EPA/600/4-88/006
January 1988
VALIDATION OF SW-846 METHODS 8010, 8015, AND 8020
by
J. E. Gebhart, S. V. Lucas, S. J. Naber, A. M. Berry,
T. H. Danison, and H. M. Burkholder
Battelle Columbus Division
Columbus, Ohio 43201-2693
Contract Number 68-03-1760
Work Assignment 2-15
Project Officer
James E. Longbottom
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
REPRODUCED BY
NATIONAL TECHNICAL E
INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
SPRINGFIELD, VA. 22161
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA/600/4-
•88/006
3. RECIPIENT'S ACCESSION NO.
PB88 1 6 I 5 fi
TITLE AND SUBTITLE
Validation of SW-846 Methods 8010, 8015, 8020
REPORT DATE
January 1988
6. PERFORMING ORGANIZATION CODE
J?E^H6ebhart, S.V. Lucas, S.J. Naber, A.M. Berry,
T.H. Danison and H.M. Burkholder
8. PERFORMING ORG/
. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201-2693
10. PROGRAM ELEMEN1
11. CONTRACT/GRANT NO.
68-03-1760
2. SPONSORING AGENCY NAME AND ADDRESS
Environmental Monitoring & Support Lab.
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati. OH 45268
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-600/06
5. SUPPLEMENTARY NOTES
6. ABSTRACT
A hierarchical approach is being implemented for the development and
validation of analytical methods for the determination of the over 400 RCRA
Appendix VIII and Michigan List compounds in wastes. The first phase of this
approach involved testing GC/MS methods for the detection and measurement of
these compounds. Next, semivolatile compounds determined to be amenable to
GC/MS were used to evaluate the performance of SW-846 Method 3510. In the
study described in this report, volatile organic compounds determined to be
amenable to GC/MS were used to evaluate the performance of SW-846 Method 5030.
The performance of Method 5030 was evaluated in conjunction with SW-846
Methods 8010, 8015, and 8020. In these studies, purge-trap-desorb sample
introduction techniques were used for synthetic aqueous and solid samples, and
direct liquid injection was used for synthetic nonaqueous liquid wastes. The
results of these studies are presented, including purging efficiencies and
estimated method detection limits for compounds in aqueous samples and method
»ompnimds in nonaqiif>i->iis linilid
limits fc
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COSATl Field/Group
U.S. Enviror
Region 5, Li
77 West Jac
Chicago, IL
mental Protection Agency
•ary (PL-12J)
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DISCLAIMER
The information in this document has been funded wholly or in part by
the United States Environmental Protection Agency under Contract Number 68-
03-1760 to Battelle Columbus Division. It has been subject to the Agency's
peer and administrative review, and it has been approved for publication as
an EPA document. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
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CONTENTS
Foreword iv
Abstract v
Tables .vi
Acknowledgements viii
1. Introduction 1
2. Conclusions 4
3. Recommendations 5
4. Experimental Procedures 6
Materials 6
5. Results and Discussion 17
Preliminary Activities 17
Instrumentation Range 21
Preliminary Method Evaluation . 31
References 39
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FOREWORD
Environmental measurements are required to determine the quality of
ambient waters and the character of waste effluents. The Environmental
Monitoring and Support Laboratory-Cincinnati conducts research to:
• Develop and evaluate methods to measure the presence and
concentration of physical, chemical, and radiological
pollutants in water, wastewater, bottom sediments, and
solid waste.
• Investigate methods for the concentration, recovery, and
identification of viruses, bacteria and other
microbiological organisms in water; and, to determine the
responses of aquatic organisms to water quality.
• Develop and operate an Agency-wide quality assurance
program to assure standardization and quality control of
systems for monitoring water and wastewater.
• Develop and operate a computerized system for instrument
automation leading to improved data collection, analysis
and quality control.
This report summarizes the evaluation of several SW-846 methods for the
determination of volatile organic compounds in wastes.
Robert L. Booth, Director
Environmental Monitoring and Support
Laboratory-Cincinnati
IV
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ABSTRACT
A hierarchical approach is being implemented for the development and
validation of analytical methods for the determination of the over 400 RCRA
Appendix VIII and Michigan List organic compounds in wastes. The first phase
of this approach involved testing GC/MS methods for the detection and
measurement of these compounds. Next, semi volatile compounds determined to
be amenable to GC/MS were used to evaluate the performance of SW-846 Method
3510. In the study described in this report, volatile organic compounds
determined to be amenable to GC/MS were used to evaluate the performance of
SW-846 Method 5030.
The performance of Method 5030 was evaluated in conjunction with SW-846
Methods 8010, 8015, and 8020. In these studies, purge-trap-desorb sample
introduction techniques were used for synthetic aqueous and solid samples,
and direct liquid injection was used for synthetic nonaqueous liquid wastes.
The results of these studies are presented, including purging efficiencies
and estimated method detection limits for compounds in aqueous samples and
method detection limits for compounds in nonaqueous liquid wastes.
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TABLES
Number paqe
1 Compounds recommended for inclusion in the scope of methods
8010, 8015, and 8020 4 0
2 Compounds recommended for exclusion from the scopes of methods
8010, 8015, and 8020 43
3 Compounds recommended for inclusion in method 8240 performance
testing 45
4 Compounds considered for inclusion in the suitability testing
of methods 8010, 8015, and 8020 47
5 Instrument conditions specified in methods 8010, 8015, and 8020
and used in these method evaluations 50
6 Retention times, purging efficiencies, and estimated detection
limits determined for method 8010 analytes 51
7 Retention times, purging efficiencies, and estimated detection
limits determined for method 8015 analytes 54
8 Retention times, purging efficiencies, and estimated detection
limits determined for method 8020 analytes 56
9 Compounds not included in evaluations of Methods 8010, 8015,
and 8020. 57
10 Response factors determined for method 8010 analytes using PTD. 58
11 Response factors determined for method 8010 analytes using DLL 59
12 Response factors determined for method 8015 analytes using PTD. 60
13 Response factors determined for method 8015 analytes using DLL 61
14 Response factors determined for method 8010 analytes using PTD. 62
15 Response factors determined for method 8020 analytes using DLL 63
16 Results of instrument range determination for method 8010 using
PTD sample introduction 64
vi
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TABLES
Number £ase
17 Results of instrument range determination for method 8010 using
DLI sample introduction 66
18 Results of instrument range determination for method 8015 using
PTD sample introduction 68
19 Results of instrument range determination for method 8015 using
DLI sample introduction . 69
20 Results of instrument range determination for method 8020 using
PTD sample introduction 70
21 Results of instrument range determination for method 8020 using
DLI sample introduction (M9/9) 71
22 Results of preliminary method evaluation for method 8010 using
aqueous samples 72
23 Results of preliminary method evaluation for method 8010 using
solid samples 73
24 Results of preliminary method evaluation for method 8015 using
aqueous samples 74
25 Results of preliminary method evaluation for method 8015 using
solid samples • 75
26 Results of preliminary method evaluation for method 8020 using
aqueous samples 76
27 Results of preliminary method evaluation for method 8020 using
solid samples 77
vn
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ACKNOWLEDGEMENTS
The authors are grateful for the advice and guidance provided by
James E. Longbottom and Robert Graves of the Environmental Monitoring and
Support Laboratory - Cincinnati. Their technical insights were key in the
successful conduct and completion of this program.
The assistance of Ms. Susan Champagne of Battelle Columbus Division in
the preparation of innumerable standard solutions is gratefully acknowledged.
The efforts of Ms. Maria Pozz of Battelle Columbus Division in the
coordination and production of this report is also appreciated.
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SECTION 1
INTRODUCTION
The Resource Conservation and Recovery Act (RCRA) specifies over 300
toxic organic compounds in its Appendix VIII to 40 CFR Part 261 listing which
may be used to identify hazardous wastes. In response to a petition by the
state of Michigan, the U.S. Environmental Protection Agency (USEPA) has
proposed the amendment of RCRA Appendix VIII (1) by the addition of over 100
other organic compounds to give a total of over 400 organic constituents.
Various gas chromatographic (GC) methods for determining Appendix VIII
compounds in wastes are given in SW-846, "Test Methods for Evaluating Solid
Wastes" (2). In many cases, these methods are modifications of procedures
cited under the Clean Water Act for determining some, but not all, of
Appendix VIII and Michigan List compounds in wastewater. EPA is currently
attempting to validate the appropriate SW-846 analytical methods for as many
of the 400 plus target compounds as possible. A hierarchical approach to
these validation efforts is being pursued.
A schematic illustration of the hierarchical approach to the development
and validation of analytical methods for the determination of over 400
organic compounds in wastes is presented in Figure 1. The first phase of
this approach was conducted under Work Assignment 4 of EPA Contract Number
68-03-3224 (3) and involved the identification of volatile and semivolatile
compounds which are amenable to GC separation and mass spectrometric (MS)
detection. Next, the semivolatile compounds determined to be amenable to
GS/MS were then used to evaluate the performance of SW-846 Method 3510 (4).
This work focussed on the recovery from water and aqueous stability of the
semivolatile compounds using standardized storage and extraction procedures.
These experiments were conducted under Work Assignment 8 of EPA Contract
Number 68-03-3224. In the study described in this report, volatile compounds
determined to be amenable to GC separation were used to evaluate SW-846
Methods 8010, 8015, and 8020. Evaluating these methods was one of the
1
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also provided in this report. The other major objective of this Work
Assignment was to use the results of Methods 8010, 8015, and 8020 testing to
formulate recommendations for inclusion of specific compounds in the scope of
Method 5030 for the validation of Method 8240. These recommendations are
made based on the recovery and precision of the determination of these
analytes using procedures specified in Methods 8010, 8015, and 8020.
Methods 8010, 8015, and 8020 provide packed-column GC conditions for the
determination of certain VOCs. Waste samples are analyzed using these
Methods in conjunction with purge-trap-desorb (PTD), Method 5030; direct
liquid injection (DLI); or headspace sampling, Method 5020, sample
introduction techniques. Temperature programs are used in the GC to separate
organic compounds. Detection is achieved by a halogen specific detector for
Method 8010, a flame ionization detector for Method 8015, and a
photoionization detector for Method 8020.
These Methods were evaluated using procedures described in the "Single
Laboratory Method Validation Protocol" (SLMVP) (5) which was developed under
Work Assignment 1 of EPA Contract Number 68-03-3224. While the SLMVP
specifies six steps for full method validation, only the first two steps,
Instrumentation Range Determination and Preliminary Method Evaluation, were
used in these evaluations. This approach was taken because US EPA
anticipated that many laboratories would soon have the capability to conduct
PTD analysis using capillary column GC. Consequently, full validation of
packed-column methods was not considered necessary or appropriate. Research
results provided in this report are intended to define the scope of the three
packed column methods and establish a basis for testing of capillary column-
based methods for the determination of VOC in waste samples.
In evaluating Methods 8010, 8015, and 8020, the Instrumentation Range
Determination was conducted for each of the Methods using PTD for aqueous
calibration standards and DLI for nonaqueous calibration standards as sample
introduction techniques. Sufficient data were collected using DLI to
calculate an method estimated detection limit (EDL) for each analyte used in
these evaluations. The Preliminary Method Evaluation step of the SLMVP was
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performed for each of the Methods with synthetic aqueous and solid samples
using only PTD as the sample introduction technique.
The analytes used in these evaluations included all those listed for
each of the Methods in SW-846, including the priority pollutant compounds,
the volatile compounds appearing in the Michigan List for which suitable GC
behavior had been obtained in the earlier research, and other selected
analytes. The priority pollutant compounds served as reference compounds
throughout these studies. The Michigan List compounds were assigned to
Methods based on the GC detector which was considered to be most appropriate.
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SECTION 2
CONCLUSIONS
Based on the studies described and the results presented in this
report, the following conclusions are drawn.
o A total of 51 compounds were used to evaluate Method 8010. This
Method was determined to be suitable for the determination of 36
of these analytes in aqueous and solid samples using the PTD
sample introduction technique. When the DLI sample introduction
technique was used, Method 8010 was found to be suitable for the
determination of 46 of the test compounds in nonaqueous liquid
samples.
o Using the PTD sample introduction technique, Method 8015 was
found to be suitable for the determination of 5 of the 21 test
compounds in aqueous and solid samples. This Method, in
combination with DLI sample introduction, was demonstrated to be
successful for the determination of 19 of the 21 analytes in
nonaqueous liquid samples.
o Method 8020 was determined to be suitable for the determination
of 11 of the 14 test compounds in aqueous and solid samples
using PTD sample introduction. Using DLI sample introduction,
this Method was demonstrated to be successful in the
determination of 12 of the 14 compounds in nonaqueous liquid
samples.
o Poor purging efficiency and poor chromatographic behavior for a
number of the test compounds prevented Methods 8010, 8015, and
8020 from performing successfully for these analytes.
Table 1 lists the compounds for which these Methods were determined to be
suitable based on the experiments conducted during these studies. Table 2
lists the compounds for which the performance of these Methods was found to
be unacceptable. This table also provides a brief comment on the
difficulties encountered with each of these compounds. More thorough
discussions are provided in Section 5 of this report.
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, SECTION 3
RECOMMENDATIONS
Based on the experiments described and the results presented in this
report, the following recommendations are made.
o Pending further method suitability testing, the compounds listed
i5ic : .. ;«o«u1d. be 1ncluded in the scopes of Methods 8010,
8015, and 8020 as indicated.
o At this time, compounds listed in Table 2 should be excluded
from the scopes of Methods 8010, 8015, and 8020 as indicated.
o Further method suitability testing should involve the use of
capillary columns and should include those analytes excluded
Trom this study on the basis of poor chromatographic behavior.
o Further evaluations of these Methods should include analysis of
??«"? ^Mn^5?13165^ n'9°rous determination of method detection
limits (MDLs) for all analytes, and the conduct of the referee
validation step of the SLMVP.
o Compounds listed in Table 3 have been determined to purge with
acceptable efficiency and precision from aqueous samples. These
MeKn8240 Deluded in performance testing of SW-846
o
For future studies involving these and other methods for the
determination of volatile compounds , more reliable procedures
for the preparation of spiked aqueous and solid samples should
be developed and implemented. Emphasis should be placed on
minimizing analyte losses during the preparation of replicate
samples. r
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SECTION 4
EXPERIMENTAL PROCEDURES
MATERIALS
Standards
Compounds considered for inclusion in the Methods 8010, 8015, and 8020
testing are listed in Table 4. This table is organized by Method and, for
each compound, presents the Chemical Abstract Services (CAS) registry number,
the regulatory list or lists on which the compound appears, and the
commercial source of the standard material used in this research.
Solvents
Solvents used in this research included methanol, pentane, and
oxylene which were designated as "high purity" quality obtained from Burdick
and Jackson Laboratories. These solvents were used without further
purification.
Sample Matrices
Aqueous Matrix--
The aqueous matrix used in these studies consisted of reagent grade (RG)
water. The RG water was prepared from commercial distilled water with a
Milli-Q system, boiled for 15 minutes, cooled to room temperature, and passed
through a column of activated charcoal immediately prior to use. Sufficient
RG water was prepared each morning for use in the laboratory that day and was
stored in a Teflon-lined screw cap bottle until it was passed through
activated charcoal and used. Any RG water unused at the end of the day was
discarded and fresh water was prepared on the following day. This RG water
was used both for the aqueous calibration standards and for the aqueous
sample matrix used with PTD sample introduction in Preliminary Method
Evaluation.
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Solid Matrix—
A synthetic solid matrix was used in this research. A single batch of
this solid matrix was prepared by combining 250 g of Celite 503 obtained from
Aldrich with 250 g of Kaolin obtained from J. T. Baker in a wide-mouth 5 Ib
jar. To this mixture was added 625 ml of RG water. The mixture was stirred
with a large spatula and the jar was sealed with a Teflon-lined screw cap.
The jar was then tumbled manually end-over-end for 100 complete rotations and
allowed to settle thoroughly. After decanting the excess water, the settled
material was bottled in multiple aliquots in 4 oz Teflon-lined screw cap
jars. For each experiment involving solid sample matrix, all of the sample
used was taken from the same fresh, previously unused jar.
INSTRUMENTATION
FTP System
An automated PTD system was used in the portions of these studies
involving Method 5030 as the sample introduction technique. The system used
consisted of a Tekmar Automated Liquid Sampler (ALS) purging component
coupled to either a Tekmar Model LSC 2 or a Tekmar Model 4000 trap and desorb
unit. The Tekmar ALS has ten positions for purging vessels and accommodates
any combination of standards, samples, and blanks. The automated PTD system
was used because it operates unattended and, therefore, improved the cost-
effectiveness of data acquisition. The PTD conditions used for each of the
Methods were exactly as prescribed in SW-846 and are presented in Table 5.
Autosampler System
An autosampler was used in the portion of these studies involving DLI of
the sample into the GC system. The system used was a Hewlett-Packard Model
7376A Automatic Sampler. This device has 100 positions and can accommodate
any combination of standards, samples, and blanks. The autosampler was used
because it operates unattended and, therefore, improved the cost-effectiveness
of data acquisition.
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Gas Chromatographs
Because a different detector is required for each of the Methods
evaluated, several different GC systems were used. This approach permitted
the PTD studies on one Method to be conducted simultaneously with the DLI
studies on the same or on another Method. The GC columns and conditions used
in evaluating these Methods were exactly as prescribed in SW-846 and are
presented in Table 4 along with an identification of the GC system used for
each Method.
Laboratory Data System
Data acquisition and peak area integration were accomplished using a
Computer Automated Laboratory System (CALS) purchased from Smith-Beckman.
CALS is implemented on a Hewlett-Packard Model 1000 computer.
METHODS
Preliminary Activities
Preparation of Stock Solutions--
Single component stock solutions of all compounds used in these
evaluations were prepared in methanol at a concentration of 10 mg/mL. Stock
standard solutions were stored headspace free at -10°C in screw cap vials
with Teflon-faced septa until use. Stock solutions of compounds with boiling
points less than 30°C were prepared weekly and stock solutions of compounds
with boiling points greater than 30°C were prepared monthly.
Determination of Retention Times--
Retention times for each of the Method 8010, 8015, and 8020 analytes
were determined using the GC conditions associated with the appropriate
Method and the DLI sample introduction technique. Approximately 160 ng of
each compound was injected into the GC system either as a single component
methanol dilution of the stock solution or in simple mixtures prepared by
methanol. For early eluting Method 8015 compounds which coeluted with
combining appropriate aliquots of the stock solutions and diluting with
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methanol, single component o-xylene stock solutions were prepared and diluted
with this same solvent.
Determination of Purging Efficiency—
The purging efficiency of each compound used in these evaluations was
determined using the PTD and GC conditions specified in the appropriate
Method. DLI calibration solutions were prepared as single component
solutions or simple mixtures in methanol by diluting the single component
stock solutions or by combining appropriate aliquots of the single component
stock solutions and then diluting. Aqueous calibration solutions were then
prepared by adding an appropriate volume of the DLI calibration solution to 5
ml of RG water. For each compound, aqueous calibration standards were first
prepared at approximately 40 ug/L. If no peak was observed from the analysis
of this solution, another aqueous calibration solution containing the
compound at a higher concentration was prepared and analyzed. Generally, the
highest concentration tested for any compound was 400 ug/L. However, if a
small signal was detected at this concentration, the compound was retested at
a concentration of 800 ug/L. The results of triplicate analyses of each
aqueous calibration solution were compared to the results obtained when the
corresponding DLI calibration solution was analyzed and these data were used
to calculate purging efficiency for each compound.
Establishment of Solution Sets--
Compounds previously reported to be unamendable to GC separation (3) or
found to have a PTD recovery of less than 10 percent, were excluded from any
further evaluation of the Methods using the PTD sample introduction
technique. Compounds previously reported to be unamendable to GC separation
were also excluded from Method evaluations using DLI as the sample
introduction technique. However, compounds with low purging efficiency were
included in the DLI Method evaluations. Based on information obtained in the
retention time determinations, the compounds associated with each Method were
divided into several solution sets. The goal in establishing these sets was
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to avoid coelution of the analytes while generating the minimum number of
solution sets possible for each Method to ensure cost-effective data
acquisition. Since some compounds included in the DLI studies were not
included in the PTD studies because of poor purging efficiency, the PTD and DLI
solution sets were not identical.
Instrumentation Range Determination
Thq Instrumentation Range Determination studies for Methods 8010, 8015,
and 8020 were conducted according to the procedures developed under EPA
Contract Number 68-03-3224, Work Assignment 1 entitled, "Single Laboratory
Method Validation Protocol." The initial step of the SLMVP is determination of
the concentration range over which the analytical instrumentation will perform
for the method analytes. Results obtained in this validation step establish a
basis for determining the test concentrations and the calibration function to
be used in later steps of the validation. A flow diagram illustrating specific
activities of the Instrumentation Range Determination step is shown in Figure
2. A brief summary of the activities included in this phase of the Method
8010, 8015, and 8020 Validation is presented below.
Determination of the Signal-to-Noise Ratio for the Standard--
For the PTD portion of these studies, an aqueous calibration standard of
each of the solution sets for the three Methods was prepared. Each of these
calibration standards contained the analytes included in that solution set at a
concentration approximating the EDLs. Detection limits for each compound were
estimated based on previous experience with the analyte including the
anticipated response of the GC detector to the compound and the purging
efficiency of the compound from water. The multicomponent working standard
solutions were prepared by combining appropriate aliquots of the single
component stock standard solutions and diluting with methanol. The analyte
concentrations in the working standard solutions were selected so that addition
of 5 uL of each solution into 5 mL of RG water produced the desired
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concentration for the calibration standard. For the portion of the study
involving DLI as the sample introduction technique, multicomponent
calibration standards of late eluting compounds were prepared in methanol or
pentane and multicomponent calibration standards of early eluting compounds
were prepared in oxylene.
Four replicates of each of these calibration standards were analyzed
along with a reagent blank. The PTD reagent blank was composed of RG water
and the DLI reagent blank consisted of the appropriate solvent. As
necessary, the multicomponent working standard solutions were remade with the
concentration of specific analytes being adjusted to provide a signal-to-
noise ratio (S/N) between 3 and 10. From the data generated in this
experiment, the amount of each analyte required to give a S/N of 5 was
calculated.
Preparation of Calibration Standard Solutions—
To prepare the aqueous calibration standard solutions for the PTD
studies, the amount of each analyte required to produce a S/N of 5,000 was
first calculated. Ten milliliters of each solution set standard was prepared
by combining appropriate aliquots of the single component stock standard
solutions to achieve the analyte concentrations corresponding to a S/N of
5,000. To prepare the 5, 15, 50, 150, 500, and 1500 S/N solution set
standards, single dilutions of the 5,000 S/N solution set standards were
made. The aqueous calibration standards were then prepared by adding 5 uL of
one of these solutions to 5 ml of RG water. This procedure involved removing
the plunger from a 5 ml gas-tight syringe equipped with a syringe valve and
luerlock adapter, filling the barrel of the syringe to overflowing with the
RG water, and replacing the plunger. The plunger was then adjusted to the
5 ml mark and the valve of the syringe was opened to allow introduction of 5
uL of the appropriate solution set standard. The contents of the syringe
were then delivered into one of the purging tubes which was then connected to
the Tekmar ALS.
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To prepare the calibration standards for the DLI portion of the study
for Methods 8010, 8015, and 8020, the amount of each analyte needed to
produce an S/N of 5,000 was calculated. Ten milliliters of each solution set
standard was prepared by combining appropriate aliquots of the single
component stock standard solutions and diluting with methanol or pentane for
the solution sets containing the late eluting compounds or with
oxylene for the solution sets containing the early eluting compounds. The 5,
15, 50, 150, 500, and 1500 S/N solution set standards were then prepared by
single dilutions of the 5,000 S/N solution set standard.
For the DLI portion of the Method 8015 validation, difficulties were
encountered with trace impurities in the methanol which coeluted with some of
the analytes. Since this Method involved the use of an FID detector, the
presence of these impurities caused inaccurate integration of the GC peaks
associated with the affected analytes. Consequently, the single component
stock standard solutions used in these studies were prepared in pentane or o-
xylene as appropriate for the solution set in which they were included. The
5,000 S/N was then prepared by combining appropriate aliquots of these
solutions and diluting with the same solvent. The other solution set
standards including the 5, 15, 50, 150, 500, and 1500 S/N were prepared by
single dilutions of the 5,000 S/N standard using the same solvent.
Determination of Interference Concentration Limit—
The interference concentration limit for each analyte was determined as
described in the SLMVP. This process was fairly straight forward for the DLI
portion of these studies. However, for the PTD studies, carryover was
also detected when a reagent blank was placed in the same position on the ALS
previously occupied by some of the high level aqueous calibration standards.
Carryover was not detected in the second reagent blank subsequently placed in
that position. Consequently, reagent blanks were always placed in the
positions occupied by certain of the high level aqueous calibration standards
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to eliminate interferences in analyses of subsequent solutions placed in
those positions. The concentrations of the aqueous calibration standards
requiring reagent blanks was highly dependent on the specific analytes.
Certain analytes required reagent blanks even after the 150 S/N standard.
Data Acquisition--
Data to be used in determining the Instrument Range for Methods 8010,
8015, and 8020 were acquired by analyzing four replicates of each level of
the calibration standards for each Method. For the DLI portion of the study,
at least eight replicates of the two lowest level calibration standards for
each of the Methods was analyzed to provide data for calculation of an EDL
for each analyte using the DLI sample introduction technique.
Evaluation of Results--
The data obtained as described above were evaluated according to the
procedures described in the SLMVP. Evaluation of the instrumentation range
determination results involves testing several calibration models for the
method analytes. The following models are tested sequentially:
Response Factor: X = biC + E
Linear: x = bQ + biC + E
Quadratic: X = bg + biC + b2C2 + E
where:
X = Instrument response for analysis
C = Concentration of standard or sample
E = Random error term
bQ = Intercept parameter for linear and quadratic calibration
models
bi = Slope parameter
b£ = Quadratic coefficient for quadratic calibration model.
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The calibration model parameters are estimated using the method of least
squares after dividing both sides of the calibration equation by C. The
models are evaluated sequentially for the ability to describe the
experimental data. The criteria used in these evaluations are described in
detail elsewhere (5). These statistical tests had originally been conducted
with the use of a Computer Data Corporation mainframe computer. For this
effort, the programs were transferred to an IBM PC compatible format to
enhance the cost-effectiveness and efficiency of conducting these evaluations
with such a large number of analytes.
Preliminary Method Evaluation
In these studies, the Preliminary Method Evaluation step of the single
laboratory validation of Methods 8010, 8015, and 8020 consisted of the
analysis of spiked liquid and solid samples using the PTD sample introduction
technique. No experiments involving the use of DLI were conducted during the
Preliminary Method Evaluation. This step of the SLMVP is conducted to
determine if the method performs adequately for specified analytes before
actual validation begins. This preliminary evaluation ensures that no major
technical difficulties are inherent in the method, that reasonable results
can be obtained for method analytes, and that the time, effort, and cost of a
validation study will not be spent on an unsatisfactory method. A flow
diagram illustrating specific activities of the Preliminary Method Evaluation
step is shown in Figure 3. A brief summary of the activities included in the
phase of the Methods 8010, 8015, and 8020 validation are presented below.
Preparation and Analysis of Liquid Samples—
The liquid samples used in the Preliminary Method Evaluation experiments
consisted of RG water spiked with the analyte at concentrations which gave a
S/N of 100. These samples were prepared by adding 10 uL of the 5,000 S/N
solution set standard to 500 ml of RG water and, after mixing, immediately
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bottling 9 to 11 replicate samples in 40 ml vials sealed headspace free with
Teflon-lined silicone septa and screw caps. These replicates were stored
inverted overnight at 4<>C prior to analysis. On the following day, at least
eight of the samples were analyzed along with appropriate calibration
standards as outlined in the Method being validated.
Preparation and Analysis of Solid Samples—
As described previously, spiked solid samples consisting of equal parts
of Celite 503 and Kaolin were used in the Preliminary Method Evaluation of
Methods 8010, 8015, and 8020. For each Method, eight replicate 2 g aliquots
of the solid sample were spiked with 20 uL of the 5,000 S/N solution set
standard. This spiking level was selected to provide an analyte
concentration in the final extract that would give rise to a 100 S/N
response. The mixtures were stirred thoroughly using a vortex mixer, sealed
in screw cap vials equipped with Teflon-lined septa, and stored at 4<>c
overnight. On the following morning, the sample preparation procedures used
were those specified in Method 5030. Each sample was dispersed in 40 ml of
extracting solvent, agitated vigorously for 1 minute, and centrifuged to
effect phase separation. Methanol was used as the extracting solvent for
Methods 8010 and 8020. For Method 8015, polyethylene glycol (PEG) was used
to extract the solid samples. A 100 uL portion of each sample extract was
then added to 5 ml of RG water and this mixture was introduced into a purge
tube attached to the Tekmar ALS. The samples were then analyzed along with
10, 30, and 100 percent recovery standards as described in the Method being
validated. The recovery standards consisted of RG water spiked with the same
solution used to fortify the solid samples at levels which spanned the
expected range for recovery of analytes from the solid samples.
Data Acquisition-
Data to be used in conducting the Preliminary Method Evaluation for
Methods 8010, 8015, and 8020 were acquired by analyzing at least eight
15
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replicates of the aqueous and solid samples prepared as described above. All
analyses in this step of the Method validation were conducted using the PTD
sample introduction technique.
Evaluation of Results--
The data obtained as described above was evaluated according to the
procedures described in the SLMVP. These evaluations involved determining
the recovery and precision for each Method analyte. These values were then
compared to the method performance obtained for the Priority Pollutant
compounds.
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SECTION 5
RESULTS AND DISCUSSION
PRELIMINARY ACTIVITIES
Preliminary activities in the validation of Methods 8010, 8015, and 8020
included the determination of retention times and purging efficiencies for
each of the analytes being used in the evaluation of these Methods. The
results of these activities for Methods 8010, 8015, and 8020 are presented in
Tables 6, 7, and 8, respectively which also includes an estimated detection
limit for each analyte using the PTD sample introduction technique and a
method detection limits for each analyte calculated on the basis of replicate
analyses of standards using the DLI sample introduction technique. Based on
efforts to determine retention times and purging efficiencies, several
compounds were excluded from the PTD and/or the DLI portions of these
studies. These analytes are listed by Method in Table 9 along with the
reason for each exclusion. These reasons for exclusion are discussed in
greater detail below.
Method 8010
Chloroacetaldehyde was excluded from all Method 8010 testing because a
commercial source could not be identified. Bis (2-chloroisopropyl) ether was
also excluded from Method 8010 testing because the standard material that had
been obtained was found to be impure and another batch could not be obtained
in time for use. Bis (2-chloroethyl) sulfide, chloral, 3-chloropropio-
nitrile, and pentachloroethane were excluded from all Method 8010 experiments
because of poor chromatographic behavior when either PTD or DLI was used for
sample introduction. Unacceptably low response factors had been determined
for bis (2-chloroethyl) sulfide and chloral, or chloral hydrate, in the GC/MS
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suitability testing conducted under Work Assignment 4 of EPA Contract Number
68-03-3224 suggesting that some difficulty had been encountered with these
two compounds in this earlier work. The chromatographic column and condi-
tions used in the Method 8010 testing were identical to those used in the
GC/MS suitability testing with the exception that the column itself was metal,
as specified in Method 8010, as opposed to the glass column used in the
earlier work. Contact with this hot metal surface may be the cause of the
low, broad chromatographic peaks observed for bis (2-chloroethyl) sulfide and
for 3-chloropropionitrile. This contact may also have been responsible for
the apparent decomposition of chloral and of pentachloroethane. Chromato-
grams of single component solutions of each of these analytes contained two
peaks. These peaks were assumed to indicate the presence of decomposition
products since impurities had not been observed in the GC/MS suitability
testing which involved the use of standards from the same commercial supplier
and lot number. Chloroprene was observed to have poor chromatographic
behavior when DLI was used as the sample introduction technique. Similar
difficulties were not observed with this compound when the sample introduc-
tion technique was PTD. Using DLI, chloroprene appeared to be decomposing in
the injector when higher concentrations were introduced into the GC system.
This process may not be significant when the analyte is introduced more
gradually during the desorption cycle of the PTD sample introduction.
Chloroprene was included in the PTD portion of the study but was excluded
from the experiments involving DLI as the sample introduction technique.
Bis (2-chloroethoxy) methane, bromoacetone, 2-chloroethanol, 2-chloro-
ethyl vinyl ether, chloromethyl methyl ether, l,3-dichloro-2-propanol, and
epichlorohydrin were eliminated from Method 8010 PTD studies because of poor
purging efficiency. However, these compounds were included in the DLI
studies of this Method. These seven compounds were not detected using the
PTD sample introduction technique at the 400 ug/L level in reagent water.
Poor purging efficiencies for these compounds are undoubtedly due to their
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aqueous solubility. 2-chloroethyl vinyl ether, a priority pollutant, was not
detected in the purging efficiency studies when tested at a concentration of
160 ug/L. This concentration is close to the reported detection limit of 130
ug/L. The purging efficiency for this compound should probably have been
evaluated at higher concentrations.
Purging efficiencies determined for most of the other compounds used in
the Method 8010 testing ranged from 70 to 110 percent. Analytes for which
purging efficiencies outside this range were determined include several
relatively polar, water-soluble compounds such as benzyl chloride and 1,4-
dichlorobutene; and higher molecular weight, less volatile compounds such as
bromoform, l,2-dibromo-3-chloropropane, and 1,2,3-trichloropropane. These
compounds were included in both the PTD and DLI portions of Method 8010 in
order to develop method performance data for as wide a variety of compounds
as possible. Anomalous data were obtained for chlorobenzene and tetrachloro-
ethylene which were both determined to have a purging efficiency of 51
percent. These compounds are both priority pollutants and are known to purge
more efficiently from aqueous samples. Because of this fact and because the
relative standard deviation values of the purging efficiency measurements
were relatively high, the assumption was made that the purging efficiency
data were in error and these two compounds were included in the Method 8010
testing. No attempts were made to determine the cause of these erroneous
data.
Based on these preliminary experiments, a total of 40 analytes including
26 priority pollutant compounds were initially used in the PTD portion of
Method 8010 testing. In the DLI portion of these evaluations, a total of 46
compounds including 27 priority pollutants were used.
Method 8015
Acrylamide and 2-hydroxypropionitrile were eliminated from both the PTD
and the DLI portions of Method 8015 testing because of poor chromatographic
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behavior. These findings agree with those obtained in the GC/MS testing in
which aery1 amide, tested as a semi volatile compound, was not detected and 2-
hydroxypropionitrile, tested as a volatile compound, was found to have an
unacceptably low response. Under the Method 8015 chromatographic conditions,
these two compounds were found to have a low response and to produce low,
broad chromatographic peaks. A number of the analytes intended for Method
8015 testing were determined to have very poor purging efficiencies. Purging
efficiencies of less than 10 percent were determined for acetonitrile; ally!
alcohol; carbon disulfide; 1,2,3,4-diepoxybutane; 1,4-dioxane; ethylene
oxide; isobutanol; malononitrile; methyl mercaptan; paraldehyde; propargyl
alcohol; 6-propiolactone; and propionitrie. These compounds were excluded
from the PTD portion of this study, but were included in the DLI portion of
Method 8015 testing. With the exception of diethyl ether, which was deter-
mined to have a purging efficiency of 90 percent, the measured purging
efficiencies for the remaining compounds ranged from 14 to 55 percent. These
compounds were included in the Method 8015 PTD studies to develop method
performance data for as many compounds as possible.
Due to the results of these preliminary experiments, six analytes were
used in the PTD portion of Method 8015 testing and 19 compounds were used in
the DLI experiments. None of these compounds were priority pollutants.
Method 8020
Pyridine and thiophenol were excluded from Method 8020 PTD and DLI
testing because of poor chromatographic behavior. Both of these compounds
had been included in the GC/MS suitability testing and this approach was
determined to be successful for these two analytes. The PID detector used in
Method 8020 exhibited a relatively low response for both of these compounds;
2,000 ng of thiophenol was barely detectable by this Method. The relatively
large amounts of material required for detection may have overloaded the
chromatographic column and/or interacted with the hot metal surface of the
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column resulting in decomposition or interfering with the chromatographic
processes. In either event, broad low peaks were observed in the chromato
grams resulting from the analyses of these two compounds. Only 2-picoline
was eliminated from the Method 8020 PTD studies because of poor purging
efficiency. Using the PTD sample introduction technique, this analyte was
not detected at a concentration of 800 ug/L in reagent water. 2-picoline was
included in the DLI portion of Method 8020 testing. The purging efficiencies
determined for the other analytes used in this testing ranged from 77 to 99
percent with the exception of chlorobenzene. The purging efficiency for this
compound was not reevaluated and data presented in the Method 8020 portion of
Table 8 are the results of the same determinations reported in the Method
8010 section. As discussed, since chlorobenzene is a Priority Pollutant and
known to purge efficiently, these data were judged to be in error and this
compound was included in the Method 8020 PTD studies.
Data obtained during these preliminary experiments resulted in the use
of 11 compounds in the PTD portion of Method 8020 testing and 12 analytes in
the DLI studies. In each case, seven of the compounds used are priority pol-
lutants.
INSTRUMENTATION RANGE
Data used in establishing the instrumentation range for each Method are
obtained by replicate analyses of standards for each Method analyte at
concentrations which span three orders of magnitude. As described pre-
viously, evaluation of these data involve testing several calibration models
for each of the compounds used in the Method testing. The calibration model
which is the best fit of the data is selected for use in the subsequent steps
of the method validation.
In these studies, four replicate standards of each method analyte were
analyzed at each of seven concentrations. In the DLI portion of each study,
21
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at least eight replicate standards of each compound were analyzed at the two
lowest concentrations to permit calculation of an estimated detection limit.
A summary of the data generated in these analyses is presented for the PTD
and DLI studies, respectively, in Tables 10 and 11 for Method 8010, in Tables
12 and 13 for Method 8015, and in Tables 14 and 15 for Method 8020. Each of
these tables presents the solution set in which each analyte was included and
the concentration of each compound that gave rise to a signal equal to the
instrumental noise, the mean response factor, and the relative standard
deviation determined at each of the concentrations tested. These tables are
included for reference during the discussions presented below.
Method 8010
PTD Studies—
The results of the Instrumentation Range Determination for Method 8010
using the PTD sample introduction technique are summarized in Table 16 which
presents the concentration ranges over which each of the three calibration
models was accepted for each analyte. A total of 26 priority pollutant
compounds was included in the Method 8010 evaluations. For 18 of these
compounds, either all three or two of the calibration models were accepted
over the entire three-orders-of-magnitude concentration range tested. In
cases in which two calibration models were accepted, the response factor
model was the one rejected. The response factor model is a special case of
the linear model. Given a graph of concentration versus response for an
analyte, the response factor model requires that the y-intercept value be
zero. For the linear model, the y-intercept on this graph is some non-zero
value. Since these two calibration models are very similar, if the linear
model was accepted, attempts were not made to determine the analyte con-
centration range over which the response factor model would be accepted. Two
or three calibration models were accepted when the lowest concentration was
excluded from the evaluations for four more priority pollutants including
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chloroform, dichloromethane, 1,1,1-trichloroethane, and trichlorofluoro-
methane. As shown in Table 10, the response factor determined for each of
these compounds at the lowest concentration tested was substantially higher
those determined at other concentrations. For these compounds, the con-
centrations determined for the 5 S/N levels may have been too low for
reliable instrument performance. However, an instrumentation range of two-
and-a-half orders of magnitude is certainly acceptable, and in terms of this
step of the evaluation, Method 8010 performed acceptably for these four
compounds as well as for the other 18 compounds discussed previously. Since
these 22 compounds are priority pollutants for which the Method has been
demonstrated to perform well for aqueous samples, the suitability of Method
8010 for the determination of the other test compounds will be discussed in
terms of these reference compounds.
For one priority pollutant, bromoform, only the quadratic calibration
model was accepted after the lowest concentration had been eliminated from
the concentration range being evaluated. Response factors determined for
bromoform using the PTD sample introduction technique, presented in Table 10,
seem to increase with analyte concentration. With the exception of the
lowest level, response factors determined at each concentration are very
reproducible. While the reason for this concentration dependence is not well
understood, decomposition on the hot metal of the chromatographic column may
be a contributing factor. This process would be most easily observed at the
lower concentrations at which the amount of material being decomposed is a
relatively larger fraction of the total amount of analyte introduced into the
GC system. This effect is observed, but less pronounced, for other bro-
minated compounds included in the Method 8010 testing. These materials are
more thermally labile than the chlorinated compounds and, therefore, might be
expected to be more affected by contact with hot metal. Use of a glass
column or a fused silica capillary column is expected to provide better
performance of Method 8010 for these compounds.
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The performance of Method 8010 for the other three priority pollutants
included in these evaluations was not as expected, although some of the
discrepancies can be explained. Calibration models were accepted for
chloroethane and for 1,1,2,2-tetrachloroethane only after the two lowest
concentrations were removed from the concentration range tested. For both of
these compounds, the two lowest concentrations tested were below previously
reported estimated detection limits for these compounds in aqueous samples.
These estimated detection limits are 0.52 and 0.03 ug/L for chloroethane and
1,1,2,2-tetrachloroethane, respectively. Again, for these compounds, Method
8010 should probably have been evaluated over a higher concentration range.
None of the calibration models were accepted for bromomethane over the
concentration range evaluated. Examination of the response factors, pre-
sented in Table 10, determined for this compound at each concentration tested
indicate the dependence on concentration observed for some of the other
brominated compounds. This trend is somewhat more pronounced than for
bromoform as discussed above. Again, the thermal degradation of the analyte
in the injector or on the metal column is suspected of being the cause of
this trend and use of a glass column or a fused silica capillary column is
expected to provide better method performance for this compound. However,
since bromomethane is a priority pollutant, it was included in the next step
of this evaluation.
For 12 of the 14 remaining compounds included in these evaluations,
Method 8010 performed as it had for the priority pollutant reference com-
pounds. For these analytes, at least two calibration models were accepted
over a concentration range of two-and-a-half or three-orders of magnitude.
As shown in Table 10, these compounds include allyl chloride, benzyl chlor-
ide, bromobenzene, 1-chlorohexane, chloroprene, 4-chlorotoluene, dibromo-
methane, l,4-dichloro-2-butene, dichlorodifluoromethane, ethylene dibromide,
1,1,1,2-tetrachloroethane, and 1,2,3-trichloropropane. All three calibration
models were accepted for l,2-dibromo-3-chloropropane after the two lowest
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concentrations were eliminated from the concentration range being evaluated.
As shown in Table 8, the response factors determined for this analyte for the
two lowest levels were substantially higher than those determined for this
compound at higher concentrations. Again, this trend was observed for other
brominated compounds included in this study and may be due to the use of the
metal chromatographic column. None of the calibration models were accepted
for methyl iodide over any portion of the concentration range tested. Exami-
nation of the response factors presented in Table 10 for this compound
indicated substantial variability between concentrations as well as sub-
stantial variability in the response factors determined at any single
concentration. Contact with the metal chromatographic column and the
relative thermal lability of these compounds are probably the causes of this
imprecision. For both of these compounds use of a glass column or a fused
silica capillary column is expected to improve the performance of Method
8010.
Based on the results of the Instrumentation Range Determination, 39 of
the 40 analytes used in these experiments were included in the Preliminary
Method Evaluation of Method 8010 suitability testing. Only methyl iodide was
excluded from this next set of experiments because an appropriate calibration
model could not be found for this analyte over any portion of the concen
tration range tested.
DLI Studies—
The results of the Instrumentation Range Determination for the 46
compounds used in evaluating Method 8010 using the DLI sample introduction
technique are summarized in Table 17 which presents the concentration range
over which each calibration model was accepted for each analyte. For 16 of
the 27 priority pollutant compounds, at least two calibration models were
accepted over a concentration range of two, two-and-a-half, or three orders
of magnitude. The lowest or the two lowest concentrations were eliminated
25
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from the range being evaluated for those compounds for which calibration
models were accepted over less than three orders of magnitude. For these
compounds including, bromomethane, 2-chloroethyl vinyl ether, the three
dichlorobenzene isomers, trichlorofluoromethane, and vinyl chloride, the
analyte concentrations used at these lower levels may have been selected
under ideal conditions when the GC system was performing optimally and may be
too low for consistent instrument operation. For the remaining 11 priority
pollutants, only the quadratic calibration model was accepted over the
concentration range of two, two-and-a-half, or three orders of magnitude.
The reasons for the observed relatively poorer performance of Method 8010 for
these compounds are not well understood. Examination of the response factors
determined for these analytes, shown in Table 11, does not reveal any
consistent trend. In some cases, substantial differences exist among the
response factors for all of the concentrations tested. For other compounds,
the response factors determined at the intermediate concentrations are
relatively consistent, but those determined for the highest and the lowest
concentrations are substantially different. Eight of these 11 compounds were
included in Solution Sets 1 or 6 for the DLI portion of the Method 8010.
Perhaps some unidentified error in the preparation of the stock solution or
the dilutions is the cause of these anomalous results. In any event, since
acceptable performance of Method 8010 for priority pollutants has been
demonstrated and well documented, the conclusion must be drawn that the
Instrumentation Range Determination data for these compounds are the result
of some laboratory anomaly or error and not due to performance of Method 8010
for these analytes.
Of the remaining 19 compounds included in the DLI portion of the step of
the Method 8010 evaluation, at least two calibration models were accepted for
14 analytes over a concentration range of two, two-and-a-half, or three
orders of magnitude. For these compounds, the performance of Method 8010 was
equivalent to that observed for the priority pollutants used as reference
26
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compounds. Therefore, Method 8010 is considered suitable for these compounds
at this stage of the evaluations. For the other five compounds, which
include bromobenzene, chloromethyl methyl ether, l,2-dibromo-3-chloropropane,
dibromomethane, and dichlorodifluoromethane, either only the quadratic model
was accepted over a concentration range of two-and-a-half or three orders of
magnitude or the two or three calibration models accepted were found to
suitable over a concentration range of only one-and-a-half orders of mag-
nitude. Four of these five compounds were included in Solution Sets 1 or 6
during this portion of the study and, as discussed above, some laboratory
error may be the cause of these anomalous data. Since data obtained for
these analytes are equivalent to that generated for priority pollutant
compounds, Method 8010 was considered to have performed acceptably for all
of the analytes included in the DLI portion of the Instrumentation Range
Determination.
Method 8015
PTD Studies—
The results obtained for the Instrumentation Range Determination for
Method 8015 using the PTD sample introduction technique are summarized in
Table 18. Only six analytes were included in this portion of the method
evaluation and none of these compounds are priority pollutants. For five
compounds, at least two calibration models were accepted over a concentration
range of two, two-and-a-half, or three orders of magnitude. This method
performance is equivalent to that obtained for the priority pollutant
reference compounds in the PTD portion of Method 8010 testing. These
compounds include diethyl ether, ethyl methacrylate, methacrylonitrile,
methyl ethyl ketone, and methyl methacrylate. None of the calibration models
were accepted over any portion of the concentration range tested for methyl
isobutyl ketone. Examination of the response factors determined for this
27
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compound and presented in Table 12 reveal substantial variability between
concentrations. This variability may be associated with the low purging
efficiency of this compound.
DLI Studies--
Table 19 presents a summary of the results obtained for the Instrumen-
tation Range Determination of Method 8015 using the DLI sample introduction
technique. A total of nineteen compounds, none of which are priority
pollutants, were included in these evaluations. For 13 of these analytes, at
least two calibration models were accepted over a two, two-and-a-half, or
three orders of magnitude concentration range. Again, the performance of
Method 8015 for these compounds is equivalent to that observed for Method
8010 priority pollutant reference compounds. For three compounds including
1,2,3,4-diepoxybutane, methyl mercaptan, and B-propiolactone, only the
quadratic calibration model was accepted over a concentration range of two,
two-and-a-half, or three orders of magnitude. As shown in Table 13, the
response factors determined for these compounds are very consistent at each
concentration but are more variable between concentrations. Again, these
results are similar to those obtained for some of the priority pollutant
compounds in the DLI portion of Method 8010 testing. Consequently, Method
8015 is assumed to be performing suitably for these compounds in this portion
of the study. For the remaining three compounds used in the Method 8015
testing, none of the calibration models were accepted over any portion of the
concentration range evaluated. As shown in Table 13, response factors
determined for carbon disulfide and malononitrile were quite low which
suggests that the FID detector used in Method 8015 is not very sensitive for
the detection of these compounds. In fact, such a large amount of malononi-
trile was required to obtain a reliable response that solubility difficulties
were encountered at the higher concentration levels and the two highest
concentration standards could not be prepared in the solvents used in this
28
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study. The response factors determined forB-propiolactone are quite
consistent at each concentration but appear to increase with increasing con-
centration. Consequently, Method 8015 appears to be unsuitable for the
determination of carbon disulfide, malononitrile, and e-propiolactone.
However, based on the Instrumentation Range Determination, Method 8015
appears to be suitable for the determination of the other 16 compounds in
nonaqueous samples using the DLI sample introduction technique.
Method 8020
PTD Studies—
The results obtained for the Instrumentation Range Determination for
Method 8020 using the PTD sample introduction technique are summarized in
Table 20. Seven of the 11 compounds used in this portion of the method
evaluation are priority pollutants. For five of these compounds, only the
quadratic model was accepted over a concentration range of two-and-a-half or
three orders of magnitude. These analytes included chlorobenzene, 1,2- and
1,4-dichlorobenzene, ethyl benzene, and toluene. Two calibration models were
accepted for benzene and for 1,3-dichlorobenzene over a one-and-a-half order
of magnitude concentration range. For each of these compounds, the con-
centration selected for lowest level standards was equivalent to or, for some
analytes such as chlorobenzene and ethyl benzene, substantially less than the
estimated method detection limit previously reported. To characterize the
performance of Method 8020 fully for these compounds, higher concentration
ranges may have been more useful. However, these analytes can still be used
as reference compounds, and the performance of the Method for other compounds
will be discussed in terms of the results obtained for these priority
pollutant compounds.
For the other four compounds used in this evaluation including, styrene
and the three xylene isomers, the performance of Method 8020 was essentially
equivalent to that obtained for the priority pollutant reference compounds.
29
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The quadratic calibration model was accepted for styrene and for p-xylene
over a three order of magnitude concentration range and for o- and m-xylene
over a concentration range of two orders of magnitude. As for the priority
pollutant compounds, use of higher concentration ranges to test the calibra-
tion models may have provided a fuller evaluation of the Method performance
for these compounds. Based on these data, Method 8020 performed suitable for
all of the analytes used in these experiments and all of these analytes were
included in the Preliminary Method Evaluation step of the Method 8015
testing.
DLI Studies-
Table 21 presents a summary of the results obtained for the Instrumen-
tation Range Determination for Method 8020 using the DLI sample introduction
technique. A total of 12 compounds were used in this portion of the testing.
Again the seven priority pollutant compounds will serve as reference com-
pounds and the performance of the Method for the other analytes will be
discussed in terms of results obtained for these compounds. Over a con-
centration range of two-and-a-half or three orders of magnitude, only the
quadratic calibration model was accepted for six of the priority pollutant
compounds. For the remaining reference analyte, 1,3-dichlorobenzene, both
the linear and the quadratic models were accepted over a three order of
magnitude concentration range. For three of the remaining compounds in-
cluding 2-picoline, styrene, and m-xylene, the quadratic calibration model
was accepted over a concentration range of two-and-a-half or three orders of
magnitude. For these compounds, the performance of Method 8020 was equiv-
alent to that obtained for the priority pollutant compounds. For o-xylene,
two calibration models were accepted only after the concentration range being
tested had been reduced to one-and-a-half orders of magnitude. None of the
calibration models were accepted for p-xylene over any portion of the
concentration range tested. Results obtained for these two compounds must be
30
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considered anomalous. Since the Method performed suitable for m-xylene,
there is no reason that it should not be suitable for the ortho and para
isomers of this compound. The cause of these anomalous data is not known but
may be some error in preparation of the stock solutions or in acquisition of
the data. Consequently, Method 8020 is assumed to perform suitably for these
two compounds and for the other 10 analytes in this step of the evaluation.
PRELIMINARY METHOD EVALUATION
As discussed in detail previously, the Preliminary Method Evaluation
phase of the testing of each of these Methods was conducted using the PTD
sample introduction technique only. In these experiments, replicate reagent
water and synthetic solid matrix samples were prepared by spiking with
solutions containing the test analytes at levels within the concentration
range over which the calibration models had been accepted in the Instrumen-
tation Range Determination phase of these studies. These samples were then
stored at 4<>c overnight and analyzed the following day using the appropriate
Method and the PTD sample introduction techniques as described in Method
5030. The criteria used in evaluating method performance in this phase of
the testing were the recovery of each analyte, expressed as a percent of the
amount of material spiked into the replicate samples, and the precision of
the measurement of the compound recovered, expressed as the relative standard
deviation of the measurement.
The SLMVP specifies 70 to 130 percent as the range for acceptable
recoveries and 15 percent as the maximum RSD value for acceptable method
precision. For many of the analytes included in this step of the method
suitability testing, this performance was not obtained. These Methods failed
to achieve the specified performance even for some of the Priority Pollutant
compounds for which these Methods have previously been demonstrated to be
suitable in these sample types. The cause of these anomalous results must be
variable analyte losses in the spiking, handling, and/or storage of the
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aqueous and solid samples used in these experiments. For the aqueous
samples, a single 500 ml sample was spiked with the solution set being used
in the testing. This large sample was then mixed by repeated inversions of
the sample container and portions were then poured into 40 ml containers.
These containers were filled to overflowing, sealed with a Teflon-lined
septum screw cap and stored inverted until analysis on the following day.
Variable analyte losses could have easily occurred during the inversion
mixing of the large sample and/or during transfer of the sample to smaller
bottles for storage. For the solid samples, individual 2 g aliquots were
spiked with 20 uL of the solution set being tested. Each aliquot was then
stirred with a vortex mixer in a attempt to disperse the test compounds
evenly through out the sample. Each sample was then sealed using a Teflon-
lined septum screw cap and stored until analysis the next day. Variable
analyte losses could have occurred during the sample mixing. Variability
could also be due to heterogeneous distribution of the spike through out the
sample.
Because of these difficulties, evaluation of the performance of these
Methods using the criteria specified in the SLMVP is not reasonable.
Instead, the priority pollutant compounds will be considered reference
analytes and method performance will be discussed in terms of the results
obtained for these compounds.
Method 8010
A summary of the results of the Preliminary Method Evaluation for Method
8010 is presented in Table 22 for aqueous sample and in Table 23 for solid
samples. A total of 39 compounds, including 26 priority pollutants, were
used in this phase of the method testing.
Aqueous Samples—
In experiments involving the aqueous samples, recoveries for the
priority pollutants ranged from 21.8 to 112 percent. With the exception of
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three analytes, recoveries for these reference compounds exceeded 50 percent.
Recoveries for trichlorofluoromethane, vinyl chloride, and 1,1,1-trichloro-
ethane were determined to be 21.8, 45.1, and 48.2 percent, respectively.
These compounds are among the more volatile analytes included in this
testing. Therefore, somewhat higher losses during sample preparation are not
surprising. The precision of the determination of the priority pollutant
compounds was generally good. RSD values for the measurement of these
compounds were all less than 22 percent and many were less than 10 percent.
Based on the performance of Method 8010 for these reference compounds, the
criteria used in evaluating the suitability of this Method for the non-
priority pollutant compounds were recoveries in the range of 45 to 1201
percent and variability, as evidenced by RSD values, of less than 25 percent.
Method 8010 achieved these performance criteria for 10 of the remaining
13 compounds used in these evaluations. These compounds for which Method
8010 was determined to be suitable include allyl chloride, bromobenzene, 1-
chlorohexane, chloroprene, l,2-dibromo-3-chloropropane, dibromomethane, 1,4-
dichloro-2-butene, ethylene dibromide, 1,1,1,2-tetrachloroethane, and 1,2,3-
trichloropropane.
For the three remaining compounds the following results were obtained.
Reproducibility of the Method was poor for benzyl chloride and 4-chloro-
toluene for which RSD values of 46 and 40 percent, respectively were deter-
mined. Poor performance of Method 8010 is not unexpected for benzyl chloride
since, as the purging efficiency experiments indicated, this compound is
somewhat water soluble. Poor performance of the Method for 4-chlorotoluene
is somewhat surprising, however. As the purging efficiency experiments
demonstrate, chlorotoluene is efficiently recovered from aqueous samples by
purging. This compound is somewhat less volatile than other analytes
included in this testing, consequently, it should be somewhat less prone to
variable losses due to sample preparation techniques. However, as discussed
33
-------
below, an unacceptably high variability was also observed for this compound
in the solid sample experiments. Perhaps the boiling point and/or molecular
weight of chlorotoluene exceed the range that can be consistently determined
using ambient temperature PTD sample introduction techniques. A poor
recovery of 4.74 percent and an unacceptably high RSD value of 37 percent
were determined for dichlorodifluoromethane. This result is not surprising,
since this compound is very volatile and, therefore, might be expected to be
especially sensitive to vigorous mixing techniques during sample preparation.
Based on these results, Method 8010 is suitable for the determination of
all but three of the test compounds in aqueous samples. The three compounds
which can not be included in the scope of this Method include benzyl chlo-
ride, 4-chlorotoluene, and dichlorodifluoromethane.
Solid Samples—
In experiments involving solid samples, recoveries of the priority
pollutant compounds ranged from 6.32 to 76.6 percent. Only two of these
reference compounds were determined to have recoveries of less than 25
percent. Recoveries of 6.32 and 10.0 percent were determined for chloro-
methane and chloroethane, respectively. These compounds are among the most
volatile analytes included in this study and, therefore, are more likely to
be lost during sample preparation operations. RSD values for the deter-
mination of the priority pollutants in solid samples were generally less than
40 percent and less than 20 percent for many of these analytes. For two
compounds, vinyl chloride and 1,1,1-trichloroethane, RSD values of 43 and 77
percent, respectively were determined. Since vinyl chloride is relatively
volatile, it may be expected to be more susceptible to variable losses during
sample preparation. No explanation is apparent for the high degree of
variability associated with the determination of 1,1,1-trichloroethane.
Results for this compound must be considered anomalous. Based on the
performance of Method 8010 for these reference analytes, the criteria used to
34
-------
evaluate the suitability of this Method for the determination of the other
test compounds were recoveries of greater than 25 percent and RSD values of
less than 40 percent.
Method 8010 achieved these performance criteria for 11 of the remaining
13 compounds. Compounds for which the Method performed successfully in solid
samples included the 10 non-priority pollutants for which the Method was
determined to be suitable in aqueous samples plus dichlorodifluoromethane.
The 25.1 percent recovery determined for dichlorodifluoromethane was just
barely in the acceptable range indicating that this volatile compound is very
susceptible to losses during sample handling.
As with the aqueous samples, the variability of the Method for the
determination of benzyl chloride and 4-chlorotoluene in solids exceeded the
performance criteria. RSD values of 54 and 50 percent, respectively, were
determined for these compounds. Discussions of these results are identical
to those provided for the determination of these analytes in aqueous samples
provided above.
Evaluation of the results of Method 8010 using solid samples indicate
that this Method is suitable for the determination of 36 of the 39 test
analytes. The three compounds excluded on the basis of these experiments are
the same ones eliminated on the basis of the results obtained from the
analysis of aqueous samples. The performance of this Method for
dichlorodifluoromethane is marginal and performance for benzyl chloride and
4-chlorotoluene is unacceptable.
Method 8015
A summary of the results of the Preliminary Method Evaluation for Method
8015 is presented in Table 24 for aqueous samples and in Table 25 for solid
samples. Method 8015 was determined to perform acceptably for five compounds
in the Instrumentation Range Determination step. None of these compounds are
priority pollutants. Therefore, the performance of Method 8010 for the
35
-------
priority pollutant compounds used in evaluating the suitability of that
Method will be applied in discussing the performance of Method 8015. For
aqueous samples, these criteria include a recovery in the range of 45 to 120
percent and variability, as evidenced by the RSD value, of less than 25
percent. The criteria applied in evaluating method performance for solid
samples includes a recovery of greater than 25 percent and RSD value of less
than 40 percent.
Aqueous Samples--
In experiments involving aqueous samples, the performance of Method 8015
achieved the established criteria for all five of the compounds used in this
testing. Recoveries for these compounds ranged from 70.0 to 98.3 percent and
RSD values ranged from 2.8 to 20 percent. For these compounds, the perfor-
mance of Method 8015 was well within the established criteria.
Solid Samples—
For four of the five analytes included in the solid sample experiments,
Method 8015 exceeded the criteria established for determining suitability.
These compounds included diethyl ether, methacrylonitrile, methyl ethyl
ketone, and methyl methacrylate. The recovery of the fifth compound, ethyl
methacrylate was very poor. This compound is not expected to be particularly
susceptible to loss during sample preparation, so the cause of this low
recovery is not well understood. Since the recovery of this compound in the
aqueous sample experiments was quite good and no explanation is available for
poor recovery from the solid samples, these results may be due to an error in
preparation or dilution of the standards. Consequently, Method 8015 is
considered to be suitable for the determination of all five of the analytes
included in this portion of the testing.
36
-------
Method 8020
Table 26 provides a summary of the results of the Preliminary Method
Evaluation for Method 8020 for aqueous samples and Table 27 presents this
information for the solid sample experiments. Eleven compounds, including
seven priority pollutants were included in this step of the method
performance testing. In the discussions presented below, the priority
pollutants will be considered reference compounds and the performance of the
Method for other analytes will be discussed in terms of the results obtained
for these analytes.
Aqueous Samples—
For the experiments involving aqueous samples, the recoveries for the
seven reference compounds ranged from 61.9 to 98.2 percent and the RSD values
associated with these determinations were all less than 22 percent. Using a
60 percent minimum recovery and a 20 percent RSD value as the criteria for
evaluating method performance for the other four compounds, Method 8020 was
determined to be suitable for the determination of these compounds in aqueous
samples.
Solid Samples--
Recoveries of the seven priority pollutants from the solid samples
ranged from 15.4 to 59.0 percent. For five of these compounds, recoveries
exceeded 35 percent. For 1,3-dichlorobenzene and toluene, recoveries of 15.4
and 21.4, respectively, were determined. The cause of these very low
recoveries is not known. These compounds are not expected to be particularly
susceptible to losses during sample preparation. Since recoveries of these
compounds from aqueous samples were acceptable and no rationale is available
for poor recovery of these compounds from solids, the assumption will be made
that Method 8020 is suitable for the determination of these reference
compounds and that these data are anomalous. RSD values associated with the
37
-------
determination of the seven reference compounds in solids ranged from 13 to 71
percent. For most of these compounds, RSD values of less than 35 percent
were determined. The relatively high variability in the determination of
benzene can be attributed to the chromatographic interference presented by
the methanol used as the extracting solvent. The spiking concentration for
benzene had to be increased substantially to ensure a reliable signal for
this compound. However, even at a concentration of 300 ug/g, consistent
integration of this peak in the presence of a large amount of methanol was
very difficult. Use of the alternate extracting solvent, PEG, was precluded
by the presence of a number of impurities which were detected by the PID and
which interfered with the determination of some of the later eluting com-
pounds, such as the xylene isomers. The reason for the high RSD value
associated with the determination of 1,2-dichlorobenzene is not known.
Possibly this observed variability is due to incomplete mixing of the solid
sample following spiking. Based on the performance of Method 8020 for the
reference compounds, the criteria that will be used in discussing the
suitability of the Method for the remaining four compounds include a recovery
minimum of 40 percent and an RSD maximum of 35 percent.
For the remaining four compounds, the performance of Method 8020 was
well within the acceptance established based on results obtained for the
reference compounds. Consequently, Method 8020 was determined to be suitable
for the determination in solids of all eleven analytes used in this portion
of the testing.
38
-------
6.0 REFERENCES
1. Federal Register, 49, No. 247, December 21, 1984, pp 49784-49793.
2. "Test Methods for Evaluating Solid Waste," U.S. Environmental Protection
Agency, Office of Solid Waste and Emergency Response, SW-846, Third
Edition, November, 19868.
3. "GM-MS Suitability Testing," U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory - Cincinnati, EPA
Contract Number 68-03-3224, Work Assignment 1-04.
4. "Screening of Semivolatile Organic Compounds for Extractability and
Aqueous Stability by SW-846 Method 3510," U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory - Cincinnati, EPA
Contract Number 68-03-3224, Work Assignment 2-08.
5. "Development of a Single Laboratory Method Validation Protocol," U.S.
Environmental Protection Agency, Environmental Monitoring and Support
Laboratory, EPA Contract Number 68-03-3224, Work Assignment 1-01.
39
-------
TABLE 1. COMPOUNDS RECOMMENDED FOR INCLUSION IN THE
SCOPES OF METHODS 8010, 8015, AND 8020
Compound
List(a)
Sample Matrix for Which Method
Was Found to Be Suitable
Aqueous/Solids Nonaqueous
Sample Matrices(b) Sample Matrices(°)
METHOD 8010
Ally! chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bromoacetone
Bromobenzene
Bromod i chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chl oromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Dibromochl oromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1 , 3-D i ch 1 orobenzene
1,4-Di chlorobenzene
l,4-Dichloro-2-butene
Dichlorodif luoromethane
1,1-Di chl oroethane
1,2-Di chl oroethane
1,1-Dichloroethylene
Trans- 1,2-dichloroethylene
Di chl oromethane
1,2-Dichloropropane
1 , 3-D i ch 1 oro-2-propanol
Cis-l,3-dichloropropylene
Epichlorhydrin
Ethyl ene di bromide
Methyl iodide
1,1,2, 2-Tetrach 1 oroethane
1,1,1, 2-Tetrach 1 oroethane
8,9,M
8
8,9
8
—
PP,8,9
PP,8,9
PP.8,9
PP,8,9
PP,8,9
PP,9
M
PP,8,9
. —
PP,8
PP,8,9
8
8,9,M
—
PP,9
8,9
8
PP,8,9
PP,8,9
PP,8,9
8,9
8,9
PP,8,9
PP,8,9
PP,8,9
PP.8,9
PP,8,9
PP.8,9
8
PP
8
8
8,9
PP,8,9
8,9
X
(d)
(e)
(e)
X
X
X
X
X
X
X
(e)
X
X
(e)
X
(e)
X
(d)
X
X
X
X
X
X
X
(d)
X
X
X
X
X
X
(e)
X
(e)
X
(e)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(f)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
40
-------
TABLE 1. (Continued)
Compound
List(a)
Sample Matrix for Which Method
Was Found to Be Suitable
Aqueous/Solids Nonaqueous
Sample Matricesw) Sample Matrices(c)
METHOD 8010 (Continued)
Tetrachloroethylene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl chloride
PP,8,9
PP
PP,8,9
PP,8,9
PP,8,9
8,9
PP,8,9
X
X
X
X
X
X
X
X
X
X
X
X
X
X
METHOD 8015
Acetonitrile
Ally! alcohol
1,2,3,4-D i epoxy bu t ane
Diethyl ether
1,4-Dioxane
Ethylene oxide
Ethyl methacrylate
Isobutanol
Methacrylonitrile
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
6-Propiolactone
Propionitrile
8
8
8
8
8
8,9
8
8
8,9
8
8,9
8
M
8
(e)
(e)
(e)
X
(e)
(e)
X
(e)
X
X
(d)
(e)
X
(e)
(e)
(e)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
METHOD 8020
Benzene
Chlorobenzene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
2-Picoline
Styrene
PP.8,9
PP,8,9
PP,8,9
PP,8,9
PP.8,9
PP,9
8,9
9,M
X
X
X
X
X
X
(d)
X
X
X
X
X
X
X
X
X
41
-------
TABLE 1. (Continued)
Compound
List(a)
Sample Matrix for Which Method
Was Found to Be Suitable
Aqueous/Solids Nonaqueous
Sample Matrices(b) Sample Matrices(c)
METHOD 8020 (Continued)
Toluene
o-Xylene
m-Xylene
p-Xylene
PP,8,9
9
9
9
X
X
X
X
X
X
X
X
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List;
— = not on any list.
(b) Method testing with aqueous and solid samples involved the use of PTD sample
introduction.
(c) Method testing with nonaqueous liquid samples involved the use of DLI sample
introduction.
(d) Method determined to be unsuitable for determination of this compound in the
sample matrix indicated.
(e) Compound not included in this portion of testing due to poor purging efficiency.
(f) Chloroprene not included in this portion of testing due to poor chromatographic
behavior with DLI sample introduction under conditions specified in method. See
text for discussion.
42
-------
TABLE 2. COMPOUNDS RECOMMENDED FOR EXCLUSION FROM THE
SCOPES OF METHODS 8010, 8015, AND 8020
Compound
List(a)
Sample Matrix for
Method was Found
to be Unsuitable
Aqueo
Sol id
Nonaqueous
Liquid(c)
Comments
METHOD 8010
Benzyl chloride 8 X
Bis(2-chloroethoxy)methane 8,9 X
Bis(2-chloroethyl)sulfide 8,M X
Bis(2-chloroisopropyl)ether 8 X
Bromoacetone 8 X
Chloroacetaldehyde 8 X
Chloral 8 X
2-Chloroethanol M X
Chloroethyl vinyl ether PP,8 X
Chloromethyl methyl ether 8 X
Chloroprene 8,9,M (e)
3-Chloropropionitrile 8 X
Chlorotoluene ~ X
Dichlorodifluoromethane 8,9 X
1,3-Dichloropropanol 8 X
Epichlorohydrin 8 X
Methyl iodide 8,9 X
Pentachloroethane 8,9 X
(d) Method not suitable(f)
(d) Poor purging efficiency
X Poor chromatographic behavior
X Standard impure
(d) Poor purging efficiency
X Standard not available
X Poor chromatographic behavior
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Poor purging efficiency
X Poor chromatographic behavior
X Poor chromatographic behavior
(d) Method not suitable(f)
(d) Method not suitable(f)
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Method not suitable(f)
X Poor chromatographic behavior
METHOD 8015
Acetonitrile
Allyl alcohol
Aery1 amide
Carbon disulfide
1,4-dioxane
Ethyl oxide
2-hydroxypropionitrile
Isobutanol
Malononitrile
Methyl mercaptan
Paraldehyde
Propargyl alcohol
6-Propiolactone
Propionitrile
8
8
8
8,9
8
8
M
8
8
8
8
8
M
8
X
X
X
X
X
X
X
X
X
X
X
X
X
X
(d) Poor purging efficiency
(d) Poor purging efficiency
X Poor chromatographic behavior
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Poor purging efficiency
X Poor chromatographic behavior
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Poor purging efficiency
(d) Poor purging efficiency
d) Poor purging efficiency
d) Poor purging efficiency
43
-------
TABLE 2. (Continued)
Sample Matrix for
Method was Found
to be Unsuitable
Compound
List(a)
Aqueous
Solidfb)
Nonaqueous
Liquid(c)
Comments
METHOD 8020
2-Picoline
Pyridine
Thiophenol
8,9
8,9
8
X
X
X
(d) Poor purging efficiency
X Poor chromatographic behavior
X Poor chromatographic behavior
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List;
— = not on any list.
(b) Method testing with aqueous and solid samples involved the use of PTD sample
introduction.
(c) Method testing with nonaqueous liquids involved the use of DLI sample introduction.
(d) Method suitable for this compound in nonaqueous liquids using DLI sample introduction.
(e) Method suitable for this compound in aqueous and solid samples using PTD sample
introduction. See text for discussion.
(f) See Section 5 for detailed discussions.
44
-------
TABLE 3. COMPOUNDS RECOMMENDED FOR INCLUSION IN
METHOD 8240 PERFORMANCE TESTING
Compound
Ally! chloride
Benzene
Bromobenzene
Bromodichlomethane
Bromoform
Bromomethane
Carbon Tetrachloride
Chlorobenzene
Chloroethane
Chloroform
1-Chlorohexane
Chloromethane
Chloroprene
Di bromochl oromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1 , 2-D i ch 1 orobenzene
1,3-Di Chlorobenzene
1,4-Dlchlorobenzene
l,4-Dichloro-2-butene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
Trans-l,2-Dichloroethylene
Di chloromethane
1,2-Dichloropropane
Cis-l,3-Dichloropropylene
Diethyl ether
Ethyl benzene
Ethyl methacrylate
Ethylene di bromide
Methacrylonitrile
Methyl ethyl ketone
Methyl methacrylate
Styrene
1,1,2, 2-Tetrach 1 oroet hane
1,1,1, 2-Tetrach 1 oroet hane
Tetrach 1 oroet hy 1 ene
1,1,1-Trichloroethane
1,1,2-Tri chloroethane
Trichloroethylene
Trichlorofluoromethane
CAS
Number
107-05-1
73-41-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
106-90-7
75-00-3
67-66-3
544-10-5
74-87-3
126-99-8
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
10061-01-5
60-29-7
100-41-4
97-63-2
106-93-4
126-98-7
78-93-1
80-62-6
100-42-5
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
Retention
Time
(minutes)
10.17
2.59
29.05
15.44
21.12
2.90
14.58
25.49
5.18
12.62
26.26
1.40
15.60
18.22
28.09
13.83
37.96
36.88
38.64
23.45
11.21
13.14
10.04
11.97
7.56
16.69
17.00
11.24
8.12
23.98
19.59
13.09
12.93
20.22
11.60
23.12
21.10
23.05
14.48
18.27
17.40
9.26
Purging
Efficiency
(percent)
88
77
81
107
65
77
81
51
85
88
76
73
90
109
14
78
83
82
80
30
86
103
78
107
86
90
100
90
94
55
71
37
14
55
86
102
85
51
97
83
85
82
Estimated
Detection
Limit
(yg/L)
0.272
0.0554
0.278
0 138
VX • X *J\J
0.951
0.850
0 111
w • x x J.
0 701
W • / V X
0 755
w • / *j
-------
TABLE 3. (Continued)
CAS
Compound Number
Retention
Time
(minutes)
Purging
Efficiency
(percent)
Estimated
Detection
Limit
1,2,3-Trichloropropane 96-18-4 22.95 50 0.346
Toluene 108-88-3 5.14 99 0.0867
Vinyl chloride 75-01-4 3.25 81 0.733
o-Xylene 95-47-6 10.54 92 0.0326
m-Xylene 1477-55-0 9.77 99 0.125
p-Xylene 106-42-3 9.18 98 0.0759
46
-------
TABLE 4. COMPOUNDS CONSIDERED FOR INCLUSION IN THE SUITABILITY TESTING
OF METHODS 8010, 8015, AND 8020
Compound
CAS Number
List(a)
Source
METHOD 8010
Allyl chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
B1s(2-chloroethy1)sulfide
B1s(2-chloroisopropyl)ether
Bromoacetone
Bromobenzene
Bromod i ch1oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chloroacetaldehyde
Chloral
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chioromethane
Chloromethyl methyl ether
Chloroprene
3-Chloroprop1onitrile
4-Chlorotoluene
D i bromoch1oromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,4-Dichloro-2-butene
107-05-1
100-44-7
111-91-1
505-60-2
108-60-1
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
75-87-6
106-90-7
75-00-3
107-07-3
67-66-3
544-10-5
100-75-8
74-87-3
107-30-2
126-99-8
542-76-7
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
8, 9, M
8
8, 9
8, M
8
8
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
8
8
PP, 8, 9
PP, 9
M
PP, 8, 9
PP, 8
PP, 8, 9
8
8, 9, M
8
PP, 9
8, 9
8
PP, 8, 9
PP, 8, 9
PP, 8, 9
8, 9
Aldrich Chemical Company
Fisher Scientific Company
Pfaltz and Bauer, Inc.
Chem Services, Inc.
Chem Services, Inc.
Chem Services, Inc.
Fluka AG Chemical Company
Aldrich Chemical Company
Eastman Organic Chemical -Products
Matheson Gas Products
Fluka AG Chemical Company
No commercial source
Fisher Scientific Company
Matheson, Coleman, and Bell
Chem Services, Inc.
Eastman Organic Chemical Products
Burdick and Jackson Laboratories
Fluka AG Chemical Company
Aldrich Chemical Company
Matheson Gas Products
Sigma Chemical Company
Alfa Products
Aldrich Chemical Company
Chem Services, Inc.
Alfa Products
Chem Services, Inc.
Analabs
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
-------
TABLE 4. (Continued)
Compound
CAS Number
List(a)
Source
METHOD 8010 (Continued)
D1chlorod1fluoromethane
l,l-D1chloroethane
l,2-D1chloroethane
1,1-Dichloroethylene
Trans-l,2-dichloroethylene
Dlchloromethane
1,2-Dichloropropane
l,3-Dichloro-2-propanol
Cis-l,3-dichloropropylene
Epichlorohydrin
Ethylene dlbromlde
Methyl iodide
Pentachloroethane
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
1,1;l-Tr1chloroethane
1,1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
1,2,3-Tr i ch1oropropane
Vinyl chloride
METHOD 8015
Acetonitrile
Allyl alcohol
Aery1 amide
Carbon disulfide
1,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Ethylene oxide
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
106-89-8
106-93-4
74-88-4
76-01-7
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
75-05-8
107-18-6
79-06-1
75-15-0
1464-53-5
60-29-7
123-91-1
75-21-8
8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
8
PP
8
8
8, 9
8, 9
PP, 8, 9
8, 9
PP, 8, 9
PP
PP, 8, 9
PP, 8, 9
PP, 8, 9
8, 9
PP, 8, 9
8
8
8
8, 9
8
8
8
Matheson Gas Products
Aldrich Chemical Company
Burdick and Jackson Laboratories
Fluka AG Chemical Company
Fluka AG Chemical Company
Burdick and Jackson Laboratories
Aldrich Chemical Company
Aldrich Chemical Company
Fluka AG Chemical Company
Aldrich Chemical Company
Fluka AG Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
J. T. Baker Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Fisher Scientific Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Aldrich Chemical Company
Matheson Gas Products
Burdick and Jackson Laboratories
Aldrich Chemical Company
Aldrich Chemical Company
Matheson, Coleman, and Bell
Sigma Chemical Company
Burdick and Jackson Laboratories
Burdick and Jackson Laboratories
Matheson Gas Products
-------
TABLE 4. (Continued)
Compound
CAS Number
L1st(a)
Source
METHOD 8015 (Continued)
Ethyl methacrylate
2-Hydroxyprop1on1tr1le
Isobutanol
Malononltrile
Methacrylonitrlle
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
Propargyl alcohol
8-propiolactone
Proplonitrile
METHOD 8020
Benzene
Chlorobenzene
l,2-D1chlorobenzene
l,3-D1chlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
2-P1coline
Pyr1d1ne
Styrene
Thiophenol
Toluene
o-Xylene
m-Xylene
p-Xylene
97-63-2
78-97-7
78-83-1
109-77-3
126-98-7
78-93-3
108-10-1
74-93-1
80-62-6
123-63-7
107-19-7
57-57-8
107-12-0
71-43-2
106-90-7
95-50-1
541-73-1
106-46-7
100-41-4
109-06-8
110-86-1
100-42-5
108-98-5
108-88-3
95-47-6
1477-55-0
106-42-3
8, 9
M
8
8
8
8, 9
8
8, 9
8
8
M
8
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 8, 9
PP, 9
8, 9
8, 9
9, M
8
PP, 8, 9
9
9
9
Aldrlch Chemical Company
Aldrich Chemical Company
Aldrlch Chemical Company
Aldrich Chemical Company
Aldrlch Chemical Company
Burdick and Jackson Laboratories
Aldrich Chemical Company
Matheson Gas Products
Matheson Gas Products
Sigma Chemical Company
Aldrich Chemical Company
Sigma Chemical Company
Aldrich Chemical Company
Burdick and Jackson Laboratories
Matheson, Coleman, and Bell
Aldrich Chemical Company
Aldrlch Chemical Coompany
Aldrich Chemical Company
Poly Science Corporation
Aldrich Chemical Company
Aldrich Chemical Company
Chem Services, Inc.
Aldrich Chemical Company
Burdick and Jackson Laboratories
Burdick and Jackson Laboratories
Chem Services, Inc.
Matheson, Coleman, and Bell
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List; - = not on any list.
-------
TABLE 5. INSTRUMENT CONDITIONS SPECIFIED IN METHODS 8010, 8015, AND 8020 AND USED IN THESE METHOD EVALUATIONS
en
o
Parameter
Purge gas
Purge gas flow rate
ml/min
Purge time (min)
Purge temperature (°C)
Desorb time (m1n)
Desorb temperature (°C)
Trap material
Method 8010
Helium
30 ml/m1n
15 m1n
Ambient
1.5 m1n
180°C
1 cm 3% SP2100 60/80 mesh
Method 8015
Helium
30 ml/m1n
15 min
Ambient
1.5 m1n
180°C
1 cm 3% SP2100 60/80 mesh
Method 8020
Helium
30 ml/m1n
15 min
Ambient
1.5 m1n
180°C
1 cm 3% SP2100 60/80 mesh
GC system
GC column
7.7 cm Tenax, 60/80 mesh
7.7 cm Silica gel 15,
60/80 mesh
7.7 cm Charcoal, 6/10 mesh
Tracer Model 5830 with Hall
Detector
23 cm Tenax, 60/80 mesh
Hewlett-Packard Model 5890
with FID Detector
8 ft x 0.1 in. I.D. stainless 8 ft x 0.1 in. I.D. stainless
Carrier gas
Oven program
Injector temperature
Detector temperature
steel
1% SP-1000 on 60/80 mesh
Carbo Pack B
Helium at 40 ml/min
45°C (3 min), 8°C/min,
220°C (15 min)
200°C
200°C
steel
1% SP-1000 on 60/80 mesh
Carbo Pack B
Helium at 40 ml/min
45°C (3 min), 8°C/min
200°C (15 min)
220 °C
250°C
23 cm Tenax, 60/80 mesh
Tracor Model 560 with PID
Detector
6 ft x 0.082 in. I.D.
stain-
less steel
5% SP-1200/1.75% Bentone 34
on 100/120 mesh
Supelcoport
Helium at 30 ml/min
50°C (2 min), 3°C/min
110°C (15 min)
200 °C
200° C
-------
TABLE 6. RETENTION TIMES, PURGING EFFICIENCIES, AND ESTIMATED DETECTION LIMITS
DETERMINED FOR METHOD 8010 ANALYTES
PTD(a)
Compound
Ally! chloride
Benzyl chloride
B1s(2-chloroethoxy)methane
B1s(2-ch1oro1sopropy1)ether
Bromoacetone
Bromobenzene
Bromod 1 ch 1 oromet hane
Bromoform
Bromomethane
Carbon tetrachlorlde
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chloromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Dlbromochloromethane
l,2-D1bromo-3-ch1oropropane
Dlbromome thane
1,2-Dlchlorobenzene
l,3-D1chlorobenzene
CAS
Number
107-05-1
100-44-7
111-91-1
108-60-1
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
106-90-7
75-00-3
107-07-3
67-66-3
544-10-5
100-75-8
74-87-3
107-30-2
126-99-8
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
Retention
Time
(minutes)
10
30
38
34
18
29
15
21
2
14
25
5
15
12
26
19
1
8
.17
.29
.60
.79
.92
.05
.44
.12
.90
.58
.49
•
%
•
•
B
•
.
15.
34.
18.
28.
13.
37.
36.
18
18
62
26
23
40
88
60
46
22
09
83
96
88
Purqlnq
Efficiency
Test
Concentration Recovery
(ng/L) (RSD)
40
800
400
400
400
100
200
200
100
100
100
100
400
100
80
160
100
400
400
80
80
160
40
160
80
88 (2.1)
25 (6.0)
ND
ND
ND
81
107
65
77
81
4.3)
0.8)
12)
12)
5.9)
51 (20)'
85 (13)
ND
88 (18)
76 (3)
ND
73 (18)
ND
90 (3.6)
83 (3.2)
109 i
14
78
83
/
5.1)
8.1)
4.0)
0.4
82 (1.7)
5 S/N
0.400
10.0
(c)
(c)
(c)
0.850
0.800
1.45
0.850
0.155
0.625
0.015
(c)
0.210
1.20
(c)
0.500
(c)
\**7
2.50
1.95
0.120
5.35
0.800
1.40
0.400
Estimated
Detection
Limit
0.272
3.05
__
0.278
0.138
0.951
0.850
0.111
0.701
0.755
0.123
0.283
0.258
2.50
0.671
0.488
1.66
0.900
1.59
0.274
DLl(b)
5 S/N
0.400
1.50
2.00
0.25
6.00
1.50
0.400
1.50
1.00
0.300
0.750
0.600
1.50
0.300
0.750
1.50
1.00
4.00
2.50
1.50
1.00
2.00
1.50
1 00
i. • \J\J
0.750
Method
Detection
Limit
(mg/L)
0.400
1.27
0.310
0.088
2.66
0.376
0.246
1.03
0.500
0.150
0.596
1.07
1.47
0.181
0.358
5.98
0.314
40 0
*tu • u
(d)
OQPfl
• 7£Q
0.887
0.387
1.17
y ?n
c . cu
0.375
-------
TABLE 6. (Continued)
en
ro
Compound
1 , 4-D 1 ch 1 orobenzene
1.4-01 chl oro-2-butene
0 1 ch 1 orod 1 f 1 uoromethane
1,1-Dlchloroethane
1,2-Dlchloroethane
1,1-Dlchloroethylene
Trans-l,2-D1ch1oroethylene
Dlchlorome thane
l.2-D1ch1oropropane
l,3-D1chloro-2-propanol
C 1 s- 1 , 3-d 1 ch 1 oropropy 1 ene
Eplchlorohydrln
Ethylene d1 bromide
Methyl Iodide
1,1,2,2,-Tetrachloroethane
1,1,1, 2-Tetrach 1 oroethane
Tetrach 1 oroe thy 1 ene
1,1,1-Trlchloroethane
1,1,2-Trlchloroethane
Trlchloroethylene
Trlchlorofluoromethane
CAS
Number
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
106-89-8
106-93-4
74-88-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
Retention
Time
(minutes)
38.64
23.45
3.68
11.21
13.14
10.04
11.97
7.56
16.69
24.28
17.00
13.65
19.59
7.57
23.12
21.10
23.05
14.48
18.27
17.40
9.26
Purging Efficiency
Test
Concentration
(M9/L)
160
160
80
100
200
100
200
100
100
400
400
400
80
80
200
160
100
200
40
100
100
Recovery
(RSD)
80
30
109
86
103
78
107
86
90
NO
100
NO
71
87
102
85
51
97 i
83
85
82
2.1)
6.7)
0.8)
|16)
0.8)
3.1)
3.2)
14)
18)
[1.4)
5.7)
2.7)
2.1)
6.8)
17)
3.5)
5.1)
15)
13)
5 S/N
1.25
2.78
0.500
0.300
0.300
0.550
0.400
0.210
0.455
(c)
0.550
(c)
1.55
2.00
0.010
0.400
0.200
0.050
0.250
0.180
0.420
PTD(a)
Estimated
Detection
Limit
(wg/L)
0.362
0.488
0.130
0.164
0.129
0.180
0.897
2.93
0.300
0.317
0.645
2.52
0.140
0.117
0.402
0.082
0.049
0.124
0.191
5 S/N
0.750
0.600
0.200
0.200
0.750
0.200
1.20
0.200
0.750
0.500
0.750
0.900
1.00
4.00
0.450
0.750
0.400
0.200
0.200
0.450
0.300
OLl(b)
Method
Detection
Limit
(mg/L)
0.483
0.244
0.236
0.235
0.221
0.234
1.60
4.20
0.451
0.884
0.528
0.495
0.763
3.65
0.239
0.166
0.342
0.133
0.068
0.175
0.261
-------
TABLE 6, (Continued)
en
CO
Purging Efficiency
Retention test
CAS Time Concentration
Compound Number (minutes) (ug/L)
1,2,3-TMchloropropane 96-18-4 22.95 40
Vinyl chloride 75-01-4 3.25 100
(a) PTD Estimated Detection Limits calculated as follows:
rDL _ DLI Method Detection Limit (mq/L) x Injection Volume (3 ul)
Purging Efficiency x Sample Volume (5 ml) '
Recovery
(RSD)
50 (6.6)
81 (16)
PTD(a) D
Estimated
Detection
Limit
5 S/N (Mg/L) 5 S/N
0.360 0.346 0.200
0.400 0.733 0.700
LI(«>)
Method
Detection
Limit
(mg/L)
0.288
0.989
(b) DLI Method Detection Limits calculated as follows:
MDL - tn.1 (SO)
where tn_j = student t value for n-1 degree of freedom
n = number of replicate analyzed
SO * standard deviation associated with analysis of n replicates.
(c) Compound not Included In this portion of study due to poor purging efficiency.
(d) Compound not Included In this portion of study due to poor chromatographlc behavior. See text.
-------
TABLE 7. RETENTION TIMES, PURGING EFFICIENCIES, AND ESTIMATED DETECTION LIMITS
DETERMINED FOR METHOD 8015 ANALYTES
en
Compound
Acetonltrlle
Ally! alcohol
Carbon dlsulflde
1,2,3,4-01 epoxy butane
Dlethyl ether
1,4-Dloxane
Ethylene oxide
Ethyl methacrylate
Isobutanol
Malonon1tr1le
Methacrylonltrlle
Methyl ethyl ketone
Methyl Isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Par aldehyde
Propargyl alcohol
"~
CAS
Number
75-05-8
107-18-6
75-15-0
1464-53-5
60-29-7
123-91-1
75-21-8
97-63-2
78-83-1
109-77-3
126-98-7
78-93-1
108-10-1
74-93-1
80-62-6
123-63-7
107-19-7
Retention
Time
(minutes)
3.78
9.60
8.59
15.37
11.24
14.44
1.96
23.98
14.30
19.80
13.09
12.93
20.92
2.16
20.22
21.37
10.68
Purqlnq
Test
PTD(a)
Efficiency
Concentration Recovery
(ng/L) (RSD)
800
800
200
800
200
800
800
200
800
800
800
200
200
800
200
800
800
ND
ND
ND
ND
90
ND
ND
55
2
ND
37
14
20
ND
55
ND
ND
(11)
(14)
(0)
(5)
(12)
(34)
(11)
5 S/N
(c)
(c)
!c!
0.075
(c)
(c)
0.0200
13
0.150
1.50
0.250
(C)
0.200
(c)
(c)
Estimated
Detection
Limit
(u9/L)
0.013
0.389
2.53
0.189
0.051
0.064
DLl(b)
5 S/N.
1.02
1.20
3.40
0.400
0.250
0.250
0.260
0.300
0.140
2.00
0.250
0.170
0.150
0.850
0.140
0.320
1.19
Method
Detection
Limit
(mg/L)
1.32
0.879
0.310
0.037
0.019
0.022
0.293
0.357
0.029
1.56
0.019
0.044
0.017
0.399
0.059
0.071
1.82
-------
01
en
TABLE 7. (Continued)
Purqlnq Efficiency
Compound
B-Prop1olactone
Proplonltrlle
Retention Test
CAS Time Concentration
Number (minutes) (ug/L)
57-57-8 13.83
107-12-0 8.48
800
800
Recovery
(RSD)
1 (32)
7 (22)
PTD(a) DLl(b)
Estimated Method
Detection Detection
Limit Limit
5 S/N (Mg/L) 5 S/N (mg/L)
(c) — 1.50 0.242
(c) -- 0.700 0.231
(a) PTD Estimated Detection Limits calculated as follows:
EDL _ DLI Method Detection Limit (mq/L) x Injection Volume {3 pi)
(b) DLI Method Detection Limits calculated as follows:
HDL
VI
(SD)
where tn_j = student t value for n-1 degree of freedom
n = number of replicate analyzed
SD = standard deviation associated with analysis of n replicates.
(c) Compound not Included 1n this portion of study due to poor purging efficiency.
-------
TABLE 8. RETENTION TIMES. PURGING EFFICIENCIES, AND ESTIMATED DETECTION LIMITS
DETERMINED FOR METHOD 8020 ANALYTES
PTD(a)
DLl(b)
tn
Compound
Benzene
Chlorobenzene
l,2-D1chlorobenzene
1,3-01 ch 1 orobenzene
1,4-Dlchlorobenzene
Ethyl benzene
2-P1co11ne
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
CAS
Number
73-41-2
106-90-7
95-50-1
541-73-1
106-46-7
100-41-4
109-06-8
100-42-5
108-88-3
95-47-6
1477-55-0
106-42-3
Retention
Time
(minutes)
2.59
9.38
20.60
17.54
16.42
8.12
9.18
11.60
5.14
10.54
9.77
9.18
Purqlnq
Efficiency
Test
Concentration Recovery
(yg/L) (RSD)
200
100
160
80
160
200
800
200
200
200
200
200
77
51
83
82
80
94
NO
86
99
92
99
98
(8)
(20)
(0.4)
!!!
(0.4)
18
if!
(l)
5 S/N
0.036
0.028
0.064
0.025
0.048
0.016
(C)
0.036
0.012
0.035
0.025
0.061
Estimated
Detection
Limit
(wg/L)
0.0554
0.134
0.124
0.395
0.110
0.0957
0.118
0.0867
0.0326
0.125
0.0759
5 S/N
0.250
0.250
0.300
0.500
0.300
0.500
1.50
0.500
0.400
0.300
0.500
0.500
Method
Detection
Limit
(«g/L)
0.0712
0.114
0.172
0.540
0.146
0.150
0.424
0.169
0.143
0.050
0.206
0.124
(a) PTD Estimated Detection Limits calculated as follows:
EDL - DL! Method. Detection Limit (mg/Ll x Injection Volume (3 ,.i)
furglng Efficiency x Sample Volume (5 ml) '
(b) DLI Method Detection Limits calculated as follows:
MDL = tn j (SO)
where tn_j = student t value for n-1 degree of freedom
n - number of replicate analyzed
SD = standard deviation associated with analysis of n replicates.
(c) Compound not Included 1n this portion of study due to poor purging efficiency.
-------
TABLE 9. COMPOUNDS NOT INCLUDED IN EVALUATIONS OF
METHODS 8010, 8015, AND 8020
Compound
Reasons for Exclusion
Portion of Study From Which
Compound Excluded
PTD
DLI
METHOD 8010
Bis(2-chloroethoxy)methane
Bis(2-ch1oroethy1)sulfide
Bis(2-chloroisopropyl)ether
Bromoacetone
Ch1oroacetaldehyde
Chloral
2-Chloroethanol
Chloroethyl vinyl ether
Chloromethyl methyl ether
Chloroprene
3-Chloropropionitrile
1,3-Dichloropropanol
Epichlorohydrin
Pentach1oroethane
METHOD 8015
Acetonitrile
Ally! alcohol
Aery1 amide
Carbon disulfide
1,4-Dioxane
Ethyl oxide
2-Hydroxypropionitrile
Isobutanol
Malononitrile
Methyl mercaptan
Paraldehyde
Propargyl alcohol
6-Propiolactone
Propionitrile
METHOD 8020
2-Picoline
Pyridine
Thiophenol
Poor purging efficiency
Poor chromatographic behavior
Standard impure
Poor purging efficiency
Standard not available
Poor chromatographic behavior
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor chromatographic behavior
Poor chromatographic behavior
Poor purging efficiency
Poor purging efficiency
Poor chromatographic behavior
Poor purging efficiency
Poor purging efficiency
Poor chromatographic behavior
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor chromatographic behavior
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor purging efficiency
Poor chromatographic behavior
Poor chromatographic behavior
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
57
-------
TABLE 10. RESPONSE FACTORS DETERMINED FOR METHOD 8010 ANALYTES USING PTD
Allyl chloride
Benzyl chloride
B1s(2-ch1oro1sopropy1)ether
Bromobenzene
Bromod 1 chl oromethane
Bromoform
Bromomethane
Carbon tetrachlorlde
Chlorobenzene
Chl oroe thane
Chloroform
1-Chlorohexane
Chl oromethane
Chloroprene
4-Chlorotoluene
01 bromochl oromethane
1,2-01 bromo-3-chloropropane
Dibrontomethane
1,2-Dichlorobenzene
1,3-Dlchlorobenzene
1,4-Dlchlorobenzene
l,4-01chloro-2-butene
Dlchlorodi fluoromethane
1,1-Dlchloroethane
1,2-Dlchloroethane
1,1-Dichloroethylene
Tra ns-l,2-D1ch1 oroethyl ene
Dichloromethane
1,2-01 chl oro propane
C1s-l,3-dichloropropylene
Ethyl ene d1 bromide
Methyl Iodide
1,1,2,2-Tetrachloroethane
1,1 ,1,2-Tetrachloroethane
Tet rachl oroethyl ene
1,1 ,1-Trichloroethane
1,1,2-Trlchloroethane
Trl chl oroethyl ene
Trl chl orof 1 uoromethane
1 ,2 ,3-Trlchl oro pro pane
Vinyl chloride
Solution
3
1
1
3
3
3
3
1
2
3
1
1
1
2
2
3
2
3
1
3
2
2
2
2
2
1
3
1
1
3
1
2
3
1
1
2
2
2
2
2
1
S/N
Concentration,
M9/L
0.080
2.0
1.2
0.17
0.16
0.29
0.17
0.031
0.12
0.003
0.070
0.24
0.10
0.50
0.39
0.024
1.07
0.16
0.28
0.080
0.25
0.55
0.10
0.060
0.060
0.11
0.080
0.042
0.091
0.11
0.31
0.40
0.002
0.080
0.040
0.010
0.050
0.036
0.084
0.072
0.080
Response Factor (Relative Standard Deviation)
5 S/N 15 S/N 50 S/N 150 S/N 500 S/N . 1500 S/N 5000 S/N "
8-23 (24) 6.74 (6.2) 5.73 (7.0) 6.20 (6.9) 6.47 1.6) 6.53 (6.5) 6 84 (3 9)
0.885 (28) 0.489 (60) 0.647 (13.0) 0.650 (16 1.08 6.9 0953 (9 0848 79
0.913 91 0.280 (0.74) 0.199 11.0 0.192 (21 0.262 (13 0208 (19 oizOZ 39
1-01 (21) 1.31 (11 1.46 (2.6) 1.65 (6.7 1.85 6.7 1.87 5.9 1 99 22
5-97 10) 7.13 (3.1) 8.10 (1.2) 9.02 (4.8 9.33 1.3 9.14 2.0 8.'™ 17
0.377 25 0.940 (10) 1.64 (4.8) 2.22 (5.6) 2.59 5.6 2.59 3.2 2.80 22
0.846 44 1.39 6.8) 2.14 (9.1) 3.26 (13) 4.13 (3.1) 3.92 7.5 4.33 51
8.76 17 8.23 (4.5) 8.51 (8.1) 8.86 (8.0) 13.5 (4.2) 10.6 5.7 11.2 41
2.85 (29) 2.94 (20) 2.82 (7.4) 3.11 (2.2 3.09 (6.4 3.05 3.0 2.90 (13)
48.0 (53 26.7 (19) 9.71 (3.8) 7.74 (2.4 7.85 6.0 6.92 2.3 10.0 (012
17-4 (2.0) 12.5 (4.0) 11.8 (4.2) 12.0 (5.7 16.7 6.0 13.4 2.5 128 (40
3.68 (23) 2.68 (16) 2.79 (1.5) 2.81 (6.1 3.91 5.6 2.80 4.0 293 54
4.53 (4.0 4.87 (20) 4.81 (11) 5.28 (14 7.61 (14) 6.49 (0.79 6.63 63
0.721 (16) 0.697 (11) 0.729 (7.8) 0.778 (3.7) 0.807 (4.0) 0.838 (4.6 0.787 56
0.995 24 0.778 (8.8) 0.804 (8.2 0.870 (0.59 0.828 5.3) 0.788 (5.2 0.751 (16
10-7 16 12.4 (13) 16.1 (1.1) 18.2 (6.4 18.3 7.3) 21.1 (0.63 20.7 (5.1
0.942 45 0.950 (36) 0.622 (17) 0.645 (14) 0.738 6.1) 0.699 (5.4 0.705 5.8
1.91 (16) 2.68 (12) .00 (1.7) 4.99 (5.3) 5.34 1.4) 5.41 (0.54 5.55 17
2.49 (24) 1.81 (0.24) .69 (4.7) 1.67 (6.4) 2.20 3.7) 1.61 (3.4 1.67 3.'?
}-94 (6.9) 2.77 (33) .99 (4.7) 1.82 (8.0) 1.99 (2.2) 1.87 (10) 2.20 3.5
1.45 31 1.24 (19) .08 (4.9) 1.20 (3.7) 1.13 (2.6) 1.11 (6.1 1.54 2.5
1-40 (11 1.52 (14) .47 (11) 0.963 (70) 1.72 (30 2.07 3.8 1.95 8.5
15-0 (7.4) 7.17 (7.1) 3.88 (6.9) 3.29 (11) 3.04 (16) 2.98 (14) 3.51 3.4
5-88 (16) 5.50 (8.1) 6.31 (5.8) 6.66 (3.6) 6.99 (5.9) 7.04 (6.7) 5.26 5.7
6-87 (30) 5.76 (5.3) 6.62 (7.0) 6.92 (5.8) 7.38 (3.1) 7.52 (3.5) 5.34 (4.8)
6-98 13 6.67 (6.0) 6.67 (3.7) 6.95 (8.7) 9.64 (9.9) 7.90 (5.1) 7.64 (5.1)
5-74 23) 8.26 (4.1) 8.11 (5.7) 9.63 (7.1) 10.1 (0.55) 9.91 (6.2) 10.4 (3.2)
35.9 (59) 17 0 (18 0) 13 8 (17) 11 2 (63) 14 7 9 3) 11 9 (2 7) 11 7 (3 9)
6-91 (12) 7.27 (3.0) 7.99 (3.7) 8^2 (S^) ll'.3 *'.7) 9io2 (2JO) 8!40 (3.7)
2-15 (23) 3.00 (6.4) 3.34 (1.8) 3.79 (9.8) 3.96 1.4) 4.10 (2.2) 4.16 (2.7)
2.50 (8.6) 2.79 (5.7) 3.40 (6.1) 3.76 (7.6 5.09 3.8) 4.01 (3.9) 3.87 (3.8)
3.20 (61) 1.04 (33) 0.397 (8.3) 0.296 (22 0.127 (59) 0.0901 (62) 0.172 (56)
48.7 (38) 101.0 (83) 11.3 (26) 10.8 (20 7.79 (1.9) 8.14 (5.3) 8.83 (0.40
7-58 (10) 7.75 (0.47) 8.40 (2.4) 8.97 (7.8 12.7 (4.0) 9.75 (3.2) 9.62 (1.9)
15.2 (8.7) 11.6 (25) 10.2 (2.0) 9.98 (8.1 14.2 (3.0) 10.4 (1.3) 11.0 5.6
75.5 (0.83) 26.8 (10) 13.2 (8.9) 8.85 (6.1) 7.47 (5.3) 7.52 (4.9) 7.26 (9.9)
6-92 (10) 6.50 (16) 6.81 (3.4) 7.25 (4.9) 7.56 (5.0) 7.53 (3.5) 4.86 (13)
10.6 19 8.21 (19 7.26 (5.8 7.58 2.9) 7.73 5.1) 7.74 (4.0 7.43 12
51-6 (12) 19.5 (7.3) 11.3 (8.8) 8.69 (4.6) 7.78 6.2) 7.87 (5.8 7.19 (6.4)
4-01 (11) 4.37 (10) 4.34 (6.4) 4.60 (6.0) 4.95 (4.1) 4.84 (4.1) 4.87 (1.2)
7-17 (24) 6.96 (6.6) 6.91 (2.4) 7.03 (10) 10.4 (16) 8.88 (7.5) 9.22 (3.7)
-------
TABLE 11. RESPONSE FACTORS DETERMINED FOR METHOD 8010 ANALYTES USING DLl
S/N
Solution Concentration,
Compound Set mg/L 5 S/N
Response Factor (Relative Standard Deviation)
15 S/N 50 S/N
150 S/N 500 S/N 1500 S/N 5000 S/N
Ally! chloride 5 0.080 1.77 (98) 0.98 (3.3) 1.43 (3.3) 1.45 (4.0) 1.39 (0.1) 1.42
Benzyl chloride 2 0.30 2.71 (26) 2.48 (5.5) 2.75 (1.7) 3.40 (11) 3.18 (0.37) 3.53
B1s(2-chloroethoxy)methane 1 0.40 0.706 (73) 1.12 (14) 1.37 (11) 1.64 (6.7) 1.74 (4.5) 0.872
B1s(2-chloro1sopropyl)ether 1 0.050 12.7 2
Bromoacetone 3 1.2 1.49 1
8) 17.2 (30) 15.3 (11
4) 2.09 (4.2) 2.87 (5.7
Bromobenzene 1 0.30 1.64 (13) 2.22 (3.8) 2.21 (1.2
17.0 3.9) 17.1 (1.4) 16.0
3.24 1.4) 3.39 (4.0) 2.93
(2.7) 1.30 (2.3)
[2.3) 3.52 (2.1
!4.1) 0.877 (1.2
3.2) 11.6 (8.5
4.0) 1.38 (30
4.91 1.7) 2.77 (0.74) 2.58 (2.2) 1.88 (7.1)
Bromodichloromethane 2 0.10 3.95 (19) 6.67 (3.6) 9.26 (3.4) 10.8 8.3) 10.9 (1.4) 11.5 (1.6) 10.9 (2.3)
Bromoform 1 0.30 0.698 (21) 1.22 (16) 1.72 (7.5) 2.18 (4.2) 2.37 (1.8) 2.23 (3.1) 1,69 (6.3
Bromomethane 6 0.60 0.833 (17) 2.27 (9.5) 2.71 (1.6) 4.02 (11) 3.36 (3.1) 0.467 (0.65)
Carbon tetrachlorlde 4 0.20 2.13 (5.
Chlorobenzene 3 0.15 6.41 (2
Chloroethane 5 0.12 0.491 (8.
2-Chloroethanol 5 0.30 0.179 (2
Chloroform 4 0.20 1.44 (8.
2 2.65 (2.1) 2.48 (6.1) 2.46 (1.1) 2.31 (4.1) 2.20
5 6.28 (10) 6.04 (7.3) 5.68 (2.7) 5.58 (2.4) 5.20
5 0.970 (16) 1.36 (6.7) 1.50 (3.1) 1.55 (2.2) 1.57
1.9) 1.81 2.2)
7.1) 4.27 6.9
1.5) 1.32 (4.2
7 0.574 (15) 0.752 (8.4) 1.05 (2.8) 1.15 (0.99) 1.16 (0.91) 1.04 (2.9)
2) 2.07 (3.5) 2.14 (2.7) 2.24 (0.95) 2.25 (2.4) 2.18 (2.3) 1.79 (2.9
1-Chlorohexane 2 0.15 3.77 (14) 4.61 (7.0) 4.75 (2.4) 5.52 (9.8) 5.24 (2.2) 5.50 (2.5) 5.02 (1.5)
2-Chloroethyl vinyl ether 1 0.30 ND
Chloromethane 5 0.20 0.762 (8.
Chloromethyl methyl ether 6 0.80 ND
0.319 (24) 0.411 (15
5) 1.03 (8.9) 1.41 (3.6
NO -- 0.179 (4.8
4-Chlorotoluene 3 0.30 5.59 (19) 5.60 (12) 5.36 (5.1
0.582 7.0) 0.584 (8.8) 0.597
(16) 0.399 (8.5
1.54 2.2) 1.57 (2.2) 1.56 (0.69) 1.15 (5.0
0.673 (5.0) 1.36 (6.7) 1.34 (6.2) 1.57 (0.51
5.01 (1.2) 4.82 (3.2) 4.43 (7.1) 3.77 (6.7'
Dibromochloromethane 1 0.20 1.10 (28) 1.97 (11) 2.49 (6.2) 3.13 (1.5) 3.28 (1.4) 3.11 (2.5) 2.21 (3.3)
l,2-D1bromo-3-chloropropane 3 0.40 3.19 (6.
Dlbromomethane 1 0.30 0.558 2
1,2-Dichlorobenzene 3 0.20 5.72 7
1,3-Dichlorobenzene 2 0.15 7.30 1
l,4-D1chlorobenzene 2 0.15 5.29 2
l,4-D1chloro-2-butene 4 0.40 0.957 (1
D1chlorod1f1uoromethane 6 0.040 ND
1,1-Dlchloroethane 6 0.040 ND
0) 3.47 (8.3) 4.05 (5.4) 3.88 (0.88) 4.04 (2.8) 4.21 (4.3) 4.18 (4.9)
4 1.28 (4.9) 1.82 (8.9) 2.41 (5.9) 2.57
9 7.57 (39) 7.99 (14) 7.85 (2.4) 7.61
6 6.86 (2.6) 7.64 (3.7) 9.72 (11) 8.85
0 6.26 (6.2) 6.94 (3.7) 9.84 (12) 8.97
2.1) 2.42 (1.1) 1.71 (8.3)
5.4) 7.13
1.6) 9.22
1.7) 9.26
7.4) 6.10 5.5;
3.0) 8.58 1.5]
3.1) 8.55 1.2]
0 1.05 (1.5) 1.01 (1.6) 1.06 (0.73) 1.08 (0.91) 1.05 (1.8) 0.911 (1.3)
3.03 (11) 6.99 (8.4) 6.94 (7.6) 7.38
3.24 (14) 7.11 (6.5
1,2-Dlchloroethane 3 0.15 4.32 (28) 8.85 (6.6) 10.8 (5.4
Trans-l,2-D1chloroethylene 1 0.24 0.814 (42) 1.62 (12) 2.11 (6.3
Dlchloromethane 6 0.040 ND
1,1-Dlchloroethylene 6 0.040 ND
1,2-Dlchloropropane 1 0.15 1.88 1
l,3-D1chloro-2-propanol 2 0.10 4.49 5
C1s-1.3-dichloropropylene 2 0.15 2.04 2
Eplchlorohydrin 4 0.60 0.451 (9.
7.29 (6.9) 9.28
11.9 1.5) 12.1
2.62 1.9) 2.81
4.20 (10) 7.17 (8.8) 7.43 (5.1) 10.7
3.73 (10) 9.79 (4.5) 9.89 (2.7) 12.0
9) 2.92 (6.9) 3.74 (5.9) 4.11 (2.2) 4.05
8.9) 5.60
7.9) 7.76
2.9) 11.1
2.9) 3.75 (2.3)
3.5) 6.15 (6.8]
6.3) 8.81 (4.i;
3.3) 2.66 (2.4) 1.89 (7.8)
(11) 8.87 (3.7) 7.41 (1.7]
8.8) 9.23 (0.83) 7.03 (5.9]
1.4) 3.76 (1.0) 2.63 (5.9]
5) 4.19 (14) 6.24 (5.1) 8.58 (11) 8.41 (2.2) 9.34 (2.8) 8.99 (1.7]
2) 3.81 (5.0) 5.06 (3.2) 6.06 (6.5) 5.89 (2.3) 6.13 (2.4) 5.77 (2.3]
8) 0.696 (2.4) 0.786 (1.2) 0.867 (4.6) 0.908 (0.68) 0.884 (1.6) 0.692 (1.7]
Ethylene dlbromlde 2 0.20 3.17 (24) 4.73 (2.8) 5.91 (2.0) 7.51 (10) 7.23 (1.8) 7.53 (2.8) 6.99 (2.2)
Methyl Iodide 5 0.80 0.077 (20) 0.180 (4.7) 0.448 (9.0) 0.62 (1.4) 0.703 (2.7) 0.717 (1.1) 0.615 (1.5]
1,1,2,2-Tetrachloroethane 1 0.090 2.66 (16) 4.18 (7.3) 4.56 (5.0) 5.03 (1.7) 4.91 (1.7) 4.58 (2.2) 3.32 (8.2)
1,1,1.2-Tetrachloroethane 3 0.15 3.15 2
Tetrachloroethylene 3 0.080 11.5 2
1.1,1-Trlchloroethane 2 0.040 6.08 2
1 4.78 (4.7) 4.79 (7.7) 5.98 (1.6) 5.22
(14) 6.42
7 15.2 (4.6) 15.5 (5.6) 15.1 (1.4) 14.4 (1.2) 13.5
3.4) 5.94 3.8]
5.8) 10.3 6.2]
1 8.59 (7.0) 12.1 (2.1) 12.4 (9.9) 14.1 (1.3) 14.9 (1.9) 13.8 (2.6)
I,l,2-Tr1 Chloroethane 2 0.040 15.6 (11) 23.8 (2.8) 28.9 (1.9) 34.0 (10) 31.4 (2.1) 32.6 (2.4) 30.1 (1.8)
Trlchloroethylene 4 0.30 1.43 (10) 1.66 (0.84) 1.57 (3.0) 1.62 (0.77) 1.58 (2.7) 1.56 (1.3) 1.30 (0.88)
Trlchlorofluoromethane 5 0.060 0.737 (21) 1.27 (12) 1.98 (8.2) 2.18 (1.8) 2.17 (1.3) 2.17 (1.8) 1.92 jl.9]
1,2,3-Trlchloropropane 2 0.040 15.3 (45) 17.6 (7.7) 16.3 (9.0) 18.4 (16) 15.7 (2.2) 15.7 (2.8) 13.9 (2.0]
Vinyl chloride 5 0.14 0.222 (30) 0.544 (23) 0.953 (8.0) 1.16 (2.0) 1.24 (1.7) 1.29 (0.83) 1.06 (5.9)
-------
TABLE 12. RESPONSE FACTORS DETERMINED FOR METHOD 8015 ANALTTES USING PTD
Compound
Dlethyl ether
Ethyl methacrylate
Methacrylonltrlle
Methyl ethyl ketone
Methyl Isobutyl ketone
Methyl methacrylate
Solution
Set
2
2
1
2
2
2
S/N
Concentration,
9/1
0
0
0
0
0
0
.015
.040
.030
.30
.050
.040
Response Factor (Relative Standard Deviation)
5
20.6
14.3
1.15
1.86
8.59
6.84
S/N
(75)
(140)
(62)
(48)
(17)
(82)
15
11.0
5.98
0.356
1.74
9.75
5.07
S/N
(2.2)
(73)
(9.3)
(15)
(17)
(46)
50
14.9
7.35
0.316
1.96
6.25
6.16
S/N
(23)
(27)
(4.2)
(48)
(52)
(70)
150
12.5
7.30
0.281
1.87
5.53
6.56
S/N
(8.6)
(12)
(14)
(3.3)
(2.0)
(23)
500
12.5
6.89
0.273
2.10
5.64
6.08
S/N
(6?5)
5.0)
(6.3)
(25)
1500 S/N
12.7 (2.1
7.17 (18
0.288 (3.6
2.15 (2.2
5.61 (4.1
6.64 (8.8
5000
12.2
7.21
0.290
2.23
5.73
6.47
S/N
(5.3!
(7.2;
(4.6!
(1.0'
(2.4!
(6.4
-------
TABLE 13. RESPONSE FACTORS DETERMINED FOR METHOD 8015 ANALYTES USING DLI
cr>
Compound
AcetonHHIe
Allyl alcohol
Carbon dlsulflde
1,2,3,4-Dlepoxybutane
Dlethyl ether
1,4-Dioxane
Ethyl ene oxide
Ethyl methacrylate
Isobutanol
Malononitrlle
Methacrylonltrlle
Methyl ethyl ketone
Methyl Isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
Propargyl alcohol
B-Propiolactone
Proplonltrlle
Solution
Set
1
2
1
1
2
2
1
3
1
3
2
1
2
2
1
1
1
2
2
S/N
Concentration,
mg/L
0.21
0.24
0.78
0.080
0.050
0.050
0.052
0.060
0.028
0.40
0.050
0.034
0.030
0.170
0.028
0.064
0.24
0.30
0.14
Response Factor (Relative Standard Deviation)
5 S/N 15 S/N 50 S/N 150 S/N 500 S/N 1500 S/N 5000 S/N
2.09 (14) 3.40 (12) 5.11 (0.80) 5.93 (1.4) 6.45 (2.2) 6.54 (1.9) 6.63 (0.91)
4.59 (5.7) 6.56 (1.3) 8.04 (1.0) 8.65 (1.0) 9.01 (1.1) 9.42 (1.4) 9.46 (1.0)
0.539 (6.7) 0.644 (5.2) 0.493 (1.2) 0.480 (0.50) 0.389 (1.1) 0.282 (5.5) 0.187 (0.82)
6.90 (2.9) 7.37 1.3) 5.68 (0.33) 7.71 (0.01 7.80 (0.15) 7.89 1.2) 6.01 (1.3)
8.13 (2.5) 8.53 1.3) 8.48 (1.1) 8.36 (1.0 8.23 (1.1) 8.36 1.2) 8.26 (1.3)
11.9 (3.0) 10.0 1.4) 8.56 (5.1) 7.73 (1.8 7.08 (1.0) 6.81 1.1) 6.42 (1.0)
4.11 (36) 3.88 5.8) 4.58 (3.3) 4.32 (1.8 4.53 (0.91) 4.61 4.5) 4.77 (1.6)
9.70 (11) 10.5 (13) 10.6 (2.6) 10.1 (1.5) 9.59 (1.0) 9.69 1.0) 9.19 (2.0)
17.6 (6.5) 14.8 4.7) 12.0 (0.86) 13.2 (0.46 13.1 (0.43) 12.7 (5.5) 12.8 (6.0)
0.122 (33) 0.351 8.1) 0.868 (1.3) 1.02 (1.6 2.15 (7.1)
10.7 (2.5 11.1 1.5) 11.1 (1.7) 11.0 (1.0 10.9 1.5) 11.0 1.4) 10.8 (1.1)
11.5 (8.1) 8.53 7.5) 9.62 (0.67) 9.73 (0.82 9.97 1.4) 9.96 1.1) 9.94 (0.95)
12.0 (3.7) 12.1 (1.9) 12.5 (1.0) 11.8 (1.2 11.5 1.2) 11.5 (1.0) 11.2 (1.0)
1.54 (16) 2.57 (7.3) 2.67 (1.0) 3.38 (1.3) 4.50 1.0) 3.88 (1.0) 3.95 (1.7)
14.6 (13) 12.0 (1.9) 9.8 (7.4) 10.6 (0.21) 10.4 (0.34) 10.1 (4.1) 10.0 (0.62)
4.28 (7.1) 5.61 (0.80) 6.40 (0.37) 6.29 (0.11) 6.24 (0.29) 6.22 (1.2) 6.08 (1.4)
3.09 (10) 4.68 (2.9) 6.27 (1.4) 8.26 (0.97) 9.30 (0.49) 9.84 (2.4) 9.69 (0.83)
1.31 (5.4) 2.21 (5.3) 3.11 (1.5) 3.64 (1.0) 4.05 (1.1) 4.42 (1.1) 4.55 (1.0)
4.81 (11) 6.93 (3.9) 8.24 (1.0) 8.39 (1.0) 8.52 (1.1) 8.73 (1.3) 8.60 (1.0)
-------
TABLE 14. RESPONSE FACTORS DETERMINED FOR METHOD 8020 ANALYTES USING PTD
Ol
INJ
Compound
Benzene
Chloro benzene
l,Z-D1ch1orobenzene
1 ,3-Dlchlorobenzene
l,4-D1ch1orobenzene
Ethyl benzene
Styrene
Tol uene
o-Xylene
m-Xylene
p-Xylene
Solution
Set
2
1
1
2
1
2
2
2
1
. 2
2
S/N
Concentration,
9/L
0.0072
0.0056
0.013
0.005
0.0096
0.0032
0.0072
0.0024
0.0070
0.0050
0.012
Response Factor (Relative Standard Deviation)
5
198.0
2.82
1.36
17.6
1.79
57.8
6.87
51.3
4.59
13.3
4.89
S/N
(4.7)
(11)
(28)
(38)
(30)
(38)
(19)
(16)
(7.1)
(36)
(69)
65
1
0
7
1
15
4
20
3
9
5
15 S/N
SO
.6 (5.2) 23.4
.98 (9.2) 1.48
.929 (24) 0.712
.42 (37) 5.43
.13 (19) 0.908
.2 (13) 7.98
.54 (44) 5.58
.5 (6.0
.08 (11
.10 (13
11.4
1.56
6.99
.00 (21) 4. 92
S/N
(4.1)
(7.5)
(8.6)
(13)
(4.6)
(22)
(12)
(8.4)
(11)
(7.5)
(ID
150
12.3
1.42
0.705
4.07
0.883
4.79
4.99
7.72
1.30
6.59
4.78
S/N
(6.2)
(7.0)
(8.0)
(19)
(6.5)
(13)
(8.8)
(9.5)
(15)
(12)
(13)
500
11.8
1.42
0.729
3.81
0.917
4.11
5. ,25.
6.H
l.ta
6.31
5.19
S/N
(8.0)
(4.8)
(5.1)
(16)
(4.4)
(11)
(12)
(12)
(3.3)
(15)
(14)
1500
13.2
1.78
0.952
4.80
0.182
4.70
7.19
7.39
1.36
7.76
6.99
S/N
(5.6)
(12)
(ID
(2.1)
(13)
(8.5)
(1.9)
(7.6)
(11)
(9.8)
(1.8)
5000
15.0
2.11
1.08
5.34
4.37
5.93
7.86
8.99
1.62
8.45
8.10
S/N
(2.4)
(11)
(9.5)
(1.4)
(11)
(3.5)
(2.2)
(2.3)
(9.5)
(2.9)
(3.2)
-------
TABLE 15. RESPONSE FACTORS DETERMINED FOR METHOD 8020 ANALYTES USING DLI
o>
Compound
Benzene
Chi oro benzene
1,2-Dlchloro benzene
1 ,3-Dichlorobenzene
1 ,4-D1chlorobenzene
Ethyl benzene
2-P1coline
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Solution
Set
1
1
1
2
1
2
3
2
2
1
2
2
S/N
Concentration,
0.050
0.050
0.060
0.100
0.060
0.100
0.30
0.100
0.080
0.060
0.010
0.010
j-— ,, c Response Factor (Relative Standard Deviation)
3 "" 1S >/n 50 5/n 150 S/N 500 S/N 1500 S/N 5000 S/N
IlillllllllSll
: ' l:s ill ,;i 11 15 I"! « »:i -^ ":« a !^
If* (K! 1:8 !?:39i !:5 ,}!!! f:S IS:!! i:SS |L1) 111 |s:jj i:» |;;|j
-------
TABLE 16. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8010 USING PTD SAMPLE INTRODUCTION
Concentration Range Over
Which Calibration Models Ir
Were Accepted (uQ/L)
Compound
Ally! chloride
Benzyl chloride
Bromobenzene
Bromod i ch 1 oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
1-Chlorohexane
Chi oromethane
Chloroprene
4-Chlorotoluene
D i bromoch 1 oromethane
1 , 2-D i bromo-3-ch 1 oropropane
Dibromomethane
1 , 2-D i ch 1 orobenzene
1, 3-D i Chlorobenzene
1,4-Dichlorobenzene
1 , 4-D i ch 1 oro-2-butene
Dlchlorofluoromethane
1,1-Dichloroethane
1, 2-D i chloroethane
1,1-Dichloroethylene
Trans-l,2-Dichloroethylene
List(a)
8,9,M
8
—
PP.8,9
PP,8,9
PP.8,9
PP.8,9
PP,8,9
PP,9
PP,8,9
—
PP.8,9
8,9,M
—
PP,9
8,9
8
PP,8,9
PP,8,9
PP,8,9
8,9
8,9
PP,8,9
PP,8,9
PP,8,9
PP.8,9
Response Factor Linear Quadratic (C
Regression Regression Regression Ma
0.400-400
10-10,000
(b)
(b)
(b)
(c)
(b)
0.625-625
(b)
0.630-210
3.60-1,200
0.500-500
2.50-2,500
1.95-1,950
(b)
53.5-5,350
(b)
1.40-1,400
0.400-400
1.25-1,250
(b)
(b)
0.300-300
0.300-300
0.550-550
(b)
0.400-400
10-10,000
0.850-850
0.800-800
(b)
(c)
0.155-155
0.625-625
0.150-15.0
0.630-210
3.60-1,200
0.500-500
2.50-2,500
1.95-1,950
0.120-120
53.5-5,350
2.40-800
1.40-1,400
0.400-400
1.25-1,250
2.78-2,780
0.500-500
0.300-300
0.300-300
0.550-550
0.400-400
0.400-400
10-10,000
0.850-850
0.800-800
4.35-1,450
(c)
0.155-155
0.625-625
0.150-15.0
0.630-210
3.60-1,200
0.500-500
2.50-2,500
1.95-1,950
0.120-120
53.5-5,350
2.40-800
1.40-1,400
0.400-400
1.25-1,250
2.78-2,780
0.500-500
0.300-300
0.300-300
0.550-550
0.400-400
istrument
Range
)rders of
ignitude)
3
3
3
3
2.5
(c)
3
3
2
2.5
2.5
3
3
3
3
2
2.5
3
3
3
3
3
3
3
3
3
64
-------
TABLE 16. (Continued)
Concentration Range Over
Which Calibration Models Ir
Were Accepted (uQ/L)
Compound
Dichloromethane
1 , 2-D i ch 1 oropropane
Cis-l,3-dichloropropylene
Ethylene dibromide
Methyl iodide
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
1,1, 1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethylene
Tr i ch 1 orof 1 uoromethane
1,2,3-Trichloropropane
Vinyl chloride
Response Factor Linear Quadratic (C
ListU) Regression Regression Regression Me
PP,8,9 0.630-210
PP,8,9 (b)
8 (b)
8 (b)
8,9 (c)
PP,8,9 0.100-10.0
8,9 (b)
PP,8,9 0.200-200
PP (b)
PP,8,9 0.250-250
PP,8,9 0.180-180
PP.8,9 (b)
8,9 0.360-360
PP,8,9 (b)
0.630-210 0.630-210
0.455-455 0.455-455
0.550-550 0.550-550
1.55-1,550 1.55-1,550
(c) (c)
0.100-10.0 0.100-10.0
0.400-400 0.400-400
0.200-200 0.200-200
0.150-50 0.150-50
0.250-250 0.250-250
0.180-180 0.180-180
1.26-420 1.26-420
0.360-360 0.360-360
0.400-400 0.400-400
istrument
Range
Jrders of
ignitude)
2.5
3
3
3
(c)
2
3
3
2.5
3
3
2.5
3
3
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List;
— = not on any list.
(b) Smaller concentration ranges than that accepted by another calibration model were
not evaluated.
(c) Instrument range data generated for this compound did not fit any of the three
calibration models tested even when the concentration range being considered was
reduced to one-and-a-half orders of magnitude.
65
-------
TABLE 17. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8010 USING DLI SAMPLE INTRODUCTION
Concentration Range Over
Which Calibration Models I
Were Accepted (mq/L)
Compound
Ally! chloride
Benzyl chloride
Bi s (2-chl oroethoxy )methane
Bromoacetone
Bromobenzene
Bromod i chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chl oromethane
Chloromethyl methyl ether
4-Chlorotoluene
D i bromoch 1 oromethane
1 ,2-Dibromo-3-chl oropropane
Dibromomethane
1 , 2-D i ch 1 orobenzene
1 , 3-D i ch 1 orobenzene
1 , 4-D i ch 1 orobenzene
l,4-Dichloro-2-butene
List (a)
8,9,M
8
8,9
8
—
PP,8,9
PP,8,9
PP,8,9
PP.8,9
PP,8,9
PP,9
M
PP,8,9
—
PP,8
PP,8,9
8
—
PP,9
8,9
8
PP.8,9
PP,8,9
PP.8,9
8,9
Response Factor Linear
Regression Regression
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
0.750-750
(b)
(b)
(b)
(b)
(b)
(b)
(b)
1.50-1,500
(b)
(b)
(b)
10-1,000
(b)
(b)
(b)
0.400-400
1.50-1,500
2.00-2,000
18.0-1,800
(b)
0.400-400
(b)
10.0-1,000
0.300-300
0.750-750
0.600-600
15.0-1,500
0.300-300
0.750-75.0
4.50-1,500
(b)
120-4,000
1.50-1,500
(b)
(b)
(b)
10-1,000
2.25-750
(b)
0.600-600
Quadratic (
Regression M
0.400-400
1.50-1,500
2.00-2,000
18.0-1,800
1.50-1,500
0.400-400
1.50-1,500
10.0-1,000
0.300-300
0.750-750
0.600-600
15.0-1,500
0.300-300
0.750-75.0
4.50-1,500
1.00-1,000
120-4,000
1.50-1,500
1.00-1,000
2.00-2,000
4.50-1,500
10-1,000
2.25-750
7.50-750
0.600-600
nstrument
Range
Orders of
agnitude)
3
3
3
2
3
3
3
2
3
3
3
2
3
3
2.5
3
1.5
3
3
3
2.5
2
2.5
2
3
66
-------
TABLE 17. (Continued)
Concentration Range Over
Which Calibration Models I
Were Accepted (ma/H
Compound
Dlchlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
Trans-l,2-Dichloroethylene
Dichloromethane
1,2-Dichloropropane
l,3-Dichloro-2-propanol
Ci s-1 , 3-dichl oropropy 1 ene
Epichlorohydrin
Ethyl ene di bromide
Methyl iodide
1,1, 2, 2-Tetrach 1 oroethane
1,1,1, 2-Tetrach 1 oroethane
Tetrachl oroethy 1 ene
1,1,1-Trichl oroethane
1,1,2-Trichl oroethane
Tr ichl oroethy 1 ene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl chloride
List(a)
8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP.8,9
PP,8,9
8
8
8
8
8,9
PP,8,9
8,9
PP,8,9
PP
PP.8,9
PP,8,9
PP.8,9
8,9
PP,8,9
Kesponse I- actor Linear
Regression Regression
2.00-60.0
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
0.450-450
3.00-300
0.200-200
(b)
2.00-60.0
(b)
(b)
(b)
(b)
(b)
(b)
5.00-500
0.750-750
3.00-900
10.0-1,000
12.0-4,000
(b)
0.750-750
(b)
(b)
0.200-200
0.450-450
3.00-300
0.200-200
2.10-700
Quadratic (
Regression M
2.00-60.0
0.600-200
0.750-750
2.00-200
1.20-1,200
2.00-200
0.750-750
5.00-500
0.750-750
3.00-900
10.0-1,000
12.0-4,000
0.450-450
0.750-750
0.400-400
0.200-200
0.200-200
0.450-450
3.00-300
0.200-200
2.10-700
nstrument
Range
Orders of
agnitude)
1.5
2.5
3
2
3
2
3
2
3
2.5
2
2.5
3
3
3
3
3
3
3
3
2.5
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List;
-- = not on any list.
(b) Smaller concentration ranges than that accepted by another calibration model were
not evaluated.
67
-------
TABLE 18. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8015 USING PTD SAMPLE INTRODUCTION
Concentration Range Over
Which Calibration Models In
Were Accepted (yq/L)
Compound
Di ethyl ether
Ethyl methacrylate
Methacrylonitrile
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl methacrylate
Response Factor Linear
List(a) Regression Regression
— ~
8,9
8
8,9
—
8,9
0.225-75.0
0.600-200
(b)
1.50-1,500
(c)
0.200-200
0.225-75.0
0.600-200
0.450-150
1.50-1,500
(c)
0.200-200
Quadratic (0
Regression Mai
0.225-75.0
0.600-200
0.450-150
1.50-1,500
(c)
0.200-200
strument
Range
rders of
gnitude)
2.5
2.5
2.5
3
(c)
3
(a) 8 = Appendix VIII; 9 = Appendix IX; — = not on any list.
(b) Smaller concentration ranges than that accepted by another calibration model were
not evaluated.
(c) Instrument range data generated for this compound did not fit any of the three
calibration models tested even when the concentration range being considered was
reduced to one-and-a-half orders of magnitude.
68
-------
TABLE 19. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8015 USING DLI SAMPLE INTRODUCTION
Concentration Range Over
Which Calibration Models I
Were Accepted (mq/L}
Compound
Acetonitrile
Ally! alcohol
Carbon disulfide
1,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Ethylene oxide
Ethyl methacrylate
Isobutanol
Malononitrile
Methacrylonitrile
Methyl ethyl ketone
Methyl isobutyl ketone
Methyl mercaptan
Methyl methacrylate
Paraldehyde
Propargyl alcohol
s-propiolactone
Propionitrile
List(a)
8
8
8,9
8
—
8
8
8,9
8
8
8
8,9
—
8
8,9
8
8
M
8
Response Factor Linear
Regression Regression
(b)
(b)
(c)
(b)
0.250-250
(b)
0.260-260
0.300-300
0.140-140
(c)
0.250-250
(b)
0.150-150
(b)
0.140-140
3.20-320
(c)
(b)
(b)
1.02-1,020
1.20-1,200
(c)
(b)
0.250-250
0.250-250
0.260-260
0.300-300
0.140-140
(c)
0.250-250
0.510-170
0.150-150
(b)
0.140-140
3.20-320
(c)
(b)
0.700-700
Quadratic (
Regression M
1.02-1,020
1.20-1,200
(c)
4.00-400
0.250-250
0.250-250
0.260-260
0.300-300
0.140-140
(c)
0.250-250
0.510-170
0.050-150
2.55-850
0.140-140
3.20-320
(c)
1.50-1,500
0.700-700
nstrument
Range
Orders of
agnitude)
3
3
(c)
2
3
3
3
3
3
(c)
3
2.5
3
2.5
3
2
(c)
3
3
(a) 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List; — = not on any list.
(b) Smaller concentration ranges than that accepted by another calibration model were
not evaluated.
(c) Instrument range data generated for this compound did not fit any of the three
calibration models tested even when the concentration range being considered was
reduced to one-and-a-half orders of magnitude.
69
-------
TABLE 20. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8020 USING PTD SAMPLE INTRODUCTION
Concentration Range Over
Which Calibration Models I
Were Accepted (yq/L)
Compound
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Response Factor Linear
List(a) Regression Regression
PP.8,9
PP,8,9
PP.8,9
PP,8,9
PP,8,9
PP,9
9,M
PP,8,9
9
9
9
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
1.08-36.0
(b)
(b)
0.250-7.50
(b)
(b)
(b)
(b)
(b)
(b)
(b)
Quadratic (
Regression N
1.08-36.0
0.028-28.0
0.064-64.0
0.250-7.50
0.048-48.0
0.048-16.0
0.036-35.5
0.036-12.0
0.345-34.5
0.250-25.0
0.061-61.0
instrument
Range
Orders of
lagnitude)
1.5
3
3
1.5
3
2.5
3
2.5
2
2
3
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List.
(b) Smaller concentration ranges than that accepted by another calibration model were
not evaluated.
70
-------
TABLE 21. RESULTS OF INSTRUMENT RANGE DETERMINATION FOR
METHOD 8020 USING DLI SAMPLE INTRODUCTION (yg/g)
Concentration Range Over
Which Calibration Models
Were Accepted (mq/L)
Compound
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
2-Picoline
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Response Factor Linear Quadratic
ListU) Regression Regression Regression
PP,8,9
PP.8,9
PP,8,9
PP,8,9
PP.8,9
PP,9
8,9
9.M
PP.8,9
9
9
9
(a) PP = Priority Pollutant; 8 = Appendix
(b) Smaller concentration ranges than that
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(c)
VIII;
accei
b
(b)
(b)
0.500-500
(b)
(b)
(b)
(b)
(b)
(b)
(b)
(c)
9 = Appendix IX;
Jted by another c<
0.250-250
0.250-250
0.300-300
0.500-500
0.300-300
1.50-500
1.50-1500
1.50-500
0.400-400
9.00-300
0.500-500
(c)
M = Michigan
ili brat ion moc
Instrument
Range
(Orders of
Magnitude)
3
3
3
3
3
2.5
3
2.5
3
1.5
3
(c)
List.
Jel were
not evaluated.
(c) Instrument range data generated for this compound did not fit any of the three
calibration models tested even when the concentration range being considered was
reduced to one-and-a-half orders of magnitude.
71
-------
TABLE 22. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8010 USING AQUEOUS SAMPLES
Compounds
Ally! chloride
Benzyl chloride
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chl oroethane
Chloroform
1-Chlorohexane
Chloromethane
Chloroprene
4-Chlorotoluene
Dibromochloromethane
1 , 2-Di bromo-3-ch 1 oropropane
Dibromomethane
1, 2-Di Chlorobenzene
1,3-Di Chlorobenzene
1,4-Di Chlorobenzene
l,4-Dichloro-2-butene
Di chl orod i f 1 uoromethane
1,1-Di chl oroethane
1,2-Dichloroethane
1,1-Di chl oroethylene
Trans-l,2-Dichloroethylene
Di Chloromethane
1, 2-Di chl oropropane
Cis-l,3-dichloropropylene
Ethylene dibromide
1 , 1 , 2 , 2-Tetrach 1 oroethane
1,1,1, 2-Tetrachl oroethane
Tetrach 1 oroethy 1 ene
1,1, 1-Tri chloroethane
1,1,2-Trichloroethane
Trichloroethylene
Trichlorofluoromethane
1,2, 3-Tri chl oropropane
Vinyl chloride
Number
/ x Of
List(a) Replicates
8,9,M
8
—
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,9
PP,8,9
—
PP,8,9
8,9,M
—
PP,9
8,9
8
PP,8,9
PP,8,9
PP,8,9
8,9
8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
8
8
PP,8,9
8,9
PP,8,9
PP
PP,8,9
PP,8,9
PP,8,9
8,9
PP,8,9
8
7
8
8
8
8
7
9
8
7
7
7
10
7
8
10
8
7
8
9
7
8
10
10
7
8
7
7
8
7
6
7
7
6
10
10
6
10
7
Spike Recovery
Concentration Percent
(vg/L) (RSD)
8.00
200
17.0
16.0
29.0
17.0
3.10
12.5
0.300
4.20
24.0
10.0
50.0
39.0
2.40
107
16.0
28.0
8.00
25.0
55.6
10.0
6.00
6.00
11.0
8.00
4.20
9.10
11.0
31.0
0.300
8.00
4.00
1.00
5.00
3.60
8.40
7.20
8.00
70.2
55.5
84.7
91.2
73.8
74.7
53.9
87.2
112
61.2
57.1
52.9
68.4
104
92.9
85.4
89.4
76.8
87.4
68.4
81.7
4.74
83.3
90.7
58.7
81.0
70.5
71.8
84.5
76.1
71.0
68.8
57.8
48.2
92.6
74.2
21.8
95.0
45.1
(9.6)
(46)
(7.5)
(6.8)
(5.6)
(9.4)
(11)
(6.4)
(7.1)
(4.3)
(3.6)
(10)
(12)
(40)
(6.7)
(8.1)
(6.3)
(3.7)
(11)
(9.5)
(15)
(37)
(8.2)
(8.8)
(6.2)
(8.0)
(19)
(4.3)
(6.6)
(5.9)
(22)
(2.2)
(5.2)
(8.7)
(8.0)
(9.4)
(11)
(6.1)
(9.3)
Method
Successful
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9
~ = not on any list.
Appendix IX; M = Michigan List;
72
-------
TABLE 23. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8010 USING SOLID SAMPLES
Compounds
Allyl chloride
Benzyl chloride
Bromobenzene
Bromod i ch 1 oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
1-Chlorohexane
Chi oromethane
Chloroprene
4-Chlorotoluene
D i bromoch 1 oromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1,3-Di Chlorobenzene
1,4-Dichlorobenzene
l,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1 , 2-D i ch 1 oroet hane
1,1-Dichloroethylene
Trans-l,2-Dichloroethylene
Dichloromethane
1,2-Dichloropropane
Cis-l,3-dichloropropylene
Ethylene dibromide
1,1,2,2-Tetrachloroethane
1,1, 1 ,2-Tetrachl oroethane
Tetrachl oroethy 1 ene
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethylene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl chloride
Number
, ^ Of
ListW Replicates
8,9,M
8
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP,9
PP,8,9
PP,8,9
8,9,M
PP.9
8,9
8
PP,8,9
PP,8,9
PP,8,9
8,9
8,9
PP.8,9
PP.8,9
PP,8,9
PP,8,9
PP,8,9
PP,8,9
PP
8
PP,8,9
8,9
PP,8,9
PP
PP,8,9
PP,8,9
PP,8,9
8,9
PP,8,9
6
9
6
6
6
6
9
6
6
8
9
9
6
6
6
6
6
8
6
6
6
6
6
6
8
6
8
8
6
8
5
8
9
6
6
6
6
6
9
Spike Recovery
Concentration Percent
(yg/g) (RSD)
8.00
200
17.0
16.0
29.0
17.5
3.1
12.5
8.00
4.20
24.0
10.0
50.0
39.0
2.40
107
16.0
4.00
8.00
25.0
55.6
10.0
6.00
6.00
11.0
8.00
4.2
9.1
11.0
31.0
0.200
4.00
4.00
1.00
5.00
3.60
8.40
7.20
8.00
39.2
69.5
59.4
56.9
76.6
37.5
25.5
38.5
10.0
45.2
41.0
6.32
34.4
30.3
65.4
35.8
68.1
37.5
44.0
39.6
49.6
25.1
35.0
34.3
27.8
39.2
33.8
56.0
59.3
72.2
27.0
62.5
40.0
48.5
27.0
30.3
39.4
37.1
4.38
(21)
\*-j- 1
(53)
\~j-j i
(14)
(13)
\ /
(5.4)
(15)
\±~> i
(5 5)
V J« J/
(26)
(12)
(18)
(30)
(22)
(24)
(50)
\du/
(11)
(30)
\**w/
(15)
(20)
(12)
\it/
(36)
\ju/
(38)
\J°/
(31)
(23)
(27)
(36)
\ jw/
(18)
\ *"/
(14)
\ 4-^/
(12)
V **• /
(14)
V i^/
(7.1)
\ " * /
(37)
V*" /
(12)
V •"• /
(28)
Vtu/
(77)
\ ' ' /
(15)
V ***/
(19)
\ /
(25)
\ ^ /
(30)
\ /
(43)
Method
Successfi
Yes
ico
No
llw
Yes
Yes
Yes
Yes
1 C O
Vpc
I CO
Yes
Yes
Yes
Yes
Yes
Yes
No
11 U
Yes
Yes
i c J
Yes
Yes
Yes
1 C J
Yes
ICO
Vpc
ICO
No
Yes
Yes
Yes
ICO
Yes
ICO
Yes
ICO
Yes
ICO
Yes
• CO
Yes
Yes
ICO
Yes
ICO
Yes
1 CO
Yes
ICO
Yes
ICO
Yes
I %• W
Yes
Yes
Yes
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9
— = not on any list.
Appendix IX; M = Michigan List;
73
-------
TABLE 24. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8015 USING AQUEOUS SAMPLES
Compounds
Di ethyl ether
Ethyl methacrylate
Methacrylonitrile
Methyl ethyl ketone
Methyl methacrylate
List(a)
„
8,9
8
8,9
8,9
Number
of
Replicates
6
6
8
6
6
Spike
Concentration
(yg/L)
1.50
4.00
3.00
30.0
4.00
Recovery
Percent
(RSD)
82.3 (2.8)
70.0 (16)
98.3 (11)
74.0 (3.8)
70.2 (20)
Method
Successful
Yes
Yes
Yes
Yes
Yes
(a) 8 = Appendix VIII; 9 = Appendix IX; -- = not on any list.
74
-------
TABLE 25. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8015 USING SOLID SAMPLES
Compounds
Di ethyl ether
Ethyl methacrylate
Methacrylonitrile
Methyl ethyl ketone
Methyl methacrylate
Number
/ A °f
ListU) Replicates
8,9
8
8,9
8,9
7
6
8
7
7
Spike Recovery
Concentration Percent Method
(n9/g) (RSD) Successfi
1.50
4.00
0.030
30.0
4.00
35.1
2.30
66.7
82.0
100
(40)
(18)
(9.8)
(7.6)
(23)
Yes
Yes
Yes
Yes
Yes
(a) PP = Priority Pollutant; 8
-- = not on any list.
= Appendix VIII; 9 = Appendix IX; M = Michigan List;
75
-------
TABLE 26. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8020 USING AQUEOUS SAMPLES
Compounds
Benzene
Chi orobenzene
1,2-Dichlorobenzene
1 , 3-D i ch 1 orobenzene
1 , 4-D i ch 1 orobenzene
Ethyl benzene
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
(a) PP - Priority Pollutant;
Number Spike Recovery
of Concentration Percent
List (&) Replicates (yg/L)
PP.8,9
PP,8,9
PP.8,9
PP,8,9
PP.8,9
PP,9
9,M
PP,8,9
9
9
9
8 = Appendix
8
9
9
8
9
6
8
8
9
8
8
VIII;
0.720
0.560
1.28
0.500
0.960
0.320
0.710
0.240
0.690
0.500
1.22
9 = Appendix IX;
Method
(RSD) Successful
98.2
79.6
79.7
73.4
78.6
61.9
83.8
78.3
85.4
84.6
79.5
(4.2)
(7.6)
(4.9)
(22)
(7.0)
(14)
(19)
(19)
(21)
(15)
(13)
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
M = Michigan List.
76
-------
TABLE 27. RESULTS OF PRELIMINARY METHOD EVALUATION FOR
METHOD 8020 USING SOLID SAMPLES
Compounds
Benzene
Chi orobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 , 4-D i ch 1 orobenzene
Ethyl benzene
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Number
, N °f
List(a) Replicates
PP,8,9
PP,8,9
PP,8,9
PP.8,9
PP.8,9
PP.9
9,M
PP,8,9
9
9
9
8
8
7
8
8
8
8
8
7
8
8
Spike Recovery
Concentration Percent
(yg/g) (RSD)
300
2.40
1.28
40.0
0.960
50.0
7.00
50.0
4.00
12.0
12.0
36.3
47.1
47.7
15.4
54.3
59.0
70.3
21.4
48.0
61.6
52.0
(45)
(22)
(71)
(13)
(21)
(23)
(20)
(35)
(17)
(27)
(25)
Method
Successful
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
(a) PP = Priority Pollutant; 8 = Appendix VIII; 9 = Appendix IX; M = Michigan List.
77
-------
-------
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