.CHEM.2
710 MECH PRODUCTS
720 ELEC + ELECTRON
730 EXPLOSIVES
740 AUTO + OTHER
750 PHOSPHATES
760 SHIPBUILDING
770 LANDFILL
780 MISC.ENVIRON
790 FRUITS + VEG.
800 SYN. FUELS
810 METAL.FINISHING
-------
2/08/84 PAGE
ISOTOPE DILUTION
INDUSTRIAL CATEGORY CODE TABLE
CODE DESCRIPTION
820 OSW
830 NURP
840 FERTILIZERS
850 OWPO
860 ENFORCEMENT
870 NONFERROUS FORMING
880 WATER SUPPLY
-------
ELEMENT NAME: INSTRUMENT
Definition: A coded value assigned by the laboratory that uniquely identifies each
GC/MS instrument within a laboratory. All Calibration, Precision and Recovery,
Standards and Blank Quantitation files will be tracked by this instrument member
within Laboratory. Changing of this instrument number by the laboratory would
necessitate the submittal of new calibration and other initial quantitation runs by the
laboratory.
Input Type/Length
Quantitation Report X(2)
As Stored Internally X(2)
Unit of Measure
N/A
Edit Criteria:
Range: 01-99, AA-ZZ or any two character combination.
-------
ELEMENT NAME: LABORATORY
Definition: A numerical code used to identify the specific laboratory where the
sample was analyzed.
Input Type/Length
SAMTRAC 9(3)
As Stored Internally 9(3)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the SAMTRAC Laboratory Code Table.
See attached Laboratory Code Table for a list of valid codes.
-------
2/08/84 PAGE
ISOTOPE DILUTION
LABORATORY CODE TABLE
CODE DESCRIPTION
100 ERCO
110 SPECTRIX
120 FOREMOST
130 RADIAN(SAC)
140 S3
, 150 WCTS
160 ARL
170 RADIAN(AUS)
180 TAG
190 RALTECH
200 MONSANTO
210 EMS
220 MCCRONE
230 CARB-LEX
240 OTHER
250 MRI
260 VARC
270 BATTELLE
280 BARRINGE
290 TRW
300 JACOBS P
310 REG IV
320 REG V
330 REG VII
340 REG VI.II
350 ACUREX
360 ENVIRO
370 STI
380 BCL-OSW
390 EMSL-OSW
400 SRI
410 IT-ENVI.
420 VERSAR
430 CENTEC
440 ARTHUR D. LITTLE
450 GSRI
460 ESE
470 SHELL
480 MIDWEST RESEARCH INSTITUTE
490 USEPA REGION 2
500 U.S. TESTING
-------
ELEMENT NAME: MASS TO CHARGE RATIO
Definition: Designates the quantitation ion. Abbreviated as M/Z, or M/E.
Input Type/Length
Quantitation Report Z2Z9
As Stored InternaiJy 9(4)
Unit of Measure
N/A
Edit Criteria:
Ranges: Volatiles: 20-250; Semi-Volatiles: 35-450.
-------
ELEMENT NAME; METHOD
Definition: A coded value which uniquely identifies the method protocol that was
followed during analysis.
Input Type/Length
Quantitation Report X(5)
As Stored Internally X(5)
Unit of Measure
N/A
Edit Criteria:
Acceptable Codes:
1624A
1625A
613
613E
713
-------
ELEMENT NAME: PEAK AREA
Definition: The area beneath the peak of a mass chromatogram. The peak area is
proportional to the amount of the detected compound at an observed mass to charge
ratio. It is used to compute the concentration of the compound present in the sample.
Input Type/Length
Quantitation Report ZZZ2ZZZZZZ9.
As Stored Internally 9(10)
Unit of Measure
N/A
Edit Criteria:
-------
ELEMENT NAME: PH LEVEL
Definition: The negative logarithm of the effective hydrogen ion concentration as
expressed in grain equivalents per liter.
Input Type/Length
Traffic Report Z9.999
As Stored Internally 9(2)V9(3)
Unit of Measure
N/A
Edit Criteria:
-------
ELEMENT NAME: PLANT CODE
Definition: A numeric code used to distinguish specific industrial plants which have
been sampled.
Input Type/Length
SAMTRAC 9(4)
As Stored Internally 9(4)
Unit of Measure
N/A
Edit Criteria:
Must be a four digit number.
Comment:
1. Plant ID's are unique within the isotope dilution program.
2. The episode number for the first occurrence of a plant visit is used as the plant's
identification number.
3. See attached Plant Code Table for a list of current codes.
-------
2/08/84
ISOTOPE
PLANT-ID CODE TABLE
DILUTION
PAGE
CODE
0389
0523
0709
0711
0712
0713
0727
0760
0761
0766
0769
0770
0788
0793
0801
0806
0821
0346
0848
0852
0868
0928
0929
0931
0932
0933
0934
0950
0951
DESCRIPTION
47A
50
HOLSTON ARMY AMMO PL
FT SNELLIN6
FT LEWIS
MORGANTOWN TECH CNTR
POPE AND TALBOT
SHELL OIL
.AMOCO
GULF OF MEXICO
GENERAL ELECTRIC
ARCO
SEATTLE CSO
ST. PAUL CSO
PROVIDENCE CSO
ST. LOUIS CSO
PLANT #2
PLANT #3
PLANT #4
PLANT *5
HUNTINGTON ALLOYS
PLANT #6
PLANT t7
BALL CORPORATION
PLANT #9
PLANT tlO
BRUSH WELLMAN
PLANT ill
PLANT #12
K ' TN
TR NJ
KINGSPORT TN
FT SNELLING MN
DUPONT WA
MORGANTOWN WV
EAU CLAIRE MI
KENAI AK
KENAI AK
NEW ORLEANS LA
SCHENECTADY NY
PRUDHOE BAY AK
SEATTLE WA
ST. PAUL MN
PROVIDENCE RI
ST. LOUIS MO
MH NC
W WV
DP ' TX
GF WV
BURNAUGH KY
B NJ
NM ' WV
GREENVILLE TN
A TX
P LA
ELMORE OH
GC IL
C TX
-------
ELEMENT NAME: PROPRIETARY INDICATOR
Definition: A coded value which designates whether or not the analysis data from a
sample is proprietary. Also indicates that confidentiality papers have been signed.
Input Type/Length
Traffic Report X(l)
Lab Chronicles
As Stored Internally X(l)
Unit of Measure
N/A
Edit Criteria:
Must be one of the following codes:
CODE VALUE
P Proprietary
N Not Proprietary
-------
ELEMENT NAME: QUANTITATION REPORT TYPE
Definition: A coded value that uniquely identifies the particular type of quantitation
report that is being submitted.
Input
Quantitation Report
As Stored Internally
Unit of Measure
N/A
Edit Criteria:
Type/Length
X(3)
X(3)
CODE
APS
BLK
CAL
EPA
PAR
STD
VER
VALUE
Aqueous Performance Standard
Blank
Calibration
EPA Sample
Precision and Recovery
Standard
Calibration Verification
-------
ELEMENT NAME: REFERENCE COMPOUND
Definition: A numeric code that is used as a pointer to the internal standard or
isotopic diluent within a quantitation report..
Input Type/Length
Quantitation Report ZZ9
As Stored Internally 9(3)
Unit of Measure
N/A
Edit Criteria:
Range: 001-250
-------
ELEMENT NAME: RELATIVE RETENTION TIME
Definition: The quotient of the retention time of a compound divided by its internal
standard or isotopic diluent.
toput Type/Length
Quantitation Report Z9.999
As Stored Internally 99V9(3)
Unit of Measure
N/A
Edit Criteria:
-------
ELEMENT NAME: RELATIVE RETENTION TIME (LIBRARY)
Definition: The relative retention time stored in the library. The value is based on
the analysis of a standard containing both compounds.
Input Type/Length
Quantitation Report Z9.999
As Stored Internally 9(2)V9(3)
Unit of Measure
N/A
Edit Criteria:
-------
ELEMENT NAME: RESPONSE FACTOR
Definition: The ratio between the response for the sample and a response for a
standard under identical analytical conditions. Computed per the following equation:
RF = ASCIS
AISCS
where
A- is the PEAK AREA for the compound from analysis of a standard.
A.- is the PEAK AREA for the internal standard.
C,r is the concentration of the internal standard.
Cr is the concentration of the compound.
Input Type/Length
Quantitation Report ZZZ9.99
As Stored Internally 9(f)V9(3)
Unit of Measure
N/A
Edit Criteria:
-------
ELEMENT NAME: RESPONSE FACTOR (LIBRARY)
Definition: The response factor stored in the library. The value is determined from
analysis of a standard.
Input Type/Length
Quantitation Report ZZZ9.999
As Stored Internally 9(4)V9(3)
Unit of Measure
N/A
Edit Criteria:
Example: See RESPONSE FACTOR.
-------
ELEMENT NAME: RETENTION TIME
Definition: The time it takes the identified compound to elute from the gas
chromatograph.
Input Type/Length
Quantitation Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: HH:MM:SS
MM:SS
55
Where HH is hours; MM is minutes; 55 is seconds.
-------
ELEMENT NAME: RETENTION TIME (LIBRARY)
Definition: The known time it takes an identified compound to elute from the gas
chromatograph. The time is determined from analysis of a standard.
Input Type/Length
Quantitation Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: HH:MM:S5
MM:SS
SS
Where HH is hours; MM is minutes; SS is seconds.
-------
ELEMENT NAME: SAMPLE COMMENT CODE
Definition: A coded value for any optional text that may be associated with each
sample.
Input Type/Length
Traffic Reports
Lab Chronicles
As Stored Internally X(»)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Sample Comment code table. Range S001-S999
See attached Sample Comment Code Table for a list of valid codes.
-------
2/08/84
ISOTOPE
SAMPLE LEVEL COMMENT CODE TABLE
PAGE
DILUTION
CODE
S001
S002
S003
5004
S005
S006
5007
S008
S009
S010
S011
S012
S013
5015
5016
5017
5018
5019
5020
5021
5022
5023
5024
S025
5026
5027
5028
5029
5030
5031
5032
5033
5034
5035
5036
5037
5038
5039
5040
5041
5042
S043
5044
5045
5046
5047
5048
5049
5050
DESCRIPTION
SAMPLE ANALYZED IN DUPLICATE
PESTICIDES ANALYZED IN B/N FRACTION-REGULAR
PESTICIDES ANALYZED IN B/N FRACTION-REGULAR
VAT AREA TO INFLUENT TO TREATMENT PLANT
A20 AREA INFLUENT TO TREATMENT PLANT
TREATED WASTE
DECANT TANK(EFFLUENT)
GASIFIER SLUICE H20
CYCLONE QUENCH
SCRUBBER H20
COAL PILE RUNOFF
MANHOLE #4
MANHOLE *5
MANHOLE f6
SOUR WATER STRIPPER
BIO UNIT EFFLUENT
FILTER EFFLUENT
STILLING BASIN
OIL/WATER SEP. EFFLUENT
SAND FILTER
CARBON FILTER EFFLUENT
LAB WASTE
VENTURI SCRUBBER DAY 1
VENTURI SCRUBBER DAY 2
VENTURI SCRUBBER DAY 3
DIRECT COOLER DAY 1
DIRECT COOLER DAY 2
DIRECT COOLER DAY 3
SOURCE WATER
MAKE-UP WATER
DECANTER LIQUOR
INLET-FREE WATER KNOCKOUT #4
OUTLET FLOTATION CELL-DISCHARGE
FREE WATER KNOCKOUT
OVERBOARD DISCHARGE
PLATFORM EC33A
PLATFORM EC14CF
PLATFORM V39DCV22D)
PLATFORM V119D
PLATFORM SMI6A
PLATFORM SMI105ACSMI106A)
PLATFORM EI120CF
PLATFORM SMI208B
PLATFORM EI296B
PLATFORM V225ACV247AO
PLATFORM SMI23BAUX
PLATFORM SMI130B
PLATFORM EI18CF
PLATFORM EI57A-E
PLATFORM EI238E
QA
-------
2/08/84
ISOTOPE
SAMPLE LEVEL COMMENT CODE TABLE
PAGE'
DILUTION
CODE
S051
S052
5053
5054
S055
S056
S057
S058
S059
S060
5061
5062
5063
5064
5065
5066
5067
5068
5069
5070
5071
5072
5073
5074
5075
5076
5077
5078
5079
5080
5081
5082
5083
5084
5085
5086
5087
5088
5089
5090
5091
S092
5093
5094
5095
5096
5097
5098
5099
5100
DESCRIPTION
PLATFORM SS107S-94
PLATFORM SS107S-93
PLATFORM SS219A
PLATFORM ST177
PLATFORM BM2C-AM
PLATFORM BM2C-PM
PLATFORM BDCCF5-AM
PLATFORM BDCCF5-PM
PLATFORM GIBDB600
PLATFORM SP62A
PLATFORM WD70I
PLATFORM WD105C
PLATFORM ST135
PLATFORM WD90A
PLATFORM SP24/27
PLATFORM SP62A
PLATFORM SP65A
PLATFORM WD45E-AM
PLATFORM WD45E-PM
QUENCH RECYCLE LIQUOR
DS 1-13 WATER AND GAS PRODUCTION
FS 1 TRAIN B TREATER OUTLET
S-l RAW INFLUENT
S-2 ROUTE FILTER EFFLUENT
S-3 DEPHENOLI2ED EFFLUENT
S-4 FREE NH3 STILL EFFLUENT
S-5 FIXED NH3 EFFLUENT
S-6 BIOLOGICAL TREATMENT INFLUENT
S-7 BIOLOGICAL TREATMENT EFFLUENT
S-8 FILTER EFFLUENT
S-9 ACTIVATED CARBON EFFLUENT
S-10 RESIN COLUMN EFFLUENT
BATCH TEST1 BIOLOGICAL TREATMENT EFFLUENT
BACKGROUND WATER
ALL FRACTIONS 24 HOUR COMPOSITE
ALL FRACTIONS COMPOSITE
100 UG/L LABELLED B/N AND A ADDED
LAB RECEIVED SAMPLE 4 DAYS AFTER COLLECTION
AVG VALUE ASSN TO INDIST ISOMERIC PEAKS
LANDER DW BACKGROUND/STORM WATER RUNOFF
EXTRACTABLE ORGANICS - 24 HOUR COMPOSITE
MICHIGAN DRY WEATHER BACK/STORM WATER RUNOFF
CITY WATER/TAP WATER
LAND WW BACK/SEWERAGE/STORM WATER RO
SEWERAGE/STORM WATER RUNOFF
LANDER CSO/SEWERAGE/STORM WATER RO
LANDER 1ST FLUSH SEWERAGE/STORM WATER RO
LANDER RUNOFF/STORM WATER RUNOFF
MICH WW BACK/SEWERAGE/STORM WATER RO
MICH CS FLOW/STORM WATER RUNOFF
-------
2/08/84
ISOTOPE
SAMPLE LEVEL COMMENT CODE TABLE
PAGE
DILUTION
CODE
S101
S102
5103
S104
S105
S106
S107
5108
5109
S110
Sill
5112
5113
S114
S115
5116
5117
5118
5119
5120
5121
S122
5123
S124
5125
5126
5127
5128
5129
5130
5131
5132
5133
5134
5135
5136
5137
5138
5139
5140
5141
5142
5143
5144
5145
5146
5147
5148
5149
5150
DESCRIPTION
MICHIGAN CSO/STORM WATER RUNOFF
MICHIGAN FIRST FLUSH/STORM WATER RUNOFF
MICH RUNOFF/STORM WATER RUNOFF
PRECIPITATION/STORM WATER RUNOFF
EUS DW COMP
PHA DW COMP
1 VOA VIAL FOR 19:00 WAS BROKEN
PHN STORM DW COMP
TAP WATER
E AND A DWC
E AND E
1 HOUR COMPOSITE-EXTRACTABLE ORGANICS
WHEN ISOS NOT DISCREET, AVE VALUE ASSIGNED TO SPECIES
E AND A WW BACKGROUND
E AND A CS FL
E AND A CSO
E AND A FIRST FLOW
E AND A RUNOFF.
E AND E WW BACKGROUND
E AND E CS FLOW
E AND E CSO
E AND E FIRST FLOW
E AND E RUNOFF
EXTRACTABLE ORGANICS - 8 HOUR COMPOSITE
BCH DW COMP
POOR CHROMATOGRAPHIC RESULTS WITH DIRTY SAMPLE
EUS WASTE WATER BACKGROUND
EUS COMBINED SEWER FLOW
EXTRACTABLE ORGANICS - 1.5 HR. COMPOSITE
EXTRACTABLE ORGANICS - .25 HR. COMPOSITE
EUS CSO
EUS FIRST FLOW
EUS RUNOFF
EXTRACTABLE ORGANICS - .50 HR. COMPOSITE
EUS PRECIPIT
BCH WASTE WATER BACKGROUND
BCH COMBINED SEWER FLOW
BCH CSO
BCH FIRST FLOW
BCH RUNOFF
PIE WASTE WATER BACKGROUND
PIE CS FLOW
PIE CSO
PIE FIRST FLOW
PIE RUNOFF
EQUALIZATION POND-EFFLUENT TO PREAERATION
CLARIFIER EFF. AT CHLORINE CONTACT-CHAMBER INF.
RAW WASTE INFLUENT TO EQUALIZATION
DIOXIN 1 LITER SAMPLE
DIOXIN 10 LITER SAMPLE
-------
2/08/84
ISOTOPE
SAMPLE LEVEL COMMENT CODE TABLE
PAGE
DILUTION
CODE
S151
5152
S153
5154
S155
S156
S157
S158
5159
5160
5161
5162
5163
5164
5165
5166
5167
5168
5169
5170
5171
5172
5173
5174
5175
5176
5177
5178
5179
S180
S181
S1S2
S1S3
5184
5185
5186
5187
5188
5189
5190
5191
5192
5193
5194
5195
5196
5197
5198
5199
5200
DESCRIPTION
SURGE BASIN EFF. AFTER NEUTRALIZATION
SECONDARY CLARIFIER GRAB
NEUTRALIZATION SURGE TANK EFFLUENT
EQUALIZATION EFF. TO AERATION
SEC. CLARIFIER EFF. TO PRESSURE FILTER
PRESSURE FILTER EFF. TO RIVER
ALKALINE SEWER RAM WASTE GRAB
CLARIFIER EFFLUENT GRAB
ACID SEWER BASIN PUMP TO NEUT.
PRIMARY CLARIFIER INFLUENT
SECONDARY CLARIFIER EFFLUENT
RAW WASTE TO CLARIFIER THICKENER
REACTOR CLARIFIER EFFLUENT TO AERATION
SEC. CLARIFIER TO PRESSURE FILTERS
FINAL PRESSURE TO FILTER EFFLUENT
SOURCE CITY WATER
BATTERY CAN RINSE WASTEWATER
SURFACE TREATMENT RINSE WASTEWATER
OLEFIN UNIT #2 API SEPARATOR EFFLUENT
NEW SURGE TANK EFF. TO AERATION BASIN
SEC. CLARIFIER EFF. TO POLISHING BASIN WEST CLARIFIER
FINAL EFFLUENT FROM POLISHING POND
FINAL CLARIFIER EFFLUENT
18 INCH HEADER INF. PIPE TO EQUALIZATION EG1
EQUALIZATION EC1 TO UNOX
SIB CLARIFIER EFF. TO S2A AND S2B CLARIFIERS
SOURCE WELL WATER
BILLET WASHING AFTER VACUUM CASTING
BILLET WASHING AFTER SINTERING
SAWING/GRINDING COOLANT/LUBRICANT 2C
BE NITRIC ACID PICKLING BATH
BE NITRIC ACID PICKLING RINSE DAY 1
BE NITRIC ACID PICKLING RINSE DAY 2
BE SAWING/GRINDING COOLANT
BE QUALITY INSPECTION WATER
HOT ROLLING BE NI CONTACT COOLING WATER
PROCESS WATER DAY 1
NUMBER 6 LAGOON EFFLUENT DAY 1
PROCESS WATER DAY 2
PROCESS WATER DUP DAY 2
NUMBER 6 LAGOON EFFLUENT DAY 2
NUMBER 6 LAGOON EFFLUENT DAY 3
STEAM STRIPPER INFLUENT GRAB
STEAM STRIPPER EFFLUENT GRAB
INFLUENT TO EQUALIZATION BASIN EC-1
INFLUENT TO AERATION UNITS AB-1
EFFLUENT FROM CLARIFIER Sl-A
FINAL EFFLUENT FROM CLARIFIER S2-A
INFLUENT TO STEAM STRIPPER
EFFLUENT FROM STEAM STRIPPER
-------
2/08/84
ISOTOPE
SAMPLE LEVEL COMMENT CODE TABLE
PAGE
DILUTION
CODE
S201
5202
S203
5204
S205
S206
S207
S208
S209
S210
S211
S212
5213
5214
5215
5216
5217
5218
S219
5220
5221
5222
5223
5224
S225
5226
5227
DESCRIPTION
OILY WASTEWATER TREATMENT INF-DAY1
OILY WASTEWATER TREATMENT EFF-DAY 1
OILY WASTEWATER TREATMENT INF-DAY 2
OILY WASTEWATER TREATMENT EFF-DAY 2
VACUUM MELTING STEAM CONDENSATE
EXTRUSION PRESS HEAT TREATMENT CONTACT COOLING H20
OILY WASTEWATER TREATMENT INF-DAY 3
OILY WASTEWATER TREATMENT EFF-DAY 3
PICKLING RINSEWATER TREATMENT INF-DAY 3
INF. TO WWTP API SEPARATOR (APII)
NEW SURGE BASIN EFFLUENT TO AERATION (NSBE)
SECONDARY CLARIFIER EFFLUENT TO POLISHING BASIN CSCE)
FINAL EFFLUENT FROM POLISHING POND (FNE)
SLUDGE RECYCLE GRAB
RECYCLE SLUDGE FROM S1A AND SIB CLARIFIERS
TANK 99 SKIMMER EFFLUENT TO EQUALIZATION
FINAL CLARIFIER EFFLUENT AT 1330 HOURS
SOUTH PLANT WIER BOX-SECONDARY CLARIFIER EFF.
SOUTH PLANT FEED SPLITTER BOX-INF. TO AERATION
EAST SIDE PLANT SECONDARY CLARIFIER EFFLUENT
EAST SIDE PLANT TK1715 OVERFLOW TO AERATION
EAST SIDE PLANT WEST PLANT NEUTRALIZATION SUMP
OP-1 PLANT SECONDARY CLARIFIER EFFLUENT
OP-1 PLANT WASTE H20 TK1721 OVERFLOW INF TO AERA.
OP-1 PLANT TRICKLING FILTER INF. TK1722 OVERFLOW
NEUTRALIZATION BASIN FLAME TO NORTH POND-RAW WASTE
ACTIVATED CARBON FINAL EFFLUENT IN MONITOR BLDG.
-------
ELEMENT NAME: SAMPLE NUMBER
Definition: The SCC assigned identification code which identifies the individual
samples. For calibration and performance standards, is used to indicate the nominal
concentration of the standard.
Input Type/Length
Quantitation Report Z2999
As Stored Internally 9(5)
Unit of Measure
N/A
Edit Criteria:
a. Must be a five digit number.
b. Range: 00001-99999
Examples: 00100 accompanied by a QUANTITATION REPORT TYPE of VER would
define a Calibration Verification standard at a nominal concentration of 100 ug/mL
(or 100 ug/L for volatiles). '
-------
ELEMENT NAME: SAMPLE POINT (SITE)
Definition: The specific point within an industrial wastestream where a sample was
taken.
Input Type/Length
Traffic Report X(l)
Lab Chronicles
As Stored Internally X(l)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Sample Site Table.
See attached Sample Site Table for a valid list.
-------
2/08/84 PAGE
ISOTOPE DILUTION
SITE DESCRIPTION TABLE
CODE DESCRIPTION
A (SUP)-RAW WATER (SUPPLY WATER)
B (PRO-IN-LINE PROCESS (PROCESS)
C (INF)-UNTREATED EFFLUENT (RAW WASTE WATER)
D (EFF)-TREATED EFFLUENT
E (RUN)-RUNOFF
F (PRI)-PRIMARY EFFLUENT
S (INT)-INTERMEDIATE POINT
H (OTH)-OTHER
I (INl)-INTERMEDIATE POINT 1
J (IN2)-INTERMEDIATE POINT 2
K (IN3)-INTERMEDIATE POINT 3
L (IN4J-INTERMEDIATE POINT 4
M (INS)-INTERMEDIATE POINT 5
-------
ELEMENT NAME: SAMPLE POINT FLOW
•
Definition: The flow rate at the point at which the sample was taken. Value is
recorded from a flow meter or other flow measuring device.
Input Type/Length
Traffic Report X(5)
As Stored Internally X(5)
Unit of Measure
Per 1,000 gallons/day.
Edit Criteria:
-------
ELEMENT NAME: SAMPLE TYPE
Definition: A coded value which describes the type of sample.
Input Type/Length
Traffic Report X(2)
As Stored Internally X(2)
Unit of Measure
N/A
Edit Criteria:
Must be a valid code in the Sample Type Code Table.
See attached table for valid codes.
-------
2/OS/84
ISOTOPE
SAMPLE TYPE CODE TABLE
PAGE
DILUTION
CODE
AD
CB
EP
MB
MD
ME
MS
Q
Ql
Q2
R
RB
RQ
TB
DESCRIPTION
ADDITIONAL OR MISCELLANEOUS DATA
COMPOSITE BLANK
EPA SAMPLE
METHOD BLANK
MATRIX REPLICATECDUPLICATE)
METHOD SPIKE
MATRIX SPIKE
UNSPIKED FRACTION
SPIKED FRACTION 1
SPIKED FRACTION 2
REGULAR SAMPLE
REAGENT BLANK
REGULAR AND QA SAMPLE
VOA TRIP BLANK
-------
ELEMENT NAME: SCAN NUMBER
Definition: Gives the scan at which the compound was detected by the mass
spectrometer.
Input Type/Length
Quantitation Report ZZ999
As Stored Internally 9(5)
Unit of Measure
N/A
Edit Criteria:
Range: 00001-99999
-------
ELEMENT NAME: SHIFT
Definition: The scheduled period of operation of the GC/MS instrument. Operation
is divided into three shifts/day.
Input Type/Length
Quantitation Report X(l)
As Stored Internally X(l)
Unit of Measure
N/A
Edit Criteria:
Code Meaning
G Graveyard (0000-0759; Midnight to 8 AM)
D Day (0800 - 1559; 8 AM to * PM)
5 Swing (1600- 1159; * PM to Midnight)
-------
ELEMENT NAME: TIME ANALYZED
Definition: The time thtat the sample fraction was analyzed by the laboratory.
Input Type/Length
Quantitation Report X(8)
As Stored Internally X(8)
Unit of Measure
N/A
Edit Criteria:
Format: HH:MM:SS
-------
Appendix F
EVALUATION OF PRR SAMPLE
In doing calculations for calibration linearity and ongoing
calibration/verification testing, the variability of analysis results on
calibration standards is needed. The CAL 100, VER, and PRR samples are all
prepared from standards at 100 ug/mL in organic solvent. The PRR sample was
prepared at the central laboratory by mixing solutions of the pollutants and
labeled compounds; the 100 ug/mL calibration solution (used for both
calibration and calibration verification) was prepared by each laboratory by
mixing the same volumes of the same solutions. Because this mixing process
was performed in different locations and at different times, the possibility
existed that the operations were not performed identically and that results
might not be equivalent. Because the PRR sample adds considerably to the
number of observations in the procedure, it was decided to include the PRR
if it was first checked for bias relative to the CAL 100 and VER samples.
Bias was assessed by performing an analysis of variance of the measured
amounts of each compound. A two-way layout was used by laboratory and
sample (CAL 100 and VER were assigned the same sample identifier for this
test, to be contrasted with PRR). The analysis was conducted on the
logarithms of the amounts. The hypothesis tested was that the average
amount measured in the PRR sample was equal to that measured in the CAL 100
and VER sample, for each laboratory. Significant results at the .05 level
were found in only about 5 percent of the cases. This was likely due to
random chance, and no bias was judged to be present in the PRR sample.
F-l
-------
Appendix G
LABORATORY EXTREMAL RANK SCREENING
The extreme rank sum test for outliers Is a nonparametric analysis of a
two-way layout ("objects" x "judges") to decide whether any of the objects
has a different mean response from the other objects. This method, proposed
by Youden (1963) and discussed by Thompson and Willke (1963), proceeds by
calculating the sum, across judges, of the ranking of the set of objects for
each judge. If all the objects are equivalent, then the ranking for each
judge will be random. Under this null hypothesis, Thompson and Willke
present asymptotic significance formulas and small-sample simulation
results. For use in this study, the "objects" are the laboratories, the
"judges" are the samples, and the quantity of interest is the absolute
deviation of the measured amount for each laboratory from the median
concentration across all laboratories for the sample. This procedure then
tests whether any single laboratory has results that are on the average
farther from the common median result than other laboratories' results (in
either direction). Since there are usually 7 to 11 laboratories (objects)
in the comparison for each compound and 8 to 10 samples (judges), the
asymptotic formulas for the significance points were used. At a
significance level a (a = .05 in this study), if (aJl)/2I <_ 1 (where J is
the number of judges and I is the number of objects), the null hypothesis is
rejected for any object with rank sum outside of the interval (J + R,
IJ - R), where
„ . ,,-
j>
-
If oJVZI > 1, then the interval is
where
G-l
-------
N is the inverse cumulative distribution of a standard normal random
variable, and N[(l - a) ] is used to obtain an approximate {1 - o)th
quantile point of the maximum of I normal variates.
In this study, only large values of the absolute deviation are of
interest, so only the right-hand limit was tested, and the significance
point was adjusted appropriately.
G-2
-------
where tabled values are given. In preliminary runs with these two methods
QSCREEN found many more points than FSCREEN when both were used at level
a = .01. To evaluate the source of this difference, several simulation runs
were performed to test the methods. One thousand sets each of 5, 10, and 15
standard normal variates were tested with each method at o = .01 and
a = .05, and the mean proportion of rejected points was computed. The
results of the simulation are presented in Table H-l.
Table H-l
SIMULATION RESULTS FOR OUTLIER SCREENING METHODS
a = .01
Set Size
5
10
15
Number
of Sets
1000
1000
1000
Mean Proportion Rejected
QSCREEN
0.0000*
0.0149 * 0.0012
0.0192 * 0.0013
FSCREEN
0.0022 * 0.0007
0.0017 ± 0.0004
0.0009 * 0.0002
a - .05
Set Size
5
10
15
Number
of Sets
1000
1000
1000
Mean Proportion Rejected
QSCREEN
0.0076 * 0.0012
0.0422 * 0.0020
0.0517 * 0.0022
FSCREEN
0.0104 * 0.0014
0.0076 * 0.0009
0.0040 * 0.0005
The interquantile range (IQR) used in QSCREEN is computed by SAS using a
weighted linear combination of adjacent order statistics. For N < 8 this
includes the extreme points in the scale calculation, hence only very
extreme points are rejected by QSCREEN for very small N.
H-2
-------
Appendix H
OUTLIER SCREENING METHODS
Two methods of screening individual data values were used in this study
to screen across the set of laboratory results for each compound and sample
type. The.first method, a robust quantile screening method (QSCREEN), was
suggested in Hoaglin, Mosteller, and Tukey, Understanding Robust and
Exploratory Data Analysis, pp. 30-39. QSCREEN (a) estimates the (1 - o/2)th
and a/2th percentiles of its data by
M±rRt75T'IQR •
where M is the median, IQR is the interquantile range (75th percentile -
25th percentile), and N is the inverse distribution function of the normal
distribution. Points outside this range are rejected.
The second method, called Ferguson's method (FSCREEN) and based on the
sample kurtosis, is described in the "Standard Practice for Dealing with
Outlying Observations" 1982 Annual Book of ASTM Standards. FSCREEN (a)
computes
T-> •* / *-^ *'
b.
= n £ (X. - 7) /
and compares it to tabled percentiles of the sample kurtosis. If the tabled
value is exceeded at the a level, the farthest point from the mean is
dropped. Then b2 is recomputed on the remaining points, and this
procedure is iterated to convergence.
The levels (.001 for QSCREEN, .01 for FSCREEN) used for these
screenings were chosen for several reasons. QSCREEN can be adjusted to any
desired a level, whereas FSCREEN can be used only at o = .01 and o = .05,
H-l
-------
Therefore, QSCREEN is seen to be performing at very close to its
nominal level on normal data, but FSCREEN does not find as many points as it
should according to its level. Because extensive checking failed to reveal
any problems with the implementation, it can only be suggested that the same
problem may exist in the cited tables of .significance levels.
So that both methods would perform in practice at approximately the
same power, QSCREEN was used for the actual screening at level a = .001 and
FSCREEN at level o = .01. Approximately 2 percent of the actual data was
identified as outliers by one or both of these methods.
H-3
-------
Appendix I
ESTIMATION OF VARIANCE COMPONENTS
For the purpose of calculating quality control limits from the data in
this study, the variance components model assumes that the logarithm of the
measured amount X^m measured by laboratory 1 and replicate m can be
written as
log(Xlm) . „ * E] + Alm ,
for 1 = 1, .... L laboratories and m = 1 n-j replicate measurements
at laboratory 1. \i is the (fixed) average response; E, is the (random)
2
interlaboratory effect with mean 0 and variance 0?', A, is the (random)
intralaboratory effect, with mean 0 and variance a .
A
The variance components analysis was performed by the maximum
likelihood method using BMDP3Y to estimate the inter- and intralaboratory
variance components of the logarithms of the measured amounts. For the
start-up and ongoing limits, the replicates used were the BLK, APS, and EPA
samples (SAMGRP = WTR), using only the labeled compound results from the BLK
and EPA samples.* For the calibration verification limits, the replicates
used were the CAL 100, VER, and PRR samples (SAMGRP = CAL). Table 1-1 gives
the results of the variance components analysis for each sample type and
compound series (1 = compounds by internal standard, 2 = labeled analogues
by internal standard, 3 = compounds by isotope dilution). For each
compound, the total number of observations, the total number of
laboratories, the logarithmic mean M (labeled "MU"), the square roots of the
variance components S^ (interlaboratory) and SA (intralaboratory), and the
percentage of the total variance due to interlaboratory variation
100 x $£/($£ + sj) are given.
*
No unlabeled compounds were included in the BLK sample, and the unlabeled
compounds in the EPA sample were at varying amounts and only a few
compounds were actually present.
1-1
-------
Because Intralaboratory replicates were not available for series 1 and
2 2
series 3 compounds for the WTR samples, the total variance S^ * S^ for these
cases was estimated by the variance among the available measurements (one
per lab on the APS sample), and then decomposed Into the components
according to the ratio of Inter- and Intralaboratory variance found for the
WTR series 2 compounds.
1-2
-------
Table 1-1
RESULTS OF VARIANCE COMPONENTS ANALYSIS
______ -_ 5tK_E5=l S«nUKf = i;«ij
COMPOUXD TOTAL TOTAL
MU
S_E
S_A 7,
OBS LABS
001B
005B
008B
009B
012B
018B
020B
021A
022A
024A
025B
026B
027B
028B
031A
034A
035B
036B
037B
039B
040B
041B
042B
OS2B
053B
054B
OS5B
056B
057A
058A
059A
060A
052B
064A
065A
066B
068B
069B
070B
071B
072B
073B
0714B
07SB
076B
077B
078B
079B
080B
081B
984B
502B
503B
504B
505B
506B
S07B
S08B
S09B
510B
51 IB
512B
513B
517B
S19B
521B
523B
S26B
ACEHAPHTHEHE
BEHZIDINE
1,2, 4-TRICHLOROBENZENE
HEXACHLOROBEKZEHE
HEXACHLOROETHANE
BIS C2-CHLOROETH YD ETHER
2-CHLORONAPHTHALENE
2 , 4 , 6-TRICHLOROPHEHOL
P-CHLORO-M-CRESOL
2-CHLOROPHEMOL
1 , 2-DICHLOROBEHZEME
1 . 3-OICHLOROBEHZEMC
1 , 4-DICHLOROBENZENE
3,3' -DICHLOROBEHZIDINE
2,4-DICHLOROPHENOL
2,4-DIMETHYLPHENOL
2 , 4-DIHITROTOLUENE
2 , 6-DINITROTOLUENE
1 , 2-DIPHENYLHYDRAZINE
FLUORAKTHENE
4-CHLOROPHENYL PHENYL ETH
4-BROMOPHENYL PHENYL ETHE
BIS C2-CHLOROISOPROPYL) E
HEXACHLOROBUTADIENE
HEXACHLOROCYCLOPENTADIENE
ISOPHOROHE
NAPHTHALENE
NITROBENZENE
2-NITROPHENOL
4-HITROPHENOL
2,4-DINITROPHENOL
l»,6-DINITRO-0-CRESOL
N-NITROSODIPHENYLAMINE
PENTACHLOROPHENOL
PHENOL
BIS (2-ETHYLHEXYL) PHTHAL
DI-N-BUTYL PHTHALATE
DI-N-OCTYL PHTHALATE
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BENZOC AJANTHRANCENE
BENZO(A)PYRENE
BENZO(B)FLUORANTHENE
BEHZO(K)FLUORANTHENE
CHRYSENE
ACENAPHTHYLENE
ANTHRACENE
BENZOtGHDPERYLENE
FLUORENE
PHENANTHRENE
PYRENE
BETA NAPHTHYLAHINE
ALPHA PICOLINE
DIBENZOTHIOPHENE
DIBENZOFURAN
N-DODECANE
DIPHENYLAMINE
DIPHENYLETHER
ALPHA TERPINEOL
STYRENE
DI-N-BUTYL AHINE
BIPHENYL
P-CYMENE
N-DECANE C10
N-HEXADECANE C16
N-EICOSANE C20
N-TETRACOSANE C24
N-TRIACONTANE C30
36
33
34
37
31
37
26
31
29
37
37
37
35
32
37
33
36
38
30
33
36
25
29
34
35
35
37
17
35
28
37
33
1 1
34
37
35
34
36
36
38
34
34
31
35
36
28
38
31
38
38
31
30
31
34
37
34
31
33
35
34
8
34
36
36
38
38
36
32
13
1 1
12
13
1 1
13
9
12
1 1
13
13
13
13
1 1
13
12
13
13
1 1
12
13
13
10
13
13
13
13
6
13
10
13
12
4
12
13
12
12
13
13
13
12
12
1 1
12
13
1 1
13
1 1
13
13
1 1
1 1
1 1
12
13
12
1 1
12
12
12
3
12
13
12
13
13
12
12
4.
4.
4.
4 .
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4 .
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4 .
4.
4.
4 .
4.
4.
4.
4 .
4.
4.
4.
4 .
4.
4.
4.
4 .
<« .
4.
4 .
4.
4.
4.
4.
4 .
4.
4.
4.
4.
4.
4.
4 .
4.
56
59
59
65
61
61
53
61
50
57
60
56
58
66
62
50
65
58
61
60
58
65
65
60
65
57
54
63
60
69
80
66
71
73
56
66
60
60
58
60
63
47
62
46
60
57
57
56
58
60
57
60
59
60
60
64
62
55
58
59
81
59
63
62
58
61
66
67
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.07
.27
.08
.07
. 13
.07
.08
.09
.05
.06
.04
.08
.06
. 19
.00
.05
.00
. 13
.00
.07
.04
.09
.04
.06
.03
. 14
.09
.06
.06
. 13
. 19
. 10
.05
.09
.07
. 17
. 10
. 17
.05
. 14
.09
.22
.23
.30
. 12
.06
. 1 1
.03
. 10
. 12
. 10
. 15
.09
. 10
.03
. 10
.00
. 14
. 15
.07
.24
.07
.04
. 13
. 08
.20
. 1 1
.25
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
VAR DUE
TO LAB
.08
.45
. 1 1
.21
. 16
. 18
. 14
. 12
.06
. 13
. 17
. 12
. 12
.27
. 13
.08
.20
.20
. 13
. 18
. 14
. 13
. 17
. 1 1
. 14
. 15
. 14
. 1 1
.12
.28
.21
. 19
. 12
.22
. 15
.24
. 15
.32
. 18
. 18
.27
.49
. 41
.45
. 42
.08
.20
. 42
. 17
.20
. 19
.26
.21
. 16
. 15
.21
. 17
. 17
. 16
. 18
.46
. 1 1
. 16
.25
. 19
.20
. 19
.28
43
25
36
9
38
12
23
34
41
15
6
29
17
32
0
22
0
27
0
14
6
31
6
21
3
46
27
20
20
17
44
21
14
14
18
34
30
22
7
39
9
16
23
30
8
42
21
0
24
26
22
24
15
25
3
17
0
41
44
13
21
29
5
19
14
49
25
44
. 10
.93
. 94
.6?
. 19
.21
. 15
.92
.02
.94
.22
.45
.82
.35
.00
.87
.00
.85
.00
.55
.37
. 13
. 18
.03
.89
.23
.71
. 04
.83
.55
.21
.54
.99
.32
. 63
. 27
.80
.68
. 44
. 10
.29
.40
.59
.21
. 00
.26
.74
.45
.75
. 35
. 98
.95
.78
. 68
. 13
. 95
. 00
. 62
. 31
.80
. 30
. uo
. 96
.46
.77
.53
. 88
. 90
1-3
-------
Table 1-1 (Continued)
SERIES»1 !
COMPOUND TOTAL 1
OBS I
00 IB ACENAPHTHENE
005B BENZIDINE
008B 1 ,2, 4-TRICHLOROBENZENE
009B HEXACHLOROBENZEHE
012B HEXACHLOROETHANE
018B BISC2-CHLOROETHYDETHER
020B 2-CHLORONAPHTHALENE
021A 2.4,6-TRICHLOHOPHENOL - .
022A P-CHLORO-H-CRESOL
024A 2-CHLOROPHENOL
025B 1 ,2-DICHLOROBENZEHE
026B 1,3-DICHLOROBENZENE
027B 1.4-DICHLOROBENZENE
028B 3,3'-DICHLOROBENZIDINE
031A 2.4-DICHLOROPHEKOL
034A 2,4-DIIIETHYLPHENOL
03SB 2.4-DINITROTOLUENE
036B 2,6-DIKITROTOLUEXE
037B 1,2-DIPHENYLHYDRAZINE
039B FLUORANTHENE
040B 4-CHLOROPHENYL PHENYL ETH
041B 4-BROMOPHENYL PHENYL ETHE
042B BIS (2-CHLOROISOPROPYL) E
052B HEXACHLOROBUTADIENE
053B HEXACHLOROCYCLOPENTADIENE
05MB ISOPHORONE
055B NAPHTHALENE
056B NITROBENZENE
OS7A 2-NITROPHENOL
058A 4-NITROPHENOL
OS9A 2,4-DINITROPHENOL
060A 4,6-DINITRO-O-CRESOL
062B N-NITROSODIPHENYLAMINE
064A PENTACHLOROPHENOL
065A PHENOL
066B BIS (2-ETHYLHEXYL) PHTHAL
068B DI-N-BUTYL PHTHALATE
069B DI-N-OCTYL PHTHALATE
070B DIETHYL PHTHALATE
071B DIMETHYL PHTHALATE
072B BENZO( A) AMTHRANCEKE
073B BENZOC AJPYRENE
074B BENZO(B)FLUORANTHENE
07SB BENZOCKJFLUORANTHENE
076B CHRYSENE
077B ACENAPHTHYLENE
078B ANTHRACENE
0798 BENZOCGHDPERYLENE
0803 FLUORENE
08 IB PHENANTHRENE
034B PYRENE
502B BETA KAPHTHYL ArtlHE
503B ALPHA PICOLINE
501*8 DIBEHZOTHIOPHENE
505B OIBENZOFURAN
506B N-DODECANE
507B DIPHENYLAHINE
508B DIPHENYLETHER
509B ALPHA TERPINEOL
510B STYRENE
511B DI-N-BUTYL AMINE
512B BIPHENYL
513B P-CYHENE
517B N-DECANE CIO
S19B N-HEXADECANE C16
521B N-EICOSANE C20
S23B N-T-ETRACOSANE C24
S26B N-TRIACONTANE C30
iAMGRP'
•OTAL
.ABS
12
8
11
12
10
12
9
10
10
12
11
12
12
9
12
11
12
12
10
10
12
12
9
12
10
1 1
12
5
12
9
12
11
4
11
12
9
1 1
1 1
1 1
12
9
10
10
1 1
10
10
12
9
12
1 1
10
9
9
1 1
12
11
10
1 1
1
1
2
1
1
1
10
12
10
10
'WTR
HU
4.29
3.03
H.OH
4.42
3.44
4.39
3.74
4.48
4.33
4.38
4.03
3.88
3.92
3.83
4.44
3.92
4.48
4.46
4.41
4.30
4.35
4.39
4.31
3.33
2.23
4.39
4.14
4.35
4.40
4.29
4.51
4.63
4.57
4.35
4. 34
4.47
4.19
4.34
3.90
3.52
4.37
4.39
4.00
3.74
4.34
4.34
4.25
4.39
4.38
4.30
4.19
3.69
4.11
4.32
4. 17
3. :;e
4.33
4.23
4. 40
3.75
1 .45
4.26
3.84
3.03
4.33
4.41
4.46
4.40
S_E
0.11
0.92
0.35
0. 13
0.78
0.18
0.43
0. 10
0.05
0.22
0.29
0.37
0.33
0.65
0. 17
0.52
0. 19
0. 12 •
0.24
0.21
0.13
.
0.12
0.55
1 .59
0. 19
0.24
0.13
0. 19
0.22
0.32
0.40
0. 10
0.24
0 .00
0.20
0.36
0.21
0.43
0.71
0.21
0.24
0.59
0.84
0. 13
0. 12
0. 17
0.34
0.07
0.09
0.37
1 .29
0.28
0.11
0. 13
0.89
0.20
0.12
0. 12
0.41
0.00
0.10
0.38
1 .02
0.14
0. 17
0.21
0.23
S_A 7.
I
0. 14
0.80
0.36
0.21
0.72
0. 13
0.44
0.13
0.35
0. 14
0. 19
0.35
0.31
0.47
0.13
0.20
0.11
0.22
0.20
0.20
0.21
.
0. 10
0.46
0.88
0. 18
0.25
0. 10
0. 13
0.43
0.27
0.43
0.31
0.24
0.33
0.11
0. 17
0.11
0.49
0.66
0. 12
0. 13
0.71
0.76
0. 17
0.11
0. 18
0.23
0. 17
0.18
0.25
0.29
0.39
0. 17
0. 17
0.62
0. 18
0.13
0.08
0. 30
0.75
0.26
0.30
0.96
0. 18
0. 14
0.11
0. 16
VAS DUE
0 LAB
39.55
57.01
47.61
28.45
53.69
66.44
48.87
39.72
2.02
72.02
68.46
53.40
52.55
66.05
65.33
86.37
72.61
23.82
57.26
53. 15
27.58
.
57.29
58.39
76.40
52.24
47.48
64.65
66.21
21-24
58.76
47.09
9.35
51 .25
0.00
74.49
81.78
78.01
43.72
53.22
76.50
75.95
41 .07
54.83
37.25
51.03
46. 18
69.35
14.31
20 . 42
67.66
95.09
33.77
32.39
38.41
66.93
54.56
46.45
68.35
64. 12
0.00
11.92
60.31
52.90
38.26
58.01
77.54
68.30
1-4
-------
Table 1-1 (Continued)
--- — -._ __-- 5EKJ.E5»2
COMPOUND TOTAL
DBS
201B
205B
208B
209B
212B
218B
220B
221A
222A
224*
225B
226B
227B
228B
231A
234A
23SB
236B
237B
239B
210B
2M2B
2S2B
2S3B
25<4B
255B
256B
2S7A
258A
259A
260A
262B
264A
265A
266B
268B
269B
270B
271B
272B
273B
27MB
275B
276B
277B
278B
279B
280B
281B
28MB
602B
603B
604B
605B
606B
607B
608B
609B
610B
61 IB
612B
613B
617B
619B
621B
623B
626B
ACENAPHTHENE-D10
BEHZIDINE-D8 (RINGS-D8)
1 , 2.4-TRICHLOROBENZENE-D3
HEXACHLOROBENZENE- 1 3C6
HEXACHLOROETHANE-1-13C
BIS(2-CHLOROETHYL)-D8 ETH
2-CHLORONAPHTHALENE-D7
2,4. 6-TRICHLOROPHEHOL-3 . S
4-CHLORO-3-HETHYLPHEHOL-2
2-CHLOROPHENOL-3 , "4 , 5 , 6-D4
1 , 2-DICHLOROBEHZENE-D4
1 , 3-DICHLOROBENZENE-D4
1 . 4-DICHLOROBENZENE-D4
3, 3'-DICHLOROBENZIDINE-D6
2,4-DICHLOROPHENOL-3,5,6-
2,4-DinETHYLPHEHOL-3,5. 6-
2 , 4-DINITROTOLUENE-3 , 5 , 6-
2 , 6-DINITROTOLUENE-D3
1 ,2-DIPHENYL-DIO-HYDRAZIN
FLUORANTHEHE-D10
4-CHLOROPHENYL PHENYL-D5
BISC2-CHLOROISOPROPYDETH
HEXACHLORO-1 , 3-BUTADIENE-
HEXACHLOROCYCLOPEHTADIENE
ISOPHORONE-D8
HAPHTHALENE-D8
KITROBENZENE-D5
2-MITROPHENOL-3,4,5, 6-D4
4-NITROPHEKOL-2. 3,5.6-04
2, 4-DINITROFHENOL-3,5, 6-D
4 , 6-DIMITRO-0-CRESOL-D2
H-KITP.OSODIPHEHYLAMINE-D6
PENTACHLOROPHENOL-13C6
PHENOL-2.3,4,5.6-D5
BISC2-ETHYLHEXYDPHTHALAT
DI-H-BUTYL PHTHALATE-D4
DI-M-OCTYL PHTHALATE-D4
DIETHYL PHTHALATE-3,4,5,6
DIMETHYL PHTHALATE-3 . 4 , S ,
BEHZO( A)ANTHRACEHE-D12
BENZO(A)PYREHE-D12
BENZO(B)FLUORANTHENE-D12
BENZOCK)FLUORANTHENE-D12
CHRYSEHE-D 12
ACENAPHTHYLENE-D8
AMTHRACEHE-D10
BENZOCGHDPERYLENE-D12
FLUORENE-D10
PHENANTHRENE-D10
PYRENE-D10
2-NAPHTHYL-D7-AniME
2-HETHYLPYRIDINE-D7
DIBENZOTHIOPHEHE-D8
DIBENZOFURAH-D8
H-DODECANE-D26
DIPHENYL-D10-AMIHE
DIPHENYL-D10 ETHER
ALPHA-TERPINEOL-D3
STYREHE-2, 3, 4 ,5,6-D5
DI-N-BUTYL-D18-AMINE
DIPHENYL-D10
P-CYMEHE-D14
N-DECAHE-D22
K-HEXADECANE-D34
K-EICOSANE-D42
K-TETRACOSANE-D50
K-TRIACOHTAME-D62
33
31
30
31
27
29
35
27
35
34
31
33
33
31
35
37
27
23
33
34
36
29
31
28
36
35
14
36
30
34
33
22
34
36
31
32
35
36
37
32
34
32
35
34
35
29
34
35
33
31
30
34
27
33
39
24
31
33
34
12
12
34
36
37
31
35
33
SAnijKr =
TOTAL
LABS
12
1 1
12
1 1
10
10
13
10
13
12
12
12
13
1 1
13
13
10
9
12
13
13
10
12
10
13
13
5
13
1 1
12
12
8
12
13-
1 1
12
13
13
13
12
12
1 1
12
12
13
1 1
12
13
12
12
1 1
12
1 1
12
•13
9
12
1 1
12
4
4
13
13
13
1 1
12
12
CA.L
nu
S_E
S_A 7.
VAR DUE
TO LAB
4.
4.
4.
<* .
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4 .
4 .
4 .
4.
4.
4.
4.
4.
4 .
4.
4.
4.
4.
4.
4.
4.
4 .
4.
4 .
4.
4 .
4.
4.
4.
4.
4 .
4 .
4.
4.
4.
4.
4.
4.
4.
4 .
4 .
4 .
60
74
63
67
62
59
59
60
62
60
62
60
62
68
63
59
64
59
61
67
60
63
61
74
62
59
60
62
77
73
69
59
68
61
64
6 1
66
62
59
65
56
59
57
62
60
58
54
6 1
63
70
73
61
61
60
62
63
62
68
59
71
59
60
69
60
6 1
67
6 1
0.
0.
0.
0 .
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0 .
0.
0.
0.
0.
0.
0.
0.
0.
0.
0 .
0.
0.
0.
0.
0.
0 .
0.
0 .
0.
0 .
0.
0 .
0.
0.
0 .
0.
0 .
0.
0.
0 .
0.
0 .
0.
0.
0 .
0.
0 .
0.
00
00
00
03
00
03
00
08
00
00
00
00
00
14
00
03
00
00
02
00
04
00
00
00
00
00
00
04
21
06
05
00
04
01
16
05
10
00
03
09
17
14
00
07
00
00
00
00
06
17
15
00
04
00
05
03
00
05
09
00
10
00
10
00
07
10
23
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.07
.52
. 10
.20
. 15
. 14
.07
.07
.08
. 12
. 10
. 14
.09
.36
. 10
. 12
.12
. 19
. 12
. 16
. 12
. 17
.08
. 15
. 14
.07
. 12
. 10
.22
.20
. 12
. 10
. 18
. 16
. 17
. 13
.33
. 16
. 15
.26
.44
. 41
.43
.30
. 09
. 1 1
.43
. 10
. 08
. 15
. 17
.25
.07
.09
; 19
. 10
.05
.34
. 17
.53
.09
.09
. 17
. 13
. 10
. 15
. 30
0 .
0-
0.
1 .
0.
4.
• o.
56.
0 .
0.
0.
0.
0.
12.
0.
5.
0.
0.
2.
0.
7.
0.
0.
0 .
0.
0.
0.
14.
48.
9.
13.
0.
4 .
0.
44.
1 1 .
8.
0.
4.
1 1 .
13.
10.
0 .
5.
0 .
0.
0 .
0.
34.
54.
44 .
0.
26 .
0 .
6.
7 .
0 .
1 .
21 .
0 .
56 .
0.
24.
0 .
3,0.
33.
37.
00
00
00
91
00
16
00
79
00
00
00
00
00
72
00
20
00
00
45
00
97
00
00
00
00
00
00
68
77
10
65
00
3 3
74
70
51
0 1
00
27
35
25
49
00
62
00
00
00
00
Q Q
73
20
00
9U
00
38
44
00
87
82
00
59
00
32
00
17
57
27
1-5
-------
Table 1-1 (Continued)
COHPOUKD TOTAL TOTAL
no
S_B
OBS LABS
201B ACEXAPHTHEKE-010
205B BEXZIDINE-D8 (RIXGS-D8)
208B 1 ,2,4-TRICHLOROBEXZEME-D3
209B HEXACHLOROBEXZENE-13C6
212B HEXACHLOROETHAME-1-13C
218B BISC2-CHLOROETHYD-D8 ETH
220B 2-CHLORONAPHTHALEHE-D7
221A 2,4.6-TRICHLOROPHEXOL-3,5
222A 4-CHLORO-3-METHYLPHEXOL-2
224A 2-CHLOROPHEKOL-3,4,5,6-D4
22SB 1,2-DICHLOROBEXZEHE-D4
226B 1,3-DICHLOROBEKZENE-D4
227B 1 .4-DICHLOROBEHZEXE-D4
228B 3. 3'-DICHLOROBEHZIDINE-D6
231A 2,4-OICHLOROPHEXOL-3,5.6-
234A 2,4-DIHETHYLPHEXOL-3,5,6-
235B 2.4-DINITROTOLUENE-3.5.6-
236B 2.6-DIXITROTOLUEKE-D3
237B 1 ,2-DIPHEXYL-DIO-HYDHAZIN
239B FLUORAKTHEKE-D10
240B 4-CHLOROPHEXYL PHEXYL-D5
242B BISC2-CHLOROISOPROPYDETH
252B HEXACHLORO-1 , 3-BUTADIEXE-
253B HEXACHLOROCYCLOPEKTADIEME
254B ISOPHOROXE-D8
255B KAPHTHALENE-D8
256B HITROBEHZEHE-DS
257A 2-HITROPHEXOL-3,4,S, 6-D4
258A 4-XITROPHEXOL-2, 3,5,6-04
259A 2,4-DIXITROPHEXOL-3,5,6-D
260A 4,6-DIMITRO-0-CRESOL-D2
262B X-XITROSODIPHEXYLAniXE-06
264A PEXTACHLOROPHEKOL-13C6
265A PHEXOL-2,3,4,5,6-D5
266B BIS(2-ETHYLHEXYL)PHTHALAT
268B DI-H-BUTYL PHTHALATE-D4
269B DI-X-OCTYL PHTHALATE-D4
270B DIETHYL PHTHALATE-3 , 4 , 5 , 6
271B DIMETHYL PHTHALATE-3 , 4 , 5 ,
272B BENZCH A) ANTHRACENE-D12
273B BEHZOC A)PYREXE-D12
274B BENZOCB>FLUORAHTHEXE-D12
275B BEHZOCKJFLUORAXTHEXE-D12
276B CHRYSEXE-D12
277B ACEHAPHTHYLEXE-D8
278B AXTHRACENE-D10
279B BEXZO(GHI)PERYLEXE-D12
280B FLUOREXE-D10
281B PHEXAMTHREXE-D10
284B PYREXE-D10
502B 2-MAPHTHYL-D7-AO1XE
603B 2-HETHYLPYRIDIXE-D7
604B DI3EXZOTHIOPHEXE-D8
605B DIBENZOFURAN-D8
606B N-DODECANE-D26
607B DIPHEXYL-D10-AMIXE
608B DIPHEXYL-D10 ETHER
609B ALPHA-TERPIXEOL-D3
610B STYREXE-2, 3,4, 5, 6-D5
6118 DI-X-BUTYL-D18-AMIXE
612B DIPHEMYL-D10
613B P-CYP1EXE-D14
617B X-DECAXE-D22
619B X-HEXADECAXE-D34
621B M-EICOSAXE-D42
623B X-TETRACOSAXE-D50
626B X-TRIACONTAXE-D62
33
21
32
29
26
30
36
24
33
30
32
32
35
30
33
34
28
23
33
34
36
27
32
20
32
35
.12
33
29
31
30
20
30
33 -
28
32
34
34
35
31
30
28
31
30
36
30
30
34
33
31
24
32
28
32
35
24
32
30
32
8
12
35
34
32
33
31
31
11
8
11
10
9
10
12
9
12
11
11
11
12
10
12
12
10
8
11
12
12
9
11
9
11
12
4
12
10
1 1
1 1
7
11
12
10
1 1
12
12
12
11
11
10
1 1
1 1
12
10
1 1
12
1 1
1 1
10
1 1
10
1 1
12
3
1 1
10
1 1
3
4
12
12
12
1 1
1 1
11
4.29
3.45
3.98
4.46
3.71
4.30
4.24
4.47
4.19
4.33
3.96
3.89
3.96
4.04
4.36
4.05
4.28
4.48
4.28
4.31
4.36
4.27
3.82
2.33
4.39
4. 17
4.23
4.33
4. 17
4.38
4.53
4.40
4.46
•4.05
4.38
4.21
4.19
3.78
3.24
4. 44
4. 37
4.24
4.39
4. 40
4. 31
4.32
4.46
4.39
4. 32
4. 30
3.66
4.04
4. 36
4.37
3.79
4.29
4.30
4. 37
3.81
3.38
4.20
3.79
3.78
4.32
4.32
4.32
4.37
0. 17
1.12
0.35
0.21
0.55
0.27
0.24
0. 17
0.07
0.22
0.39
0.37
0.35
0.61
0.21
0.42
0.34
0. 14
0.24
0.21
0. 17
0. 19
0.51
1.50
. 0. 13
0.23
0. 19
0. 19
0.33
0.36
0.25
0.06
0.24
0.00
0.26
0.31
0.52
0.45
0.82
0.36
0.24
0.49
0 .48
0.24
0. 18
0.24
0.32
0.09
0.11
0 24
1.33
0.42
0.12
0.13
0.57
0.25
0. 19
0.36
0.50
0.00
0.08
0.57
0.51
0.19
0.23
0. 30
0.32
S_A *
VAH DUE
TO LAB
0.22
0.97
0.37
0.33
0.51
0. 19
0.24
0.21
0.49
0.13
0.26
0.35
0.33
0.44
0.15
0. 17
0.21
0.25
0.20
0.20
0.27
0. 16
0.43
0.83
0.13
0.25
0. 14
0. 13
0.64
0.31
0.27
0. 18
0.23
0.63
0. 15
0. 15
0.27
0.51
0.77
0.20
0. 13
0.58
0.44
0.31
0. 18
0.26
0.21
0.22
0 . 22
0 17
0.30
0.59
0. 17
0. 17
0.40
0.23
0.21
0.24
0.37
1 .05
0.21
0.46
0.48
0 .24
0.19
0. 16
0.21
39.55
57.01
47.61
28.45
53.69
66.44
48.87
39.72
2.02
72.02
68.46
53.40
52.55
66.05
65.33
86.37
72.61
23.82
57.26
53. 15
27.58
57.29
58.39
76.40
52.24
47.48
64.65
66. T. ?
21 .2".
58.75
47.09
9.35
51 .25
0.00
74. <|i
81 .78
78.01
43.72
53.22
76.50
75.95
41 .07
54.83
37.25
51.03
46. 18
69.35
14.31
20. 42
67 66
95.0?
33.77
32.39
38.41
66.93
54.56
46.45
68.35
64. 12
0.00
1 1 .92
60.31
52.90
38.26
58.01
77.54
68.80
1-6
-------
Table 1-1 (Continued)
-- — ________--- _____ 5_H__5=3 SAniiKr^UA
COMPOUND TOTAL TOTAL
i.
tiu
S_E
OBS LABS
301B
305B
308B
309B
312B
318B
320B
321A
322A
324A
325B
326B
327B
328B
331A
334A
335B
336B
337B
339B
340B
342B
3S2B
3S3B
354B
355B
356B
357A
358A
3S9A
360A
362B
364A
365A
366B
368B
369B
370B
371B
372B
373B
374B
375B
376B
377B
378B
379B
380B
381B
33<4B
702B
703B
704B
705B
706B
707B
708B
709B
710B
71 IB
712B
713B
717B
719B
721B
723B
726B
ACENAPHTHENE
BENZIDINE
1.2. 4-TRICHLOROBENZENE
HEXACHLOROBENZENE
HEXACHLOROETHANE
BIS (2-CHLOROETH YD ETHER
2-CHLORONAPHTHALENE
2.1. 6-TRICHLOROPHEMOL
P-CHLORO-M-CRESOL
2-CHLOROPHENOL
1 . 2-DICHLOROBENZENE
1 , 3-DICHLOROBEHZEHE
1 , 4-DICHLOROBENZENE
3.3' -DICHLOROBEHZIDIKE
2 , 4-DICHLOROPHENOL
2 , 4-DIMETHYLPHENOL
2 . 4-DINITROTOLUENE
2 , 6-DIKITROTOLUEKE
1 , 2-DIPHENYLHYDRAZINE
rLUORAHTHEHE
4-CHLOROFHENYL PHENYL ETH
BIS (2-CHLOROISOPROPYL) E
HEXACHLOROBUTADIENE
HCXACHLOROCYCLOPENTADIENE
ISOPHORONE
NAPHTHALENE
NITROBENZENE
2-NITROPHENOL
4-NITROPHENOL
2 , 4-DINITROPHENOL
4,6-DINITRO-O-CRESOL
N-NITROSODIPHEHYLAMINE
PENTACHLOROPHENOL
PHENOL
BIS C2-ETHYLHEXYD PHTHAL
DI-N-BUTYL PHTHALATE
DI-H-OCTYL PHTHALATE
DIETHYL PHTHALATE
DIMETHYL PHTHALATE
BENZOC A)ANTHRANCENE
BENZOC AJPYRENE
BEHZOt BJFLUORANTHENE
BENZO
-------
Table 1-1 (Concluded)
COMPOUND
301B ACENAPHTHEHE
305B 8ENZIDIHE
308B 1,2.4-TRICHLOROSENZENE
309B HEXACHLOROBENZENE
312B HEXACHLOROETHANE
318B BIS(2-CHLOROETHYL)ETHEH
320B 2-CHLORONAPHTHALEHE
321A 2.4,6-TRICHLOROPHEHOL
322A P-CHLORO-M-CRESOL
324A 2-CHLOROPHENOL
325B 1,2-DICHLOROBENZENE
326B 1,3-DICHLOROBENZEHE
327B 1.4-DXCHLOROBEXZEHr
328B 3,3'-DICHLOROBEHZIDINE
331A 2.4-DICHLOROPHEHOL
334A 2.4-DIMETHYLPHENOL
335B 2,4-DINITROTOLUENE
336B 2,6-DINITROTOLUENE
337B 1,2-DIPHEKYLHYDRAZIHE
339B FLUORAHTHEKE
3UOB 4-CHLOROPHENYL PHEKYL ETH
3428 BIS (2-CHLOROISOPROPYL) E
352B HEXACHLOROBUTADIEKE
353B HEXACHLOROCYCLOPENTADIENE
3548 ISOPHORONE
3S5B HAPHTHALEHE
3S6B NITROBENZENE
357A 2-HITROPHEHOL
356A 4-NITROPHENOL
359A 2,4-DINITROPHENOL
360A 4.6-DINITRO-O-CRESOL
3628 H-NITROSODIPHENYLAniNE
364A PENTACHLOROPHENOL
365A PHENOL
366B BIS (2-ETHYLHEXYL) PHTHAL
368B DI-N-BUTYL PHTHALATE
369B DI-N-OCTYL PHTHALATE
370B DIETHYL PHTHALATE
371B DIMETHYL PHTHALATE
3728 BENZO(A)ANTHRANCENE
373B BENZO(A)PYRENE
374B BENZOCBIFLUORANTHEKE
375B BENZO(K>FLUORANTHENE
376B CHRYSENE
377B ACENAPHTHYLENE
378B ANTHRACENE
379B BEKZOCGHDPERYLENE
3808 FLUORENE
3318 PHENANTHREKE
38MB PYRENE
702B BETA NAPHTHYLAHINE
703B ALPHA PICOLIKE
70MB DIBEKZOTHIOPHENE
705B DIBENZOFURAH
7068 N-DODECANE C12
707B DIPHENYLAMINE
708B DIPHENYLETHER
709B ALPHA TERPINEOL
7108 STYREME
711B DI-N-BUTYL AOINE
712B BIPHENYL
713B P-CYMEKE
7178 N-DECAHE CIO
719B N-HEXADECAHE C16
721B N-EICOSANE C20
723B N-TETRACOSANE C2M
726B N-TRIACONTANE C30
E5»3 SAnGRF
TOTAL TOTAL
OBS LABS
10
8
9
9
8
9
9
9
9
10
10
10
11
10
12
10
g
8
11
11
12
9
11
5
11
1 1
4
12
8
1 1
9
5
11
12
11
9
12
12
1 1
9
1 1
9
9
12
11
1 1
9
12
10
10
6
9
10
10
1 1
8
9
6
10
2
7
9
9
11
12
9
12
nu
4.63
4 . 47
4.66
4.66
4.88
4.64
4.83
4.69
4.60
4.63
4.64
4.72
4.68
4.69
4.66
4.57
4.69
4.66
4.79
4.71
4.71
4.66
4.71
4.60
4.69
4.66
4.65
4.65
4.55
4.58
4.62
4.56
4.63
4.58
4.81
4.72
4.71
4.79
4.77
4.65
4.70
4.83
4.51
4.64
4.73
4.61
4.67
4.63
4. 65
4.67
4. 69
4.54
4.69
4.67
4.71
4.69
4.66
4.59
4.68
3.46
4.65
4.63
4.21
4.73
4.76
4.66
4.70
S E
0.06
0.42
0.06
0.03
0.45
0.17
0.25
0. 14
0.02
0.07
0.09
0. 15
0. 15
0. 13
0.06
0. 13
0.10
0.05
0.25
0. 12
0.09
0.07
0.22
0.07
0. 10
0.07
0.06
0. 08
0.08
0.09
0.07
0.04
0.08
0.00
0. 17
0.11
0.11
0.13
0. 12
0. 13
0.16
0.33
0.11
0. 14
0. 13
0.14
0.11
0.05
0.02
0.10
0.55
0. 10
0.07
0.06
0.33
0. 15
0.06
0. 18
0. 19
0 .00
0.05
0.08
0.26
0.09
0.22
0.07
0. 17
S A
0.08
0.36
0.06
0.05
0.42
0. 12
0.26
0. 18
0. 13
0.05
0.06
0. 14
0.15
0.09
0.04
0.05
0.06
0. 10
0.22
0.11
0. 15
0.06
0. 18
0.04
0.09
0.08
0.04
0.06
0. 15
0.07
0.07
0.11
0.08
0. 14
0. 10
0.05
0.06
0. 14
0. 12
0.07
0.09
0.39
0. 10
0.19
0. 13
0. 15
0.07
0.11
0.05
0.07
0. 13
0. 14
0.11
0.07
0.23
0. 14
0.07
0. 12
0.14
2.93
0. 12
0.06
0.24
0.11
0. 19
0 .04
0.12
X VAR DUE
TO LAB
39.55
57.01
47.61
28.45
53.69
66.44
48.87
39.72
2.02
72.02
68.46
53.40
52.55
£6.03
65.33
86.37
72.61
23.82
57.26
53.15
27.58
57.29
58.39
76.40
52.24
47.48
64.65
66.21
21:24
58.76
47.09
9.35
51.25
0.00
74.49
81 .78
78.01
43.72
53.22
76.50
75.95
41 .07
54.83
37.25
51.03
46. 18
69.33
14.31
20.42
57.66
95.0"
33.77
32.39
38.41
66.93
54.56
46.45
68.35
64. 12
0.00
11.92
60.31
52.90
38. 2«
58.0 1
77.54
68.80
1-8
-------
Appendix J
BINOMIAL CALCULATIONS FOR MULTIPLE TESTS
Because of the large number of compounds that may be tested in
Method 1625A, the individual compound test criteria probability levels are
determined in the start-up and continuing QA/QC tests to account for the
simultaneous testing of multiple compounds. In other EPA method validation
studies, the compound-specific performance specifications have usually been
determined using a 5 percent probability level. However, for Method 1625,
if the individual test level is left at .05, the chance that at least one
test will fail approaches certainty as the number of tests increases. In
particular, for the start-up test on Method 1625A, there are over 150
compounds, each tested for precision and accuracy, for a total of over 300
tests. If each item is tested at the .05 level, the odds are about 1 in
5 million* of all tests being passed, even if the equipment is perfect, due
to random variation, assuming tests are passed or failed independently.
Two factors can be adjusted to account for this effect: the rejection
level for the test can be made smaller, and a retest can be allowed for
those items that failed the first round. Table J-l presents the
probabilities associated with various possibilities. Assume that N tests
are performed in the first round, each with individual test level p. In the
calculations that follow, it is assumed that the results for each individual
test are independent.
The probability of failure for one or more items on the first round is
* .95300 = 2 x ID'7
J-l
-------
Table J-l
PROBABILITY OF FAILING QUALITY CONTROL TESTS
Number of
Tests
10
50
60
120
150
300
Individual
Test Level
0.050
0.020
0.010
0.001
0.050
0.020
0.010
0.001
0.050
0.020
0.010
0.001
0.050
0.020
0.010
0.001
0.050
0.020
0.010
0.001
0.050
0.020
0.010
0.001
Probability
Fall Round 1
0.401
0.183
0.096
0.010
0.923
0.636
0.395
0.049
0.954
0.702
0.453
0.058
0.998
0.911
0.701
0.113
1.000
0.952
0.779
0.139
1.000
0.998
0.951
0.259
Probability
Fall Round 2
0.025
0.004
0.001
0.000
0.118
0.020
0.005
0.000
0.139
0.024
0.006
0.000
0.259
0.047
0.012
0.000
0.313
0.058
0.015
0.000
0.528
0.113
0.030
0.000
J-2
-------
The average probability of failure in the second round is obtained by averaging
the probabilities of failure given K failures in the first round, i.e.,
P(fail in round 2) = 1 - £ HJ) pK (l-p)N"K (l-p)K .
K=0
As the table demonstrates, even for small values of N, there is a
significant probability of failure in the first round with .05 level tests,
though the probability of failure on the second round is quite small. For
300 tests, even with the retest allowed, the overall probability of failure
is over 50 percent. Dropping the test level to .01 decreases the
second-round failure probability to under 5 percent, and therefore this
would be the recommended procedure in situations with more than a few tests.
In order to avoid the second round of tests, smaller test levels are
necessary. For instance, for 50 tests, if the test levels are set at .001,
the chance of failing on one or more test criteria on the first round is
reduced to less than 5 percent. This would allow a test procedure which can
be performed in one round of testing. For more than 50 tests, even smaller
rejecton levels would be necessary. For instance, an individual level of
.0001 would achieve 5 percent overall for up^to 500 tests.
In considering a two-round test, it would be useful to calculate limits
on the number of failures in the first round of testing, such that if the
analyst observes this many failures or more, he will not waste time with a
second round of testing, but instead proceed to correcting and recalibrating
his instrumentation. These limits would not be considered part of the actual
test procedure, but instead could be considered as cost/benefit guidelines
for the analyst in deciding whether to attempt the second round of testing.
A reasonable way to calculate such a limit involves a retrospective
test of the hypothesis that the test failures are not actually occurring at
the specified level p, and suggests that the operator abandon the second
round if a binomial test with K failures out of N tries rejects the level p
at significance level .05.
J-3
-------
If this many failures are seen in the first round, it is highly likely
that there is a problem with the instrument, and the chances of passing the
second round are probably low. (Note this does not imply the converse, since
if there are problems with only a few compounds, only a few failures might
be seen in the first round and the problem compounds will only be detected
on the second round of testing.) This cutoff number depends on both the
number of initial tests N and the individual level p. The recommended value
of K for each current EPA analytical method is given in Table J-2.
Table J-2
FIRST-ROUND CUTOFFS FOR TWO-ROUND TESTING
Method
601
602
602/605
606
607
608
609
610
611
612
613
624
625 A
625 B/N
1624
1625A
Number of
Compounds
28
7
2
6
3
24
4
16
5
9
1
31
12
48
60
154
Number of
Start-up
Items
56
14
4
12
6
48
8
32
10
18
2
62
24
96
120
308
Individual
p Level
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.05
.01
Cutoff for1
Start-up
7
3
2
3
2
6
3
5
3
4
2
7
4
9
11
7
Cutoff for2
Ongoi ng
4
2
2
2
2
4
2
3
2
3
1
5
3
6
7
5
1
N = number of start-up items
"N = number of compounds
J-4
-------
Appendix K
DERIVATION OF QUALITY CONTROL LIMITS FOR ACCURACY
If we observe a test series Xj, ... XN independently drawn from a
normal distribution with unknown mean u and unknown variance o , the mean
and variance can be estimated by
N
7 = TT 2- X.
N -1.1 i
N
S2 = Jy L (X. - Y)2
N-l j=1 i
A 100{l-p) percent confidence interval for a single independent future
observation X from the same distribution ("prediction interval") can be
constructed by noting that X - X" has mean zero and variance (1 + IT), hence
+ )S, X + tN_1(l
with probability exactly 1-p, where t^_^ is the inverse cumulative
t distribution with N-l degrees of freedom. All of the quality control
limits formulas for accuracy used in this report are extensions of this
concept.
Known Mean
If u is known, the interval can be replaced by
with probability 1-p.
K-l
-------
Lognormal Data
If -Instead of X and the X^ being distributed normally, they have a
lognormal distribution, with logarithmic mean u and logarithmic variance a ,
o
the limit can be derived by letting Y. = log (X.) and computing Y and SY, the
2
analogous estimates of u and a . Because of the monotonlclty of the log
transform, the prediction interval for the future value of Y = log (X) can
be exponentiated to obtain
X e (exp[Y - tN_1(l - f) yd * jj)SY]' exp[Y + tN_1(l -
with probability 1-p.
Average of Lognormal Values
Because the start-up test is to be based on the arithmetic average of
four observations, we consider the case where we are interested in a
prediction interval for the average of n future values 7 when the data are
2
drawn from a lognormal distribution, with parameters u and a . Even though
7 will have neither a normal nor a lognormal distribution, for small values
of n the distribution will be.very similar to a lognormal distribution.
(See for instance the EPA Development Document for Electroplating,
Appendix E.) Therefore, we let
Y = log (7n)
and derive a prediction interval for Y which can then be exponentiated to
produce a prediction interval for 7 .
By standard properties of the lognormal distribution and averaging, 7
has mean
1 2
m = exp(u + -p )
and variance « ?
m n /n ,
where „ ?
n = exp(a ) - 1
K-2
-------
By the delta method (see for instance Rao, p 388) applied to
f(x) = log(x), Y = log dn) will have mean
f(«n) + f'(m) E(Yn - m) + ^f"(m) E(7n - m)2 + ...
+ 1 2 1 n2
= » f - I n '
2
Similarly expanding f (X) around X = m, subtracting the square of the mean,
and dropping higher order terms shows that Y will have variance
2f'(m)2 E(7 - m)2 + ...
1 J 2
l . m n .
'7 — -
2
_ _n
~ n
2 ' 2
Since u and a are estimated by Y.. and SY as before, we have that
•*• -S - -
Y -
2 2
(where ny = exp(Sy) -1) has asymptotic mean zero and variance approximately
2 2 . .2,4
n + ° + 1/1 i\ ^g
n IT 4"(1 ' nj TTTTT '
2222 2
using the fact that n = exp(a ) - 1 a for small o to combine the Sv and
22
riy terms and noting that Sy and YN are independent.
Therefore, an approximate lOO(l-p) percent confidence interval for Y
can be computed as
(exp[(YN * | S2 - -^y/n) - tN_1(l - f)' S] ,
exp[(YN + I S2 - -Jn2/n) + tN_1(l - |)' S]) ,
K-3
-------
where
2, . .2 1 . 1M I.2 SY
nY/n * Sy H * 7(1-)
Variance Components
If the data are drawn from a hierarchical variance structure
X.. = u + a< + e.. 1 = 1, ..., I
Mj - " U1 MJ
j = 1, .... J
2 2
where a. ~ N(0, a ) and e.. ~ N(0, a ) and are independent, the estimates M,
2 2 ° iJ 2 e2
Sa> and Se of the parameters ua, and a~, respectively are obtainable through
a variance components analysis (i.e. the maximum likelihood variance
components analysis computed by BMDP program 3V). The asymptotic variance
of M will be
2/ + 2/
VI ff«/IJ '
2 2
KJ-DS /a will have a chl-squared distribution with I(J-l) degrees of
22
freedom, and (I-l)Sa/aa can be approximated by a chi-squared distribution
with 1-1 degrees of freedom.
Since the difference X-M has mean 0 and asymptotic variance
2222
aa * ae * aa/J * ae/IJ> an aPProximate lOO(l-p) percent prediction
interval is given by
(M - td(l - ) S, M + td(l - |) S)
where S = \/S2 + S2. + S2/I + S^/IJ . .
2 2
Because Sa and Sg have different degrees of freedom, the choice of
d = min(KJ-l), 1-1) gives the conservatively widest t-interval, and
ensures coverage probability of at least 1-p.
K-4
-------
Applications
Combinations of these techniques yield the prediction intervals for
each test series, as described below.
The limits for the arithmetic average (7 ) of the four startup amounts
are obtained by combining the "average of lognormal" and variance components
ideas above to give
exp[(m
V^^^^— -^^^— —'-•— »-^^^^ " ....... ^^^^^^^^^
(SE + nA/n + SE/L * S
A/N
2 2
where M, S., and SE are as above, ru = exp(S.) - 1, n is the number of
replicates in the start-up test (i.e., 4), N is the number of measurements in
the study, L is the number of laboratories in the study, and t(d, l-p/2) is
the appropriate two-sided t value for test level p, based on d degrees of
freedom. In order to produce conservative intervals, the degrees of freedom
used was the minimum of those appropriate to either of the variances
appearing in the formula, i.e., min(N-L, L-l). (For the WTR series 1 and 3
calculations, L-l was used.)
The ongoing calibration verification limits are obtained from the
analysis of the CAL type samples as
expCln(lOO) * t(d, 1 - |)SAJ ,
where d = N-L, the degrees of freedom in the estimation of S., using
the lognormal and known-mean concepts.
The ongoing QA/QC limits are obtained from the analysis of the WTR
type samples _ __
expCM * t(d, l-p/2) ys2. + SJ; + S*/L + SJ-/N)] ,
where d = min(N-L, L-l) using the lognormal and variance components concepts.
K-5
-------
Appendix L
DERIVATION OF QUALITY CONTROL LIMITS FOR PRECISION
Since the start-up precision test for this method is to be based on the
standard deviation of the amounts measured 1n the four start-up samples, we
need to determine the distribution of
n
O _ 1 V IV T7 \2
1 = 1 ' "
where the X. are distributed a lognormally, with logarithmic mean u and
2
logarithmic variance a . As S does not appear to have any common
distributional form, a simulation was performed to estimate the percentiles,
as described below. The distribution of S depends Intrinsically upon the
2
logarithmic variance o , but u can be removed from consideration by noting
that S1 = S/exp(u) can be considered to come from a lognormal distribution
2
with parameters 0 and o , by scale translation of the lognormal. Finally,
2
for a range of o values, the upper quantiles of S1 were determined by
simulation. The results are shown in Table L-l as Q(l-p, a) for p = .05
and .01. The simulations were performed with SAS, using 10,000 replicates,
and the quantiles were estimated with PROC UNIVARIATE, definition 4.*
An approximate 100(l-p)th percentile of S, then would be estimated by
2 2
exp(Y..) Q(l-p, Sy), where Y., and SY are the estimates of u and a based on
the logarithms of the data, as discussed in Appendix K. In order to correct
* th
Let X,v < ... X/ be the ordered observation. For the t
£ /n)
percentile, where q = t/100, let (n+l)q = j + g, where j is the integer
part and g the fractional part of (n+l)q. Then the tth percentile by
definition 4 is the weighted average of adjacent order statistics aimed at
X(q[n+l])* 1'-e- {1-9)X(j) * 9X(j+l)« where X(n+l) taken to be
See the SAS User's Guide: Basics, p. 579.
L-l
-------
2 2
for the effect of the use of the estimated Sy in the place of a in Q, a
correction term of
), d) =
was suggested, where F and C are the inverse cumulative distributions of the
F and chi-squared distributions, respectively. This correction represents
the ratio between the percent!'les of F-limits and chi-squared limits for a
standard deviation in the ordinary (nonlogarithmic) situation, and should be
approximately correct for use in this situation.*
The precision limit on the standard deviation was then calculated as
exp(M) QU-p, SA) K(l-p, d) ,
where Q is the quantile function at 1-p of SA tabulated above, linearly
interpolated; K is the approximate correction factor for the estimation of
SA; and d is the degrees of freedom in the estimate of SA, e.g., N-L.
In a nominal-scale analysis from N(u, a2), the test with a2 known is
to compare s/a with a chi-square limit: yCp j^l-pj/n-l. If a2 is
unknown, the tests is an F-test comparing S/S with /F , d(l-p).
The ratio of these two limits is the difference due to estimating a2 in
the nominal-scale case, and should be approximately appropriate in the
situation of interest.
L-2
-------
Table L-l
PERCENTILES OF THE STANDARD DEVIATION
OF FOUR OBSERVATIONS FROM LN(0, o2)
Logarithmic 95th 99th
Std(g) PercentHe Percentile
.02 0.0319 0.0385
.04 0.0639 0.0774
.06 0.0963 0.1166
.08 0.1290 0.1559
.10 0.1623 0.1694
.15 0.2476 0.3032
.20 0.3397 0.4186
.25 0.4362 0.5474
.30 0.5410 0.7010
.35 0.6595 0.8728
.40 0.7888 1.0673
.45 0.9336 1.2835
.50 1.0906 1.4559
.60 1.4559 2.1796
.70 1.9180 3.0131
.80 2.5033 4.1054
.90 3.2186 5.5222
1.00 4.1196 7.4720
1.10 5.2213 10.0262
1.20 6.6588 13.3723
L-3
-------
08 June 19S4 Draft
Appendix M
Method 1625 Revision B
Semivolatile Organic Compounds by Isotope Dilution GCMS
1 Scope and application
1.1 This method is designed to determine the semi volatile toxic
organic pollutants associated with the 1976 Consent Decree and
additional compounds amenable to extraction and analysis by
capillary column gas chromatography-mass spectrometry (GCMS).
1.2 The chemical compounds listed in tables 1 and 2 may be
determined in municipal and industrial discharges by this method.
The method is designed to meet the survey requirements of Effluent
Guidelines Division
-------
2 Summary of method
2.1 Stable isotopically labeled analogs of the compounds of
interest are added to a one liter wastewater sample. The sample, is
extracted at pH 12-13, then at pH <2. with methylene chloride using
continuous extraction techniques. The extract is dried over sodium
sulfate and concentrated to a volume of one mL. An internal
standard is added to the extract, and the extract is injected into
the gas chromatograph (GO. The compounds are separated by SC and
detected by a mass spectrometer (MS). The labeled compounds serye
to correct the variability of the analytical technique.
2.2 Identification of a compound (qualitative analysis) is
performed by comparing the GC retention time and background
corrected^ characteristic spectral masses with those of authentic
standards.
2.3 Quantitative analysis is performed by GCMS using extracted ion
current profile (EICP) areas. Isotope dilution is used when
labeled compounds are available; otherwise, an internal or external
standard method is used.
2.4 Quality is assured through reproducible calibration and
testing of the extraction and GCMS systems.
3 Contamination and interferences
3.1 Solvents, reagents, glassware, and other sample processing
hardware may yield artifacts and/or elevated baselines causing
misinterpretation of chromatograms and spectra. All materials
shall be demonstrated to be free from interfernces under the
conditions of analysis by running method blanks initially and with
each sample lot (samples started through the extraction process on
a given 3 hr shift, to a maximum of 20). Specific selection of
1625B -2-
-------
reagents and purification of solvents by distillation in all-glass
systems may be required. Glassware and, where possible, reagents
are cleaned by solvent rinse and baking at 450 xC for one hour
minimum.
3.2 Interferences coextracted from samples will vary considerably
from source to source, depending on the diversity of the industrial
complex or municipality being samples.
4 Safety
4.1 The toxicity or carcinogenic!ty of each compound or reagent
used in this method has not been precisely determined; however,
each chemical compound should be treated as a potential health
hazard. Exposure to these compounds should be reduced to the
lowest possible level. The laboratory is responsible for
maintaining a current awareness file of OSHA regulations regarding
the safe handling of the chemicals specified in this method. A
reference file of data handling sheets should also be made
available to all personnel involved in these analyses. Additional
information on laboratory safety can be found in references 2-4.
4.2 The following compounds covered by this method have been
tentatively classified as know or suspected human or mammalian
carcinogens: benzo(a)anthracene, 3,3'-dichlorobenzidine,
benzo(a)pyrene, dibenzo (a,h)anthracene, N—nitrosodimethyl amine, and
B-naphthylamine. Primary standards of these compounds shall be
prepared in a hood, and a NIOSH/MESA approved toxic gas respirator
should be worn when high concentrations are handled.
5 Apparatus and materials
5.1 Sampling equipment for discrete or composite sampling.
-------
5.1.1 Sample bottle, amber glass, 1.1 liters minimum. If amber
battles are not available, samples shall be protected from light.
Bottles are detergent water washed, then solvent rinsed or baked at
450 C for one hour minimum before use.
5.1.2 Bottle caps—threaded to fit sample battles. Caps are lined
with Teflon. Aluminum foil may be substituted if the sample in not
corrosive. Liners are detergent water washed, then reagent water
(section 6.5) and solvent rinsed, and baked at approx 200 xC for
one hour minimum before use.
5.1.3 Compositing equipment—automatic or manual compositing
system incorporating glass containers for collection of a mimimum
1.1 liters. Sample containers are kept at 0 to 4 xC during
sampling. Glass or Teflon tubing only shall be used. If the
sampler uses a peristaltic pump, a. minimum length of compressible
silicone rubber tubing may be used in the pump only. Before use,
the tubing is thoroughly rinsed with methanol, followed by repeated
rinsings with reagent water (section 6.5) to minimise sample
contamination. An integrating flow meter is used to collect
proportional composite samples.
5.2 Continuous liquid-liquid extractor Teflon or glass connecting
joints and stopcocks without lubrication (Hershberg-Wolf Extractor)
one liter capacity. Ace Glass 6841-10, or equivalent.
5.3 Drying column—15 to 20 mm i.d. Pyrex chromatographic column
equipped with coarse glass frit or glass wool plug.
5.4 Kuderna-Danish (K-D) apparatus
5.4.1 Concentrator tube—10mL, graduated (Kontes K-570050-1025, or
equivalent) with calibration verified. Ground glass stopper (size
19/22 joint) is used to prevent evaporation of extracts.
5.4.2 Evaporation flask—500 ml_ (Kontes K-570001-0500, or
1625B -4-
-------
equivalent), attached to concentrator tube with springs (Kontes
K-662750-0012).
5.4.3 Snyder column—three ball macro (Kontes K-503000-0232, or
equi valent).
5.4.4 Snyder column—two bal.l micro (Kontes K-469002-0219, or
equivalent).
5.4.5 Boiling chips—approx 10/40 mesh, extracted with methylene
chloride and baked at 450 xC for one hr minimum.
5.5 Water bath—heated, with concentric ring cover, capable of
temperature control (q 2 xC), installed in a fume hood.
5.6 Sample vials—amber glass, 2-5 ml_ with Teflon-lined screw
cap.
5.7 Analytical balance—capable o-f weighing 0.1 mg.
5.8 Gas chromatograph—shall have splitless or on-column injection
port for capillary column, temperature-program with 30 xC hold, and
shall meet all of the performance specifications in section 12.
5. S.I Column—30 q 5 m :< 0.25 q 0.02 mm i.d. 57. phenyl , 94V.
methyl, I"/, vinyl silicone bonded phase fused silica capillary
column (J & W DB-5, or equivalent).
5.9 Mass spectrometer 70 eV electron impact ionization, shall
repetitively scan from 35 to 450 amu in 0.95 to 1.00 second, and
shall produce a unit resolution (valleys between m/z 441-442 less
than 10 percent of the height of the 441 peak), background
corrected mass spectrum from 50 ng decaf 1uorotriphenylphosphine
(DFTF'P) introduced through the GC inlet. The spectrum shall meet
the mass-intensity criteria in table 5 (reference 5). The mass
spectrometer shall be interfaced to the GC such that the end of the
capillary column terminates within one centimeter of the ion source
but does not intercept the electron or ion beams. All portions of
1&25B -5-
-------
the column which connect the GC to the ion source shall remain at
or above the column temperature during analysis to preclude
condensation of less volatile compounds.
5.10 Data system—shall collect and record MS data, store
mass-intensity data in spectral libraries, process GCMS data,
generate reports, and shall compute and record response factors.
5.1(3.1 Data acquisition—mass spectra shall be collected
continuously throughout the analysis and stored on a mass storage
device.
5.10.2 Mass spectral libraries—user created libraries containing
mass spectra obtained from analysis of authentic standards shall be
employed to reverse search GCMS runs for the compounds of interest
(section 7. 2) .
5.10.3 Data processing—the data system shall be used to search,
locate, identify, and quantify the compounds of interest in each
GCMS analysis. Software routines shall be employed to compute
retention times and peak areas. Displays of spectra, mass
chromatograms, and library comparisons are required to verify
results.
5.10.4 Response factors and multipoint calibrations—the data
system shall be used to record and maintain lists of response
factors (response ratios for isotope dilution) and multi-point
calibration curves (section 7). Computations of relative standard
deviation (coefficient of variation) are useful for testing
calibration linearity. Statistics on initial (section 3.2) and
on-going (section 12.7) performance shall be computed and
maintai ned.
6 Reagents and standards
1625B -6-
-------
6.1 Sodium hydroxide—reagent grade, 6N in reagent water.
6.2 Sulfuric acid—reagent grade, 6N in reagent water.
6.3 Sodium sul-fate—reagent grade, granular anhydrous, rinsed with
methylene chloride (20 mL/g) and conditioned at 450 xC for one hour
mini mum.
6.4 Methylene chloride—distilled in glass (Burdick and Jackson,
or equivalent).
6.5 Reagent water water in which the compounds of interest and
interfering compounds are not detected by this method.
6.6 Standard solutions—purchased as solutions or mixtures with
certification to their purity, concentration, and authenticity, or
prepared from materials of known purity and composition. If
compound purity is 96 percent or greater, the weight may be used
without correction to compute the concentration of the standard.
When not being used, standards are stored in the dark at -20 to -10
xC in screw-capped vials with Teflon-lined lids. A mark is placed
on the vial at the level of the solution so that solvent
evaporation loss can be detected. The vials are brought to room
temperature prior to use. Any precipitate is redissolved and
solvent is added if solvent loss has occurred.
6.7 Preparation of stock solutions—prepare in methylene chloride,
benzene, p-dioxane, or a mixture of these solvents per the steps
below. Observe the safety precautions in section 4. The large
number of labeled and unlabeled acid, base/neutral, and Appendix C
compounds used for combined calibration (section 7) and calibration
/
verification (12.5) require high concentrations (approx 40 mg/mL)
when individual stock solutions are prepared, so that dilutions of
mixtures will permit calibration with all compounds in a single set
of solutions. The working range for most compounds is 10-200
1625B -7-
-------
fg/mL. Compounds with a reduced MS response may be prepared at
higher concentrations.
6.7.1 Dissolve an appropriate amount of assayed re-ference material
in a suitable solvent. For example, weigh 400 mg naphthalene in a
10 mL ground glass stoppered volumetric -flask and fill to the mark
with benzene. After the naphthalene is completely dissolved,
transfer the solution to a 15 mL vial with Teflon-lined cap.
6.7.2 Stock standard solutions should be checked for signs of
degradation prior to the preparation of calibration or performance
test standards. Qaulity control check samples that can be used to
determine the accuracy of calibration standards are available from
the US Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Qhio 4526S.
6.7.3 Stock standard solutions shall be replaced after six months,
or sooner if comparison with quality control check samples
indicates a change in concentration.
6.8 Labeled compound spiking solution—from stock standard
solutions prepared as above, or from mixtures, prepare the spiking
solution at a concentration of 200 fq/mL, or at a concentration
appropriate to the MS response of each compound.
6.9 Secondary standard—using stock solutions (section 6.7),
prepare a secondary standard containing all of the compounds in
tables 1 and 2 at a concentration of 400 fq/mL, or higher
concentration appropriate to the MS response of the compound.
6.10 Internal standard solution—prepare 2,2'-difluorobiphenyl
(DFB) at a concentration of 10 mg/mL in benzene.
6.11 DFTPP solution—prepare at 50 fg/mL in acetone.
6.12 Solutions for obtaining authentic mass spectra (section
7.2)—prepare mixtures of compounds at concentrations which will
1625B -S-
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assure authentic spectra are obtained -for storage in libraries.
6.13 Calibration solutions—combine 0.5 ml_ of the solution in
section 6.S with 25, 50, 125, 250, and 500 fL o-f the solution in
section 6.9 and bring to 1.00 ml_ total volume each. This will
produce calibration solutions o-f nominal 10, 20, 50, 100 and 200
fg/mL of the pollutants and a constant nominal 100 fg/mL of the
labeled compounds. Spike each solution with 10 fL of the internal
standard solution (section 6.10). These solutions permit the
relative response (labeled to unlabeled) to be measured as a
•function of concentration (section 7.4).
6.14 Precision and recovery standard—used for determination of
initial (section 8.2) and on-going (section 12.7) precision and
recovery. This solution shall contain the pollutants and labeled
compounds at a nominal concentration of 100 fg/mL.
6.15 Stability of solutions—all standard solutions (sections 6.S
- 6.14) shall be analyzed within 48 hours of preparation and on a
monthly basis thereafter for signs of degradation. Standards will
remain acceptable if the peak area at the quantitation mass
relative to the DFB internal standard remains within q 15 percent
of the area obtained in the initial analysis of the standard.
7 Calibration
7.1 Assemble the GCMS and establish the operating conditions in
table 3. Analyze standards per the procedure in section 11 to
demonstrate that the analytical system meets the detection limits
in tables 3 and 4, and the mass-intensity criteria in table 5 for
50 ng DFTPP-
7.2 Mass spectral libraries—detection and identification of
compounds of interest are dependent upon spectra stored in user
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created libraries.
7.2.1 Obtain a mass spectrum of each pollutant, labeled compound,
and the internal standard by analyzing an authentic standard either
singly or as part of a mixture in which there is no interference
between closely eluted components. That only a single compound is
present is determined by examination of the spectrum. Fragments
not attributable to the compound under study indicate the presence
of an interfering compound.
7.2.2 Adjust the analytical conditions and scan rate (for this
test only) to produce an undistorted spectrum at the BC peak
maximum. An undistorted spectrum will usually be obtained if five
complete spectra are collected across the upper half of the BC
peak. Software algorithms designed to "enhance" the spectrum may
eliminate distortion, but may also eliminate authentic masses or
introduce other distortion.
7.2.3 The authentic reference spectrum is obtained under DFTPP
tuning conditions (section 7.1 and tabl'e 5) to normalize it to
spectra from other instruments.
7.2.4 The spectrum is edited by saving the 5 most intense mass
spectral peaks and all other mass spectral peaks greater than 10
percent of the base peak. This edited spectrum is stored for
reverse search and for compound confirmation.
7.3 Analytical range—demonstrate that 20 ng anthracene or
phenanthrene produces an area at m/z 173 approx one-tenth that
required to exceed the linear range of the system. The exact value
must be determined by experience for each instrument. It is used
to match the calibration range of the instrument to the analytical
range and detection limits required, and to diagnose instrument
sensitivity problems (section 15.4). The 20 fq/mL calibration
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standard (section 6.13) can be used to demonstrate this
performance.
7.3.1 Polar compound detection—demonstrate that unlabeled
pentachlorophenol and benzidine are detectable at the 50 fg/mL
level (per all criteria in section 13). The 50 fg/mL calibration
standard (section 6.13) can be used to demonstrate this
performance.
7.4 Calibration with isotope dilution—isotope dilution is used
when 1) labeled compounds are available, 2) interferences do not
preclude its use, and 3) the quantitation mass extracted ion
current profile (EICP) area for the compound is in the calibration
range. If any of these conditions preclude isotope dilution,
internal or external standard methods (section 7.5 or 7.6) are
used.
7.4.1 A calibration curve encompassing the concentration range is
prepared for each compound to be determined. The relative response
(pollutant to labeled) vs concentration in standard solutions is
plotted or computed using a linear regression. The example in
Figure 1 shows a calibration curve for phenol using phenal-d5 as
the isotopic diluent. Also shown are the q 10 percent error limits
(dotted lines). Relative Response (RR) is determined according to
the procedures described below. A minimum of five data points are
employed for calibration.
7.4.2 The relative response of a pollutant to its labeled analog
is determined from isotope ratio values computed from acquired
data. Three isotope ratios are used in this process:
RM = the isotope ratio measured for the pure pollutant.
Rv = the isotope ratio measured for the labeled compound.
Rm = the isotope ratio of an analytical mixture of pollutant and
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labeled compounds.
The m/z's are selected such that RM > Rv. If Rm is not
between 2RV and 0.5RM!i the method does not apply and the sample
is analyzed by internal or external standard methods.
7.4.3 Capillary columns usually separate the pollutant-labeled
pair, with the labeled compound eluted first (figure 2). For this
case,
R« = [area nu/z3/l, at the retention time of .the pollutant
(RTa>.
Ry = 1/Carea ma/z3, at the retention time of the labeled
compound RTi)
Rm = Carea at mi/z (at RTa)D/Carea at ms/z (at RTi)3, as
measured in the mixture of the pollutant and labeled compounds
(figure 2), and RR = Rm.
7.4.4 Special precautions are taken when the pollutant-labeled
pair is not separated, or when another labeled compound with
interfering spectral masses overlaps the pollutant (a case which
can occur with isomeric compounds). In this case, it is necessary
to determine the respective contributions of the pollutant, and
labeled compounds to the respective EICP areas. If the peaks are
separated well_enough to permit the data system or operator to
remove the contributions of the compounds to each other, the
equations in section 7.4.3 apply. This usually occurs when the
height of the valley between the two GC peaks at the same m/z is
less than 10 percent of the height of the shorter of the two
peaks. If significant GC and spectral overlap occur, RR is
computed using the fallowing equation:
RR =
-------
3B, and Rm is measured as shown in -figure 3C. For the example,
R« = 46100/4780 = 9.644, Ry = 2650/43600 = 0.0608, Rm =
49200/48300 = 1.019, and RR = 1.114.
7.4.5 To calibrate the analytical system by isotope dilution,
analyze a 1.0 fL aliquot of each of the calibration standards
(section 6.13) using the procedure in section 11. Compute the RR
at each concentration.
7.4.6 Linearity—if the ratio of relative response to
concentration for any compound is constant (less than 20 percent
coefficient of variation) over the 5 point calibration range, an
averaged relative response/concentration ratio may be used for that
compound; otherwise, the complete calibration curve for that
compound shall be used over the 5 point calibration range.
7.5 Calibration by internal standard—used when criteria for
isotope dilution (section 7.4) cannot be met. The internal
standard to be used for both acid and base/neutral analyses is
2,2'-difluorobiphenyl. The internal standard method is also
applied to determination of compounds having no labeled analog, and
to measurement of labeled compounds for intra-laboratory statistics
(sections 8.4 and 12.7.4).
7.5.1 Response factors—calibration requires the determination of
response factors (RF) which are defined by the following equation:
RF = (A. x d.)/(Ai. x C,), where
A. is the area of the characteristic mass for the compound in the
daily standard
Ai. is the area of the characteristric mass for the internal
standard
C±m is the concentration of the internal standard (fg/mL)
C. is the concentration of the compound in the daily standard
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(fq/mL)
7.5.1.1 The response factor is determined -for at least five
concentrations appropriate to the response of each compound
(section 6.13); nominally, 10, 20, 50, 100, and 200 fg/mL. The
amount of internal standard added to each extract is the same (100
fg/mL) so that Ct, remains constant. The RF is plotted vs
concentration for each compound in the standard (C.) to produce a
calibration curve.
7.5.1.2 Linearity—if the response factor
-------
(section 12.5) by analyzing the 100 fg/mL calibration standard
(section 6.13). Recalibration is required only if calibration
verification (section 12.5) criteria cannot be met.
S Quality assurance/quality control
S.I Each laboratory that uses this method is required to operate a
formal quality assurance program. The minimum requirements of this
program consist of an initial demonstration of laboratory
capability, analysis of samples spiked with labeled compounds to
evaluate and document data quality, and analysis of standards and
blanks as tests of continued performance. Laboratory performance
is compared to established performance criteria to determine if the
results of analyses meet the performance characteristics of the
method.
8.1.1 The analyst shall make an initial demonstration of the
ability to generate acceptable accuracy and precision with this
method. This ability is established as described in section 3.2.
8.1.2 The analyst is permitted to modify this method to improve
separations or lower the costs of measurements., provided all
performance specifications are met. Each time a modification is
made to the method, the analyst is required to repeat the procedure
'in section 8.2 to demonstrate method performance.
8.1.3 Analyses of blanks are required to demonstrate freedom from
contamination. The procedures and criteria for analysis of a blank
are described in section 8.5.
8.1.4 The laboratory shall spike all samples with labeled
compounds to monitor method performance. This test is described in
section 8.3. When results of these spikes indicate atypical method
performance for samples, the samples are diluted to bring method
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performance within acceptable limits (section 15).
8.1.5 The laboratory shall, on an on-going basis, demonstrate
through calibration verification and the analysis of the precision
and recovery standard (section 6.14) that the analysis system is in
control. These procedures are described in sections 12.1, 12.5,
and 12.7.
S. 1.6 The laboratory shall maintain records to define the quality
of data that is generated. Development of accuracy statements is
described in section B.4.
8.2 Initial precisian and accuracy—to establish the ability to
generate acceptable precisian and accuracy, the analyst shall
perform the following operations:
8.2.1 Extract, concentrate, and analyze two sets of four one-liter
aliquots (3 aliquots total) of the precision and recovery standard
(section 6.14) according to the procedure in section 10.
8.2.2 Using results of the first set of four analyses, compute the
average recovery (X) in fg/mL and the standard deviation of the
recovery (s) in fg/mL for each compound, by isotope dilution for
pollutants with a labeled analog, and by internal standard for
labeled compounds and pollutants with no labeled analog.
8.2.3 For each compound, compare s and X with the corresponding
limits for initial precisian and accuracy in table 3. If s and X
far all compounds meet the acceptance criteria, system performance
is acceptable and analysis of blanks and samples may begin. If,
however, any individual s exceeds the precisian limit or any
individual X falls outside the range far accuracy, system
performance is unacceptable for that compound.
NOTE: The large number of compounds in table 3 present a
substantial probability that one or more will fail the acceptance
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criteria when all compounds are analyzed. To determine if the
analytical system is out of control, or if the failure can be
attributed to probability, proceed as follows:
8.2.4 Using the results of the second set of four analyses,
compute s and X for only those compounds which failed the test of
the first set of -four analyses (section S.2.3). If these compounds
now pass, system performance is acceptable for all compounds and
analysis of blanks and samples may begin. If, however, any of the
same compounds fail again, the analysis system is not performing
properly for these compounds. In this event, correct the problem
and repeat the entire test (section 8.2.1).
S.3 The laboratory shall spike all samples with labeled compounds
to assess method performance on the sample matrix.
S.3.1 Analyze each sample according to the method beginning in
section 10.
8.3.2 Compute the percent recovery (P) of the labeled compounds
using the internal standard method (section 7.5).
8.3.3 Compare the labeled compound recovery for each compound with
the corresponding limits in table 8. If the recovery of any
compound falls outside its warning limit, method performance is
unacceptable for that compound in that sample. Therefore, the
sample is complex and is to be diluted and reanalyzed per section
15.4.
8.4 As part of the QA program for the laboratory, method accuracy
for wastewater samples shall be assessed and records shall be
maintained. After the analysis of five wastewater samples for
which the labeled compounds pass the tests in section 8.3, compute
the average percent recovery (P) and the standard deviation of the
percent recovery (sp) for the labeled compounds only. Express
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the accuracy assessment as a percent recovery interval from P -
2sp to P + 2sp. For example, if P = 907. and se = 107., the
accuracy interval is expressed as 70 - 110%. Update the accuracy
assessment for each compound on a regular basis (e.g. after each 5
- 10 new accuracy measurements).
3.5 Blanks—reagent water blanks are analyzed to demonstrate
freedom from contamination.
3.5.1 Extract and concentrate a blank with each sample lot
(samples started through the extraction process on the same 8 hr
shift, to a maximum of 20 samples). Analyze the blank immediately
after analysis of the precision and recovery standard (section
6.14) to demonstrate freedom from contamination.
8.5.2 If any of the compounds of interest (tables 1 and 2) or any
potentially interfering compound is found in a blank at greater
than 10 fq/L (assuming a response factor of 1 relative to the
internal standard for compounds not listed in tables 1 and 2),
analysis of samples is. halted until the source of contamination is
eliminated and a blank shows no evidence of contamination at this
level.
3.6 The specifications contained in this method can be met if the
apparatus used is calibrated properly, then maintained in a
calibrated state. The standards used for calibration (section 7),
calibration verification (section 12.5), and for initial (section
8.2) and on-going (section 12.7) precisian and recovery should be
identical, so that the most precise results will be obtained. The
GCMS instrument in particular will provide the most reproducible
results if dedicated to the settings and conditions required for
the analyses of semi-volatiles by this method.
8.7 Depending on specific program requirements., field replicates
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may be collected to determine the precision of the sampling
technique, and spiked samples may be required to determine the
accuracy of the analysis when internal or external standard methods
are used.
9 Sample collection, preservation, and handling
9.1 Collect samples in glass containers following conventional
sampling practices (reference 7). Composite samples ar,e collected
in refrigerated glass containers (section 5.1.3) in accordance with
the requirements of the sampling program.
9.2 Maintain samples at 0-4 A'C from the time of collection until
extraction. If residual chlorine is present, add 80 mg sodium
thiosulfate per liter of water. EPA methods 330.4 and 330.5 may be
used to measure residual chlorine (reference 8).
9.3 Begin sample extraction within seven days of collection, and
analyse all extracts within 40 days of extraction.
10 Sample extraction and concentration (See figure 4)
10.1 Labeled compound spiking—measure 1.00 q 0.01 liter of sample
into a glass container. For untreated effluents, and samples which
are expected to be difficult to extract and/or concentrate, measure
an additional 10.0 q 0. 1 ml_ and dilute to a final volume of 1.00 q
0.01 liter with reagent water in a glass container.
10.1.1 For each sample or sample lot (to a maximum of 20) to be
extracted at the same time, place three 1.00 q 0.01 liter aliquots
of reagent water in glass containers.
10.1.2 Spike 0.5 mL of the labeled compound spiking solution
(section 6.8) into all samples and one reagent water aliquot.
10.1.3 Spike 1.0 mL of the precision and recovery standard
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(section 6.14) into the two remaining reagent water aliquots.
10.1.4 Stir and equilibrate all solutions for 1-2 hr.
10.2 Base/neutral extraction—place 100-150 ml_ methylene chloride
in each continuous extractor and 200-300 in each distilling flask.
10.2.1 Pour the sample(s), blank, and standard aliquots into the
extractors. Rinse the glass containers with 50-100 mL methylene
chloride and add to the respective extractor.
10.2.2 Adjust the pH of the waters in the extractors to 12-13 with
6N NaOH while monitoring with a pH meter. Begin the extraction by
heating the flask until the methylene chloride is bailing. When
properly adjusted, 1-2 drops of methylene chloride per second will
fall from the condenser tip into the water- After 1—2 hours of
extraction, test the pH and readjust to 12-13 if required. Extract
for 18-24 hours.
10.2.3 Remove the distilling flask, estimate and record the volume
of extract (to the nearest. 100 mL) , and pour the contents through a
drying column containing 7 to £0 cm anhydrous sodium sulfate:
Rinse the distilling flask with 30-50 mL of methylene chloride and
pour through the drying column. Collect the solution in a 500 mL
K-D evaporator flask equipped with a 10 mL concentrator tube.
Seal, label as the base/neutral fraction, and concentrate per
sections 10.4 to 10.5.
10.3 Acid extraction—adjust the pH of the waters in the
extractors to 2 or less using 6N sulfuric acid. Charge clean
distilling flasks with 300-400 mL of methylene chloride. Test and
adjust the pH of the waters after the first 1-2 hr of extraction.
Extract for 13-24 hours.
10.3.1 Repeat section 10.2.3, except label as the acid fraction.
10.4 Concentration—concentrate the extracts in separate 500 mL
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K-;D -flasks equipped with 10 ml_ concentrator tubes.
10.4.1 Add 1 to 2 clean boiling chips to the -flask and attach a
three-ball macro Snyder column. Prewet the column by adding approx
one ml_ of methylene chloride through the top. Place the K-D
apparatus in a hot water bath so that the entire lower rounded
sur-face of the flask is bathed with steam. Adjust the vertical
position of the apparatus and the water temperature as required to
complete the concentration in 15 to 20 minutes. At the proper rate
of distillation, the balls of the column- will actively chatter but
the chambers will not flood. When the liquid has reached an
apparent volume of 1 ml_, remove the K-D apparatus from the bath and
allow the solvent to drain and cool for at least 10 minutes.
Remove the Snyder column and rinse the flask and its lowers joint
into the concentrator tube with 1-2 mL of methylene chloride. A
5-mL syringe is recommended for this operation.
10.4.2 For performance standards (sections 8.2 and 12.7) and for
blanks (section B.5), combine the acid and base/neutral extracts
\
for each at this point. Do not combine the acid and base/neutral
extracts for samples.
10.5 Add a clean boiling chip and attach a two ball micro Snyder
column to the concentrator tube. Prewet the column by adding
approx 0.5 mL methylene chloride through the top. Place the
apparatus in the hot water bath. Adjust the vertical position and
the water temperature as required to complete the concentration in
5-10 minutes. At the proper rate of distillation, the balls of the
column will actively chatter but the chambers will not flood. When
the liquid reaches an apparent volume of approx 0.5 mL, remove the
apparatus from the water bath and allow to drain and cool far at
least 10 minutes. Remove the micro Snyder column and rinse its
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lower joint into the concentrator tube with approx 0.2 mL of
methylene chloride. Adjust the -final volume to 1.0 mL.
10.6 Transfer the concentrated extract to a clean screw-cap vial.
Seal the vial with a Teflon-lined lid, and mark the level on the
vial. Label with the sample number and fraction, and store in the
dark at -20 to -10 xC until ready for analysis.
11 GCMS analysis
11.1 Establish the operating conditions given in tables 3 or 4 for
analysis of the base/neutral or acid extracts, respectively. For
analysis of combined extracts (section 10.-4.2), use the operating
conditions in table 3.
11.2 Bring the concentrated extract (section 10.6) or standard
(sections 6.13-6.14) to room temperature and verify that any
precipitate has redissolved. Verify the level on the extract
(sections 6.6 and 10.6) and bring to the mark with solvent if
required.
11.3 Add the internal standard solution (section 6.10) to the
extract (use 1.0 fL of solution per 0.1 mL of extract) immediately
prior to injection to minimize the possibility of lass by
evaporation, adsorption, or reaction. Mix thoroughly.
11.4 Inject a volume of the standard solution or extract such that
100 ng of the internal standard will be injected, using on-column
or splitless injection. For 1 mL extracts, this volume will be 1.0
fL. Start the GC column initial isothermal hold upon injection.
Start MS data collection after the solvent peak elutes. Stop data
collection after the benzo (ghi) perylene or pentacnlorophenol peak
elutes for the base/neutral or acid fraction, respectively. Return
the column to the initial temperature for analysis of the next
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sample.
12 System and laboratory performance
12.1 At the beginning of each 8 hr shift during which analyses are
performed, GCMS system performance and calibration are verified for
all pollutants and labeled compounds. For these tests, analysis of
the 100 fq/tnL calibration standard (section 6.13) shall be used to
verify all performance criteria. Adjustment and/or recalibration
(per section 7) shall be performed until all performance criteria
are met. Only after all performance criteria are met may samples,
blanks, and precisian and recovery standards be analyzed.
12.2 DFTPP spectrum validity—inject 1 fL of the DFTPP solution
(section 6.11) either separately or within a few seconds of
injection of the standard (section 12.1) analyzed at the beginning
of each shift. The criteria in table 5 shall be met.
12.3 Retention times—the absolute retention time of
2,2'-difluorobiphenyl shall be within the range of 107S to 124S
seconds and the relative retention times of all pollutants and
labeled compounds shall fall within the limits given in tables 3
and 4.
12.4 SC resolution—the valley height between anthracene and
phenanthrene at m/z 178 (or the analogs at m/z 188) shall not
exceed 10 percent of the taller of the two peaks.
12.5 Calibration verification—compute the concentration of each
pollutant (tables 1 and 2) by isotope dilution (section 7.4) for
those compounds which have labeled analogs. Compute the
concentration of each pollutant which has no labeled analog by the
internal standard method (section 7.5). Compute the concentration
of the labeled compounds by the internal standard method. These
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concentrations are computed based on the calibration data
determined in section 7.
12.5.1 For each pollutant and labeled compound being tested,
compare the concentration with the calibration verification limit
in table 8. If all compounds meet the acceptance criteria,
calibration has been verified and analysis of blanks, samples, and
precisian and recovery standards may proceed. If, however, any
compound fails, the measurement system is not performing properly
for that compound. In this event, prepare a fresh calibration
standard or correct the- problem causing the failure and repeat the
test (section 12.1), or recalibrate (section 7).
12.6 Multiple peaks—each compound injected shall give a single,
distinct GC peak.
12.7 On-going precision and accuracy.
12.7.1 Analyze the extract of one of the pair of precision and
recovery standards (section 10.1.3) prior to analysis of samples
from the same lot.
12.7.2 Compute the concentration of each pollutant (tables 1 and
2) by isotope dilution (section 7.4) for those compounds which have
labeled analogs. Compute the concentration of each pollutant which
has no labeled analog by the internal standard method (section
7.5). Compute the concentration of the labeled compounds by the
internal standard method.
12.7.3 For each pollutant and labeled compound, compare the
concentration with the limits for on-going accuracy in table 8. If
all compounds meet the acceptance criteria, system performance is
acceptable and analysis of blanks and samples may proceed. If,
however, any individual concentration falls outside of the range
given, system performance is unacceptable for that compound.
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NOTE: The large number of compounds in table 8 present a
substantial probability that one or more will fail when all
compounds are analyzed. To determine if the extraction/
concentration system is out of control or if the failure is caused
by probability, proceed as follows:1
12.7.3.1 Analyze the second aliquot of the pair of precisian and
recovery standards (section 10.1.3).
12.7.3.2 Compute the concentration of only those pollutants or
labeled compounds that failed the previous test (section 12.7.3).
If these compounds now pass, the extraction/concentration processes
are in control and analysis of blanks and samples may proceed. If,
however, any of the same compounds fail again, the extraction/
concentration processes are not being performed properly for these
compounds. In this event, correct the problem, re-extract the
sample lot (section 10) and repeat the on-going precision and
recovery test (section 12.7).
12.7.4 Add results which pass the specifications in section 12.7.2
to initial and previous on-going data. Update QC charts to form a
graphic representation of continued laboratory performance (Figure
5). Develop a statement of laboratory accuracy for each pollutant
and labeled compound by calculating the average percent recovery
(R) and the standard deviation of percent recovery (s,_). Express
the accuracy as a recovery interval from R - 2s,- to R + 2s,-.
For example, if R = 95X and s,_ = 57., the accuracy i s 85 - 1057..
13 Qualitative determination
13.1 Qualitative determination is accomplished by comparison of
data from analysis of a sample or blank with data from analysis of
the shift standard (section 12.1) and with data stored in the
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spectral libraries (section 7.2.4). Identification is can-firmed
when spectra and retention times agree per the criteria below.
13.2 Labeled compounds and pollutants having no labeled analog:
13.2.1 The signals for all characteristic masses stored in the
spectral library (section 7.2.4) shall be present and shall
maximize within the same two consecutive scans.
13.2.2 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC
peak maximum shall agree within a -factor o-f two (0.5 to 2 times)
f
for all masses stored in the library.
13.2.3 The retention time relative to the nearest eluted internal
standard shall be within q 15 scans or q 15 seconds, whichever is
greater.
13.3 Pollutants having a labeled analog:
13.3.1 The signals for all characteristic masses stored in the
spectral library (section 7.2.4) shall be present and shall
maximize within the same two consecutive scans.
13.3.2 Either (1) the background corrected EICP areas, or (2) the
corrected relative intensities of the mass spectral peaks at the GC
peak maximum shall agree within a factor of two for all masses
stared in the spectral library.
13.3.3 The retention time difference between the pollutant and its
labeled analog shall agree within q 6 scans or q 6 seconds
(whichever is greater) of this difference in the shift standard
(section 12.1).
13.4 Masses present in the experimental mass spectrum that are not
present in the reference mass spectrum shall be accounted for by
contaminant or background ions. If the experimental mass spectrum
is contaminated, an experienced spectrometrist (section 1.4) is to
1625B -26- -
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determine the presence or absence o-f the compound.
14 Quantitative determination
14.1 Isotope dilution—by adding a known amount of a labeled
compound to every sample prior to extraction, correction -for
recovery o-f the pollutant can be made because the pollutant and its
labeled analog exhibit the same e-f-fects upon extraction,
concentration, and gas chromatography. Relative response (RR)
values for sample mixtures are used in conjunction with calibration
curves described in section 7.4 to determine concentrations
directly, so long as labeled compound spiking levels are constant.
For the phenol example given in figure 1 (section 7.4.1), RR would
be equal to 1.114. For this RR value, the phenol calibration curve
given in -figure 1 indicates a concentration of 10.S fg/mL in the
sample extract (C.M).
14.2 Internal standard—compute the concentration in the extract
using the response factor determined from calibration data (section
7.5) and the fallowing equation:
C.M (fg/mL) = (A. x C1.)/(A1_ x RF)
where C.M is the concentration of the compound in the extract,
and the other terms are as defined in section 7.5.1.
14.3 External standard—compute the concentration in the extract
(C.w) from the calibration curve or calibration factor determined
from data in section 7.7.
14.5 The concentration of the pollutant in water is computed using
the volumes of the original water sample (section 10.1) and the
final extract volume (section 10.5), as follows:
Concentration in water (fg/L) = (C.M x V»,,)/Vm
where v1.,, is the extract volume in mL, and V. is the sample
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volume in liters.
14.4 If the EICP area at the quantitation mass for any compound
exceeds the calibration range of the system, the extract of the
dilute aliquot (section 10.1) is analyzed by isotope dilution;
otherwise, the extract is diluted by a factor of 10, 9 fL of
internal standard solution (section 6.10) are added to a 1.0 ml_
aliquot, and this diluted extract is analyzed by the internal
standard method (section 14.2). Quantify each compound at the
highest concentration level within the calibration range.
14.5 Report results for all pollutants and labeled compounds
(tables 1 and 2) found in all standards, blanks, and samples, in
fq/L, to three significant figures. Results for samples which have
been diluted are reported at the least dilute level at which the
area at the quantitation mass is within the calibration range
(section 14.4) and the labeled compound recovery is within the
normal range for the method (section IS.4).
15 Analysis of complex samples
15.1 Untreated effluents and other samples frequently contain high
levels O1000 fg/L) of the compounds of interest, interfering
compounds, and/or polymeric materials. Some samples will not
concentrate to one ml_ (section 10.5); others will overload the GC
column and/or mass spectrometer.
15.2 Analyze the dilute aliquot (section 10.1) when the sample
will not concentrate to 1.0 ml_. If a dilute aliquot was not
extracted, and the sample holding time (section 9.3) has not been
exceeded, dilute an aliquot of the sample with reagent water and
re-extract (section 10.1); otherwise, dilute the extract (section
14.4) and analyze by the internal standard method (section 14.2).
1625B -23-
-------
15.3 Recovery of internal standard—the EICP area of the internal
standard should be within a factor of two of the area in the shift
standard (section 12.1). If the absolute areas of the labeled
compounds are within a factor of two of the respective areas in the
shift standard, and the internal standard area is less than
one-half of its respective area, then internal standard loss in the
extract has occurred. In this case, use one of the labeled
compounds (preferably a polynuclear aromatic hydrocarbon) to
compute the concentration of a pollutant with no labeled analog.
15.4 Recovery of labeled compounds—in most samples, labeled
compound recoveries will be similar to those from reagent water
(section 12.7). If the labeled compound recovery is outside the
limits given in table 8, the dilute extract (section. 10.1) is
analyzed as in section 14.4. If the recoveries of all labeled
compounds and the internal standard are low (per the criteria
above), then a loss in instrument sensitivity is the most likely
cause. In this case, the 100 fg/mL calibration standard (section
12.1) shall be analyzed and calibration verified (section 12.5).
If a loss in sensitivity has occurred, the instrument shall be
repaired, the performance specifications in section 12 shall be
met, and the extract reanalyzed. If a loss in instrument
sensitivity has not occurred, the method does not work on the
sample being analyzed and the result may not be reported for
regulatory compliance purposes.
16 Method performance
16.1 Interlaboratory performance for this method is detailed in
references 9 and 10.
1625B -29-
-------
References
1. "Performance Tests for the Evaluation of Computerized Gas
Chromatography/Mass Spectrometry Equipment and Laboratories" USEPA,
EMSL Cincinnati, Ohio 45268, EPA-600/4-80-025 (April 19S0).
2. "Working with Carcinogens," DHEW, PHS, CDC, IMIOSH, Publication
77-206, (Aug 1977).
3. "QSHA Safety and Health Standards, General Industry" QSHA 2206,
29 CFR 1910 (Jan 1976).
4. "Safety in Academic Chemistry Laboratories," ACS Committee on
Chemical Safety (1979).
5. "Reference Compound to Calibrate Ion Abundance Measurement in
Gas Chromatography-Mass Spectrometry Systems," J.W. Eichelberger,
L.E. Harris, and W.L. Budde, Anal. Chem., 47, 955 (1975).
6. "Handbook of Analytical Quality Control in Water and Wastewater
Laboratories," USEPA, EMSL, Cincinnati, OH 45268, EPA-600/4-79-019
(March 1979).
7. "Standard Practice for Sampling Water," ASTM Annual Book of
Standards, ASTM, Philadelphia, PA, 76 (1980).
3. "Methods 330.4 and 330.5 for Total Residual Chlorine," USEPA,-
EMSL, Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979).
9. Colby, B.N., Beimer, R.G., Rushneck, D.R., and Telliard, W.A.,
"Isotope Dilution Gas Chromatography-Mass Spectrometry for the
Determination of Priority Pollutants in Industrial Effluents."
USEPA, Effluent Guidelines Division, Washington, DC 20460 (1930).
10. "Inter-laboratory Validation of US Environmental Protection
Agency Method 1625," USEPA, Effluent Guidelines Division,
Washington, DC 20460 (June 15, 1984).
1625B -30-
-------
Table 1
Base/Neutral Extractable Compounds
Comgound
acenaphthene
acenaphthyl ene
anthracene
benzidine
benzo (a) anthracene
benzo (b) f luoranthene
benzo (k) f luoranthene
benzo (a) pyrene
benzo (ghi ) perylene
biphenyl (Appendix C)
bis(2-chloroethyl ) ether
bis (2-chloroethoxy) methane
bis (2-chloroi sopropyl ) ether
bis (2-ethylhexyl ) phthalate
4-bromophenyl phenyl ether
butyl benzyl phthalate
n-C10 (Appendix C)
n-C12 (Appendix C)
n-C14 (Appendix C)
n-C16 (Appendix C)
n-CIS (Appendix C)
n-C20 (Appendix C)
n-C22 (Appendix C)
n-C24 (Appendix C)
n-C26 (Appendix C)
n-C28 (Appendix C)
Storet
34205
34200
34220
39120
34526
34230
34242
34247
34521
81513
34273
34278
34283
39100
34636
34292
77427
77588
77691
77757
77804
77830
77859
77886 •
77901
78116
1625B -31-
CAS Registry
83-32-9
208-96-8
120-12-7
92-87-5
56-55-3
205-99-2
207-08-9
50-32-8
191-24-2
92-52-4
111-44-4
111-91-1
108-60-1
117-81-7
101-55-3
85-68-7
124-18-5
112-40-2
629-59-4
544-76-3
593-45-3
112-95-8
629-97-0
646-31-1
630-01-3
630-02-4
EPA-EGD NPDES
001
077
078
005
072
074
075
073
079
512
018
043
042
066
041
067
517
506
513
519
520
521
522
523
524
525
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
B
001 B
002 B
003 B
004 B
005 B
007 B
009 B
006 B
008 B
011 B
010 B
012 B
013 B
014 B
015 B
•
-------
n-C30 (Appendix C)
carbazole (4c)
2-chloronaphthalene
4-chloraphenyl phenyl ether
chrysene
p-cymene (Appendix C)
dibenzo(a,h)anthracene
dibenzo-furan (Appendix C)
dibenzothiophene (Synfuel)
di-n-butyl phthalate
1,2-dichlorobenzene
J., 3-dichlorobenzene
1,4—dichlorobenzene
3,3'-dichlorobenzidine
diethyl phthalate
2,4-dimethyl phenol
dimethyl phthalate
2,4-dini trotoluene
2,6-di ni trotoluene
di-n—actyl phthalate
diphenylamine (Appendix C)
diphenyl ether (Appendix C)
1,2-di phenylhydrazine
fluoranthene
f1uorene
hexachlorobenzene
hexachlorobutadiene
hex ach1 oroethane
hexachlorocyclopentadiene
78117
77571
34581
34641
34320
77356
34556
81302
77639
39110
34536
34566
34571
34631
34336
34606
34341
34611
34626
34596
77579
77587
34346
34376
34381
39700
34391
34396
34386
1625B -32-
638-68-6
86-74-8
91-58-7
7005-72-3
218-01-9
99-87-6
53-70-3
132-64-9
132-65-0
84-74-2
95-50-1
541-73-1
106-46-7
91-94-1
84-66-2
105-67-9
131-11-3
121-14-2
606-20-2
117-84-0
122-39-4
101-34-8
122-66-7
206-44-0
36-73-7
113-74-1
37-63-3
67-72-1
77-47-4
526 B
528 B
020 B
040 B
076 B
513 B
082 B
505 B
• 504 B
068 B
025 B
026 B
027 B
028 B
070 B
034 A
071 B
035 B
036 B
069 B
507 B
508 B
037 B
039 B
080 B
009 B
052 B
012 B
053 B
016
017
013
019
026
020
021
022
023
024
003
025
027
029
029
030
031
032
033
034
036
035
-------
ideno(1,2,3-cd>pyrene
i saphorone
naphthalene
a-naphthylamine (Appendix C)
ni trobenzene
N-nitrosodimethyl amine
N-ni trosodi-n-proplyamine
N-ni trosodiphenylamine
phenanthrene
phenol
r-piColine (Syn-fuel )
pyrene
styrene (Appendix C)
'-terpineol (Appendix C)
1,2,3-trichlorobenzene (4c)
1,2,4-trichlorobenzene
34403
34403
34696*
S2553
34447
34438
34428
34433
34461
34694
77088
34469
77128
77493
77613
34551
193-39-5
78-59-1
91-20-3
91-59-8
98-95-3
62-75-9
621-64-7
86-30-3
85-01-8
108-95-2
109-06-8
129-00-0
100-42-5
98-55-5
87-61-6
120-82-1
083
054
055
502
056
061
063
062
081
065
503
084
510
509
529
008
B
B
B
B
B
B
B
B
B
A
B
B
B
B
B
B
037
038
039
040
041
042
043
044
010
.
045
046
B
B
B
B
B
B
B
B
A
B
B
-------
Table 2
Acid Ex tractable Compounds
Comgound
4-chloro-3-methyl phenol
2-chlorophenol
2, 4-dichlorophenol
2, 4-dini trophenol
2-methyl-4, 6-dini trophenol
2-nitrophenol
4-nitropnenal
pentachlorophenal
2,3,6-trichlaraphenal (4c)
2, 4, 5-trichlorophenal (4c)
2,4, 6-trichlarophenal
Staret
34452
34586
34601
34616
34657
34591
34646
39032
77688
34621
CAS Registry
59-50-7
. 95-57-8
120-83-2
51-28-5
534-52-1
88-75-5
100-02-7
87-86-5
93-37-55
95-95-4
88-06-2
EPA-EBD
022 A
024 A
031 A
059 A
060 A
057 A
058 A
064 A
530 A
531 A
021 A
WEE
00e
001
002
005
004
006
007
009
011
1625B -34-
-------
Table 3
Gas Chromatography of Base/neutral Extractable Compounds
Ret en t ion_t i.me Detect i on
EGD Mean EGD * limit
-------
063
256
356
254
354
234
334
043
208
308
255
355
609
709
606
706
529
252
320
513
612
712
60B
-7(7(0
277
N-nitrosodi—n-propylamine
nitrabenzene-d5
nitrobenzene
isaphorone-da
isophorone
2,4-dimethyl phenol
2,4-dimethyl phenol
bis(2-chloroethoxy) methane
1,2,4-trichlorobenzene-d3
1,2,4-trichlorobenzene
naphthalene-dS
naphthalene
alpha-terpineol-d3
alpha-terpineal
n-dodecane-d26
n-dodecane
1,2,3-trichlorobenzene
hexachlorobutadiene-13C4
hexachlorobutadiene
hexachlorocyclopentadi ene—13C4
hexachlorocyclopentadiene
2-chloronaphthalene-d7
2—chloronaphthalene
n-tetradecane
biphenyl-d10
biphenyl
diphenyl ether-d!0
diphenyl ether
acenaphthylene—dS
1625B
330
345
849
881
889
921
924
939
955
958
963
967
973
975
953
981
1003
1005
1006
1
1
1
1
1
147
142
135
200
203
1205
1
1
1
1
195
211
216
265
164
164
256
164
254
164
234
164
164
20S
164
255
164
609
164
606
164
164
252
164
253
164
220
164
164
612
164
603
164
0.
1.
0.
0.
0.
0.
0.
1.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
1.
1.
1.
0.
1.
706
002
747
999
781
999
813
000
819
001
829
998
730
986
856
999
976
999
014
997
016
001
036
997
080
ns
- 0.
- 1.
- 0.
- 1.
- 0.
- 1.
ns
- 0.
- 1.
- 0.
- 1.
- 0.
- 1.
- 0.
- 1.
ns
- 0.
- 1.
- 0.
- 1.
- 1.
- 1.
ns
- 1.
- 1.
- 1.
- 1.
- 1.
727
007
767
017
803
003
830
005
836
006
844
008
908
051
371
002
986
001
024
007
027
006
047
009
095
20
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
-------
377
271
371
236
O-J>Q
201
301
605
705
602
702
280
380
240
340
270
370
619
719
235
335
237
337
607
707
*-\ t *"1
-L.O-1
362
041
209
acenaphthylene
dimethyl phthalate-d4
dimethyl phthalate
2,6-dini trotaluene-d3
2,6-dinitrotoluene
acenaphthene-d!0
acenaphthene
dibenzofuran-dS
dibenzofuran
beta-naphthylamine-d7
beta-naphthylamine
-Fluorene—d!0
•f luorene
4-chlorophenyl phenyl ether—d5
4-chlorophenyl phenyl ether
diethyl phthalate-d4
diethyl phthalate
n-hexadecane-d34
n-hexadecane
2,4-dini trotoluene-d3
2,4-dinitrotoluene
1,2—di phenylhydraz i ne—dS
1,2-diphenylhydrazine (note 2)
diphenylamine-d!0
diphenylami ne
N-ni trosodiphenylamine-d6
N-nitrosodiphenylamine
-------
309
231
520
331
2/8
373
604
704
523
621
721
268
363
239
339
234
334
205
305
522
623
723
067
276
376
272
T-7O
•_• / j^
223
323
hexachlorobenzene
phenanthrene-d!0
n-octadecane
phenanthrene
anthracene-d!0
anthracene
dibenzothiophene-dS
dibenzothiaphene
carbazole
n-eicosane-d42
n-eicosane
di-n-butyl phthalate-d4 '
di-n-butyl phthalate .v-
-f 1 uoranthene-d 10
f1uaranthene
pyrene-d!0
pyrene
benzi di ne—dS
benzidine
n—dacosane
n-tetracosane-d50
n-tetraco'sane
butylbenzyl phthalate
chrysene—d!2
chrysene
benza (a)anthracene—d12
benzo(a)anthracene
3,3'—di chlorobenz i di ne—d6
Z,3'-dichlarobenzi di ne
1625B
1522
1573
15S0
1583
1588
1592
1559
1564
1650
1655
1677
1719
1723
1813
1S17
1844
1852
1354
1853
1339.
1997
2025
2060
2031
2033
2032
2090
2033
2036
53-
209
164
164
231
164
273
164
604
164
164
621
164
263
164
239
164
234
164
205
164
164
612
164
164
276
164
272
164
228
0.
1.
1.
1.
0.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
0.
1.
1.
999
334
000
342
998
314
000
134
010
446
000
522
000
523
001
549
000
671
012
743
000
735
999
744
000
- 1
~« 1
ns
- 1
— 1
- 1
— 1
- 1
ns
- 1
- 1
- 1
- 1
- 1
- 1
- 1
- 1
- 1
- 1
ns
- 1
- 1
ns
- 1
- 1
- 1
- 1
- 1
- 1
.001
.380
.005
• wSS
.006
.361
.006
.662
.021
.510
.003
.596
.004
.644
.003
.632
.002
.764
.015
.337
.004
.346
. 007
.843
. 00 1
10
10
10
10
10
10
10
10
.20
10
10
10
10
10
10
10
10
50
50
10
10
10
10
10
10
10
10
50
50
-------
266 bis(2-ethylhexyl) phthalate-d4
366 bis(2-ethylhexyl) phthalate
525 n-hexacosane
269 di-n-octyl phthalate-d4
369 di-n-octyl phthalate
525 n—actacDsane
274 benzo(b)-fluoranthene-d!2
374 benzo (b)fluoranthene
275 benzo
-------
Gas velocity: 30 q 5 cm/sec
1625B -40-
-------
Table 4
Gas Chromatagraphy o-f Acid Extractable
EGD
N°JL
164
224
324
257
357
231
331
221
321
531
530
259
359
258
358
260
360
264
364
Qomg,gund
2, 2' -di-f luorobiphenyl (int std)
2-chlorophenol-d4
2-chlorophenol
2-ni trophenol-d4
2-nitrophenol
2,4-di chlorophenol-d3
2,4-dichlorophenol
4—chloro—3—methyl phenol —d2
4-chloro-3-methylphenol
2,4,6—trichlorophenol-d2
2,4,6-tri chlorophenol
2,4,5-trichlorophenol
2,3,6-tri chlorophenol
2,4-dinitrophenol-d3
2,4-dinitrophenol
4-nitrophenol-d4
4-ni trophenol
2-methyl-4,6-dini trophenol-d2
2-methyl-4,6-dini trophenol
pentachlorophenol-13C6
pentachlorophenol
Compounds
Retentign_ti.me
Mean EGD
!§§£). Ref B§i§ti.ye_.
1163 164 1.000 - 1.
701 164 0.587 - 0.
705 224 0.997 - 1.
898 164 0.761 - 0.
900 257 0.994 - 1.
v 944 164 0.802 - 0.
947 231 0.997 - 1.
1086 164 0.930 - 0.
1091 222 0.998 - 1.
1162 164 0.994 - 1.
1165 221 0.998 - 1.
1170 164 ns
1195 164 ns
1323 164 1.127 - 1.
1325 259 1.000 - 1.
1349 164 1.147 - 1.
1354 258 0.997 - 1.
1433 164 1.216 - 1.
1435 260 1.000 - 1.
1559 164 1.320 - 1.
1561 264 0.998 - 1.
000
618
010
783
009
822
006
943
003
005
004
149
005
175
006
249
002
363
002
Detecti an
limit (fg/L)
lnote_il__
10
10
10
20
20
10
10
10
10
10
10
10
10
50
50
50
50
20
20
50
50
note l: This is a minimum level at which the entire GCMS system must
give recognizable mass spectra (background corrected) and acceptable
1625B -41-
-------
calibration points
ns = specification not available at time of release of method
Column: 30 q 2 m x 0.25 q 0.02 mm i.d. 94% methyl, 47. phenyl, 1% vinyl
bonded phase fused silica capillary
Temperature program: 5 min at '30 A-C; 30 - 250 xC or until
pentachlorophenol elutes
Gas velocity: 30 g 5 cm/sec
1625B -42-
-------
Table 5
DFTPP Mass-intensity Specifications
51" 30 - 80 percent of mass 198
68 less than 2 percent of mass 69
70 less than 2 percent of mass 69
127 30 - 60 percent of mass 198
197 less than 1 percent of mass 198
199 5-9 percent of mass 198
275 10 - 30 percent of mass 198
441 less than mass 443
442 40 - 100 percent of mass 198
443 17 - 23 percent of mass 442
1625B -43-
-------
Table 6
Base/neutral Extractable Compound Characteristic Masses
Labeled
Compound analog Primary m/z
acenaphthene
acenaphthyl ene
anthracene
benzidine
benzo (a) anthracene-
benzo (b) f luoranthene
benzo (k) f luoranthene
benzo (a) pyrene
benzo (ghi ) per yl ene
biphenyl
bis (2-chloroethyl ) ether
bis (2-chloroethoxy) methane
bi s (2-chloroisopropyl ) ether
bis<2-ethylhexyl) phthalate
4-bromophenyl phenyl ether
butyl benzyl phthalate
n-C10
n-C12
n-C14
n-C16
n-ClS
n-C20
n-C22
n-C24
d!0
dS
d!0
dS
d!2
d!2
d!2
d!2
d!2
d!0
dS
d!2
d4
d22
d26
d34
d42
d50
1625B -44-
154/164
152/160
17S/1SS
184/192
228/240
252/264
252/264
252/264
276/288
154/164
93/101
93
121/131
149/153
248
149
55/66
55/66
55
55/66
55
55/66
55
55/66
-------
n-C26
n-cza
n-C30
carbazale
2-chloronaphthalene
4-chlorophenyl phenyl ether
chrysene
p-cymene
dibensa(a,h)anthracene
dibenzo-f uran
dibenzothiophene
di-n-butyl phthalate
1,2-dichlorobenzene
1,3-dichlorobenzene
1,4-di chlorobenzene
3,3'-dichlorobenzidine
diethyl phthalate
2,4-dimenthylphenol
dimethyl phthalate
2,4-dini trotoluene
2,6-dini trotoluene
di-n-octyl phthalate
di phenylami ne
diphenyl ether
1., 2-di phenylhydrazine*
-f 1 uoranthene
•f 1 uorene
hexachlorobenzene
hexachlorobutadi ene
d62
d8
d7
d5
d!2
d!4
dS
dS
d4
d4
d4
d4
d6
d4
d3
d4
d3
d3
d4
d!0
d!0
d!0
d!0
d!0
13C6
13C4
1625B -45-
55
55
55/66
167/175
162/169
204/209
228/240
114/130
278
168/176
184/192
149/153
146/152
146/152
146/152
252/258
149/153
122/125
163/167
164/168
165/167
149/153
169/179
170/180
77/82
202/212
166/176
284/292
TIC" / i~\T* 4
— *-_-/ *-•-> 1
-------
hexachloraethane
hexachlorocyclopentadiene
ideno(1,2,3-cd)pyrene
i sopharone
naphthalene
B-naphthylamine
ni trobenzene
N-nitrosadimethyl amine
N-ni trosodi-n-proplyamine
N-ni trosodi phenylami ne**
phenanthrene
phenol
a-picoline
pyrene
styrene
a—terpineol
1,2,3-tri chlorobenzene
1,2,4-trichlorabenzene
*detected as azobenzene
**detected as diphenylamine
!C
BC4
dS
d8
d7
d5
d6
d!0
d5
d7
dl0
d5
d3
d3
d3
201/204
237/241
276
82/88
128/136
143/150
128/128
74
70
169/175
178/188
94/71
93/100
202/212
104/109
59/62
180/183
180/183
1625B -46-
-------
Table 7
Acid Ex tractable Compound Characteristic Masses
Labeled
Compound analog Primary m/:
4-chl or o-3-methyl phenol
2-chl orophenol
2, 4-dichlorophenol
2, 4-dini trophenol
2-methyl— 4, 6-dini trophenol
2-ni trophenol
4-ni trophenol
pen tachl orophenol
2,3, 6-trichl orophenol
2, 4, 5-t rich 1 orophenol
2, 4, 6-trichl orophenol
d2
d4
d3
d3
d2
d4
d4
13C6
d2
d2
d2
107/109
128/132
162/167
184/187
198/200
139/143
139/143
266/272
196/200
196/200
196/200
1625B -47-
-------
Table B
Acceptance Criteria -far Performance Tests
EGD
Initial
precisian
and accuracy
Section 3.2.3
___ l£g/Li ____
_s_ ___ X ____
21 79 - 134
38 38 - 147
38 69 - 186
31 39 - 146
41 58 - 174
49 31 - 194
119 16 - 518
269 ns - ns
20 65-168
41 25 - 298
183 32 - 545
168 11 - 577
26 59 - 143
114 15 - 514
•26 62 - 195
24 35 - 131
21 72 - 160
45 29 - 263
41 75 - 148
1625B -43-
labeled
compound
recovery
Sec 8.3
and 14.2
calibra-
tion
verifi- On-ge
cation accur
Sec 12.5 Sec 1
301
201
377
277
378
273
305
205
372
272
374
274
375
275
373
273
379
279
712
acenaphthene
acenaphthene-d!0
acenaphthylene
acenapnthylene-dS
anthracene
anthracene-d!0
benzidine
bensidine-dS
benzo (a) anthracene
benzo
-------
612 biphenyl-d!0 43 23
313 bis(2-chloraethyl > ether 34 55
218 bis(2-chloroethyl > ethei — dS 33 29
043 bis(2-chlaroethaxy) methane* 27 43
342 bis(2-chloroisopropyl ) ether 17 '31
242 bis(2-chlaroisapropyl ) ether — d!2 27 35
366 bis(2-ethylhexyl) phthalate 31 69
266 bis(2-ethylnexyl) phthalate-d4 29 32
041 4-bromophenyl phenyl ether* 44 44
067 butyl benzyl phthalate* 31 19
717 n-C10 (Appendix C) 51 24
617 n-C10-d22 70 ns
706 n-C12 (Appendix C) 74 35
606 n-C12-d26 53 ns
518 n-C14 (Appendix O* 109 ns
719 n-C16 (Appendix C) 33 80
619 n-C16-d34 46 ~37
520 n-CIS (Appendix O* 39 42
721 n-C20 (Appendix C) 59 53
621 n-C20-d42 34 34
522 n-C22 (Appendix O* 31 45
723 n-C24 (Appendix C) 11 30
623 n-C24-d50 28 27
524 n-C26 (Appendix O* 35 35
525 n-C28 (Appendix O* 35 35
726 n-C30 (Appendix C) 3
626 n-C30-d62
52S carbazole (4c)*
320 2-chl oronaphthalene
165 ns
196
196 15
0
61
41 27
38 36
100 46
1625B -49-
138
149
220
205 18
140
233
195
293 ns
369
331 ns
985
162
162 18
131
263
172 19
152
139
211 15
193
193
200
242 13
165
357
- ns 52 -
61 -
- 372 52 -
44 -
67 -
- 260 44 -
76 -
- 364 43 -
52 -
42
ns 44
60
ns 41
37
72
308 54
40
54
306 62
40
65
376 50
26
26
66
479 24
44
192 17
164 50
194 25
148 77
229 30
131 64
232 28
193 35
450 35
267
213
T*'?'?
166
145
169
"?"^2
224
172
170
19 -
227 ns - 504
166 29 - 424
242 ns
268 ns
138 71
186 28
184 46
162 29
249 39
154 73
199 25
392 31
392 31
152 56
423 23
403
ns
131
202
167
301
19S
195
142
- 227 31 -
274
18E
442
-------
220 2-chloronaphthalene-d7
322 4-chlaro-3-methylphenol
222 4-chlora-3-metHylphenol-d2
324 2-chlaraphenal
224 2-chlorophenol-d4
340 4-chloraphenyl phenyl ether
41 30
37 76
111 -30
13 79
24 36
42 75
240 4-chlorophenyl phenyl ether-d5 52 40 -
376 chrysene
276 chrysene-d!2
713 p-cymene (Appendix C)
613 p-cymene-d!4
082 dibenzo(a,h)anthracene*
705 dibenzofuran (Appendix C)
605 dibenzofuran-dS
704 dibenzothiophene (Synfuel)
604 dibenzothiophene-dS
368 di-n-butyl phthalate
268 di-n-butyl phthalate-d4
325 1,2-dichlorobenzene
225 1,2-dichlorobenzene-d4
326 1,3-dichlorobenzene
226 1,3-dichlarobenzene-d4
327 1,4-dichlarobenzene
227 1,4-dichlarobenzene-d4
328 3,3'-dichlarobenzidine
223 3,3'—dichlarabenzidine—d6
331 2,4-dichlarophenol
231 2,4-dichlaraphenal-d3
370 diethyl phthalate
51 59
69 33
IS 76
/
67 ns
55 23
20 85
31 47
31 79
31 48
15 76
23 23
17 73
35 14
43 63
48 13
42 61
48 15
26 68
30 ns
12 85
28 33
44 75
1625B -50-
168 15
131
174 ns
135
162 23
166
161 19
186
219 13
140
359 ns
299
136
136 28
150
130 29
165
195 13
146
212 ns
201
203 ns
194
193 ns
174
562 ns
131
164 24
196
324 72.
as
613 68
78
255 55
71
325 57
70
512 24
79
ns 66
13
73
220 66
72
215 69
71
346 52
74
494 61
65
550 52
62
474 65
77
ns 13
67
260 64
74
139 24
115 62
147 14
129 76
180 33
142 63
175 29
142 48
411 23
127 72
152 ns
761 19
136 79
150 39
140 70
145 40
142 74
192 22
135 70
164 11
154 55
192 ns
161 53
153 11
130 64
558 ns
149 S3
157 34
135 65
-------
270 diethyl phthalate-d4
334 2,4-dimethyl phenol
234 2,4-dimethyl phenol-d3
371 dimethyl phthalate
271 dimethyl phthalate-d4
359 2,4-dinitrophenol
259 2,4-dinitrophenol-d3
335 2,4-dinitrotoluene
235 2,4-dinitrotoluene-d3
336 2,6-dinitrotoluene
236 2,6-dinitrotoluene-d3
369 di-n-octyl phthalate
269 di-n-octyl phthalate-d4
707 diphenylamine (Appendix C)
607 diphenylamine-d!0
70S diphenyl ether (Appendix C)
608 diphenyl ether—d!0
337 1,2-diphenylhydrazine
237 1,2-diphenylhydrazine-dl0
339 f1uoranthene
239 fIuoranthene-dl0
380 fluorene
280 fluorene-d!0
309 hexachlorobensene
209 hexachlorobenzene-13C6
352 hexachlorobutadiene
252 nexachlorobutadiene-13C4
312 hexachloroethane
212 hexachloroethane-13Cl
78
13
22
36
108
18
66
18
37
30
59
16
46
45
42
19
37
73
35
33
35
29
43
16
81
56
63
*?'~?~7
77
1625B -5
ns -
62 -
15 -
74 -
ns -
72 -
22 -
75 -
22 -
80 -
44 -
77 -
12 -
58 -
(Z-
82 -
36 -
49 -
31 -
71 -
36 -
81 -
51 -
90 -
36 -
51 -
ns -
21 -
ns -
1-
260 ns - ns
153
228 ns - 449
188
640 ns - ns
134
308 ns - ns
158
245 10 - 514
141
184 17 - 442
161
383 ns - ns
205
206 11 - 488
136
155 19 - 281
308
173 17 - 316
177
161 20 - 278
132
131 27 - 238
124
228 13 - 595
251
316 ns - ns
ns
400 ns - ns
47
67
58
73
50
75
39
79
53
55
36
71
21
57
59
83
77
75
58
67
47
74
61
73
38
74
68
71
47
- 211
- 150
- 172
- 137
- 201
- 133
- 256
- 127
- 187
- 183
- 278
- 140
- 467
- 176
- 169
- 120
- 129
- 134
- 174
- 149
- 215
- 135
- 164
- 128
- 265
- 135
- 148
- 141
<••* H ^-\
JL J. ji.
ns
60
14
67
ns
68
17
72
19
70
31
74
10
51
21
77
29
40
26
64
30
70
33
85
'•"IT
j^'_'
43
ns
13
ns
— n =
- 156
- 242
- 207
- n =
- 141
- 37E
- 16^
- 27=
- 15<:
- 25!i
- 16<£
- 43"
- 23]
— T'AC
- 14^
- 1S,£
- 36k
- 20!i
- 19-
- is:
- 151
- 17:
- 13:
- 321
- 2s:
- 41;
- n =
er / -
~>c>:
-------
353 hexachlorocyclopentadiene 15 69
253 he>:achlorocyclapentadiene-13C4 60 ns
083 ideno(l,2,3-cd)pyrene* 55 23
354 isaphorone 25 76
254 isopharone-dS . 23 49
360 2-methyl-4.,6-dinitraphenol' 19 77
260 2-methyl-4,6-dinitrophenol-d2 64 / 36
355 naphthalene
255 naphthalene-dS
702 a-naphthylamine (Appendix C)
602 a-naphthylamine-d7
356 nitrobenzene
256 nitrobenzene-d5
357 '2-nitrophenol
257 2-nitrophenol-d4
358 4-nitrophenol
258 4-nitrophenol-d4
061 N-nitrosadimethylamine*
063 N-nitrosodi-n-proplyamine*
362 N-nitrosodiphenylamine
262 N-nitrosodiphenylamine-d6
364 pentachlarophenol
264 pentachlarophenal-13C6
381 phenanthrene
281 phenanthrene-d!0
365 phenol
265 phenol-d5
703 r-picoline (Syn-f uel )
603 '— pi coline—d7
20 80
39 28
49 10
33 ns
25 69
28 18
15 78
23 41
42 62
-188 14
198 21
198 21
45 65
37 54
21 76
49 37
13 93
40 45
36 77
161 21
38 59
138 11
1625B -52-
144
ns ns
299
156
133 33
133
247 16
139
157 14
ns
ns ns
161
265 ns
140
• 145 27
146
398 ns
472
472
142
126 26
140
212
119
130 24
127
210 ns
149
380 ns
77
ns 47
13
70
193 52
69
527 56
73
305 71
39
ns 44
85
ns 46
77
217 61
55
ns 35
40
40
68
256 59
77
412 42
75
241 67
65
ns 48
60
ns 31
129 67
211 ns
761 19
142 70
194 44
145 72
177 23
137 75
141 22
256 ns
230 ns
115 65
219 15
129 75
163 37
133 51
2S7 ns
249 12
249 12
148 53
170 40
130 71
237 29
133 87
149 34
155 62
208 ns
165 50
324 ns
-------
384 pyrene 19 76 - 152 76 - 132 72 - 15^
284 pyrene-d!0 ' 29 32 - 176 13 - 303 48 - 210 28 - 19£
710 styrene (Appendix C) 42 53 - 221 65 - 153 48 - 24-
610 styrene-d5 49 ns ~ 281 ns - ns 44 - 223 ns - 34E
709 '-terpineol (Appendix C) 44 42 - 234 54 - 186 38 - 25E
609 r-terpineol-d3 ' 48 22 - 292 ns - 672 20 - 502 13 - 33^
529 1,2,3-trichlorobenzene <4c>* 69 15 - 229 60 - 167 11 - 297
303 1,2,4-trichlorobenzene 19 82 - 136 78 - 123 77 - 144
208 l,2,4-trichlorobenzene-d3 57 15 - 212 ns - 592 61 - 163 10 - 282
530 2,3,6-trichlorophenol (4c)* 30 58 - 137 56 - 130 51 - 153
531 2,4,5-trichlorophenol (4c)* 30 58 - 137 56 - 180 51 - 153
321 2,4,6-trichlorophenol 57 59 - 205 81 - 123 48 - 244
221 2,4,6-trichlorophenol-d2 47 43 - 183 21 - 363 69 - 144 34 - 226
*measured by internal standard: specification derived -from related compound.
d = detected; result must be greater than zero.
ns = no specification; limit is outside" the range that can be measured
reliably.
-------
100-
IT
uj
>
H
ui
cc
10 -I
1.0-
0.1-
0.01
\ 0.1 1.0 10 100
CONCENTRATION (gg/L)
FIGURE 1 Relative Response Calibration Curve for Phenol. The
Dotted Lines Enclose a ± 10 Percent Error Window.
AREA AT
AREA AT
M,/Z
FIGURE 2 Extracted Ion Current Profiles for Chroma-
tographically Resolved Labeled (m^z) and Unlabeled (mJz) Pairs.
-------
(3A)
AREA = 46100
AREA = 4780
AREA = 43600
AREA =48300
FIGURE 3 Extracted Ion Current Profiles for (3A) Unlabeled
Compound, (3B) Labeled Compound, and (3C) Equal Mixture of
Unlabeled and Labeled Compounds.
-------
STANDARD
BLANK
SAMPLE
[10.1.1]
[10.1.2]
[10.1.3]
[10.1.4]
[10.2]
[10.3]
[10.4.2]
[10.4,10.5]
[11.3]
[11.4]
CONCENTRATE
TO 1.0 mL
ADD INTERNAL
STANDARD
FIGURE 4 Flow Chart for Extraction/Concentration of Precision and Recovery Standard Blank
and Sample by Method 1625. Numbers in Brackets [ ] Refer to Section Numbers in the Method.'
-------
g 45,000
35,000'
X
Si 25,000
' i J 1 1 1 1 L
ANTHRACENE-D,0
••- +33
-3s
123456789 10
ANALYSIS NUMBER
s
a
iii
in o
2 1
i2£
LU fl
1- UJ
CC 5 0.90 -
1 1 1 1 1 1 1 1 1
ANTHRACENE
•'",.-"
_ ' • '
< 6/1 6/1 6/1 6/1 6/2 6/2 6/3 6/3 6/4 6/5
5 DATE ANALYZED
FIGURE 5 Quality Control Charts Showing Area (top graph) and
Relative Response of Anthracene to Anthracene-d10 (lower graph)
Plotted as a Function of Time or Analysis Number.
-------
REFERENCES
Aitchisen, J., and Brown, J. A. C. The Lognormal Distribution. Cambridge
University Press, Cambridge, 1957.
D1xon W. J., et al. (eds). BMDP Statistical Software. 1983 printing with
Additions. University of California Press, Berkeley, 1983.
Draper, N., and Smith, M. Applied Regression Analysis. 2nd Ed. John Wiley
and Sons, New York, 1981.
Hoaglln, D. C., Hosteller, F., and Tukey. J. S. Understanding Robust and
Exploratory Data Analysis. John Wiley and Sons, New York, 1983.
Rao, C. R., Linear Statistical Inference and its Applications, Second
Edition. John Wiley and Sons, New York 1973.
Thompson, W. A., and Willke, T. A. "On an Extreme Rank Sum Test for
Outliers," Biometrika (1963) 50:3 and :4, pp. 375-383.
SAS Institute, Inc. SAS User's Guide: Basics. 1982 Edition. SAS Institute
Inc., Cary NC, 1982.
"Standard Practice for Dealing with Outlying Observations," 1982 Annual Book
of ASTM Standards, p. 211.
Youden, W. J. "Ranking Laboratories by Round-Robin Tests," Materials
Research and Standards 3, pp. 9-13, 1963.
U.S. EPA Development Document for Existing Source Pretreatment Standards for
the Electroplating Point Source Category. EPA Document 440/1-79/003.
August 1979.
R-l
-------
|