United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA-454/R-99-012
January 1994
Air
r/EPA
1993 Nonmethane Organic
Compounds
And
Speciated Nonmethane
Organic Compounds
Monitoring Program
-------
DCN: 93-298-130-12-10
EPA No: 68-D2-0160
1993 NONMETHANE ORGANIC COMPOUNDS AND SPECIATED
NONMETHANE ORGANIC COMPOUNDS
MONITORING PROGRAM
FINAL REPORT
U.S. Environmental Protection Agency
5 Library (PL.12J)
Prepared for:
Neil J. Berg, Jr.
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
January 7, 1994
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Table of Contents
Section Page
1.0 BACKGROUND AND SUMMARY 1-1
1.1 NMOC Monitoring Program 1-3
1.2 Three-Hour Air Toxics Monitoring Program 1-11
1.3 Carbonyl 1-14
1.4 SNMOC 1-15
2.0 NMOC DATA SUMMARY 2-1
3.0 NMOC TECHNICAL NOTES 3-1
3.1 NMOC Field Sampling Equipment 3-1
3.2 NMOC Analysis 3-9
3.3 Canister Cleanup System 3-13
4.0 NMOC QUALITY ASSURANCE/QUALITY CONTROL
PROCEDURES 4-1
4.1 Introduction and Conclusions 4-1
4.2 Calibration and Instrument Performance 4-2
4.3 In-House QC Samples 4-16
4.4 Repeated Analyses 4-23
4.5 Duplicate Sample Results 4-26
4.6 Canister Pressure Results 4-26
4.7 Canister Cleanup Results 4-30
4.8 External Audit Results 4-32
4.9 Data Validation 4-32
4.10 NMOC Monitoring Program Records 4-36
5.0 NMOC DATA ANALYSIS AND CHARACTERIZATION 5-1
5.1 Overall Characterization 5-1
5.2 Monthly Variations, 1993 5-7
6.0 THREE-HOUR AIR TOXICS DATA SUMMARY 6-1
6.1 Overall Results 6-3
6.2 Site Results 6-3
JBS441
11
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Table of Contents, continued
Page
7.0 THREE-HOUR AIR TOXICS TECHNICAL NOTES 7-1
7.1 Sampling Equipment and Gas Chromatograph/Multiple
Detector Analytical System 7-1
7.2 Three-Hour Air Toxics Sampling Systems Certification 7-5
7.3 Calibration Standard Preparation .. '. 7-6
7.4 Daily Calibration Check 7-8
7.5 Gas Chromatograph/Mass Spectrometer Analysis and
Compound Identification Confirmation 7-8
7.6 QA/QC Data 7-9
7.7 Sample Dilutions 7-16
7.8 Data Records 7-19
8 0 CARBONYL COMPOUNDS SAMPLING, ANALYSIS, AND QUALITY
ASSURANCE PROCEDURES 8-1
8.1 Data Summary 8-1
8.2 Sampling Equipment and Procedures 8-1
8.3 Analytical Procedures 8-9
8.4 Calibration Procedures 8-11
8.5 Quality Assurance/Quality Control Data 8-15
9.0 SNMOC DATA SUMMARY 9-1
9.1 Sample Collection Summary 9-1
9.2 Site Specific Summary Statistics 9-1
9.3 Overall Data Summary 9-46
9.4 Individual Sample Results 9-46
10.0 SNMOC TECHNICAL NOTES 10-1
10.1 Sampling Equipment and Procedure 10-1
10.2 Analytical System 10-1
JBS441 m
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Table of Contents, continued
Section
11.0
12.0
13.0
Page
SNMOC QUALITY ASSURANCE AND CONTROL
PROCEDURES 11-1
11.1 Standards Preparation 11-1
11.2 Target Compounds Database 11-1
11.3 GC/FID Monthly Calibration 11-2
11.4 Daily Quality Control Check 11-4
11.5 Daily Analytical System Blank 11-5
11.6 Precision of Sampling and Analysis 11-5
11.7 Accuracy 11-18
11.8 Data Acquisition and Reduction Procedures 11-1&
RECOMMENDATIONS 12-1
12.1 General 12-1
12.2 Equipment 12-2
12.3 SNMOC 12-3
12.4 Air Toxics 12-3
12.5 Carbonyls 12-4
REFERENCES 13-1
APPENDICES
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Appendix F
Appendix G
1993 NMOC/SNMOC Program Sites
Cryogenic Preconcentration and Direct Flame lonization
Detection Method
1993 NMOC Data Summaries
1993 NMOC Void or Invalid Samples
PDFID Integrator Programing Instructions
1993 NMOC Daily Calibrations
1993 NMOC QC Samples
JBS441
IV
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Table of Contents, continued
APPENDICES, continued
Appendix H 1993 NMOC 3-Hour Toxics Data Summaries
Appendix I Audit Results
Appendix J Speciated NMOC Analysis Method
Appendix K Speciated NMOC Analytical Results
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List of Tables
Page
1-1 1993 NMOC Completeness Results ......................... 1-4
1-2 NMOC Overall Statistics, By Site ........................... 1-6
1-3 Linear Regression Parameters for In-House Quality Control Data . . 1-9
1-4 NMOC External Audit Sample Results ..................... 1-10
1-5 Compound Identification Confirmation ..................... 1-13
1-6 Samples Analyzed for 1993 SNMOC Program Sites ............ 1-16
1-7 Samples Analyzed for 1993 SNMOC Option Sites ............. 1-16
1-8 1993 SNMOC Target Compounds ......................... 1-17
1-9 Summary of Monthly Benzene and Propane Calibration Curves ... 1-21
2-1 1993 NMOC Completeness Results ......................... 2-2
2-2 NMOC Overall Statistics, by Site ........................... 2-4
2-3 1993 LNMOC Overall Statistics, by Site ...................... 2-6
4-1 1993 Performance Assessment Summary, Radian Channels ........ 4-3
4-2 Summary NMOC Calibration Factor Drift Results ............. 4-15
4-3 Linear Regression Parameters for In-House Quality Control Data . 4-19
4-4 In-House Quality Control Statistics, by Radian Channel ......... 4-20
4-5 Overall In-House Quality Control Statistics .................. 4-22
4-6 Replicate Analysis Results for the 1993 NMOC Program ........ 4-24
4-7 Duplicate Samples for the 1993 NMOC Program .............. 4-27
4-8 NMOC Pressure Statistics ............................... 4-31
4-9 NMOC External Audit Sample Results ..................... 4-33
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List of Tables, continued
Page
4-10 Bias of Audit Samples from Theoretical Concentrations 4-34
5-1 Summary Statistics for 1993 NMOC Sites, By Month 5-8
6-1 Three-Hour Ambient Air Samples and Analyses 6-2
6-2 Air Toxics Compound Identifications Summary for All Sites - 1993 . 6-4
6-3 1993 Air Toxic Compounds Frequency of Occurrence 6-5
6-4 Air Toxics Compound Identifications Summary for B1AL - 1993 ... 6-6
6-5 Air Toxics Compound Identifications Summary for B2AL - 1993 ... 6-7
6-6 Air Toxics Compound Identifications Summary for B3AL - 1993 ... 6-8
6-7 Air Toxics Compound Identifications Summary for NWNJ - 1993 ... 6-9
6-8 Air Toxics Compound Identifications Summary for P1PA - 1993 ... 6-10
6-9 Air Toxics Compound Identifications Summary for P2PA - 1993 ... 6-11
6-10 Air Toxics Compound Identifications Summary for PLNJ - 1993 . . . 6-12
7-1 Three-hour Air Toxics Target Compounds 7-3
7-2 1993 NMOC Three-Hour Replicate and Duplicates, ppbv 7-10
7-3 Compound Identification Confirmation 7-17
7-4 Three-hour Toxics External Audit Results 7-18
8-1 1993 NMOC Plainfield, New Jersey Carbonyl Results 8-2
8-2 1993 NMOC Newark, New Jersey Carbonyl Results 8-4
8-3 1993 NMOC Plainfield, New Jersey Site Summary 8-6
8-4 1993 NMOC Newark, New Jersey Site Summary 8-7
8-5 Detection Limits for Target Carbonyl Compounds 8-12
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List of Tables, continued
Page
8-6 1993 NMOC Carbonyl Calibration Curve Summary ............ 8-13
8-7 1993 NMOC Daily Quality Control Standards Recoveries ........ 8-14
8-8 1993 NMOC Plainfield, New Jersey Sampling Precision Statistics . . 8-18
8-9 1993 NMOC Newark, New Jersey Sampling Precision Statistics ... 8-19
8-10 1993 NMOC Plainfield, New Jersey Analytical Precision Statistics . 8-20
8-11 1993 NMOC Newark New Jersey Analytical Precision Statistics . . . 8-23
8-12 1993 NMOC Daily Quality Control Standards Statistics ......... 8-26
9-1 1993 SNMOC Target Compound List ....................... 9-2
9-2 Samples Collected and Analyzed for 1993 SNMOC Program Sites . . 9-5
9-3 Samples Collected and Analyzed for 1993 SNMOC Option Sites ... 9-6
9-4 1993 Summary Statistics for Birmingham, AL (B1AL) ........... 9-7
9-5 1993 Summary Statistics for Birmingham, AL (B2AL) .......... 9-10
9-6 1993 Summary Statistics for Birmingham, AL (B3AL) .......... 9-13
9-7 1993 Summary Statistics for Beaumont, Texas (BMTX) ......... 9-16
9-8 1993 Summary Statistics for Dallas, Texas (DLTX) ............ 9-19
9-9 1993 Summary Statistics for El Paso, Texas (EPTX) ............ 9-22
9-10 1993 Summary Statistics for Fort Worth, Texas (FWTX) ........ 9-25
9-11 1993 Summary Statistics for Juarez, Mexico (JUMX) ........... 9-28
9-12 1993 Summary Statistics for Long Island, New York (NINY) ..... 9-31
9-13 1993 Summary Statistics for Newark, New Jersey (NWNJ) ....... 9-34
9-14 1993 Summary Statistics for Bristol, Pennsylvania (P1PA) ........ 9-37
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List of Tables, continued
9-15 1993 Summary Statistics for Harrisburg, Pennsylvania (P2PA) .... 9-40
9-16 1993 Summary Statistics for Plainfield, New Jersey (PLNJ) 9-43
9-17 1993 Summary Statistics for All Program Sites 9-47
9-18 1993 Summary Statistics for the Option Sites 9-50
10-1 1993 SNMOC GC/FID Operating Conditions 10-3
11-1 Summary of Monthly Benzene and Propane Calibration Curves ... 11-3
11-2 1993 Duplicate Statistics for All Program Sites 11-6
11-3 1993 Duplicate Statistics for the Option Sites 11-9
11-4 1993 Replicate Statistics for All Program Sites 11-12
11-5 1993 Replicate Statistics for the Option Sites 11-15
11-6 Speciated NMOC External Audit Results for Audit Sample 1862 . . 11-19
11-7 Speciated NMOC External Audit Results for Audit Sample 1865 . . 11-20
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List of Figures
Page
1-1 In-house Quality Control Results, Channel C 1-8
1-2 In-house Quality Control Results, Channel D 1-8
3-1 Style A Sampling System for Collecting 3-hour Integrated Ambient
Air Samples 3-2
3-2 Style B Sampling System for Collecting 3-hour Integrated Ambient
Air Samples 3-2
3-3 NMOC Sampling Field Data Form 3-7
3-4 NMOC Invalid Sample Form 3-10
3-5 NMOC Analytical Equipment 3-12
3-6 Canister Cleanup Apparatus 3-14
4-1 NMOC Performance Results, Channel A 4-5
4-2 NMOC Performance Results, Channel B 4-6
4-3 NMOC Performance Results, Channel C 4-7
4-4 NMOC Performance Results, Channel D 4-8
4-5 Daily Calibration Zero, Channel A 4-9
4-6 Daily Calibration Zero, Channel B 4-9
4-7 Daily Calibration Zero, Channel C 4-10
4-8 Daily Calibration Zero, Channel D 4-10
4-9 Daily Calibration Span, Channel A 4-11
4-10 Daily Calibration Span, Channel B 4-11
4-11 Daily Calibration Span, Channel C 4-12
4-12 Daily Calibration Span, Channel D 4-12
JBS441
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List of Figures, continued
Page
4-13 Daily Calibration Percent Drift, Channel A 4-13
4-14 Daily Calibration Percent Drift, Channel B 4-13
4-15 Daily Calibration Percent Drift, Channel C 4-14
4-16 Daily Calibration Percent Drift, Channel D 4-14
4-17 In-house Quality Control Results, Channel C 4-18
4-18 In-house Quality Control Results, Channel D 4-18
5-1 Stem-and-leaf Plot of the 1993 NMOC Data 5-2
5-2 Stem-and-leaf of the Ln(NMOC) Data 5-4
5-3 Cumulative Frequency Distribution for the 1993 NMOC Data 5-5
5-4 Cumulative Frequency Distribution for the 1993 Ln(NMOC) Data . . 5-6
7-1 Typical Gas Chromatograph/Multiple Detector System 7-2
8-1 3-Hour Carbonyl Sampling Subsystem 8-8
8-2 Carbonyl Field Data and Custody Sheet 8-16
10-1 Hydrocarbon Analysis System 10-4
10-2 Radian Sample Interface in Sample Load Mode 10-5
10-3 Radian Sample Interface in Sample Inject Mode 10-6
10-4 Automated Sample Analysis System 10-7
JBS441
XI
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1.0 BACKGROUND AND SUMMARY
In certain areas of the country where the National Ambient Air Quality Standard
(NAAQS) for ozone is being exceeded, additional measurements of ambient nonmethane
organic compounds (NMOC) are needed to assist the affected states in developing
revised ozone control strategies. Because of previous difficulty in obtaining accurate
^
NMOC measurements, the United States Environmental Protection Agency (EPA) has
provided monitoring and analytical assistance to these states through Radian
Corporation. This assistance began in 1984 and continues through the 1993 NMOC
monitoring program.
Between 7 June and 30 September 1993, Radian analyzed 1027 ambient air
samples collected in SUMMA* polished stainless steel canisters at 13 different sites.
The primary analysis for each sample was either for total NMOC or speciated NMOC
(SNMOC).
The NMOC analyses were performed in accordance with the cryogenic preconcen-
tration, direct flame ionization detection (PDFID) methodology described in
compendium Method TO-12.1 Based on the 1984 through 1992 studies2'3'4-5'6'7'8'9'10'11, the
method was shown to be precise, accurate, and cost effective relative to the capillary
column gas chromatographic, flame ionization detection (GC/FID) methodology. The
1993 study continued to confirmed these findings and supported the conclusion that the
PDFID method is the method of choice to measure total NMOC concentration in
ambient air.
In 1987, a gas chromatographic multiple detector (GC/MD) method to determine
the concentration of 38 selected toxic organic compounds in ambient air was developed
and evaluated for use on EPA's national ambient air toxics programs. In 1993, air toxic
analyses were performed in addition to the NMOC or SNMOC determinations at 7 of
the 14 sites. Air toxics monitoring was also a component of the 1987 through the 1992
programs.
JBS441
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Beginning with the 1989 monitoring season, selected carbonyls were measured and
reported. In 1989, 3-hour samples were collected and analyzed for selected carbonyls -
formaldehyde, acetaldehyde, and acetone. In the 1990 monitoring season, ozone
scrubbers were added to the sampling assemblies to scavenge any ozone present in the
ambient air sampled, prior to its being drawn through the 2,4-dinitrophenylhydrazine
(DNPH) cartridges. In the 1993 monitoring season, Radian Corporation prepared the
DNPH cartridges, supervised the ambient air sampling, and performed the analyses.
During the 1993 program, ten 3-hour carbonyl samples were collected from 6:00 a.m. to
9:00 a.m. at two sites and analyzed for 14 carbonyls -- formaldehyde, acetaldehyde,
acrolein, acetone, propionaldehyde, crotonaldehyde, butyr/isobutyraldehyde,
benzaldehyde, isovaleraldehyde, valeraldehyde, tolualdehyde, hexanaldehyde, and
2,5-dimethylbenzaldehyde.
Beginning in 1991 and continuing through 1993, SNMOC concentrations were
measured at several sites. Seventy-eight hydrocarbons are speciated and quantitated in
this analysis. Each sample is cryogenically preconcentrated then transferred through two
gas chromatographic columns to separate flame ionization detectors (FIDs). One
column separates the Q and C3 hydrocarbons (ethane, ethene, acetylene, propylene and
oropane). The c ar coin separates ^e remaining 73 target hydrocarbon:
Chlorinated and genau jecies in ... ambient air are not identified in the SNMOC
procedure.
The final report for the 1993 NMOC monitoring program is included in Sections 1
through 13 of this report. Sections 2 through 5 report the data, procedures, and
assessment of the NMOC portion of the monitoring program. Sections 6 and 7 report
the data, procedures, and assessment of the 3-hour air toxics portion of the monitoring
program. Section 8 reports the 3-hour carbonyl portion of the monitoring program.
Sections 9 through 11 report the SNMOC portion of the monitoring program. Section 12
lists recommendations and Section 13 lists references.
JBS441
1-2
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The sampling sites for the 1993 NMOC monitoring program are listed in
Appendix A, Appendix A also gives the EPA Regions for each site, the Radian site
code, the Aerometric Information Retrieval System (AIRS) site code and site
information, and indicates the base program (NMOC or SNMOC) it participated in,
whether or not 3-hour air toxics analyses or SNMOC analyses were performed on
selected ambient ai "amples from the site and whether or not carbonyl samples were
collected and anal}
Appendix B contains the detailed procedures on the PDFID method. Appendix C
lists the 1993. NMOC analytical results. Appendix D lists the 1993 NMOC and SNMOC
invalid and missing samples information. Appendix E gives PDFID integrator
programming instructions. Appendix F gives 1993 NMOC daily calibration data.
Appendix G gives 1993 NMOC .in-house quality control samples, and Appendix H gives
multiple detector speciated 3-hour site data summaries. Appendix I.contains the external
audit results for the NMOC, 3-hour toxics, and SNMOC programs. The SNMOC
analytical method is described in Appendix J. Appendix K lists the 1993 SNMOC
analytical results and can be obtained from Neil Berg, U.S. EPA.
1.1 NMOC Monitoring Program
1.1.1 Introduction and Data Summary
Detailed information on the 1993 program and the sampling schedule is given in
the 1993 NMOC quality assurance project plan (QAPP).2 For the five sites in the 1993
NMOC monitoring program, sampling occurred from 6:00 a.m. to 9:00 a.m. local time,
Monday through Friday, from 7 June through 30 September 1993. Site codes for the
1993 NMOC monitoring program are listed in Appendix A. Table 1-1 gives details of
the sample completeness results. Completeness, which ratios the number of valid
samples to the number of scheduled samples, averaged 94.5% in 1993 compared to
90.7% in 1992, 94.1% in 1991, 95.8% in 1990, 95.5% in 1989, 93.4% in 1988, 95.0% in
1987, 96.8% in 1986, 95.8% in 1985, and 90.6% in 1984. Percent completeness for 1993
JBS441
1-3
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Table 1-1
1993 NMOC Completeness Results
Site Location
Long Island, NY
Newark, NJ
Plainfield, NJ
Bristol, PA
Harrisburg, PA
,MV- S
ftrifeir$fe
Ctafe
LINY
NWNJ
PLNJ
P1PA
P2PA
Overall
jtattttlbur dfcyft .
82
82
81
42
42
329
1W*I S^wufnVxi
SAmpkx :
8
8
8
4
4
32
Total Scheduled
' -iAttfeipe* ; •
90
90
89
46
46
361
Total V«fid
:- &kn^bt
9
8
7
2
2
28
Mw,
89
90
80
39
43
341
<
PCtQCIII
.: -Ott»plete:,:::,
98.89
100.0
89.89
84.78
93.48
94.46
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ranged from 84.8 at Bristol, PA (P1PA), to 100.0 for Newark, NJ (NWNJ). Statistics for
the NMOC concentrations in parts per million carbon (ppmC) by volume are listed in
Table 1-2. This table also includes all duplicate sample concentration statistics.
1.12 Calibration
Each PDFIT ;alysis channel was calibrated using propane standards referenced
to the propane Nas jal Institute of Science and Technology (NIST) Certified Reference
Material (CRM) No. 1666B. Daily, before instrument zero and calibration checks were
performed, the analytical systems were purged with cleaned, dried air that had been
humidified. Zero readings were determined with cleaned, dried air. Daily percent drift
of the calibration factor ranged from -9.6% to +3.3 percent. The absolute value of the
percent drift of the daily calibration factors ranged from 0.0 to + 9.6 percent.
1.13 NMOC Precision
Analytical precision was determined by repeated analyses of 24 site samples.
Percent differences between the second and the first analysis averaged -9.76 percent.
The average of the absolute values of the percent difference was 22.54% with a standard
deviation of 26.9 ppmC. The analytical precision includes the variability between Radian
analytical measurement channels and within Radian analytical measurement channels.
The data quality objective for the percent difference as published in the QAPP2 was
± 15%, based on previous NMOC program experience3'415'6'7'8'9'10'11 with this measurement.
Overall precision, including sampling and analysis variability, was determined by
analysis of 28 site sample pairs, simultaneously collected in two canisters from a common
sampling system (a total of 56 canister samples). Percent difference for Radian's
analyses of the duplicates averaged +0.479 percent. The average absolute percent
difference was 12.6% with a standard deviation of 11.4 ppmC. The data quality
objectives for this measurement was ±20%, based on previous experience.3'4-5'6'7'8'9'10'11
JBS441
1-5
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Table 1-2
NMOC Overall Statistics, By Site
f
Ste
LINY
NWMJ
PLNJ
P1PA
P2PA
Overall
QM>
80
82
73
37
41
313
***««,
0.060
0.090
0.069
0.085
0.059
0.059
-:;.;
«^-
0.9%
1.446
1.754
5.749
4.076
5.749
t;..:y:;^
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1.1.4 Accuracy
Because the NMOC measurements encompass a range of mixtures of organic
compounds whose individual concentrations are unknown, it was not possible to define
absolute accuracy. Instead, accuracy was determined relative to propane standards with
internal and external r. :dit samples.
Accuracy was monitored internally throughout the program by the use of in-house
propane standards. Periodically, an in-house propane quality control (QC) sample was
prepared with a flow dilution apparatus and analyzed by the PDFID method. The
propane used to prepare the in-house QC standards was referenced to propane NIST
CRM, No. 1666B.
Figures 1-1 and 1-2 show the in-house QC results for Radian Channels C and D.
Measured propane values are plotted against calculated propane standard concentration
values. Table 1-3 shows the linear regression parameters for the Radian in-house QC
data. The regression used the propane concentration calculated from the blending
operation as the independent variable and concentration determined by each Radian
analytical measurement channel as the dependent variable. The concentration range of
the in-house quality control samples was 0.800 to 1.326 ppmC. Table 1-3 indicates
excellent QC for each channel. As expected, the intercepts are all near zero, and the
slopes and coefficients of correlation are all near 1.0.
External propane audit samples were provided by the EPA through their quality
assurance (QA) contractor. The propane samples were referenced to propane NIST
CRM 1667B or 1665B. The audit samples were given Radian ID Numbers upon receipt.
The average percent bias for the Radian channels was +4.1%, ranging from +1.8 to
+ 8.5 percent. Table 1-4 shows the external audit results.
JBS441
1-7
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In-house Propane QC Results
Channel C
1.40-
1.30-
1.20-
o
Q.
Q.
I
re
•E 1-10-1
0)
u
<§ i.«H
8 J
2 0.90-
Z
3 0.80-
t/9
re
0.70-
0.60
0.70 0.80 0.90 1.00 1.10 1.20
Calculated NMOC Concentration, ppmC
1.30
1.40
Figure 1-1. In-house Quality Control Results, Channel C
1.40-
0 1.3
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Table 1-3
Linear Regression Parameters for In-House Quality Control Data
Radian
Cfeanne?
C
D
"^••:olw:^
19
19
;;S;3:f-i'\.
'..i;-;.C;«wSitW^t:-; . H
-0.014
-0.051
Ki^;'^
0.958
0.989
Coeffident
0.980
0.984
aDue to the limited number of data for Channels A and B, regressions were not possible.
JBS441
1-9
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Table 1-4
NMOC External Audit Sample Results
ID
Number
1863
1864
ineixetical
1.12
0.66
Ctfficentrai^n. i»m<
*****"*''' _T*^* iV1^
3-' - ::"r.\-:
' Analysis * * . '.'\'-' ';':
Radian A
1.180
0.685
Radian B
1.140
0.716
Radian C
1.160
0.690
Radian D
1.160
0.673
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1-10
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1.1.5 Other Quality Assurance Measurements
Canister cleanup results showed that there was little carryover of NMOC from one
sample to the next, using the canister cleanup apparatus and procedure developed for
this study. In over 150 separate determinations, percent cleanup averaged 98.76 percent.
Cleanliness was defined in terms of the percent of the NMOC concentration that was
removed from each canister considered during the cleanup procedure.
Ten percent of the NMOC data base was validated by checking data transcriptions
from original data sheets to the computerized data for 36 entries per sample. The errors
found equal a data base error rate of 0.007 percent. All identified errors were corrected.
1.2 Three-Hour Air Toxics Monitoring Program
At seven sites, (NWNJ, PLNJ, B1AL, B2AL, B3AL, P1PA, and P2PA) 3-hour
NMOC samples were analyzed by a GC/MD analytical system for 38 air toxic target
compounds. After NMOC or SNMOC analysis, the sample canisters were bled to
atmospheric pressure, allowed to equilibrate for at least 18 hours, and then analyzed by
GC/MD. Duplicate samples were collected at the sites and analyzed individually by
GC/MD. Replicate analyses were performed on one duplicate sample per site. A total
of 70 GC/MD analyses were performed, including the analysis of duplicate samples and
the replicate analyses. These data summaries are presented in Appendix H.
12.1 Overall Data Summary
Twenty-two target compounds were identified in the 70 analyses. Chloroform,
1,1,1-trichloroethane, benzene, carbon tetrachloride, toluene, tetrachloroethylene, and
m/p-xylene/bromoform were identified in every sample. Concentrations of the target
compounds identified ranged from 0.01 parts per billion by volume (ppbv) for
tetrachloroethylene to 15.18 ppbv for toluene. The overall average concentration of the
target compounds identified was 0.67 ppbv, averaged over all sites and target compounds.
JBS441
1-11
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The air toxics data are tabulated in Section 7. Results presented include numbers of
cases identified, minima, maxima, and means for all target compounds.
122 Individual Site Results
Overall site total concentrations for the target compounds averaged 8.45 ppbv for
DIAL, 2.99 ppbv for B2AL> 3.89 ppbv for B3AL, 15.88 ppbv for NWNJ, 10.92 ppbv for
P1PA, 7.39 ppbv for P2PA, and 14.50 ppbv for PLNJ. The air toxic data are presented
in Section 7.
123 Gas Chromatography/Mass Spectrometry (GC/MS) Confirmation Results
Confirmation of compounds identified was based on seven GC/MS analyses of the
3-hour air toxics samples, one from each site location. The GC/MS analyses confirmed
93.19% of the GC/MD identifications. The results are summarized in Table 1-5.
Comparisons labeled "negative GC/MD-positive GC/MS" refer to specific samples in
which a compound was not identified by GC/MD but positively identified by GC/MS
analysis. Comparisons labeled "positive GC/MD-negative GC/MS" indicate specific
samples in which a compound was positively identified by GC/MD but not identified by
GC/MS analysis. Because GC/MD is more sensitive than GC/MS, this last comparison
is of limited value. There were 47 cases where the GC/MD identified a compound at a
concentration below the detection limit of the GC/MS.
1.2.4 Precision
Sampling and analytical precision of 3-hour air toxics samples was estimated by
analyzing duplicate samples. In terms of overall average absolute percent difference, the
sampling and analysis precision was 19.21 percent.
JBS441
1-12
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Table 1-5
Compound Identification Confirmation
GC/MD versa* GC/MS Comparison*
Positive GC/MD - Positive GC/MS
Positive GC/MD - Negative GC/MS
Negative GC/MD - Positive GC/MS
Negative GC/MD - Negative GC/MS
Total
-'' '"'" -':Ciase*-: ".-• ..-
26
7
6
152
191
Percentage
13.61
3.67
3.14
79.58
100.00
Note: Total compound identification confirmation = 13.61% + 79.58% = 93.19%
"There were 47 cases where the GC/MD identified a compound at a concentration
below the detection limit of the GC/MS.
JBS441
1-13
-------
Analytical precision was estimated based on the results of one repeated analysis
from one of the duplicate sample canisters from each site. The analytical precision
measured by the overall average absolute percent difference was 20.80 percent. Both the
sampling and analytical precision results are excellent in view of the low concentration
range found in this study.
Both the duplicate sample and repeated analyses results are discussed in
Section 7.6.
1.2.5 External Audit
In the past years, the external audit for the 3-hour air toxics compounds was
conducted in conjunction with the Urban Air Toxics Program (UATMP). Because the
UATMP was not being conducted by Radian during the 1993 NMOC program, an
external audit sample from the SNMOC program was used as the external sample for the
3-hour air toxics program.
The external audit sample contained 27 compounds, three of which were target
compounds for the 3-hour air toxic analyses. For these three compounds, percent
differences range from -59.1% (for ethylbenzene) to +46.7% (for o-xylene/
1,1,2,2-tetrachloroethane) with an average of -4.9 percent.
13 Carbonvl
Carbonyl samples were collected at two sites (NWNJ and PLNJ), for the 1993
monitoring season. Three-hour samples were taken from 6:00 a.m. to 9:00 a.m., local
time, simultaneously with the NMOC canister samples at the two sites. Samples were
collected in duplicate from July through September 1993. The carbonyl sampler has its
own inlet manifold, capillary, critical orifice and separate Metal-Bellows* pump. The
inlet manifold leads into an ozone scrubber and then splits into duplicate DNPH-coated
parallel cartridges.
JBS441
1-14
-------
Carbonyl concentrations ranged from 0.04 ppbv for butyr/isobutyraJdehyde at
NWNJ to 42.02 ppbv for formaldehyde at PLNJ. Of the 16 targeted carbonyl analytes,
2,5-dimethylbenzaldehyde, isovaleraldehyde, and tolualdehyde were not detected in any
of the samples.
1.4 SNMOC
1.4.1 Introduction and Data Summary
Eight sites participated in the 1993 SNMOC monitoring program. Samples were
collected from 6:00 a.m. to 9:00 a.m. local time, Monday through Friday from 7 June
through 30 September 1993. Five sites that participated in the NMOC monitoring
program also had SNMOC analysis performed on ten randomly selected samples. Site
codes are listed in Appendix A. Tables 1-6 and 1-7 give the details of the sample
completeness results for the program and option sites, respectively. Table 1-8 lists the 78
target compounds for the SNMOC program.
1.4.2 Calibration
Certified standards from Scott* Speciality Gases were used to prepare analytical
calibration standards. Gas-tight syringes were used to inject aliquots of the certified
standard into cleaned, evacuated SUMMA® canisters. The canisters were then filled to
ambient pressure with cleaned, humidified air using a standards preparation flow dilution
system. The canisters were then pressurized with nitrogen to approximately 25 psig using
a precision canister dilution system.
The analytical systems were calibrated monthly by analyzing three hydrocarbon
standards and a system blank of cleaned, humidified air. The calibration was considered
valid if the coefficient of correlation of the four points was at least 0.995. A least
squares linear regression calculation was performed for the data from each detector.
The resulting slopes were used as the benzene response factor for the primary
JBS441
1-15
-------
Table 1-6
Samples Analyzed for 1993 SNMOC Program Sites
.-'. "v :-' v
.'. \ . .'t ,.• ' •:
jSfce&S
B1AL
B2AL
B3AL
BMTX
DLTX
EPTX
FWTX
JUMX
Total
Total
DoDlicate
Samples
16
14
16
18
16
16
16
14
126
Total
Reoikate
Analyses
8
8
12
10
8
8
8
8
70
Total
$>*wfe
*?»•£,»? .
Samples
74
76
58
69
74
71
72
66
560
Total
Valid
Events
82
83
66
78
82
79
80
73
623
Total
Valid
* Samples
90
90
74
87
90
87
88
80
686
Total
• Analyses
Reported
98
98
86
97
98
95
96
88
756
Table 1-7
Samples Analyzed for 1993 SNMOC Option Sites
'• ' "-'Site ; .
LINY
NWNJ
PLNJ
P1PA
P2PA
Total
Total >
-------
Table 1-8
1993 SNMOC Target Compounds
tl >
Compou&d
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl- 1-pentene
Cyclopentane
2,3-Dimethylbutane
2-Methylpentane
,--';:CASV-,; ,.
• Number
74-86-1
74-86-2
74-84-0
77-99-7
75-28-5
106-98-9
115-11-7
115-07-1
106-99-0
106-97-8
74-98-6
624-64-6
590-18-1
563-45-1
78-78-4
109-67-1
563-46-2
109-66-0
78-79-5
646-04-8
627-20-3
513-35-9
75-83-2
142-29-0
691-37-2
287-92-3
79-29-8
107-83-5
AIRS Parameter
Code
43203
43206
43202
43144
43214
43280
43270
43205
43218
43212
43204
43216
43217
43282
43221
43224
43225
43220
43243
43226
43227
43228
43244
43283
43234
43242
43284
43285
JBS441
1-17
-------
Table 1-8, continued
: . j
Compound
f •
3-Methylpentane
2-Methyl- 1-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
2,3-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,2,3-Trimethylpentane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
p-Xylene + m-Xylene
Styrene
CAS
Piunibcr ;
96-14-0
763-29-1
592-41-6
760-21-4
110-54-3
4050-47-7
7688-21-3
96-37-7
108-08-7
71-43-2
110-82-7
565-59-3
591-76-4
589-34-4
540-84-1
142-82-5
108-87-2
592-76-7
564-02-3
565-75-3
108-88-3
592-27-8
589-81-1
111-66-0
111-65-9
100-41-4
NA
100-42-5
AIRSParametex
Code
43230
43246
43245
43236
43231
43289
43290
43262
43247
45201
43248
43291
43263
43249
43250
43232
43261
43328
43292
43252
45202
43960
43253
43145
43233
45203
45109
45220
JBS441
1-18
-------
Table 1-8, continued
Compound :
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
a-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
1,3,5-Trimethylbenzene
o-Ethyltoluene
b-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,2,3-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
" .; CAS -. -;-|
i Number -•';
95-47-6
124-11-8
111-84-2
98-82-8
7785-70-8
103-65-1
620-14-4
622-96-8
108-67-8
611-14-3
127-91-3
872-05-9
95-63-6
124-18-5
526-73-8
105-05-5
821-95-4
1120-21-4
112-41-4
112-40-3
2437-56-1
629-59-5
AIRS Parameter
Code
45204
43279
43235
45210
43256
45209
45212
45228
45207
45211
43257
43298
45208
43238
45225
45219
45299
43241
43330
43141
43142
43143
JBS441
1-19
-------
column/detector and the propane response factor for the secondary column/detector.
Table 1-9 summarizes the monthly calibration information.
Prior to sample analysis, a QC standard was analyzed to ensure the validity of the
current monthly response factors. Benzene and propane concentration biases of no more
than 30% were considered acceptable. For the 1993 SNMOC program, the 30% criteria
was met on the first standard analysis for every sample analysis day.
Following the analysis of the QC standard, a sample of cleaned humidified air was
analyzed to assess the presence of any potential contamination.
1.43 SNMOC Precision
Analytical precision was determined by the repeated analysis of 70 samples.
These samples were a single canister of a duplicate collection. For those concentrations
above the detection limit, the average concentration ranged from 0.65 ppbC (for
1-tridecene) to 30.10 ppbC (for propane).
Overall precision, including sampling and analysis variability, was determined by
analysis of 62 duplicate site sample pairs, simultaneously collected in two canisters from
a common sampling system (a total of 124 canister samples). Average concentrations
ranged from 0.78 ppbC for c-2-hexane and 1-heptene to 28.84 ppbC for isopentane.
1.4.4 Accuracy
Two external audit samples were provided by the EPA through their QA
contractor. Percent bias ranged from -20.4% to +16.1%, averaging -7.6 percent.
JBS441 1-20
-------
Table 1-9
Summary of Monthly Benzene and Propane Calibration Curves
Calibration
Date
(^amA
Correlation
Coeffeoeni
Benzene
Response
- ^jFMKifafi £p
'xiXHrrCw&iosi
CoeSecient
Propane
Response
Factor
t AC/nl-O
Manual Interface System
05/18/93
06/21/93
07/21/93
08/23/93
09/23/93
1.0000
1.0000
1.0000
0.9995
1.0000
2169.0
2234.8
2324.2
2263.3
2104.5
1.0000
1.0000
1.0000
0.9995
0.9998
1582.9
1644.9
1691.2
1616.1
1625.2
Automated Interface System
06/03/93
07/02/93
08/02/93
09/02/93
10/04/93
1.0000
1.0000
1.0000
1.0000
1.0000
1624.6
1507.7
1613.8
1557.0
1575.8
1.0000
0.9998
1.0000
1.0000
0.9999
1623.8
1395.4
1548.3
1473.0
1600.6
JBS441
1-21
-------
2.0 NMOC DATA SUMMARY
The data summary for the 1993 NMOC monitoring program conducted during
June, July, August, and September is presented in this section. Daily NMOC
concentrations and other pertinent monitoring data are given by site in Appendix C.
The data presented in this section summarize the NMOC concentrations measured for
samples collected at five sites throughout the continental United States. Sites were
selected in urban and/or industrial locations and they are described in Appendix A along
with the site codes used throughout the report to ideratify the sites. Samples were
collected in 6-liter (L) stainless steel canisters by locall site operators trained on-site by
Radian Corporation personnel. The sampling procedure was described in detailed
written instructions and provided to the site operators. The sampling procedure
instructions appear in Section 3.1.2. Analytkal measurements of the samples collected
were made in the Radian Corporation Research Triage Park (RTF) laboratory
according to the PDFID Method TO-121. The complete PDFID methodology is
presented in Appendix B.
The concentration of oxides of nitrogen (NOJ,. site temperature, barometric
pressure, wind direction, and weather conditions were provided on the field sampling
forms by site personnel at the time of sampling. These data were recorded in the
1993 NMOC data base, but are not presented in this steport because they were not
measured by Radian equipment or personnel, nor were the data subjected to project QA
procedures.
Table 2-1 lists the NMOC monitoring program completeness results by site code.
The scheduling of sample days and the scheduling of duplicate analyses is given in the
QAPP2. For the 1993 NMOC sites, completeness was 94.5 percent. A complete listing
of invalid samples and the reasons for the invalidation, are given in Appendix D.
JBS441
-------
Table 2-1
1993 NMOC Completeness Results
Site Xocatktt '
Long Island, NY
Newark, NJ
Plainf.eld, NJ
Bristol, PA
Harrisburg, PA
. -^g-^,
''.$&&&&*•
LINY
NWNJ
PLNJ
P1PA
P2PA
Overall
Scheduled
f^ ^& , y •
82
82
81
42
42
329
Total Scheduled
Duplicate
Sample* ;
8
8
8
4
4
32
Total Scheduled
Canister
Analyses
90
90
89
46
46
361
Total Valid
Duptoate
Samples ":
9
8
7
2
2
28
ToUlVafid
89
90
80
39
43
341
Percent v
Cboipfete
98.89
100.0
89.89
84.78
93.48
94.46
to
-------
Completeness was defined as the percentage of samples, scheduled in the QAPP2,
that were collected and analyzed as valid samples, beginning with the first valid sample
and ending with the last scheduled sample.
Overall completeness figures for the 1993 NMOC program was 94.5 percent. This
compares with 90.7% in 1992, 94.1% in 1991, 95.8% in 1990, 95.5% in 1989, 93.4% in
1988, 95.0% in 1987, 96.8% in 1986, 95.8% in 1985 and 90.6% in 1984.3'4-5'6'7-8'9-10'11
Table 2-2 summarizes overall statistics by site. All sites collected an integrated
sample from 6:00 a.m. to 9:00 a.m., local time. The overall average of the NMOC
concentration is 0.404 ppmC.
In Table 2-2, the means presented are the arithmetic averages of the NMOC
concentrations at each site. The numbers given for standard deviation, skewness, and
kurtosis are the second, third, and fourth moments, respectively, about the arithmetic
means. A skewness value greater than zero applies to distributions having a longer tail
to the right. A distribution that is normally distributed would have a kurtosis of 3.0. A
distribution more peaked (or pointed) than a normal distribution, having the same
variance, would have a kurtosis greater than 3.0. All the kurtosis figures listed in this
report are zero centered, which means that 3.0 has been subtracted from the fourth
moment to give a reported kurtosis of 0.0 for a symmetrical distribution. The Shapiro-
Wilk statistic (W) tests the normality of the data and ranges from zero to one. The
closer the statistic is to one, the better the fit of the data to normality. Table 2-3
summarizes the 1993 NMOC data using the definitions that characterize a lognormal
distribution overall and for each site. MU and SIGMA are the mean and standard
deviation, respectively, of the logarithm of NMOC to the Napierian base e. The
geometric mean is e raised to the power MU; the geometric standard deviation is e
raised to the power SIGMA. The mode is the most frequently occurring NMOC value
for a continuous probability distribution function.
JBS441
-------
Table 2-2
NMOC Overall Statistics, by Site
.;,<;)'•. "* '• -. . , ,-
£:$W^
LINY
NWNJ
P1PA
P2PA
PLNJ
OVERALL
\ Ca$e$ ....
80
82
37
41
73
313
Concentration, ppmC
Mitt
0.060
0.090
0.085
0.059
0.069
0.059
'••• Mat*
0.996
1.446
5.749
4.076
1.754
5.749
Mediant
0.225
0.368
0.285
0.259
0.368
0.298
• Meatt
0.283
0.402
0.547
0.445
0.442
0.404
Std Dcv
0.180
0.199
0.923
0.649
0.301
0.445
Skewoess
1.942
1.953
5.249
4.685
1.556
7.644
Kurtosis
4.280
8.138
29.935
25.408
3.949
80.607
4. ^ . ^ .• , •
1W*
0.806
. 0.887
0.409
0.486
0.884
0.511
NJ
"Shapiro-Wilk statistic to test normality of data.
-------
Comparing W for a site in Tables 2-2 and 2-3 shows that the logarithmic
transformation of the NMOC concentrations more nearly approximates the normal
distribution. NMOC monitoring data can, therefore, be better characterized by a
lognormal distribution than by a normal distribution, considering the findings of this and
previous NMOC programs.3'4-5'6'7-8-9'10'11
Appendix C gives the daily NMOC concentration data listed chronologically for
the entire sampling season. In addition, figures are given for each site for which NMOC
concentrations in ppmC are plotted versus the 1993 Julian date when the sample was
taken. Data tables for each site include the following:
• Calendar date sampled;
• Julian date samples;
• Sample ID number, assigned consecutively upon receipt of the sample;
• Sample canister number;
• Radian analytical measurement channel; and
• NMOC concentration in ppmC.
Appendix D lists invalidated or missing samples. Table D-l lists these data
chronologically for the sites participating in the NMOC program, while Table D-2 lists
these data for the sites participating in the SNMOC program. For each sample, the
tables list the site code, the date of the missing or invalid sample, a brief description of
the possible cause of the invalid or missing sample, and the assigned cause for the
failure.
JBS441 2-5
-------
Table 2-3
1993 LNMOC* Overall Statistics, by Site
w';jsti*"^-
LINY
NWNJ
P1PA
P2PA
PLNJ
OVERALL
Ca«S 7
80
82
37
41
73
313
Concentration, ppmC
a^Mta
0.060
0.090
0.085
0.059
0.069
0.059
Max
0.996
1.446
5.749
4.076
1.754
5.749
Median
0.225
0.368
0.285
0.259
0.368
0.298
Mean"
0.281
0.404
0.483
0.406
0.451
0.390
Mode
0.198
0.253
0.085
0.188
0.188
0.188
Concentration, ln(ppmC)
Mil*!
-1.42
-1.02
-1.06
-1.23
-1.04
-1.16
Sigma*
0.552
0.477
0.816
0.810
0.698
0.661
vr
0.971
0.990
0.939
0.946
0.976
0.981
•LNMOC = In(NMOC), when NMOC is in ppmC.
bMean = exp (Mu + Sigma2/2).
cMu is the mean of In(NMOC). eMU is the geometric mean.
dSigma is the standard deviation of In(NMOC). eSIGMA is called the geometric standard
deviation.
'Shapiro-Wilk statistic to test normality of data.
-------
3.0 NMOC TECHNICAL NOTES
This section summarizes descriptions of the installation and operation of the field
sampling equipment, a summary of the analytical equipment and procedures for NMOC
measurement, and a description of the canister cleanup equipment and procedures.
3.1 NMOC Field .Sampling F/piipment
Two types (A and B) of field sampling equipment were used to collect ambient air
samples for NMOC measurement. In Type A, ambient air is drawn through a sintered
stainless steel filter (2 micron) and critical orifice by a Metal Bellows* pump and
delivered to a SUMMA® canister. In Type B, the ambient air is drawn through a
sintered stainless steel filter and then through a fine adjust micrometering valve, a glass
rotameter, a pump, and delivered to a SUMMA* canister. Components of both the
samplers are made of stainless steel. Figures 3-1 and 3-2 are schematic diagrams of the
NMOC sampling systems.
3.1.1 Installation
NMOC sampler installation configurations were site dependent. All field sites
were installed by or under the direction of Radian personnel. Installation requirements
included a temperature-controlled environment (70° to 86°F), close proximity to the
atmosphere to be sampled, and noncontaminating sampler connections. Glass tubing or
gas-chromatographic-grade stainless steel tubing and stainless steel fittings are the
preferred materials of construction for all connections contacting the sampk. Typical
sampler installations involved three configurations, including slip stream connection off
of a constant flow glass manifold, a slipstream connection (prior to the air monitoring
station's NOX analyzer) off of a stainless steel manifold with a bypass pump, and separate
but collocated NMOC and NOX sample inlet lines. For sites where the distance between
the sample inlet and the stainless steel probe was greater than 8 feet, an auxiliary
(by-pass) pump, as shown in Figures 3-1 and 3-2, was used. The auxiliary pump ensured
JBS441
3-1
-------
Metd Bellows
PumpMB-151
Auxiliary
Pwnp
CentaterU)
Figure 3-1. Style A Sampling System
for Collecting 3-hour Integrated Ambient Air Samples
In-line
PraMUiWVac
Auxiliary
Pump
Cmbterte)
Figure 3-2. Style B Sampling System
for Collecting 3-hour Integrated Ambient Air Samples
3-2
£
*•
S
-------
that the air in the sample line was representative of the ambient air being sampled by
pulling an excess of sample air in slipstream connection.
The critical orifice in the Style A sampler (Figure 3-1) was sized to maintain a
constant collection flow rate that allowed a 6-L stainless steel canister to be taken from
0.5 mm mercury (Hg) vacuum (initial pressure) to about 15 psig (final pressure) in
3 hours. When duplicate samples were taken, the critical orifice used for single sample
collection was replaced with an orifice sized to accommodate two 6-L canisters during
the 3-hour sampling period.
For the Style B sampling system (Figure 3-2), the adjustable micro-metering valve
was used to set a collection flow rate as indicated on the rotameter that allowed a 6-L
stainless steel canister to be taken from the 0.5 mm Hg initial vacuum to about 15 psig
in 3 hours. For duplicate samples, the indicated flow rate was doubled in order to
accommodate two 6-L canisters during the sampling period. The rotameter settings for
single and duplicate samples were determined in the lab using a bubble flow meter and
were provided to the operators at installation.
3.12 Operation
Presampling - Style A System
The following instructions pertain to the sampling operation prior to collection of
the field sample.
1. Verify timer program (see timer instructions). Set to MANUAL position
to leak check sampling system. Once the system passes the leak check,
turn timer to AUTO position.
2. With no canisters connected to the sampling system, turn the timer switch
to the MANUAL position.
JBS441
3-3
-------
3. Disconnect the sample inlet from the top of the orifice/filter assembly
mounted on the pump inlet. Connect the rotameter to the top of the
orifice/filter assembly. Tighten Swagelok* (1/4") fitting securely with a
wrench. Do not over-tighten.
4. Turn timer switch ON. Do not turn the power off and on rapidly. Wait
20 seconds between cycles to prevent premature timer/solenoid failure.
The pump should run and the latching valve should open. Verify that the
rotameter reading is approximately the same (±15%) as the reading
obtained during installation as recommended on the orifice tag. If the
rotameter reading is not correct, see the troubleshooting instructions.
5. Allow the pump to run for at least 20 seconds, then press the timer OFF
button.
6. Connect a cleaned, evacuated canister to the sampling system. If duplicate
samples are to be collected, remove the plug from the second port of the
tee and connect a second canister to the sampling system. Remove the
orifice assembly marked with an "S," denoting a single orifice. Install the
orifice assembly marked with a "D," denoting a double orifice. Replace the
filter holder on the "D" orifice. After obtaining scheduled duplicate
samples, replace the plug and the "S" orifice assembly to return to single
sample collection status.
7. With the pump off, open completely the valve on the canister (or on one of
the canisters if two are connected) and verify that no flow is registered on
the rotameter. If any flow is detected by the rotameter, immediately close
the canister valve and see the troubleshooting instructions.
8. If no flow is observed, disconnect the rotameter and reconnect the inlet
sample line to the filter assembly. If two canisters are connected,
completely open the valve on the second canister.
9. Reverify that the canister valve(s) is (are) completely open and the timer is
properly set for sampling from 6 a.m. to 9 a.m. the next weekday. Set
timer to AUTO mode.
10. Reset the elapsed time counter.
Presampling - Style B System
The following instructions pertain to the sampling operation prior to collection of
the field sample.
JBS441
3-4
-------
1. Verify timer program (see timer instructions). Set to MANUAL position
to leak check sampling system. Once the system passes the leak check,
turn timer to AUTO position.
2. With no canisters connected to the sampling system, turn the timer switch
to the MANUAL position.
3. Turn timer switch ON. Do not turn the power off and on rapidly. Wait
20 seconds between cycles to prevent premature timer/ solenoid failure.
The pump should run and the latching valve should open (audible click
with 2 to 5 seconds delay). Verify that the rotameter reading is
approximately the same (±15%) as the reading obtained during installation
as recommended in the installation instructions. If the duplicate samples
are to be collected set the rotar j-.er to the du, ucate flow rate. If the
rotameter reading is not correc: _ee the troubleshooting instructions.
5. Allow the pump to run for at least 20 seconds, then press the timer OFF
button.
6. Connect a cleaned, evacuated canister to the sampling system. If duplicate
samples are to be collected, remove the plug from the second port of the
tee and connect a second canister to the sampling system.
7. With the pump off, open completely the valve on the canister (or on one of
the canisters if two are connected) and verify that a 29" vacuum exists.
Close the can and observe the vacuum gauge. If the vacuum begins to
drop see the troubleshooting instructions, a leak probably exists.
8. If two canisters are connected, completely open the valve on the second
canister.
9. Reverify that the canister valve(s) is (are) completely open and the timer is
properly set for sampling from 6 a.m. to 9 a.m. the next weekday. Set
timer to AUTO mode.
10. Reset the elapsed time counter.
Postsampling
The following instructions outline the NMOC postsampling operation procedures
in the field.
JBS441 3-5
-------
1. Close the canister valve(s) firmly.
2. Record the pressure reading(s) on the data sheet(s). Disconnect the
canister(s). If the pressure reading is not at least 11 psig, see the
troubleshooting instructions.
3. Fill in the required information on the NMOC sampling field data form.
PLEASE PRESS HARD AND WRITE WITH A BALLPOINT PEN;
YOU ARE MAKING THREE COPIES, (see Figure 3-3).
4. Verify elapsed time counter reading equals 3 hours.
5. Verify that the timer shows the correct time setting. If not, note that fact
on the sample form along with any information pertaining to the possible
cause. Reset the timer to the correct time, if necessary.
6. Verify that the canister valves are closed firmly. Do not over-tighten them.
Put the protective cap(s) on the valve(s) and prepare the canister(s) for
shipment to the Radian, RTF laboratory.
3.13 Troubleshooting Instructions
A list of troubleshooting instructions was given to each field site during site
installation and operator training. Typical problems encountered with the field sampling
apparatus included: loose fittings, misprogrammed timer, or clogged orifices. To
minimize downtime, field site operators were encouraged to relay sampling problems to
the Radian laboratory daily by telephone. Most sampling problems were addressed
promptly through these telephone discussions.
3.1.4 Sampler Performance for 1993
The NMOC sampler was modified in 1989 to improve performance. This
modification involved replacing the mechanical timer previously used with an electronic
version. The electronic timer improved sample integration. An elapsed time meter was
added to the sampler to verify sample collection duration. This system was used as the
JBS441
3-6
-------
NMOC SAMPLING FIELD DATA FORM
Site Location : City:
Sample Collection Date :
Operator :
Sampling Period :
Elapsed Time :
Final Canister Pressure (psig) :
Sample Canister Number :
Sample Duplicate for this Date : Yesu
If yes. Duplicate Canister Number :
NOx Analyzer Operating? YesC Nou
If yes, Average Reading (ppmv as NOx) :
Average Wind Speed :
Average Wind Direction :
Orifice Number :
Rotameter Indicated Flow Rate :
Average Barometric Pressure (mm Hg or inches Hg) :
Ambient Temperature (°F) : Relative Humidity :
THC Model (if available) : Average THC :
Sky/Weather Conditions :
Site Conditions/Remarks :
Canister Number :
Initial Canister Vacuum
Received By :
Date :
Sample Validity :
If Invalid, Reason :
Figure 3-3. NMOC Sampling Field Data Form
3-7
-------
Style A sampler during the 1993 program. The NMOC sampling system was also
modified for the 1992 season. The Style B system eliminated the use of orifices and
instead used an adjustable micro-metering valve and in-line rotameter.
In addition to the modifications, all samplers and canisters were subjected to a
preseason QC check to ensure field performance. All orifices provided with each
.Style A sampling system were checked against the removable rotameter and referenced
to a primary standard (bubble flowmeter). For the Style B sampler, the in-line
rotameters were also calibrated against a primary standard (bubble flowmeter). Prior to
field installation, each sampler was operated in the laboratory to establish an expected
final sample pressure range. For the Style A samplers, two single orifices and one
double orifice were tested for each sampler kit.
Due to the preseason checks and modifications, the NMOC sampler performance
was improved for the 1993 sampling season. Invalid samples were primarily due to
operator error and equipment malfunctions. Completeness can be improved at all sites
through greater attention to sampling procedure, and by ensuring that trained site
personnel are available. A further improvement in completeness may be possible as site
operators gain familiarity with the electronic timer. Revised sampler operating
instructions will focus additional attention on timer programming and operation, and will
include a daily checklist to eliminate common operator errors.
A total of 63 invalid/missing samples were recorded in the 1993 NMOC
monitoring program (this included 18 samples for NMOC and 45 samples for SNMOC).
Appendix D lists the invalid/missing samples in chronological order, along with the
reason for invalidation. Avoidable operator error accounts for 29% and equipment
problems account for 46% of the invalidated samples. Twenty-four percent were missed
sample collections for unknown reasons. The remaining 1% reflects missed sample
collections due to site inaccessibility.
JBS441
3-8
-------
3.1.5 Field Documentation
The field sample collection information was documented by the site operator on
pre-printed multiple part forms. Figure 3-3 is an example NMOC sampling field data
form. Each canister sent to the field was accompanied by this form. A copy of the field
data form was retained by the site operator for the site notebook. Figure 3-4 is an
example of the invalid sample form. This form was completed by the site operator to
document the reasons for a missed sample or an invalid field sample collection.
32 NMOG Analysis
The NMOC analysis equipment and the analysis procedure are described in detail
in Appendix B. A brief description of the equipment and operating procedure used in
this study follows.
3.2.1 Instrumentation
Two gas chromatographs were used by Radian. Each was a dual-channel
Hewlett-Packard Model 5880 (HP-5880).using flame ionization detection (FID).
NMOC instrument Channels A and B refer to the two FIDs on one HP-5880 unit, and
Channels C and D refer to the two FIDs on the other HP-5880 unit. These
chromatographs were configured for PDFID analysis, consistent with the reference
system (EPA-QAD instrument), described in Appendix B.
322 Hewlett-Packard, Model 5880, Gas Chromatograph Operating Conditions
The sample trap consisted of 30 cm of 1/8-inch outside diameter (o.d.) stainless
steel tubing, packed with 60/80 mesh glass beads.
Three support gases were used for PDFID analysis: helium, hydrogen, and
hydrocarbon-free air.
JBS441
3-9
-------
RADIAN
NMOC INVALID SAMPLE FORM
AIRS
Site Code :
City
Sample Collection Date
Sample Canister Number •
Sample Duplicate for this Date Yes D No D
If Yes. Duplicate Canister Number
Reason for Invalid or Missed Sample :
Average NOx Analyzer Reading for this Collection Date :
Wind Speed : Wind Direction :
Rotameter Indicated Flow Rate
Orifice Number
Average Barometric Pressure (mm Hg or inches Hg):
Ambient Temperature (*F). Relative Humidity :
Sky/Weather Conditions:
Received By :
Date :
Action Taken:
Field Invalid or In-house Invalid
Figure 3-4. NMOC Invalid Sample Form
3-10
-------
The operating temperatures of the HP-5880 were controlled for the PDFID
a .lysis. The FED and auxiliary zone were controlled at 250°C and 90°C, respectively.
The oven temperature was programmed from 30°C to 90°C at a rate of 30°C per minute
for 4 minutes, holding at 90°C for the fourth minute. Oven and integration parameters
v.\ controlled by Hewlett-Packard HP Level 4 programmable integrators. A complete
listing of the integrator programming sequence for NMOC measurement by the PDFID
method is given in Appendix E.
NMOC Analytical Technique
The modified HP-5880, dual-FID chromatographs were operated during the
19r study according to a project specific Standard Operating Procedure (SOP). Further
description is given below to help explain the analytical apparatus and procedure.
The six-port valve shown in Figure 3-5 was installed in the auxiliary heated zone
of the HP-5880 and was pneumatically actuated using chromatographic valve control
signals to apply either compressed air or vacuum to the valve. The sample trap itself
was located inside the chromatograph's column oven. A section of 1/8-inch o.d. stainless
steel tubing was sized to a length that prevented pressure surges from extinguishing the
FID flame. This length was determined experimentally and differs for each
chromatograph and for each channel within chromatographs. Although the length of
tubing effectively substitutes for the pressure restriction provided by a column, it does
not perform the separation function of a column.
During sample trapping, an excess of sample gas flow from the canister was
maintained to ensure back diffusion of room air into the trap did not occur. A pressure
change of 80 mm Hg in a 1.7-L vacuum reservoir was used to gauge and control the
volume of sample gas cryogenically trapped. After the trapping cycle was complete, the
HP-5880 program shown in Appendix E was initiated. When the program triggered a
horn emitting an audible beep, the cryogen was removed from the trap and the oven
JBS441
3-11
-------
*
Vacuum
Valve
Vacuum Pump
Canister Valve
Absolute
Pressure Gauge
Low Pressure
Regulator
&—I
Sample
Valve
Sample
Metering Valve
1.7 Liter
Reservoir
Vent
J
Sample Injection
Bypass
Rotameter
He
Glass Beads
FID
Cryogenic
Sample Trap
Air
Hydrogen
Liquid Argon
Integrator
Recorder
Sample Canister
ci
r~-
10
Figure 3-5. NMOC Analytical Equipment
-------
door was closed. The chromatographic program then assumed control of raising the
oven temperature, at the preset rate, to release the trapped sample to the FID, and set
up the integration parameters.
33 Canister Cleanup System
A canister cleanup system was developed and used to prepare sample canisters for
reuse after analysis. A cleanup cycle consisted of first pulling a vacuum of 0.5 mm Hg
absolute pressure in the canister, followed by pressurizing the canister to 20 psig with
cleaned, dried air that had been humidified. This cycle was repeated two more times
during the canister cleanup procedure. The cleanness of the canister was qualified by
PDFID analysis. Upon meeting the cleanness criterion of 20 ppbC, the canister was
evacuated to 0.5 mm Hg absolute pressure a fourth time, in preparation for shipment to
the site.
33.1 Canister Cleanup Equipment
A diagram of the canister cleanup system is shown in Figure 3-6. An oil-free
compressor with a 12-gallon reservoir provided source air for the system. The oil-free
compressor was chosen to minimize hydrocarbon contamination. A coalescing filter
provided water mist and particulate matter removal down to a particle size of one
micron. Permeation dryers removed water vapor from the compressor source air. These
permeation dryers were followed by moisture indicators to show detectable moisture in
the air leaving the dryer. The moisture indicators never showed any water, indicating
that the permeation dryers effectively removed all water vapor.
Air was then passed through catalytic oxidizers to destroy residual hydrocarbons.
The oxidizers were followed by in-line filters for secondary particulate matter removal
and by a cryogenic trap to condense any water formed in the catalytic oxidizers and any
organic compound not destroyed by the catalytic oxidizer. A single-stage regulator
controlled the final air pressure in the canisters and a metering valve was used to control
JBS441
3-13
-------
5.Of/ Filter
Assembly
Cryotrap Purge Valve
Air Flow
Rotameters
Dry Rotameter
Air Bypaai
Vacuum Source
Selector Valve
Roughing
Pump
8-Port
Manifold
OODDODOO
To Certification System
A. Manifold Air Pressure Valve
B. Manifold Vacuum Valve
C. Manifold Pressure Release Valve
O. Manifold Port for Connecting Canisters to be Cleaned
Figure 3-6. Canister Cleanup Apparatus
-------
the flow rate at which the canisters were filled during each cleanup cycle. The air flow
was indicated by a rotameter installed in the clean, dried air line. There was a shutoff
valve between the rotameters and the humidifier system. The humidifier system
consisted of a SUMMA® treated 6-L canister partially filled with high performance liquid
chromatographic-grade (HPLC-grade) water. One flowmeter and flow-control valve
routed the cleaned, dried air into the 6-L canister where it was bubbled through the
HPLC-grade water. A second flow-control valve and flowmeter allowed air to bypass the
canister/bubbler. By. setting the flow-control valves separately, the downstream relative
humidity was regulated. Since the 1990 study, 80% relative humidity has been used for
canister cleaning. There was another shutoff valve between the humidifier and the
8-port manifold where the canisters were connected for cleanup.
The vacuum system consisted of a Precision Model DD-310 turbomolecular
vacuum pump, a cryogenic trap, an absolute pressure gauge, and a bellows valve
connected as shown in Figure 3-6. The cryogenic trap prevented the sample canisters
from being contaminated by back diffusion of hydrocarbons from the vacuum pump into
the cleanup system. The bellows valves enabled isolation of the vacuum pump from the
system without shutting off the vacuum pump.
332 Canister Cleanup Procedures
After all analyses were completed, a bank of eight canisters was connected to each
manifold shown in Figure 3-6. The valve on each canister was opened, with the shutoff
valves and the bellows valves closed. The vacuum pump was started and one of the
bellows valves was opened, drawing a vacuum on the canisters connected to the
corresponding manifold. After reaching 0.5 mm Hg absolute pressure as indicated by the
absolute pressure gauge, the vacuum was maintained for 30 minutes on the eight
canisters connected to the manifold. The bellows valve was then closed and the cleaned,
dried air that had been humidified was introduced into the evacuated canisters until the
pressure reached 20 psig. The canisters were filled from the clean air system at the rate
of 7.0 L/min. This flow rate was recommended by the manufacturer as the highest flow
JBS441
-------
rate at which the catalytic oxidizers could handle elimination of hydrocarbons with a
minimum of 99.7% efficiency.
When the first manifold had completed the evacuation phase and was being
pressurized, the second manifold was then subjected to vacuum by opening its bellows
valve. After 30 minutes, the second manifold was isolated from the vacuum and
.connected to the clean, dried air that had been humidified. The first manifold of
canisters was then taken through a second cycle of evacuation and pressurization. Each
manifold bank of eight canisters was subjected to three cleanup cycles.
During the third cleanup cycle, the canisters were pressurized to 20 psig with
clean, dried air that had been humidified. For each bank of eight canisters, the canister
having the highest pre-cleanup NMOC concentration was selected for NMOC analysis to
determine potential hydrocarbon residues. If the analysis measured less than
0.020 ppmC, then the eight canisters on the manifold were considered to be clean.
Finally, the canisters were again evacuated to 0.5 mm Hg pressure absolute, capped
under vacuum, and then packed in the containers used for shipping to the field sites.
JBS441
3-16
-------
4.0 NMOC QUALITY ASSURANCE/QUALITY CONTROL PROCEDURES
This section details the steps taken in the 1993 NMOC monitoring program to
ensure that the data collected were of known quality and were well documented.
Analysis results are given in terms of precision, completeness, and accuracy. Repeated
analyses provided analytical precision. Duplicate samples provided sampling and analysis
precision. Completeness was measured in terms of percent of scheduled samples that
resulted in valid samples, beginning with the first valid site-specific sample collected and
ending with the last scheduled site-specific sample. Accuracy of NMOC concentrations
was reported as percent bias of audit samples of or referenced to a propane NIST
standard reference mateiral (SRM) by a U.S. EPA contractor.
4.1 Introduction ^nd Conclusions
Completeness for the 1993 NMOC study was 94.5% indicating that good
communication and planning were maintained between the site personnel and the
laboratory personnel. Precision for the 1993 NMOC study averaged 22.54% absolute
percent difference of repeated analysis and compared to 21.61% for 1992, 14.2% for
1991, 7.6% for 1990, 14.2% for 1989, 10.1% for 1988, 9.61% for 1987, 9.01% for 1986,
and 10% for 1985. These are excellent results based on the low concentrations
measured during the program.
Bias of the Radian channels for the 1993 audit results ranged from + 1.8% to
+ 8.5 percent. In 1992, the accuracy determined from the external audit samples ranged
from -3.4% to +24.0%, from +1.9% to +8.9% in 1991, from -3.2% to +6.2% in 1990,
from + 1.3% to +4.5% in 1989, from 1.3% to 4.5% in 1988, and from -2.9% to -0.06% in
1987. In 1986 bias ranged from -0.52% to -3.3% and in 1985 bias ranged from -2.3% to
+5.2 percent.
JBS441
4-1
-------
An initial multipoint performance evaluation was conducted using the propane
responses for each of the four analytical measurement channels. Daily calibration checks
and in-house propane QC samples monitored instrument and operator performance.
Duplicate site samples demonstrated good overall sampling and analysis precision.
Data validation was performed on 10% of the 1993 NMOC data base, as
described later in this section.
Calibration and drift determinations showed that the instrumentation was stable
and the calibration procedures were consistent. Canister cleanup results showed there
was negligible carryover from one sample to the next. In-house QC samples of propane
demonstrated that the analytical systems were in control.
Precision, accuracy, and completeness results for 1993 are comparable to results
from previous years and indicate that the data is of good quality and meet the data
quality objectives specified in the QAPP2.
4.2 Calibration and Instrument Performance
Initial performance assessments for NMOC were conducted with propane. Daily
calibrations were checked with approximately 3.0 ppmC propane for the NMOC
measurements.
42.1 Performance Assessment
An initial multipoint performance evaluation was conducted on each analytical
measurement channel, using propane referenced to a propane NIST CRM No. 1666B.
The concentration of the propane used in the performance assessment ranged from
2.971 to 19.073 ppmC. The "zero" value was determined using cleaned, dried air from
the canister cleanup system described previously in Section 3. Table 4-1 summarizes the
performance assessments. The FID responses for multiple concentration propane
JBS441
4-2
-------
Table 4-1
1993 Performance Assessment Summary, Radian Channels
Radian
Channel
A
B
C
D
Cases
20
20
20
20
Lin.
Intercept
248.774
265.721
435.067
778.488
ear Rejgrcssioa 1
' Slope
3181.774
3231.343
3082.526
2907.654
Results*,;^ :• •--•:.
Coefficient '
of Correlation
0.999772
0.999815
0.999649
0.999178
'Figures 4-1 through 4-4 plot propane area counts vs. concentration in ppmC.
JBS441
4-3
-------
standards were linear, having coefficients of correlation from 0.999178 to 0.999815.
Figures 4-1 through 4-4 show plots of the NMOC performance results for Radian
Channels A, B, C, and D, respectively. The plots show the regression line.
422 Calibration Zero, Span, and Drift
Radian PDFID channels were tested daily for zero and span. Zero readings were
measured using cleaned, dried air. The zero air was supplied by the same system that
cleans air for the canister cleanup system. Span readings used a mixture of about
3.0 ppmC propane in dry air. Calibration factors were calculated from the span and
zero readings for each measurement channel. Initial calibration factors were determined
in the morning before any site samples were analyzed and final calibration factors were
determined in the afternoon on randomly selected days after all the ambient air samples
had been analyzed. Percent calibration factor drifts were determined based on the initial
calibration factor. The data for zeros, calibration factors, and calibration factor drifts are
given in Appendix F for each Radian channel and each calendar day of the analysis
season. Figures 4-5 through 4-8 show plots for daily calibration zeros for Radian
Channels A, B, C, and D. Figures 4-9 through 4-12 show the daily calibration span data
as a function of the 1993 Julian date. Figures 4-13 through 4-16 show the daily percent
drift data for Radian Channels A, B, C, and D indicating the maximum percent drift was
3.32. The average absolute percent drift ranged from 0.023% for Channel B to 0.549%
for Channel C.
4.23 Calibration Drift
Summary calibration factor drift data are given in Table 4-2. The table presents
calibration factor drift, percent calibration factor drift, and absolute percent calibration
factor drift. Calibration factors were calculated from an analysis of a propane-air
JBS441
4-4
-------
0)
(0
C
o
Q.
(0
0)
tc
70-
c
8
(0
C c
(0
-------
70-
c
=1
CO
CD
CD
C
CO'
Q.
co
~a
CO
60-
50-
40-
2 o
^ |E 30-
k_ V •
0)
(0
o
Q.
CC
20-
10-
0
Four-Point Calibration -1993
Channel B
T"
4
T~
8
—r~
12
6 8 10 12 14
Propane Concentration, ppmC
16
18
20
Figure 4-2. NMOC performance results, Channel B.
-------
Four-Point Calibration -1993
Channel C
0
4 6 8 10 12 14
Propane Concentration, ppmC
Figure 4-3. NMOC performance results, Channel C.
18
20
-------
Four-Point Calibration -1993
Channel D
70-
-------
0.003-r
0.002-
0.001-
O
Q.
Q.
0.000-
-0.001
100
DAILY CALIBRATION - ZERO
Radian Channel A
150
200
250
300
350
Julian Date, 1993
Figure 4-5. Daily Calibration Zero, Channel A
100
DAILY CALIBRATION - ZERO
Radian Channel 6
0.003-
0.002-
0.001-
o
Q.
a
o 0-00°-
o
z
•0.001 J
-0.002-
jinrw-
•
•
•
•
150
200
250
300
350
Julian Date, 1993
Figure 4-6. Daily Calibration Zero, Channel B
4-9
-------
100
DAILY CALIBRATION - ZERO
Radian Channel C
u.wo-
0.002-
OOOI-i
o
Q.
Q.
o
o
2
-0.001-
-0.002-
-0.003-
'
• " " • •
" .1 .---.
• ** •
. . *rf • ."" .
150
200
250
300
350
Julian Date, 1993
Figure 4-7. Daily Calibration Zero, Channel C
0.003-
0.002-
O
Q.
Q.
-0.001'
-0.002-
100
DAILY CALIBRATION - ZERO
Radian Channel D
150
200
250
300
350
Julian Dale, 1993
Figure 4-8. Daily Calibration Zero, Channel D
4-10
-------
DAILY CALIBRATION - SPAN
Radian Channel A
U.UW4U-
co
"c
o
ra
-------
DAILY CALIBRATION - SPAN
Radian Channel C
u.iAWtv-
«
H
o
0.
a
0
2
1
|
- . • • «*v"
*• *•""«*••*. A ^
-
DO 150 200 250 300 3J
Julian Date, 1993
Figure 4-11. Daily Calibration Span, Channel C
DAILY CALIBRATION - SPAN
Radian Channel 0
U.OOO4U-
0.00035-
c
§ 0.00030-
O
ppmC/Area
o
i
O
O 0.00020-
z
0.0001 5^
ononio-
-fc-** * •*
" "*" " "™*
•
too
150
200
250
300
350
Julian Date. 1993
Figure 4-12. Daily Calibration Span, Channel D
4-12
-------
DAILY CALIBRATION - PERCENT DRIFT
Radian Channel A
30.00-
20.00-
10.00-
0)
u
I
0.00
-10.00
-20.00
-30.00
100
150
200 250
Julian Date, 1993
300
350
Figure 4-13. Daily Calibration Percent Drift, Channel A
DAILY CALIBRATION - PERCENT DRIFT
Radian Channel B
Percent Dfift
20.00-
15.00-
10.00-
5.00-
0.00-
-5.00-
-10.00-
-15.00-
150
200
Julian Date, 1993
Figure 4-14. Daily Calibration Percent Drift, Channel B
4-13
-------
DAILY CALIBRATION - PERCENT DRIFT
Radian Channel C
20.00-
15.00-
10.00-
500-
c
Q
1 0.00-
a.
-5.00-
-10.00-
-15.00-
-2000-
100
150
200
250
300
350
Julian Date, 1993
Figure 4-15. Daily Calibration Percent Drift, Channel C
20.00-
15.00-
10.00-
5.00-
c 0.00-
o
CD
Q.
-5.00-
-10.00-
-15.00-
-2a.oo-
100
DAILY CALIBRATION - PERCENT DRIFT
Radian Channel D
150
200
250
300
350
Julian Date, 1993
Figure 4-16. Daily Calibration Percent Drift, Channel D
4-14
-------
Table 4-2
Summary NMOC Calibration Factor Drift Results
- lUdiw
^GJfrjMMtlfel
A
B
C
D
Overall
-;i->
d&tt. ••
6
4
56
50
116
,•;., CtJAnrfm Factor Drift
IfcV ppwC/AwwOwwtxtO*
'£, '
f'Mfcfruaft
-3.9
0.0
-29
-10
-29
Mean
-0.1
0.1
-0.9
-1.3
-0.1
MaSttM*
3.3
0.3
1.1
5.5
5.5
+
Fcrccoi fwtor JPfm
tate.
-1.181
0.000
-9.568
-3.341
-9568
Mean
-0.032
0.023
-0.310
-0.397
-0322
*******
0.987
0.091
3.318
1.722
3318
•• Absolute ftfttttat Rich* V '
:. fMfc^M^;.t
• Mew
0.361
0.023
0.549
0.483
0.493
>']fe«&itkMt-.:
0.563
0.045
1.413
0.728
1.098
-------
mixture whose concentration was known and was referenced to a propane NIST
CRM 1666B reference standard as follows:
calibration _ concentration of propane standard (ppm) x 3 ppmC/ppm
factor (propane standard response (area counts) - zero response (area counts))
Daily calibration factors ranged from 0.000270 ppmC/area count to
0.000344 ppmC/area count, depending on the channel. Maxima, minima, and mean
values are given in Table 4-2 for calibration factor drift and percent calibration factor
drift. If drift and percent drift are random variables and normally distributed, the mean
values would be expected to be zero. The means shown in Table 4-2 for the drift and
percent drift are approximately zero, showing little bias overall, or for any channel. The
overall mean values shown in Table 4-2 were weighted according to the number of
calibration drift data for each channel. The last two columns of Table 4-2 show the
means and standard deviations of the absolute percent calibration factor drifts. The fact
that the standard deviations are the same order of magnitude as the means indicates that
the mean calibration factor drifts are not significantly different from zero.
Calibration factor drift was defined as final calibration factor for the day, minus
initial calibration factor. Percent calibration factor drift was defined as the calibration
factor drift divided by the initial calibration factor, expressed as a percentage. The
absolute percent calibration factor drift is a measure of the calibration drift variability
and averaged 0.493% overall. The mean absolute percent calibration drift ranged from
0.023% for Radian Channel B to 0.549% for Radian Channel C.
43 In-House OC Samples
In-house QC samples were prepared by Radian personnel by diluting dry propane
with cleaned, dried air using calibrated flowmeters. The propane used for the in-house
quality control samples was certified against an NIST Reference Standard. The
concentration of the in-house standard ranged from approximately 0.800 ppmC to
JBS441
4-16
-------
1.326 ppmC. The analyst did not know the concentration of the in-house standard prior
to analysis.
The daily in-house QC data for each Radian channel are given in Appendix G,
and include:
• Calendar date analyzed;
• Julian date for 1993;
• Radian ID Number;
• Calculated NMOC concentration in ppmC;
• Measured NMOC concentration in ppmC;
• Bias (measured NMOC - calculated NMOC); and
• Percent Bias (Bias * 100 / calculated NMOC).
Because of the limited number of analyses per day, generally only two analysis
channels (C and D) were used. Therefore, there are only a few data for Channels A and
B.
Measured versus calculated NMOC concentrations in Figures 4-17 and 4-18 show
excellent agreement. Table 4-3 summarizes the results of the linear regressions for the
Radian in-house QC data, showing regression intercepts near zero, and slopes and
coefficients of correlation all near 1.0.
Tables 4-4 and 4-5 give statistics for in-house QC measurements. DIFF is the
ppmC difference between the measured and the calculated NMOC concentrations, and
PCDIFF is the percentage of the difference relative to the calculated value. Both DIFF
and PCDIFF may be considered to be bias terms, assuming that the calculated value is
the correct NMOC concentration for the in-house QC sample. Overall, PCDIFF shows a
mean bias of -5.971%, and ranges from -6.188% for Channel D to -5.549% for
Channel C. APCDDFF, absolute value of PCDIFF, was used as a measure of precision.
The absolute percent difference ranged from 5.549 for Channel C to 6.188 for Channel
D and averaged 5.97 percent. These figures show excellent agreement and consistency
JBS441
-------
In-house Propane QC Results
Channel C
O
a
a
1.40-
1.30-
1.20-
TO
^ 1.10-
o
o
5 0.90-
z
T3
CD
3 0.80-
m
s
5 0.70-
0.60-
0.70 0.80 0.90 1.00 1.10 1.20
Calculated NMOC Concentration, ppmC
1.30
1.40
Figure 4-17. In-house Quality Control Results, Channel C
1.40-
1.30H
75
1.00-
8 ,
2 0.90-
J
0.8CH
0.70-
0.60-
In-house Propane QC Results
Channel D
0.70
0.80
0.90
1.00
1.10
1.20
1.30
1.40
Calculated NMOC Concentration, ppmC
Figure 4-18. In-house Quality Control Results, Channel D
4-18
-------
Table 4-3
Linear Regression Parameters for In-House Quality Control Data
Radiant .-'•:
C
D
•:*$m.
19
19
ISi^fe-
••'••'.. ... .IT
-0.014
-0.051
&HIS
0.958
0,989
'•*€oefficieBr *
• of Correlation
0.980
0.984
"Due to the limited number of data for Channel A or B, regressions were not possible.
JBS441
4-19
-------
Table
In-House Quality Control Statistics, by Radian Channel
. •>:
Statistics
Channel A
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
Channel B
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
Channel C
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
DEFF*
2
-0.082
0.041
-0.062
0.029
0.021
d
'
1
-0.105
-0.105
-0.105
•
•
•
•
19
-0.135
-0.021
-0.056
-0.029
-0.007
-1.336
1.940
vanames .y.vv
..-•"• ~ . ;' ;--
K30IFF*"
2
-7.374
-4.162
-5.768
2.271
1.606
•
•
1
-9.442
-9.442
-9.442
•
•
•
•
19
-11.250
-2.005
-5.594
2.664
0.611
-0.731
0.080
'"'- '' '•'•''•". '•'• . '•-. ':: •'
•:•: APCDIFF
2
4.162'
7.374
5.768
2.271
1.606
•
•
1
-9.442
-9.442
-9.442
•
•
•
•
19
11.250
2.005
5.594
2.664'
0.611
-0.731
0.080
JBS441
4-20
-------
Table
Continued
Statistics
£H*-
Variable*
JK3&W&
ApCDflSF
Channel D
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
19
-0.112
-0.025
-0.061
-0.026
0.006
-0.287
-0.872
19
-11.405
-2.336
-6.188
2.512
0.576
0.053
-0.476
19
2.331
6.188
6.188
2.512
0.576
0.053
-0.476
*DIFF = Measured NMOC concentration - Calculated NMOC concentration, ppmC.
"PCDIFF = DIFF/calculated NMOC concentration x 100.
CAPCDIFF = Absolute value of PCDIFF.
d . = Calculation not possible due to limited data.
JBS441
4-21
-------
Table 4-5
Overall In-House Quality Control Statistics
Statistics . :
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
DDPP
41
-0.135
-0.021
-0.060
0.028
0.004
-0.717
-0.007
FODIFF**
41
-11.405
-2.005
-5.971
2.560
0.400
-0.275
-0.593
APCDEFF
41
2.005
11.405
5.971
2.560
0.400
0.275
0.593
'DIFF = Measured NMOC concentration - Calculated NMOC concentration, ppmC.
"PCDIFF = DIFF/calculated NMOC concentration x 100.
CAPCDIFF = Absolute value of PCDIFF.
JBS441
4-22
-------
for the in-house quality control data and include variability not only in the instrumental
analysis but also in the apparatus and method used to generate the QC samples.
4.4 Repeated
Replicate (or repeated) analyses results are listed in Table 4-6. Repeated
analyses from the contents of a canister are used to estimate analytical precision. The
first analysis was performed at the Radian laboratory on the day the canister was
received from the sample site, and is designated in the table by an I. The second
analysis from the canister, designated by an R in the sample identification (ID) number
(see Table 4-6), was performed at least 24 hours after the first analysis. This procedure
was followed to ensure that sufficient time had elapsed between removal of an aliquot
for analysis to allow the canister contents to equilibrate with the solid surfaces and to
allow any concentration gradients within the canister to disperse.
Sample number, site code, date sampled, sample ID number, measured
concentrations for Injections 1 and 2, mean NMOC concentration, analysis average
concentration, canister mean, difference between replicate analyses, percent difference
between replicate analyses, and absolute percent difference are given in Table 4-6. The
mean concentration in Column 5, in parts per million carbon by volume (ppmC), is the
arithmetic average of the NMOC concentrations for the two analyses shown in Columns
3 and 4, headed "Inj 1 and Inj 2." Column 6, labeled "Canister Mean" is the
concentration for each sample number and is the average of the mean concentrations for
each analysis.
Percent differences are calculated by the following equation:
% Diff = —— 1— • 100
JBS441
4-23
-------
Table 4-6
Replicate Analysis Results for the 1993 NMOC Program
Cflflrrtino
Date
Radian
ID
N*
NMOC
<»«e)
faj2
NMOC
(ppmC)
Avan&i
max
&p*Q
Courier
WWHtJC
(ppmC)
Biff
BlMiJ<*wimt
n-1-i.rjran.wi.B
%tm
LINY
06/14/93
06/14/93
07/06/93
07/06/93
07/06/93
07/06/93
07/12/93
07/12/93
07/14/93
07/14/93
07/14/93
07/14/93
08/10/93
08/10/93
08/10/93
08/10/93
09/17/93
09/17/93
09/17/93
09/17/93
10671
1067 R
12471
1247 R
12481
1248 R
12911
1291 R
13081
1308R
13091
1309R
15591
1559 R
15601
1560R
19461
1946 R
19471
1947 R
0.1%
0.197
0.162
0.235
0238
0239
0.441
0.443
0.253
0335
0353
0311
0.434
0.437
0.488
0.431
0.196
0.226
0.190
0.154
0.194
0.167
0.174
0.236
0.245
0.236
0.432
0.441
0.263
0332
0351
0337
0.430
0.445
0.500
0.432
0200
0.192
0.175
0.170
0.195
0.182
0.168
0.235
0241
0.237
0.437
0.442
0.258
0333
0352
0324
0.432
0.441
0.494
0.431
0.198
0.209
0.182
0.162
0.189
0.202
0.239
0.439
0.296
0338
0.436
0.462
0.204
0.172
-0.013
0.067
-0.004
0.005
0.075
-0.028
0.009
-0.062
0.011
-0.020
-6.888
33335
-1.615
1.170
25.469
-8.254
2.000
-13.460
5.405
-11.628
At«%
Biff
6.888
33335
1.615
1.170
25.469
8.254
2.000
13.460
5.405
11.628
NWNJ
06/29/93
06/29/93
08/24/93
08/24/93
08/24/93
08/24/93
12201
1220 R
17121
1712 R
17131
1713 R
0260
0.267
0.443
0.458
0.444
0351
0.230
0.254
0.445
0.449
0.429
0360
0.245
0.261
0.444
0.453
0.437
0355
0253
0.449
0396
0.016
0.009
-0.082
6298
2.030
-20.651
6298
2.030
20.651
4-24
-------
Table 4-6
Continued
{^iftftrtfaiff
ftftt*
Radian
n>
id|i
NMOC
te-Q
InjS
NMOC
-e>
Average
NMOC
frP-O
r>m*Xfit*+-
NMOC
fcM3
PiftpltftfCt
Biff
%Diff
At»%
Diff
P2PA
07/21/93
07/21/93
14051
1405 R
0.105
0.067
0.073
0.063
0.089
0.065
0.077
-0.024
-30.612
30.612
PLNJ
06/21/93
06/21/93
06/28/93
06/28/93
06/28/93
06/28/93
07/07/93
07/07/93
07/16/93
07/16/93
07/16/93
07/16/93
08/25/93
08/25/93
08/25/93
08/25/93
08/27/93
08/27/93
09/30/93
09/30/93
11231
1123 R
11921
1192 R
11931
1193 R
12751
1275 R
13571
1357 R
13581
1358 R
17351
1735 R
17361
1736 R
17511
1751 R
20441
2044 R
0.189
0239
0328
0282
0297
0.111
0246
0310
0.119
0.046
0.193
0.079
0352
0.478
0.410
0339
1.790
1.722
0.442
0.432
0.194
0.242
0298
0279
0297
0.121
0246
0312
0.111
0.052
0.172
0.054
0350
0.438
0.420
0339
1.759
1.743
0.410
0.461
0.192
0241
0313
0281
0.297
0.116
0.246
0311
0.115
0.049
0.182
0.067
0351
0.458
0.415
0339
1.775
1.733
0.426
0.448
Count
Average
Standard Deviation
0216
0.297
0206
0.279
0.082
0.125
0.405
0377
1.754
0.437
24
0347
0322
0.049
-0.032
-0.181
0.065
-0.066
-0.116
0.108
-0.076
•0.042
0.022
24
-0.013
0.065
22.599
-10.769
-87.656
23340
-80.869
-92.731
26.619
-20.132
-2376
5.034
24
-9.764
33.935
22.599
10.769
87.656
23340
80.869
92.731
26.619
20.132
2376
5.034
24
22^39
26.851
4-25
-------
where:
X\ = The mean NMOC concentration for the first analysis; and
X2 = The mean NMOC concentration for the second (or repeated)
analysis.
A total of 48 analyses on 24 canister samples are shown in Table 4-6. The percent
difference ranged from -92.731 to +33.355 and averaged -9.764 overall. The low value
of the overall average percent difference indicated that there was an insignificant average
bias between the second and the first analyses.
The final column in Table 4-6 lists absolute percent difference. The overall
absolute percent difference was 22.54 for 1993. In 1992, the average absolute percent
difference was 21.61, 14.29 in 1991, 7.59 in 1990, and 8.24 in 1989. Experience has
shown that in general the lower the concentration, the higher the percent difference, and
especially the absolute percent difference.
4.5 Duplicate Sample Results
Duplicate analysis results are given in Table 4-7. Percent differences (between the
canister means) ranged from -36.520 to +41.753 and averaged +0.479 overall. The low
overall average percent difference indicates that there was no systematic bias between
samples. The absolute percent difference averaged 12.633. Absolute percent differences
averaged 15.626 in 1992, 15.768 in 1991, 7.594 in 1990, and 10.621 in 1989.
4.6 O**"ster Pressure Results
Canister pressure results for the NMOC monitoring program are an important
gauge to assess whether the ambient air samples obtained are representative. The
NMOC sampling systems are designed to obtain an integrated ambient air sample
between 6:00 a.m, and 9:00 a.m. local time, or at other programmed intervals. Canister
pressures are measured to obtain a better understanding of the range and magnitude of
JBS441
4-26
-------
Table 4-7
Duplicate Samples for the 1993 NMOC Program
rtqfojfat
B*e
LINY
06/14/93
06/14/93
06/14/93
06/24/93
06/24/93
07/06/93
07/06/93
07/06/93
07/06/93
07/14/93
07/14/93
07/14/93
07/14/93
08/10/93
08/10/93
08/10/93
08/10/93
08/23/93
08/23/93
09/08/93
09/08/93
09/17/93
09/17/93
09/17/93
09/17/93
09/30/93
09/30/93
*»$•»
ID
1067
1067
1068
1172
1173
1247
1247
1248
1248
1308
1308
1309
1309
1559
1559
1560
1560
1716
1717
1828
1829
1946
1946
1947
1947
2052
2053
lajectiMl
NMOC
-------
Table 4-7
Continued
Cafec&«
B»te
NWNI
06/15/93
06/15/93
06/25/93
06/25/93
07/07/93
07/07/93
07/15/93
07/15/93
08/11/93
08/11/93
08/24/93
08/24/93
08/24/93
08/24/93
09/08/93
09/08/93
09/17/93
09/17/93
PITA
08/18/93
08/18/93
09/21/93
09/21/93
P2PA
07/21/93
07/21/93
07/21/93
ftaimt
a>
1078
1079
1184
1185
1264
1265
1327
1328
1589
1590
1712
1712
1713
1713
1839
1840
1930
1931
1644
1645
1965
1966
1405
1405
1406
Yntr rfirMl ^
NMOC
0386
0.410
0337
0.457
0387
0312
0.239
0.186
0.522
0.587
0.443
0.458
0.444
0351
0284
0.284
0.119
0.143
0.115
0.120
0.157
0.112
0.105
0.067
0.082
f
fikir^iiTM ^
NMOC
0393
0.404
0337
0.418
0399
0308
0.234
0.194
0.536
0.589
0.445
0.449
0.429
0360
0284
0.283
0.154
0.129
0.123
0.113
0.161
0.108
0.073
0.063
0.063
*!.,.-.
NMOC
&V*Q
0389
0.407
0337
0.437
0.393
0310
0.236
0.190
0.529
0.588
0.444
0.453
0.437
0355
0284
0.284
0.137
0.136
0.119
0.116
0.159
0.110
0.089
0.065
0.063
I**iiir1**
NMOC
0389
0.407
0337
0.437
0393
0310
0.236
0.190
0.529
0.588
0.449
03%
0.284
0.284
0.137
0.136
0.119
0.116
0.159
0.110
0.077
0.063
Biff
0.017
0.100
-0.083
-0.046
0.059
-0.053
0.000
-0.001
-0.003
-0.049
0.006
DttfertB
%DJff
4392
25.949
-23.651
-21.741
10.638
-12.464
0.000
-0.733
-2251
-36.520
7.157
Al»%
Diff
4392
25.949
23.651
21.741
10.638
12.464
0.000
0.733
2.251
36.520
7.157
4-28
-------
Table 4-7
Continued
OtifortmM
»**
09/09/93
09/09/93
Kadttft
n>
1870
1871
l&^c&ttl
NMOC
te*Q
0325
0332
iajec&al
wfiMBUC
to*sz
0289
0330
Average
NMOC
(pp-e>
0307
0331
f*mmmitt
*WwD\*
(PI»C)
0307
0331
DBpBata
.'sS
ffX.
Biff
0.024
%Dar
7524
Ai»%
Diff
7J24
PLNJ
06/28/93
06/28/93
06/28/93
06/28/93
07/16/93
07/16/93
07/16/93
07/16/93
08/12/93
08/12/93
08/25/93
08/25/93
08/25/93
08/25/93
09/10/93
09/10/93
09/21/93
09/21/93
09/30/93
09/30/93
09/30/93
1192
1192
1193
1193
1357
1357
1358
1358
1582
1583
1735
1735
1736
1736
1900
1901
1942
1943
2044
2044
2045
0328
0.282
0.297
0.111
0.119
0.046
0.193
0.079
0.591
0.695
0352
0.478
0.410
0339
0.437
0.476
0.586
0.530
0.442
0.432
0.424
0.298
0.279
0.297
0.121
0.111
0.052
0.172
0.054
0.578
0.662
0350
0.438
0.420
0339
0.457
0.463
0.569
0.558
0.410
0.461
0.424
0313
0.281
0.297
0.116
0.115
0.049
0.182
0.067
0.584
0.679
0351
0.458
0.415
0339
0.447
0.470
0.578
0.545
0.426
0.448
0.424
Count
Avenge
Standard Deviation
0297
0.206
0.082
0.125
0.584
0.679
0.405
0377
0.447
0.470
0.578
0.545
0.437
0.424
56
0325
0.181
-0.091
0.043
0.095
-0.028
0.023
-0.033
-0.013
28
0.0033
0.046
-35.985
41.753
15.022
-7.087
5.016
-5.877
-3.020
28
0.4794
17.157
35.985
41.753
15.022
7.087
5.016
5.877
3.020
28
12.633
11363
4-29
-------
pressures being generated by the NMOC sampling systems and to assess possible canister
leakage. Canister pressure data are given in Table 4-8 for both single canister samples
and duplicate samples. The pressures reported in Table 4-8 are the canister sampling
pressures measured immediately before analysis in the laboratory. A significant decrease
between the field sampling pressure and the laboratory value might indicate a leak.
All sample canisters averaged 14.2 psig, while duplicate samples averaged
15.8 psig. The column entitled "All Samples" includes pressures from both single
samples and duplicate samples. Standard deviations were 2.9 and 3.3 psig, respectively.
These results indicate reproducible positive pressures, reasonably consistent operation of
the samplers, and consistent performance of .the samplers.
4.7 Canister Cleanup Results
Prior to the start of the 1993 NMOC monitoring program all of the canisters were
cleaned and analyzed for their NMOC content to establish canister initial conditions.
The resulting analysis with cleaned, dried air that had been humidified averaged
0.0050 ppmC, ranging from 0.0000 to 0.0200 ppmC. Any canisters that produced more
than 0.020 ppmC were recleaned.
Continual monitoring of canister cleanup was important to ensure that there was
negligible carryover from one site sample to the next. The daily canister cleanup
procedure was described in detail in Section 3.4. If the NMOC content was below
0.020 ppmC, cleanup was considered to be satisfactory.
Average percent recoveries, or average percent cleanup, in 1993 averaged 98.76%
(98.79% in 1992, 99.75% in 1991, 99.75% in 1990, 99.74% in 1989, 99.69% in 1988,
99.37% in 1987, 99.89% in 1986, and 99.90% in 1985). The reported average percent
recovery is based on average NMOC concentration and average cleanup concentration.
JBS441
4-30
-------
Table 4-8
NMOC Pressure* Statistics
Statistics
Dumber of Cases
Minimum Pressure, psig
Maximum Pressure, psig
Mean Pressure, psig
Median Pressure, psig
Standard Deviation, psig
Skewness, psig
Kurtosis, psig
Aft $3mpie$
314
6.0
21.0
14.2
14.0
2.9
0.07
-0.02
Duplicate
Sample
Canisters
56
8.0
20.0
15.8
16.5
3.3
0.67
-0.35
"Measured immediately prior to analysis.
JBS441
4-31
-------
The reported percent cleanup figures should be considered minimum values. The actual
percent cleanup was greater than the reported values because, after the percent cleanup
was measured, the canister was evacuated a third time before being shipped to the site.
4.8 Rrternal Audit Results
Primary measures of accuracy for the NMOC monitoring data were calculated
from the results of the analysis of propane audit samples provided by the EPA. Results
are reported in terms of percent bias relative to the EPA concentration spiked.
Two audit samples, ID 1863 and 1864, were analyzed during the NMOC program.
The EPA Audit Report is given in Appendix I. Table 4-9 gives the concentrations
reported by the four Radian channels. The theoretical concentration reported in
Table 4-9 was calculated using dilution factors estimated when the audit samples were
prepared by the EPA Auditor. The percent bias results are presented in Table 4-10 and
were calculated relative to the theoretical values. The Radian bias ranged from +1.79%
to -(-8.48%, and averaged +4.13% for the audit canisters.
4.9 Data Validation
Secondary backup disks were updated daily on 20 megabyte hard disks. At the
completion of the sampling and analysis phase, 10% of the data base was checked to
verify its validity. Items checked included original data sheets, checks of all the
calculations, and data transfers. In making the calculations for the final report and other
reports, corrections were made to the data base as errors or omissions were encountered.
A total of 414 NMOC concentration measurements were performed by Radian
from June through October 1993. This included 341 sample analyses, 24 repeated
analyses, 41 in-house QC analyses (on 19 in-house QC samples), and 2 audit samples (x
4 analyses each).
JBS441
4-32
-------
Table 4-9
NMCX: External Audit Sample Results
m
Number
1863
1864
-
_
1.12
0.66
Concentration, IJJH
mC ' * '- -
Aaafcsfe
Radiaa
A
1.180
0.685
Radian
8
1.140
0.716
Radian
C
1.160
0.690
Radian
0
1.160
0.673
JBS441
4-33
-------
Table 4-10
Bias of Audit Samples from Theoretical Concentrations
Number
1863
1864
Theoretical
CooccfttrflrtHwt.
^^fijinC'-- '•:•'
1.12
0.66
Penrnt Difference from Theoretical
'•••' '-Kadiaii <"'"
^:;.:'X'^;
5.357
3.788
•:^Ra&m''^
•:?..or.B' •••"•'.!
1.786
8.485
Raduui
"~ •! . e ' -
3.571
4.545
Radian
D
3.571
1.970
Percent Difference = (Analysis Channel - Theoretical) / Theoretical * 100
JBS441
4-34
-------
Ten percent of the data base was validated according to the procedure outlined
below.
• Calibration factors were checked.
The area count from the strip chart that was used to determine the
calibration factor was examined to verify that the data had been
properly transferred to the calibration form.
~ The calibration form was examined to verify that the calculations
had been correctly made.
Each datum on the disk was compared to the corresponding datum
on the calibration sheet for accuracy.
• Analysis data were checked.
Area counts were verified from the appropriate strip chart.
Calculations were reverified on the analysis forms.
Each datum on the disk was compared to the corresponding item on
the analysis form.
• Field data sheet was checked.
Each datum on the disk was compared to the corresponding datum
on the field data sheet.
The error rate was calculated in terms of the number of items transferred from the
original data sources. For each NMOC value in the 1993 data set, 36 items were
transferred from original sources to the magnetic disks. In the data validation study each
item on the disk was compared with the corresponding value on the original source of
data. One error was found (and corrected) for an expected error percentage of
0.007 percent.
Each time the data file was opened and a suspected error found, the error was
checked against the original archived documents, and corrected where appropriate.
JBS441
4-35
-------
4.10 NMQC Monitoring Program Records
The QA records developed by Radian for this project are extensive and will be
preserved as archives. One of the most important objectives of the study was to develop
a data base that is well planned and documented and contains NMOC data of known
and verifiable quality. Achieving that objective has involved keeping and preserving a
number of records that trace the project from planning through reporting.
4.10.1 Archives
In order to keep detailed records that document the quality of the measurements
made, Radian developed the following material:
• Quality Assurance Project Plan (QAPP);
• Notebooks;
• Field data sheets;
• Laboratory calibration sheets;
• Laboratory analysis sheets;
• Chromatographic strip charts;
• Bi-weekly, monthly reports to the EPA;
• Memoranda and correspondence; and
• Final report.
In addition to the above items, any papers to be presented at technical meetings
and symposia and published in technical journals will be added to the archives.
The QAPP2 was the Quality Assurance Project Plan and the workplan. The
QAPP was designed according to the EPA Quality Assurance Guidelines and set the
JBS441
-------
pattern of steps necessary to document and control the quality of the data obtained
throughout the study.
Several notebooks were necessary to maintain day-to-day records of the project.
Field and laboratory data sheets were designed in advance, so that the data recorded
appeared in a logical sequence and filled in blanks on the sheet. Additional space was
provided for other comments. Each NMOC analysis was assigned a unique Radian
Identification Number. Field data sheets and shipping records accompanied the canisters
in transit.
4.102 Magnetic Disks
In order to manage the data base for report generation and data analysis,
pertinent data from the various data sheets and notebooks were transferred to
20 megabyte magnetic disks. The following software were used in the construction of the
data base: Paradox 3.5*, QUATTRO®, and Freelance*. Statistical calculations were
performed using SAS® and SYSTAT® software. The data access is rapid and in a
convenient form. The primary 20 megabyte magnetic disk has three backup disks.
JBS441 4-37
-------
5.0 NMOC DATA ANALYSIS AND CHARACTERIZATION
The purpose of this section is to characterize the NMOC data qualitatively as well
as quantitatively. The NMOC data are shown to fit a two-parameter lognormal
distribution better than a normal Gaussian distribution. The summary NMOC data for
the sites of the 1993 study are given in Appendix C.
5.1 Overall Characterization
Figure 5-1 gives a stem-and-leaf plot of the 1993 NMOC data along with statistics
for NMOC. The stem-and-leaf plots show the actual NMOC concentrations truncated to
two or three decimal points. The digits to the left of the vertical open space are called
stems and the digits to the right of the open space are the leaves. The data are sorted
from the smallest at the top of the graph to the largest at the bottom of the graph. The
minimum NMOC value measured was 0.059 ppmC and is shown as "0 5" on the first
row at the top of the plot. The maximum NMOC concentration measured was 5.749
shown as "57 4" in the bottom row of the chart. The plot shows 367 leaves, one for
each NMOC site datum in the 1993 program. The H's in the open vertical space locate
the stem and leaf for the upper and lower hinges, and the M locates the stem and leaf
for the median. The median separates the sorted NMOC concentrations into two equal
halves; the hinges (or quartiles) separate each half into halves. The "H spread" or
interquartile range is the difference between the NMOC values of the two hinges.
Statistics shown for NMOC are number of cases, minimum, maximum, mean,
median, standard deviation, standard error, skewness, kurtosis, and the two hinges. Each
NMOC determination is the average of two or three injections of the site samples. In
the case of replicates, each NMOC determination is the average of the original and
repeated analysis concentrations. In the case of duplicates, the NMOC sample
determinations were averaged to represent the NMOC concentration for the sample
date.
JBS441
5-1
-------
0
1
1
2H
2M
3
3
4
4H
5
5
6
6
7
7
8
8
9
10
11
14
17
40
57
56667 78889
00001 12223 33333 33444 4444
55555 55666 66666 66777 77778 88888 88899 99999 9999
00000 01111111111 2222 22222 23333 33333 44444 4444
55555 55566 66666 66666 77777 88888 88999 99
00000 001 1 1 1 2233 33344 444
55556 66666 67778 88999 99999
0011222234444
55555 55666 67888 89
00001 1122344
55666 7889
00001 2222 334
66777 8999
00023
56677 889
012234
57
59
6678
57
45
5
7
4
NMOC, ppmC
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
313
0.059
5.749
0.404
0.445
0.025
7.644
Kurtosis 80.607
Lower Hinge (H)
Median (M)
Upper Hinge (H)
0.200
0.298
0.486
Figure 5-1. Stem-and-leaf Plot of the 1993 NMOC Data
5-2
-------
The standard error is the standard deviation divided by the square root of the
number of cases. Positive skewness is a third moment about the mean value, and
characterizes a tail to the right of the mean value. A normal Gaussian distribution has a
skewness of zero. The skewness of 7.644 for the 1993 NMOC data suggests a nonnormai
frequency distribution. Kurtosis is the fourth moment about the mean and relates to the
pointedness of the distribution. A distribution more pointed than a normal distribution,
having the same standard deviation, has a kurtosis greater than 3.0. The numerical
values of kurtosis listed in this report are zero centered. That is, 3.0 has been subtracted
from the fourth moment to give 0.0 for a distribution shaped similar to a normal
distribution.
Figure 5-2 is a stem-and-leaf plot of the 1993 In(NMOC) data. The plot shows an
approximately symmetrical distribution (skewness - 0.410). The kurtosis equal to
1.195 indicates the In(NMOC) distribution to be slightly more pointed than a normal
distribution.
The shape of the stem-and-leaf plots suggests a lognormal distribution.
Figures 5-3 and 5-4 support the lognormal distribution hypothesis for NMOC. The
vertical scales in Figures 5-3 and 5-4 are arranged so that if the cumulative frequency of
occurrence of NMOC were normally distributed, the points would plot into a straight
line. The line in Figure 5-3 has a noticeable concave downward trend, indicating that
the data do not fit a normal distribution well. Figure 5-4 plots the logarithm of NMOC
on the same vertical scale. The fact that the squares on the graph plot into
approximately a straight line supports the hypothesis that the NMOC data are
approximately lognormally distributed. A solid square on the graph indicates the
location of a single datum. The results, although qualitative, show a dramatic difference
between the normal and lognormal hypotheses, and suggest that the latter more nearly
describes the NMOC data.
JBS441
5-3
-------
-2
-2
-2
•2
-2
-1
-1 H
-1
•1 M
-1
-0
-OH
-0
-0
-0
0
0
1
88
766
54444
2 2
1 00 00000 0
99999 99998 88888 88888 888
77777 77777 66666 66666 66666 66666 66
55555 55555 55555 55544 44444 44444 44444 44444 4
33333 33333 33333 33333 33222 ????? 22222 2222
11111 11111 11111000000000000000
99999 99999 99999 99988 88888 88888 8
77777 77777 77777 76666 66666 666
55555 55555 54444 44444 444
33333 33333 33222 22222 22
11111 100
00001 1
A A
33
5
47
LNMOC, In(ppmC)
Cases
Minimum
Maximum
Mean
Standard Deviation
Standard Error
Skewness
Kurtosis
Lower Hinge (H)
Median (M)
Upper Hinge (H)
313
-2.830
1.749
-1.160
0.661
0.037
0.410
1.195
-1.609
•1.211
-0.722
Figure 5-2. Stem-and-leaf of the Ln(NMOC) Data
5-4
-------
UJ
o
UJ
o
UJ
Q.
X
UJ
-1
-2
NMOC
Figure 5-3. Cumulative Frequency Distribution for the 1993 NMOC Data
5-5
-------
LLJ
1
O
LU
O
LU
GL
X
UJ
-1
-2
J
-3
-3 -2
-1
LNMOC
Figure 5-4. Cumulative Frequency Distribution for the 1993 Ln(NMOC) Data
5-6
-------
52 Monthly Variations. 1993
Table 5-1 partitions the NMOC data for the summer of 1993 into groups that
correspond to monthly intervals. For the summer of 1993, the monthly means and
medians of the NMOC sites for June, July, August, and September parallel one another.
That is, the NMOC mean and median concentrations for July 1993 are less than the
mean and median for June 1993. Means and median for August show dramatic
increases compared to July 1993. The mean and median for September are less than the
mean and median for August 1993, but greater than the mean and median for July 1993.
Arithmetic means are used in Table 5-1 in spite of the observations given previously in
Section 5.1 which conclude that the frequency distribution of NMOC concentrations in
ambient air are approximately logarithmic normal distributed. Table 5-1 also gives
monthly minima, medians, and maxima which are independent of the probability
distribution from which they are derived.
5-7
-------
Table 5-1
Summary Statistics for 1993 NMOC Sites, by Month
Sample
Month
19*3
June
July
August
September
••-••'• -•• •'-. ' v-.-* '.•'•• NMOC Concentration, ppmC : ••" '<' ':';.' "j-lr "
Mb^niUBt
0.069
- 0.085
0.088
0.059
Median
0.260
0.246
0.471
0.279
i-
Mean
0.336
0.272
0.612
0.356
Maximum
.
1.171
0.694
5.749
1.150
Standard
Deviation
0.201
0.125
0.739
0.233
Cases
62
80
89
82
JBS441
5-8
-------
6.0 THREE-HOUR AIR TOXICS DATA SUMMARY
The 1993 NMOC program included 3-hour air toxics sample collection at seven
NMOC sites (see Table 6-1) located in the contiguous United States. Overall
concentration results are reported in ppbv in Section 6.1, and site-specific results are
given in Section 6.2.
Analyses were performed using a GC/MD system incorporating a FID,
photoionization detection (PID), and electron capture detection (ECD). Compound
identifications were made using a combination of retention time ratios for PID/FID
and/or ECD/FID responses, and analyst's experience and judgement. Quantitation was
done using the FID response, with the exception of halogenated compounds that were
quantitated using the ECD. If there was an indication that the quantitation detector
response for the target compound had interference from a known or unknown source,
quantitation was performed on one of the alternate detectors, if possible. Propylene was
quantitated from the PID since the FID has interference a peak (propane) that coelutes
with this compound. Table 6-1 indicates the number of 3-hour samples taken for
GC/MD analyses to speciate for 38 air toxic compounds. Ten analyses were performed
on samples from a given site. One duplicate sample was collected from each site, and
the analysis of one of the samples from each site was repeated. One of the samples
from each site was analyzed by GC/MS for confirmation of compound identification.
Three-hour air toxics samples were regular NMOC or SNMOC Monitoring
Program samples that were collected in 6-L stainless steel canisters from 6:00 a.m. to
9:00 a.m. local time. The final canister pressure was approximately 15 psig. The
samples that were speciated by GC/MD were selected at random during the summer.
Each selected sample was first analyzed by the PDFID method for its total NMOC
concentration or by the SNMOC method for its speciated target compound
concentrations. Then the canister pressure was bled to atmospheric pressure and the
canister bellows valve was closed. The canister was allowed to equilibrate at least 18
tours before the GC/MD analysis was performed.
JBS441
6-1
-------
Table 6-1
Three-Hour Ambient Air Samples and Analyses
:_;•-,_:. ' • .' . .1
Site Code
B1AL
B2AL
B3AL
NWNJ
PLNH
P1PA
P2PA
Total
••••::•• --• I
Ambfefrt
Air Samples
8
8
8
8
8
8
8
56
€
Duplicate
Canister
1
1
1
1
1
1
1
7
C/MDAnafya
Replicate
Analysis
1
1
1
1
1
1
1
7
&
Total
10
10
10
10
10
10
10
70
-
GC/MS
Analyses
1
1
1
1
1
1
1
7
JBS441
6-2
-------
6.1 Overall Results
Concentrations of the air toxic compounds detected are summarized in Table 6-2
for the 1993 three-hour ambient air samples that were speciated. The table shows the
number of cases (samples), the percent of cases in which the compound was identified,
the minimum, maximum, and mean (arithmetic average) concentration of the compound
in ppbv. In cases where duplicate samples were taken, or replicate analyses were
performed, the results of all the analyses were averaged for each sample. The mean
refers to the daily sample averages, not the averages of all the analyses. The frequency
of occurrence of target compounds fall into four prominent percentile categories:
• Those occurring in more than 89% of the samples tested;
• Those occurring from 60% to 66% of the samples tested;
• Those occurring in less than 35% of the samples tested; and
• Those not identified in any of the 3-hour air samples.
These results are summarized in Table 6-3.
The overall concentration ranged from 0.01 ppbv for tetrachloroethylene to
15.18 ppbv for toluene. Chloroprene was present but not quantitated due to an
interference peak on both the FID and PID. Acetylene was not quantitated due to
interference peaks on the FID.
62 Site Results
Tables 6-4 through 6-10 give 3-hour ambient air concentrations by site code for
the 38 air toxics target compounds. The site mean individual target compound
concentration, averaged over all target compounds, ranges from 0.269 ppbv for B2AL to
1.278 for PLNJ. Appendix H contains the tabulations of the complete analytical results
and includes the NMOC concentrations for each of the 3-hour air toxics samples.
JBS441
6-3
-------
Table 6-2
Air Toxics Compound Identifications Summary for All Sites - 1993
*..ifr:' }•:?-:':/ ••••••''" •'•.':"
'i .;' :'.;j ••(?,•. < V.\.-- .-' t : ••••__,. '.. .. \
":•:•• ••::'*?•• ' ••-; : : ' :_ ' ..'£•'-.. \. --.: . V .
•:" ;:;::.;v> ; ': ' Co«pb«i&«.4&:^:'*^;- .
Propylene
Chloromethane
1,3-Butadiene
Methylene chloride
Chloroform
1,1,1-Trichloroethanc
Benzene
Carbon tetrachloride
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
m-Dichlorobenzene
p-Dichlorobenzene
o-Dichlorobenzene
A total of 56 samples were collected and
CMM?
'MJMidLJ-hAA'-
wwBucr
51
6
20
4
56
56
56
56
6
56
37
56
4
52
56
34
50
1
8
6
ftefCCfllr
Ptequeftty
91.07
10.71
35.71
7.14
100.00
100.00
100.00
100.00
10.71
100.00
66.07
100.00
7.14
92.86
100.00
60.71
89.29
1.79
14.29
10.71
Minimum
foi**>
0.08
0.42
0.03
0.52
0.02
0.26
0.09
0.20
0.19
0.16
0.02
0.01
0.02
0.02
0.09
0.02
0.06
0.52
0.10
0.06
Mfloonnun
(«**)
11.03
0.79
0.31
3.28
0.28
4.24
3.09
0.46
0.61
15.18
0.57
1.82
0.05
1.67
8.41
0.55
3.92
0.52
0.43
0.27
• MeiwT'
(I**)
1.82
0.61
0.12
2.41
0.07
1.01
0.64
0.30
0.41
2.41
0.09
0.24
0.04
0.30
1.35
0.13
0.75
0.52
0.21
0.15
jrliMF.
: <**/**)
3.19
1.27
0.27
8.52
0.36
5.63
2.08
1.91
2.21
9.24
0.41
1.67
0.18
1.31
26.06
0.55
8.54
3.18
1.31
0.91
Mean4
fop*)
1.66
0.15
0.07
0.22
0.07
1.01
0.64
0.30
0.05
2.41
0.06
0.24
0.01
0.28
1.35
0.08
0.67
0.02
0.07
0.02
"•|fti^
(a**)
1.66
0.06
0.04
0.17
0.07
1.01
0.64
0.30
0.04
2.41
0.06
0.24
0.00
0.28
1.35
0.08
0.67
0.01
0.03
0.02
analyzed by CKJ/MD.
hfhe percent of the total in which the compound was identified.
°The arithmetic average concentration of all the compound identification cases.
''The arithmetic average concentration of all the sample cases using half the MDL values for compoiunds not
"The arithmetic average concentration of all the sample cases using zero for compounds not detected.
detected.
-------
Table 6-3
1993 Air Toxic Compounds Frequency of Occurance
Frequency of
Occurrence Range
Target Compounds
89 to 100
Propylene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
o-Xylene/1,1,2,2-Tetrachloroethane
Toluene
60 to 66
Styrene
n-Octane
>0to35
1,3-Butadiene
Chloromethane
Methylene chloride
Trichloroethylene
m-Dichlorobenzene
p-Dichlorobenzene
o-Dichlorobenzene
Chlorobenzene
Zero
Acetylene*
Vinyl chloride
Bromomethane
Chloroprene"
Bromochloromethane
Bromodichloromethane
cis-l,3-Dichloropropylene
trans- 1,3-Dichloropropylene
1,1,2-Trichloroethane
Dibromochloromethane
aNot quantitated due to interference peaks.
JBS441
6-5
-------
Table 64
Air Toxics Compound Identifications Summary for B1AL - 1993
/
Propylene
1,3-Butadiene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-TetrachIoroethane
o-Dichlurobenzene
Cm**
8
3
8
8
8
8
8
4
8
8
8
5
7
1
Minimum
0.46
0.04
0.03
0.30
0.21
0.22
0.55
0.02
0.03
0.08
0.31
0.03
0.35
0.16
MttinMBtt
'i
2.41
0.33
0.28
2.46
2.84
1.85
7.70
0.42
0.76
1.72
34.56
0.39
12.16
0.98
'••v.-Meatf
?~-fc«^
1.38
0.09
0.06
0.44
0.87
0.29
2.01
0.05
0.11
0.39
1.79
0.06
0.94
0.03
::s-.Mii&'ty
^fcfcC^
138
0.06
0.06
0.44
0.87
0.29
2.01
0.04
0.11
0.39
1.79
0.06
0.93
0.02
*A total of 8 samples were collected and analyzed by GC/MD.
''The arithmetic average concentration of all the compound identification cases.
cThe arithmetic average concentration of all the sample cases using half the MDL values for compounds not detected.
dThe arithmetic average concentration of all the sample cases using zero.
-------
Table 6-5
Air Toxics Compound Identifications Summary for B2AL - 1993
.
._
Compomd
Propylene
1,3-Butadiene
Chloroform
1,1,1 -Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
o-Dichlorobenzene
Owor*
8
2
8
8
8
8
8
5
8
6
8
5
6
1
Mnrjitttnm
.
CMw)
0.08
0.06
0.03
0.26
0.09
0.20
0.16
0.02
0.01
0.04
0.14
0.02
0.11
0.27
Mtaffonwmn
JPPH
1.39
0.08
0.11
0.38
0.59
0.35
1.23
0.03
0.06
0.17
0.67
0.13
0.42
0.27
Mean**
(W * *»'•'•'
C»«M
1.06
0.16
0.27
1.80
0.95
1.84
2.38
0.10
0.28
0.44
7.61
0.23
3.00
1.65
Mean*
-------
Table
Air Toxics Compound Identifications Summary for B3AL - 1993
i •% 4^'
<*'-'*Li*'^' 5
Propylene
Chloromethane
Methyicne chloride
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
'::V»&tt**-:::;;.:
• • CPfWVI :"'•;:
0.34
0.16
0.42
0.05
0.47
0.29
0.31
0.77
0.02
0.38
0.09
0.40
0.04
0.18
'A total of 8 samples were collected and analyzed by GC/MD.
bThe arithmetic average concentration of all the compound identification cases.
^e arithmetic average concentration of all the sample cases using half the MDL values for compounds not
*The arithmetic average concentration of all the sample cases using zero.
detected.
-------
Table 6-7
Air Toxics Compound Identifications Summary for NWNJ - 1993
;••-'.
' » >* .4 •- '
Oowpwwwl .;•;•:•:•; . ;;;;;;
Propylene
1,3-Butadiene
Methylene chloride
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon CeCrachloride
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-TetrachIoroethane
p-Dichlorobenzene
f*V-L-r«*
8
4
1
8
8
8
8
3
8
8
8
1
8
8
8
8
2
Minima*
.
(JPPW1)
1.05
0.03
3.00
0.02
1.23
0.26
0.24
0.33
1.12
0.03
0.12
0.05
0.12
0.62
0.05
0.31
0.16
Jfc,^^
> *• -v
\P&W
11.03
0.30
3.00
0.20
4.24
2.11
0.39
0.61
10.04
0.57
1.33
0.05
1.67
8.41
0.52
3.92
0.16
Mean1'
(ppt^
3.47
0.14
3.00
0.08
2.17
0.78
0.33
0.45
3.58
0.18
0.39
0.05
0.50
2.45
0.16
1.15
0.16
'• Mean* •'
(pg/ar)
6.06
0.30
10.59
0.38
12.04
2.55
2.09
2.48
13.71
0.84
2.68
0.23
2.20
47.42
0.69
13.07
0.98
Mean*
(PP^"1)
3.47
0.09
0.42
0.08
2.17
0.78
0.33
0.17
3.58
0.18
0.39
0.02
0.50
2.45
0.16
1.15
0.07
^j^A j"
•... ,. • •': .
•.'• dPI***) : S
3.47
0.07
0.38
0.08
2.17
0.78
0.33
0.17
3.58
0.18
0.39
0.01
0.50
2.45
0.16
1.15
0.04
A total of 8 samples were collected and analyzed by GC/MD.
'The arithmetic average concentration of all the compound identification cases.
cThe arithmetic average concentration of all the sample cases using half the MDL values for compounds not detected.
dThe arithmetic average concentration of all the sample cases using zero.
JBS441
-------
Table 6-8
Air Toxics Compound Identifications Summary for PIPA - 1993
* Coropowl"' ' '
Propylene
Chloromethane
1,3-Butadiene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachlorocthylene
Chlorobcnzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-TetracWoroethane
o-Dichlorobenzene
•'• Cwc**
8
1
3
8
8
8
8
8
5
8
1
6
8
4
6
1
; Hjgy^'^1
H ?
0.55
0.79
0.07
0.03
0.30
0.26
0.21
1.04
0.04
0.11
0.04
0.12
0.53
0.04
0.30
0.11
J'-'fa*^'":--
'• -:. •(«**} 7
3.08
0.79
0.11
0.26
4.00
1.26
0.38
12.16
0.17
0.48
0.04
0.61
2.92
0.42
1.49
0.11
.....__.,...
(«**)
1.62
0.79
0.09
0.11
1.70
0.66
0.29
3.85
0.09
0.27
0.04
0.31
1.3 <>
0.19
0.74
0.11
•pmuf;':
te/w3?
2.83
1.66
0.21
0.53
9.41
2.14
1.85
14.74
0.45
1.83
0.19
1.35
26.00
0.82
8.41
0.67
'••Mao^
-------
Table 6-9
Air Toxics Compound Identifications Summary for P2PA - 1993
• t ,••,. . ••. •. ; COUipOUOU
Propylene
Chloromethane
1,3-Butadiene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Trichloroethylene
Toluene
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m /p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
m-Dichlorobenzene
p-Dichlorobenzene
o-Dichlorobenzene
<*«?
8
1
4
8
8
8
8
3
8
7
8
2
8
8
4
8
1
5
2
Minimum
(ppbv)
0.33
0.42
0.03
0.04
0.45
0.29
0.24
0.19
0.65
0.02
0.09
0.02
0.10
0.44
0.02
0.30
0.52
0.10
0.10
Mammon
(«**>
3.73
0.42
0.08
0.10
1.50
0.80
0.38
0.53
4.40
0.07
0.65
0.04
0.32
1.50
0.11
0.78
0.52
0.43
0.19
Me*ob
1.35
0.42
0.06
0.07
0.84
0.54
0.31
0.36
1.83
0.04
0.26
0.03
0.20
0.92
0.06
0.54
0.52
0.22
0.15
Mean6
2.36
0.88
0.13
0.35
4.63
1.75
2.00
1.95
7.00
0.21
1.81
0.14 .
0.87
17.86
0.25
6.14
3.18
1.36
0.89
, Mean*
1.35
0.14
0.06
0.07
0.84
0.54
0.31
0.14
1.83
0.04
0.26
0.02
0.20
0.92
0.03
0.54
0.07
0.16
0.04
Mian*
1.35
0.05
0.03
0.07
0.84
0.54
0.31
0.13
1.83
0.04
0.26
0.01
0.20
0.92
0.03
0.54
0.07
0.14
0.04
"A total of 8 samples were collected and analyzed by GC/MD.
bThe arithmetic average concentration of all the compound identification cases.
cThe arithmetic average concentration of all the sample cases using half (he MDL values for compounds not detected.
dThe arithmetic average concentration of all the sample cases using zero.
JBS44I
-------
Table 6-10
Air Toxics Compound Identifications Summary for PLNJ - 1993
.. '^~gt\ ' :
Co*npowjtf:"*- -••;• >• •
Propylene
Chloromethane
1,3-Butadiene
Methylene chloride
Chloroform
1,1,1-Trichloroethane
Benzene
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
p-Dichlorobenzene
o-Dichlorobenzene
i'-:
7.52
0.70
0.31
3.28
0.28
4.07
3.09
15.18
0.15
0.74
1.47
7.08
0.55
3.16
0.28
0.06
• Me***
•:^
-------
7.0 THREE-HOUR AER TOXICS TECHNICAL NOTES
This section describes the equipment used to sample and analyze the 3-hour air
toxics samples. Also described are sample handling procedures, sampler certification
procedures, standard generation and instrument calibration procedures, compound
identification procedures, GC/MS compound identification confirmation, QA/QC
procedures, and data records for the 3-hour air toxics compounds.
7.1 SampKng Equipment and Gas Chrornatograph/Multiple Detector
System
The NMOC monitoring program sampling equipment, as described in Section 3.1,
was identical to that used for the 3-hour air toxics sampling. The original sample was
collected as an integrated ambient air sample from 6:00 a.m. to 9:00 a.m., local time,
with a final sample pressure of approximately 15 psig. As stated above, after NMOC or
speciated NMOC analysis, the canister was bled to atmospheric pressure and allowed to
stand at least 18 hours before being analyzed by GC/MD.
The analytical system consisted of a Radian sample interface system and GC/MD.
Figure 7-1 shows the GC/MD sampling system including the sample interface system,
analytical system, and data system. When the 6-port valve was in the sample load mode,
the sample interface served to cryogenically preconcentrate a measurable sample volume.
In the sample inject mode, the cryogenically-focused water and organic compounds were
thermally desorbed and swept by helium carrier gas to the head of the GC column. The
GC oven was programmed so the sample was refocused on the column at subambient
temperatures and then compounds were chromatographically separated. The toxic
organic target compounds are listed in Table 7-1.
The Varian« 3400 gas chromatograph system consisted of a FID, PID, and ECD.
The system used one column (J & W DB-1«, 60 M x 0.32 mm, and 1 pm film thickness)
followed by a 1:10 splitter. The one-tenth portion of the splitter goes to the ECD. The
nine-tenth portion of the splitter goes to the PID and then to the FID. Compound
JBS441
7-1
-------
Sample Interlace System
Analytical System
Data System
l*nt(M
-------
Table 7-1
Three-hour Air Toxics Target Compounds
Compoasd
Acetylene
Propylene
Chloromethane
Vinyl Chloride
1,3-Butadiene
Bromomethane
Chloroethane
Methylene Chloride
trans- 1,2-Dichloroethylene
1, 1 -Dichloroethane
Chloroprene
Bromochloromethane
Chloroform
1,2-Dichloroethane
1, 1, 1-Trichloroethane
Benzene
Carbon tetrachloride
1,2-Dichloropropane
Bromodichloromethane
Trichloroethylene
cis- 1,3-Dichloropropylene
trans- 1,3-Dichloropropylene
1, 1,2-Trichloroethane
Toluene
Dibromochloromethane
CAS Number
74-86-2
115-07-1
74-87-3
75-01-4
106-99-3
74-83-9
75-00-3
75-09-2
156-60-5
75-34-3
126-99-8
74-97-5
67-66-3
107-06-2
71-88-6
71-43-2
56-23-5
78-87-5
75-27-4
79-01-6
10061-01-5
10061-02-6
79-00-5
108-88-3
124-48-1
AIRS Parameter
Code
43206
43205
43801
43860
43218
43819
43812
43802
43827
43813
43835
43836
43803
43815
43814
45201
43804
43829
43828
43524
43831
43830
43820
45202
43832
JBS441
7-3
-------
Table 7-1, Continued
* Compound
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m/p-Xylene/Bromofonn
Styrene
o-Xylene/ 1, 1,2,2-Tetrachloroethane
m-Dichlorobenzene
p-Dichlorobenzene
o-Dichlorobenzene
CAS Number
111-65-9
127-18-4
108-90-7
100-41-4
NA
100-42-5
NA
541-73-1
106-46-7
95-50-1
AIRS Parameter
'"•; {C&ir-*? "r •.'
43233
43817
45801
45203
45111
45220
45112
45806
45807
45805
JBS441
7-4
-------
identification was made using a combination of retention time, ratios of PED/FID and/or
ECD/FTD responses, and analyst experience and judgment. Quantitation was performed
using the FID response, with the exception of halogenated compounds that were
quantitated using the ECD. Propylene was quantitated from the PID as the FID had an
interference peak (propane) with this compound. The sample concentrations were
calculated by using the monthly calibration curve and daily standard response factors
times the sample area counts of each target compound.
7.2 Three-Hour Air Toxics flampling System^ Certification
The sampling systems used to collect 3-hour air toxics samples were certified for
use per the specifications described in the EPA Compendium of Methods TO-14.12
72.1 Sampler Certification Blanks-Humidified Zero Air
Zero certification consisted of purging the sampler with cleaned, humidified air,
followed by collecting a sample of the cleaned, dried air that had been humidified
through the purged NMOC samplers for GC/MD analysis. The purpose of the wet
purge was to help remove any adherent contaminant from the sampler. The
chromatograms from these certification sample analyses were archived for each sampler.
Results showed a range of 0.0 ppbv to 0.32 ppbv (for benzene), with an average of
0.04 ppbv. The sampling systems were determined to be clean and showed no
characteristics of additive bias.
122 Sampler Certification Challenge - Selected Target Compound
Following the NMOC sampler blank certification, a challenge gas containing five
selected target compounds was passed through the samplers. The average concentration
of the compounds in the challenge gas was 15.98 ppbv/species. Average percent
recoveries ranged from 91.12% to 107.74% with an overall average of 100.20 percent.
JBS441
7-5
-------
73 PalihratJon s*ft"*fa**d Preparation
Calibration curves for .the multi-detector included a 5-point calibration initially,
and daily calibration checks at an average 5 ppbv concentration for the target
compounds. The origin of the calibration curve was used as one of the calibration
points.
73.1 Calibration Standard Generation
A monthly calibration of the target compounds was performed by analyzing
humidified standards prepared at levels of approximately 0.5, 1, 3, 5, and 10 ppbv from
Scott* Specialty Gases certified standards. A standard prepared at a level of
approximately 5 ppbv from a Scott* Specialty Gases certified standard was used for daily
calibration. These standards were prepared using the dynamic flow dilution system. The
gases were mixed in a SUMMA*-treated mixing sphere and bled into evacuated
canisters. One dilution air stream was routed through a SUMMA*-treated bubbler
containing HPLC-grade water to humidify, and the other stream was not humidified.
The dilution air streams were brought together to mix with the streams for the certified
cylinders. Flow rates from all five streams (four from the certified cylinders and one
from the dilution cylinder) were gauged and controlled by mass flow controllers. The
split air dilution streams were metered by "wet" and "dry" rotameters from the humidified
and unhumidified dilutions air streams, respectively. The system was evacuated with a
vacuum pump while the closed canister was connected. A precision absolute pressure
gauge measured the canister pressure before and after filling. The lines leading to the
canister and to the mixing sphere were flushed for at least 15 minutes with standard gas
before being connected to the canister for filling.
JBS441
7-6
-------
732 GC/MD Calibration
Initial and monthly calibration curve standards were made at 0.5, 1, 3, 5, and
10 ppbv for each of the target compounds. In addition, the point at 0.0 was considered
to be a calibration point. A linear regression was performed for each of the compounds
with the objective for the correlation coefficient being 0.990 or better (for 5 or 6 points)
for selected compounds on the detector used for quantitation. The zero air used for
canister cleaning and for standards dilution was analyzed at the time of calibration, but
the results were not used in the calibration curve. Daily calibration was done with in-
house standards made from the certified gases with an average concentration of 5 ppbv.
The calibration standard concentrations and area counts for each compound were
entered into a spreadsheet. The result response factors of each compound were
compared to the monthly calibration curve's response factors. An absolute value of the
less than or equal to 30% was the guideline for the quantitated compounds.
All daily calibration data were used to calculate calibration factors for each
compound on each detector. Minima, means, maxima, and standard deviations were
recorded and tabulated for each detector. The FID calibration factors were used for
quantitation for most of the compounds except some halocarbons. The ECD calibration
factors were used in most cases of halqgenated compound quantitation because of the
greater sensitivity of the ECD at low concentrations. The PID calibration factor was
used for propylene.
733 GC/MD Calibration Results
Two calibration curves were used during the analysis period. In the first
calibration curve, 7 of the 38 compound linear regression coefficients were less than
0.990. They ranged from 0.973 to 0.988. The 30% objective was exceeded by 4 of the
38 compounds. They ranged from 30.23 to 37.52 percent.
JBS441
-------
In the second calibration curve, 8 of the 38 compound linear regression
coefficients were less than 0.990. They ranged from 0.940 to 0.988. The 30% objective
was exceeded by 9 of the 38 compounds. They ranged from 30.98 to 66.27 percent.
7.4 Daily Calibration Check
Prior to sample analysis, a 5 ppbv standard was analyzed to ensure the validity of
the current monthly response factor. This daily check was at the middle range of the
calibration curve to show consistency with the monthly calibration curve. The daily
standard concentrations and area counts for each compound were entered into a
spreadsheet. The resulting response factors of.each compound were compared to the
monthly calibration curve's response factors. An absolute value of less than or equal to
30% was the guideline for the quantitated compounds. After acceptance of the daily
standard, a wet zero was analyzed. Resulting concentrations for target amounts of less
than 0.2 ppbv was the objective except for known detector interferences. If more than a
0.2 ppbv concentration was found, a second wet zero was run. If a second wet zero
failed, system maintenance was performed.
7.5 Gas Chromatograph/Mass Spectrometer Analysis and Compound Identification
Confirmation
Seven of the 3-hour air toxics samples were analyzed by GC/MS for compound
identification confirmation following completion of the GC/MD analyses. The GC/MS
was operated in a full scan mode.
No comparison of the quantitative results for GC/MD and GC/MS was made
because the purpose of the GC/MS analyses was compound identification confirmation
only. This comparison is discussed in Section 7.6.1.
JBS441
7-8
-------
7.6 OA/OC Data
Precision was estimated from duplicate samples and repeated analysis. Table 7-2
summarizes the duplicate and replicate analyses performed on the five 3-hour air toxics
samples. Columns headed Dl, R, and D2 were taken from the tables in Appendix H.
Columns Dl and D2 show the results of the samples in duplicate Canisters 1 and 2,
respectively. Column R shows the results of the second analysis of duplicate
Canister Dl. The analytical precision was estimated from the replicate analyses,
Columns R and Dl. The sampling and analytical precisions was estimated from the
duplicate canister analyses.
In the columns under "Replicate Analyses", the following applies:
• Replicate Average represents the average concentrations (in
analyses Columns Dl and R);
• Standard Deviation represents the standard deviation (between analyses
Columns Dl and R);
• %CV (standard deviation/average * 100); and
• Abs %Diff represents the absolute percent difference.
The %CV for replicates ranged from 0.00 to 60.6%, and absolute percent difference
ranged from 0.00 to 85.71 percent. The pooled %CV was 22.01, while the average
absolute percent difference was 20.80. These are excellent results, considering the small
number of samples involved, and compare favorably with previous 3-hour air toxics
replicate analysis results.
Duplicate sample statistics are shown in the last four columns of Table 7-2.
Duplicate average represents the best estimate of the sample mean. It was calculated
first by averaging Columns Dl and R analyses in the first duplicate canister and then
averagmg the first average with Column D2. The duplicate standard deviation was
calculated using the average of Columns Dl and R and comparing it with Column D2.
JBS441
7-9
-------
Table 7-2
1993 NMOC Three-Hour Replicate and Duplicates, ppbv
<
Oowpwwdl
Dl
*
D2
" RcftBa^AJtttytts ;"
Avenge;
Standard
IKWIPOW
. :-:: •.
'•#CV'
Ahtdlute
%vm
•.'/..?..: •:,-.,.•.. -V'i:
DvpSctte
: Awwapp:'
DIAL
Propylene
1,3-Butadiene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/l,l,2,2-TetrachJoroe thane
1.00
0.05
0.03
0.29
0.54
0.22
1.16
0.15
0.07
0.20
0.93
0.06
0.47
0.83
0.02
0.03
0.32
0.65
0.24
1.13
0.10
0.08
0.19
0.88
0.06
0.49
0.76
0.06
0.05
0.30
0.64
0.22
1.33
0.12
0.08
0.24
1.18
0.08
0.57
0.915
0.035
0.030
0.305
0.595
0.230
1.145
0.125
0.075
0.195
0.905
0.060
0.480
0.120
0.021
0.000
0.021
0.078
0.014
0.021
0.035
0.007
0.007
0.035
0.000
0.014
13.138
60.609
0.000
6.955
13.073
6.149
1.853
28.284
9.428
3.626
3.907
0.000
2.946
18.579
85.714
0.000
9.836
18.487
8.6%
2.620
40.000
13.333
5.128
5.525
0.000
4.167
0.838
0.048
0.040
0.303
0.618
0.225
1.238
0.123
0.078
0.218
1.043
0.070
0.525
...-..: Duplicate
Standard
Ekrviation
0.110
0.018
0.014
0.004
0.032
0.007
0.131
0.004
0.004
0.032
0.194
0.014
0.064
A*4fc^.V^K'
;:%ar.;
13.087
37.216
35.355
1.169
5.153
3.143
10.571
2.886
4.562
14.630
18.653
20.203
12.122
Ahwlute
•'•%*>»;
18.507
52.632
50.000
1.653
7.287
4.444
14.949
4.082
6.452
20.690
26.379
28.571
17.143
B2AL
Propylene
1,3-Butadiene
Chloroform
1.50
0.09
0.04
1.19
0.05
0.07
1.47
0.09
0.23
1.345
0.070
0.055
0.219
0.028
0.021
16.298
40.406
38.569
23.048
57.143
54.545
1.408
0.080
0.143
0.088
0.014
0.124
6.280
17.678
86.838
8.881
25.000
122.807
-------
Table 7-2
Continued
V
Compound
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
ra/p-Xylene/Bromoform
Styrene
o-Xylenc/l,l,2,2-Tetrachloroethane
m
0.29
0.44
0.22
1.03
0.03
0.04
0.15
0.62
0.11
0.36
*•>.
0.34
0.61
0.23
1.25
0.05
0.17
0.72
0.17
0.55
•''!&,.
0.29
0.41
0.21
1.09
0.02
0.08
0.15
0.63
0.10
0.36
.. !' Replicate Aaaityx* . ' _'.. . _
Rftnlirate
"Mi i • "•""••}
Average
0.315
0.525
0.225
1.140
0.045
0.160
0.670
0.140
0.455
Standard
Deviation
0.035
0.120
0.007
0.156
0.007
0.014
0.071
0.042
0.134
•- • •". -:';: •"•:'•
=:*cv:-.
11.224
22.897
3.143
13.646
15.713
8.839
10.554
30.305
29.528
Absolute
fcfciff
15.873
32.381
4.444
19.298
22.222
12.500
14.925
42.857
41.758
, , y; Dtipfcate Aaafytt* ' * ' V:'.?. ; ' • • •
Duplicate
Average..
0.303
0.468
0.218
1.115
0.063
0.155
0.650
0.120
0.408
Standard
Deviation
0.018
0.081
0.011
0.035
0.025
0.007
0.028
0.028
0.067
:;#ev' :
5.844
17.394
4.877
3.171
39.598
4.562
4.351
23.570
16.485
Abjdfute/
• *iwir,'-
8.264
24.599
6.897
4.484
56.000
6.452
6.154
33.333
23.313
B3AL
Propylene
Methylene Chloride
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
1.40
2.61
0.06
0.70
0.61
0.24
1.81
1.46
0.09
0.83
0.93
0.29
2.45
1.84
3.09
0.06
0.69
0.61
0.24
1.73
1.430
0.075
0.765
0.770
0.265
2.130
0.042
0.021
0.092
0.226
0.035
0.453
2.967
28.284
12.016
29.386
13.342
21.246
4.1%
40.000
16.993
41.558
18.868
30.047
1.635
0.068
0.728
0.690
0.253
1.930
0.290
0.011
0.053
0.113
0.018
0.283
17.732
15.713
7.290
16.397
7.001
14.655
25.076
22.222
10.309
23.188
9.901
20.725
JBS411
-------
Table 7-2
Continued
^ ' '•„•.
: > '
< ::-
n-Octanc
Tetrachloroethylene
Ethylbenzene
m/p-Xylenc/Bromofonn
Styrene
o-Xylene/ 1, 1,2,2-Tetrachloroethane
'< "'•
m
0.03
1.87
0.23
0.93
0.11
0.45
K
1.74
0.26
1.15
0.14
0.61
m
0.04
1.84
0.22
0.92
0.14
0.49
Replied A*ab«a
IfanlartMta
-n.u|nmjM«i
. Average ..
1.805
0.245
1.040
0.125
0.530
Standtatd
CkcvMfMNI
0.092
0.021
0.156
0.021
0.113
#cv
5.093
8.658
14.958
16.971
21.347
NWNJ
Propylene
Chloroform
1,1, i it hloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
1.11
0.04
4.59
0.30
0.31
1.99
0.05
0.35
0.27
1.23
0.18
1.09
3.93
0.25
0.24
1.73
0.04
0.29
0.21
1.02
0.11
0.%
0.03
3.%
0.22
0.25
1.58
0.28
0.21
1.05
0.12
1.100
4.260
0.275
0.275
1.860
0.045
0.320
0.240
1.125
0.145
0.014
0.467
0.035
0.049
0.184
0.007
0.042
0.042
0.148
0.049
1.286
10.955
12.856
17.999
9.884
15.713
13.258
17.678
13.199
34.136
Absolute
*ttiff
7.202
12.245
21.154
24.000
30.189
1.818
15.493
18.182
25.455
13.978
22.222
18.750
25.000
18.667
48.276
Duplicate Aiufytt*
Dupfcate
AVWUjpB-
1.823
0.233
0.980
0.133
0.510
1.030
4.110
0.248
0.263
1.720
0.300
0.225
1.088
0.133
Standard
Deviation
0.025
0.018
0.085
0.011
0.028
0.099
0.212
0.039
0.018
0.198
0.028
0.021
0.053
0.018
*ev
1.358
7.603
8.658
8.005
5.546
9.611
5.161
15.713
6.734
11.511
9.428
9.428
4.877
13.342
Ahtftfcrtft
%vm
1.920
10.753
12.245
11.321
7.843
13.592
7.299
22.222
9.524
16.279
13333
13.333
6.897
18.868
-------
Table 7-2
Continued
% *' : *s
•* WWffVWM
o-Xylene/l,l,2,2-Tetrachloroethane
p-Dichlorobenzene
m
0.64
0.16
R
0.41
m
0.40
... ; . • .' ';.;. Itapfcate Analytics, •' .
8an&ate
Avcngp
0.525
Standard
0.163
•<**•
30.978
Absolute
43.810
: '• :.:.." Duplicate Anafytit* ;,/: .By' '
- Average
0.463
Standard
Deviation
0.088
.'*of'
19.111
AbMtute
27.027
-
P1PA
Propylene
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
0.61
0.02
0.26
0.26
0.20
0.70
n-Octane
Tetrachloroethylene
Ethylbenzene
m/p-Xylene/Bromoform
0.20
0.09
0.45
Styrene
o-Xylene/ 1, 1,2,2-Tetrachloroet hane
0.31
0.57
0.02
0.30
0.26
0.22
0.77
0.03
0.28
0.10
0.51
0.33
0.59
0.04
0.35
0.26
0.22
2.28
0.26
0.16
0.67
0.04
0.32
0.590
0.020
0.280
0.260
0.210
0.735
0.240
0.095
0.480
0.320
0.028
0.000
0.028
0.000
0.014
0.049
0.057
0.007
0.042
0.014
4.794
0.000
10.102
0.000
6.734
6.734
23.570
7.443
8.839
4.419
6.780
0.000
14.286
0.000
9.524
9.524
33.333
10.526
12.500
6.250
0.590
0.030
0.315
0.260
0.215
1.508
0.250
0.128
0.575
0.320
0.000
0.014
0.049
0.000
0.007
1.092
0.014
0.046
0.134
0.000
0.000
47.140
15.713
0.000
3.289
72.470
5.657
36.049
23.365
0.000
0.000
66.667
22.222
0.000
4.651
102.488
8.000
50.980
33.043
0.000
P2PA
Propylene
1,3-Butadiene
1.75
0.07
1.45
0.08
1.41
0.08
1.600
0.075
0.212
0.007
13.258
9.428
18.750
13.333
1.505
0.078
0.134
0.004
8.927
4.562
12.625
6.452
JBS411
-------
Table 7-2
Continued
''
f ^•"•WWjprv WIFW ^ ^
Chloroform
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
Toluene
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/1,1,2,2 i . Irachloroethane
01
0.05
0.69
0.79
0.25
2.38
0.09
0.73
0.02
0.29
1.46
0.10
0.75
*
0.04
0.63
0.85
0.24
2.30
0.50
0.33
1.44
0.58
m
0.07
0.67
0.77
0.24
2.32
0.05
0.72
0.28
1.40
0.12
0.72
••,.,- • - Refi&ate Analyse*
RedEkate
Awn*...
0.045
0.660
0.820
0.245
2.340
0.615
0.310
1.450
0.665
Dcvwtioa
0.007
0.042
0.042
0.007
0.057
0.163
0.028
0.014
0.120
,*cv
15.713
6.428
5.174
2.886
2.417
26.445
9.124
0,975
18.076
Absolute
22222
9.091
7.317
4.082
3.419
37.398
12.903
1.379
25.564
pupi^Attipi*
*&
0.058
0.665
0.795
0.243
2.330
0.668
0.295
1,425
0.693
£££
0.018
0.007
0.035
0.004
0.014
0.074
0.021
0,035
0.039
*cv
30.744
1.063
4.447
1.458
0.607
11.123
7.191
2.481
5.616
*%£
43.478
1.504
6.289
2.062
0.858
15.730
10.169
3,509
7.942
PLKI
Propylene
1,3-Butadiene
Chloroform
1,1,1-Trichloroetbane
Benzene
3.29
0.11
0.05
0.60
1.20
3.12
0.09
0.02
0.48
1.06
3.62
0.15
0.05
0.52
1.02
3.205
0.100
0.035
0.540
1.130
0.120
0.014
0.021
0.085
0.099
3.751
14.142
60.609
15.713
8.761
5.304
20.000
85.714
22.222
12.389
3.413
0.125
0.043
0.530
1.075
0.293
0.035
0.011
0.014
0.078
8.599
28.284
24.957
2.668
7.236
12.161
40.000
35.294
3.774
10.233
-------
Table 7-2
Continued
. ••:;..: :••;•• ' •;•; yi ;• • •• ^\nggfgmgJJL \ \-: '':, '' •'_ 'v y . ' ..
•.-.•....•.•. .•./:?':.. "™'JTT*.""T.:: :...::: •••'••
Carbon tetrachloride
Toluene
n-Octane
Tctrachloroethylene
Elhylbenzene
m/p-Xylenc/Bromoform
Styrene
o-Xylene/l,l,2,2-Tetrachloroethane
' ' ::< : .. .-.'
?>r^v;
•?& '
0.26
4.69
0.09
0.15
0.49
2.32
0.22
1.20
*
0.23
3.80
0.11
0.34
1.61
0.28
1.98
m
0.22
4.03
0.10
0.14
0.38
1.83
0.17
0.88
Average
Median
Cases
Pooled Standard Deviation
Pooled %CV
Rfipncdte AttaiytiCS • •'
Hm&f*t*
i ™ j
Avenge
0.245
4.245
0.130
0.415
l.%5
0.250
1.590
0.694
0.315
80
Standard
Deviation
0.021
0.629
0.028
0.106
0.502
0.042
0.552
0.153
^.#CV:;
8.658
14.825
21.757
25.558
25.549
16.971
34.688
22.014
Absolute
%TW
12.245
20.966
30.769
36.145
36.132
24.000
49.057
20.804
:' . •' • Duplicate Analyse* :•-.• %:t,£;
Duplicate
'AWIIBR
0.233
4.138
0.135
0.398
1.898
0.210
1.235
0.702
0.309
79
Standard
Deviation
0.018
0.152
0.007
0.025
0.095
0.057
0.502
0.161
v#<*v::."
7.603
3.674
5.238
6.226
5.031
26.937
40.651
22.888
AbMlote
•"' %'t&HV
10.753
5.1%
7.407
8.805
7.115
38.095
57.490
19.213
•-4
JBS4H
-------
The %CV for duplicates was calculated as the quotient of the standard deviation and the
average, multiplied by 100. Finally, the absolute percent difference was calculated from
the difference between the average concentrations of the duplicate canisters, divided by
the average concentration in the duplicate canisters, expressed as a percentage. The
%CV ranged from 0.00 to 86.84. The pooled %CV was 22.89. Absolute percent
difference ranged from 0.00 to 122.81. The average absolute percent difference for
duplicates was 19.21, which is an excellent result.
7.6.1 GC/MS Confirmation Results
Based on seven GC/MS analyses of the 3-hour air toxics samples, one from each
site location, the following results were obtained. The GC/MS analyses confirmed
93.19% of the GC/MD analyses. The results are summarized in Table 7-3, showing
13.61% positive GC/MD-positive GC/MS confirmation, 3.67% positive GC/
MD-negative GC/MS comparisons 3.14% negative GC/MD-positive GC/MS
comparisons, and 79.58% negative GC/MD-negative GC/MS confirmation.
1.62 External Audits
The external audit for the 3-hour air toxics compounds was conducted with the
SNMOC external audit. Table 7-4 presents the results from the external audit. The
external audit sample was provided by an EPA contractor.
7.7 Sample Dilutions
Upon review of the sample analysis results, when a compound concentration was
outside the calibration range, the sample was diluted and reanalyzed for the compound
or compounds out of range. The dilutions were performed in accordance with the
Radian SOP, "Standard Operating Procedure for Dilution of Canister Samples Using the
Vacuum Assessment Dilution System."
JBS441 7'16
-------
Table 7-3
Compound Identification Confirmation
GC/MD versus GC/MS Comparison*
Positive GC/MD - Positive GC/MS
Positive GC/MD - Negative GC/MS
Negative GC/MD - Positive GC/MS
Negative GC/MD - Negative GC/MS
Total
:'- -Cases .-'.'.;
26
7
6
152
191
Percentage
13.61
3.67
3.14
79.58
100.00
Total compound identification confirmation = 13.61% + 79.58% = 93.19%
"There were 47 cases where the GC/MD identified a compound at a concentration
below the detection limit of the GC/MS.
JBS441
7-17
-------
Table 7-4
Three-hour Toxics External Audit Results
Compound
Benzene
Toluene
Ethylbenzene
m/p-Xylene/Bromoform
o-Xylene/ 1, 1,2,2-Tetrachlorethane
Spiked
0.0
0.0
9.3
9.3
9.0
* :
Reported ;
0.02
0.03
3.8
9.1
13.2
jM "%;,;; %\
Difference
NAa
NA
-59.1
-2.2
46.7
•NA = Not Applicable.
JBS441
7-18
-------
The procedure required that the canister be connected to the vacuum assessment
system. The initial canister vacuum was recorded and the canister was then filled with
nitrogen to a known final pressure. The room temperature and barometric pressure at
the time of dilution were also recorded. The initial vacuum, final pressure, room
temperature, and barometric pressure were used to calculate the dilution factor. The
sample was allowed to equilibrate for at least 18 hours. The sample was then bled to
atmospheric pressure, allowed to equilibrate for an additional 18 hours and reanalyzed.
Analysis was only for the compound or compounds initially out of the calibration range.
For the 1993 NMOC program, four samples were diluted by the procedure
outlined above. Sample 1209 (P1PA) was diluted for toluene and Sample 1751 (PLNJ)
was diluted for toluene and propylene. Because of low initial sample pressures,
Samples 1754 (NWNJ) and 1752 (P1PA) were also diluted in order to achieve a required
minimum sample pressure for GC/MS analysis. Because the GC/MS analysis was
performed prior to the GC/MD analysis for these two samples, the dilution factor was
applied to both GC/MS and GC/MD analysis results.
7.8 Data Records
Data records for the 3-hour air toxics samples included:
• NMOC concentration of the sample;
• Copies of the gas chromatographic trace for FID, PID, and ECD;
• Response data on removable hard disk;
• Retention times for each compound; and
• Area counts for each detector.
In addition, daily calibration response factors were recorded on magnetic disk
along with the retention time and area counts for each compound in the standard.
JBS441
-------
8.0 CARBONYL COMPOUNDS SAMPLING, ANALYSIS, AND QUALITY
ASSURANCE PROCEDURES
Carbonyl sampling and analysis procedures and QA procedures used to assess
data quality are described in this section.
8.1 Data
Analytical results of ambjent air samples and trip blanks for carbonyl compounds
at Plainfield, New Jersey (PLNJ) and Newark, New Jersey (NWNJ) are given in
Tables 8-1 and 8-2, respectively. The concentrations of targeted carbonyl compounds in
the trip blanks were calculated assuming the sample volume calculated for the
accompanying samples. In cases where duplicate samples were taken, or replicate
analyses were performed, the results of all the analyses were averaged for each sample.
The mean refers to the daily sample averages, not the averages of all the analyses. The
concentrations given for the samples were not blank corrected. Table 8-3 gives the
average, maximum, and minimum carbonyl concentration as well as the standard
deviation and frequency of occurrence for each of the targeted carbonyl compounds for
PLNJ. Table 8-4 gives the same statistical values listed above for NWNJ. For PLNJ, the
average of those compounds identified ranged from 0.063 ppbv for acetaldehyde to
42.02 ppbv for formaldehyde. For NWNJ, the average of those compounds identified
ranged from 0.75 ppbv for acetaldehyde to 14.54 ppbv for acetone.
8.2 Sampling Equipment and Procedures
A schematic diagram of the 3-hour carbonyl sampling sub-system is shown in
Figure 8-1. The 3-hour carbonyl sampling subsystem collects a discrete sample
concurrent with the collection of the NMOC canister sample through the use of a
common control system.
JBS441 8*1
-------
Table 8-1
1993 NMOC Plainfieid, New Jersey Carbonyl Results
NMQCS*»pfclD
Dal* Pile ID
I)*teS«mj)ldl
THtftt IRnfuwtei
Dwtd AmwyWHi
DtatioanMtar
imA
«.?•>
RC3Z784
OB/04/»
10/05/93
W)/Ol$/9)
* LOO
imADUF
fltfNV
ROZ7B5
mivtflte:
«W»;:I
W&fn&..fi-
Utia.1- /.A
mz-B
. v:..'.12£WO;.::.
•; v iowii^:
>fl$/0«M
«Wft*%
«vw*<
u»
1222-BDUP
,^.mjW; ;'•>
••? ':VIX%XVft» '
;«vo«^
IO/05/*»
«vov»: :::
--'.luoo -.--'
immK
RC32788
^r «8/04/!l>
10/05/93
10/tf/»
tl»
122^BUtDUP
'^•-jafcwf
RC32789
:^Q8/0«/»
10/DlS/W
IO/OS/W
."•••uoo :;',-•
1630*B
12WMf
RO27811
Q8/i3/9i;
10/05/93
10/ttS/«
100
165ft*
12091
8027814
«/tw
10/05/93
W/05/93
; U»?;--:
Concentration (ppbv)
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyr aldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2,5-Dimethylbenzaldehyde
7.46
5.19
NDb
14.46
ND
ND
ND
ND
ND
ND
ND
ND
ND
8.24
6.09
ND
15.30
ND
ND
ND
ND
ND
ND
ND
ND
ND
8.98
4.54
ND
13.93
0.47
0.34
0.94
ND
ND
ND
ND
0.42
ND
Sample volume is assumed to be the same as the accompanying samples for
bND = Not Detected.
'Estimated concentration is less than the detection limit for the given sample
9.26
4.35
ND
13.33
0.34C
0.44
ND
ND
ND
ND
ND
0.48
ND
7.52
1.24
ND
3.11
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.67
1.38
ND
3.32
ND
ND
ND
ND
ND
ND
ND
ND
ND
4.69
2.78.
ND
4.41
ND
ND
ND
ND
ND
ND
ND
ND
ND
12.22
4.32
ND
8.08
o.or
ND
ND
ND
ND
ND
ND
ND
ND
blank samples.
volume.
oo
K)
JBS441
-------
Table 8-1
Continued
NMOC Sample ID
jfiupuun ITWWMT .- •
Concentration (ppbv)
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2,5-Dimethylbenzaldehyde
10fl&f9$ ..
tt/fc/»i;^
•AjWI . f
42.02
5.35
0.92
10.64
O.^
ND
1.08
0.07°
ND
0.75
ND
2.62
ND
1838-B
KM*
RC327822
09/03/93
10/05/93
iflo
***»
5.58
6.60
ND
7.64
ND
ND
0.40
ND
ND
ND
ND
0.100
ND
1832-B
RO27&25
09/08/93
10/05/93
MMlr
4.43
1.24
ND
3.09
ND
ND
ND
ND
ND
ND
ND
ND
ND
195841
tltll
RC327B33
09/17/W
10/05/93
too
3.51
0.63C
ND
2.06
ND
ND
ND
ND
ND
ND
ND
ND
ND
1957-B
WCXZftM
09/20/93
10/05/93
10/06/93
ifid
2.89
1.16
ND
4.17
ND
ND
ND
ND
ND
ND
ND
ND
ND
RC327836
10/05/93
.:
3.64
1.21
ND
2.%
ND
ND
ND
ND
ND
ND
ND
ND
ND
203W& -
RC3278»
10/05/93
2.77
0.%
ND
3.69
ND
ND
ND
ND
ND
ND
ND
ND
ND
Sample volume is assumed to be the same as the accompanying samples lor blank samples.
bND = Not Detected.
cEstimated concentration is less than the detection limit for the given sample volume.
-------
Table 8-2
1993 NMOC Newark, New Jersey Carbonyl Results
NMOC Sample H>
D*f*BleID
ftftffi fljjmnAjgf
Date Extracted
D&Xtaft P**ot
IS&A
14U5
RC32794
08/04/93
10/05/93
W/06/93
JJO
1533-ADUP
I4M5
RC32795
08/04/W
IO/05/9S
J4/&6/&M
UOG ••:••>»
153MB
I4SJS
RCS2796
08/04/S3
10/05/fc*
10/06/93
U»
1533-BDUP
RC3i239T
«yO
-------
Table 8-2
Continued
%
... J± • « ? ^
IjHKB uflDKDlOfll ''^ ^ vi
i&utioftfacto* ,",.... , V;
CoocentralMM (pplw)
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/lsohutyr aldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolual I- liydes
Hexanaldehyde
2,5-Dimetbylbenzaldehyde
V-lttJ*
RC327919
08/26/93
10/05/93
10/07/95
100
1790-B
ii&Sft
RC3Z79231
08/30/9$
10/05/93
10/07/98
too
18&A
14L45
RC327924
10/05/93
10/07/93
100
1839-B
139.4Q
RC327930
09/08/93
10/05/93
10/07/93
LOO
tfcMQ
RC32793J
09/16/S3
10/05/93
10/07/93
IjOO
1971-B
143^0
RC327936
09/20/93
10/05/93
W/07/93
UOO
2030-B
RC327939
10/05/93
10/07/93 -
100
5.94
2.82
ND
14.54
ND
0.13C
ND
ND
ND
ND
ND
0.38
ND
7.87
3.76
ND
8.18
0.31C
0.13C
0.04C
ND
ND
ND
ND
0.52
ND
2.61
2.57
ND
2.44
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.41
1.53
ND
3.16
ND
0.08C
ND
ND
ND
ND
ND
ND
ND
2.14
0.75
ND
2.48
ND
ND
ND
ND
ND
ND
ND
ND
ND
3.76
2.01
ND
9.28
ND
ND
0.40
ND
ND
ND
ND
ND
ND
2.86
1.14
ND
3.19
ND
ND
ND
ND
ND
ND
ND
ND
ND
Sample volume is assumed to be t e same as the accompanying samples for blank samples.
bND = Not Detected.
cEstimated concentration is less than the detection limit for the given sample volume.
I/I
-------
Table 8-3
1993 NMOC Plainfield, New Jersey Site Summary
Awty*
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/IsobutyraJdehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-DimethyIbenzaldehyde
A?cngc
•.V;:':Cdbc-'- •
fa**
9.02
2.93
0.09
6.10
0.05
0.02
0.17
0.01
ND
0.08
ND
0.29
ND
Mmmmn
' <• Coat - - "
42.02
6.60
0.92
14.26
0.20
0.20
1.08
0.07
ND
0.75
ND
2.62
ND
. . m •*>* * ' : -.
' '.-CM*-: •:
fcpfcr)
2.77
0.63
0.00
2.06
ND*
ND
ND
ND
ND
ND
ND
ND
ND
Standard
Deviatiaa
1135
2.09
0.28
3.76
0.08
0.06
033
0.02
ND
0.23
ND
0.78
ND
Frequency
(%>
100
100
10
100
30
10
30
10
ND
10
ND
30
ND
a _
= Not Detected.
JBS441
8-6
-------
. Table 8-4
1993 NMOC Newark, New Jersey Site Summaiy
Analyte
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyr aldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
AHMMMMM
Average
fv—*
lufOBC
936
4.09
ND
14.54
0.41
0.68
1.07
ND
ND
0.41
ND
1.01
ND
Uuinnmi
•WWMUHU-
ViOHCi
tort
2.14
0.75
ND
2.44
ND
ND
ND
ND
ND
ND
ND
ND
ND
4&*n
100
100
ND
100
20
40
30
ND
ND
10
ND
30
ND
aND = Not Detected.
JBS441
8-7
-------
Sample Manifold
To NMOC
Collection System
By-Pass
Pump
Programmable
Electronic
Timer
^Temperature Controlled
Ozone Scrubber
110 VAC
Line Supply
Figure 8-1. 3-Hour Carbonyl Sampling Subsytem
8-8
-------
Ambient air was drawn from a glass manifold, through an ozone scrubber, and
then through the carbonyl sample cartridges. The ozone scrubber was maintained at
200°F to prevent moisture condensation. The carbonyl samples were collected in
duplicate parallel cartridges during each sample collection period. The carbonyl
cartridges used were commercially available (Waters Co.) silica gel DNPH-coated
Sep-Pak* cartridges.
The carbonyl cartridges were installed in the sampling sub-system one day prior to
scheduled sample collection. A 3-hour sample collection period, concurrent with the
NMOC canister collection, was utilized. In addition to the carbonyl cartridges installed
in the sampling sub-system, a third cartridge was transported to the site as a trip blank or
spare cartridge.
The flow rates through each of the duplicate carbonyl samples were controlled by
flow restrictors (or critical orifices). The collection flow rates were quantified and the
rotameters were calibrated before the sampling sub-systems were shipped to the sites.
The volume of ambient air sampled through each cartridge was calculated in the Radian
RTF laboratory based on the field-recorded sampling duration and flow rate information.
83 Analytical Procedures
The analytical procedures for carbonyls are given below. Sample preparation and
analyses were performed at the Radian RTF laboratory. The preparation procedures of
the cartridge samples are as follows:
• Remove cartridge from its shipping container.
• Attach cartridge to the end of a 10-mL glass syringe.
• Add 4 milliliters of acetonitrile to the syringe and catch drainage in a
graduated centrifuge tube.
• After the syringe has finished draining, add acetonitrile to the graduated
centrifuge tube until the total volume is 4 milliliters, and mix the solution.
JBS441
-------
• Transfer the solution in the graduated centrifuge tube to a 4-mL sample
vial fitted with a Teflon®-lined self-sealing septum.
• Store the solution in a refrigerator until analysis.
The EPA Method TO-II13 high pressure liquid chromatography (HPLC) column
and elution solvents used for this analysis were modified to decrease analysis time, as
shown in the following gradient elution, at a flow rate of 0.9 ml/min:
Time (Min.) % Water % Acetonitrile % Methanol
0.0 40 20 40
12 25 5 70
18 23 5 72
28 15 10 75
32 40 20 40
For the analysis, 25 //I samples are injected with an automatic sampling injector.
Compound separation is accomplished using a 25 cm x 4.6 mm CIS 5-micron particle
size analytical column. Output signals from a multi-wavelength ultraviolet (UV) detector
are collected for 39 minutes at 360 nanometers (nm).
Chromatographic peaks for targeted compounds were determined by retention
time, the area of the integrated peak, and concentrations calculated using calibration
curves.
Target carbonyl compounds detected were formaldehyde, acetone, acetaldehyde,
acrolein, propionaldehyde, crotonaldehyde, butyraldehyde, isobutyraldehyde,
benzaldehyde, isovaleraldehyde, valeraldehyde, o-, m-, and p-tolualdehyde,
hexanaldehyde and dimethylbenzaldehyde. All measured concentrations were reported
in ppbv. The results for the field blanks were also reported in ppbv, assuming the same
sample volume as the accompanying samples.
JBS441
8-10
-------
Instrument detection limits are given in Table 8-5 for the target carbonyl
compounds in this study. The detection limits were determined by performing nine
replicate analyses of a standard that was hah0 the concentration of the lowest calibration
standard, which follows the method listed in the Federal Register, Appendix B, Part 136.
8.4 Calibration Procedures
The HPLC was calibrated from 0.5 to 20 ^g/ml nominal concentration of the
derivatized targeted compounds contained in a solution of acetonitrile. The calibration
curve consisted of five concentration levels between 0.5 to 20 ^g/ml, and each was
analyzed in replicate. A standard linear regression analysis was performed on the data
for each analyte with the acceptance criteria being that the correlation coefficient must
be greater than or equal to 0.995. Table 8-6 presents the calibration curve summary
results. As indicated, the correlation coefficients for all compounds met the acceptance
criteria.
8.4.1 Daily Quality Control Procedures
Daily calibration checks were used to ensure that the analytical procedures were
in control. Daily QC checks were performed after every ten samples on each day that
samples were analyzed. The QC standards analyzed during the program indicate that
the analyses remained in control throughout the program as indicated in Table 8-7.
There was a total of eight QC standards.
JBS441
-------
Table 8-5
Detection Limits for Target Carbonyl Compounds
..':• H • " . : '
Carbonyl v
Fonnaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehyde
Hexanaldehyde
2,5-Dimethylbenzaldehyde
Uttferivatizttl ;; .'
;:': x - Vsr • TfULirunMuit
:^' &*%:•: -^-
0.26
0.54
0.42
0.37
0.40
0.23
0.29
0.19
0.19
0.20
0.43
0.13
0.22
r •' .'. ' -\-... ' ' '.-" .1
"••••• -..'.. ".•-•::
C^S Number •
"50-00-0
75-07-0
107-02-8
67-64-1
123-38-6
123-73-9
NA
100-52-7
590-86-3
110-62-3
1334-78-7
66-25-1
5779-94-2
ATR>
. JrarEmeter
Cbde
43502
43503
43505
43551
43504
43516
43329
45501
43513
43518
45504
43517
45503
"Detection limit is based upon an average 140 L sample.
JBS441
8-12
-------
Table 8-6
1993 NMOC Carbonyl Calibration Curve Summary
!• % ' '
, ' '' J
' AB*lyte :
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldchyde
2,5-Dimcthylbenzaldehyde
5
*• \
Slope
109704.88
124828.69
141814.86
108101.04
102718.21
129597.81
95311.81
121777.63
82902.11
92827.30
112808.79
83511.02
115747.45
-1601.58
9570.55
-2267.61
2583.06
7176.35
7889.09
16255.25
16222.58
3636.09
2536.40
14871.74
5904.29
7559.38
fc
0.99986
0.99992
0.99976
0.99986
0.99979
0.99977
0.99961
0.99981
0.99972
0.99980
0.99987
0.99986
0.99983
**
0.99972
0.99984
0.99952
0.99972
0.99958
0.99953
0.99922
0.99962
0.99944
0.99959
0.99975
0.99972
0.99965
Relative Bttt*
bSjqtfnA
(%)
3.73
-2.06
5.01
0.25
-8.11
-8.20
-11.50
-14.56
-7.68
-4.71
-7.84
-6.50
-6.58
UO^g/ntl
(%)
-1.93
-7.26
1.19
0.49
-1.95
-8.50
-9.83
-8.85
-8.09
-3.51
-8.81
-8.22
-10.07
fijDjtfg^Mt
<*>
2.03
2.58
1.97
1.85
3.32
3.43
3.64
4.24
4.30
2.81
3.36
3.70
2.96
I2>lg/*t
<*>
-1.77
-0.61
-2.47
-1.74
-1.70 -
-0.48
-0.07
-0.48
-1.39
-1.29
-0.40
-0.95
0.07
20/*g/*i
<%)
0.46
0.01
0.71
0.46
0.32
-0.11
-0.27
-0.18
0.14
0.22
-0.13
0.03
-0.26
00
-------
Table 8-7
1993 NMOC Daily Quality Control Standards Recoveries
NMQC $•»»*«> *
^*fc»
.- .
too
•JM*.
' N4 :
tw
IS*
***&
".]£?•
ItittMRttBKrie.
Formaldehyde
Acetaldchyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/lsobulyraldehyde
Benzaldehyde
Isovaleraldehyde
ValerakJehyde
Tolualdehydes
Hexanaldehyde
25-Dimethylbenzaldehyde
105.13
99.86
108.35
109.37
10055
112.05
112.93
105.46
ND*
100.80
105.74
114.16
ND
103.74
98.99
107.36
109.66
109.68
108.18
113.71
103.85
ND
101.26
102.27
108.86
ND
104.41
99.63
108.88
112.81
11453
111.33
11559
105.71
ND
99.97
105.48
112.06
ND
104.38
98.39
10652
107.99
101.26
110.65
111.67
105.60
ND
99.62
103.42
11157
ND
101.36
102.32
112.31
117.74
115.62
114.22
11550
10853
ND
102.11
106.92
118.71
ND
108.46
10250
113.39
119.32
124.09
114.18
120.30
109.62
ND
95.33
107.25
108.10
ND
,,: .HA....V
Vtfnfc i
1JW
|Sfil
105.98
100.89
11257
119.23
120.80
113.08
118.90
107.04
ND
94.71
105.75
117.39
ND
107.37
103.00
111.76
112.02
103.66
115.88
12056
108.86
ND
108.84
108.78
117.26
ND
•ND - Not Detected.
JBS441
-------
8.42 Duplicate Samples
Duplicate field samples were collected in duplicate cartridges during each
sampling episode, as shown in Figure 8-1. One set of field duplicates from each site was
prepared and analyzed in replicate to determine both the sampling and analytical
precision.
8.43 Trip Blanks
A total of three DNPH cartridges were shipped to each site. Two cartridges were
used to collect the sample, while the third tube, a trip blank, was used to assess the
potential for field contamination. The blank cartridge accompanied the duplicate sample
cartridges, but at no time was exposed to ambient air.
One trip blank cartridge from each site was analyzed for the target carbonyl
analytes. The carbonyl sample results presented in this report are not blank corrected.
8.5 Quality Assurance/Quality Control Data
Quality assurance procedures relative to calibration data for all of the analytes
and daily QC procedures are discussed below. Sampling and analysis precision was
determined from the analysis of duplicate field samples and replicate laboratory analyses.
Sample custody records were maintained throughout the program. Figure 8-2 shows the
multipage field data and custody sheet used for carbonyl sampling documentation. The
site operator's task involved recognizing problems with sampling equipment and
procedures, and notifying Radian personnel so that appropriate corrective action might
be taken. All Radian reported analyses were identified by the NMOC identification
numbers which were recorded on the preformatted field data sheets when the samples
were received.
JBS441
-------
RADIAN
Aldehyde Data Sheet
City Sample Date
SAROAD No. • • -A05 Sampler No.
Cartridge
Port A (red)
Port B (green)
(blank)
Tune No
1 nt No
Rntameter No
Rntameter Reading' „ / (before!
Rotameter Reading' / (after)
Sampling Time/Duration _. (hours)
Sampling Volume3 (liters!
Average Ambient Temperature
Flow Rate2
Before
After
Average
,
O
0
"o
LPM 0
U
0
O.
t/>
Average Barometric Pressure
Site Operator
. (mm Hg)
Comments/Remarks
1 Rotameter reading center of black ball.
2 Calculated from calibration curve by the laboratory.
3 Calculated by laboratory.
Figure 8-2. Carbonyl Field Data and Custody Sheet
8-16
-------
8.5.1 Sampling Precision
The sampling precision was measured as the average standard deviation for the
results from the field duplicate samples which were analyzed in replicate. The sampling
precision results for PLNJ are given in Table 8-8. The sampling precision results for
NWNJ site are given in Table 8-9. The duplicate analyses were performed on 10% of
the samples from each site. The average standard deviation was 0.70 ppbv for PLNJ and
0.17 ppbv for the NWNJ.
8.5.2 Analytical Precision
The analytical precision was measured as the average standard deviation of the
replicate analyses performed on the paired duplicate samples. The analytical precision
results for PLNJ are given in Table 8-10. The analytical precision results for NWNJ are
given in Table 8-11. The replicate analyses were performed on 10% of the samples from
each site. The overall average standard deviation for all of the replicate analyses was
0.17 ppbv.
8.53 Quality Control Standards
As a QC procedure on the analytical results for all of the quantitated analytes, a
solution containing 11 targeted carbonyl compounds at a known concentration was
prepared. Quality control samples were analyzed after every 10 samples. Table 8-5
gives the percent recoveries for the QC standards that were analyzed during this
program. Shown in Table 8-12 are the average, maximum, and minimum percent
recovery and two standard deviations about the average percent recovery for each
targeted carbonyl analyte. These results show that the analyses remained in control.
The overall average percent recovery ranged from 94.71% for valeraldehyde to 124.09%
fc: oropionaldehyde.
JBS441
-------
Tabled
1993 NMOC Plainfield, New Jersey Sampling Precision Statistics
JNMO&lfc *;'s
0*1*131*10
Ptte Analyzed
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2,5-Dimethylbenzaldchyde
1
RC32784
wA>v«JI:
7.46
5.19
ND"
14.46
ND
ND
ND
ND
ND
ND
ND
ND
ND
¥h«!>/ttw%:'
8.24
6.09
ND
15.30
ND
ND
ND
ND
ND
ND
ND
ND
ND
\ •',.,;.!. ,\
;tiytt$/»&
8.98
4.54
ND
13.93
0.47
0.34
0.94
ND
ND
ND
ND
0.42
ND
.>•::*•:/• -
WVOS/»"
9.26
4.35
ND
13.33
0.34
0.44
ND
ND
ND
ND
ND
0.48
ND
. " :•" ' :-.v--'' • :•. '
• \. ..•:'•• • /; • . : : :
•'. .. -::- '•_'•:,.''-'' . .-:;..;•
8.49
5.04
NAb
14.26
NA
NA
NA
NA
NA
NA
NA
NA
NA
Average
,.'.;.; •••••.•• - • • • _ • • • -.
Standard •
0.70
0.68
NA
0.72
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.70
• Devifetimt
8.24
13.49
NA
5.08
NA
NA
NA
NA
NA
NA
NA
NA
NA
8.94
00
>—»
00
•ND = Not Detected.
bNA = Not Applicable.
-------
Table 8-9
1993 NMOC Newark, New Jersey Sampling Precision Statistics
DI Factor fj&&.
NMOCO) , ' ;f ;/{,
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutryaldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehydc
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
** RC32794
* m/m/0j
JO/ttS/93
10/W/K
9.36
4.05
ND"
13.34
0.46
0.29
1.33
ND
ND
0.43
ND
0.%
ND
1
I5&MT0W
RC32795
08/04/93
10/05/93
10/06/93
9.24
4.25
ND
13.%
0.44
0.22
1.15
ND
ND
0.48
ND
0.85
ND
1
RC327%
08/04/93
10/05/91
10/06/93
9.13
3.99
ND
13.04
0.39
0.15
H.45
ND
ND
0.42
ND
1.06
ND
1
1S&&DUT
RC32797
08/04/93
10/05/93
10/06/W
9.72
4.08
ND
13.80
0.35
0.43
1.36
ND
ND
0.56
ND
1.15
ND
-
9.36
4.09
NAb
13.54
0.41
0.27
1.07
NA
NA
0.47
NA
1.01
NA
Average
Standard
0.22
0.10
NA
0.37
0.04
0.10
0.37
NA
NA
0.06
NA
0.11
NA
0.17
Standard
237
2.36
NA
2.70
10.49
37.99
34.34
NA
NA
11.72
NA
11.14
NA
14.14
oo
'ND = Not Detected.
bNA = Not Applicable.
-------
Table 8-10
1993 NMOC Plainfield, New Jersey
Analytical Precision Statistics
Di Factor T
NMOC1D !
Date File ID L.::."-:. V
Date Sampled 'v:;; -::, v ;v-:
* i ..:.'*'.••.'.:• .;• ......
Train F^tfracfcfl ••••'•••• • -• • •'-
•;-..::••: .' . ..':•:
flpjlif^ AlMliySBfjB
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
RCJ2784
08/04/93
10/OS/»
7.46 •
5.19
NDa
14.46
ND
ND
ND
ND
ND
ND
ND
ND
ND
1222- A DUP
08/M/W
10/%»/!»
8.24
6.09
ND
15 JO
ND
ND
ND
ND
ND
ND
ND
ND
ND
,
Average
7.85
5.64
NAb
14.88
NA
NA
NA
NA
NA
NA
NA
NA
NA
Average
Atxwfate
9.94
15.96
NA
5.65
NA
NA
NA
NA
NA
NA
NA
NA
NA
10.51
Standard
Devotion
OJ9
0.45
NA
0.42
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.42
Rdatiw
Standard
Devutiott
<*J
4.97
7.98
NA
2.82
NA
NA
NA
NA
NA
NA
NA
NA
NA
526
'ND = Noc Detected.
bNA = Not Applicable.
JBS441
8-20
-------
Table 8-10
Continued
DT Factor
NMOCID
Data File ID
Date Sanpipd.
Date Analyzed
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2,5-Dimethylbenzaldehyde
uao
mz-B
RC32786
08/04/W
10/05/53
HJ/05/93
8.98
434
ND*
13.93
0.47
034
0.94
ND
ND
ND
ND
0.42
ND
> U»
££32787
08/04/83
Jfl/05/93
10/05/93
9.26
435
ND
1333
0.34
0.44
ND
ND
ND
ND
ND
0.48
ND
Average
9.12
4.45
NAb
13.63
0.41
039
NA
NA
NA
NA
NA
0.45
NA
Avenge
sr
<*>
3.07
4.27
NA
4.40
32.10
25.64
NA
NA
NA
NA
NA
1333
NA
13.80
Standard
DcwatioB
0.14
0.10
NA
030
0.06
0.05
NA
NA
NA
NA
NA
0.03
NA
0.11
Relative
134
2.14
NA
2.02
16.05
12.82
NA
NA
NA
NA
NA
6.67
NA
6.90
*ND = Not Detected.
bNA = Not Applicable.
JBS441
8-21
-------
Table 8-10
Continued
J# Factor
NMOCID
Data Files ID
Date Sampled
Date Aaafyzed
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
WO
JRO2788
08/04/93
10/05/93
10/05/93
7.52
1.24
NDa
3.11
ND
ND
ND
ND
ND
ND
ND
ND
ND
I', :.-...' .U»
vSSS-
lo/os/sa
7.67
138
ND
332
ND
ND
ND
ND
ND
ND
ND
ND
ND
,
Avenge
7.60
131
NAb
3.22
NA
NA
NA
NA
NA
NA
NA
NA
NA
Average
Afasofate
FtfCGSt .
<%)
1.97
10.69
NA
6.53
NA
NA
NA
NA
NA
NA
NA
NA
NA
6.40
-
•StafKhnl
Deviation
0.08
0.07
NA
0.10
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.08
.
Relative
Standard
DevtatKM
(*>
0.99
534
NA
3.27
NA
NA
NA
NA
NA
NA
NA
NA
NA
3.20
aND = Not Detected.
bNA = Not Applicable.
JBS441
8-22
-------
Table 8-11
1993 NMCX: Newark, New Jersey
Analytical Precision Statistics
TA Factor
NMOCED
PatstffelD
' I^ate Sampled
T)ate Biiii'iK'tfttf
DateAaalped
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
Uf»
1SB-A
HC3Z794
08/04/93
28/dS/!&
10/06/93
936
4.05
NDa
1334
0.46
0.29
133
ND
ND
0.43
ND
0.96
ND
19$
1533-ADUF
RC32795
06/04/9)
18/95/93
10/06/W
9.24
425
ND
13.%
0.44
022
1.15
ND
ND
0.48
ND
055
ND
>»
Average
930
4.15
NAb
13.65
0.45
0.26
124
NA
.NA
0.46
NA
0.9'
NA
Average
Absolute
PefCBOt
imffbrrncc
m
129
4.82
NA
4J4
4.44
27.45
14.52
NA
NA
10.99
NA
12.15
NA
10.03
Standardl
•Hfc....-» .»»-_,
UCWBuOB
0.06
0.10
NA
031
0.01
0.03
0.09
NA
NA
0.02
NA
0.06
NA
OD9
ftcfefec
SUttdani
Pcviatikw
{%}
0.65
2.41
NA
2.27
2.22
1.75
4.50
NA
NA
5.49
NA
6.08
NA
3.17
'ND = Not Detected.
bNA = Not Applicable.
JBS441
8-23
-------
Table 8-11
Continued
DI Factor " ^!&: ' ;: • •• •'••/;
Date Sampled • -: ....
• Bate Aaaiyzed •':" ••£":* :;: .^
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyr aldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
ToluaJdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
•mCSSO96
t*ttt»AitnJ
•-, iRfjW/S^
lfi/06/93
9.D
3.99
ND»
13.04
0.39
0.15
0.45
ND
ND
0.42
ND
1.06
ND
\;::r:.fcC33797
•••••• -. vo/Or|p5K^
: • ifi/Q5/93
9.72
4.08
ND
13.80
0.35
0.43
1.36
ND
ND
0.56
ND
1.15
ND
~
Average
9.43
4.04
NAb
13.42
037
0.29
0.91
NA
NA
0.49
NA
1.11
NA
Average
Abtttate
• xTCFCCllL
' Diffisumttf
626
223
NA
5.66
10.81
96.55
100 J55
NA
NA
28.57
NA
8.14
NA
3235
Standard
Deviation
0.29
0.04
NA
038
0.02
0.14
0.46
NA
NA
0.07
NA
0.04
NA
0.18
Relative
' Deviafkw
3.D
1.12
NA
2.83
5.415
48.28
5028
NA
NA
14.29
NA
4.07
NA
16.17
aND = Not Detected.
bNA = Not Applicable.
JBS441
8-24
-------
Table 8-11
Continued
Df Factor
NMOCID
:ltatki$eIB
Date Sampled
n+t»ft*tv*rtf£
Bate Analyzed
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyr aldehyde
Benzaldehyde
Isovaleraldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
2^-Dimethylbenzaldehyde
LflO
t?£LRr Jf
JRC3279B
08/04/93
10/05/93
lfl/06/93
ND"
ND
ND
0.48
ND
ND
ND
ND
ND
ND
ND
ND
ND
Ut»
l$&BLX.TWf
RC3279& -
OB/04/3J
l(tf05/& ~-
*f*f}**g-**r
10/tJ6/« -
ND
ND
ND
0.49
ND
ND
ND
ND
ND
ND
ND
ND
ND
•£.;
"'£*
'? '
' , ¥;
*(?•'•
Aketag^
NAb
NA
NA
0.49
NA
NA
NA
NA
NA
NA
NA
NA
NA
Avenge
^
Pcxcut
P^fefeaoe
&i
NA
NA
NA
48.75
NA
NA
NA
NA
NA
NA
NA
NA
NA
48.75
ftimfan?
Deviation
NA
NA
NA
0.49
NA
NA
NA
NA
NA
NA
NA
NA
NA
0.49
"* •,
Bdbdve
Standard
TVrvwUKM"
w
NA
NA
NA
48.69
NA
NA
NA
NA
NA
NA
NA
NA
NA
4&69
'ND = Not Detected.
bNA = Not Applicable.
JBS441
8-25
-------
Table 8-12
1993 NMOC Daily Quality Control Standards Statistics
,
^ Anatyte
Formaldehyde
Acetaldehyde
Acrolein
Acetone
Propionaldehyde
Crotonaldehyde
Butyr/Isobutyraldehyde
Benzaldehyde
Valeraldehyde
Tolualdehydes
Hexanaldehyde
Average
m
105.10
100.70
110.14
113.52
111.27
112.45
116.15
106.83
100.33
105.70
113.51
Standard
Deviation
2.06
1.63
2.49
4.32
8.37
2.27
3.19-
1.88
4.09
1.95
3.76
Maxutnun
~&W "
108.46
103.00
113.39
119.32
124.09
115.88
120.56
109.62
108.84
108.78
118.71
Minfoiuxn
":::U*>
101.36
98.39
106.52
107.99
100.55
108.18
111.67
103.85
94.71
102.27
108.10
AVg4l*St*D
109.23
103.96
115.11
122.16
128.01
116.98
122.52
110.60
108.51
109.60
121.04
Avg"l*STD
100.98
97.43
105.17
104.87
94.54
107.91
109.77
103.07
92.15
101.80
105.99
oo
-------
9.0 SNMOC DATA SUMMARY
This section presents the data summary for the SNMOC portion of the
1993 NMOC monitoring program. Presented is information on the number of samples
collected, summary statistics, and individual sample results. For the 1993 SNMOC
monitoring program 686 valid ambient air samples were received; 756 sample analyses
were performed including 70 replicate analyses. The samples were analyzed by GC/FID
to determine concentrations of 78 target hydrocarbons. Table 9-1 presents the target
compounds. The samples were collected from 13 sites; 8 of these sites conducted daily
(Monday-Friday) sampling from 7 June to 30 September, 1993. Five sites participated in
an optional analysis program for which nine samples from each site collected for NMOC
analysis were randomly selected to receive analysis by the speciation method.
Appendix A presents the site information and the site codes used throughout this report.
9.1 Sample Collection
Tables 9-2 and 9-3 summarize sample collection information for program and
option sites, respectively. Program sites were scheduled to collect samples from 7 June
to 30 September 1993.
92 Site Specific Summary Statistics
Site specific statistics are given in Tables 9-4 through 9-16. Duplicate and
duplicate/replicate results were averaged into single compound specific values for the
sample date and considered as one sample for summary statistics. The target compounds
for the 1993 monitoring season are given in the first column of the summary statistics
tables. The cases column denotes the number of samples the compound was identified
in for the 1993 monitoring season. The third column in the tables presents the percent
of the samples in which a particular compound was identified. The minimum, maximum,
median, average, standard deviation, skewness, and kurtosis of the measured
concentrations in ppbC are also listed in each table for each target compound. The
JBS441
-------
Table 9-1
1993 SNMOC Target Compounds
1 Compound
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4- Methyl- 1-pentene
Cyclopentane
2,3-Dimethylbutane
2-Methylpentane
:,.x €*&-•• ••• '•-.
Number
74-86-1
74-86-2
74-84-0
77-99-7
75-28-5
106-98-9
115-11-7
115-07-1
106-99-0
106-97-8
74-98-6
624-64-6
590-18-1
563-45-1
78-78-4
109-67-1
563-46-2
109-66-0
78-79-5
646-04-8
627-20-3
513-35-9
75-83-2
142-29-0
691-37-2
287-92-3
79-29-8
107-83-5
AIRS Parameter
Code
• 43203
43206
43202
43144
43214
43280
43270
43205
43218
43212
43204
43216
43217
43282
43221
43224
43225
43220
43243
43226
43227
43228
43244
43283
43234
43242
43284
43285
JBS441
9-2
-------
Table 9-1, continued
, ..-..: .,.>..,.
: . . - • •• •;•-• K A iH.ll ft HttHj •'
. ....'... *
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
2,3-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
MethylcycL r. i ,ane
1-Heptene
2,2,3-Trimethylpentane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethv'^enzene
p-Xy:~ae + m-Xylene
Styrene
CAS
^Number ;
96-14-0
763-29-1
592-41-6
760-21-4
110-54-3
4050-47-7
7688-21-3
96-37-7
108-08-7
71-43-2
110-82-7
565-59-3
591-76-4
589-34-4
540-84-1
142-82-5
108-87-2
592-76-7
564-02-3
565-75-3
108-88-3
592-27-8
589-81-1
111-66-0
111-65-9
100-41-4
NA
100-42-5
AIRS Parameter
' 1 jRCftC ' ' *'"'*'*" ' ' '
•
43230
43246
43245
432?r
43231
43289
43290
43262
43247
45201
43248
43291
43263
43249
43250
43232
43261
43328
43292
43252
45202
43960
43253
43145
43233
45203
45109
45220
JBS441
9-3
-------
Table 9-1, continued
'. • '• .'•"'" Compound ; "; •" • • ' '.": ::••""•"" '
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
a-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
1,3,5-Trimethylbenzene
o-Ethyltoluene
b-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,2,3-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
;.^:%.;C&S?---.,¥^
:-H':-r-Jtaiber'- "•
95-47-6
124-11-8
111-84-2
98-82-8
7785-70-8
103-65-1
620-14-4
622-96-8
108-67-8
611-14-3
127-91-3
872-05-9
95-63-6
124-18-5
526-73-8
105-05-5
821-95-4
1120-21-4
112-41-4
112-40-3
2437-56-1
629-59-5
AIRS Parameter
Gxfc
45204
43279
43235
45210
43256
45209
45212
45228
45207
45211
43257
43298
45208
43238
45225
45219
45299
43241
43330
43141
43142
43143
JBS441
9-4
-------
Table 9-2
Samples Collected and Analyzed for 1993 SNMOC Program Sites
Site
DIAL
B2AL
B3AL
BMTX
DLTX
EPTX
FWTX
JUMX
Total
Total
Duplicate
Samples
16
14
16
18
16
16
16
14
126
Total
Replicate
Analyses
8
8
12
10
8
8
8
8
70
Total
Single
"
74
76
58
69
74
71
72
66
560
Total
Valid
Sampling
Events
82
83
66
78
82
79
80
73
623
Total
Valid
.... «..»...
90
90
74
87
90
87
88
80
686
Total
Analyse*
Reported
98
98
86
97
98
95
96
88
756
JBS441
9-5
-------
Table 9-3
Samples Collected and Analyzed for 1993 SNMOC Option Sites
Site
LINY
NWNJ
P1PA
P2PA
PLNJ
Total
Stoat
fttiriffeof*
. Vjvu^ruwmM
^HBJH'ftl
2
2
2
2
2
10
Total
Replicate
Analyse*
1
1
1
1
1
5
Total Single
Sample*
7
7
7
8
7
36
Total Valid
Samples
9
9
9
10
9
46
Total
Analyses
Repotted
10
10
10
11
10
51
JBS441
9-6
-------
Table 9-4
1993 Summary Statistics for Binningham, AL (BIAL)
*
f'VuHiuinmt
%^UUI|KJtUIU
Etbylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentcne
4-Methyl-l-pentene
Cyclopentane
23-Dimethylbutane
i
Orte*
82
82
81
0
79
78
0
82
30
80
82
41
33
40
82
58
73
82
81
73
60
76
76
42
60
58
77
-
Froflj
C*)
100.0
100.0
98.8
0.00
963
95.1
0.00
100.0
36.6
97.6
100.0
50.0
40.2
48.8
100.0
70.7
89.0
100.0
98.8
89.0
73.2
92.7
92.7
512
73.2
70.7
93.9
: f|*C -
Win*
2.2
1.9
1.9
a
0.6
0.6
.
1.2
0.4
0.8
1.9
0.4
0.5
0.4
3.7
0.4
0.4
1.7
0.5
0.6
0.4
0.5
0.4
0.5
0.5
0.4
0.6
11**
81.0
36.1
37.7
.
27.1
63
.
17.6
3.9
31.7
140.5
33
4.1
2.0
115.1
103
5.7
29.8
153
6.7
33
7.8
28.7
1.6
2.9
4.0
6.5
Mcd*
15.0
10.2
12.9
.
3.6
2.2
.
53
1.0
7.0
15.0
0.9
0.9
0.8
203
1.1
13
8.2
2.8
2.0
1.1
2.0
8.9
0.7
1.1
1.0
23
AV
15.6
12.5
12.9
.
43
2.4
.
6.1
1.2
8.2
18.5
1.2
1.1
0.9
23.6
1.7
1.6
9.0
3.9
2.1
13
2.4
8.4
0.8
13
1.1
2.6
Std
Dew«
10.8
9.1
73
.
3.4
1.4
.
4.0
0.7
5.5
19.5
0.7
0.7
0.4
17.5
1.9
1.0
5.8
3.1
13
0.6
1.5
5.4
03
0.6
0.6
1.5
S«
2.9
0.9
0.7
4.1
0.9
.
0.8
2.0
1.5
4.2
1.3
2.6
1.2
2.2
2.9
1.4
1.0
1.6
0.9
1.0
0.9
0.8
1.2
1.1
2.4
0.5
JK«
15.4
-0.1
0.4
.
25.5
0.3
.
-0.0
6.1
3.7
22.2
1.4
8.2
1.0
8.3
9.0
3.2
1.3
2.7
0.9
0.7
0.6
1.6
0.5
0.7
9.9
-0.7
JBS441
9-7
-------
Table 9-4
Continued
Cboipoonii
2-Methylpentanc
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcydopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dunethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethyipentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpentane
23,4-Trimethytpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octanc
Ethyfbenzene
Can*
82
81
15
39
2
81
48
33
82
74
82
66
44
75
82
82
78
71
1
61
78
82
74
67
54
68
82
VVSfff
<%)
100.0
98.8
183
47.6
2.4
98.8
58.5
40.2
100.0
90.2
100.0
80.5
53.7
91.5
100.0
100.0
95.1
86.6
1.2
74.4
95.1
100.0
90.2
81.7
65.9
82.9
100.0
w*e
Mai*
1.8
0.6
0.4
0.5
0.4
1.1
0.5
0.5
0.6
0.4
1.6
0.6
0.4
0.4
1.0
0.9
0-5
0.5
1.1
0.5
0.6
4.7
0.5
0.5
0.4
0.4
0.8
tta**
212
18.2
2.7
2.8
1.4
22.1
1.9
1.2
9.4
7.1
373
24.3
4.6
11.1
8.9
18.5
5.9
33
1.1
2.7
6.4
583
3.5
3.1
4.7
33
12.0
Med*
7.6
53
0.9
13
0.9
5.0
0.9
0.7
2.8
1.9
9.1
33
1.6
23
3.5
6.0
2.4
1.6
1.1
1.2
23
22.1
1.6
13
1.0
1.4
4.4
Atf
7.8
6.5
1.1
13
0.9
6.2
0.9
0.7
33
2.1
103
4.8
1.7
33
3.7
6.5
15
1.6
1.1
1.2
2.5
23.0
1.6
1.4
1.1
1.4
4.6
Std
DC*-
4.8
4.4
0.6
0.5
0.7
4.6
03
02
2.1
13
6.9
4.9
1.0
2.7
1.9
43
1.4
0.8
.
0.5
1.6
12.9
0.8
0.7
0.7
0.7
2.7
s«
0.5
0.7
1.4
0.9
1.0
1.1
1.1
0.6
1.0
1.6
1.9
0.8
13
0.4
0.7
05
03
03
0.6
0.5
0.4
0.5
33
0.6
0.5
X*
-0.8
-0.4
1.7
1.1
0.6
1.6
0.8
-0.4
1.9
4.1
3.7
0.2
0.7
-0.8
-03
-0.8
-1.1
.
-0.7
-0.5
-0.5
-1.1
-0.7
16.2
-0.1
-0.6
JBS441
9-8
-------
Table 9-4
Continued
?StM»U%lMut
p-Xylene + m-Xylene
Styrene
o-Xyleoe
1-Noncne
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyitolueoe
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethyibenzene
1-Undecene
n-Undecane
1-Dodeccne
n-Dodecane
1-Trideceoe
n-Tridecane
CMC*
82
71
82
13
68
31
64
64
82
51
71
45
66
81
78
71
79
51
65
79
73
77
26
75
'
Fretf
<*)
100.0
86.6
100.0
15.9
82.9
37.8
78.1
78.1
100.0
622
86.6
54.9
80.5
98.8
95.1
86.6
963
622
793
963
89.0
93.9
31.7
91.5
ppbC * , ' •
Mm*
23
0.4
0.5
0.5
0.5
0.4
0.5
0.5
0.8
0.5
0.6
0.7
0.5
0.4
1.0
0.4
0.7
0.5
0.4
0.4
0.4
0.5
0.4
0.5
Ua*
435
22
13.2
1.1
3.5
25
13.8
3.8
11.1
3.4
10,8
5.6
8.1
10.8
16.2
43.5
9.9
3.6
4.9
13.9
5.1
11.6
1.8
3.6
M*f
13.6
1.1
5.0
0.8
1.5
0.7
1.2
13
4.0
12
22
23
1.4
13
33
1.8
3.5
1.0
1.1
2.7
1.1
2.2
1.0
1.1
**f
15.4
1.2
5.2
0.8
1.6
0.9
2.0
1.4
42
12
25
2.6
1.7
2.7
5.7
2.7
3.8
13
13
3.4
13
2.6
1.0
12
Std
tk*
95
05
3.1
0.2
0.7
0.4
2.0
0.7
25
0.6
1.6
1.4
13
2.7
3.7
5.4
2.2
0.8
0.8
2.7
0.9
1.9
0.4
0.6
S"
0.6
0.4
0.4
-0.1
0.4
1.9
3.6
1.0
0.8
1.1
2.4
0.5
25
15
1.1
6.8
0.8
1.4
2.1
1.7
22
2.7
0.4
1.9
1?
-03
-0.8
-0.7
-0.2
-0.5
5.1
18.1
1.0
0.1
1.9
10.0
-0.8
9.2
1.0
0.4
50.1
0.1
1.0
5.8
3.2
5.7
10.4
-0.8
42
*Freq = Frequency, Min = Minimum; Max = Maximum; Med
Std Dev = Standard Deviation; S - Skewncss; K = Kurtosis
bCalculation not possible due to limited data.
Median; Avg = Average;
JBS441
9-9
-------
Table 9-5
1993 Summary Statistics for Birmingham, AL (B2AL)
-.•••;:: '•:,••'*•-..••;•• ;
ODDUXMB^I
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3- Methyl- 1-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
23-Dimethylbutane
Cases
83
81
79
0
66
74
0
81
15
81
83
24
7
12
83
42
39
83
81
53
23
66
83
20
39
18
65
Bceif
(%)
100.0
97.6
95.2
0.00
79.5
89.2
0.00
97.6
18.1
97.6
100.0
28.9
8.4
14.5
100.0
50.6
47.0
100.0
97.6
63.9
27.7
79.5
100.0
24.1
47.0
21.7
783
pffcC
Ma?
0.6
0.7
0.9
b
0.6
0.5
.
0.8
0.5
1.0
1.4
0.4
0.4
0.6
1.7
0.5
0.4
0.7
0.7
0.5
0.4
0.4
1.2
0.4
0.4
0.4
0.4
Max4
21.4
14.7
10.4
.
60.2
3.6
.
6.9
1.0
49.2
13.6
3.9
4.5
2.7
668.2
15.9
8.4
162.7
14.0
113
6.0
13.0
9.5
2.0
2.6
22.1
5.7
Med"
63
4.4
4.8
.
1.6
1.4
.
2.6
0.6
3.0
6.7
1.1
0.6
1.1
7.9
0.7
0.7
3.1
4.9
0.8
0.8
0.9
3.0
0.7
1.0
0.8
1.0
w
7.1
43
5.0
.
3.4
1.5
.
2.6
0.7
5.0
6.6
1.4
13
1.2
24.1
13
1.1
6.4
5.1
1.2
1.0
13
3.1
0.8
1.1
3.0
12
sat
DC**
4.2
2.2
2.0
.
8.9
0.6
.
1.1
0.2
8.5
2.6
0.9
1.4
0.6
83.8
2.4
13
18.4
33
1.5
1.1
1.6
1.2
03
0.6
6.1
0.7
Sf
1.2
1.4
0.5
5.6
0.8
.
0.7
0.7
4.6
0.5
13
23
1.6
6.6
5.6
5.2
7.8
0.8
6.1
43
6.7
2.9
2.4
13
2.8
43
**
1.9
4.7
03
323
1.1
.
1.5
-0.7
20.9
0.2
1.3
5.5
2.6
46.9
33.6
29.6
65.0
03
41.0
193
50.1
13.6
8.2
13
6.8
25.0
JBS441
9-10
-------
Table 9-5
Continued
-
Compound \
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexcne
2-Ethyl-l-but
n-Hexane
t-2-Hexene
c-2-Hexcne
Methylcyclopentane
2,4-Dimethyipentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2^3-Trimethyipentane
23,4-Trimethylpentane
Toluene
2-Methyiheptane
3-Methylheptane
1-Octene
n-Octanc
Ethylbenzene
.
Cue*
81
79
19
11
2
79
9
4
70
53
83
51
23
58
81
79
51
34
0
24
65
83
34
21
15
33
78
Ereq-
<*>
97.6
95.2
22.9
133
2.4
95.2
10.8
4.8
843
63.9
100.0
61.5
27.7
69.9
97.6
95.2
613
41.0
0.0
28.9
783
100.0
41.0
253
18.1
39.8
94.0
+
Mm»
0.7
0.6
0.4
03
0.6
03
03
03
0.4
0.4
0.7
0.4
0.4
0.4
0.6
03
0.4
0.4
.
0.4
0.4
1.4
03
0.4
03
0.4
03
V "
Ite*
16.7
163
2.9
23
0.6
243
1.8
12
8.6
2.9
11.1
10.0
1.9
43
10.0
6.6
6.9
3.8
.
2.9
2.2
983
1.9
13
23
13
7.2
% v
Med«
2.6
23
0.8
0.7
0.6
1.8
0.6
1.0
12
0.8
3.7
1.2
0.8
1.0
1.6
2.4
0.8
0.7
.
0.6
0.9
6.9
-»
5
0.7
0.7
1.4
HpbC
,\ !
Atf
3.1
33
1.1
0.9
0.6
2.6
0.9
0.9
13
0.9
3.8
1.9
0.9
13
1.9
2.4
1.1
1.0
.
0.7
1.0
10.4
0.8
0.6
-.9
0.8
1.6
std
Dcw»
22
33
0.7
03
0.0
3.1
03
03
1.4
0.4
1.7
2.0
03
0.8
13
1.0
1.1
0.8
.
03
03
16.4
03
0.2
0.6
03
1.0
-
s*
3.4
23
13
*,.»
,
5.0
13
-1.0
3.4
23
1.2
2.4
13
1.7
4.2
1.0
4.1
2.6
4.1
0.8
4.8
2.0
2.0
2.0
1.1
3.1
*•
18.7
53
1.6
5.8
.
313
03
-03
133
9.7
3.1
6.1
2.6
3.2
21.6
2.7
19.2
6.7
183
0.6
23.0
4.6
3.2
2.8
0.7
13.7
JBS441
9-11
-------
Table 9-5
Continued
Compoimi
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethykoluene
p-Ethyltoluene
135-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecanc
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Cases
83
55
80
3
33
6
47
27
82
10
63
39
46
75
82
18
83
21
59
70
68
76
21
69
Bcetf
(#)
100.0
663
96.4
3.6
39.8
7.2
56.6
32.5
98.8
12.1
75.9
47.0
55.4
90.4
98.8
21.7
100.0
253
71.1
843
81.9
91.6
253
83.1
0?1>C
Mia»
0.7
0.4
0.5
0.5
0.5
0.5
0.5
0.4
0.5
0.4
0.4
0.5
0.5
05
05
0.4
0.6
0.4
0.6
05
05
0.6
05
0.4
M«*
19.1
13.9
6.9
0.9
2.1
1.1
12.6
15
8.0
3.2
2.9
4.0
6.7
45
18.7
80.9
85
15
7.7
536.1
8.0
471.4
0.9
59.4
Mcd*
42
0.7
1.7
0.6
0.8
0.8
4.0
0.6
25
0.7
0.9
1.2
3.2
13
2.1
0.8
3.4
0.6
1.0
1.4
0.8
13
05
0.9
Atf
4.6
1.2
1.8
0.6
0.9
0.8
45
0.7
3.0
1.0
0.9
1.4
3.0
15
25
5.8
33
0.7
15
10.0
1.1
9.1
0.6
23
std
i***
2.9
2.1
1.0
0.1
05
0.2
3.1
03
1.8
0.9
0.4
0.7
1.4
0.8
2.4
18.8
1.6
03
13
63.9
1.0
54.0
0.1
12
&
22
5.2
23
0.6
1.4
03
0.6
2.0
0.8
2.0
2.4
2.4
0.0
0.9
4.6
4.2
0.7
15
2.9
83
5.0
8.6
1.4
7.6
TS*
7.9
275
9.6
.
0.6
-0.3
-03
4.3
-0.2
3.6
93
7.1
0.0
1.1
27.3
17.7
15
1.7
10.4
69.6
30.9
74.6
0.9
60.8
aFreq = Frequency; Mia = Minimum; Max = Maximum; Med = Median; Avg = Average
Std Dev = Standard Deviation; S = Skevmess; K = Kurtosis
bCalculaikm not possible due to limited data.
JBS441
9-12
-------
Table 9-6
1993 Summary Statistics for Birmingham, AL (B3AL)
tf^MHVMWMut I
Ethylenc
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propyiene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-MethyI-2-butene
22-Dimethylbutane
Cydopentene
4-Methyl- 1-pentene
Cyclopentane
23-Dimethylbutane
;
<*foati
62
60
66
0
58
57
0
64
10
65
66
23
22
22
66
46
44
66
65
47
35
50
59
20
39
31
56
;
Fiwf
{%)
93.9
90.9
100.0
0.0
87.9
86.4
0.0
97.0
152
98.5
100.0
34.9
333
333
100.0
69.7
66.7
100.0
98.5
712
53.0
75.8
89.4
303
59.1
47.0
84.9
H*C
*fia»
0.9
0.8
0.8
b
0.5
0.5
0.6
0.5
1.0
1.8
0.6
0.6
0.5
1.8
0.4
0.4
0.5
0.6
0.5
0.4
0.5
0.6
0.4
0.5
0.4
0.4
f \
\ **«x*
21.1
9.6
23.0
.
19.5
4.0
.
10.5
1.1
833
380.1
4.1
2.9
2.6
89.5
4.1
5.4
24.6
27.9
5.7
32
7.8
16.8
3.0
2.8
2.6
6.9
MedF
6.5
25
6.4
.
2.4
13
.
2.0
0.5
5.4
6.9
1.1
13
0.9
12.2
0.9
1.1
4.4
4.8
12
0.9
13
8.0
0.7
1.1
0.9
13
Atf
7.5
33
6.8
.
33
1.4
.
25
0.6
10.6
12.8
1.4
12
1.1
19.1
13
1.4
6.1
7.1
1.7
1.1
1.9
7.7
0.9
12
1.0
1.9
Strf
BW*
5.0
22
3.8
.
3.0
0.7
,
1.8
02
13.7
46.0
0.9
0.6
05
20.7
0.8
1.1
5.7
62
1.4
0.7
1.7
3.2
0.6
0.6
0.6
1.5
s* i
0.8
1.1
1.8
.
3.1
1.2
.
2.1
2.1
32
8.1
1.8
1.1
15
2.1
1.7
2.0
1.9
1.5
1.6
1.5
2.0
03
33
13
15
1.9
K* .
0.1
0.6
5.8
13.7
2.0
.
6.4
5.0
12.5
65.4
3.7
1.9
3.1
3.7
2.7
4.7
3.1
2.1
2.0
1.8
3.7
0.5
12.7
1.7
2.0
2.9
JBS441
9-13
-------
Table 9-6
Continued
••: _ ,-• '^.•'..-x_\''-v:" \
uwipomul
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
2,3-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methyicyclohexane
1-Heptene
2,23-Trimethyipentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
66
63
16
17
5
64
15
6
56
45
66
32
31
47
65
65
43
30
2
30
50
66
28
24
27
28
60
m.
100.0
95.5
24.2
25.8
7.6
97.0
22.7
9.1
84.9
68.2
100.0
48.5
47.0
712
98.5
98.5
65.2
45.5
3.03
45.5
75.8
100.0
42.4
36.4
40.9
42.4
90.9
.:-<:: -i ^.^••'•••^.^^•••^ :~r>p:^-"
&*1
0.8
0.7
0.5
0.5
0.5
0.5
0.4
0.5
0.5
0.4
0.9
0.4
0.4
0.4
0.6
0.7
0.4
0.5
0.78
0.4
0.5
23
0.4
0.5
0.4
0.4
0.5
[i»|.:
17.9
173
1.7
1.7
13
7.3
1.5
0.7
4.6
3.7
113
3.5
2.8
2.8
4.2
8.6
2.2
2.4
0.89
2.5
2.7
71.4
1.1
13
0.9
2.4
42.9
W
32
3.0
1.1
0.8
1.0
2.0
0.7
0.7
13
0.9
3.5
1.1
0.8
1.0
1.8
1.5
1.0
0.9
0.84
0.7
1.1
83
0.7
0.7
0.6
0.8
13
M^
43
3.7
0.9
0.9
0.9
23
0.8
0.6
1.6
1.2
4.1
1.2
1.0
1.1
2.0
3.0
1.1
1.0
0.84
0.8
12
10.6
0.7
0.73
0.6
0.9
2.2
'^:
3.7
3.0
0.4
0.4
0.3
1.6
03
0.1
0.9
0.7
2.4
0.8
0.6
0.6
0.9
2.0
0.5
0.5
0.08
0.4
0.6
9.6
0.2
02
0.2
0.5
5.4
:-> ;
1.8
2.1
0.4
1.0
-0.0
1.4
1.5
-0.8
1.5
1.9
0.8
1.6
1.4
1.4
0.7
1.1
0.9
1.6
.
3.2
0.9
4.1
0.5
0.9
0.8
2.0
15
'*• :
•33
6.4
-0.5
-0.1
-0.5
1.8
3.5
-1.4
2.4
3.6
03
23
1.5
1.4
-0.4
0.5
03
23
.
13.9
0.1
24.4
-0.6
0.9
-03
42
57.7
JBS441
9-14
-------
Table 9-6
Continued
Cdmpooui
p-Xylene + m-Xylene
Styrene
o-Xylenc
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propyibenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimcthylbeiizene
p-Diethylbenzene
1-Undeccne
n-Undecane
1-Dodecene
n-Dodecane
1-Trideccnc
n-Tridecanc
;
CUe»
66
41
60
4
29
6
42
22
65
17
39
39
48
62
64
38
65
19
48
62
56
62
13
54
;
Fretf
{%)
100.0
62.1
90.9
6.1
43.9
9.1
63.6
333
98.5
25.8
59.1
59.1
72.7
93.9
97.0
57.6
98.5
28.8
72.7
93.9
84.9
93.9
19.7
81.8
...' OT&G
*&•
0.9
0.4
0.5
0.4
0.4
0.7
0.5
0.4
0.7
0.4
0.5
0.6
0.6
.0.5
0.5
0.4
0.7
0.4
0.5
0.4
0.5
0.4
0.4
0.4
*ias*
129.2
1.4
283
12
2.9
1.1
21.9
2.2
8.8
1.9
23
2.5
8.4
5.0
11.6
41.7
53
2.4
8.5
8.9
4.6
9.5
3.1
3.4
Med*
3.8
0.7
1.4
0.6
0.8
0.8
3.9
0.6
2.2
0.5
1.0
1.2
2.5
1.2
1.8
0.8
2.2
0.6
1.1
1.1
0.9
13
0.6
0.9
Atf
6.1
0.8
2.1
0.7
1.0
0.8
5.4
0.7
2.6
0.6
1.1
13
2.8
1.4
25
2.9
2.4
0.9
1.6
1.8
12
1.8
0.9
1.2
St*
Bcv*
15.6
0.2
3.6
03
0.6
0.2
5.5
0.4
1.7
0.4
0.4
0.5
1.8
0.9
2.1
82
1.1
0.6
1.6
1.7
1.0
1.9
0.7
0.8
$•
7.8
0.7
7.1
1.6
2.2
1.1
1.7
2.4
1.9
3.6
0.9
0.7
1.0
1.9
2.2
4.8
0.9
1.6
32
2.6
23
2.8
2.7
1.5
s r
K*
62.9
-0.1
52.7
2.4
4.7
1.2
2.8
6.7
3.9
13.8
0.8
0.0
1.0
3.8
6.2
25.2
0.5
2.0
11.2
6.9
4.5
7.9
7.5
1.4
*Freq = Frequency, Min = Minimum; Max = Maximum; Med = Median; Avg = Average
Std Dev = Standard Deviation; S = Skewncss; K - Kurtosis
bCalculation not possible due to limited data.
JBS441
9-15
-------
Table 9-7
1993 Summary Statistics for Beaumont, Texas (BMTX)
:V--- \>-^'^:i::\-<
*-^ .
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyi-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprcne
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-DimethyIbutane
Cydopentene
4-Methyl- 1-pentene
Cyclopentane
23-Dimethylbutane
Cage*
78
74
78
0
78
74
0
76
36
78
78
49
52
47
78
62
67
78
66
67
60
74
78
40
40
72
76
<*)
100.0
94.9
100.0
0.0
100.0
94.9
0.0
97.4
46.2
100.0
100.0
62.8
66.7
60.3
100.0
79.5
85.9
100.0
84.6
85.9
76.9
94.9
100.0
513
513
923
97.4
•:-.' t' v...-J;-|^.;r^v:;:^-:---,;-;-x;
**«»
0.6
0.6
4.5
b
0.9
05
.
0.7
0.5
2.8
4.2
05
05
0.4
4.5
05
0.6
22
0.6
0.6
0.5
0.7
0.9
0.4
05
0.6
0.5
Mai*
146.0
42.9
79.8
.
143.0
38.4
.
64.4
3.7
502.4
532.6
32.5
24.4
10.9
875.8
19.6
32.7
436.1
7.1
28.0
15.2
40.6
8.7
43
35
243
31.2
ifc*
17.7
53
25.4
.
15.6
2.8
4.7
1.0
20.5
28.8
1.5
1.1
1.1
31.9
1.4
1.7
135
2.1
2.2
1.5
25
33
0.7
0.7
1.9
2.5
Avg*
33.8
8.1
28.2
20.7
4.1
.
9.9
1.2
363
77.0
2.5
2.0
1.6
63.6
25
2.7
28.4
25
33
2.1
3.9
3.6
0.9
0.9
2.8
3.6
sri '
Dcv*
36.2
8.2
16.2
,
22.5
5.2
.
11.3
0.7
64.7
131.8
4.7
3.5
1.7
1183
3.4
4.2
58.1
1.6
3.9
22
5.4
13
0.7
0.6
3.4
4.2
'•.*•
1.6
23
0.9
.
3.8
4.7
t
2.3
1.7
5.7
2.7
5.9
5.6
4.2
53
3.4
5.9
5.7
1.2
4.4
4.2
4.9
1.1
3.5
3.0
4.6
4.7
%-
2.0
6.4
0.8
g
18.0
215
.
6.8
3.4
37.1
6.0
37.9
35.9
22.2
323
12.6
402
35.4
0.9
243
22.0
30.2
22
16.0
11.8
24.5
26.7
JBS441
9-16
-------
Table 9-7
Continued
fl*Vwn*uMMut
2-Methylpentane
3-Methylpentane
2-Methyl-l-pcntenc
1-Hexenc
2-Ethyl-l-butenc
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentanc
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexanc
3-Methylhexane
2,2,4-Trimethylpentane
n-Hcptane
Methylcyclohcxane
1-Hcptcnc
2,23-Trimethyipentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
Owe*
- 78
78
13
43
1
78
33
18
78
67
78
74
33
75
76
77
76
77
0
57
70
78
65
61
31
68
75
Kwtf
<*>
100.0
100.0
16:7
55.1
13
100.0
423
23.1
100.0
85.9
100.0
94.9
423
96.2
97.4
98.7
97.4
98.7
0.0
73.1
89.7
100.0
833
782
39.7
872
962
\
Mia*
13
0.7
0.4
0.5
0.8
0.9
0.5
0.4
0.6
0.5
0.9
0.6
0.5
0.7
0.9
0.8
0.7
0.5
.
0.5
0.5
1.8
0.5
0.6
0.4
0.4
0.7
«*c
M*»*
83.2
59.5
2.9
6.4
0.9
783
3.5
2.0
35.0
10.1
42.0
14.7
2.9
17.7
11.2
49.5
30.5
15.7
.
4.8
11.7
325.0
4.7
2.9
2.1
6.4
11.2
MaF
8.4
7.1
0.7
1.1
0.9
8.0
0.7
0.6
4.1
1.1
6.7
33
0.9
23
3.0
4.5
2,8
2.9
.
0.8
1.7
13.8
13
1.0
0.6
12
2S
AV
13.1
8.7
1.0
IS
0.9
11.0
0.8
0.7
53
1.4
83
3.8
1.1
2.9
3.4
5.4
3.6
3.7
1.0
2.0
19.0
IS
1.1
0.8
IS
2.8
std
Dew*
14.1
8.5
0.8
13
.
11.1
0.6
0.4
5.1
13
6.2
2.8
0.6
23
1.9
5.8
3.9
3.0
0.6
1.5
36.1
0.8
0.5
0.4
1.1
1.5
3*
3.1
3.8
1.9
2.2
.
3.8
3.8
2.6
3.6
5.4
2.9
2.1
1.8
3.7
2.0
6.1
4.8
2.2
.
4.6
4.4
8.1
1.7
1.6
22
2,0
2.4
g*
11.1
18.7
3.0
5.4
.
18.6
16.7
7.8
17.0
36.0
11.5
5.6
3.2
20.8
5.4
46.4
29.8
5.7
.
27.5
273
69.1
3.6
33
5.5
5.1
10.8
JBS441
9-17
-------
Table 9-7
• Continued
'•.-.'• *
LriHnpotuul
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
134-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undeccne
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
'Cues'
78
59
76
5
63
28
52
53
76
34
61
33
46
72
69
69
73
30
62
77
70
75
18
65
Xtst?
<*)
100.0
75.6
97.4
6.4
80.8
35.9
66.7
68.0
97.4
43.6
782
423
59.0
923
88.5
88.5
93.6
38.5
79.5
98.7
89.7
96.2
23.1
833
.*• ^.Hte^-^vj^^
Mfc*
0.9
0.5
0.8
0.5
0.5
0.4
0.6
0.5
0.5
0.4
0.5
0.5
0.5
0.5
0.7
0.4
0.6
0.5
0.5
0.6
0.5
0.5
0.4
0.4
««-
25.1
5.9
8.6
1.0
8.2
2.1
13.5
1.6
103
2.0
13.4
2.9
5.8
7.2
6.6
20.4
8.0
29.6
16.4
83
1.9
18.7
2.7
7.4
Mod"
6.6
0.9
2.5
0.5
1.0
0.7
1.8
0.9
23
0.8
13
1.5
1.0
1.7
1.8
1.2
2.7
0.7
1.0
1.6
0.9
1.5
0.6
0.8
W
12
1.7
2.8
0.6
13
0.8
3.0
0.9
2.9
0.9
1.6
1.6
1.8
23
2.4
1.9
3.1
2.0
1.5
2.0
1.0
2.2
0.7
1.2
'n£
4.2
1.6
U
03
1.1
03
3.4
03
23
0.4
1.7
0.7
1.6
1.7
1.7
2.7
1.9
53
2.1
1.4
0.4
2.6
0.5
1.1
;.:£?
L5
1.4
1.2
1.9
4.0
2.5
2.2
0.6
1.8
1.1
6.4
03
1.2
1.0
1.1
5.4
0.7
5.2
6.5
2.0
0.9
4.5
3.8
4.0
&1
4.1
0.4
2.1
3.5
21.0
8.7
3.6
-0.6
3.2
1.2
46.1
-1.1
0.2
03
03
34.0
-03
27.4
47.0
53
-0.1
24.1
15.1
19.6
*Freq = Frequency; Min = Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
Calculation not possible due to limited data.
JBS441
9-18
-------
Table 9-8
1993 Summary Statistics for Dallas, Texas (DLTX)
:
VriOotpotuu*
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
22-Dimethylbutane
Cydopeotene
4-Methyt-l-pentene
Cyclopentane
23-Dimethylbutane
Case*
80
81
82
0
76
79
0
81
28
82
82
27
25
20
82
50
53
82
73
72
44
78
82
18
32
47
73
Req*
<*>
97.6
98.8
100.0
0.0
92.7
96.3
0.0
98.8
34.2
100.0
100.0
32.9
30.5
24.4
100.0
61.0
64.6
100.0
89.0
87.8
53.7
95.1
100.0
22.0
39.0
573
89.0
flpfcC
MiB»
0.8
0.9
0.8
b
0.7
0.6
.
0.7
0.5
1.7
2.6
0.5
0.5
0.4
4.0
0.5
0.4
13
0.4
0.5
0.4
0.5
1.2
0.5
0.5
0.4
0.6
i Mai- j
48.6
31.6
49.9
.
2153
8.6
.
16.1
2.9
38.5
683
2.8
2.8
4.6
817.1
5.1
. 4.2
263
3.4
6.7
3.4
92
19.1
1.5
23
29.7
7.7
Mof
8.8
5.4
10.7
.
3.5
1.7
3.1
0.7
73
14.2
0.9
0.7
0.7
D.I
1.0
1.1
5.5
1.2
1.2
0.8
1.4
6.5
0.8
1.0
0.8
1.5
A*"1
10.1
7.0
12.7
.
6.5
2.0
3.6
0.9
8.5
163
1.2
1.0
1.1
25.4
1.2
13
63
1.4
1.5
1.0
1.7
15
0.8
1.0
1.8
1.8
Std
Dcv*
73
5.8
83
.
24.4
13
.
2.5
0.6
63
11.0
0.6
0.6
1.0
893
0.9
0.8
4.2
0.6
1.2
0.6
13
33
03
0.5
43
13
s*
2.7
2.1
1.6
.
8.6
2.6
.
25
2.2
2.4
2.3
1.2
2.0
2.6
8.8
33
1.8
2.4
1.1
2.9
2.2
3.4
1.1
1.0
0.9
6.1
2.7
K*
11.7
53
4.0
74.8
8.6
8.1
53
7.9
7.6
1.1
4.7
6.6
79.2
12.1
3.8
7.8
0.9
9.0
4.8
15.1
1.7
03
0.5
393
8.6
JBS441
9-19
-------
Table 9-8
Continued
: - ' . '.":•"•".•'"
Cbmpooad
2-Methylpeotane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Metbylcyclopentane
2,4-Dimethylpentane
Benzene
Cydohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trunethylpentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
i-Octene
n-Octane
Edodbenzene
Cases
82
82
12
24
2
82
19
10
80
56
82
48
23
79
82
82
75
69
0
48
78
82
62
48
26
54
81
;'••-. . . • - .:
fteq*
(%)
100.0
100.0
14.6
293
2.4
100.0
23.2
12.2
97.6
683
100.0
58.5
28.1
963
100.0
100.0
91.5
84.2
0.0
58.5
95.1
100.0
75.6
58.5
31.7
65.9
98.8
Min*
1.4
0.9
0.5
0.5
0.5
0.7
0.4
0.5
0.7
0.5
0.9
0.4
0.6
0.6
1.0
0.8
0.5
0.4
0.4
0.5
3.1
0.5
0.5
0.4
0.4
0.8
Max* :
25.1
20.1
2.0
23
0.7
33.7
4.4
1.0
19.7
4.7
23.6
13.4
3.9
15.7
12.5
22.7
15.9
92.2
.
3.7
8.9
198.0
5.6
4.1
23
4.6
12.9
%fcd»
4.5
3.3
0.6
0.7
0.6
2.9
0.6
0.6
1.6
0.8
4.0
1.0
1.0
1.6
23
3.3
1.6
1.2
0.8
13
11.7
1.0
0.9
0.7
0.8
1.9
ppbC
•^
5.4
4.2-
0.9
0.9
0.6
3.7
1.0
0.7
2.0
1.2
5.0
1.4
1.2
2.2
3.0
43
2.2
2.7
.
1.0
1.7
18.1
13
1.1
1.0
1.1
2.6
'--••• :-'.'- ''•
std
Dev*
4.1
33
OJ
0.5
0.1
4.2
0.9
0.2
23
0.8
3.5
1.9
0.9
2.1
2.0
3.7
23
11.0
.
0.7
1.5
25.2
0.9
0.8
0.6
0.8
23
• ".-.•" •'•''• • '•
:;>•••
2.7
2.4
1.6
1.5
.
5.2
3.0
1.0
5.9
2.7
2.8
5.9
2.4
4.3
2.9
3.0
3.9
8.2
.
2.4
3.0
5.2
3.0
25
1.1
3.1
2.9
•vb^- •
IS*
8.6
7.5
1.6
1.6
33.6
9.8
0.6
42.4
7.9
10.4
38.6
5.6
24.4
10.2
10.2
193
68.2
.
5.2
10.0
33.0
10.5
6.1
0.1
11.1
8.8
JBS441
9-20
-------
Table 9-8
Continued
i
k , :
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13J-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decaae
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecanc
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
:
<^
-------
Table 9-9
Continued
i*\_-__,-__Jt
2-Methylpcntane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hcxane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethyipentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethyipentane
23,4-Trimethyipentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octanc
Ethylbenzene
f^anfa.
79
79
14
58
1
79
46
31
79
79
79
79
76
79
79
79
79
79
0
72
79
79
78
77
61
79
79
, i
Raj*
ftCl
Vf
100.0
100.0
17.7
73.4
13
100.0
58.2
392
100.0
100.0
100.0
100.0
96.2
100.0
100.0
100.0
100.0
100.0
0.0
91.1
100.0
100.0
98.7
97.5
772
100.0
100.0
k
Mm*
3.0
2.1
0.5
0.5
0.9
2.6
0.4
0.5
1.7
0.9
4.4
0.5
1.1
0.7
2.0
2.7
0.8
0.8
0.5
0.9
10.8
0.6
0.6
0.5
0.6
22
Mia*
26.7
27.7
1.7
2.4
0.9
23.9
1.5
12
16.1
7.0
31.7
8.0
10.3
13.0
11.9
19.9
9.2
5.9
.
2.8
6.7
84.4
5.4
4.9
3.9
4.1
16.9
MedP
8.2
5.8
0.7
1.0
0.9
6.8
0.8
0.6
4.8
2.6
12.0
2.6
3.2
2.0
4.0
73
3.0
2.1
.
1.1
2.6
27.2
1.8
1.5
1.1
1.1
5.6
ppbC
AW*
*vvg
9.4
6.8
0.8
1.1
0.9
7.8
0.8
0.7
55
3.0
132
2.9
3.7
2.6
4.6
8.1
3.4
23
.
1.2
2.8
30.6
2.1
1.7
12
1.4
62
std
Ttcnf
4.7
3.9
0.4
0.4
.
3.9
0.2
0.2
2.7
1.4
5.6
1.5
2.0
1.8
1.9
3.7
1.8
1.0
.
0.5
12
13.8
1.0
0.8
0.6
0.7
2.8
S*
13
2.4
1.5
1.0
.
1.5
1.0
12
1.4
1.0
12
0.9
1.4
2.9
13
1.0
1.1
1.0
.
1.1
1.0
13
12
1.5
1.9
5
1.4
+
K*
1.9
10.0
2.1
0.6
2.9
0.9
0.5
2.5
0.7
1.7
0.8
1.9
12.8
2.2
0.8
0.8
0.9
.
0.8
0.9
2.4
1.4
2.8
5.9
2.4
2.6
JBS441
9-23
-------
Table 9-9
Continued
•'• GbotpoBui
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
aJpha-Pinene
n-Propylbcnzene
m-Ethyltolueoe
p-Ethyltoluene
133-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Uodecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Cfraff
79
79
79
44
75
53
67
78
79
77
79
36
51
76
79
77
79
45
70
79
76
79
31
76
Bcof
(%>
100.0
100.0
100.0
55.7
94.9
67.1
84.8
98.7
100.0
973
100.0
45.6
64.6
96.2
100.0
973
100.0
57.0
88.6
100.0
96.2
100.0
39.2
96.2
: ppbc . -v^;-.®^;-.
Mb*
03
03
2.2
0.4
0.7
0.4
0.6
0.6
1.2
0.7
0.6
1.4
0.4
0.6
0.7
03
0.9
0.4
03
0.6
0.4
0.7
0.4
03
Mo*
38.3
2.9
15.7
1.7
14.9
23
6.6
5.0
11.2
4.4
6.2
29.1
4.8
15.8
503
30.0
15.1
3.4
7.7
273
33
59.4
1.8
123
*!ed*
14.9
13
5.6
0.8
1.8
0.8
1.8
13
3.8
13
23
2.7
1.0
33
4.6
2.2
3.1
1.1
1.2
2.6
1.1
1.7
0.8
1.0
Atf
162
1.4
6.1
0.8
23
0.9
2.0
1.7
43
1.7
2.5
3.7
1.2
4.4
6.4
3.2
33
13
1.4
3.4
1.2
33
0.9
1.4
•'m.:.
»ev*
6.9
03
2.7
03
1.9
0.4
1.1
0.8
1.9
0.8
13
4.6
0.8
3.8
7.0
3.9
2.2
0.6
1.0
33
0.6
7.2
03
1.6
> •'•
0.8
1.0
1.2
1.4
4.2
1.1
2.0
13
1.2
1.4
0.8
5.1
23
1.1
3.8
5.0
2.4
1.1
43
4.8
1.1
6.6
1.0
5.2
:'k*
0.8
0.6
2.0
2.7
24.8
1.0
5.7
2.8
13
2.2
0.1
283
7.5
03
20.8
31.0
93
1.4
25.9
28.9
0.9
483
0.4
31.7
aFreq = Frequency, Min - Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
JBS441
9-24
-------
Table 9-10
1993 Summnry Statistics for Fort Worth, Texas (FWTX)
Compound
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
2,3-Dimethylbutane
Case*
79
79
79
0
74
77
1
80
17
80
80
21
18
18
80
34
52
80
56
64
31
71
80
10
33
42
70
;
Fre
98.8
98.8
98.8
0.0
92.5
96.3
13
100.0
213
100.0
100.0
263
22.5
223
100.0
423
65.0
100.0
70.0
80.0
38.8
88.8
100.0
12.5
413
52.5
87.5
ppbC
Mm*
0.9
1.2
0.7
b
0.6
0.5
1.8
0.6
0.4
1.6
3.5
03
0.4
0.4
43
0.4
0.5
1.7
0.5
0.4
0.4
03
3.6
0.5
0.4
0.4
0.4
Max"
47.7
33.4
612
.
28.2
12..
1.8
163
23
161.0
723
18.9
20.4
7.7
236.6
11.6
18.7
85.4
2.1
20.2
10.8
343
85.5
33
2.8
8.5
15.4
Ifef*
7.7
3.5
8.6
.
2.8
1.5
1.8
2.0
1.0
6.0
9.9
0.9
0.8
1.0
9.4
0.8
0.9
4.1
1.0
1.0
0.7
1.0
8.8
0.8
1.0
0.8
12
AV
9.7
5.8
11.0
.
4.1
2.0
1.8
2.9
1.0
11.0
13.7
2.0
2.2
1.5
18.2
1.6
1.7
8.5
1.1
1.7
1.5
2.0
18.0
1.0
1.0
1.4
1.9
Std
»e/*
7.6
5.8
9.6
.
4.6
1.8
.
2.7
0.5
21.4
11.9
3.9
4.6
1.7
31.1
2.1
2.6
12.2
0.5
2.7
2.0
4.1
17.2
0.8
03
1.6
23
^
2.4
25
2.9
.
33
33
.
2.8
1.2
5.6
3.0
4.4
4.1
3.1
53
3.9
5.8
4.0
0.7
5.6
4.0
7.0
1.7
2.9
1.8
3.1
4.1
K*
8:1
7.4
10.7
.
147
I4-7
.
9.1
2.2
34.7
12.0
19.7
16.8
103
32.8
17.7
37.4
20.4
-0.6
37.2
183
54.6
2.8
8.9
3.9
10.9
19.6
JBS441
9-25
-------
Table 9-10
Continued
Compound
2-Methylpentane
3-Methylpentane
2-Methyl- 1-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimetbylpentaae
Benzene
Cyciohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,2,3-Trimethylpentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
Gases
80
80
24
14
0
80
16
9
78
45
79
48
19
74
80
79
73
64
0
42
75
80
56
42
20
42
77
Wtccf
(%)
100.0
100.0
30.0
17.5
0.0
100.0
20.0
113
97.5
56.3
98.8
60.0
23.8
92.5
100.0
98.8
913
80.0
0.0
52.5
93.8
100.0
70.0
52.5
25.0
52.5
963
=• ' : - K*C • : ' , :, •;
Mia*
13
0.8
0.5
0.4
.
0.8
0.5
0.5
0.7
0.4
0.9
0.5
0.6
0.6
0.9
0.9
0.4
0.4
0.4
0.5
1.2
0.4
0.4
0.4
0.5
0.6
Max1
43.9
263
1.8
3.4
223
2.2
1.5
12.2
5.7
23.5
2.7
3.4
10.2
9.4
26.0
7.4
4.6
.
4.1
9.6
68.5
43
3.4
22
4.8
10.8
Med*
33
2.6
0.9
1.0
.
2.2
0.8
0.7
13
0.8
3.3
1.3
1.0
1.6
2.0
2.6
1.2
0.9
.
0.8
1.0
8.1
0.9
0.7
0.9
0.8
1.5
AV
5.5
3.9
1.0
1.2
.
3.4
0.9
0.8
2.0
13
4.6
1.4
1.4
2.0
2.6
45
1.7
13
1.1
1.7
12.6
1.2
1.1
1.0
1.1
2.2
Std
D«>
6.6
4.2
0.5
0.8
.
3.4
0.4
03
1.9
1.1
4.2
0.6
0.9
1.8
1.8
4.9
1.5
0.9
.
0.9
1.7
12.0
0.9
0.8
0.5
0.8
2.0
•"$« :
3.7
3.2
0.5
1.7
3.2
1.8
2.0
3.2
2.4
2.7
0.5
1.4
2.6
23
2.9
2.4
1.8
.
1.9
2.8
2.7
2.0
1.8
12
2.7
2.5
IS?
16.6
12.1
-1.2
3.7
,
12.8
3.8
4.6
11.8
6.2
8.0
-0.8
1.0
7.4
4.9
9.0
5.2
2.7
.
3.2
83
7.6
33
2.0
1.6
9.2
6.2
JBS441
9-26
-------
Table 9-10
Continued
Compound •
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pincne
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Dicthylbenzene
1-Undecene
o-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Case*
79
42
77
0
37
14
48
45
76
40
61
36
28
74
72
51
76
25
57
77
68
74
22
69
:>:.. ;•..;•:. :,. . \
Xttff
&>
98.8
52.5
963
0.0
46.3
17.5
60.0
563
95.0
50.0
763
45.0
35.0
92.5
90.0
63.8
95.0
313
713
963
85.0
9LS
27.5
863
^>v. Hpbc ' !
Min'
1.0
0.4
0.5
.
0.4
0.6
0.6
0.4
0.7
0.4
0.5
0.5
0.4
0.6
0.6
0.4
0.6
0.4
0.5
0.4
0.4
0.5
0.4
0.5
ItaP
37.1
4.8
14.6
.
1.9
1.5
3.1
3.2
10.5
4.4
63
4.8
33
18.1
13.6
4.1
16.4
1.5
4.1
19.8
2.8
22,4
1.2
5.9
ifef
4.7
0.8
1.8
.
0.7
0.8
1.7
0.8
1.6
0.7
1.0
13
0.9
1.4
1.7
0.9
2.1
0.7
13
1.1
1.0
1.5
0.6
0.9
Avrf
7.1 -
1.1
2.7
.
0.8
0.9
1.6
1.0
2.2
1.1
13
1.6
1.1
2.6
2.2
1.1
2.4
0.8
1.4
IS
1.1
2.7
0.7
12
Sid
DC*
6.5
0.9
2.5
.
0.4
03
0.6
0.6
1.8
0.9
1.1
0.8
0.6
3.1
2.0
0.7
2.4
03
0.8
2.4
0.5
3.6
02
1.0
s*
2.7
2.9
2.7
.
13
1.0
0.4
1.9
23
2.0
2.6
2.7
2.0
2.9
3.7
2.4
4.4
1.0
13
5.7
1.8
3.4
0.8
3.0
& :
15
9.7
7.7
.
0.9
0.3
03
33
62
4.0
7.9
9.5
5.2
9.6
17.3
7.9
23.1
0.2
2.0
403
2.6
13.0
-03
10.5
*Freq = Frequency, Min - Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
JBS441
9-27
-------
Table 9-11
1993 Summary Statistics for Juarez, Mexico (JUMX)
CbBtpOQoa
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl- 1-pentene
Cyclopentane
2,3-Dimethyftnitane
Qavnt
68
71
72
0
70
69
0
73
22
73
73
26
27
19
73
42
40
73
57
44
28
53
73
6
23
47
61
Fteif
(%)
91.9
96.0
973
0.0
94.6
933
0.0
98.7
29.7
98.7
98.7
35.1
36.5
25.7
98.7
56.8
54.1
98.7
77.0
59.5
37.8
71.6
98.7
8.1
31.1
63.5
82.4
:. ••-.'• .;. '" : H*e .- •• :
Mm*
1.7
'is
13
b
0.8
0.5
0.8
0.4
1.6
3.2
0.5
0.5
0.5
1.0
0.5
0.4
0.7
0.5
0.6
OS
0.6
43
0.5
0.5
OS
0.5
Max*
62.6
60.1
61.9
.
109.8
12.9
.
30.5
2.9
92.1
297.6
4.6
4.1
2.6
859.5
23.0
8.1
73.8
33
7.9
4.6
9.8
20.4
2.0
1.1
6.6
10.1
Med*
9.7
7.2
7.7
.
4.4
1.9
.
3.7
0.8
12.9
44.7
1.1
1.0
0.8
10.7
1.1
1.0
7.1
1.2
1.2
0.9
1.2
8.8
0.9
0.7
0.9
1.4
AV
11.7
9.2
10.7
8.4
2S
.
4.4
1.0
17.5
60.5
IS
1.2
1.0
32.9
1.7
1.4
11.7
1.3
1.6
13
1.9
9.2
1.1
0.7
1.4
1.8
Std
De^
9.7
8.6
10.0
.
15.5
1.8
4.1
0.7
16.6
55.2
1.0
0.8
0.6
107.0
3.4
13
13.9
0.7
1.4
1.0
1.7
2.6
0.6
0.2
13
1.5
S*
3.0
3.7
2.9
.
5.1
3.5
4.1
1.9
23
2.1
1.5
2.0
1.6
6.9
63
3.9
2.8
1.1
2.7
23
2.7
1.4
0.9
0.7
2.4
3.5
K*
12.5
18.7
11.1
t
29S
16.9
23.4
3.7
6.3
5S
2.8
4.6
2.2
51.3
40.0
18.2
8.2
0.8
8.2
5.8
8.6
43
-0.2
OS
6.0
17.6
JBS441
9-28
-------
Table 9-11
• Continued
umpotutu
2-Methyipentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpcntane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
22,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
;
V**""
73
71
D
22
0
72
13
7
70
62
73
62
62
62
73
70
68
58
0
35
59
73
50
51
24
52
73
:
Retf
\7fe/
98.7
96.0
17.6
29.7
0.0
973
17.6
93
94.6
83.8
98.7
83.8
83.8
83.8
98.7
94.6
91.9
78.4
0.0
473
79.7
98.7
67.6
68.9
32.4
703
98.7
Mm*
cms
0.7
0.7
0.4
0.4
.
0.7
03
03
03
03
0.9
0.4
03
03
0.8
0.6
03
0.6
.
0.4
0.4
1.8
0.4
03
03
0.4
0.6
Mm**
rail*
383
25.1
2.1
43
.
37.4
4.1
23
22.6
10.1
46.4
19.4
103
7.2
16.6
25.0
14.6
6.9
;
4.4
9.7
164.7
5.4
14.1
53
83
47.4
ur«
-------
Table 9-11
Continued
Compound
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoiuene
13,5-TrimethyIbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,2,3-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Case*
• 73
61
71
20
52
25.
48
49
71
37
57
31
21
74
74
64
71
28
55
71
65
73
22
66
fScof
W
98.7
82.4
96.0
27.0
703
33.8
64.9
66.2
96.0
50.0
77.0
41.9
28.4
100.0
100.0
86.5
96.0
37.8
743
96.0
87.8
98.7
29.7
89.2
' . ". = '. '"*>*&f* •'•'':/ .:- .' "'• • ':•'•'• \ : '•••'"• \S.. • •
' •••• .. PPW"» : .-. •:..".. • .•;. V' • ;• -- '-
Win*
0.8
0.4
0.6
0.4
0.5
0.5
0.6
0.5
0.6
0.5
0.6
0.6
0.4
0.5
0.4
0.5
0.5
0.4
0.5
0.6
0.4
0.6
0.4
0.5
"kaa*'
134.2
9.1
45.5
6.1
10.8
9.7
223
7.8
18.5
6.2
16.0
11.6
3.0
9.6
31.6
12.4
133
2.8
3.4
23.0
2.8
38.6
1.8
13.9
1 Med»
73
0.9
2.8
0.8
0.9
1.0
2.0
1.0
1.8
0.9
1.1
13
1.0
2.0
1.6
1.1
1.8
1.1
1.1
1.7
1.0
1.5
0.8
1.1
•i£':
12.3
1.6
4.5
1.8
1.5
2.4
2.8
1.2
2.4
13
2.5
1.8
1.2
2.4
2.7
1.9
2.2
1.1
13
3.1
1.1
3.6
0.9
1.7
Std
Dc^
17.6
1.8
63
1.6
1.9
2.6
3.4
1.1
23
1.2
3.5
2.0
0.6
1.7
3.8
2.3
2.0
0.6
0.7
4.3
0.5
6.5
0.5
22
•=: SV
5.1
3.0
4.6
13
4.2
1.5
4.2
5.2
5.1
3.1
2.6
4.5
1.6
1.8
6.1
3.4
3.8
1.2
13
3.5
1.4
4.1
1.0
3.8
. Kf
323
9.6
263
1.2
18.4
13
22.3
31.0
333
9.5
6.6
22.4
33
4.1
44.9
12.4
17.8
2.4
1.0
12.5
23
17.2
-03
173
"Freq = Frequency, Min = Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculatiou HOC possible due to limited data.
JBS441
9-30
-------
Table 9-12
1993 Summary Statistics for Long Island, New York (LINY)
Gompomiii :
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl- 1-pentene
Cyclopentane
23-Dimethylbutane
Oases
8
8
8
1
8
8
0
8
2
8
8
7
6
3
8
5
7
8
8
7
7
8
4
1
5
5
8
;
Fretf
<*>
100.0
100.0
100.0
12.5
100.0
100.0
0.0
100.0
25.0
100.0
100.0
87.5
75.0
37.5
100.0
62.50
87.50
100.0
100.0
87.5
87J
100.0
50.0
12.5
62.5
62.5
100.0
«*c
Mm*
5.0
2.0
3.5
0.7
1.6
1.0
.
1.6
0.5
2.8
4.9
0.5
0.6
0.6
5.5
0.59
0.63
1.6
0.4
0.7
0.5
0.6
0.5
0.8
0.4
0.5
0.8
*&*#
17.9
6.9
15.2
0.7
7.3
3.9
.
6.0
0.8
12.2
42.4
1.7
1.5
0.7
293
1.%
. 1.54
8.4
4.4
1.8
1.0
1.9
0.6
0.8
13
1.0
2.5
Mof
8.7 .
4.8
7.0
0.7
3.9
2.5
.
3.7
0.7
8.4
5.5
1.2
1.0
0.7
15.7
0.70
120
4.9
1.1
13
0.8
13
0.5
0.8
OJ
0.7
12
AV
9.9
4.5
7.6
0.7
4.3
2.4
,
3.6
0.7
7.7
10.6
1.2
1.0
0.7
15.4
1.00
1.11
4.7
1.8
13
0.8
13
0.5
0.8
0.7
0.7
1.4
Std
Dw*
4.4
1.7
3.6
b
2.1
1.0
.
1.4
0.2
3.5
12.9
0.4
0.3
0.1
7.4
0.57
032
2.1
1.6
0.4
0.2
0.4
0.1
.
0.4
02
0.6
s*
0:9
-0.4
1.4
,
0.4
0.0
.
0.1
.
-0.2
2.8
-1.1
0.1
-0.2
0.7
1.68
-0.29
0.4
13
-03
-0.4
-0.6
-0.8
.
2.1
03
12
**
-6.2
-0.5
2.7
.
-1.2
-0.4
.
-0.4
.
-1.7
7.7
2.5
0.5
.
0.8
2.61
-0.88
0.7
-0.2
-13
-1.4
-03
03
.
4.5
-22
1.0
JBS441
9-31
-------
Table 9-12
Continued
Compound
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
2,3-Dimethylpentane
2-Methylbexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpentane
23,4-Trimethyipentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
Case* ;
8
8
1
4
0
8
1
1
8
7
8
7
3
. 8
8
8
7
8
0
6
8
8
8
5
3
4
8
LHteif :
rw
100.0
100.0
12.5
50.0
0.0
100.0
115
12.5
100.0
87.5
100.0
875
375
100.0
100.0
100.0
875
100.0
0.0
75.0
100.0
100.0
100.0
625
375
50.0
100.0
;••-•. ' : .,"•. "...•••••'• : pjpfeC "\ • . : ':- •'.- '; -:"- .
Mb*
15
1.9
0.8
0.5
0.9
0.4
05
0.6
0.4
2.6
0.6
05
0.8
1.1
0.9
0.7
05
.
0.5
05
63
0.4
0.6
05
0.6
1.0
' Mrf
93
6.4
0.8
0.8
.
35
0.4
05
2.7
1.4
93
2.0
1.0
2.6
3.9
55
2.4
13
1.0
2.1
36.1
1.9
15
0.7
1.4
4.6
Mtxf
35
3.1
0.8
05
.
2.0
0.4
0.5
1.4
0.7
55
1.2
0.8
1.6
2.2
2.9
13
0.7
.
0.6
1.2
14.0
0.7
0.8
05
0.8
1.9
AV
45
3.6
0.8
0.6
.
2.0
0.4
0.5
1.4
0.8
55
1.1
0.8
1.7
23
2.8
15
0.8
0.7
1.2
15.6
0.9
0.9
0.6
0.9
2.2
Sid
tta*
3.0
1.5
.
0.2
0.8
.
.
0.6
03
2.0
0.5
0.3
0.7
0.8
1.4
0.6
03
0.2
05
9.0
05
0.4
0.1
0.4
1.1
s*:
1.2
0.9
.
1.9
.
0.6
.
1.20
1.2
1.5
05
-0.9
0.2
0.9
0.7
0.6
1.8
,
1.2
0.6
2.0
13
2.1
12
0.8
1.8
jj.
-0.2
-0.1
3.8
03
,
3.1
2.4
1.2
-03
-1.8
1.9
0.8
-1.1
4.0
0.5
0.7
5.1
0.9
45
.
-15
4.1
JBS441
9-32
-------
Table 9-12
Continued
" Compound
'p-Xyiene + m-Xylene
Styrene
o-Xylene
1-Nonenc
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Etbyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
o-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecanc
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
CM**
8
6
8
2
7
2
8
6
8
4
8
7
2
8
8
6
8
3
7
8
8
8
5
8
Req*
(*>
100.0
75.0
100.0
25.0
87.5
25.0
100.0
75.0
100.0
50.0
100.0
87.5
25.0
100.0
100.0
75.0
100.0
37.5
87.5
100.0
100.0
100.0
62.5
100.0
f
Mm*
3.1
0.5
1.1
0.5
0.6
0.5
0.6
0.6
1.0
0.5
0.6
0.7
0.6
0.7
0.8
0.6
1.8
0.6
0.9
0.6
0.6
0.6
0.4
0.6
ppbc
Mia*
15.6
0.8
53
0.6
1.9
0.5
3.0
1.4
4.0
1.1
2.1
2.5
IS
3.4
7.2
13
6.2
0.7
83
3.1
1.9
8.5
1.4
3.1
Med*
7.2
0.6
2.4
0.5
0.6
0.5
1.1
0.6
1.9
0.6
1.0
1.6
1.0
1.1
2.8
0.9
3.2
0.6
3.4
1.4
13
1.6
0.5
13
AV
7.5
0.6
2.5
0.5
0.9
0.5
1.4
0.7
2.2
0.7
1.1
1.5
1.0
1.4
3.0
0.9
3.7
0.7
3.7
1.5
1.2
2.4
0.7
U
Std
Bei*
3.7
0.1
13
0.1
0.5
0.0
0.8
03
1.1
03
0.5
0.6
0.6
0.9
2.0
0.2
1.5
0.0
2.5
0.7
OS
2.6
0.4
0.9
s*
1.6
02
1.4
.
1.6
t
1.2
2.4
1.0
1.9
13
0.1
t
2.2
IS
0.7
0.6
1.5
1.0
13
0.0
23
13
0.9
| K*
3.7
-1.1
3.1
t
23
.
03
5.6
-0.5
3.7
2.1
-0.4
t
5.2
3.2
03
-0.9
.
1.1
3.2
-1.4
5.7
0.7
-0.1
*Freq = Frequency, Min = Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K - Kurtosis
bCalculation not possible due to limited data.
JBS441
9-33
-------
Table 9-13
1993 Summary Statistics for Newark, New Jersey (NWNJ)
Compound
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
23-Dimethylbutaue
Cases
8
8
8
0
8
8
0
8
4
8
8
8
6
6
8
5
7
8
7
7
5
8
6
1
7
6
7
Req"
(%)
100.0
100.0
100.0
0.0
100.0
100.0
0.0
100.0
50.0
100.0
100.0
100.0
75.0
75.0
100.0
62.5
87.5
100.0
87.5
87.5
62.5
100.0
75.0
12.5
87.5
75.0
87.5
••''./ ^i '. ...••/'. '•'• :' iffoc /.•"'••;' ••"W> .'
Mm*
7.7
2.4
8.4
b
2.5
1.4
.
3.6
0.7
3.4
6.0
0.4
0.5
0.4
5.7
0.5
0.4
2.2
0.7
0.6
0.6
0.5
0.4
0.8
0.4
0.5
0.9
Maa*
49.1
25.5
53.8
.
24.1
9.1
31.7
2.0
39.2
64.4
3.7
2.9
1.9
70.1
4.8
4.0
23.6
3.1
9.5
3.0
4.8
1.4
0.8
1.5
6.9
4.0
Med*
19.9
7.6
173
.
6.6
3.4
9.2
1.2
9.2
18.0
1.1
1.0
1.0
19.1
1.0
1.3
6.1
13
1.4
13
13
0.6
0.8
0.9
13
2.2
A#
20.6
8.5
19.9
.
93
4.0
10:8
13
14.5
24.0
1.7
1.4
1.2
27.5
1.8
1.9
9.8
1.6
2.8
1.7
1.8
0.7
0.8
1.0
2.1
23
Std
t>«>
12.9
7.6
14.6
.
7.7
2.8
.
9.3
0.5
13.8
20.9
1.2
1.0
0.7
25.1
1.7
13
9.1
0.9
3.2
1.0
1.4
0.4
.
0.4
2.4
1.0
; -5*
1.7
1.9
2.2
,
1.2
0.9
1.9
1.1
1.2
13
1.2
0.8
0.2
1.1
1.8
0.8
1.0
1.1
2.1
0.5
1.7
1.8
.
0.0
22
0.4
K*
3.9
4.2
5.3
0.6
-0.3
.
4.2
2.0
-0.0
0.8
-0.1
-1.6
-2.4
-0.4
3.4
-0.9
-0.8
0.1
4.7
-2.2
3.0
3.6
.
-0.4
5.0
0.2
JBS441
9-34
-------
Table 9-13
Continued
SifsST t
• Im • *> "•
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Metbylhexane
3-Metbylhexane
2^,4-Trimethylpentane
n-Heptane
Methylcydohexane
1-Heptene
2A3-Trimethylpcntane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
Cases"
8
8
0
4
0
8
5
2
8
7
8
8
5
8
8
8
8
8
0
6
8
8
7
8
4
6
8
W-
100.0
100.0
0.0
. 50.0
0.0
100.0
62.5
25.0
100.0
87.5
100.0
100.0
62.5
100.0
100.0
100.0
100.0
100.0
0.0
75.0
100.0
100.0
87.5
100.0
50.0
75.0
100.0
^&^&^*&C '-: . *
li>-
1.4
0.6
.
0.6
.
1.0
0.5
0.6
0.9
0.4
2.6
1.5
0.4
0.5
1.8
22
0.5
0.5
0.5
0.6
11.6
0.7
0.5
0.6
0.6
1.5
"&.
IT*
11.7
.
1.4
.
' 10.2
1.0
0.8
7.2
4.1
193
5.8
2.8
53
10.1
16.0
5.9
2.9
.
23
5.7
87.5
4.7
4.2
12
3.9
17.6
;lS:i
3.9
5.6
.
0.7
.
3.2
0.7
0.7
23
1.5
7.0
3.5
1.0
1.8
3.0
5.2
1.7
1.0
.
1.1
2.1
28.9
1.6
13
0.8
1.0
43
S|!
5.8
6.0
,
0.8
,
4.2
0.7
0.7
2.8
1.7
7.9
3.4
1.2
2.4
4.1
6.2
2.1
1.4
.
1.2
23
333
1.9
1.5
0.8
1.5
5.5
srd
5.5
4.2
,
0.4
,
3.3
02
0.1
2.2
1.2
5.4
1.5
0.9
1.8
2.7
4.6
1.8
1.0
0.6
1.7
24.4
1.4
1.2
03
12
5.1
1 s*
1.8
0.2
t
1.9
.
1.0
-0.0
t
13
1.4
1.4
03
1.8
0.9
1.8
1.5
1.4
1.0
,
1.0
1.4
1.8
1.7
1.9
0.6
L2
2,4
K*
3.2
-1.2
.
3.6
-0.2
-2.6
.
1.4
2.4
2.4
-0.7
3.4
-0.7
3.5
2.4
1.7
-0.8
,
13
23
3.9
3.4
4.4
-2.5
5.1
6.1
JBS441
9-35
-------
Table 9-13
Continued
Compound
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
oEthyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Cases
8
8
8
1
8
3
8
6
8
6
8
8
3
8
8
8
8
7
7
8
8
8
3
8
f-IJteqp
(%)
100.0
100.0
100.0
12.5
100.0
37.5
100.0
75.0
100.0
75.0
100.0
100.0
37.5
100.0
100.0
100.0
100.0
87.5
87.5
100.0
100.0
100.0
37.5
100.0
F : • WAG -A ';••;• i ^>-
Mm*
0.5
0.5
1.8
0.8
0.9
1.1
0.9
0.6
13
0.7
0.5
0.7
0.5
0.7
2.4
0.7
2.9
0.5
1.2
13
0.7
0.5
0.5
0.5
Mar*
60.4
2.2
18.7
0.8
5.8
• 13
3.0
4.0
9.8
3.2
4.1
5.9
2.3
1.4
19.3
10.4
12.1
1.5
2.6
8.5
2.0
26.4
1.2
7.7
Med»
11.9
0.9
5.0
0.8
1.4
1.2
1.9
1.4
3.1
1.1
1.4
2.0
0.5
0.9
6.2
23
3.4
0.5
1.7
2.5
0.9
2.0
0.9
0.7
A*f?
16.9
1.0
6.0
0.8
2.0
1.2
1.9
1.7
3.5
1.4
1.7
2.2
1.1
1.0
6.8
3.1
4.8
0.9
1.7
3.4
1.0
4.8
0.8
1.7
Std
be*,!
18.6
0.5
5.4
1.6
0.1
0.8
1.2
2.8
0.9
1.2
1.6
1.0
03
5.5
3.1
3.3
0.5
0.5
2.4
0.4
8.8
03
2.4
' s*:
2.2
1.8
2.2
.
2.5
1.1
-0.1
1.9
1.9
2.1
1.4
2.0
1.7
0.9
1.9
2.5
2.1
0.4
0.6
1.7
1.8
2.8
-0.1
2.7
•~K*>
5.6
3.9
5.5
,
6.5
.
-1.2
4.4
4.4
4.8
2.1
4.8
-0.5
4.4
6.5
4.2
-2.6
-0.7
25
32
7.8
.
73
"Freq = Frequency; Min = Minimum; Max = Maximum; Med
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCaioilatioQ not possible due to limited data.
Median; Avg = Average;
JBS441
9-36
-------
Table 9-14
1993 Summary Statistics for Bristol, Pennsylvania (PIPA)
^9lCvlHf:fi^:-<:;i::l
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Mcthyl-l-butene
Isopentanc
1-Pentene
2-Methyl-l-butcne
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2^-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cydopentane
23-Dimethylbutane
•. .:\ :-'-•: ••••:':'••
Cases"
8
8
8
0
8
8
0
8
2
8
8
5
3
4
8
6
7
8
7
8
5
8
4
1
7
8
8
••:•:•:•.: • • •. . ::
':y.; '''•;%. /;';.;
•:3Rte«f::
1 <%)
100.0
100.0
100.0
0.0
100.0
100.0
0.00
100.0
25.0
100.0
100.0
62.5
37.5
50.0
100.0
75.0
87.5
100.0
87.5
100.0
62J
100.0
50.0
115
87.5
100.0
100.0
K*C
Mb*
53
13
5.0
b
23
1.4
.
1.9
0.6
6.1
5.4
0.8
0.7
0.4
11.5
0.5
0.5
5.0
13
0.5
0.5
0.6
1.2
0.7
0.6
0.6
1.1
Mia*
25.5
11.4
14.6
.
13.4
4.5
.
9.2
1.1
303
63.9
2.2
0.9
1.9
48.9
1.8
2.7
17.2
6.1
3.4
32
3.9
20.1
0.7
1.4
1.8
4.7
Mcd*
11.2
4.5
7.6
.
5.5
1.8
.
5.1
0.9
11.9
18.6
0.9
0.7
0.8
17.1
0.8
1.6
8.8
4.0
0.9
1.5
12
16.8
0.7
0.8
1.1
2J
Atf
13.2
53
8.7
.
63
2.4
.
53
0.9
14.1
27.2
13
0.8
1.0
22.0
1.0
1.4
9.4
3.6
13
1.7
1.6
13.7
0.7
0.9
1.1
2.6
Std
Ve*
7.7
3.6
3.4
.
4.0
12
.
3.0
0.4
8.1
21.6
0.6
0.2
0.7
12.5
0.5
0.7
4.1
1.7
1.0
13
12
8.5
.
03
0.5
1.4
s*
0.6
0.7
12
0.8
1.4
0.1
.
1.4
0.8
1.4
1.7
1.4
1.8
1.1
0.6
1.0
-03
1.6
03
1.4
-1.8
.
0.6
0.5
0.4
J£V
-13
-0.7
0.0
-03
0.2
,
-2.0
.
1.4
-0.9
1.1
.
2.5
3.0
03
0.2
1.0
-0.6
1.6
-2.9
0.5
3.4
.
-1.6
-1.0
•IS
JBS441
9-37
-------
Table 9-14
Continued
':-..• Cbrnpcmnd :
2-Methylpeotane
3-Methylpentane
2-Methyl- 1-pentene
1-Hexene
2-Etbyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methyicydopentane
2,4-Dimethylpentane
Benzene
Cydohexane
23-DimethyIpentane
2-Methylhexane
3-Methyihexane
2,2,4-Trimethylpentane
n-Heptane
Methylcydohexane
1-Heptcnc
2,23-Trimethylpeotane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
. :-:
Cases
8
8
0
3
1
8
3
1
8
7
8
8
1
8
8
8
8
7
0
7
8
8
8
8
3
6
8
.'Vtcef'i
(*>)
100.0
100.0
0.0
37.5
12.5
100.0
37.5
12.5
100.0
87.5
100.0
100.0
12.5
100.0
100.0
100.0
100.0
87.5
0.0
87.5
100.0
100.0
100.0
100.0
37.5
75.0
100.0
::: -'•'• •".'_. ppbC •••"••
Mm*
33
2.4
.
1.1
0.6
2.0
0.7
0.6
1.0
0.6
3.5
0.6
0.7
1.6
1.7
13
1.0
13
03
0.7
83
0.8
0.6
0.4
0.5
13
Mar»
16j6
2532.8
.
1.6
0.6
16.8
1.2
0.6
1613
23
12.8
4.6
0.7
64.4
57.7
9.7
28.2
6.6
.
1.6
33
121.6
4.2
4.2
0.9
1.1
6.8
Mod*
52
6.1
.
13
0.6
3.8
0.9
0.6
23
0.9
63
2.4
0.7
4.8
4.2
2.4
33
22
.
0.8
1.1
24.2
1.6
0.9
03
0.7
2.4
-•':•' >:• :
AV
6.7
321.9
.
1.4
0.6
5.6
0.9
0.6
223
13
7.0
2.3
0.7
17.7
15.9
3.7
83
3.0
0.9
13
363
1.8
1.4
0.6
0.7
33
Std 1
De>
4.4
8933
.
0.2
.
4.9
0.2
.
56.2
0.7
3.2
1.2
253
22.6
2.9
10.0
1.8
.
0.4
1.0
37.7
1.1
12
03
03
2.0
3*
2.0
2.8
.
-1.6
2.0
0.1
2.8
1.0
1.0
0.7
,
13
13
1.7
1.6
1.6
.
0.6
13
2.0
1.6
2.0
1.7
03
0.9
&
4.2
8.0
.
.
.43
.
.
8.0
-0.2
03
1.7
.
0.4
03
2.0
1.2
2.2
.
-1.1
1.4
43
2.9
4.2
.
•22
-0.7
JBS441
9-38
-------
Table 9-14
Continued
1
CbBtpowi
p-Xylenc + m-Xylene
Styrene
o-Xylene
1-Noncne
n-Nonane
Isopropylbenzcne
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13J-Trimcthylbcnzene
o-Ethyltoluenc
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
123-Trimetnylbenzene
p-Diethylbcnzcne
1-Undeccnc
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Case*
8
7
8
1
8
6
8
6
8
6
8
8
6
8
8
7
8
8
8
8
8
8
5
8
Retf
(#>
100.0
87.5
100.0
12.5
100.0
75.0
100.0
75.0
100.0
75.0
100.0
100.0
75.0
100.0
100.0
87.5
100.0
100.0
100.0
100.0
100.0
100.0
62.5
100.0
ppbC
ttht*
4.9
0.5
1.6
0.6
0.6
0.7
OJ
OJ
0.9
0.4
0.8
0.9
0.4
0.6
2.0
0.7
2.4
OJ
0.9
0.8
0.9
0.7
OJ
0.9
Max*
24J
4.6
22J
0.6
33
5.9
2J
2.0
5.8
5.2
3.7
4.8
4.6
1.7
10.2
11.6
8.6
123
3.9
38.4
2.9
22.1
4.1
3.9
Med*
8.4
1.0
3.7
0.6
1.4
1.0
1.6
1.1
23
1.4
1.2
2.8
1.0
1.1
3.6
2.6
4.1
0.8
2.4
3J
13
2.9
0.7
3.1
AV
11.4
1.8
63
0.6
1.6
1.8
1.7
1.2
2.8
1.8
1.8
2.7
1.5
1.2
4.8
43
4.8
2.4
2.4
132
U
8.9
13
2.8
Std
£>«*
7.4
1.6
7.0
.
0.9
2.1
0.7
0.6
1.8
1.8
1.2
1.6
1.6
0.4
3.0
4.4
2.2
4.1
1.1
16J
0.7
9.6
1.6
0.9
S*
0.9
13
22
.
0.8
2.4
-0.6
03
0.9
2.0
0.9
0.1
2.2
0.2
1.1
1.1
1.1
2.7
•02
1.0
1.9
0.6
22
-1.4
**
-0.6
0.6
5.0
.
03
5.6
OJ
-2.0
-0.4
42
-1.0
-1.7
5.1
-1.8
-0.2
-OJ
-0.0
7.4
-1.4
-0.9
3J
-2.1
4.7
2.7
"Freq = Frequency, Min = Minimum; Max = Maximum; Med
Std Dev - Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
Median; Avg = Average;
JBS441
9-39
-------
Table 9-15
1993 Summary Statistics for Harrisburg, Pennsylvania (P2PA)
''fSuwvuuMui
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentanc
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
23-Dimethylbutane
Caen
9
9
9
0
9
9
0
9
4
9
9
3
5
4
9
7
6
9
8
4
4
5
3
1
8
7
9
Vttxf
(%>
100.0
100.0
100.0
0.0
100.0
100.0
0.0
100.0
44.4
100.0
100.0
333
55.6
44.4
100.0
77.8
66.7
100.0
88.9
44.4
44.4
55.6
333
11.1
88.9
77.8
100.0
«*?:."—- , • • .;•;•-•
Mm*
4.9
2.0
6.5
b
2.1
1.2
.
13
0.5
3.4
6.9
0.5
0.5
0.6
7.1
0.5
0.4
3.6
0.8
0.4
0.7
0.4
0.5
0.4
0.5
0.4
0.9
Max"
18.6
7.8
13.0
.
7.3
2.7
,
11.8
0.7
13.7
50.0
1.7
1.6
0.8
23.4
1.7
13
9.0
25
1.1
1.4
13
0:6
0.4
1.1
0.8
2.8
Mcd*
8.0
33
9.2
.
5.0
2.1
.
3.8
0.5
93
12.9
0.8
1.4
0.7
12.0
1.0
1.0
5.0
1.6
0.8
1.0
0.5
0.5
0.4
0.7
0.5
1.7
AV
10.0
3.9
9.6
.
5.0
1.9
.
4.5
0.5
8.6
17.6
1.0
1.1
0.7
153
1.0
1.0
5.9
1.6
0.8
1.0
0.7
0.5
0.4
0.7
0.6
1.7
sta
T*&
4.4
1.9
23
.
2.0
0.5
.
3.1
0.1
3.5
13.0
0.6
0.5
0.1
6.2
0.4
03
2.1
0.7
0.4
03
0.4
0.0
.
0.2
0.2
0.6
s*
0.9
1.1
0.4
.
-0.2
0.0
1.9
1.0
-0.2
2.3
13
-0.5
-1.0
0.2
0.8
-0.6
0.3
0.1
-0.2
03
0.8
-0.5
.
1.4
0.5
0.7
' K? ;
03
0.8
-0.9
.
-1.4
-1.4
4.3
-0.6
-13
6.0
-2.8
13
-2.0
1.6
-1.0
-1.8
-2.0
-4.7
-4.0
-1.9
.
2.6
-2.0
-03
JBS441
9-40
-------
Table 9-15
' Continued
i
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hcxcne
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopcntane
2,4-Dimethyipentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpentane
23,4-Trimethylpentane
Toluene
2-Methylhcptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenzene
Gua.
9
9
2
5
0
9
1
0
9
9
9
9
1
9
9
9
9
7
0
8
9
9
9
9
5
7
9
;
Req*
<*>
100.0
100.0
22.2
55.6
0.0
100.0
11.1
0.0
100.0
100.0
100.0
100.0
11.1
100.0
100.0
100.0
100.0
77.8
0.0
88.9
100.0
100.0
100.0
100.0
55.6
77.8
100.0
"^UffeC" - -. • • ••• ••-' '••
Mm*
0.5
4.0
0.7
0.5
.
1.6
0.5
12
0.4
2.9
0.6
0.7
0.7
1.7
1.6
0.4
0.6
.
0.4
0.6
15
03
0.4
0.5
0.4
1.4
Ha*
8.4
112
2.1
0.8
3.7
03
.
2.8
1.1
7.7
22
0.7
63
5.9
4.6
4.0
1.7
.
1.4
1.7
422
3.2
2.6
0.7
1.6
3.6
fctof
3.0
4.9
1.4
0.6
.
2.6
03
.
13
0.8
5.4
1.4
0.7
3.7
33
2.7
1.7
1.0
.
0.6
1.0
12.4
1.0
0.6
0.6
03
1.9
AV
3.9
5.6
1.4
0.6
2.6
033
1.9
0.8
5.3
1.4
0.7
3.2
3.3
3.0
2.1
1.1
0.7
1.1
17.2
1.1
0.9
0.6
0.7
23
SB*
{Be*=l
23
2.2
1.0
0.1
.
0.8
.
0.7
0.2
1.4
0.6
.
1.8
1.3
1.2
1.2
03
.
0.3
0.4
10.6
0.8
0.7
0.2
0.4
0.8
*'•••&•
0.1
2.6
1.3
0.0
.
0.4
0.2
-0.1
-0.2
.
0.3
0.6
0.3
0.4
0.3
1.8
03
1.9
23
2.7
0.1
2.4
0.7
'"'#. '
-0.5
7.0
.
2.9
.
-13
.
-2.0
-1.4
0.2
-1.8
.
-0.3
0.1
-1.8
-0.6
-2.0
.
4.1
-1.8
4.2
6.8
7.4
-1.1
5.9
-0.8
JBS441
9-41
-------
Table 9-15
Continued
p-Xylene + m-Xylene '
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
aJpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13J-Trimethylbenzene
o-Ethyltoluene
bcta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Dicthylbenzenc
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
i Cases
9
7
9
5
7
6
9
7
9
6
9
9
7
9
9
8
9
6
9
9
9
9
8
9
Ijtefl
;<%>:
100.0
77.8
100.0
55.6
77.8
66.7
100.0
77.8
100.0
66.7
100.0
100.0
77.8
100.0
100.0
88.9
100.0
66.7
100.0
100.0
100.0
100.0
88.9
100.0
ppfeC
Mm*
4.5
0.5
1.4
0.7
0,4
OJ
0.6
0.5
1.3
0.6
OJ
1.0
0.5
0.7
1.7
0.4
2.4
OJ
0.5
0.7
1.0
1.0
0.4
0.7
Mas'
D.I
0.8
4.2
13
1.1
2.2
2.9
0.9
3.5
0.9
1.5
2.1
1.9
1.2
4.7
2.0
23.9
0.8
2J
2.1
2.0
4.2
0.6
2.2
Maf
7J
0.6
23
1.1
0.7
1.6
1.9
0.6
2.0
0.7
0.9
1.6
0.8
0.9
3.0
1.1
3.1
OJ
1.7
1J
U
1.1
OJ
0.9
AV
8.0
0.6
2.6
1.0
0.8
1.4
1.7
0.6
2.1
0.7
1.0
1.6
1.0
0.9
3.1
13
5.6
0.6
1.6
1.5
1J
1.6
0.5
1.1
Sid
De^
2.9
0.1
1.0
03
0.2
0.7
0.9
0.2
0.7
0.1
0.3
0.3
0.6
0.2
1.1
OJ
6.9
0.2
0.6
0.4
0.4
1.1
0.1
0.6
S*
0.7
1.0
0.5
-0.6
0.1
-0.4
0.2
0.8
1.0
0.5
0.4
-0.6
0.6
0.2
0.2
0.1
2.9
1.0
-0.4
-0.9
0.1
2J
-0.1
13
K?
-0.4
0.7
-1.1
-0.7
1.1
-2.1
-1.7
-0.9
13
-1.6
-0.6
1.3
-1.6
-1.1
-1.4
-0.9
8.7
-0.9
-0.4
2.5
-1.6
6.1
-0.9
03
"Freq = Frequency, Mia = Minimum; Max = Maximum; Med
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
Median; Avg = Average;
JBS441
9-42
-------
Table 9-16
1993 Summary Statistics for Plainfield, New Jersey (PLNJ)
• %•!•••• -:••:
' : • f**ru»»uuMut
• ' " ^>i»lt|H HIIIM
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butcne
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
22-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
23-Dimethyibutane
Case*
8
8
8
0
8
8
0
8
5
8
8
6
6
6
8
5
6
8
8
6
5
7
5
3
6
5
8
;
Preq*
(*>
100.0
100.0
100.0
0.0
100.0
100.0
0.0
100.0
62.5
100.0
100.0
75.0
75.0
75.0
100.0
62.5
75.0
100.0
100.0
75.0
62.5
87.5
62.5
37.5
75.0
62.5
100.0
Mm*
42
13
63
b
1.4
0.7
.
13
0.6
1.8
2.2
0.6
0.6
0.6
4.6
0.8
0.4
12
1.1
0.8
1.0
0.6
0.6
0.5
0.5
1.4
1.0
*to*
84.8
108.2
923
.
24.5
11.6
.
213
2.2
37.4
85.6
5.7
5.9
2.2
102.4
6.7
9.2
46.4
73
113
7.0
13.6
1.6
2.6
3.1
5.4
9.2
a*c
Mod*
23.1
15.7
17.5
.
8.0
4.5
,
7.4
1.0
12.8
19.7
2.2
1.5
1.4
23.7
1.2
2.6
10.4
4.0
3.2
1.6
2.6
1.0
12
1.0
1.7
2.9
Atf
353
27.0
37.1
,
9.7
4.7
.
8.9
1.2
13.8
24.2
2.9
2.4
13
31.9
2.2
3.4
12.9
3.7
42
2.7
43
1.1
1.4
13
2.4
33
Sfd
De*
31.8
353
35.7
.
7.7
3.9
.
7.2
0.6
11.1
26.0
2.1
2.0
0.6
31.7
25
3.1
14.5
2.1
3.8
2.5
4.5
03
1.1
0.9
1.7
2.7
S*
6.7
2.1
0.8
1.1
0.8
.
0.8
1.3
1.5
23
0.5
1.4
0.3
1.8
2.2
1.6
2.2
0.3
1.6
2.0
1.8
0.5
1.0
2.2
2.0
1.6
K»
-1.4
4.9
-1.4
0.8
-0.4
,
-0.4
1.4
2.9
6.0
-1.8
1.5
-0.2
3.9
4.9
3.1
5.2
-0.6
2.9
4.0
3.5
1.4
.
4.9
4.1
2.8
JBS441
9-43
-------
-8
1
'1
<§
y
i
CM
j,
*
*
<
$1
-V
*
tu
1
\
1
s
s
3r«
1
,1
*°
r^
•n
rH
^
rH
NO
00
rH
ft
O
rH
O
8
oo
1 2-MethyIpentane
00
v>
<*.
00
.
r-
ON
V~>
00
fi
rH
O
8
00
3-Methylpentane
o
f>
00
oo
rH
O
O
NO
">
Q
O
rH
r-
o
1/1
00
O
(N
^
f>
r-
2
NO
rH
O
§
00
| 3-Methylhexane
<^i
*>
r~
^
ON
NO
rH
a
o
o
§
oo
u
3
[J 2,2,4-Trimethylpent
ON
*""'
«
rH
04
r4
r-4
N
o
NO
o
s
-
u
1
u
a
o
**
ON
1-1
O
fS
rH
10
^
o
"1
00
-
| Methylcyclohexane
.
o
o
0
u
ts,
w
s
rH
f*1
f-;
04
1-1
NO
••'
1-1
en
o
p
NO
U
9
| 2,23-Trimethylpent
n
•o
00
0»
rH
0
*
04
ON
O
O
8
00
u
3
| 23,4-Trimethylpent
NO
Tt
O
ON
fc
ON
»
ON
»
r-4
^
NO
^
rH
04
rH
04
10
NO
O
p
wS
r-
NO
2-Methylheptane
>0
to
oq
rH
04
04
*-H
00
rH
f-H
a
NO
»o
1 3-Methylheptane
rH
„.
>0
0
rH
rH
ON
0
rH
t-
o
o
s
'
1-Octene
TH
^
p
NO
o
rH
rH
ON
0
rH
04
NO
O
04
NO
-
| n-Octane
"*
t-;
NO
ON
ON
f^
ON
rH
00
o
1
rH
OO
U
a
1
-------
Table 9-16
Continued
:
Compooarf
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzcne
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluenc
13,5-TrimethyIbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
o-Undecane
1-Dodecene
o-Dodecaoe
1-Tridecene
n-Tridecane
Catt*
8
6
8
1
8
4
7
6
8
5
6
7
4
7
8
6
8
6
6
8
6
8
4
6
i
Xtsf
<%>
100.0
75.0
100.0
12.5
100.0
50.0
87.5
75.0
100.0
62.5
75.0
87.5
50.0
87.5
100.0
75.0
100.0
75.0
75.0
100.0
75.0
100.0
50.0
75.0
* - • a*c ::rU;f;:
ife*
2.7
0.9
0.5
0.6
0.7
0.5
0.7
0.8
0.9
1.0
OJ
0.7
0.6
0.9
1.4
0.5
1.8
0.6
0.8
12
0.6
0.5
0.7
0.6
Mitt*
52.5
2.8
17.8
0.6
3.6
1.4
2.9
4.1
11.4
3.1
53
7.1
2.4
4.0
19.6
3.5
9.1
1.9
D.I
7.0
6.6
14.9
1.2
2.8
Me*
0.2
1.2
4.4
0.6
13
1.0
1.4
1.6
3.5
1.5
2.5
2.1
0.8
1.4
6.0
13
5.2
1.5
1.7
2.2
13
1.1
1.0
1.1
AV
16.7
1.4
5.7
0.6
1.4
0.9
1.5
1.9
4.1
1.7
2.6
2.9
1.1
1.7
6.9
1.6
53
1.4
3.5
2.8
2.6
3.0
1.0
1.3
Std
Dev«
16.5
0.7
5.6
.
1.0
0.4
0.8
1.2
3.5
0.9
1.6
2.2
0.8
1.1
6.2
1.1
2.4
0.5
4.8
2.0
25
4.9
0.2
0.8
S*
1.7
2.2
1.6
.
1.9
-0.0
0.8
1.5
1.4
1.6
0.6
1.4
1.9
2.4
13
13
0.2
-0.7
23
1.7
1.1
2.6
-1.4
1.8
K* r
3.2
5.1
3.1
.
4.3
-2.0
0.0
2.5
2.3
2.6
0.9
2.4
3.7
6.1
1.8
1.6
-0.7
-0.4
5.5
2.9
-0.9
7.2
2.5
4.0
"Freq * Frequency; Min = Minimum; Max = Maximum; Med
Std Dev = Standard Deviation, S - Skewness; K = Kurtosis
"Calculation not possible due to limited data.
Median; Avg = Average
JBS441
9-45
-------
number given for standard deviation, skewness, and kuritosis are the second, third, and
fourth moments, respectively, about the arithmetic means. A skewness value greater
than zero applies to distributions having a longer tail to the right, whereas a value less
than zero applies to distributions having a longer tail to the left. A distribution that is
normally distributed would have a kurtosis of 3.0. A distribution more peaked (or
pointed) than a normal distribution, having the same variance, would have a kurtosis
greater than 3.0, whereas a less peaked than a normal distribution, having the same
variance, would have a kurtosis less than 3.0. All the kurtosis figures listed in this report
are zero centered, which means that 3.0 has been subtracted from the fourth moment to
give a reported kurtosis of 0.0 for a symmetrical distribution.
93 Overall Data Summary
Table 9-17 presents the overall summary statistics for all daily monitoring sites in
the 1993 monitoring program. The analysis results of 624 samples were considered for
these statistics. Duplicate and duplicate/replicate data for a given sample date were
averaged and considered as one sample. Average concentrations ranged from 0.72 ppbC
for c-2-hexene to 29.85 ppbC for propane. The largest standard deviation of
concentration, 73.99 ppbC, was observed for isopentane.
Table 9-18 contains overall summary statistics for all optional analysis sites in the
1993 monitoring program. A total of 41 samples were considered, and statistics are
reported in the same manner as the daily monitoring summary statistics. Average
concentrations ranged from 0.61 ppbC for 2-ethyl-l-butene to 2532.80 ppbC for
3-methylpentane. The largest standard deviation was 394.68 ppbC for 3-methylpentane.
9.4 Individual Sample Results
Appendix K contains the results from individual sample analyses. For each site
sample, all target compounds are listed along with the concentration reported for each
sample. There is also an unidentified compound sum concentration reported for each
JBS441
9-46
-------
Table 9-17
1993 Summary Statistics for All Program Sites
• • rf^MBWMlMMl' '
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Mcthyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
22-Dimethylbutane
Cyclopentene
4-Mcthyl-l-pentene
Cydopentane
23-Dimethyibutane
Caaa
611
607
614
0
578
587
1
616
213
617
623
275
255
218
622
408
444
623
537
499
354
547
610
189
323
391
557
Req*
(*>
97.9
973
98.4
0.00
92.6
94.1
02
98.7
34.1
98.9
99.8
44.1
40.9
34.9
99.7
65.4
712
99.8
86.1
80.0
56.7
87.7
97.8
303
51.8
617
893
ppbC
fcCa"
0.6
0.6
0.6
b
0.5
0.5
1.8
0.6
0.4
0.8
1.4
0.4
0.4
0.4
1.0
0.4
0.4
0.5
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
Max-
146.0
60.1
82.6
.
2153
. 38.4
1.8
64.4
3.7
502.4
532.6
32.5
24.4
10.9
875.8
23.0
32.7
436.1
27.9
28.0
152
40.6
85.5
43
3.5
29.7
31.2
MedP
10.0
5.7
8.8
.
3.7
1.9
1.8
3.4
0.9
7.8
133
12
1.0
0.9
14.2
1.0
12
6.4
1.8
1.4
1.0
1.5
6.7
0.7
0.9
1.1
1.6
w
M.7
8.4
12,6
.
7.4
2.6
1.8
5.1
1.1
142
29.9
1.6
1.4
12
29.2
1.6
1.7
11.5
3.1
2.0
1.4
23
8.4
0.8
1.0
1.7
22
Sbf
Be/
17.1
7.7
11.5
.
14.9
25
.
5.5
0.6
27.6
60.0
2.4
2.1
1.1
74.0
22
2,1
24.0
3.5
2.1
13
2.9
8.4
0.5
0.5
2.7
2.2
s^
4.1
2.0
2.4
,
8.2
6.7
.
43
1.5
11.1
5.8
9.9
8.5
53
7
5.8
9.2
11.9
2.9
6.1
5.6
7.7
4.1
3.8
1.7
6.9
5.9
Kf
22.9
5.9
7.9
90.3
77.6
,
29.8
2.7
172.6
38.7
118.3
84.6
39.9
so.2
41.4
119.4
183.8
11.4
583
48.0
85.4
23.6
21.1
3.5
573
60.2
JBS441
9-47
-------
Table 9-17
Continued
..;, .. '
"•• •
ConipooDB
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
2,3-Dimethylpentane
2-MethyIhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpcntane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
n-Octane
Ethylbenztw
;
Ofcbt'
621
613
126
228
13
615
199
118
593
481
622
460
311
549
618
613
543
482
3
369
554
623
447
391
258
424
605
Pteq*
! C*>
99.5
98.2
20.2
36.5
2.1
98.6
31.9
18.9
95.0
77.1
99.7
73.7
49.8
88.0
99.0
98.2
87.0
77.2
0.5
59.1
88.8
99.8
71.6
62.7
41.4
68.0
97.0
- ffftC
Ifi^
0.7
0.6
0.4
0.4
0.4
0.5
0.4
0.4
0.4
0.4
0.7
0.4
0.4
0.4
0.6
0.5
0.4
0.4
0.8
0.4
0.4
1.1
0.4
0.4
0.4
0.4
0.5
Hat
83.2
59.5
2.9
6.4
1.4
783
4.4
2.4
35.0
10.1
46.4
243
103
17.7
16.6
49.5
30.5
92.2
1.1
4.8
11.7
325.0
5.6
14.1
53
8.5
47.4
Me*
4.8
3.8
0.8
1.0
0.7
3.4
0.7
0.6
2.0
1.2
5.1
1.8
1.5
1.6
2.5
3.5
1.7
1.4
0.9
0.9
1.4
12.4
1.1
1.0
0.9
1.0
2.2
A*"
6.8
53
1.0
12
0.8
53
0.9
0.7
3.1
1.7
7.0
2.7
2.0
2.2
3.1
4.8
2.4
2.1
0.9
1.1
1.8
183
1.4
1.4
1.1
13
3.4
std
tte^
73
4.9
0.6
0.8
03
6.0
0.5
03
3.1
13
5.9
2.9
1.7
2.0
2.1
43
23
4.5
0.2
0.6
15
21.8
0.9
13
0.8
1.0
3.7
&
4.7
3.9
13
3.0
0.7
4.9
4.0
2.9
3.9
23
23
3.2
2.1
3.0
2.1
33
4.9
17.6
0.7
23
2.4
6.7
1.7
52
2.8
33
5.7
K*
34.8
29.5
1.4
13.4
-0.5
43.1
21.7
12.7
26.0
8.2
8.1
14.2
5.7
13.5
6.4
22.2
44.5
352.3
7.2
8.4
74.1
3.1
38.4
10.0
14.9
56.2
JBS441
9-48
-------
Table 9-17
Continued
!
Compound
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropyibenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltolucne
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decanc
123-Trimethylbenzene
p-Diethvlbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
CfeM»
622
457
606
92
407
175
414
394
611
321
498
292
332
593
597
449
606
242
471
590
542
594
172
543
Vtvf
t*>
99.7
732
97.1
14.7
65.2
28.0
66.4
63.1
97.9
51.4
79.8
46.8
532
95.0
95.7
72.0
97.1
38.8
75.5
94.6
86.9
952
27.6
87.0
^
*Ca«
0.5
0.4
05
0.4
0.4
0.4
0.5
0.4
0.5
0.4
0.4
0.5
0.4
0.4
0.4
0.4
0.5
0.4
0.4
0.4
0.4
0.4
0.4
0.4
*fa*
1342
21.6
45.5
6.1
14.9
9.7
223
8.1
18.5
6.4
16.0
58.6
8.4
20.9
50.5
80.9
16.4
29.6
16.4
536.1
8.0
471.4
3.1
59.4
Wed-
6.4
0.9
2.4
0.7
1.1
0.8
1.7
1.0
23
1.0
13
1.5
13
1.6
2.1
13
2J
0.8
12
1.6
0.9
1.5
0.6
0.9
fpbq
Atf
9.6
13
3.6
1.0
1.5
1.1
2.7
12
3.0
12
1.8
2.1
1.9
2.6
3.4
2^
2.9
12
1.4
3.4
1.1
3.4
0.8
1.4
Std
Dcv»
10.6
1.6
3.5
0.9
1.5
1.2
3.1
0.8
2.2
0.9
1.8
3.9
1.5
2.6
3.9
5.8
2.0
2.0
1.2
222
0.7
19.7
0.4
2.8
S*
5.7 '
73
4.5
3.6
5.0
4.6
32
3.6
1.9
2.6
4.2
11.8
1.6
2.7
5.1
8.9
23
12.6
5.9
23.7
3.4
22.6
23
16.7
K*
57.4
74.8
38.9
14.9
34.7
24.9
13.5
21.5
5.5
92
24.0
160.6
25
9.5
443
97.7
93
179.9
53.9
570.8
203
535.6
7.2
334.0
"Freq = Frequency, Min = Minimum; Max - Maximum; Med
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
Median; Avg = Average;
JBS441
9-49
-------
Table 9-18
1993 Summary Statistics for the Option Sites
Gooipouittf -
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyl-l-pentene
Cyclopentane
23-Dimethylbutane
Qua
41
41
41
1
41
41
0
41
17
41
41
29
26
23
41
28
33
41
38
32
26
36
22
7
33
31
40
¥-
100.0
100.0
100.0
2.4
100.0
100.0
0.0
100.0
41.5
100.0
100.0
70.7
63.4
56.1
100.0
683
803
100.0
92.7
78.1
63.4
87.8
53.7
17.1
803
75.6
97.6
ppbC
*&*
4.2
13
33
0.7
1.4
0.7
13
0.5
1.8
2.2
0.4
0.5
0.4
4.6
03
0.4
1.2
0.4
0.4
03
0.4
0.4
0.4
0.4
0.4
0.8
iw*
84.8
108.2
923
0.7
24.5
11.6
.
31.7
2.2
39.2
85.6
5.7
5.9
2.2
102.4
6.7
9.2
46.4
7.3
11.3
7.0
13.6
20.1
2.6
3.1
6.9
9.2
Mcd*
11.7
4.9
9.7
0.7
5.1
2.2
4.1
0.8
9.7
12.9
1.2
1.1
0.8
16.0
1.0
13
5.7
1.7
1.2
1.0
1.3
0.7
0.8
0.8
0.8
1.8
A*
17.6
9.7
16.4
0.7
6.9
3.1
6.6
1.0
11.7
20.6
1.7
1.4
1.0
22.2
1.4
1.7
8.4
2.5
2.1
1.5
2.0
3.1
1.0
0.9
1.3
23
Std
DC**
17.8
17.6
19.8
b
5.5
2.4
6.0
0.5
8.9
19.4
1.3
1.2
0.6
19.4
1.3
1.7
8.0
1.7
2.5
1.4
2.4
6.1
0.8
03
1.4
1.6
s.
23
4.8
2.9
.
1.9
2.0
2.5
1.4
1.8
1.7
1.9
2.6
0.9
2.5
3.2
3.2
3.1
1.0
2.8
2.7
3.7
23
2.1
3.0
3.1
23
K*
. 63
25.8
8.1
3.6
4.0
7.5
1.4
3.0
2.5
33
8.1
-0.6
7.2
10.8
13.0
12.2
0.2
7.8
93
16.3
3.8
4.7
12.4
10.1
8.7
JBS441
9-50
-------
51
li
g
.K
•• :
•c
%t
w
1°\
^fl
: >
, ^
%
1
1
1
*t*
tg
i
is
3
1
a
VO
rH
rH
fO
oo
VO
>0
VO
fO
1_(
Ov
ro
"1
o
o
8
rH
1 2-Methylpentane
o
rH
rf
Tf
o
o
3
rH
| 1-Hexene
o
o
VO
o
VO
o
vO
0
VO
O
Tf
-
U
1
rH
1
f
U
(S
^
r-'
rH
Ov
fO
•0
f)
Tf
00
N
r»
rH
VO
O
O
8
rH
O
X
a
vO
rH
rH
ro
m
rH
^
rH
00
o
Tf
>o
Tf
O
3
Tf
rH
1 t-2-Hexene
r~
vO
n
>n
o
00
o
VO
o
rH
n
•0
o
p
Ov
| c-2-Hexene
Ov
fO
fO
vO
O
«
>o
VO
vO
rH
"1
>o
rH
Tf
O
o
8
rH
Methylcydopentane
rH
O
Ov
ts
rH
rH
tO
rH
Ov
O
vO
rf
0
i
R
1 2,4-Dimethylpentane
oo
00
vO
n
o
>o
rH
r-
00
•0
Ov
a
vO
(S
vO
°
O
rH
Ov
O
00
ri
rf
O
«N
$
rf
rH
23-Dim ethylpentane
o
rH
O
Tf
VO
rH
OO
•0
Tf
CM
Tf
3
o
o
0
8
rH
rH
rf
u
1 2,2,4-Trimethylpentan
^
rH
O
rf
r,
«r>
«*)
m
Ov
rH
vO
n
o
0
rH
00
o
00
rf
O
•O
R
u
|| 2,23-Trimethylpentan
m
Ov
r--
r4
vO
rH
00
rH
CO
rH
rH
Ov
•n
0
o
8
rH
Tf
O
1 23,4-Trimethyipentan
vO
Tf
0
8
rH
rH
|| Toluene
«/•)
Ov
rH
n
rH
VO
rH
fS
rH
•0
Tf
O
r--
SJ
&
2-Methylheptane
to
0
M
rH
rH
CO
rH
Ov
O
oo
rf
Tf
O
Tf
»
| 3-Methylheptane
rH
Tf
Ov
rH
ro
O
^
O
^
o
t-~
rH
Tf
O
3
2
l-Octene
•0
rH
rH
rH
m
o
o
rH
°9
0
Ov
f>
Tf
O
3
a
a
r-
Ov
Ov
-------
Table 9-18
Continued
Cbntpofmi
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Dietbylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
CM**
41
34
41
10
38
21
40
31
41
27
39
39
22
40
41
35
41
30
37
41
39
41
25
39
" >
fcwf
{%)
100.0
82.9
100.0
24.4
92.7
51.2
97.6
75.6
100.0
65.9
95.1
95.1
53.7
97.6
100.0
85.4
100.0
73.2
90.2
100.0
95.1
100.0
61.0
95.1
Mm*
0.5
0.5
0.5
0.5
0.4
0.5
0.5
0.5
0.9
0.4
OJ)
0.7
0.4
0.6
0.8
0.4
1.8
0.5
0.5
0.6
0.6
OJ
0.4
OJ
MSB*
60.4
4.6
22.5
13
5.8
5.9
3.0
4.1
11.4
5.2
5.3
7.1
4.6
4.0
19.6
11.6
23.9
123
13.1
38.4
6.6
26.4
4.1
7.7
Mv?
8.1
0.8
2.8
0.7
1.1
1.1
1.6
0.9
2.1
0.9
1.2
1.8
0.8
1.0
3.4
1.3
3.5
0.7
2.0
1.7
1.3
1.6
0.6
1.1
ppfeC
Avg*
12.0
1.1
4.6
0.8
1.4
13
1.6
1.2
2.9
13
1.6
2.2
1.2
1.2
4.9
23
4.9
1.3
2.5
4.4
1.5
4.1
0.8
1.7
Std
DCT*
11.8
0.9
4.8
03
1.0
1.2
0.8
0.9
2.2
1.1
1.1
1.4
1.0
0.7
4.2
2.7
3.7
2.2
23
8.3
1.1
6.5
0.7
1.4
S«
2.8
2.7
2.6
0.7
2.7
3.3
0.3
2.1
2.2
2.6
1.6
1.8
2.4
2.9
2.2
2.6
3.6
5.0
33
3.6
3.3
2.4
3.9
2.4
K?
9.2
7.7
6.6
-1.0
8.9
13.1
-1.1
4.9
5.9
7.3
2.4
3.5
7.2
10.1
5.6
6.4
16.7
26.5
12.7
12.8
12.0
4.7
17.5
8.0
*Freq = Frequency, Min = Minimum; Max = Maximum; Med = Median; Avg = Average;
Std Dev = Standard Deviation; S = Skewness; K = Kurtosis
bCalculation not possible due to limited data.
JBS441
9-52
-------
sample, labeled unidentified VOC (volatile organic compounds), and a total NMOC
value which represents a sum concentration of all target compounds reported plus all
unidentified compounds measured.
For the daily monitoring program sites, the results are presented in a weekly
report format (Monday, to Friday). For days when duplicate samples were taken, the
results for one of the duplicate samples was chosen to appear on the weekly report. The
duplicate sample date can be used to reference a duplicate or duplicate/replicate report.
The duplicate reports appear after the weekly reports for each site, and show a
comparison of the results for a duplicate sample pair, or a duplicate pair with replicate
analyses when done. For the optional sites, the five column report format is used and
the analytical results are presented in chronological order based on the sample collection
date.
JBS441
-------
10.0 SNMOC TECHNICAL NOTES
This section describes the sampling and analytical equipment and procedures used
for the 1993 SNMOC monitoring program. The sample collection method follows the
general guidelines of EPA's Compendium of Methods TO-12.1 The analysis method
follows the general guidelines of EPA's "Research Protocol Method for Analysis of Q
through C12 Hydrocarbons in Ambient Air by Gas Chromatography with Cryogenic
Concentration" given in Appendix J.
10.1 Sampling Equipment and Procedure
The 1993 SNMOC monitoring program began 7 June 1993, and ended
30 September 1993. Integrated ambient air samples for program sites were collected
from 6:00 a.m. to 9:00 a.m., local time, Monday through Friday. The sampling
equipment and sampling procedures used to collect these samples were the same as
those used for the NMOC monitoring program described previously in Section 3.1.
10.2 Analytical System
Two analytical systems were used for the 1993 SNMOC analyses. One system
uses a manual sampling interface, the other an automated sampling interface, to
concentrate and transfer sample aliquots from stainless steel canisters to the GC.
The GCs connected to these sample introduction systems each contained two
fused-silica capillary columns each connected to a FID. The sample is split between the
columns in a 1:1 ratio with a 3-way press tight glass union. Each column has a
J&W DB-1® phase. One column has a phase thickness of 1 fim to separate C4 through
C13 hydrocarbons effectively. The other has a phase thickness of 5 /*m to separate Q
and Cj hydrocarbons consistently.
JBS441
10-1
-------
Each system was characterized by analyzing hydrocarbon standards and operating
conditions determined so the chromatography would be comparable between systems.
Each GC oven temperature is programmed so the sample is refocused on the GC
column at subambient conditions, then the temperature increases to chromatographically
separate the target compounds. Table 10-1 gives the operating conditions for these
analytical systems.
102.1 Manual Interface System
This analytical system consists of a manual sampling interface, a Varian* 3400
dual FID GC, and a Nelson" 2600 data acquisition system. Figure 10-1 presents the
schematic of this analytical system.
Figures 10-2 and 10-3 show the sample flow paths determined by valve position in
the manual sampling interface system during the sample loading and sample injecting
mode, respectively. When the 6-port valve is in the sample load mode (see Figure 10-2),
the sample interface cryogenically concentrates a measured aliquot of sample. In the
sample inject mode (see Figure 10-3), the cryogenically focused sample aliquot is
thermally desorbed and the sample is swept by helium carrier gas to the head of the GC
column.
1022 Automated Sampling Interface System
This analytical system consists of an automated sampling interface, a Varian* 3600
dual FID GC, and a Nelson* 2600 data acquisition system. Figure 10-4 shows a
flowchart outlining the general procedure used to concentrate and analyze a sample on
this system. Details of the GC system and data system are the same as those in
Figure 10-1, except the GC used is a Varian* 3600.
JBS441 10-2
-------
Table 10-1
1993 SNMOC GC/FID Operating Conditions
Parameter
Operating Value
Manual Interface
:•"•;•;'.. System
Automated Interface
System ''•••
Sample Volume
~ 800 mL
~ 800 mL
J&W DB-1* Capillary Columns
Column A:
Film Thickness
Length
Inside Diameter
Column B:
Film Thickness
Length
Inside Diameter
1
60m
0.32 mm
5
60m
0.32 mm
1 fim
60 m
0.32 mm
5
60 m
0.32 mm
Oven Temperature Program
-60° for 5 min.
Then:
6°C/min. to 150°C,
then
20°C/min. to 180°C.
and hold for 4 min.
-60° for 5 min.
Then:
6°C/min. to 150°C,
then
20°C/min. to 180°C.
and hold for 7 min.
Analysis Time
45 min.
50 min.
Detector Temperatures
2FIDs
300°C
300°C
Gas Flow Rates
Helium Carrier Gas
Helium Make-Up
H2 to FID
Air to HD
4 mL/min.
30 mL/min.
30 mL/min.
300 mL/min.
2 mL/min.
30 mL/min.
30 mL/min.
300 mL/min.
JBS441
10-3
-------
Sample Interface System
Analytical System
Data System
J .Vacuum ^—.
y Reservoir J
Helium
Make Up
Gai
CompuAdd 286
Personal Computer System
Row
Controller
Column B:
J4W DB1 Capillary Column
Su Film Thickness
60m X 0.32mra
Zero Grade Ait
/> Hydrogen^ \
v A I
Varianr- 3400
Gaa Chromatograph
Rama lonizatior
Ptarae/Plood Valve
Column A:
J&W DB1 Capillary Column
\u Film Thickness
SOm X 0.32mm
(Cryogenic^
i/8- SUinkw St««l
r
Temperature
Controller
2OMB
tamovable
Cartridge
Hard Onve
Unit
Velson Analytical
A/D Interface
Figure 10-1. Hydrocarbon Analysis System
-------
Sywtam PrMwra Gaug*
HaBum
Statolaai Staal
Caniati
SamplaVi
I
Figure 10-2. Radian Sample Interface in Sample Load Mode
10-5
-------
RMWvok Vacuum
G«ug«
Syttam fntmm Qcug*
Hdhan
Afuriytfcal Cofamra
In
ctvoratograph)
i
Figure 10-3. Radian Sample Interface in Sample Inject Mode
10-6
-------
Nelson 2600
Data System
Figure 10-4. Automated Sample Analysis System
10-7
-------
The automated system is capable of automatically concentrating a series of 16 air
samples. In between sample loading, the sample pathway is continuously purged with
humidified air provided by the laboratory clean air generation system.
The automated system uses a vacuum pump to pull the sample into the cryogenic
trap. The sample flow path consists of a mass flow controller (MFC) which provides a
signal used to electronically integrate the total sample volume and a Nafion® dryer to
remove water from the sample. The sample is cryogenically concentrated in a nickel
trap filled with nonsilanized glass beads. Injection of the sample on the GC column
occurs when the cryotrap is rapidly heated to vaporize any condensed organics, and
helium carrier gas sweeps the sample to the head of the GC column.
JBS441 10-8
-------
11.0 SNMOC QUALITY ASSURANCE AND CONTROL PROCEDURES
This section details the steps incorporated into the 1993 SNMOC monitoring
program to ensure the data were of high and known quality. Procedures for standard
preparation, database set-up, GC calibration, and daily analytical system checks are
described. Duplicate samples and repeated analyses (replicates) provided information on
sampling and analytical precision. Accuracy was assessed as the percent bias calculated
from the analysis of external audit samples.
11.1 Standards Preparation
Certified high pressure stock standards from Scott* Specialty Gases were used to
prepare analytical calibration standards across the measurement range of the analytical
system. Standards used to establish retention time information were prepared from stock
standards prepared using neat liquid compounds injected into cleaned, evacuated
canisters, and from certified gaseous stock standards.
All calibration and daily calibration check standards were made from certified
standard gases. Gas-tight syringes were used to inject aliquots of the certified standard
into cleaned, evacuated SUMMA® canisters. The canisters were then filled to ambient
pressure with cleaned, humidified air using a standard preparation flow dilution system,
then pressurized with nitrogen to approximately 25 psig using a canister dilution system
that consists of a precision vacuum/pressure guage and a high-pressure nitrogen tank.
11.2 Target Compounds Database
Standards used to gather retention time information and set up a reference
database using relative retention times referenced to toluene were prepared and
analyzed. These relative retention times were used to identify the target compounds in
the ambient air samples. These standards were prepared, encompassing the list of target
JBS441
11-1
-------
hydrocarbons, by using gas-tight syringes to inject aliquots of stock standards into clean,
evacuated SUMMA® canisters.
113 GC/FID Monthly Calibration
The analytical systems were calibrated monthly by analyzing three hydrocarbon
standards and a system blank of cleaned, humidified air. The three calibration standards
were prepared from a Scott* Specialty Gases certified standard to levels of 5, 15, and
50 ppbv benzene and propane. This calibration range is based on the expected levels of
target compound concentrations in ambient air, based on historical information.
The calibration standards were analyzed in order of increasing concentration, and
followed by the system blank analysis to ensure no carryover after analysis of the high
level standard. For the primary column (1 pm phase thickness), the benzene area count
recorded by the FID was correlated to nanoliters of benzene by a least squares linear
regression. For the secondary column (5 ftm phase thickness), the propane area counts
recorded by the FID was correlated to nanoliters of propane by a least squares linear
regression. The calibration was considered representative if the coefficient of correlation
for the four points was greater than or equal to 0.995 for each column/detector. The
slopes of the regression lines were then used to calculate monthly response factors.
The benzene response factor was divided by 6 (carbons/molecule of benzene) to
calculate a per carbon response factor for the primary column/detector. The propane
response factor was divided by 3 (carbons/molecule of propane) to calculate a per
carbon response factor for the secondary column/detector. These response factors were
then used to calculate sample concentrations for the following month. Monthly
calibration information is summarized in Table 11-1.
JBS441
-------
Table 11-1
Summary of Monthly Benzene and Propane Calibration Curves
Calibration
Bate
:: Primary Column
Correlatioii
Coefficient
Benzene • '
Response
Factor
(AC/al-C)
Secondary
Correlatioii
Factor
r Column
Propane
Response
Factor
Manual Interface System
05/18/93
06/21/93
07/21/93
08/23/93
09/23/93
1.0000
1.0000
1.0000
0.9995
1.0000
2169.0
2234.8
2324.2
2263.3
2104.5
1.0000
1.0000
1.0000
0.9995
0.9998
1582.9
1644.9
1691.2
1616.1
1625.2
Automated Interface System
06/03/93
07/02/93
08/02/93
09/02/93
10/04/93
1.0000
1.0000
1.0000
1.0000
1.0000
1624.6
1507.7
1613.8
1557.0
1575.8
1.0000
0.9998
1.0000
1.0000
0.9999
1623.8
1395.4
1548.3
1473.0
1600.6
JBS441
11-3
-------
11.4 Dairy Quality Control Check
Daily, prior to sample analysis, a QC standard, prepared from a Scott* Specialty
Gases certified standard, was analyzed to ensure the validity of the current monthly
response factors. This standard had an approximate concentration of 10 ppbv propane
and benzene. This level was considered representative of the majority of concentrations
expected in ambient air samples.
The load volume (in liters), benzene area count from the primary detector, and
propane area count from the secondary detector were entered into a computer
spreadsheet and the current monthly response factors were used to calculate the benzene
and propane concentrations. These concentrations were compared to the calculated
theoretical concentrations of the QC standard. A concentration percent bias of less than
or equal to 30% was considered to be acceptable and the analytical system was in
control.
For the SNMOC monitoring program, if the daily QC standard did not meet the
30% criterion a second QC standard was prepared and analyzed. If the second QC
standard met the criterion, the analytical system was considered in control. If the second
QC :heck did not pass, a leak test and system maintenance were performed, and a third
QC standard analysis was performed. If the criterion was met by the third analysis, the
analytical system was considered in control. If the maintenance caused a change in
system response, a new calibration curve was required. For the 1993 program the 30%
criterion was met on the first standard analysis for every sample analysis day on both
analytical systems.
JBS441
11-4
-------
11.5 Daily A"i>1yt''raJ System Blank
A system blank of cleaned, humidified air was analyzed after the daily QC
standard analysis and prior to sample analyses. The system was considered in control if
the total NMOC concentration for the system blank was less than or equal to 20 ppbC.
This criterion was met for every sample analysis day on both analytical systems.
11.6 Precision of Sampling and Analysis
The precision of the sampling and analytical methods used for the 1993 SNMOC
monitoring program was assessed using data from duplicate sample collections and
replicate analyses.
11.6.1 Duplicate Samples
For each program site, eight duplicate sample pairs were scheduled to be
collected and analyzed. The actual number of sample pairs collected ranged from seven
to nine. For the option sites, one duplicate pair was randomly chosen for analysis.
Pooled standard deviations for the duplicate samples were calculated as an indication of
sampling precision. Table 11-2 presents the data for all program sites. Table 11-3
presents the data for all optional analysis sites. The duplicate pooled standard deviations
show similar results for each compound. This indicates that the sampling procedure for
duplicates provided representative ambient air samples.
11.62 Replicate Analyses
For each program site, at least half of the duplicate sample pairs were chosen to
both be analyzed in replicate to measure analytical precision. For the option sites, half
of the duplicate sample pair was also selected to be analyzed in replicate. Tables 11-4
and 11-5 summarize the statistics for the replicate analyses of the program sites and
option sites, respectively, in terms of average concentrations, average absolute percent
JBS441
11-5
-------
Table 11-2
1993 Duplicate Statistics for All Program Sites
{ToBBpooiki
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butenc
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentanc
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cydopentene
4-Methyi-l-pentene
Cyclopentane
:
;
Case*
60
61
62
0
54
58
0
61
14
63
63
24
21
17
63
34
37
62
54
45
31
50
61
13
26
36
-
:.
«4. • '
ricqucacf
(%>
93.75
9531
%.88
0.00
8438
90.63
0.00
9531
21.88
98.44
98.44
37 JO
32.81
26.56
98.44
53.13
57.81
96.88
8438
7031
48.44
78.13
9531
2031
40.63
56.25
Duplicate Pair SfefttK*
Oiftmirattnfk
Me&fc
9.45
4.76
8.88
a
3.%
1.66
.
2.98
130
7.29
12.65
0.99
1.10
0.97
1339
1.13
.132
6.40
1.74
1.56
1.06
1.72
3.86
0.76
0.82
1.20
Average
12.93
7.53
10.92
.
6.52
2.47
.
5.05
138
1434
27.74
1.86
2.22
139
28.84
2.25
2.10
11.07
3.11
239
1.62
2.84
5.22
1.03
1.05
1.64
Areagp
Ab«ohite%
DtSoreace
22.76
15.45
19.62
.
16.50
1131
.
12.46
1739
8.66
7.74
31.24
19.07
21.76
3.52
21.57
9.98
3.93
5.27
6.59
8.76
931
4.51
11.05
7.72
6.82
Tooled
Standard
Devtaivw
2.41
0.72
3.01
.
0.46
0.04
.
0.12
0.05
1.08
2.21
0.21
0.04
0.09
14.84
0.81
0.06
0.29
0.03
0.01
0.02
0.07
0.07
0.01
0.00
0.01
JBS441
11-6
-------
Table 11-2
Continued
'• Compound ' • .;',.•
23-Dimethylbutane
2-Methylpentane
3-Methylpentane
2-Methyl-l-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethytpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethyipentane
23,4-Trimethyipentane
Toluene
2-Methyiheptane
3-Methylheptane
1-Octene
•::•;;;•:••.%;:
50
62
60
5
22
2
60
15
9
58
40
63
37
33
50
62
58
53
44
1
30
52
63
38
34
17
.N';:x:.::"-T:
s^*7
78.13
96.88
93.75
7.81
3438
3.D
93.75
23.44
14.06
90.63
62.50
98.44
57.81
51.56
78.13
96.88
90.63
82.81
68.75
1.56
46.88
8125
98.44
5938
53.13
26 .56
' ':' ' - • DopIfcafiR Pfrir Statiitks • '
•' Coaceatnrfifto • -;'
Median
1.94
4.23
339
1.23
0.98
0.85
3.09
0.77
0.69
1.91
1.22
4.73
1.95
1.16
1.60
2.25
. 334
1.51
1.61
0.78
0.91
131
11.13
1.13
1.01
1.04
- A«rage":
2.58
6.84
4.99
1.07
1.24
0.85
5.15
0.91
0.78
2.96
1.94
633
2.53
2.15
2.26
2.92
4.98
235
1.94
0.78
1.15
1.82
1630
1.53
1.45
1.19
" Awerago-
Absolute %
•' IXflfcrcncc
10.22
330
739
25.46
5.56
433
3.99
6.49
10.45
8.55
5.71
3.47
16.44
4.89
10.11
9.14
339
10.42
11.41
7.69
7.92
5.03
2.52
14.05
4.88
17.97
Pooled
Standard!
Deriatioft
0.22
0.02
0.25
0.05
0.01
0.00
0.03
0.00
. 0.01
0.11
0.03
0.03
0.18
0.01
0.50
0.10
0.01
0.15
0.04
0.00
0.00
0.00
11.51
0.04
0.03
0.08
JBS441
11-7
-------
Table 11-2
Continued
n-Octane
Ethylbenzene
p-Xylene -t- m-Xyiene
Styrene
o-Xylene
1-Nonene
n-Nonanc
Isopropyibenzene
alpha-Pinene
n-Propyibenzene
tn-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Deccne
12,4-Trimethyibenzene
n-Decane
123-Trimethyibenzene
p-Diethylbenzene
1-Undeccne
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Calculation not possible d
Case*
37
58
64
43
58
5
31
15
32
32
59
21
45
19
29
58
49
38
58
18
40
51
50
58
8
43
- .
l^SP
57.81
90.63
100.00
67.19
90.63
7.81
48.44
23.44
50.00
50.00
92.19
32.81
7031
L 29.69
4531
90.63
76.56
5938
90.63
28.13
62JO
79.69
78.13
90.63
12JO
67.19
* 11 rttJnffCSawCSf llttf* SBT^ ** ^
r\~«f«*w
Mafia*
126
2.08
5.68
1.08
2.24
1.10
124
1.01
135
1.06
2.12
130
1.22
1.09
1.17
220
134
135
2.16
0.82
0.99
1.68
1.04
1.60
0.70
0.96
' Average
1.58
3.05
8.16
133
3.27
1.18
1.54
131
2.64
134
3.26
1.53
1.90
1.65
1.75
3.18
2.55
1.91
2.51
1.25
1.50
2.53
1.19
2.19
0.81
1.16
Absolute %
9.01
5.64
5.06
11.24
9.69
736
1324
1732
1636
1139
13.27
9.27
9.28
20.88
6.96
11.21
14.78
2131
19.52
2122
28.18
3332
22.12
47.40
25.05
31.62
Pooled
Standard
Devtadoa
0.03
0.02
0.07
0.07
0.07
0.00
0.08
0.09
0.25
0.15
0.60
0.09
0.10
0.15
0.01
035
0.45
0.56
131
0.22
033
135
0.10
3.04
0.03
0.43
ue to limited data.
JBS441
11-8
-------
Table 11-3
1993 Duplicate Statistics for the Option Sites
CTfTfflffKMIfkf
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
1,3-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pcntane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
2,2-Dimethylbutane
Cydopentene
4-Methyl- 1-pentene
Cyclopentaoe
'Case*
5
5
5
0
5
5
0
5
1
5
5
3
1
2
5
2
3
5
2
4
4
5
2
0
2
3
1ht " '• ' i
Requeue?
(%>
100.00
100.00
100.00
0.00
100.00
100.00
0.00
100.00
20.00
100.00
100.00
60.00
20.00
40.00
100.00
40.00
60.00
100.00
40.00
80.00
80.00
100.00
40.00
0.00
40.00
60.00
Dopficafc
Qwmtfrttitrm
Median
7.79
2.49
8.21
a
4.00
1.42
.
3.51
0.87
1137
7.54
1.79
2.14
0.97
1138
0.86
153
5.11
1.01
1.02
0.76
130
0.78
.
0.90
1.60
•• Average
10.55
1127
9.29
5.23
234
.
435
0.87
8.73
10.86
2.00
2.14
0.97
14.16
0.86
1.47
5.15
1.01
1.13
0.81
133
0.78
.
0.90
1.49
P'Fwr SMittMf
Average
Absolote%
D&ercace
12.93
14.71
539
.
23.23
9.81
,
4.88
52.87
3.38
5.15
79.09
144.73
2331
433
1339
16.02
5.67
12.23
10.23
28.43
32.61
9.23
.
20.42
63.73
,
Pooled
Standard
: • Deration
0.66
0.53
0.16
.
133
0.11
,
0.03
0.11
0.07
0.20
1.87
4.77
0.03
038
0.01
0.05
0.08
0.01
0.01
0.14
0.06
0.00
.
0.02
1.03
JBS441
11-9
-------
Table 11-3
Continued
• JTSnttMtftfittMi*
23-Dimethylbutane
2-Methylpentane
3-Methylpentane
2-Methyl- 1-pentene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methyihexane
3-Methylhexane
2^,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimcthylpentane
23,4-Trimethylpentane
Toluene
2-Methytheptane
3-Methylheptane
1-Octene
Case* i
5
5
5
1
0
0
5
0
1
5
2
5
3
1
4
5
5
4
4
0
2
5
5
4
3
2
i. <
;
.--*/. .• :
Frequency
... * A . .'•
100.00
100.00
100.00
20.00
0.00
0.00
100.00
0.00
20.00
100.00
40.00
100.00
60.00
20.00
80.00
100.00
100.00
80.00
80.00
0.00
40.00
100.00
100.00
80.00
60.00
40.00
Doplkale P«r Statistici ^ .*'* * V
OMKTOtntron
Median
1.17
336
4.69
0.70
.
2.00
.
039
1.03
1.40
338
1.89
1.07
138
2.45
2.23
132
0.93
.
0.90
0.73
15.04
0.97
0!91
0.71
Average
1.45
4.65
3.83
0.70
.
2.77
.
039
1.62
1.40
5.41
1.49
1.07
1.83
2.44
3.23
137
0.93
.
0.90
1.18
1739
0.97
0.85
0.71
Absolute %
ismacBCG
7.27
836
21.67
57.14
.
.
632
.
6.78
7.77
1.10
335
2630
1432
26.69
5.28
6.97
29.05
17.06
.
21.47
5.06
039
11.15
7.88
16.92
Pooled
Standard
Bevtatioa
0.01
0.07
0.98
0.08
.
0.04
0.00
0.02
0.00
0.01
0.15
0.01
0.09
0.02
0.04
034
0.02
.
0.04
0.00
0.01
0.01
0.00
0.02
JBS441
11-10
-------
Table 11-3
Continued
".-• -
Compound
n-Octane
Ethylbenzene
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzeoe
m-Ethyltoluene
p-Ethyltoluene
135-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethylbenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Tridecene
n-Tridecane
Calculation not possible d
••••''• \-'
;£*T;:
2
5
5
3
5
0
4
2
4
2
5
1
5
5
1
4
5
4
5
1
4
5
5
3
1
3
ue to limit
I'-'-- •::•>•••:':
• .:.,... •••'•.:;.:.
'•*" ••' • :':' '"•
.Fsoqacncy
40.00
100.00
100.00
60.00
100.00
0.00
80.00
40.00
80.00
40.00
100.00
20.00
100.00
100.00
20.00
80.00
100.00
80.00
100.00
20.00
80.00
100.00
100.00
60.00
20.00
60.00
ed data.
:-.- __
• .•• '**W
Median
0.67
2.46
8.18
0.86
2.19
.
1.14
1.74
157
0.99
130
1.04
1.04
0.%
0.45
0.93
239
1.61
3.41
058
1.46
1.70
1.12
2.18
.050
0.88
DopBcai
eatntkktt " : '
nMitMiWm .. .
Awag»
0.67
253
8.47
0.98
2.71
.
1.05
1.74
1.67
0.99
2.13
1.04
1.19
1.23
0.45
0.93
330
1.46
3.77
058
1.84
1.61
134
1.93
050
0.94
ft "Pa^f $tmt1irtKV
,v Awwa&-. •
Absofatc%
Difficreacc
3635
5.09
1.49
14.19
256
.
15.98
16.00
9837
25.68
1250
2.90
20.76
15.64
5.53
20.68
1150
18.41
41.44
1035
44.42
43.40
61.70
79.18
24.88
48.90
•• •.. :';;' •''•:''•. • :
Pooled
Standard
Deviation
0.04
0.01
0.01
0.02
0.00
0.04
0.04
1.94
0.03
035
0.00
0.04
0.02
0.00
0.09
0.05
0.03
2.75
0.00
0.18
027
128
2.63
0.01
0.15
JBS441
11-11
-------
Table 11-4
1993 Replicate Statistics for AU Program Sites
OmponBa
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyl-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyl-2-butene
22-Dimethyibutane
Cyclopeotene
4-Methyi- 1-pentene
Cyclopentane
Case*
64
65
69
0
53
60
0
63
6
69
70
15
18
13
70
36
40
69
54
46
32
50
66
12
22
33
Iffr 1 i mi
Rtqueac?
(%>
90.14
91.55
97.18
0.00
74.65
84.51
0.00
88.73
8.45
97.18
98.59
21.13
2535
1831
98.59
50.70
5634
97.18
76.06
64.79
45.07
70.42
92.96
16.90
30.99
46.48
Itopftate fNwF Sta&ttct
Mafiaa
7.59
435
7.09
a
333
1.57
.
3.01
2.10
6.48
9.93
0.95
1.17
1.06
12.18
123
1.08
4.55
1.62
1.52
1.06
1.68
3.88
0.92
0.81
135
Average
8.91
630
931
.
5.80
1.95
.
3.87
1.76
11.08
30.10
1.11
135
1.08
21.70
1.85
1.46
8.88
3.97
1.88
126
123
4.72
0.94
0.91
1.60
Average ,
Ah»hte%
T£&at»tA
27.82
24.82
31.10
,
10.40
12.53
.
1434
7.62
8.92
9.65
1539
20.16
12.00
337
1430
7.98
4.04
6.73
9.00
7.90
1130
3.03
625
8.28
521
Standard
Dewatioa
430
0.99
6.17
.
0.18
0.05
.
0.15
0.01
2.07
530
0.02
0.05
0.01
037
0.06
0.04
0.06
0.03
0.02
0.01
0.04
0.03
0.00
0.00
0.01
JBS441
11-12
-------
Table 11-4
Continued
: . . -• • •-•••;..
• ;;VCo»o«i8d :' ••
: , , -n " *" : ....
23-Dimethylbutane
2-Methylpentane
3-Methylpentane
2-Methyl- 1 -peritene
1-Hexene
2-Ethyl-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methylcyclopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
2,2,4-Trimethylpentane
n-Heptane
Methylcyclohexane
1-Heptene
2,23-Trimethylpentane
23,4-Trimethylpentane
Toluene
2-Methylheptane
3-Methylheptane
1-Octene
•' '••".:>•
'• '::< ••
•taae*
.
47
67
66
4
18
4
62
10
2
58
44
70
30
38
51
68
64
50
40
0
26
52
70
32
29
14
'• '-.'"/• :''.''•'•':.:.
. :••••• •. .• .-.••••.•..
~^t%T?
:: V.'"V f .
66.20
9437
92.%
5.63
2535
5.63
8732
14.08
2.82
81.69
61.97
98.59
42.25
53.52
71.83
95.77
90.14
70.42
5634
0.00
36.62
73.24
98.59
45.07
40.85
19.72
Mediaa
1.90
3.82
2.99
1.23
0.97
0.84
2.49
0.69
0.67
1.71
1.19
3.77
1.97
0.99
139
1.98
3.29
1.46
1.45
0.94
1.19
933
1.21
1.14
0.83
. . -., ne^fc^
J»
^Jft& .-*>•; •:;
BHUMJOR- ...
:: ^kyly^.
..• .^"T1^
.239
6.03
4.18
1.19
1.00
0.85
4.69
0.78
0.67
2.73
1.58
5.09
2.29
1.86
1.83
2.56
4.16
2.23
2.01
1.04
1.61
12.42
1.50
131
1.02
»>'* Statistics
• ii
:,; ^,^3— •
; Abfidnte %
" : i u.
5.28
4.01
7.40
78.82
8.40
1133
4.45
9.84
11.90
5.63
4.49
434
16.24
6.80
10.21
7.17
4.16
11.57
13.70
.
8.13
3.61
2.43
15.66
836
5.%
Footef
Standard .
T*cviatk»
0.02
0.02
0.11
0.65
0.01
0.01
0.02
0.01
0.00
0.01
0.00
0.04
0.54
0.01
0.06
0.02
0.01
0.03
0.13
.
0.01
0.00
0.07
0.05
0.02
0.01
JBS441
11-13
-------
Table 11-4
Continued
1
+ ;
r*«M*wi«MJt '
n-Octane
Ethylbenzene
p-Xyiene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropyibenzcne
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
135-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
123-Trimethylbenzene
p-Diethyibenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Trideccnc
n-Tridecane
Calculation not possible
'•
&aet
35
61
71
42
62
6
30
9
31
31
62
16
40
12
26
61
49
39
62
14
29
53
40
61
3
41
\
i
Jtaeqtieae? 1
(%>
4930
85.92
100.00
59.15
8732
8.45
42.25
12.68
43.66
43.66
8732
2254
5634
16.90
36.62
85.92
69.01
54.93
8732
19.72
40.85
74.65
5634
85.92
423
57.75
'Tfbmffalfo #i$r $fflffflffof
CMKttBtlttiott
Median
132
2.08
530
0.80
2.26
0.83
0.99
1.24
138
0.97
2.04
124
1.19
0.76
1.11
2.69
139
138
2.08
0.84
1.18
1.63
1.14
153
051
0.95
Average
1.68
2.62
6.67
122
2.80
0.99
1.47
1.45
2.70
1.16
3.21
154
1.89
0.97
1.62
329
1.84
2.00
238
1.70
1.96
2.62
126
2,65
0.65
137
, Avcngft
Absolatc%
Difiarcace
9.71
635
4.89
736
536
8.97
20.18
1629
11.93
4.91
10.90
958
937
19.18
5.13
331
5.64
1224
8.60
10.85
858
2139
17.99
30.64
17.91
19.09
Fooled
Standard
Denadoa
0.09
0.02
0.03
0.01
0.06
0.02
0.12
0.04
0.26
0.00
0.22
0.02
0.03
0.03
0.02
0.00
0.01
0.13
0.13
0.02
0.02
0.23
0.04
0.41
0.02
0.11
ue to limited data.
JBS441
11-14
-------
Table 11-5
1993 Replicate Statistics for the Option Sites
. ,- . •.-;:. • ;•>;:• ..: -•
Ethylene
Acetylene
Ethane
Propyne
Isobutane
1-Butene
Isobutene
Propylene
13-Butadiene
n-Butane
Propane
t-2-Butene
c-2-Butene
3-Methyi-l-butene
Isopentane
1-Pentene
2-Methyl-l-butene
n-Pentane
Isoprene
t-2-Pentene
c-2-Pentene
2-Methyi-2-butene
2,2-Dimethylbutane
Cyclopentene
4-Methyi-l-pentene
Cydopentane
; CBC*
5
5
5
0
5
5
0
5
0
5
5
2
3
1
5
2
3
5
2
4
3
5
1
0
2
2
•* _....__ IM|
1- ICI^UCHi JF
m
100.00
100.00
100.00
0.00
100.00
100.00
0.00
100.00
0.00
100.00
100.00
40.00
60.00
20.00
100.00
40.00
60.00
100.00
40.00
80.00
60.00
100.00
20.00
0.00
40.00
40.00
,;-.,..€^^^ :<•;:;
. . >itWWliUH»«MMW.
-M«s*r
8.42
2.19
8.77
a
3.72
1.43
.
3.67
.
11.06
8.03
136
138
0.73
1122
0.90
1.77
4.75
0.94
0.98
0.59
1.14
0.60
.
1.00
0.85
"AvoragB
10.61
11.02
9.47
.
5.21
2.46
.
439
8.59
10.91
136
1.14
0.73
1432
0.90
1.59
5.13
0.94
1.16
0.94
130
0.60
,
1.00
0.85
•V_* ^..^ .;.
\ Absolute %
• Diflfereace
17.89
15.86
16.19
1830
20.06
.
6.06
.
4.%
3.28
45.29
63.63
81.38
5.94
12.16
6.27
4.21
10.11
15.75
51.18
25.49
1333
.
45.84
1627
: '•?i'.:;.::C.::--:|-. •
Pookd
Standard
1.10
0.40
0.95
,
037
0.61
0.03
,
0.14
0.04
0.23
0.65
0.17
0.62
0.01
0.01
0.01
0.01
0.02
0.83
0.08
0.00
.
0.14.
0.01
JBS441
11-15
-------
Table 11-5
Continued
23-Dimethylbutane
2-Methylpentane
3-Methylpentane
2-Methyl- 1-pentene
1-Hexene
2-Ethyi-l-butene
n-Hexane
t-2-Hexene
c-2-Hexene
Methyicydopentane
2,4-Dimethylpentane
Benzene
Cyclohexane
23-Dimethylpentane
2-Methylhexane
3-Methylhexane
22,4-Trimethylpentane
n-Heptane
Methylcydohexane
1-Heptene
2,23-Trimethyipentane
23,4-Trimethytpentane
Toluene
2-Methylbeptane
3-Methyiheptane
1-Octene
Case*
5
5
5
1
1
0
5
0
0
5
2
5
5
1
4
5
5
5
3
0
2
5
5
5
3
1
-
frequency
100.00
100.00
100.00
20.00
20.00
0.00
100.00
0.00
0.00
100.00
40.00
100.00
100.00
20.00
80.00
100.00
100.00
100.00
60.00
0.00
40.00
100.00
100.00
100.00
60.00
20.00
Itafrffawte Pwff Statistics
Gmctmtrritm
\i4r*p«4.-mT.T m UTR ,
Mofiaa
1.09
3.13
3.40
0.90
037
.
1.94
.
.
1.03
1.41
336
0.75
1.15
1.49
230
2.24
0.95
1.41
0.79
0.68
15.00
0.87
0.93
0.68
Average,
1.45
4.68
3.67
0.90
037
.
2.71
.
.
1.66
1.41
534
129
1.15
1.98
2.43
3.26
1.20
1.17
.
0.79
1.17
1736
0.94
0.83
0.68
•flflflf I'lUJTi
Absolute %
Difference
1022
6.03
18.18
97.78
19.47
.
7.10
.
.
1335
6.13
3.81
34.95
0.87
2.81
6.73
18.84
43.75
31.13
1930
3.19
3.62
30.68
1030
42.%
Pooled
Stsmuni
0.02
0.04
034
039
0.01
f
0.02
t
m
0.02
0.00
0.02
0.08
0.00
0.02
0.02
0.11
0.15
0.16
.
0.01
0.00
0.18
0.06
0.00
0.04
JBS441
11-16
-------
Table 11-5
Continued
Conpooad
n-Octane
Ethylbenzene
p-Xylene + m-Xylene
Styrene
o-Xylene
1-Nonene
n-Nonane
Isopropylbenzene
alpha-Pinene
n-Propylbenzene
m-Ethyltoluene
p-Ethyltoluene
13,5-Trimethylbenzene
o-Ethyltoluene
beta-Pinene
1-Decene
1,2,4-Trimethylbenzene
n-Decane
1,23-Trimethylbenzene
p-Diethyibenzene
1-Undecene
n-Undecane
1-Dodecene
n-Dodecane
1-Trideccne
n-Tridecane
Calculation not possible d
•-••:'" . '
• CSiMr
2
5
5
3
5
0
3
2
3
2
5
2
5
5
1
5
4
4
5
1
5
5
5
5
3
5
ftcqucanry
w
40.00
100.00
100.00
60.00
100.00
0.00
60.00
40.00
60.00
40.00
100.00
40.00
100.00
100.00
20.00
100.00
80.00
80.00
100.00
20.00
100.00
100.00
100.00
100.00
60.00
100.00
• ' ' • ftenfiraf* Pw Statistics ' "- ":" • •:•---•
' f"tawmtr*f >rw» ' ' :' :
Media*
0.78
2.53
8^0
0.89
221
.
1.29
1.88
0.73
0.99
1.27
0.%
1.25
0.97
0.47
0.94
3.45
1.62
3.79
1.69
2.27
1.79
1.09
2.82
1.00
1.05
':Ayeraget:"'
0.78
2J3
8.50
0.92
2.69
.
132
1.88
1.23
0.99
1.96
0.96
1.29
1.21
0.47
1.18
3.68
1.50
4.24
1.69
2.06
1.80
1.69
2.41
1.88
1.07
;,' Awragp
Absolute %
' : • r^feream •
46.91
9.86
237
8.64
5.92
t
49.82
3636
25.92
33.82
2.43
730
41.51
31.17
15.05
8.18
12.48
15.18
6.15
58.75
9.63
36.10
1054
55.91
2632
4122
Pookd
Standard
Denatkn
0.10
0.04
0.03
0.00
0.02
.
0.24
0.23
0.04
0.07
0.00
0.00
0.28
0.05
0.00
0.00
0.08
0.02
0.03
0.49
0.04
0.80
0.02
2.25
0.18
039
ue to limited data.
JBS441
11-17
-------
differences, and pooled standard deviations. The results show excellent results for
analytical precision.
11.7 Accuracy
Two external audits were supplied by the EPA QA contractor. Tables 11-6 and
11-7 summarize the results of these audits. Both audit samples were analyzed by both
GC systems. The tables designate the manual interface and the automated interface
GCs and the average concentration reported by the two systems. Both systems detected
m-ethyltoluene and 1,2,3-trimethylbenzene. Each of these two compounds was detected
in both audit samples at similar ratios with the compound of the same molecular weight
and similar structure. Radian, therefore, believes the compounds were in the audit
samples. The results show good analytical accuracy. The first audit sample showed a
percent bias ranging from -15.7% (3-methylpentane) to +16.9% (1-butene) with an
average of -7.9 percent. The second audit sample showed a percent bias ranging from
-20.4% (ethane) to +16.2% (1-butene) with an average of -7.3 percent. The overall
average is -7.6 percent.
11.8 Data Acquisition and Reduction Procedures
A PE Nelson* 2600 Chromatography Data System consisting of a 900 Series
Intelligent Interface and a PC system containing the 2600 software was used to acquire,
integrate and store the analytical data. A chromatogram and area count report from
each detector are printed for each analysis. Electronic copies of the data were stored on
20 Mb disk cartridges, and a compressed backup disk was also made.
The data were processed using Radian Peak Identification Program (RPIP)
software. The RPIP used a database containing relative retention time information for
all compounds of interest and applicable response factors to process the data files. A
preliminary report was generated containing possible peak identifications and
quantitations based on the carbon response factor in effect at the time of analysis.
JBS441
11-18
-------
Table 11-6
Speciated NMOC External Audit Results for Audit Sample 1862
Compound
Ethylene
Ethane
Propane
1-Butene
t-2-Butene
3-Methyl-l-butene
1-Pentene
Isoprene
c-2-Pentene
2,2-Dimethyibutane
4-Methyi-l-pentene
2,3-Dimethylbutane
3-Methylpentane
n-Hexane
c-2-Hexene
2,4-Dimethylpentane
Cyclohexane
2,3-Dimethylpentane
2,2,4-Trimethylpentane
Methylcyclohexane
23,4-Trimethylpentane
2-Methylheptane
Ethylbenzene
m/p-Xylene
o-Xylene
Isopropylbenzene
m-Ethyltoluene
133-Trimethylbenzene
l,23-Trimethylbenzenc
Theoretical
16.8
15.8
233
27.4
30.4
42.1
37.8
38.2
37.0
533
503
533
57.8
513
49.0
63.8
55.2
703
76.9
663
71.9
75.4
743
743
723
82.4
84.2
•V ';. CoaCTIlf IBllflB., jppoC ' ' -
,::•.::,:,.,:,,,,.. ;;f ,. 3^^.? • ;; • - •• , . X •
Manual
13.65
1330
21.70
3335
31.20
40.55
38.75
35.45
36.80
58.25
48.25
50.70
49.85
51.60
49.65
61.45
53.40
64.85
74.95
65.20
7030
75.65
73.90
74.80
72.70
80.60
2730
7935
435
Afltamtoi
15.80
1535
22.15
30.70
27.80
35.95
32.65
29.65
30.75
48.60
43.05
46.25
47.65
45.10
41.90
54.90
47.40
5730
67.05
. 57.25
6035
64.20
60.10
6130
59.20
6630
15.40
64.85
8.05
' Awnge
14.73
1433
21.93
32.03
2930
38.25
35.70
3235
33.78
53.43
45.65
48.48
48.75
4835
45.78
58.18
50.40
61.18
71.00
61.23
6533
69.93
67.00
68.05
65.95
7335
2135
72.10
6.20
Avenge
'. I f..vA... • v.=
Percent Bun frnot Theoretical
Maaoal
- -18.8
-14.6
-7.7
21.7
2.6
-3.7
23
-7.2
-0.5
8.9
-4.1
-5.2
-13.8
0.6
13
-3.7
-3.3
-8.0
-23
-1.7
-1.9
03
-03
0.4
0.6
-2.2
-5.8
-2,4
Atttoniife*
-6.0
-1.6
-5.7
12.0
-8.6
-14.6
-13.6
-22.4
-16.9
-9.2
-14.4
-13.6
-17.6
-12.1
-143
-13.9
-14.1
-18.4
-12.8
-13.7
-15.8
-14.9
-19.1
-17.7
-18.1
-193
-23.0
-133
Avenge i
-12.4
-8.1
-6.7
16.9
-3.0
-9.1
-5.6
-14.8
-8.7
-0.1
-9.2
-9.4
-15.7
-5.8
-6.6
-8.8
-8.7
-13.2
-7.7
-7.7
-8.9
-73
-9.8
-8.7
-8.8
-10.7
-14.4
-7.9 1
JBS441
11-19
-------
Table 11-7
Speciated NMOC External Audit Results for Audit Sample 1865
Ceaepomd .
Ethylene
Ethane
Propane
1-Butene
t-2-Butene
3-Methyl-l-butene
1-Pentene
Isoprene
c-2-Pentene
2,2-Dimcthylbutane
4-Methyl- 1-pentene
23-Dimethylbutane
3-Methylpentane
n-Hexane
c-2-Hexene
2,4-Dimethylpcntane
Cyclohexane
23-Dimethylpentane
2,2,4-Trimethylpentane
Methylcyclohexane
2,3,4-Trimethylpentane
2-Methylheptane
Ethylbenzene
m/p-Xylene
o-Xylene
Isopropylbenzenc
m-Ethyltoluene
13J-Trimethylbenzene
1,23-Trimethylbenzene
:
ttawrfifti
30.90
29.10
43.20
50.40
55.80
77.40
69.60
70.40
68.00
98.40
92.50
98.40
97.00
94 JO
90.00
117
102
130
141
121
132
09
137
137
133
152
155
O*cestaitib^ fipbC
: Safe* i
Muni
26 JO
18.80
4230
59.45
58 JO
72.40
68.05
62.40
63.60
100.70
85.55
90.25
90.45
9130
87.00
109.00
94.60
115.00
132.50
114.00
124.00
132.50
130.00
133.00
128 JO
143.50
48.70
144 JO
6.80
4kgtaogji@j|
29.00
27 J5
40.90
57.65
51.70
68.95
63.00
58.45
59.85
92.00
81.10
88.00
91.25
87.60
81J5
107.00
91.25
111JO
130.00
111.00
117 JO
124 JO
119JO
122JO
119.00
134.00
3425
132.00
17.85
.^4ttMAMUfe
'rtSWagC
27.75
23.18
41.60
58J5
55.10
70.68
65J3
60.43
61.73
9635
8333
89.13
90.85
89.45
84.28
108.00
92.93
113.25
131.25
112JO
120.75
128 JO
124.75
127.75
123.75
138.75
41.48
13825
1233
Average
JVarcc^BijBfraiBtVaretica}
Mural
-142
-35.4
-2.1
18.0
4.8
-6J
-2.2
-11.4
-6J
23
-7.5
-83
-6.8
-3.2
-33
-6.8
-73
-11J
-6.0
-5.8
-6.1
-4.7
-5.1
-2.9
-3.4
-5.6
-6.8
-5.7
jfcjrt
-------
A data reviewer compared the RPIP report to the chromatogram to determine
proper peak identifications. A second data review was performed to check for items
which may have been overlooked on the first pass. After the data was reviewed twice, a
final RPIP report was processed and reviewed for completeness. Final report versions
containing information on all quantitated peaks were printed and filed with the analysis
chromatogram printout and preliminary RPIP report. Electronic copies of all RPIP
reports were also kept on file.
JBS441
11-21
-------
12.0 RECOMMENDATIONS
12.1 General
12.1.1 Vertical Stratification Study
In 1987, 1988, and 1989 ambient air samples were taken at ground level (3 to 10
meters) and at the 1197-foot (364.9-meter) level at one site. In 1988, an additional site
was located on top of the World Trade Center in New York, a height of over 1000 feet.
It is recommended that further study be performed at these sampling heights and that at
least one more level (at 100 meters or some .other appropirate height above ground
level) be sampled at the same location. Upper atmospheric meteorological
characterization measurements need to be made using a Wind Profiling system.
Subsequent NMOC and meteorological data should be correlated. These samples should
be analyzed for NMOC content as well as for the air toxics compound concentrations. It
is also recommended that ozone concentrations and NOX concentrations be monitored at
the same locations and altitudes. The information gained from such a study would be
useful in validating various atmospheric model predictions.
12.1.2 Seasonal NMOC Studies
Data derived in a study qualifying NMOC and NOX in seasons other than summer
could be useful in understanding the relationship of NMOC to NOX and meteorological
conditions. Currently a year-round study for 24-hour air toxics ambient air samples is
being conducted. No study is currently in progress to determine seasonal NMOC
concentration changes.
12.13 Field Audit
It is recommended that a field audit be designed and conducted at several
NMOC/SNMOC sites during the 1994 Monitoring Program. One field audit per month
JBS441
-------
should be performed at an NMOC/SNMOC site during June, July, August, and
September 1994. The field audit should use at least one standard of known
NMOC/SNMOC concentration and should collect duplicate samples plus a zero-air
blank for each site. The audit samples should use both dry and humid standards.
12.1.4 External Analytical Audits
It is recommended that external audit results supply both the theroetical
concentration values and the auditor's analytical values. This should allow for the
resolve of potential low-level contaminant compounds.
122 Equipment
122,1 Multiple Episode Sample Collection Equipment
A design for a multiple episode sampler has been completed. It is recommended
that a prototype instrument be built according to the design. The prototype sampler
should then be checked out and tested.
122.2 Current Sampling Equipment
The NMOC Program began in 1984. Some of the sampling equipment has been
in used since 1984. Prior to the beginning of the 1992 sampling season, approximately 10
sampling systems were rebuilt using a new chassis-design (See Section 3.0). As the
current sampling equipment fails, it is recommended to rebuild the samplers according to
the more user-friendly chassis-design system (Style B) or the above mentioned multiple
episode sampler.
JBS441
12-2
-------
17..7..3 Cleaning and Analytical Equipment
Much of the current cleanup system has been in operation since 1984. The
original intended use of the equipment has been expanded to include year-round use.
As components fail, provisions need to be made for replacements.
The GCs used for the PDFID method are also .beginning to show signs of wear
and tear. Maintenance of these systems must be maintained. And as with the cleanup
system components, provisions need to be made for replacement parts as the need arises.
123 SNMOC
123.1 Expansion of Target Compound List
With the approval of the Clean Air Act Amendments (CAAA) compounds, it is
recommended to expand the list of the current target compounds to include the
appropriate ozone precursor CAAA compounds.
12.4 Air Tories
12.4.1 Compound Stability Study
Depending on the intended use of the data collected under this option of the
NMOC Program, further study may be needed to determine the compound stability in
canisters. If health risk assessment is the intended use of this data, a compound stability
study is recommended. Compound stability in this context refers to whether the
apparent concentration of a compound in a sample taken from a canister is changing
over time. The apparent change in concentration may result from a chemical reaction of
the compound while it is in the canister, or result from a change in the gas phase
concentration caused by adsorption of the compound on the interior canister surfaces.
JBS441
12-3
-------
A study needed to investigate this phenomenon would take several canisters-at
least three from each initial concentration-ranging in target compound concentration
from 0.0 to 20 ppbv. The canisters would be analyzed 24 hours after mixing, 72 hours
after mixing, 30 days after mixing, and 60 days after mixing to determine any
concentration changes. It is also recommended that the same concentration be mixed in
canisters, but that equilibration time of 7 days and 30 days be assigned before the first
samples are drawn from the canisters to determine the effect of equilibration time on the
concentration sample withdrawn from the canisters.
12.4.2 Expansion of Target Compound List
With the approval of the Clean Air Act Amendments compounds, it is
recommended to expand the list of the current target 38 air toxic compounds to include
the appropriate airborne toxic compounds.
Carbonvls
.1 Use of Ozone Scrubber
Previous studies showed that the ozone scrubber was needed to accurately
measure the carbonyl concentration in ambient air when sampling occurs with silica gel
media. It is recommended to continue using the carbonyl ozone scrubber when sampling
for carbonyl compounds.
12_5.2 Life of Ozone Scrubber
It is recommended to determine the life of the effectiveness of the ozone
scrubbers. Some preliminary studies performed by the US EPA indicated that the
effective life was approximately 6000 sample-hours. These results need to be checked
and more definitively defined with field studies that extend over several years.
JBS441
12-4
-------
13.0 REFERENCES
1. Compendium Method TO-12, "Determination of Non-Methane Organic
Compounds (NMOC) in Ambient Air Using Cryogenic Pre-Concentration and
Direct Flame lonization Detection (PDFID)," Quality Assurance Division,
Environmental Monitoring Systems Laboratory, U.S. Environmental Protection
Agency, Research Triangle Park, NC, 27711, May 1988.
2. Radian Corporation. Support for the Ozone Precursor, Toxic Emissions Initiative
Including Documentation of Nonmethane Organic Compounds (NMOC),
Speciated Volatile Organic Compounds (VOC), and Toxic Compounds, Work
Plan and Quality Assurance Project Plan. DCN No. 93-298-130-12-01. Prepared
for the U.S. Environmental Protection Agency, Research Triangle Park, NC. EPA
Contract No. 62D20160.
3. Radian Corporation. 1992 Nonmethane Organic Compounds and Speciated
Nonmethane Organic Compounds Monitoring Program Final Report. DCN
No.-93-298-017-70-13. Prepared for the U.S. Environmental Protection Agency,
Research Triangle Park, NC. April 1993.
4. Radian Corporation. 1991 Nonmethane Organic Compound, Speciated
Nonmethane Organic Compound, and Three-Hour Urban Air Toxics Monitoring
Program Final Report. DCN No. 91-262-045-90. Prepared for the U.S.
Environmental Protection Agency, Research Triangle Park, NC. August 1992.
5. Radian Corporation. 1990 Nonmethane Organic Compound and Three-Hour Air
Toxics Monitoring Program. Final Report. Prepared for U. S. Environmental
Protection Agency, Research Triangle Park, NC, 27711, DCN No. 91-262-045-04.
January 1991.
6. Radian Corporation. 1989 Nonmethane Organic Compound and Three-Hour Air
Toxics Monitoring Program. Final Report. Prepared for U. S. Environmental
Protection Agency, Research Triangle Park, NC, 27711, EPA-450/4-90-011. May
1990.
7. Radian Corporation. 1988 Nonmethane Organic Compound and Urban Air
Toxics Monitoring Program. Final Report. Volume I. U. S. Environmental
Protection Agency, Research Triangle Park, NC, 27711, EPA-450/4-89-003.
December 1988.
8. Radian Corporation, 1987 Nonmethane Organic Compound and Air Toxics
Monitoring Programs. Final Report Volume 1 - Hydrocarbons, U. S.
Environmental Protection Agency, Research Triangle Park, NC. EPA-450/4-88-
011. August 19, 1988.
JBS441
-------
9. McAllister, R. A., R. F. Jongleux, D-P. Dayton, P. L. O'Hara, and D. E. Wagoner
(Radian Corporation). Nonmethane Organic Compound Monitoring. Final
Report. Prepared for U.S. Environmental Protection Agency, Research Triangle
Park, NC. EPA Contract No. 68-02-3889, July 1987.
10. McAllister, R. A., D-P. Dayton, and D. E. Wagoner (Radian Corporation).
Nonmethane Organic Compound Monitoring. Final Project Report. Prepared for
U.S. Environmental Protection Agency, Research Triangle Park, NC. EPA
Contract No. No. 68-02-3889, January 1986.
11. Radian Corporation. Nonmethane Organic Compounds Monitoring Assistance for
Certain States in EPA Regions HI, IV, V, VI, and VH, Phase II. Final Project
Report. Prepared for the U.S. Environmental Protection Agency, Research
Triangle Park, NC. EPA Contract No. 38-02-3513, February 1985.
12. Compendium Method TO-14. The Determination of Volatile Organic
Compounds (VOCs) in Ambient Air Using SUMMA« Passivated Canister
Sampling and Gas Chromatographic Analysis. Quality Assurance Division,
Environmental Monitoring Systems Laboratory, United States Environmental
Protection Agency, Research Triangle Park, NC.
13. Compendium Method TO-11. Determination of Formaldehyde in Ambient Air
Using Adsorbent Cartridge Followed by High Performance Liquid
Chromatography. Atmospheric Research and Exposure Assessment Laboratory,
Office of Research and Development, United States Environmental Protection
Agency, Research Triangle Park, NC.
JBS441
13-2
-------
-------
APPENDIX A
SAMPLING SITES FOR 1993 NMOC MONITORING PROGRAM
-------
Table A-1. 1993 NMOC/SNMOC Program Sites
#of
Region Sites
2 1
1
1
3 1/2
1/2
4 1
1
1
6 1
1
1
1
1
1
Radian
Site
Code
LINY
NWNJ
PLNJ
P1PA
P2PA
B1AL
B2AL
B3AL
DLTX
BMTX
H1TX
FWTX
EPTX
JUMX
AIRS
Code
36-059-0005
34-013-0011
34-039-5001
42-017-0012
42-091-0013
01-073-6002
01-073-5002
01-117-0004
48-113-0069
48-245-0009
48-201-1034
48-439-1002
48-141-0027
80-006-0001
Location
Long Island, NY
Newark, NJ
Plainfield, NJ
Bristol, PA
Norristown, PA
Birmingham, AL (Tarrant)
Birmingham, AL (Pinson)
Birmingham, AL (Helena)
Dallas, TX
Beaumont TX
Houston, TX
Ft. Worth, TX
El Paso, TX
Juarez, Mexico
Base
Program SNMOC
NMOC Yes
NMOC Yes
NMOC Yes
NMOC Yes
NMOC Yes
SNMOC
SNMOC
SNMOC
SNMOC
SNMOC
SNMOC
SNMOC
SNMOC
SNMOC
Options
3-Hr
Toxics
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Carbonvf
Yes
Yes
-------
SUE DESCRIPTION INVtHIUHY
EPA REGION: o<>
SITI 10: 01-073-500?
CITY POPULATION 1
AQCR POPULATION 1,168,098
MET SITE:
SITE 10
DISTANCE SITE
DIRECTION SITE
TYPE SITE ( )
STATE (01): ALABAMA
ADDRESS: PINSON,, HIGH sen., BOX 360 HWY 75 NORTH
CITY (00000):
COUNTY (073):
DATE ESTABLISHED:
DATE TEJNitJATEO :
DATE LASfUPDATE:
MO EVAL DATE :
REGN EVAL DATE :
NOT IN A CITY
JEFFERSON CO
1992/06/22
1980/07/17
STATE/LOCAL ID:
OIST CITY: 032 K
DIFF GMT : 06
ELEV MSL : 201 M
COMP SECT: NE
UTM ZONE :"l6
UTM NORTH:. 3729242 -.
UTN EAST * 7 530604 ' "J \
LATITUDE <*»13:^2:1« ^ ^
LONGITUOEi^Oa6S40i&8 TJ
AQCR
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SITE COMMENT 1
SITE COMMENT 2
SUPPORTING AGFNCV
URBAN ARfA REPRESENTED
TANGENT STREET:
STRFET * TRAFFIC FLOW
1 13000
(O04): METROPOLITAN BIRMINGHAM
(OOOO): •• DESCRIPTION UNKNOWN •* '
(1): RESIDENTIAL
(3): RURAL
(1OOO): BIRMINGHAM, AL |
: PINSON VALLEY HIGH SCHOOL BY TENNIS COURTS IN FRONT OF SCHOOL
: NAMS OZONE
(O12): JEFFERSON COUNTY DEPARTMENT OF HEALTH
(1000): BIRMINGHAM, AL '
YP TRAFFIC DIR STREET NAME
TYPE ROAD
(5): THRU ST OR HY
SITE 10: 01-073-6002
CITY POPULATION : 8
AOCR POPULATION : 1,168
MET SITE:
SHE ID :
DISTANCE SITE :
DIRECTION SITE:
TYPE SITE ( ):
ADDRESS: TARRANT, ELEM. SCH., 1269 PORTLAND STREE
,148
,098
CITY (75000):
COUNTY (073):
DATE ESTABLISHED:
DATE TERMINATED :
DATE LAST UPDATE:
HQ EVAL DATE :
REGN EVAL DATE :
TARRANT CITY
JEFFERSON CO
1992/05/18
1980/07/17
STATE/LOCAL ID:
OIST CITY: 013 K
OIFF GMT : 06
ELEV MSL : 171
COMP SECT: NE
UTM ZONE : 16
UIM NORTH: 3715234
UTM EAST : 520984
LATITUDE : 433:34:42
LONGITUDE: -086:46:26
AQCR
CMSA LOCATED IN
LAND US'1
LOCATION SETTING
MSA LOCATED IN
SITE COMMENT 1
SITE COMMENT 2
SUPPORTING AGENCY
URBAN AREA REPRESENTED
(004): METROPOLITAN BIRMINGHAM
(OOOO): ** DESCRIPTION UNKNOWN ** I
(1): RESIDENTIAL j
(2): SUBURBAN I
(1000): BIRMINGHAM, AL '
: TARRANT ELEM. SCH. NEAR TENNIS COURTS BEHINQ
: NAMS TSP AND OZONE
(012): JEFFERSON COUNTY DEPARTMENT OF HEALTH
(1000): BIRMINGHAM, AL
SCHOOL
-------
SHE 10: 01-073-6002
TANGENT STREET:
STREET 0 TRAFFIC FLOW
1 2000
2 300
3 1500
4 30000
YR TRAFFIC OIR _JJ*EET NAME
TYPE ROAD
(6): LOCAL ST OR H\
(6): LOCAL ST OR HI
MAJ ST OR HV
MAJ ST OR HY
SITf 10: 01-117-000*
CITY POPULATION 1
AOCR POPULATION i,i6n,o98
MET SITE:
SITE 10
DISTANCE SITE
DIRECTION SITE
TYPE SITE < )
AOORESS: BEARDEN FARH
CITY
(00000): NOT IN A CITY
COUNTY C117): SHtLUY CO
DATE ESTABLISHED: 1983/01/01
DATE TERMINATED : / /
DATE LAST UPDATE: 1992/09/17
HQ EVAL DATE : / /
RECN EVALJIATE : / /
STATE/LOCAL ID:
DIST CITY:
OIFF GMT :
I ELEV MSL :
i COMP SECT:
K UIM 70NE : 16
UIM NORTH: 9686270
600 M UIM EAST : 516280
LATITUDE : +33:19:01
LONGITUDE: -086:49:30
AQCP.
CHSA LOCATcO IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SUPPORTING AGENCY
URBAN AREA REPRESENTED
TANGENT STREET:
STREET It TRAFFIC FLOW
1 1000
2 20
(004): METROPOLITAN BIRMINGHAM
(0000): *• DESCRIPTION UNKNOWN *«
(4): AGRICULTURAL
(3): RURAL
(1000): BIRMINGHAM, AL
(Oil): AL OEPT. OF ENV. MGT.
(1000): BIRMINGHAM, AL
YR TRAFFIC OIR STREET NAME
TYPE ROAD
(6): LOCAL ST OR HYJ
(6): LOCAL ST OR HY
-------
UtSLRIPIIUN INVfcNIQKY
EPA RFGION: 02
SIATE (34): NEW JERSEY
34-013-0011 ADDRESS: ST. CHARLES BETWEEN KOSSUTH t. KAMERON ST STATE
SITE ID: 34-013-0011 AOOR
CITY POPULATION 329,248
AQCR POPULATION 16,525,701
MET SITF:
SUE ID
OISTANCL SITE
OIRCCTION SIIF
SITE ( )
AQCR
CMSA I.UCATED IN
LAND USE
LOCATION SETTING
MSA LOCATFD IN
SIIF COMMENT 1
SITF COMMENT 2
SUPPORTING AGENCY
URBAN ARHA REPRESFNTED
TANGENT STREET:
STRELT H TRAFFIC FLOW
1 71000
? 2000
CITY (51000): NEWARK
COUNTY (013): ESSEX CO
DATE ESTABLISHED: 1965/01/01
DATE TERMINATED : / /
DATE LASf UPDATE: 1992/05/14
MQ EVAL DATE : / /
HE1N EVAL DATE : 1906/05/06
LOCAL ID:
OIST CITY: 015 K
_ OIFF GMT : 05
ELEV MSL : 3 M
COMP SECT: sw
UTM ZONE i ifl
UTM NORTH* 4508570„
UTM EASt IT 572280
LATITUDE I M0:43»3f
I
(043): NEW JERSEY-NEW YOHK-CONNECIICUT
(0000): •» DESCRIPTION UNKNOWN **
(3): INDUSTRIAL
(1): URBAN ANO CENTER CITY
(5640): NEWARK, NJ
: NJ §07142,START 1/1/B5,RELOC.FROM 340130008, SITTING CRITERIA?
: PMiq.DICHOI,START 3/15/86,ELEV.16«;03 DOWN 5/16/86-3/25/87
(001): NEW JERSEY STATE DEPARTMENT OF ENV IRONMENTAtl PROTEC
(5601): NEW YORK, NY-NOR'THEASI I >< NJ i
VR TRAFFIC DIR STREET NAME
TYPE ROAD
(2): EXPRESSWAY
(6): LOCAL ST OR HX
SIIF Hi: 34-039-5001
CIIY POPULATION :
AQCR POPULATION : 16,525,701
MET SITE:
SITE ID : - -
DISTANCE SITE : M
DIRfCTION SITE:
TYPE SITE ( ):
AQCR
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SITF COMMENT 1
SITE COMMENT 2
SUPPORTING AGENCY
URBAN AREA REPRESENTED
AUDPCSS: WEST THIRD AND BERGEN STREETS
CITY (59190): PLAINFIFLO
COUNTY (039): UNION CO
DATE ESTABLISHED: 1980/05/01
DATE TERMINATED : / /
DATE LAST UPDATE: 1991/04/10
HQ EVAL DATE : / /
REGN EVAL DATE : 1990/07/06
STATE/LOCAL ID:
OIST CITY: 042 K
, 01FF GMT : 05
ELEV MSL : 18 M
CONP SECT: SW
UTM ZONE : 18
UTM NORTH: 4494399
UTM EAST : 547218
LATITUDE : •40:36:03
LONGITUDES -074:26:31
(043): NEW JERSEY-NEW YORK-CONNECTICUT i
(0000): •• DESCRIPTION UNKNOWN •* ,
(1): RESIDENTIAL
(2): SUBURBAN
(5640): NEWARK, NJ
: NJ 020121, SLAMS-N02,03 1980 NE OXIOANT STU,DY;03,S02,NOX
: FORMERLY COOED 340351001 i
(001): NEW JERSEY SIATE DEPARTMENT OF ENVIRONMENTAL PROTEC
(5601): NEW YORK, NY-NORTHEASTERN NJ
-------
Silt 10: 3<,-039-500l I
TANGINT STREET: I
STRFtr f TRAFFIC FLOW YR TRAFFIC DIR STREET NAME TYPE ROAD
\ '°°° ' «>>: LOCAL ST OR HV
2 50° (6): LOCAL ST OR J
-------
S1H I1LSCRI»(|I)N INVENTORY
TPA
(, I JM: 0?
SITt II): )6-059-0005
CITV POPULATION :
AOC« POPULATION :
MET SITf:
Silt ID :
DISTANCE SITE :
f CTION SI Tf :
AOOHESS
1
16,525,701
SIAIh ( i«.) : NEW YORK
EISENHOWER PARK,MERRICK AVCOLD COUNTRY R
CITY (00000): NOT IN A CITY
COUNTY (059): NASSAU CO
DATE ESTABLISHED: 1971/01/01
DATE TERMINATED
DATE LAST UPDATE
HQ EVAL DATE
REGN EVAL DATE
1993/03/16
STATE/LOCAL ID:
OIST CITY: 033 K UTM ZONE : 18
DIFF GMT : 05 UTM NORTH: 4511200
ELEV MSL : 27 M UTM EAST t 619300
COMP SECT: E LATITUDE t 440:44x43
LONGITUDE: -073:35:13"
IVPf SITE (1): ON-SITfc MtT EQUIP
AQCR
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCMfO IN
SI If CGMIfNT 1
SHE CUHMtNT ?
SUPPOSING AGENCY
URBAN ARTA RFPRFSfNTEO
(043): NEW JERSEY-NEW YORK-CONNtCTICUI
(0000): ** DESCRIPTION UNKNOWN **
(2): COMMERCIAL
(2): SUBURBAN
(53BO): NASSAU-SUFFOLK, NY
: NVS «2950-10 SIART SU2,CO,J 1,NO?,TSP•71,Pfl«72;NECRMP•80,NO,N02,03
: 03-*334105002F01 12/82,MIDDLE SCALE,MEETS SITING.N02-2-025 - 12/86
(001): NEW YORK STATE DEPARTMENT OF ENVIRONMENTAL (JONSERVA
(S601): NEW YORK, NY-NOR-THEASTERN NJ
-------
SltF 10: 42-017-0012
CITY POPULATION
AOCR POPULATION
ME! SITE:
SIIF II)
DISTANCE
IITt
OIKFCTION Sllf
AOlWtSS:
10.P67
ROCKVIEM LANE
CUV (08760):
COUNTY (017):
DATE ESTABLISHED:
DATE TERMINATED :
OATE LAST UPDATE:
HQ EVAL OATE :
REON EVAL OATF :
lYt'F SITi: (1) ON-SIlt Ml f EQUIP
BRISTOL (BOROUGH)
BUCKS CO
1991/08/15
1988/09/16
17BB/0*/!*
STATEKoCAL 10:
OIST CITY:
DIFF GMT :
ELEV MSL :
COMP SECT:
05
12 M
UTM ZONE :
UTM NORTH:
UTM EAST :
LATITUDE :
LONGITUDE:
18
4455021
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MSA LOCATED IN
SITE COMMENT I
SITE COMMENT Z
SUPPOPTING AGENCY
URBAN AREA REPRESENTED
TANCcNI STREtl:
STREET a TRAFFIC FLOW
1 500
(045):
(OOOU):
(1):
(2):
(6160):
(001):
(0000):
METROPOLITAN PHILAUFtPHfA
•* DESCRIPTION UNKNOWN **
RESIDENTIAL
SUBURBAN
PHILADELPHIA, PA-NJ
FOR JUNIOR HIGH SCHOOL
P0900501 PA SITE CODE
PENNSYLVANIA DEPARTMENT OF
NOT IN AN URBAN AREA
ENVIRONMENTAL RESOURCES
TRAFFIC DIR STREET NAME
TYPE ROAD
(6): LOCAL ST OR HY
SITE 10: 42-091-0013
CIIV POPULATION
POPULATION 5,4H7,472
ADDHtSS: STATE ARMORY - 1046 BELVOIR RO
MET SIIF:
SIFC 10
DISTANCE SITE
DIRECTION SITE
TYPC SITE ( )
CI TY
COUNTY
UATF ESTABLISHED
DATE TERMINATED
DATE LAST UPDATE
HQ EVAL OATE
REGN EVAL OATE
(54656): NORRISIOrtN
(091): MONTGOMfRY CO
1991/08/15
STATE/LOCAL ID:
DIST CITY:
DIFF GMT :
ELtV MSI :
COMP SECT:
K UTM /ONE : 18
05 UTM NORTH: 4440048
53 M DIM EAST : 473533
LATITUDE : 440:06:44
LONGITUDE: -O75:ia:38
AQCB
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SITE COMMENT I
SUPPORTING AGENCY
URBAN AREA REPRESFNTEO
(045): METROPOLITAN PHILADELPHIA
(0000): *• DESCRIPTION UNKNOWN **
(I): RESIDENTIAL
(2): SUBURBAN
(6160): PHILADELPHIA, PA-NJ
: COPAMS REMOTE STATION 013
(001): PENNSYLVANIA DEPARTMENT OF ENVIRONMENTAL RESOURCES
(0000): NOT IN AN URBAN AREA
-------
LPA RfGIUN: 03 STATE (<•?): PENNSYLVANIA
SIIF 10: 42-091-0013
TANGENT STREET:
STREET » TRAFFIC FLOW YR TRAFFIC OIR STREET NAME TYPE ROAD
I 8500 («): HAJ ST OR MY
-------
SITC rt): 48-113-0069
ADDRESS: 1415 HINTON
CIIV
AQCR
POPULATION
POPULATION
9O4,078
3,257,903
MET SITE:
SIIF 10
DISTANCE SITE
DIRECTION SIT^
TVPF SITE ( )
AQCH
CMSA lOCATtO IN
LAMP 'JSf
LOCATION SETTING
MSA LOCATfO IM
SIU CONNF.NT I
SITE COHMFlif ?
SUPPORTING AGENCY
U«HA,C SITE ( ):
AOCfl
CMSA LOCATtr'J IN
LANU USt
LOCATION SETTING
MSA LOCATED IN
SITt COMMENT 1
SITE COMMENT 2
SUPPORTING AGENCY
URBAN AREA REPRTSENTEO
ADDRESS: 500 NORTH CAMPBELL ST.
425,2'»9
66C,HOlS
CITV (24000):
COUNTY (141):
UATE ESTABLISHED:
OAIE TERMINATED :
OATE LAST UPDATE:
HQ EtfAL OATE :
REGN EVAL OATE :
£1 PASO
EL PASO CO
1973/01/01
/ /
1993/10/12
STATE/LOCAL ID:
OIST CITY:
OIFF GMT :
ELEV MSL :
COMP SECT:
or
1140 M
UTM /ONE :
UTM NORTH:
DIM EAST :
LATI TUDE :
13
3514886
3591T9
+31:45:45
LONGITUDE: -106:29:13
(15J): EL PASO-LAS CRUCt S-ALAHO(,OKOO
(OOOU): *» DESCRIPTION UNKNOWN **
(2): COMMERCIAL
(1): URBAN AND CENTER CITY
(2320): EL PASO, TX
: SIP MONITOR
: ACTIVE 11/73
(001): TEXAS AIR CONTROL BOARD
(2)20): EL PASO, TX
-------
IPA RFGION: 06
jll! ItLSCHIPIIUN INVLNTUKV
STATE (48): TEXAS
SHE 10:
TANGENT
STREET 0
1
2
3
48-141-0027
TRAFFIC FtOM
20000
25000
16000
YR TRAFFIC OIR STREET NAME
TYPE ROAD
(4): MAJ ST OR HV
(4): HAJ ST OR HY
(3): FREEWAY
SITF 1C: A3-245-0009
CIIY POPULATION
AOCP POPULATION
MET SITF:
SIIF It)
DISTANCE SITE
DIRECTION SITE
TYPE SITE ( )
AQCR
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SI If COMMENT 1
SITF COMMENT 2
SUPPORTING AiiFNCY
URBAN ARcA REPRESENTED
110,102
,51)8
: GEORGIA AT CUNNINGHAM, UCAUMONT, TX
CITY (07000): HFAUMQNT
COUNTY (245): JFFFERSON CO
DATE ESTABLISHED: 1980/01/01
DATE TERMINATED : / /
DATE LAST UPDATE: 1993/10/12
HQ EVAL DATE : / /
REGN EVAL DATE : / /
STATE/LOCAL ID:
OIST CITY:
OIFF GMT :
ELIV MSL :
COMP SECT:
06
13 M
UIM /ONE :
UTM NORTH:
UIM EAST :
LATITUDE :
LONGITUDE:
(106): SOUTHERN LOUISIANA-SOUTHEAST
(0000): •* DESCRIPTION UNKNOWN **
(1): RESIDENTIAL
(2): SUBURBAN
(0040): BEAUMONT-PORT ARTHUR, IX
: MOVED FROM VIRGINIA ST
: LAMAR UNIVERSITY CAMPUS
(001): TEXAS AIR CONTROL BOARD
(OH39): BEAUMONT, TX
TEXAS
15
3323462
396381
•30:02:22
-094:04:29
SITE 10: 4S-439-1002
AOOPESS: ROSS AVE BETWEEN
CITY
AQCR
POPULATION
POPULATION
MET SITE:
SITE 10
DISTANCE SITE
DIRECTION SITE
1YPE SITE (1)
3d5,164 CITY (27000):
3,237,903 COUNTY (439):
DATE ESTABLISHED:
DATE TERMINATED :
DATE LASf UPDATE:
M HO EVAL DATE :
REGN EVAL DATE :
UN-SITt MFT EQUIP
LONG AND 14TH ST
FORT WOPTH
TARRANT CO
1975/01/01
1993/10/27
1980/10/28
1980/08/01
STATE/LOCAL ID:
OIST CITY: 006 K
OIFF GMT : 06
ELtV MSL : 204
COMP SECT: N
UTM /ONE :
UTM NORTH:
UTM EAST :
LATITUDE :
14
3630705
653B10
•92:48:19
LONGITUDE: -097:21:26
AQCR
CMSA LOCATED IN
LAND USF
LOCATION SETTING
MSA LOCATED IN
SITE COMMENT 1
SUPPORTING AGENCY
URBAN AREA REPRESENTED
(215): METROPOLITAN DALLAS-FORT WORTH
(0000): •* DESCRIPTION UNKNOWN *•
(2): COMMERCIAL
(1): URBAN AND CENTER CITY
(2800): FORT WORTH-ARLINGTON, IX
: CONTINUOUS MUNITRING SIATION
(001): IEXAS AIR CONTROL BOARD
(1920): OALLAS-FORT WORTH, TX
-------
SITf 10: <»8-439-l002
TANCtNT STREET:
STRFET 0 TRAFFIC FLOM YR TRAFFIC OIR $TREET NAME TYPE ROAD
1 100 ' (6): LOCAL ST OR
1
-------
UL SLR IP I ION INVtNIORY
EPA
0<>
STATE (80): COUNTRY Of MEXICO
SITE 10: 80-006-0001
CITY POPULATION
A OCR POPULATION
MET SITE:
SITE 10
OISTANCf
TVP^
SITE
SHE
SITE ( )
34923,129
AOCP
CMSA LOCATED IN
LAND USE
LOCATION SETTING
MSA LOCATED IN
SITE COMMENT I
SUPPORTING AGFNCY
URBAN ARKA REPRESENTED
ADDRESS: TECHNICAL INSTITUTE
CITY (01150): CIUDAO-JUAREZ
COUNTY (006): CHIHUAHUA STATE
DATE ESTABLISHED: 1990/06/04
DATE TERMINATED : / /
DATE LAST UPDATE: 1993/07/01
MO EVAL DATE : / /
REGN EVAL DATE : / /
(250): COUNTRY OF MEXICO
(0000): ** DESCRIPTION UNKNOWN **
(2): COMMERCIAL
(1): URBAN AND CENTER CITY
(?320): EL PASO, TK
: SPECIAL EL PASO/JUARE/ MONITORING SITE,
(002): SEDUE
(2320): EL PASO, TK
STATE/LOCAL ID:
DIST CITY:
DIFF GMT :
ELEV MSL :
COHP SECT:
UTM ZONE :
UIM NORTH:
M UTM EAST I~
LATI TUOE : +00:00:00
LONGITUDE: +000:00:00
SITF TVPt:
SHE LOCATION TYPE
(0): •••»••«••• DESCRIPTION UNKNOWN •»•••••*••
(0): •«*«••«**• DESCRIPTION UNKNOWN ••«*•••*••
(0): *•*••***** DESCRIPTION UNKNOWN ••**••*•*•
MSA OR CMSA REPRESENTED
-------
APPENDIX B
CRYOGENIC PRECONCENTRATION AND DIRECT FLAME
IONIZATION DETECTION METHOD
-------
METHOD TO-12
METHOD FOR THE DETERMINATION' OF NON-METHANE ORGANIC COMPOUNDS (NMOC)
IN AMBIENT AIR USING CRYOGENIC PRE.CONCENTRATION AND DIRECT FLAME
IONIZATION DETECTION (PDFID)
1. Scope
1.1 In recent years, the relationship between ambient concentrations
of precursor organic compounds and subsequent downwind
concentrations of ozone has been described by a variety of
photochemical dispersion models. The most important application
of such models is to determine the degree of control of precursor
organic compounds that is necessary in an urban area to achieve
compliance with applicable ambient air quality standards for ozone
(1,2).
1.2 The more elaborate theoretical models generally require detailed
organic species data obtained by multicomponent gas chromatography
(3). The Empirical Kinetic Modeling Approach (EKMA), however,
requires only the total non-methane organic compound (NMOC)
concentration data; specifically, the average total NMOC
concentration from 6 a.m. to 9 a.m. daily at the sampling
location. The use of total NMOC concentration data in the EKMA
substantially reduces the cost and complexity of the sampling and
analysis system by not requiring qualitative and quantitative
species identification.
1.3 Method T01, "Method for The Determination of Volatile Organic
Compounds in Ambient Air Using Tenax* Adsorption and Gas
Chroraatography/Mass Spectrometry (GC/MS)", employs collection of
certain volatile organic compounds on Tenax* GC with subsequent
analysis of thermal desorption/cryogenic preconcentration and
GC/MS identification. This method (T012) combines the same type
of cryogenic concentration techniques used in Method T01 for high
sensitivity with the simple flame ionization detector (FID) of the
GC for total NMOC measurements, without the GC columns and complex
procedures necessary for species separation.
1.4 In a flame ionization detector, the sample is injected into a
hydrogen-rich flame where the organic vapors burn producing
ionized molecular fragments. The resulting ion fragments are then
collected and detected. The FID is nearly a universal detector.
However, the detector response varies with the species of
[functional group in] the organic compound in an oxygen
atmosphere. Because this method employs a helium or argon carrier
gas, the detector response is nearly one'for all compounds. Thus,
the historical short-coming of the FID involving varying detector
response to different organic functional groups is minimized.
-------
T012-2
1.5 The method can be used either for direct, in situ ambient
measurements or (more commonly) for analysis of integrated samples
collected in specially .treated stainless steel canisters. EKMA
models generally require 3-hour integrated NMOC measurements over
the 6 a.m. to 9 a.m. period and are used by State or local
agencies to prepare State Implementation Plans (SIPs) for ozone
control to achieve compliance with the National Ambient Air
Quality Standards (NAAQS) for ozone. For direct, in situ ambient
measurements, the analyst must be present during the 6 a.m. to 9
a.m. period, and repeat measurements (approximately six per hour)
must be taken to obtain the 6 a.m. to 9 a.m. average NMOC
concentration. The use of sample canisters allows the collection
of integrated air samples over the 6 a.m. to 9 a.m. period by
unattended, automated samplers. This method has incorporated both
sampling approaches.
Applicable Documents
2.1 ASTM Standards
D1356 - Definition of Terms Related to Atmospheric Sampling
and Analysis
E260 - Recommended Practice for General Gas Chromatography
Procedures
E355 - Practice for Gas Chromatography Terms and
Relationships
2.2 Other Documents
U. S. Environmental Protection Agency Technical Assistance
Documents (4,5)
Laboratory and Ambient Air Studies (6-10)
Summary of Method
3.1 A whole air sample is either extracted directly from the ambient
air and analyzed on site by the GC system or collected into a
precleaned sample canister and analyzed off site.
3.2 The analysis requires drawing a fixed-volume portion of the sample
air at a low flow rate through a glass-bead filled trap that is
cooled to approximately -186°C with liquid argon. The cryogenic
trap simultaneously collects and concentrates the NMOC (either via
condensation or adsorption) while allowing the methane, nitrogen,
oxygen, etc. to pass through the trap without retention. The
system is dynamically calibrated so that the volume of sample
passing through the trap does not have to be quantitatively
measured, but must be precisely repeatable between the calibration
and the analytical phases.
-------
T012-3
3.3 After the fixed-volume air sample has been drawn through the trap,
a helium carrier gas flow is diverted to pass through the trap, in
the opposite direction to the sample flow, and into an FID. When
the residual air and methane have been flushed from the trap and
the FID baseline restablizes, the cryogen is removed and the
temperature of the trap is raised to approximately 90°C.
3.4 The organic compounds previously collected in the trap revola-'
tilize'due to the increase in temperature and are carried into the
FID, resulting in a response peak or peaks from the FID. The area
of the peak or peaks is integrated, and the integrated value is
translated to concentration units via a previously-obtained
calibration curve relating integrated peak areas with known
concentrations of propane.
3.5 By convention, concentrations of NMOC are reported in units of
parts per million carbon (ppmC), which, for a specified compound,
is the concentration of volume (ppmV) multiplied by the number of
carbon atoms in the compound.
3.6 The cryogenic trap simultaneously concentrates the NMOC while
separating and removing the methane from air samples. The
technique is thus direct reading for NMOC and, because of the
concentration step, is more sensitive than conventional continuous
NMOC analyzers.
Significance
4.1 Accurate measurements of ambient concentrations of NMOC are
important for the control of photochemical smog because these
organic compounds are primary precursors of atmospheric ozone and
other oxidants. Achieving and maintaining compliance with the
NAAQS for ozone thus depends largely on control of ambient levels
of NMOC.
4.2 The NMOC concentrations typically found at urban sites may range
up to 5-7 ppmC or higher. In order to determine transport of
precursors into an area, measurement of NMOC upwind of the area
may be necessary. Upwind NMOC concentrations are likely to be
less than a few tenths of 1 ppm.
4.3 Conventional methods that depend on gas chromatography and
qualitative and quantitative species evaluation are excessively
difficult and expensive to operate and maintain when speciated
measurements are not needed. The method described here involves a
simple, cryogenic preconcentration procedure with subsequent,
direct, flame ionization detection. The method is sensitive and
provides accurate measurements of ambient NMOC concentrations
where speciated data are not required as applicable to the EKMA.
-------
T012-4
5. Definitions
[Note: Definitions used in this document and in any user-prepared
Standard Operating Procedures (SOPs) should be consistent with
ASTM Methods D1356 and E355. All abbreviations and symbols are
defined within this document at point of use.]
5.1 Absolute pressure - Pressure measured with reference to absolute
zero pressure (as opposed to atmospheric pressure), usually
expressed as pounds-force per square inch absolute (psia).
5.2 Cryogen - A substance used to obtain very low trap temperatures in
the NMOC analysis system. Typical cryogens are liquid argon
(bp-185.7) and liquid oxygen (bp-183.0).
5.3 Dynamic calibration - Calibration of an analytical system with
pollutant concentrations that are generated in a dynamic, flowing
system, such as by quantitative, flow-rate dilution of a high .
concentration gas standard with zero gas.
5.4 EKMA - Empirical Kinetics Modeling Approach; an empirical model
that attempts to relate morning ambient concentrations of non-
methane organic compounds (NMOC) and NO, with subsequent peak,
downwind ambient ozone concentrations; used by pollution control
agencies to estimate the degree of hydrocarbon emission reduction
needed to achieve compliance with national ambient air quality
standards for ozone.
5.5 Gauge pressure - Pressure measured with reference to atmospheric
pressure (as opposed to absolute pressure). Zero gauge pressure
(0 psig) is equal to atmospheric pressure, or 14.7 psia (101 kPa).
5.6 In situ - In place; In situ measurements are obtained by direct,
on-the-spot analysis, as opposed to subsequent, remote analysis of
a collected sample.
5.7 Integrated sample - A sample obtained uniformly over a specified
time period and representative of the average levels of pollutants
during the time period.
5.8 NMOC - Nonmethane organic compounds; total organic compounds as
measured by a flame ionization detector, excluding methane.
5.9 ppmC - Concentration unit of parts per million carbon; for a
specific compound, ppmC is equivalent to parts per million by
volume (ppmv) multiplied by the number of carbon atoms in the
compound.
5.10 Sampling - The process of withdrawing or isolating a repre-
sentative portion of an ambient atmosphere, with or without the
simultaneous isolation of selected components for subsequent
analysis.
-------
T012-5
6. Interferences
6.1 In field and laboratory evaluation, water was found to cause a
positive shift in the FID baseline. The effect of this shift is
minimized by carefully selecting the integration termination point
and adjusted baseline used for calculating the area of the NMOC
peak(s).
6.2 When using helium as a carrier gas, FID response is quite uniform
for most hydrocarbon compounds, but the response can vary
considerably for other types of organic compounds.
7. Apparatus
7.1 Direct Air Sampling (Figure 1)
7.1.1 Sample manifold or sample inlet line - to bring sample
air into the analytical system.
7.1.2 Vacuum pump or blower - to draw sample air through a
sample manifold or long inlet line to reduce inlet
residence time. Maximum residence time should be no
greater than 1 minute.
7.2 Remote Sample Collection in Pressurized Canisters (Figure 2)
7.2.1 Sample canister(s) - stainless steel, Summa*-polished
vessel(s) of 4-6 L capacity (Scientific Instru-
mentation Specialists, Inc., P.O. Box 8941, Moscow, ID
83843), used for automatic collection of 3-hour
integrated field air samples. Each canister should
have a unique identification number stamped on its
frame.
7.2.2 Sample pump - stainless steel, metal bellows type
(Model MB-151, Metal Bellows Corp., 1075 Providence
Highway, Sharon, MA 02067) capable of 2 atmospheres
minimum output pressure. Pump must be free of leaks,
clean, and uncontaminated by oil or organic compounds.
7.2.3 Pressure gauge - 0-30 psig (0-240 kPa).
7.2.4 Solenoid valve - special electrically-operated,
bistable solenoid valve (Skinner Magnelatch Valve, New
Britain, CT), to control sample flow to the canister
with negligible temperature rise (Figure 3). The use
of the Skinner Magnelatch valve avoids any substantial
temperature rise that would occur with a conventional,
normally closed solenoid valve, which would have to be
energized during the entire sample period. This
temperature rise in the valve could cause outgasing of
organics from the Viton valve seat material. The
Skinner Magnelatch valve requires only a brief
electrical pulse to open or close at the appropriate
-------
T012-6
start and stop times and therefore experiences no
temperature increase. The pulses may be obtained with
an electronic timer that can be programmed for short
(5 to 60 seconds) ON periods or with a conventional
mechanical timer and a special pulse circuit. Figure
3[a] illustrates a simple electrical pulse circuit for
operating the Skinner Magnelatch solenoid valve with a
conventional mechanical timer. However, with this
simple circuit, the valve may operate unpredictably
during brief power interruptions or if the time is
manually switched on and off too fast. A better
circuit incorporating a time-delay relay to provide
more reliable valve operation is shown in Figure 3[b].
7.2.5 Stainless steel orifice (or short capillary) - capable
of maintaining a substantially constant flow over the
sampling period (see Figure 4).
7.2.6 Particulate matter filter - 2 micron stainless steel
sintered in-line type (see Figure 4).
7.2.7 Timer - used for unattended sample collection.
Capable of controlling pump(s) and solenoid valve.
7.3 Sample Canister Cleaning (Figure 5)
7.3.1 Vacuum pump - capable of evacuating sample canister(s)
to an absolute pressure of <5 mm Hg.
7.3.2 Manifold - stainless steel manifold with connections
for simultaneously cleaning several canisters.
7.3.3 Shut off valve(s) - seven required.
7.3.4 Vacuum gauge - capable of measuring vacuum in the
manifold to an absolute pressure of 5 mm Hg or less.
7.3.5 Cryogenic trap (2 required) - U-shaped open tubular
trap cooled with liquid nitrogen or argon used to
prevent contamination from back diffusion of oil from
vacuum pump, and to provide clean, zero air to sample
canister(s).
7.3.6 Pressure gauge - 0-50 psig (0-345 kPa), to monitor
zero air pressure.
7.3.7 Flow control valve - to regulate flow of zero air into
canister(s).
7.3.8 Humidifier - water bubbler or other sys-am capable of
providing moisture to the zero air suppiy.
7.4 Analytical System (Figure 1)
7.4.1 FID detector system - including flow controls for the
FID fuel and air, temperature control for the FID, and
signal processing electronics. The FID burner air,
-------
T012-7
hydrogen, and helium carrier flow rates should be set
according to the manufacturer's instructions to obtain
an adequate FID response while maintaining as stable a
flame as possible throughout all phases of the
analytical cycle.
7.4.2 Chart recorder - compatible with the FID output
signal, to record FID response.
7.4.3 Electronic integrator - capable of integrating the
area of one or more FID response peaks and calculating
peak area corrected for baseline drift. If a separate
integrator and chart recorder are used, care must be
exercised to be sure that these components do not
interfere with each other electrically. Range
selector controls on both the integrator and the FID
analyzer may not provide accurate range ratios, so
individual calibration curves should be prepared for
each range to be used. The integrator should be
capable of marking the beginning and ending of peaks,
constructing the appropriate baseline between the
start and end of the integration period, and
calculating the peak area.
Note: The FID (7.4.1), chart recorder (7.4.2),
integrator (7.4.3), valve heater (7.4.5), and a trap
heating system are conveniently provided by a standard
laboratory chromatograph and associated integrator.
EPA has adapted two such systems for the PDFID method:
a Hewlett-Packard model 5880 (Hewlett-Packard Corp.,
Avondale, PA) and a Shimadzu model GC8APF (Shimadzu
Scientific Instruments Inc., Columbia, MD; see
Reference 5). Other similar systems may also be
applicable.
7.4.4 Trap - the trap should be carefully constructed from a
single piece of chromatographic-grade stainless steel
tubing (0.32 cm O.D, 0.21 cm I.D.) as shown in Figure
6. The central portion of the trap (7-10 cm) is
packed with 60/80 mesh glass beads, with small glass
wool (dimethyldichlorosilane-treated) plugs to retain
the beads. The trap must fit conveniently into the
Dewar flask (7.4.9), and the arms must be of an
appropriate length to allow the beaded portion of the
trap to be submerged below the level of liquid cryogen
in the Dewar. The trap should connect directly to the
six-port valve, if possible, to minimize line length
-------
T012-8
between the trap and the FID. The trap must be
mounted to allow the Dewar to be slipped conveniently
on" and off the trap and also to facilitate heating of
the trap (see 7.4.13).
7.4.5 Six-port chromatographic valve - Seiscor Model VIII
(Seismograph Service Corp., Tulsa, OK), Valco Model
9110 (Valco Instruments Co., Houston, XX), or
equivalent. The six-port valve and as much of the
interconnecting tubing as-practical should be located
inside an oven or otherwise heated to 80 - 90°C to
minimize wall losses or adsorption/desorption in the
connecting tubing. All lines should be as short as
practical.
7.4.6 Multistage pressure regulators - standard two-stage,
stainless steel diaphram regulators with pressure
gauges, for helium, air, and hydrogen cylinders.
7.4.7 Pressure regulators - optional single stage, stainless
steel, with pressure gauge, if needed, to maintain
constant helium carrier and hydrogen flow rates.
7.4.8 Fine needle valve - to adjust sample flow rate through
trap.
7.4.9 Dewar flask - to hold liquid cryogen to cool the trap,
sized to contain submerged portion of trap.
7.4.10 Absolute pressure gauge - 0-450 mm Hg, (2 mm Hg [scale
divisions indicating units]), to monitor repeatable
volumes of sample air through cryogenic trap (Wallace
and Tieman, Model 61C-ID-0410, 25 Main Street,
Belleville, NJ).
7.4.11 Vacuum reservoir - 1-2 L capacity, typically 1 L.
7.4.12 Gas purifiers - gas scrubbers containing Drierite* or
silica gel and 5A molecular sieve to remove moisture
and organic impurities in the helium, air, and
hydrogen gas flows (Alltech Associates, Deerfield,
IL). Note: Check purity of gas purifiers prior to use
by passing zero-air through the unit and analyzing
according to Section 11.4. Gas purifiers are clean
if produce [contain] less than 0.02 ppmC hydrocarbons.
7.4.13 Trap heating system - chromatographic oven, hot water,
or other means to heat the trap to 80° to 90°C. A
simple heating source for the trap is a beaker or
Dewar filled with water maintained at 80-90°C. More
repeatable types of heat sources are recommended,
including a temperature-programmed chromatograph oven,
-------
T012-9
electrical heating of the trap itself, or any type of
heater that brings the temperature of the trap up to
80-90°C in 1-2 minutes.
7.4.14 Toggle shut-off valves (2) - leak free, for vacuum
valve and sample valve.
7.4.15 Vacuum pump •- general purpose laboratory pump capable
of evacuating the vacuum reservoir to an appropriate
vacuum that allows the 'desired sample volume to be
drawn through the trap.
7.4.16 Vent - to keep the trap at atmospheric pressure during
trapping when using pressurized canisters.
7.4.17 Rotameter - to verify vent flow.
7.4.18 Fine needle valve (optional) - to adjust flow rate of
sample from canister during analysis.
7.4.19 Chromatographic-grade stainless steel tubing (Alltech
Applied Science, 2051 Waukegan Road, Deerfield, IL,
60015, (312) 948-8600) and stainless steel plumbing
fittings - for interconnections. All such materials
in contact with the sample, analyte, or support gases
prior to analysis should be stainless steel or other
inert metal. Do not use plastic or Teflon* tubing or
fittings.
7.5 Commercially Available PDFID System (5)
7.5.1 A convenient and cost-effective modular PDFID system
suitable for use with a conventional laboratory
chromatograph is commercially available (NuTech
Corporation, Model 8548, 2806 Cheek Road, Durham, NC,
27704, (919) 682-0402).
7.5.2 This modular system contains almost all of the
apparatus items needed to convert the chromatograph
into a PDFID analytical system and has been designed
to be readily available and easy to assemble.
8 . Reagents and Materials
8.1 Gas cylinders of helium and hydrogen - ultrahigh purity grade.
8.2 Combustion air - cylinder containing less than 0.02 ppm
hydrocarbons, or equivalent air source.
8.3 Propane calibration standard - cylinder containing 1-100 ppm (3-
300 ppmC) propane in air. The cylinder assay should be traceable
to a National Bureau of Standards (NBS) Standard Reference
Material (SRM) or to a NBS/EPA-approved Certified Reference
Material (CRM) .
8.4 Zero air - cylinder containing less than 0.02 ppmC hydrocarbons.
Zero air may be obtained from a cylinder of zero-grade compressed
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air scrubbed with Drierite* or silica gel and 5A molecular sieve
or activated charcoal, or by catalytic cleanup of ambient air.
All zero air should be passed through a liquid argon cold trap for
final cleanup, then passed through a hydrocarbon-free water
bubbler (or other device) for humidification.
8.5 Liquid cryogen - liquid argon (bp -185.7°C) or liquid oxygen, (bp
-183°C) may be used as the cryogen. Experiments have shown no
differences in trapping efficiency between liquid argon and liquid
oxygen. However, appropriate safety precautions must be taken if
liquid oxygen is used. Liquid nitrogen (bp -195°C) should not be
used because it causes condensation of oxygen and methane in the
trap.
9. Direct Sampling
9.1 For direct ambient air sampling, the cryogenic trapping system
draws the air sample directly from a pump-ventilated distribution
manifold or sample line (see Figure 1). The connecting line
should be of small diameter (1/8" O.D.) stainless steel tubing and
as short as possible to minimize its dead volume.
9.2 Multiple analyses over the sampling period must be made to
establish hourly or 3-hour NMOC concentration averages.
10. Sample Collection in Pressurized Canister(s)
For integrated pressurized canister sampling, ambient air is sampled by
a metal bellows pump through a critical orifice (to maintain constant
flow), and pressurized into a clean, evacuated, Summa"-polished sample
canister. The critical orifice size is chosen so that the canister is
pressurized to approximately one atmosphere above ambient pressure, at a
constant flow rate over the desired sample period. Two canisters are
connected in parallel for duplicate samples. The canister(s) are then
returned to the laboratory for analysis, using the PDFID analytical
system. Collection of ambient air samples in pressurized canisters
provides the following advantages:
• Convenient integration of ambient samples over a specific
time period
• Capability of remote sampling with subsequent central
laboratory analysis
• Ability to ship and store samples, if necessary
• Unattended sample collection
• Analysis of samples from multiple sites with one analytical
system
• Collection of replicate samples for assessment of
measurement precision
With canister sampling, however, great care must be exercised in
selecting, cleaning, and handling the sample canister(s) and sampling
apparatus to avoid losses or contamination of the samples.
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10.1 Canister Cleanup and Preparation
10.1.1 All canisters must be clean and free of any
contaminants before sample collection.
10.1.2 Leak test all canisters by pressurizing them to
approximately 30 psig [200 kPa (gauge)] with zero air.
The use of the canister cleaning system (see Figure 5)
may be adequate for this task. Measure the final
pressure - close the canister valve, then check the
pressure after 24 hours. If leak tight, the pressure
should not vary more than + 2 psig over the 24-hour
period. Note leak check result on sampling data
sheet, Figure 7.
10.1.3 Assemble a canister cleaning system, as illustrated in
Figure 5. Add cryogen to both the vacuum pump and
zero air supply traps. Connect the canister(s) to the
manifold. Open the vent shut off valve and the
canister valve(s) to release any remaining pressure in
the canister. Now close the vent shut off valve and
open the vacuum shut off valve. Start the vacuum pump
and evacuate the canister(s) to s 5.0 mm Hg (for at
least one hour). [Note: On a daily basis or more
often if necessary, blow-out the cryogenic traps with
zero air to remove any trapped water from previous
canister cleaning cycles.]
10.1.4 Close the vacuum and vacuum gauge shut off valves and
open the zero air shut off valve to pressurize the
canister(s) with moist zero air to approximately 30
psig [200 kPa (gauge)]. If a zero gas generator
systems is used, the flow rate may need to be limited
to maintain the zero air quality.
10.1.5 Close the zero shut off valve and allow canister(s) to
vent down to atmospheric pressure through the vent
shut off valve. Close the vent shut off valve.
Repeat steps 10.1.3 through 10.1.5 two additional
times for a total of three (3) evacuation/
pressurization cycles for each set of canisters.
10.1.6 As a "blank" check of the canister(s) and cleanup
procedure, analyze the final zero-air fill of 100% of
the canisters until the cleanup system and canisters
are proven reliable. The check can then be reduced to
a lower percentage of canisters. Any canister that
does not test clean (compared to direct analysis of
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1012-12
humidified zero air of less than 0.02 ppmC) should not
be utilized.
10.1.7 The canister is then re-evacuated to < 5.0 mm Hg,
using the canister cleaning system, and remains in
this condition until use. Close the canister valve,
remove the canister from the canister cleaning system
and cap canister connection with a stainless steel
fitting. The canister is now ready for collection of
an air sample. Attach an identification tag to the
neck of each canister for field notes and chain-of-
custody purposes.
10.2 Collection of Integrated Whole-Air Samples
10.2.1 Assemble the sampling apparatus as shown in Figure 2.
The connecting lines between the sample pump and the
canister(s) should be as short as possible to minimize
their volume. A second canister is used when a
duplicate sample is desired for quality assurance (QA)
purposes (see Section 12.2.4). The small auxiliary
vacuum pump purges the inlet manifold or lines with a
flow of several L/min to minimize the sample residence
time. The larger metal bellows pump takes a small
portion of this sample to fill and pressurize the
sample canister(s) . Both pumps should be shock-
mounted to minimize vibration. Prior to field use,
each sampling system should be leak tested. The
outlet side of the metal bellows pump can be checked
for leaks, by attaching the 0-30 psig pressure gauge to
the canister(s) inlet via connecting tubing and
pressurizing to 2 atmospheres or approximately 29.4
psig. If pump and connecting lines are leak free
pressure should remain at ±2 psig for 15 minutes. To
check the inlet side, plug the sample inlet and insure
that there is no flow at the outlet of the pump.
10.2.2 Calculate the flow rate needed so that the canister (s)
are pressurized to approximately one atmosphere above
ambient pressure (2 atmospheres absolute pressure)
over the desired sample period, utilizing the
following equation:
(T)(60)
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where:
F - flow rate .(cni3/min)
P - final canister pressure (atmospheres absolute)
- (Pg/Pa) + 1
V - volume of the canister (cm3)
N - number of canisters connected together for
simultaneous sample collection
T - sample period (hours)
Pg - gauge pressure in banister, psig (kPa)
Pa - standard atmospheric pressure, 14.7 psig
(101 kPa)
For example, if one 6-L canister is to be filled to 2
atmospheres absolute pressure (14.7 psig) in 3 hours, the
flow rate would be calculated as follows:
2 x 6000 x 1 ,_ 3 . .
F * * 67 cnr/min
3 x 60
10.2.3 Select a critical orifice or hypodermic needle
suitable to maintain a substantially constant flow at
the calculated flow rate into the canister(s) over the
desired sample period. A 30-gauge hypodermic needle,
2.5 cm long, provides a flow of approximately 65
cm3/min with the Metal Bellows Model MBV-151 pump (see
Figure 4). Such a needle will maintain approximately
constant flow up to a. canister pressure of about 10
psig (71 kPa), after which the flow drops with
increasing pressure. At 14.7 psig (2 atmospheres
absolute pressure), the flow is about 10% below the
original flow.
10.2.4 Assemble the 2.0 micron stainless steel in-line
particulate filter and position it in front of the
critical orifice. A suggested filter-hypodermic
needle assembly can be fabricated as illustrated in
Figure 4.
10.2.5 Check the sampling system for contamination by filling
two evacuated, cleaned canister(s) (See Section 10.1)
with humidified zero air through the sampling system.
Analyze the canisters according to Section 11.4. The
sampling system is free of contamination if the
canisters contain less than 0.02 ppmC hydrocarbons,
similar to that of humidified zero air.
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10.2.6 During the system contamination check procedure, check
the critical orifice flow rate on the sampling system
to insure that sample flow rate remains relatively
constant (±10%) up to about 2 atmospheres absolute
pressure (101 kpa). Note: A drop in the flow rate
may occur near the end of the sampling period as the
canister pressure approaches two atmospheres.
10.2.7 Reassemble the sampling system. If the inlet sample
line is longer than 3 meters, install an auxiliary
pump to ventilate the sample line, as illustrated in
Figure 2.
10.2.8 Verify that the timer, pump(s) and solenoid valve are
connected and operating properly.
10.2.9 Verify that the,timer is correctly set for the desired
sample period, and that the solenoid valve is closed.
10.2.10 Connect a cleaned, evacuated canister(s) (Section
10.1) to the non-contaminated sampling system, by way
of the solenoid valve, for sample collection.
10.2.11 Make sure the solenoid valve is closed. Open the
canister valve(s). Temporarily connect a small
rotameter to the sample inlet to verify that there is
no flow. Note: Flow detection would indicate a
leaking (or open) solenoid valve. Remove the
rotameter after leak detection procedure.
10.2.12 Fill out the necessary information on the Field Data
Sheet (Figure 7).
10.2.13 Set the automatic timer to start and stop the pump or
pumps to open and close the solenoid valve at the
appropriate time for the intended sample period.
Sampling will begin at the pre-determined time.
10.2.14 After the sample period, close the canister valve(s)
and disconnect the canister(s) from the sampling
system. Connect a pressure gauge to the canister(s)
and briefly open and close the canister valve. Note
the canister pressure on the Field Data Sheet (see
Figure 7). The canister pressure should be
approximately 2 atmospheres absolute [1 atmosphere or
101 kPa (gauge)]. Note: If the canister pressure is
not approximately 2 atmospheres absolute (14.7 psig),
determine and correct the cause before next sample.
Re-cap canister valve.
10.2.15 Fill out the identification tag on the sample
canister(s) and complete the Field Data Sheet as
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necessary. Note any activities or special conditions
in the area (rain, smoke, etc.) that may affect the
sample contents on the sampling data sheet.
10.2.16 Return the canister(s) to the analytical system for
analysis.
11. Sample Analysis
11.1 Analytical System Leak Check
11.1.1 Before sample analysis, the analytical system is
assembled (see Figure 1) and leak checked.
11.1.2 To leak check the analytical system, place the six-
port gas valve in the trapping position. Disconnect
and cap the absolute pressure gauge. Insert a
pressure gauge capable of recording up to 60 psig at
the vacuum valve outlet.
11.1.3 Attach a valve and a zero air supply to the sample
inlet port. Pressurize the system to about 50 psig
(350 kPa) and close the valve.
11.1.4 Wait approximately 3 hrs. and re-check pressure. If
the pressure did not vary more than + 2 psig, the
system is considered leak tight.
11.1.5 If the system is leak free, de-pressurize and
reconnect absolute pressure gauge.
11.1.6 The analytical system leak check procedure needs to be
performed during the system checkout, during a series
of analysis or if leaks are suspected. This should be
part of the user-prepared SOP manual (see Section
12.1).
11.2 Sample Volume Determination
11.2.1 The vacuum reservoir and absolute pressure gauge are
used to meter a precisely repeatable volume of sample
air through the cryogenically-cooled trap, as follows:
With the sample valve closed and the vacuum valve
open, the reservoir is first evacuated with the vacuum
pump to a predetermined pressure (e.g., 100 mm Hg).
Then the vacuum valve is closed and the sample valve
is opened to allow sample air to be drawn through the
cryogenic trap and into the evacuated reservoir until
a second predetermined reservoir pressure is reached
(e.g., 300 mm Hg). The (fixed) volume of air thus
sampled is determined by the pressure rise in the
vacuum reservoir (difference between the predetermined
pressures) as.measured by the absolute pressure gauge
(see Section 12.2.1).
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T012-16
11.2.2 The sample volume can be calculated by:
„
where:
Vs - volume of air sampled (standard cm3)
AP - pressure difference measured by gauge (mm Hg)
Vr - volume of vacuum reservoir (cm3)
usually 1 L
Ps - standard pressure (760 mm Hg)
For example, with a vacuum reservoir of 1000 cm3 and a
pressure change of 200 mm Hg (100 to 300 mm Hg), the volume
sampled would be 263 cm . [Note: Typical sample volume
using this procedure is between 200-300 cm3.]
11.2.3 The sample volume determination need only be performed
once during the system check-out and shall be part of
the user-prepared SOP Manual (see Section 12.1).
11.3 Analytical System Dynamic Calibration
11.3.1 Before sample analysis, a complete dynamic calibration
of the analytical system should be carried out at five
or more concentrations on each range to define the
calibration curve. This should be carried out
initially and periodically thereafter [may be done
only once during a series of analyses]. This should
be part of the user-prepared SOP Manual (See Section
12.1). The calibration should be verified with two or
three-point calibration checks (including zero) each
day the analytical system is used to analyze samples.
11.3.2 Concentration standards of propane are used to
calibrate the analytical system. Propane calibration
standards may be obtained directly from low
concentration cylinder standards or by dilution of
high concentration cylinder standards with zero air
(see Section 8.3). Dilution flow rates must be
measured accurately, and the combined gas stream must
be mixed thoroughly for successful calibration of the
analyzer. Calibration standards should be sampled
directly from a vented manifold or tee. Note:
Remember that a propane NMOC concentration in ppmC is
three times the volumetric concentration in ppm.
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T012-17
11.3.3 Select one or more combinations of the following
parameters to provide the desired range or ranges
(e.g., 0-1.0 ppmC or 0-5.0 ppmC): FID attenuator
setting, output voltage setting, integrator resolution
(if applicable), and sample volume. Each individual
range should be calibrated separately and should have
a separate calibration curve. Note: Modern GC
integrators may provide automatic ranging such that
several decades of concentration may be covered in a
single range. The user-prepared SOP manual should
address variations applicable to a specific system
design (see Section 12.1).
11.3.4 Analyze each calibration standard three times
according to the procedure in Section 11.4. Insure
that flow rates, pressure gauge start and stop
readings, initial cryogen liquid level in the Dewar,
timing, heating, integrator settings, and other
variables are the same as those that will be used
during analysis of ambient samples. Typical flow
rates for the gases are: hydrogen, 30 cm3/minute;
helium carrier, 30 cm3/ninute; burner air,
400 cm3/niinute.
11.3.5 Average the three analyses for each concentration
standard and plot the calibration curve(s) as average
integrated peak area reading versus concentration in
ppmC. The relative standard deviation for the three
analyses should be less than 3% (except for zero
concentration). Linearity should be expected; points
that appear to deviate abnormally should be repeated.
Response has been shown to be linear over a wide range
(0-10,000 ppbC). If nonlinearity is observed, an
effort should be made to identify and correct the
problem. If the problem cannot be corrected,
additional points in the nonlinear region may be
needed to define the calibration curve adequately.
11.4 Analysis Procedure
11.4.1 Insure the analytical system has been assembled
properly, leaked checked, and properly calibrated
through a dynamic standard calibration. Light the FID
detector and allow to stabilize.
11.4.2 Check and adjust the helium carrier pressure to
provide the correct carrier flow rate for the system.
Helium is used to purge residual air and methane from
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T012-18
the trap at the end of the sampling phase and to carry
the re-volatilized NMOC from the trap into the FID. A
single-stage auxiliary regulator between the cylinder
and the analyzer may not be necessary, but is
recommended to regulate the helium pressure better
than the multistage cylinder regulator. When an
auxiliary regulator is used, the secondary stage of
the two-stage regulator must be set at a pressure
higher than the pressure setting of the single-stage
regulator. Also check the FID hydrogen and burner air
flow rates (see 11.3.4).
11.4.3 Close the sample valve and open the vacuum valve to
evacuate the vacuum reservoir to a specific
predetermined valve (e.g., 100 mm Hg).
11.4.4 With the trap at room temperature, place the six-port
valve in the inject position.
11.4.5 Open the sample valve and adjust the sample flow rate
needle valve for an appropriate trap flow of 50-100
cm3/nin. Note: The flow will be lower later, when
the trap is cold.
11.4.6 Check the sample canister pressure before attaching it
to the analytical system and record on Field Data
Sheet (see Figure 7). Connect the sample canister or
direct sample inlet to the six-port valve, as shown in
Figure 1. For a canister, either the canister valve
or an optional fine needle valve installed between the
canister and the vent is used to adjust the canister
flow rate to a value slightly higher than the trap
flow rate set by the sample flow rate needle valve.
The excess flow exhausts through the vent, which
assures that the sample air flowing through the trap
is at atmospheric pressure. The vent is connected to
a flow indicator such as a rotameter as an indication
of vent flow to assist in adjusting the flow control
valve. Open the canister valve and adjust the
canister valve or the sample flow needle valve to
obtain a moderate vent flow as indicated by the
rotameter. The sample flow rate will be lower (and
hence the vent flow rate will be higher) when the trap
is cold.
11.4.7 Close the sample valve and open the vacuum valve (if
not already open) to evacuate the vacuum reservoir.
With the six-port valve in the inject position and the
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T012-19
vacuum valve open, open the sample valve for 2-3
minutes [with both valves open, the pressure reading
won't change] to flush and condition the inlet lines.
11.4.8 Close the- sample valve and evacuate the reservoir to
the predetermined sample starting pressure (typically
100 mm Hg) as indicated by the absolute pressure
gauge.
11.4.9 Switch the six-port valve to the sample position.
11.4.10 Submerge the trap in the cryogen. Allow a few minutes
for the trap to cool completely (indicated when the
cryogen stops boiling). Add cryogen to the initial
level used during system dynamic calibration. The
level of the cryogenic liquid should remain constant
with respect to the trap and should completely cover
the beaded portion of the trap.
11.4.11 Open the sample valve and observe the increasing
pressure on the pressure gauge. When it reaches the
specific predetermined pressure (typically 300 mm Hg)
representative of the desired sample volume (Section
11.2), close the sample valve.
11.4.12 Add a little cryogen or elevate the Dewar to raise the
liquid level to a point slightly higher (3-15 mm) than
the initial level at the beginning of the trapping.
Note: This insures that organics do not bleed from
the trap and are counted as part of the NMOC peak(s).
11.4.13 Switch the 6-port valve to the inject position,
keeping the cryogenic liquid on the trap until the
methane and upset peaks have diminished (10-20
seconds). Now close the canister valve to conserve
the remaining sample in the canister.
11.4.14 Start the integrator and remove the Dewar flask
containing the cryogenic liquid from the trap.
11.4.15 Close the GC oven door and allow the GC oven (or
alternate trap heating system) to heat the trap at a
predetermined rate (typically, 30°C/min) to 90°.
Heating the trap volatilizes the concentrated NMOC
such that the FID produces integrated peaks. A
uniform trap temperature rise rate (above 0°C) helps
to reduce variability and facilitates more accurate
correction for the moisture-shifted baseline. With a
chromatograph oven to heat the trap, the following
parameters have been found to be acceptable: initial
temperature, 30°C; initial time, 0,20 minutes
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T012-20
(following start of the integrator); heat rate,
30°/«ninute; final temperature, 90°C.
11.4.16 Use the same heating process and temperatures for both
calibration and sample analysis. Heating the trap too
quickly may cause an initial negative response that
could hamper accurate integration. Some initial
experimentation may be necessary to determine the
optimal heating procedure for each system. Once
established, the procedure should be consistent for
each analysis as outlined in the user-prepared SOP
Manual.
11.4.17 Continue the integration (generally, in the range of
1-2 minutes is adequate) only long enough to include
all of the organic compound peaks and to establish the
end point FID baseline, as illustrated in Figure 8.
The integrator should be capable of marking the
beginning and ending of peaks, constructing the
appropriate operational baseline between the start and
end of the integration period, and calculating the
resulting corrected peak area. This ability is
necessary because the moisture in the sample, which is
also concentrated in the trap, will cause a slight
positive baseline shift. This baseline shift starts
as the trap warms and continues until all of the
moisture is swept from the trap, at which time the
baseline returns to its normal level. The shift
always continues longer than the ambient organic
peak(s). The integrator should be programmed to
correct for this shifted baseline by ending the
integration at a point after the last NMOC peak and
prior to the return of the shifted baseline to normal
(see Figure 8) so that the calculated operational
baseline effectively compensates for the water-shifted
baseline. Electronic integrators either do this
automatically or they should be programmed to make
this correction. Alternatively, analyses of
humidified zero air prior to sample analyses should be
performed to determine the water envelope and the
proper blank value for correcting the ambient air
concentration measurements accordingly. Heating and
flushing of the trap should continue after the
integration period has ended to insure all water has
been removed to prevent buildup of water in the trap.
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T012-21
Therefore, be sure that the 6-port valve remains in
the inject position until all moisture has purged from
the trap (3 minutes or longer).
11.4.18 Use the dynamic calibration curve (see Section 11.3)
to convert the integrated peak area reading into
concentration units (ppmC). Note that the NMOC peak
shape may not be precisely reproducible due to
variations in heating the trap, but the total NMOC
peak area should be reproducible.
11.4.19 Analyze each canister sample at least twice and report
the average NMOC concentration. Problems during an
analysis occasionally will cause erratic or
inconsistent results. If the first two analyses do
not agree within ± 5% relative standard deviation
(RSD), additional analyses should be made to identify
inaccurate measurements and produce a more accurate
average (see also Section 12.2).
12. Performance Criteria and Quality Assurance
This section summarizes required quality assurance measures and provides
guidance concerning performance criteria that should be achieved within
each laboratory.
12.1 Standard Operating Procedures (SOPs)
12.1.1 Users should generate SOPs describing and documenting
the following activities in their laboratory: (1)
assembly, calibration, leak check, and operation of
the specific sampling system and equipment used; (2)
preparation, storage, shipment, and handling of
samples; (3) assembly, leak check, calibration, and
operation of the analytical system, addressing the
specific equipment used; (4) canister storage and
cleaning; and (5) all aspects of data recording and
processing, including lists of computer hardware and
software used.
12.1.2 SOPs should provide specific stepwise instructions and
should be readily available to, and understood by, the
laboratory personnel conducting the work.
12.2 Method Sensitivity, Accuracy, Precision and Linearity
12.2.1 The sensitivity and precision of the method is
proportional to the sample volume. However, ice
formation in the trap may reduce or stop the sample
flow during trapping if Che sample volume exceeds 500
cm3. Sample volumes below about 100-150 cm may cause
increased measurement variability due to dead volume
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T012-22
in lines and valves. For most typical ambient NMOC
concentrations, sample volumes in the range of 200-400
cm appear to be appropriate. If a response peak
obtained with a 400 cm3 sample is off scale or exceeds
the calibration range, a second analysis can be
carried out with a smaller volume. The actual sample
volume used need not be accurately known if it is
precisely repeatable during both calibration and
analysis. Similarly, the actual volume of the vacuum
reservoir need not be accurately known. But the
reservoir volume should be matched to the pressure
range and resolution of the absolute pressure gauge so
that the measurement of the pressure change in the
reservoir, hence the sample volume, is repeatable
within 1%. A 1000 cm3 vacuum reservoir and a pressure
change of 200 mm Hg, measured with the specified
pressure gauge, have provided a sampling precision of
i 1.31 cm3. A smaller volume reservoir may be used
with a greater pressure change to accommodate absolute
pressure gauges with lower resolution, and vice versa.
12.2.2 Some FID detector systems associated with laboratory
chromatographs may have autoranging. Others may
provide attenuator control and internal full-scale
output voltage selectors. An appropriate combination
should be chosen so that an adequate output level for
accurate integration is obtained down co the detection
limit; however, the electrometer or integrator must
not be driven into saturation at the upper end of the
calibration. 'Saturation of the electrometer may be
indicated by flattening of the calibration curve at
high concentrations. Additional adjustments of range
and sensitivity can be provided by adjusting the
sample volume use, as discussed in Section 12.2.1.
12.2.3 System linearity has been documented (6) from 0 to
10,000 ppbC.
12.2.4 Some organic compounds contained in ambient air are
"sticky" and may require repeated analyses before they
fully appear in the FID output. Also, some adjustment
may have to be made in the integrator off time setting
to accommodate compounds that reach the FID late in
the analysis cycle. Similarly, "sticky" compounds
from ambient samples or from contaminated propane
standards may temporarily contaminate the analytical
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system and can affect subsequent analyses. Such
temporary contamination can usually be removed by
repeated analyses of humidified zero air.
12.2.5 Simultaneous collection of duplicate samples decreases
the possibility of lost measurement data from samples
lost due to leakage or contamination in either of the
canisters. Two (or more) canisters can be filled
simultaneously by connecting them in parallel (see
Figure 2(a)) and selecting an appropriate flow rate to
accommodate the number of canisters (Section 10.2.2).
Duplicate (or replicate) samples also allow assessment
of measurement precision based on the differences
between duplicate samples (or the standard deviations
among replicate samples).
13. Method Modification
13.1 Sample Metering System
13.1.1 Although the vacuum reservoir and absolute pressure
gauge technique for metering the sample volume during
analysis is efficient and convenient, other techniques
should work also.
13.1.2 A constant sample flow could be established with a
vacuum pump and a critical orifice, with the six-port
valve being switched to the sample position for a
measured time period. A gas volume meter, such as a
wet test meter, could also be used to measure the
total volume of sample air drawn through the trap.
These alternative techniques should be tested and
evaluated as part of a user-prepared SOP manual.
13.2 FID Detector System
13.2.1 A variety of FID detector systems should be adaptable
to the method.
13.2.2 The specific flow rates and necessary modifications
for the helium carrier for any alternative FID
instrument should be evaluated prior to use as apart
of the user-prepared SOP manual.
13.3 Range
13.3.1 It may be possible to increase the sensitivity of the
method by increasing the sample volume. However,
limitations may arise such as plugging of the trap by
ice.
13.3.2 Any attempt to increase sensitivity should be
evaluated as part of the user-prepared SOP manual.
13.4 Sub-Atmospheric Pressure Canister Sampling
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13.4.1 Collection and analysis of canister air samples at
sub-atmospheric pressure is also possible with minor
modifications to the sampling and analytical
procedures.
13.4.2 Method TO-14, "Integrated Canister Sampling for
Selective Organics: Pressurized and Sub-atmospheric
Collection Mechanism," addresses sub-atmospheric
pressure canister sampling. Additional information
can be found in the literature (11-17).
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1. Uses. Limitations, and Technical Basis of Procedures for Quantifying
Relationships Between Photochemical Oxidants and Precursors. EPA-450/2-
77-21a, U.S. Environmental Protection Agency, Research Triangle Park,
NC, November 1977.
2. Guidance for Collection of Ambient Non-Methane Organic Compound (NMOC)
Data for Use in 1982 Ozone SIP Development. EPA-450/4-80-011, U.S.
Environmental Protection Agency, Research Triangle Park, NC, June 1980.
3. H.B. Singh, Guidance for the Collection and Use of Ambient Hydrocarbons
Species Data in Development of Ozone Control Strategies. EPA-450/4-80-
008, U.S. Environmental Protection Agency, Research Triangle Park, NC,
April 1980.
4. R.M. Riggin, Technical Assistance Document for Sampling and Analysis of
Toxic Organic Compounds in Ambient Air. EPA-600/4-83-027. US.
Environmental Protection Agency, Research Triangle Park, NC, 1983.
5. M.J. Jackson, et al.. Technical Assistance Document for Assembly and
Operation of the Suggested Preconcentration Direct Flame lonization
Detection (PDFID) Analytical System, publication scheduled for late
1987; currently available in draft form from the Quality Assurance
Division, MD-77, U.S. Environmental Protection Agency, Research Triangle
Park, NC 27711.
6. R.K.M. Jayanty, et al.. Laboratory Evaluation of Non-Methane Organic
Carbon Determination in Ambient Air by Cryogenic Preconcentration and
Flame lonization Detection. EPA-600/54-82-019. U.S. Environmental
Protection Agency, Research Triangle Park, NC, July 1982.
7. R.D. Cox, et al.. "Determination of Low Levels of Total Non-Methane
Hydrocarbon Content in Ambient Air," Environ. Sci. Technol.. 16 (1):57.
1982.
8. F.F. McElroy, et al.. A Cryogenic Preconcentration - Direct FID (PDFID)
Method for Measurement of NMOC in the Ambient Air. EPA-600/4-85-063,
U.S. Environmental Protection Agency, Research Triangle Park, NC, August
1985.
9. F.W. Sexton, et al.. A Comparative Evaluation of Seven Automated Ambient
Non-Methane Organic Compound Analyzers. EPA-600/54-82-046, U.S.
Environmental Protection Agency, Research Triangle Park, NC, August
1982.
10. E.G. Richter, Analysis of Organic Compound Data Gathered During 1980 in
Northeast Corridor Cities. EPA-450/4-83-017. U.S. Environmental
Protection Agency, Research Triangle Park, NC, April 1983.
11. Cox, R.D. "Sample Collection and Analytical Techniques for Volatile
Organics in Air," presented at APCA Specialty Conference, Chicago, IL,
March 22-24, 1983.
12. Rasmussen, R.A. and Khalil, M.A.K. "Atmospheric Halocarbons:
Measurements and Analyses of Selected Trace Gases," Proc. NATO ASI on
Atmospheric Ozone, 1980, 209-231.
13. Oliver, K.D., Pleil, J.D. and McClenny, tf.A. "Sample Integrity of Trace
Level Volatile Organic Compounds in Ambient Air Stored in "SUMMA "
Polished Canisters," accepted for publication in Atmospheric Environment
as of January 1986. Draft available from tf.A. McClenny, MD-44, EMSL,
EPA, Research Triangle Park, NC 27711.
-------
T012-26
14. McClenny, W.A. Pleil, J.D., Holdren, J.W. and Smith, R.N.; 1984.
"Automated Cryogenic Preconcentration and Gas Chromatographic
Determination of Volatile Organic Compounds," Anal. Chem. 56:2947.
15. Pleil, J.D. and Oliver, K.D.., 1985, "Evaluation of Various
Configurations of Nafion Dryers: Water Removal from Air Samples Prior
to Gas Chromatographic Analysis." EPA Contract No. 68-02-4035.
16. Oliver, K.D.; Pleil, J.D. and McClenny, W.A.; 1986. "Sample Integrity
of Trace Level Volatile Organic Compounds in Ambient Air Stored in
"SUMMA*" Polished Canisters," Atmospheric Environ. 20:1403.
17. Oliver, K.D. and Pleil, J.D.. 1985, "Automated Cryogenic Sampling and
Gas Chromatographic Analysis of Ambient Vapor-Phase Organic Compounds:
Procedures and Comparison Tests," EPA Contract No. 68-02-4035, Research
Triangle Park, NC, Northrop Services, Inc. - Environmental Sciences.
-------
T012-27
•COUUIO*
FIGURE 1. SCHEMATIC OF ANALYTICAL SYSTEM FOR
NMOC-TWO SAMPLING MODES
-------
T012-28
SAMPLE
IN
PRESSURE
GAUGE
CRITICAL
ORIFICE
AUXILIARY
VACUUM
PUMP
METAL
BELLOWS
PUMP
CANISTER(S)
FIGURE 2. SAMPLE SYSTEM FOR AUTOMATIC COLLECTION
OF 3-HOUR INTEGRATED AIR SAMPLES
-------
T012-29
».
'«*
SMTCM
"
113 V AC
1
ao v oc
•MTC
MtOCUTCH
SOUNO«
VIM.VC
3(o]. SIMPLE CIRCUIT TOR OPCRATINC MACNEUTCH VALVE
TMOt
SMTCM
IIS V 1C
COL
'l»m.
Oi
«D
Ct
mnt
IMCtCLATCH
SOOXW
WM.VC
FTCURt: 3(bl. IMPROVED CIRCUIT DESIGNED TO HANDLE POWER INTERRUPTIONS
FIGURE 3. ELECTRICAL PULSE CIRCUITS FOR DRIVING
SKINNER MAGNELATCH SOLENOID VALVE
WITH A MECHANICAL TIMER
-------
T012-30
T SOWS COMPACT. MUMC
W/2 urn SS SINTERED ELEMENT
FEMALE CONMECTOR. 0.29 in 0.0. TUK TO
0.29 In FEMALE NTT
htJt Nmt 0.29 In MALE MPT BOTH CMOS
JO CMJCC i 1.0 In LONG HVPOOCKMC
PEMAU CONNCCTO*. 0.29 to 0.0. TUOC TO
a29 * FEMALE HPT
©THCMVOGMCEN IB » mm (0.29 hi)
SEPTUM (LO« aueo)
1
0.29 hi KMT CONNEaOR V/TVO 0.29 tn NUTS
FIGURE 4. FILTER AND HYPODERMIC NEEDLE
ASSEMBLY FOR SAMPLE INLET FLOW
CONTROL
-------
T012-31
ZERO AIR
SUPPLY
J-PORT
GAS
VENT VALVE WLVE
SHUT orr VKJ.VC VEMT VALVE
VENT
SAMPLE CAMSTERS
FIGURE 5. CANISTER CLEANING SYSTEM
-------
T012-32
TUBE LENGTH: -30 cm
O.O.: 0.32 cm
I.D.: 0.21 cm
CRYOGENIC UOUIO LEVEL
60/80 MESH GLASS BEADS
GLASS WOOL
(TO
••4 cm
••13 cm
FIGURE 6. CRYOGENIC SAMPLE TRAP DIMENSIONS
-------
TO12-33
PRESSURIZED CANISTER SAMPLING DATA SHEET
GENERAL INFORMATION:
PROJECT:
SITE:
LOCATION:
MONITOR STATION NUMBER:
PUMP SERIAL NUMBER:
OPERATOR:
ORIFICE IDENTIFICATION:
FLOW RATE: "
CALIBRATED BY:
LEAK CHECK
Pass
Fall
FIELD DATA:
Date
Canister
Serial
Number
Sample
Number
Sample Time
Start
Stop
Average Atmospheric Conditions
Temperature
Pressure
Relative Humidity
Canister pressure
Final , Laboratory
Comments
Date
Title
Signature
FIGURE 7. EXAMPLE 8AMPLINQ DATA SHEET
-------
T012-34
END
INTEGRATION
CONTINUED HEATINC
OF TRAP
START
INTEGRATION
\
A
\
\
X
\~.
— 5
I
t
WATER-SHFTED
BASQJNE
i
1
t
X
I
OPERATIONAL BAS£UN£ NORMAL tusfimf
CONSTRUCTED 8Y HTECRATOR NORMAL BASELINE
TO DETERMINE CORRECTED AREA
i i
TME (MINUTES)
FIGURE 8. CONSTRUCTION OF OPERATIONAL BASELINE
AND CORRESPONDING CORRECTION OF
PEAK AREA
-------
APPENDIX C
1993 NMOC MONITORING PROGRAM SITE DATA
-------
5.00
4.00
9 3.00
Q.
Q.
O
o
2.00
1.00
0.00
Long Island, New York (LINY)
1993 NMOC Program (AIRS #36-059-0005)
140
160
180
200 220
Julian Date, 1993
240
260
280
-------
1993 NMOC Data for Long Island, NY (LINY)
Site
Code
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
UNY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
Collection
Date
06/07/93
06/08/93
06/09/93
06/10/93
06/11/93
06/14/93
06/14/93
06/15/93
06/16/93
06/17/93
06/18/93
06/21/93
06/22/93
06/23/93
06/24/93
06/24/93
06/25/93
06/28/93
06/29/93
06/30/93
07/01/93
07/06/93
07/06/93
07/07/93
07/08/93
07/09/93
07/12/93
07/13/93
07/14/93
07/14/93
07/15/93
07/19/93
07/20/93
07/21/93
07/22/93
Julian
Date
158
159
160
161 .
162
165
165
166
167
168
169
172
173
174
175
175
176
179
180
181
182
187
187
188
189
190
193
194
195
195
196
200
201
202
203
Can
#
781
886
140
406
814
172
828
720
670
7
20
178
170
149
766
57
99
767
852
154
870
170
690
805
678
57
641
766
102
84
172
140
175
623
889
Radian
ID#
1012
1007
1019
1037
1047
1067
1068
- 1063
1097
1101
1102
1110
1137
1136
1172
1173
1180
117Q
1197
1206
1262
1247
1248
1253
1298
1296
1291
1311
1308
1309
1346
1374
1370
• 1410
1411
Duplicate
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
Y
Y
N
N
N
N
N
Y
Y
N
N
N
N
N
Radian
Analysis
Channel
C
D
C
D
C
C
D
D
C
C
C
A
B
A
A
A
A
A
C
D
D
C
C
C
C
C
D
C
D
D
C
C
C
C
D
NMOC
ppmC
0.550
0.309
0.214
0.129
0.224
0.195
0.218
0.162
0.236
0.123
0.262
0.226
0.222
0.106
0.229
0.253
0.374
0.406
0.208
0.228
0.170
0.168
0.241
0.298
0.694
0.464
0.437
0.201
0.258
0.352
0.463
0.194
0.149
0.161
0.198
-------
1993 NMOC Data for Long Island, NY (LINY)
Site
Code
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LIMY
LINY
LINY
Collection
Date
07/23/93
07/26/93
07/27/93
07/28/93
07/29/93
07/30/93
08/02/93
08/03/93
08/04/93
08/05/93
08/06/93
08/09/93
08/10/93
08/10/93
08/11/93
08/12/93
08/13/93
08/16/93
08/17/93
08/18/93
08/19/93
08/20/93
08/23/93
08/23/93
08/24/93
08/25/93
08/26/93
08/27/93
08/30/93
08/31/93
09/01/93
09/02/93
09/03/93
09/07/93
09/08/93
Julian
Date
204
207
208
209
210
211
214
215
216
217
218
221
222
222
223
224
225
228
229
230
231
232
235
235
236
237
238
239
242
243
244
245
246
250
251
Can
#
629
77
7
685
670
726
126
179
928
766
723
713
849
198
52
848
171
22
119
816
629
189
118
302
705
694
911
825
170
198
846
789
771
118
406
Radian
ID#
1414
1448
1451
1442
1470
1474
1500
1501
1529
1530
1566
1567
1559
1560
1593
1592
1624
1623
1627
1668
1667
1659
1716
1717
1700
1701
1742
1741
1774
1775
1808
1815
1806
1837
1828
Duplicate
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
Y
Radian
Analysis
Channel
C
C
A
B
A
B
C
D
C
C
C
D
C
C
C
D
C
C
C
D
D
C
C
C
C
D
C
C
C
C
C
C
D
C
C
NMOC
ppmC
0.176
0.104
0.133
0.308
0.198
0.453
0.268
0.569
0.624
0.198
0.225
0.879
0.432
0.494
0.336
0.231
0.193
0.227
0.146
0.088
0.140
0.220
0.871
0.836
0.190
0.287
0.212
0.996
0.539
0.242
0.119
0.152
0.235
0.268
0.145
-------
1993 NMOC Data for Long Island, NY (LINY)
Site
Code
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
LINY
Collection
Date
09/08/93
09/09/93 '
09/10/93
09/13/93
09/14/93
09/15/93
09/16/93
09/17/93
09/17/93
09/20/93
09/21/93
09/22/93
09/23/93
09/24/93
09/27/93
09/28/93
09/29/93
09/30/93
09/30/93
Julian
Date
251
252
253
256
257
258
259
260
260
263
264
265
266
267
270
271
272
273
273
Can
#
670
793
683
853
649
675
885
121
618
673
726
860
898
129
856
927
728
918
182
Radian
ID#
1.829
1869
1874
1880
1913
1912
1910
1946
1947
1948
1955
1981
1972
2027
2022
2016
2019
2052
2053
Duplicate
Y
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
Y
Y
Radian
Analysis
Channel
C
D
C
C
C
C
D
C
C
C
C
C
D
D
C
C
C
C
C
NMOC
ppmC
0.146
0.424
0.351
0.166
0.204
0.243
0.06
0.198
0.182
0.217
0.163
0.17
0.348
0.062
0.447
0.206
0.359
0.256
0.269
-------
Newark, New Jersey (NWNJ]
1993 NMOC Program (AIRS #34-013-0011
5.00-
4.00-
Q.
Q.
O
o
3.00-
2.00-
1.00
0.00-
140
—T
160
180
200 220
Julian Date, 1993
240
280
-------
1993 NMOC Data for Newark, NJ (NWNJ)
Site
Code
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
Collection
Date
06/07/93
06/08/93
06/09/93
06/10/93
06/11/93
06/14/93
06/15/93
06/15/93
06/16/93
06/17/93
06/18/93
06/21/93
06/22/93
06/23/93
06/24/93
06/25/93
06/25/93
06/28/93
06/29/93
06/30/93
07/01/93
07/02/93
07/06/93
07/07/93
07/07/93
07/08/93
07/09/93
07/12/93
07/13/93
07/14/93
07/15/93
07/15/93
07/16/93
07/19/93
07/20/93
Julian
Date
158
159
160
161
162
165
166
166
167
168
169
172
173
174
175
176
176
179
180
181
182
183
187
188
188
189
190
193
194
195
196
196
197
200
201
Can
#
837
705
658
679
784
929
712
86
640
635
37
80
681
406
111
797
164
680
762
52
927
406
77
50
850
680
89
789
189
806
7
687
807
41
28
Radian
ID*
1017
1016
1042
1046
1057
1064
1078
1079
1072
1086
1107
1131
1130
1146
1151
1184
1185
1194
1220
1215
1218
1233
1268
1264
1265
1278
1287
1314
1310
1334
1327
1328
1361
1350
1379
Duplicate
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
Y
Y
N
N
N
N
N
Y
Y
N
N
N
Radian
Analysis
Channel
D
C
C
D
C
C
D
C
C
C
B
A
A
A
A
D
D
C
C
C
D
C
D
D
D
C
D
C
D
C
D
D
D
C
D
NMOC
ppmC
0.346
0.386
0.548
0.482
0.253
0.364
0.389
0.407
0.258
0.221
0.511
0.322
0.135
0.090
0.374
0.337
0.437
0.455
0.245
0.340
0.200
0.268
0.265
0.393
0.310
0.466
0.301
0.393
0.244
0.414
0.236
0.190
0.308
0.409
0.285
-------
1993 NMOC Data for Newark, NJ (NWNJ)
Site
Code
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
Collection
Date
07/21/93
07/22/93
07/23/93
07/26/93
07/27/93
07/28/93
07/29/93
07/30/93
08/02/93
08/03/93
08/04/93
08/05/93
08/06/93
08/09/93
08/10/93
08/11/93
08/11/93
08/12/93
08/13/93
08/16/93
08/17/93
08/18/93
08/19/93
08/20/93
08/23/93
08/24/93
08/24/93
08/25/93
08/26/93
08/27/93
08/30/93
08/31/93
09/01/93
09/02/93
09/03/93
Julian
Date
202
203
204
207
208
209
210
211
214
215
216
217
218
221
222
223
223
224
225
228
229
230
231
232
235
236
236
237
238
239
242
243
244
245
246
Can
#
825
651
302
844
149
806
774
44 .
182
823
679
20
720
164
149
651
783
166
179
712
607
644
176
153
873
830
84
60
660
816
186
623
707
40 .
869
Radian
ID#
1378
1415
1444
1450
1441
1465
1478
1496
1507
1528
1533
1546
1554
1556
1578
1589
1590
1595
1614
1640
1646
1650
1671
1715
1707
1712
1713
1728
1745
1754
1790
1780
1792
1809
1819
Duplicate
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
Radian
Analysis
Channel
C
D
D
A
C
A
B
C
D
D
D
C
D
D
D
C
C
D
D
D
C
D
C
D
C
C
C
D
C
D
D
C
D
D
C
NMOC
ppmC
0.195
0.253
0.157
0.186
0.369
0.151
0.627
0.392
0.665
0.310
0.516
0.188
0.521
0.344
0.774
0.529
0.588
0.337
0.467
0.330
0.273
0.176
0.620
0.597
0.720
0.444
0.437
0.471
0.458
1.446
0.573
0.605
0.603
0.366
0.504
-------
1993 NMOC Data for Newark, NJ (NWNJ)
Site
Code
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
NWNJ
Collection
Date
09/07/93
09/08/93
09/08/93
09/09/93
09/10/93
09/13/93
09/14/93
09/15/93
09/16/93
09/17/93
09/17/93
09/20/93
09/21/93
09/22/93
09/23/93
09/24/93
09/27/93
09/28/93
09/29/93
09/30/93
Julian
Date
250
251
251
252
253
256
257
258
259
260
260
263
264
265
266
267
270
271
272
273
Can
#
928
805
108
927
910
849
305
875
15
653
871
894
303
690
783
20
830
649
819
705
Radian
ID#
1851
1839
1840
1866
1885
1887
1894
1909
1941
1930
1931
1971
1959
1978
1991
2002
2030
2029
2047
2050
Duplicate
N
Y
Y
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
Radian
Analysis
Channel
D
C
C
C
C
D
D
D
D
D
D '
D
C
C
.D
D
D
C
C
D
NMOC
ppmC
0.368
0.284
0.284
0.690
0.411
0.586
0.496
0.305
0.160
0.137
0.136
0.363
0.608
0.259
0.789
0.261
0.696
0.330
0.428
0.395
-------
5.00-
4.00-
Plainfield, New Jersey (PLNJ)
1993 NMOC Program (AIRS #34-039-5001)
3.00-
O.
CL
O
O
2.00-
1.00
0.00
140
180
200 220
Julian Date, 1993
240
260
280
-------
1993 NMOC Data for Plainfield, NJ (PLNJ)
Site
Code
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
Collection
Date
06/08/93
06/09/93
06/17/93
06/18/93
06/21/93
06/22/93
06/23/93
06/24/93
06/25/93
06/28/93
06/28/93
06/29/93
06/30/93
07/01/93
07/06/93
07/07/93
07/09/93
07/12/93
07/13/93
07/1 4/93
07/15/93
07/16/93
07/16/93
07/19/93
07/20/93
07/21/93
07/22/93
07/23/93
07/26/93
07/27/93
07/28/93
07/29/93
07/30/93
08/02/93
08/03/93
Julian
Date
159
160
168
169
172
173
174
175
176
179
179
180
181
182
187
188
190
193
194
195
196
197
197
200
201
202
203
204
207
208
209
210
211
214
215
Can
#
855
9
72
848
143
146
651
910
764
687
803
126
633
670
679
149
22
46
164
897
803
407
148
928
147
54
823
42
764
183
22
694
38
893
54
Radian
ID*
1025
1028
1127
1128
1123
1157
1187
1186
1189
1192
1193
1228
1234
1227
1274
1275
1297
1325
1322
1336
1360
1357
1358
1408
1416
1402
1399
1437
1439
1449
<464
1467
1502
1506
1527
Duplicate
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
N
N
Radian
Analysis
Channel
D
D
B
B
A
B
C
C
C
D
D
D
C
D
C
D
D
C
C
C
C
D
D
C
C
C
D
C
D
C
B
B
C
C
D
NMOC
ppmC
0.764
0.516
0.232
0.298
0.192
0.109
0.069
0.431
0.648
0.313
0.297
0.773
0.617
0.188
0.230
0.246
0.376
0.368
0.265
0.443
0.132
0.115
0.182
0.318
0.207
0.139
0.356
0.085
0.193
0.172
0.307
0.283
0.393
0.679
0.702
-------
1993 NMOC Data for Plainfield, NJ (PLNJ)
Site
Code
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
Collection
Date
08/04/93
08/05/93
08/06/93
08/09/93
08/10/93
08/11/93
08/12/93
08/12/93
08/13/93
08/16/93
08/17/93
08/18/93
08/19/93
08/20/93
08/24/93
08/25/93
08/25/93
08/26/93
08/27/93
08/30/93
08/31/93
09/01/93
09/02/93
09/03/93
09/07/93
09/08/93
09/09/93
09/10/93
09/10/93
09/13/93
09/14/93
09/15/93
09/16/93
09/17/93
09/20/93
Julian
Date
216
217
218
221
222
223
224
224
225
228
229
230
231
232
236
237
237
238
239
242
243
244
245
246
250
251
252
253
253
256
257
258
259
260
263
Can
#
730
794
762
77
131
774
764
800
177
186
147
54
170
42
57
770
305
784
145
794
119
179
630
188
91
302
140
780
867
766
27
106
813
925
787
Radian
ID#
1534
1576
1580
1569
1570
1587
1582
1583
1630
1616
1658
1651
1670
1710
1721
1735
1736
1761
1751
1793
1789
1794
1795
1838
1855
1852
1860
1900
1901
1918
1914
1907
1958
1950
1957
Duplicate
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
Radian
Analysis
Channel
D
C
D
D
D
C
D
D
D
C
C
C
D
C
D
D
D
C
D
C
C
C
D
C
C
C
D
C
C
C
C
C
D
C
C
NMOC
ppmC
1.061
0.677
0.501
0.282
0.784
0.626
0.584
0.679
0.736
0.299
0.188
0.154
0.488
0.441
0.841
0.351
0.415
0.161
1.775
0.832
0.809
0.267
0.272
0.766
1.150
0.212
0.635
0.447
0.470
0.584
0.540
0.563
0.160
0.178
0.256
-------
1993 NMOC Data for Plainfield, NJ (PLNJ)
Site
Code
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
Collection
Date
09/21/93
09/21/93
09/22/93
09/23/93
09/24/93
09/27/93
09/28/93
09/29/93
09/30/93
09/30/93
Julian
Date
264
264
265
266 '
267
270
271
272
273
273
Can
#
309
831
854
798
638
156
119
36
814
188
Radian
ID#
1942
1943
1980
1982
2024
2017
2031
2037
2044
2045
Duplicate
Y
Y
N
N
N
N
N
N
Y
Y
Radian
Analysis
Cnannel
D
D
C
C
D
C
D
D
D
D
NMOC
ppmC
0.578
0.545
0.186
0.426
0.070
1.080
0.241
0.366
0.426
0.424
-------
5.00
0.00
140
Bristol, Pennsylvania (P1 PA)
1993 NMOC Program (AIRS #42-017-0012)
180
200 220
Julian Date, 1993
240
260
280
-------
1993 NMOC Data for Bristol, PA (P1 PA)
Site
Code
P1PA
P1PA
P1PA .
P1PA
P1PA
PIPA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
P1PA
Collection
Date
06/08/93
06/10/93
06/15/93
06/17/93
06/22/93
06/24/93
06/29/93
07/01/93
07/05/93
07/12/93
07/14/93
07/16/93
07/19/93
07/21/93
07/23/93
07/26/93
08/02/93
08/04/93
08/09/93
08/11/93
08/13/93
08/16/93
08/18/93
08/18/93
08/20/93
08/23/93
08/25/93
08/27/93
08/30/93
09/01/93
09/03/93
09/07/93
09/14/93
09/16/93
09/21/93
Julian
Date
159
161
166
168
173
175
180
182
186
193
195
197
200
202
204
207
214
216
221
223
225
228
230
230
232
235
237
239
242
244
246
250
257
259
264
Can
#
915
681
19
84
46
118
658
129
929
621
927
772
115
686
800
119
929
177
899
129
43
154
406
106
635
723
109
154
656
686
627
182
89
92
902
Radian
Radian Analysis NMOC
ID # Duplicate Channel ppmC
1023 N
1033 N
1076 N
1104 N
1158 N
1159 N
1209 N
• 1258 N
1259 N
1320 N
1318 N
1372 N
1364 N
1409 N
1404 N
1443 N
1488 N
1508 N
1551 N
1575 N
1601 N
1606 N
1644 Y
1645 Y
1665 N
1719 N
1739 N
1752 N
1788 N
1807 N
1812 N
1873 N
1893 N
• 1924 N
1965 Y
. D
C
C
D
A
B
D
D
D
D
D
D
D
D
C
A
D
D
C
C
D
C
D
D
C
D
D
C
C
C
D
D
D
D
D
1.171
0.392
0.238
0.459
0.239
0.607
0.707
0.348
0.387
0.486
0.504
0.247
0.330
0.277
0.213
0.085
0.249
0.237
5.749
0.950
0.298
0.168
0.119
0.116
0.285
0.757
0.268
0.701
0.688
0.191
0.212
0.828
0.140
0.135
0.159
-------
1993 NMOC Data for Bristol, PA (P1 PA)
Site
Code
P1PA
P1PA
P1PA
P1PA
Collection
Date
09/21/93
09/23/93
09/28/93
09/30/93
Julian
Date
264
266
271
273
Can
#
836
838
804
82
Radian
ID*
1966
1986
2018
2049
Duplicate
Y
N
N
N
Radian
Analysis
Channel
D
C
C
C
NMOC
ppmC
0.110
1.070
0.176
0.186
-------
Norristown, Pennsylvania (P2PA)
1993 NMOC Program (AIRS #42-091-0013)
5.00
4.00
3.00
Q.
Q.
O
o
2.00
1.00
0.00
140 160
200 220
Julian Date, 1993
240 260
280
-------
1993 NMOC Data for Norristown, PA (P2PA)
Site
Code
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
Collection
Date
06/08/93
06/10/93
06/15/93
06/17/93
06/22/93
06/24/93
06/29/93
07/01/93
07/07/93
07/09/93
07/12/93
07/14/93
07/16/93
07/19/93
07/21/93
07/21/93
07/23/93
07/26/93
07/28/93
07/30/93
08/02/93
08/04/93
08/06/93
08/06/93
08/09/93
08/11/93
08/13/93
08/16/93
08/18/93
08/20/93
08/23/93
08/25/93
08/27/93
08/30/93
09/01/93
Julian
Date
159
161
166
168
173
175
180
182
188
190
193
195
197
200
202
202
204
207
209
210
214
216
218
218
221
223
225
228
230
232
235
237
239
242
244
Can
#
692
170
694
41
911
70
156
773
915
764
150
826
649
52
674
630
702
705
80
131
9
771
640
91
183
767
66
794
687
143
900
767
46
22
147
Radian
ID*
1026
1029
1075
1103
1156
1142
1210
1251
1272
1280
1321
1319
1371
1375
1405
1406
1413
1446
1453
1480
1487
1513
1538
1539
1550
1572
1598
1607
1639
1674
1709
1705
1740
1753
1787
Duplicate
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
Y
Y
N
N
N
N
N
N
N
N
N
N
N
Radian
Analysis
Channel
C
C
D
C
A
B
C
C
C
C
C
C
D
C
D
D
D
C
D
A
C
C
C (VOID)
C (VOID)
D
C
C
C
D
D
D
D
C
C
D
NMOC
ppmC
0.455
0.224
0.188
0.212
0.079
0.266
0.160
0.188
0.158
0.217
0.245
0.390
0.199
0.159
0.089
0.083
0.138
0.127
0.157
0.169
0.304
0.322
108.949
91 .742
4.076
1.451
0.813
1.066
0.262
0.796
0.677
0.259
0.665
0.829
0.294
-------
1993 NMOC Data for Norristown, PA (P2PA)
Site
Code
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
P2PA
Collection
Date
09/03/93
09/07/93
09/09/93
09/09/93
09/14/93
09/16/93
09/21/93
09/23/93
09/28/93
09/30/93
Julian
Date
246
250
252
252
257
259
264
266
271
273
Can
#
41
916
660
640
911
803
770
301
35
843
Radian
ID*
1831
1830
1870
1871
1892
1923
1967
1988
2026
2048
Duplicate
N
N
Y
Y
N
N
N
N
N
N
Radian
Analysis
Channel
C
D
D
D
D
D
D
C
C
C
NMOC
ppmC
0.242
0.481
0.307
0.331
0.277
0.059
0.281
0.505
0.143
0.237
-------
APPENDIX D
1993 NMOC MONITORING PROGRAM INVALIDATED AND MISSING SAMPLES
-------
APPENDIX D
TABLE 1
1993 NMOC PRORAM
VOID OR INVALID SAMPLES
Site
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
PLNJ
LINY
PLNJ
P2PA
P1PA
P1PA
LINY
P1PA
P1PA
P1PA
P2PA
PLNJ
P1PA
Date Description
06/06/93 Timer malfunction
06/ 10/93 Valve broke off canister
06/11/93 Timer malfunction (electrical storm)
06/14/93 Sampler fitting stripped
06/15/93 Sampler fitting stripped
06/16/93 Sampler fitting stripped
07/02/93 Unknown
07/02/93 Unknown
07/05/93 Sampler ran for 6 hours
07/07/93 Sampler malfunction
07/09/93 Sampler malfunction
07/16/93 Canister leak
07/28/93 Pump malfunction
07/30/93 Pump malfunction
08/06/93 Unknown
08/06/93 Contamination (Duplicate)
08/23/93 Timer malfunction
09/09/93 Timer programmed improperly
Assigned
Equipment
Equipment
Equipment
Equipment
Equipment
Equipment
Unknown
Unknown
Operator
Equipment
Equipment
Equipment
Equipment
Equipment
Unknown
Operator
Equipment
Operator
-------
APPENDIX D
TABLE 2
1993 SNMOC PRORAM
VOID OR INVALID SAMPLES
Site Date Description
B1AL 06/07/93 No sample received
B2AL 06/07/93 No sample received
B3AL 06/07/93 No sample received
JUMX 06/07/93 No sample received
JUMX 06/08/93 Canister received under vacuum
B3AL 06/16/93 Power failure at site
JUMX 06/17/93 Timer malfunction (electrical storm)
B1AL 06/18/93 Timer set in manual mode
B1AL 06/21/93 Unknown
B3AL 06/28/93 Timer set in manual mode
B3AL 07/02/93 Duplicate port open during sampling
B3AL 07/08/93 Pump failure
BMTX 07/08/' No sample collected
B3AL 07/09/:, Pump failure
BMTX 07/09/93 No sample collected
B3AL 07/12/93 Pump failure
B3AL 07/13/93 Pump failure
B3AL 07/26/93 Pump failure
B3AL 07/27/93 Pump failure
B3AL 07/28/93 Pump failure
B3AL 07/29/93 Pump failure
JUMX 08/04/93 No sample received
B2AL 08/06/93 Canister valve not opened
B3AL 08/06/93 Pump failure
B3AL 08/09/93 Pump failure
FWTX 08/09/93 No sample received
Assigned
Unknown
Unknown
Unknown
Unknown
Operator
Equipment
Equipment
Operator
Unknown
Operator
Operator
Equipment
Operator
Equipment
Operator
Equipment
Equipment
Equipment
Equipment
Equipment
Equipment
Unknown
Operator
Equipment
Equipment
Unknown
-------
APPENDIX D
TABLE 2
1993 SNMOC PRORAM
VOID OR INVALID SAMPLES
Site
JUMX
B3AL
BMTX
B3AL
B3AL
FWTX
JUMX
B1AL
JUMX
B3AL
B3AL
B3AL
EPTX
EPTX
JUMX
B2AL
BMTX
EPTX
JUMX
Date Description
08/09/93 No sample received
08/10/93 Pump failure
08/10/93 No sample received
08/11/93 Pump failure
08/12/93 Pump failure
08/27/93 No sample collected
08/30/93 Unknown
09/07/93 Timer set in manual mode
09/08/93 Canister received under vacuum
09/10/93 Canister received under vacuum
09/13/93 Canister sampled for two days
09/14/93 Canister sampled for two days
09/14/93 Canister sampled for two days
09/15/93 Canister sampled for two days
09/16/93 No sample received
09/22/93 Timer set in manual mode
09/29/93 Canister valve stripped
09/30/93 No sample received
09/30/93 Timer malfunction
Assigned
Unknown
Equipment
Unknown
Equipment
Equipment
Holiday
Unknown
Operator
Operator
Operator
Operator
Operator
Operator
Operator
Unknown
Operator
Equipment
Unknown
Equipment
-------
APPENDIX E
PDFID INTEGRATOR PROGRAMMING INSTRUCTIONS
-------
INTEGRATOR PROGRAMMING INSTRUCTIONS
:?,struct'.cns -zr rrograr.ming :*e integrators are as fsljows
= e sure to :ress ENTER ar'teV eacn eoort Annotation OFF
Slave Integrator
Detector B ON
Signal B
Chart speed 4.00
•JOffset 10
Zero
Attn 2* 4
Run Time Annotation ON
Run Table Annotation ON
ClocK Table Annotation OFF
Program Annotation OFF
Oven Temo Annotation OFF
(should say -**Warmng«**Oven Temp now owned by Chnl 2)
Reoort Annotation OFF
-------
INTEGRATOR PROGRAMMING INSTRUCTIONS (Continued)
Tave Integratnr
r'cw 3 20
riow 3 L'imt 500
Control Integrator
Valve 1 OFF
Valve 2 OFF
Valve 3 OFF
Valve 4 OFF
Valve 5 ON
Valve 5 OFF
Valve 7 OF-F
Valve 8 OFF
Valve 9 OFF
.Vive .0 OFF
•'Vive 11 OFF
•'alve 12 OFF
Thresnold 1
Peatc Width 0.04
Slave Integrator
Thresnold 1
Peak Width 0.04
Control Integrator
20 Valve 5 OFF
25 List Valve 5
23 Oven Temo Initial Value 20
25 Oven Temp OFF
•10 Wait I
50 Start
70 Oven Temp 90
30 Vale 5 ON
Sync ON
E-J
-------
APPENDIX F
1993 NMOC DAILY CALIBRATION DATA
-------
Table F-1. Daily Calibration Data Summary (Channel A)
Channel
A
A
A
A
A
A
Cal
Date
06/21/93
06/23/93
06/24/93
06/25/93
06/29/93
08/03/93
Initial
Zero
A.C.
3.23
5.55
8.77
5.14
1.27
6.93
Final
Zero
A.C.
3.23
5.55
8.77
5.85
2.57
6.93
Initial
Zero
ppmC
0.0010
0.0018
0.0030
0.0017
0.0004
0.0021
Final
Zero
ppmC
0.0010
0.0018
0.0030
0.0020
0.0008
0.0021
Initial
Cal
Factor
0.000299
0.000323
0.000342
0.000330
0.000333
0.000310
Final
Cal
Factor
0.000299
0.000323
0.000342
0.000334
0.000330
0.000310
Cal
Factor
Drift
0.000000
0.000000
0.000000
-0.000004
0.000003
0.000000
Cal
Factor
% Drift
0.000000
0.000000
0.000000
-1.180948
0.987272
0.000000
AbsCal
Factor
% Drift
0.000000
0.000000
0.000000
1.180948
0.987272
0.000000
-------
Table F-2. Daily Calibration Data Summary (Channel B)
Channel
B
B
B
B
Cal
Date
06/21/93
06/24/93
06/25/93
08/03/93
Initial
Zero
A.C.
831
5.63
5.14
9.06
Final
Zero
A.C.
831
5.63
5.15
9.06
Initial
Zero
ppmC
0.0026
0.0019
0.0017
0.0028
Final
Zero
ppmC
0.0026
0.0019
0.0017
0.0028
Initial
Cal
Factor
0.000317
0.000344
0.000336
0.000309
Final
Cal
Factor
0.000317
0.000344
0.000336
0.000309
Cal
Factor
Drift
0.000000
0.000000
0.000000
0.000000
Cal
Factor
% Drift
0.000000
0.000000
0.090574
0.000000
ADS Cal
Factor
% Drift
0.000000
0.000000
0.090574
0.000000
-------
Table F-31. Daily Calibration Data Summary (Channel C)
Channel
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Cal
Date
06/09/93
06/09/93
06/11/93
06/15/93
06/15/93
06/17/93
06/17/93
06/21/93
06/30/93
07/01/93
07/06/93
07/08/93
07/09/93
07/13/93
07/16/93
07/17/93
07/21/93
07/26/93
07/27/93
07/28/93
07/29/93
07/30/93
08/04/93
08/06/93
08/09/93
08/10/93
08/11/93
08/12/93
08/13/93
08/16/93
Initial
Zero
A.C.
2.57
6.58
'534
0.00
0.00
5.08
3.71
0.00
0.27
0.48
0.65
0.65
0.88
1.78
2.92
0.19
6.08
2.45
1.83
839
234
2.61
0.00
1.04
0.53
4.12
9.42
2.12
5.57
2.11
Final
Zero
A:C.
2.57
6.58
5.16
0.00
2.95
5.08
228
0.74
027
5.90
2.18
3.28
0.88
533
6.17
0.19
229
2.45
1.83
839
2.84
2.61
738
1.04
1.88
4.12
721
2.12
5.93
2.11
Initial
Zero
ppmC
0.0007
0.0018
0.0014
0.0000
0.0000
0.0016
0.0012
0.0000
0.0001
0.0002
0.0002
0.0002
0.0003
0.0006
0.0009
0.0001
0.0019
0.0008
0.0006
0.0026
0.0009
0.0008
0.0000
0.0003
0.0002
0.0013
0.0029
0.0007
0.0017
0.0007
Final
Zero
ppmC
0.0007
0.0018
0.0014
0.0000
0.0009
0.0016
0.0007
0.0002
0.0001
0.0019
0.0007
0.0010
0.0003
0.0017
0.0020
0.0001
0.0007
0.0008
0.0006
0.0026
0.0009
0.0008
0.0023
0.0003
0.0006
0.0013
0.0023
0.0007
0.0019
0.0007
Initial
Cal
Factor
0.000271
0.000270
0.000272
0.000314
0.000313
0.000316
0.000313
0.000310
0.000323
0.000323
0.000313
0.000315
0.000312
0.000313
0.000318
0.000312
0.000314
0.000324
0.000317
0.000311
0.000311
0.000310
0.000314
0.000310
0.000326
0.000312
0.000313
0.000313
0.000312
0.000316
Final
Cal
.Factor
0.000271
0.000270
0.000275
0.000317
0.000315
0.000316
0.000319
0.000313
0.000323
0.000315
0.000315
0.000317
0.000312
0.000315
0.000317
0.000312
0.000317
0.000324
0.000317
0.000311
0.000311
0.000310
0.000314
0.000310
0.000315
0.000312
0.000318
0.000313
0.000313
0.000316
Cal
Factor
Drift
0.000000
0.000000
-0.000003
-0.000003
-0.000002
0.000000
-0.000006
-0.000003
0.000000
0.000008
-0.000002
-0.000001
0.000000
-0.000003
0.000001
0.000000
-0.000003
0.000000
0.000000
0.000000
0.000000
0.000000
-0.000000
0.000000
0.000011
0.000000
-0.000006
0.000000
-0.000001
0.000000
Cal
Factor
. % Drift
0.000000
0.000000
-1.256415
-1.009842
-0.673519
0.000000
-1.959761
-1.000218
0.000000
2.481268
•0.602790
•0.474397
0.000000
-0.808823
0271831
0.000000
-1.078139
0.000000
0.000000
0.000000
0.000000
0.000000
-0.155450
0.000000
3318182
0.000000
-1.828840
0.000000
-0276591
0.000000
AbsCal
• Factor
% Drift
0.000000
0.000000
1.256415
1.009842
0.673519
0.000000
1.959761
1.000218
0.000000
2.481268
0.602790
0.474397
0.000000
0.808823
0271831
0.000000
1.078139
0.000000
0.000000
0.000000
0.000000
0.000000
0.155450
0.000000
3318182
0.000000
1.828840
0.000000
0.276591
0.000000
-------
Table F-31. Daily Calibration Data Summary (Channel C)
Channel
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Cal
Date
08/17/93
08/18/93
08/19/93
08/23/93
08/27/93
08/28/93
08/30/93
08/30/93
08/31/93
09/01/93
09/02/93
09/07/93
09/08/93
09/09/93
09/10/93
09/14/93
09/15/93
09/16/93
09/20/93
09/22/93
09/23/93
09/29/93
09/30/93
10/01/93
10/05/93
10/06/93
Initial
Zero
A.C.
0.00
5.70
3.80
6.44
238
3.D
0.00
2.76
6.14
4.05
3.20
7.14
533
3.02
3.53
1.16
2.51
2.06
6.09
5.02
4.52
7.52
1.61
3.47
4.58
532
Final
Zero
A.C.
0.00
5.70
3.80
7.95
238
3.13
0.00
2.76
3.41
2.78
3.20
0.70
533
3.02
3.53
1.16
1.98
2.06
6.09
5.02
1.10
7.52
1.61
1.80
4.97
5.82
Initial
Zero
ppmC
0.0000
0.0018
0.0012
0.0020
0.0007
0.0010
0.0000
0.0009
0.0019
0.0013
0.0010
0.0022
0.0016
0.0010
0.0011
0.0004
0.0008
0.0006
0.0019
0.0016
0.0015
0.0024
0.0005
0.0011
0.0015
0.0017
Final
Zero
ppmC
0.0000
0.0018
0.0012
0.0027
0.0007
0.0010
0.0000
0.0009
0.0011
0.0009
0.0010
0.0002
0.0016
0.0010
0.0011
0.0004
0.0006
0.0006
0.0019
0.0016
0.0004
0.0024
0.0005
0.0006
0.0016
0.0019
Initial
Cal
Factor
0.000310
0.000315
0.000312
0.000305
0.000308
0.000307
0.000316
0.000313
0.000312
0.000309
0.000308
0.000309
0.000306
0.000316
0.000318
0.000318
0.000316
0.000316
0.000317
0.000328
0.000324
0.000325
0.000322
0.000317
0.000322
0.000329
Final
Cal
Factor
0.000310
0.000315
0.000312
0.000334
0.000308
0.000307
0.000316
0.000313
0.000312
0.000310
0.000308
0.000308
0.000306
0.000316
0.000318
0.000318
0.000319
0.000316
0.000317
0.000328
0.000326
0.000325
0.000322
0.000322
0.000322
0.000328
Cal
Factor
Drift
0.000000
0.000000
0.000000
-0.000029
0.000000
0.000000
0.000000
0.000000
-0.000000
-0.000000
0.000000
0.000002
0.000000
0.000000
0.000000
0.000000
-0.000003
0.000000
0.000000
0.000000
-0.000002
0.000000
0.000000
-0.000005
4.000000
0.000000
Cal
Factor
% Drift
0.000000
0.000000
0.000000
-9.567978
0.000000
0.000000
0.000000
0.000000
-0.042915
-0.053477
0.000000
0348014
0.000000
0.000000
0.000000
0.000000
-0.980731
0.000000
0.000000
0.000000
-0.585259
0.000000
0.000000
-1.606890
-0.091228
0.068029
Abs Cal
Factor
% Drift
0.000000
0.000000
0.000000
9.567978
0.000000
0.000000
0.000000
0.000000
0.042915
0.053477
0.000000
0348014
0.000000
0.000000
0.000000
0.000000
0.980731
0.000000
0.000000
0.000000
0385259
0.000000
0.000000
1.606890
0.091228
0.068029
-------
Table F-4. Daily Calibration Data Summary (Channel D)
Channel
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
Cal
Date
06/11/93
06/17/93
06/21/93
06/30/93
07/01/93
07/06/93
07/08/93
07/09/93
07/13/93
07/16/93
07/17/93
07/21/93
07/26/93
07/27/93
07/28/93
07/29/93
07/30/93
08/04/93
08/06/93
08/09/93
08/10/93
08/11/93
08/12/93
08/13/93
08/16/93
08/17/93
08/18/93
08/19/93
08/23/93
08/27/93
Initial
Zero
A.C.
2.08
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.19
0.00
0.07
0.00
0.00
3.98
0.00
2.51
0.00
1.78
0.00
5.94
0.14
0.00
1.56
6.76
5.41
436
0.00
0.00
6.75
Final
Zero
A.C.
2.22
0.00
0.00
0.00
0.00
0.00
2.19
0.00
0.00
0.00
0.00
0.61
0.00
0.00
3.98
0.00
151
0.00
1.78
9.21
5.94
5.25
0.00
6.11
6.76
5.41
436
0.00
5.56
6.75
Initial
Zero
ppmC
0.0006
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0010
0.0000
0.0000
0.0000
0.0000
0.0013
0.0000
0.0008
0.0000
0.0006
0.0000
0.0019
0.0000
0.0000
0.0005
0.0022
0.0017
0.0014
0.0000
0.0000
0.0021
Final
Zero
ppmC
0.0006
0.0000
0.0000
0.0000
0.0000
0.0000
0.0007
0.0000
0.0000
0.0000
0.0000
0.0002
0.0000
0.0000
0.0013
0.0000
0.0008
0.0000
0.0006
0.0030
0.0019
0.0017
0.0000
0.0020
0.0022
0.0017
0.0014
0.0000
0.0018
0.0021
Initial
Cal
Factor
0.000271
0.000314
0.000321
0.000314
0.000315
0.000314
0.000316
0.000313
0.000315
0.000320
0.000318
0.000315
0.000324
0.000324
0.000325
0.000321
0.000321
0.000320
0.000321
0.000322
0.000321
0.000322
0.000322
0.000323
0.000325
0.000322
0.000323
0.000321
0.000315
0.000316
Final
Cal
Factor
0.000271
0.000317
0.000316
0.000314
0.000319
0.000318
0.000320
0.000313
0.000318
0.000319
0.000318
0.000320
0.000324
0.000327
0.000325
0.000321
0.000321
0.000320
0.000321
0.000327
0.000321
0.000325
0.000322
0.000323
0.000325
0.000322
0.000323
0.000321
0.000325
0.000316
Cal
Factor
Drift
0.000000
-0.000003
0.000006
0.000000
-0.000003
-0.000004
-0.000003
0.000000
-0.000003
0.000001
0.000000
-0.000005
0.000000
-0.000003
0.000000
0.000000
0.000000
0.000000
0.000000
-0.000005
0.000000
-0.000003
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
-0.000011
0.000000
Cal
Factor
% Drift
0.063887
-0.856534
1.722211
0.000000
-1.061562
-1.220664
-0.999863
0.000000
-1.035978
0.227194
0.000000
-1.500857
0.000000
-0.936007
0.000000
0.000000
0.000000
0.000000
0.000000
-1.515104
0.000000
-0.931069
0.000000
0.143152
0.000000
0.000000
0.000000
0.000000
-3341090
0.000000
AbsCal
Factor
% Drift
0.063887
0.856534
1.722211
0.000000
1.061562
1.220664
0.999863
0.000000
1.035978
0.227194
0.000000
1.500857
0.000000
0.936007
0.000000
0.000000
0.000000
0.000000
0.000000
1.515104
0.000000
0.931069
0.000000
0.143152
0.000000
0.000000
0.000000
0.000000
3341090
0.000000
-------
Table F-4. Daily Calibration Data Summary (Channel D)
. Channel
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
Cal
Date
08/28/93
08/31/93
09/01/93
09/02/93
09/07/93
09/08/93
09/09/93
09/10/93
09/14/93
09/15/93
09/16/93
09/17/93
09/20/93
09/22/93
09/23/93
09/29/93
09/30/93
10/01/93
10/05/93
10/06/93
Initial
Zero
A.C.
1.75
0.00
0.00
0.00
634
0-00
5.19
0.00
0.00
0.00
7.78
0.00
0.00
2.86
0.00
7.91
0.09
0.00
0.00
0.07
Final
Zero
A.C.
1.75
9.74
6.44
0.00
1035
0.00
5.19
0.00
0.00
2.23
7.78
0.00
0.00
2.86
0.00
7.91
0.09
0.00
5.72
3.51
Initial
Zero
ppmC
0.0006
0.0000
0.0000
0.0000
0.0020
0.0000
0.0017
0.0000
0.0000
0.0000
0.0025
0.0000
0.0000
0.0009
0.0000
0.0025
0.0000
0.0000
0.0000
0.0000
Final
Zero
ppmC
0.0006
0.0031
0.0021
0.0000
0.0033
0.0000
0.0017
0.0000
0.0000
0.0007
0.0025
0.0000
0.0000
0.0009
0.0000
0.0025
0.0000
0.0000
0.0019
0.0012
Initial
Cal
Factor
0.000317
0.000316
0.000314
0.000317
0.000316
0.000320
0.000320
0.000319
0.000321
0.000320
0.000318
0.000319
0.000320
0.000328
0.000327
0.000319
0.000327
0.000325
0.000326
0.000331
Final
Cal
Factor
0.000317
0.000317
0.000321
0.000317
0.000318
0.000320
0.000320
0.000319
0.000321
0.000322
0.000318
0.000319
0.000320
0.000328
0.000331
0.000319
0.000327
0.000331
0.000330
0.000334
Cal
Factor
Drift
0.000000
-0.000002
-0.000006
0.000000
-0.000002
0.000000
0.000000
0.000000
0.000000
-0.000002
0.000000
0.000000
0.000000
0.000000
-0.000003
0.000000
0.000000
-0.000006
-0.000004
-0.000003
Cal
Factor
% Drift
0.000000
-0.485572
-2.042962
0.000000
•0.556059
0.000000
0.000000
0.000000
0.000000
-0.511390
0.000000
0.000000
0.000000
0.000000
-0.976435
0.000000
0.000000
-1.828712
-1.193789
-1.002740
AbsCal
Factor
% Drift
0.000000
0.485572
2.042962
0.000000
0.556059
0.000000
0.000000
0.000000
0.000000
0.511390
0.000000
0.000000
0.000000
0.000000
0.976435
0.000000
0.000000
1.82^712
1.193789
1.002740
-------
APPENDIX G
1993 NMOC IN-HOUSE QUALITY CONTROL SAMPLES
-------
Table G-1. NMOC In-house Quality Control Samples
Collection
Date
06/25/93
06/29/93
Julian
Date
Analyzed
175
179
Channel
A
A
QC
ID
Number
1141
1169
Calculated
NMOC
ppmC
1.112
0.985
Measured
NMOC
ppmC
1.030
0.944
NMOC
Bias
ppmC
-0.082
-0.041
NMOC
Percent
Bias
-7.374
-4.162
-------
Table G-2. NMOC In-house Quality Control Samples
Julian QC Calculated Measured NMOC NMOC
Collection Date ID NMOC NMOC Bias Percent
Date Analyzed Channel Number ppmC ppmC ppmC Bias
06/25/93 175 B 1141 1.112 1.007 -0.105 -9.442
-------
Table G-3. NMOC In-house Quality Control Samples
Julian
Collection Date
Date Analyzed Channel
06/15/93
06/21/93
07/01/93
07/06/93
07/08/93
07/09/93
07/13/93
07/16/93
07/21/93
07/27/93
07/30/93
08/04/93
08/06/93
08/11/93
08/13/93
08/23/93
08/31/93
09/15/93
10/06/93
166
172
181
187
189
190
194
197
202
208
211
216
218
223
225
235
243
258
279
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
QC Calculated Measured
ID NMOC NMOC
Number ppmC ppmC
1050
1092
1196
1224
1245
1263
1289
1324
1362
1418
1458
1492
1517
1555
1581
1675
1746
1881
2051
0.800
0.982
1.065
0.958
1.020
1.142
0.967
1.097
1.070
0.830
0.895
0.864
1.179
1.200
0.792
1.024
0.839
0.921
1.326
0.779
0.877
1.005
0.911
0.953
1.090
0.936
1.075
1.010
0.778
0.840
0.804
1.135
1.065
0.752
0.928
0.784
0.895
1.295
NMOC
Bias
ppmC
-0.021
-0.105
-0.060
-0.047
-0.068
-0.052
-0.031
-0.022
-0.060
-0.052
-0.055
-0.060
-0.044
-0.135
-0.040
-0.096
-0.055
-0.026
-0.031
NMOC
Percent
Bias
-2.625
-10.692
-5.634
-4.958
-6.618
-4.553
-3.257
-2.005
-5.607
-6.265
-6.145
-6.944
-3.732
-11.250
-5.114
-9.375
-6.555
-2.823
-2.338
-------
Table G-4. NMOC In-house Quality Control Samples
Julian
Collection Date
Date Analyzed Channel
06/15/93
06/21/93
07/01/93
07/06/93
07/08/93
07/09/93
07/13/93
07/16/93
07/21/93
07/27/93
07/30/93
08/04/93
08/06/93
08/11/93
08/13/93
08/23/93
08/31/93
09/15/93
10/06/93
166
172
181
187
189
190
194
197
202
208
211
216
218
223
225
235
243
258
279
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
D
QC Calculated Measured
ID NMOC NMOC
Number ppmC ppmC
1050
1092
1196
1224
1245
1263
1289
1324
1362
1418
1458
1492
1517
1555
1581
1675
1746
1881
2051
0.880
0.982
1.065
0.958
1.020
1.142
0.967
1.097
1.070
0.830
0.895
0.864
1.179
1.200
0.792
1.024
0.839
0.921
1.326
0.802
0.870
0.978
0.896
0.938
1.050
0.894
1.060
1.045
0.778
0.833
0.810
1.145
1.100
0.746
0.955
0.814
0.877
1.295
NMOC
Bias
ppmC
-0.078
-0.112
-0.087
-0.063
-0.082
-0.092
-0.073
-0.037
-0.025
-0.052
-0.063
-0.054
-0.034
-0.100
-0.046
-0.070
-0.025
-0.044
-0.031
NMOC
Percent
Bias
-8.864
-11.405
-8.169
-6.524
-8.039
-8.056
-7.549
-3.373
-2.336
-6.325
-6.983
-6.308
-2.884
-8.333
-5.871
-6.787
-2.980
-4.777
-2.338
-------
APPENDIX H
1993 MULTIPLE DETECTOR SPECIATED THREE-HOUR SITE DATA SUMMARIES
-------
TABLE H1. MULTIPLE DETECTOR SPECIATED UATMP DATA SUMMARY FOR B1AL
Sample Date
Sample ID
Compound
etylene
opylene
loromethane
nyl Chloride
5 -Butadiene
anome thane
loroethane
thylene Chloride
ins-1 ,2-Oichloroethylene
I -D ich loroethane
.oroprene CA)
xnoch loromethane
oroform
!-Dichloroethane
,1-Trichloroethane
izene
bon tetrachloride
-Dichloroproparte
modi ch I oromethane
chloroethylene
•1,3-Dichloropropylene
ns-1 ,3-Dichloropropylene
,2-Trichtoroethane
uene
romoch I oromethane
ctane
rachtoroethylene
orobenzene
y I benzene
• Xy 1 ene/Bromof orm
rene
/lene/1,1,2,2-Tetrachloroethane
ich I orobenzene
ich I orobenzene
ich I orobenzene
6/15/93
1081
<1.00
0.52 CD
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.05 -CD
<0.04
0.37 CM)
0.30 (H)
0.26 CH)
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.55 CH)
<0.001
<0.03
0.07 (L)
<0.02
0.08 CH)
0.31 (D
<0.02
<0.022
<0.02
<0.09
<0.02
6/22/93
1132
<1.00
1.35
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.08
<0.04
0.62
1.45
0.34
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
2.96
<0.001
<0.03
0.18
<0.02
0.44
1.85
0.12
0.95
<0.02
<0.09
<0.02
7/12/93
1305
Concentration,
<1.00
CD 0.76
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
CD 0.04
<0.04
CH) 0.39
CH) 0.35
CH) 0.36
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
CD 0.75
<0.001
<0.03
CD 0.03
<0.02
CD 0.34
CD 1.66
CD 0.06
CD 0.60
<0.02
<0.09
0.16
7/23/93
1419
ppbv
<1..00
(D 3.54
<0.20
<0.20
0.30
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
CD 0.09
<0.04
CD 0.71
CH) 2.63
CD 0.37
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
CH) 4.78
<0.001
<0.03
CD 0.19
<0.02
CD 1.08
CD 5.02
CD <0.02
CD 2.30
<0.02
<0.09
CH) <0.02
8/04/93
1518
<1.00
CD 0.59
<0.20
<0.20
CM) <0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
CD 0.04
<0.04
CH) 0.34
CH) 0.35
CD 0.32
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
CM) 0.90
<0.001
0.04
CD 0.10
<0.02
CH) 0.13
CD 0.64
0.03
CD 0.35
<0.02
<0.09
<0.02
CD
(L)
CD
CH)
CD
CH)
CD
CD
CH)
CD
CH)
CD
High confidence level (M) Medium confidence level
Present but not quantitated due to interference
(L) Low confidence level
(Continued)
H1
-------
TABLE H1. B1AL (Continued)
Sample Date
Sample ID
Compound
Acetylene
Propylene
Chloromethane
Vinyl Chloride
1,3-Butadicne
Bromomethane
Chloroethane
Me thy I ene Chloride
trans-1,2-Dichloroethylene
1,1-Di chloroethane
Chloroprene (A)
Bromochloromethane
Chloroform
1,2-Dichloroethene
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
1 , 2 -D i ch I oropropane
B romod i ch I orome thane
Trichloroethylene
cis-1,3-Dichloropropylene
trans- 1,3-Oichloropropylene
1 , 1 ,2-Trichloroethane
Toluene
D i bromoch 1 oromethane
n- Octane
Tetrachloroethylene
Chlorobenzene
Ethylbenzene
m/p- Xy 1 ene/Bromof orm
Styrene
o-Xylene/1 , 1 ,2,2-Tetrachloroethane
m-0 i ch 1 orobenzene
p-D i ch I orobenzene
o - D i ch t orobenzene
8/13/93
16190
8/13/93
1619R
8/13/93
16200
Concentration,
<1.00
1.00
<0.20
<0.20
0.05
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.29
0.54
0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.16
<0.001
0.15
0.07
<0.02
0.20
0.93
0.06
0.47
<0.02
<0.09
<0.02
(D
(H)
(L)
CM)
(H)
(L)
CH)
(L)
(L)
(L)
(L)
(L)
(L)
<1.00
0.83
<0.20
<0.20
0.02
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.32
0.65
0.24
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.13
<0.001
0.10
0.08
<0.02
0.19
0.88
0.06
0.49
<0.02
<0.09
<0.02
(L)
U>
(L)
(H)
(H)
(H)
CH)
(L)
(H)
(L)
(H)
(L)
<1.00
0.76
<0.20
<0.20
0.06
<0.20
<0.10
<0.11
(H)
(L)
CM)
(L)
8/20/93
1676
<1.00
2.93
xO.20
<0.20
0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.08
<0.04
0.50
1.09
0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
4.27
<0.001
0.17
0.18
<0,02
0.65
2.95
0.17
1.51
<0.02
<0.09
<0.02
(L)
(M)
(L)
(H)
(H)
(L)
(H)
(L)
(L)
(L)
U)
(L)
(L)
9/02/93
1814
<1.00 -
0.46
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.32
0.21
0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.67
<0.001
0.02
0.05
<0.02
0.18
0.87
<0.02
1.25
<0.02
<0.09
<0.02
CD
CD
CD
CH)
CD
CH)
CD
CD
CD
CD
CD
CH) High confidence level CM) Mediua confidence level
R Replicate analysis D Duplicate sample
(A) Present but not quant Stated due to interference
CD Low confidence level
(Continued)
H2
-------
TABLE H2. MULTIPLE DETECTOR SPECIATED UATMP DATA SUMMARY FOR B2AL
Sample Date
Sample ID
Compound
itylene
ipylene
oromethane
lyl Chloride
-Butadiene
none thane
oroethane
hylene Chloride
ns-1,2-Dichloroethylene
-Dich I oroethane
oroprene (A)
moch I oromethane
orofortn
-Dich I oroethane
,1-Trichloroethane
zene
Don tetrachloride
-Dichloropropane
nodi ch I oromethane
:hloroethylene
•1,3-Diehloropropylene
is-1,3-Dichloropropylene
, 2- Trich I oroethane
jene
•omoch I oromethane
:tane
•achloroethylene
srobenzene
/I benzene
• Xy 1 ene/Bromof orm
•ene
'tene/1 , 1 ,2,2-Tetrachloroethane
ichlorobenzene
ichlorobenzene
ichlorobenzene
6/15/93
1080
<1.00
0.26
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.36
0.18
0.34
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.30
<0.001
<0.03
0.05
<0.02
0.04
0.17
<0.02
0.11
<0.02
<0.09
<0.02
6/22/93
1138
<1.00
(L) 0.42
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
(L) 0.03
<0.04
(L) 0.37
(H) 0.24
(H) 0.35
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 0-.56
<0.001
<0.03
(L> 0.03
<0.02
(H) <0.02
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(M) 0.44 (H)
<0.001
0.02 (H)
(L) 0.04 (L)
<0.02
0.06 (H)
(L) 0.30 (L)
0.02 (M)
0.16 (L)
<0.02
<0.09
<0.02
7/23/93
1420
<1.00
0.90
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.07
<0.04
0.36
0.59
0.31
<0.04
<0.001
<0.004
<0.04
<0.04
<0,04
1.08
<0.001
0.03
0.06
<0.02
0.17
0.67
0.04
0.40
<0.02
<0.09
<0.02
8/03/93
1514
<1.00
(L) 0.70
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
(L) 0.03
<0.04
(L) 0.38
(H) 0.30
(L) 0.33
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 0.71
<0.001
(H) 0.02
(L) 0.04
<0.02
(H) 0.10
CD 0.47
(H) 0.04
(L) 0.27
<0.02
<0.09
0.27
(D
CD
(D
(H)
(D
CH)
CH)
CD
(H)
CD
CH)
CD
CM)
High confidence level (M) Medium confidence level
Present but not quantitated due to interference
(L) Low confidence level
(Continued)
H3
-------
TABLE H2. 82AL (Continued)
Sample Date
Sample ID
Compound
Acetylene
Propylene
Chi oromethane
Vinyl Chloride
1,3 -Butadiene
Bromomethane
Chloroethane
Hethylene Chloride
trans-1,2-Dichloroethylene
1 , 1 -D i ch I oroethane
Chloroprene (A)
B romoch I oromethane
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
1 , 2 - D i ch I oropropane
B rornod i ch I oromethane
Trichloroethylene
cis-1,3-Dichloropropylene
trans- 1 ,3-Dichloropropylene
1 , 1 ,2-Tri chloroethane
Toluene
D ibromoch I oromethane
n-Octane
Tetrachloroethylene
Chlorobenzene
Ethyl benzene
m/ p- Xy 1 ene/B romof om
Styrene
o-Xylene/1 , 1 ,2,2-Tetrachloroethane
m-Di chlorobenzene
p-Oi chlorobenzene
o-Di chlorobenzene
8/16/93
1625D
8/16/93
1625R
8/16/93
16260
8/20/93
1680
Concentration,
<1.
1.
<0.
<0.
0.
<0.
<0.
<0.
<0.
<0.
<0.
<0.
0.
<0.
0.
0.
0.
<0.
<0.
<0.
<0.
<0.
<0.
1.
<0.
0.
0.
<0.
0.
0.
0.
0.
<0.
<0.
<0.
00
50
20
20
09
20
10
11
04
04
06
003
04
04
29
44
22
04
001
004
04
04
04
03
001
03
04
02
15
62
11
36
02
09
02
(L)
(H)
(L)
(L)
(H)
(H)
(H)
(L)
(L)
(L)
(L)
(H)
(L)
<1.00
1.19
<0.20
<0.20
0.05
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.07
<0.04
0.34
0.61
0.23
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.25
<0.001
<0.03
0.05
<0.02
0.17
0.72
0.17
0.55
<0.02
<0.09
<0.02
(L)
(M)
(L)
(L)
(L)
(L)
(H)
(L)
(L)
(L)
(N)
(L)
<1.00
1.47
<0.20
<0.20
0.09
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.23
<0.04
0.29
0.41
0.21
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.09
<0.001
0.02
0.08
<0.02
0.15
0.63
0.10
0.36
<0.02
<0.09
<0.02
<1
-------
TABLE H3. MULTIPLE DETECTOR SPECIATEO UATMP DATA SUMMARY FOR B3AL
Sample Date
Sample ID
Compound
tylene
pylene
oromethane
yl Chloride
-Butadiene
momethane
oroethane
lylene Chloride
•«-1 ,2-Oichloroethylene
•Dichloroethane
aroprene (A)
noch I oromethane
jroform
•Dichloroethane
1-Trichloroethane
:ene
ion tetrachloride
D i ch 1 oropropane
cdi ch I oromethane
hloroethylene
1 , 3 - D i ch I oropropy I ene
s-1, 3-D ichl oropropy lene
2- Trich I oroethane
ene
omoch I oromethane
tane
achloroethylene
robenzene
I benzene
Xylene/Bromoforn
ene
lene/1,1,2,2-Tetrachloroethane
chlorobenzene
chlorobenzene
chlorobenzene
6/15/93
1082
6/22/93
1134
7/14/93
1335
7/30/93
1486
8/10/93
1511
Concentration, ppbv
<1.00
' <0.10
0.53
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.10
<0.04
0.30
0.11
0.30
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.23
<0.001
<0.03
0.03
<0.02
0.03
0.15
<0.02
0.09
<0.02
<0.09
<0.02
<1.00
0.53
(L) <0.20
<0.20
<0.10
<0.20
<0.10
0.52
<0.04
<0.04
<0.06
<0.003
(L) 0.04
<0.04
(L) 0.45
(H) 0.20
(L) 0.30
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 0.53
<0.001
0.04
(L) 0.10
<0.02
(H) 0.07
(L) 0.34
0.05
(L) 0.18
<0.02
<0.09
<0.02
(L)
(H)
(L)
CD
(L)
(H)
(H)
(L)
(H)
(L)
(L)
(L)
High confidence level (M) MediiM confidence level
Present but not quant Stated due to interference
(L) Low confidence level
(Continued)
H5
-------
TABLE H3. B3AL (Continued)
Sample Date
Sample 10
Compound
Acetylene
Propylene
Ch 1 oromethane
Vinyl Chloride
1,3-Butadiene
Bromome thane
Chloroethane
Methylene Chloride
trans- 1 , 2-D i ch 1 oroethy lene
1,1-Di Chloroethane
Chloroprene (A)
B romoch I oromethane
Chloroform
1 , 2-D i ch loroethane
1,1, 1 -Trich loroethane
Benzene
Carbon tetrachloride
1,2-Dichloropropane
Bromodich I oromethane
Trichloroethylene
cis-1,3-Dichloropropylene
trans- 1 ,3-Dichloropropylene
1,1,2-Trichloroethane
Toluene
D i bromoch loromethane
n-Octane
Tetrach I oroethy lene
Chlorobenzene
Ethylbenzene
m/p- Xy I ene/Bromof orw
Styrene
o-Xylene/1 , 1 ,2,2-Tetrachloroethane
m-Di Chlorobenzene
p-D i ch I orobenzene
o-O i Chlorobenzene
8/17/93
16340
<1.00
1.40
<0.20
<0.20
<0.10
<0.20
<0.10
2.61
<0.04
<0.04
<0.06
<0.003
0.06
<0.04
0.70
0.61
0.24
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.81
<0.001
0.03
1.87
<0.02
0.23
0.93
0.11
0.45
<0.02
<0.09
<0.02
-------
TABLE H4. MULTIPLE DETECTOR SPECIATED UATHP DATA SUMMARY FOR NWNJ
Sample Date
Sample ID
Compound
Jtylen*
>pylene
oromethane
tyl Chloride
i-Butadiene
momethane
oroethane
.hylene Chloride
ins-1,2-Dichloroethylene
-Dichloroethane
oroprene (A)
moch I oromethane
oroform
-Dichloroethane
,1-Trichloroethane
zene
bon tetrachloride
- D i ch I oropropane
mod i ch I oromethane
chloroethylene
- 1 , 3-D i chloropropylene
ns-1 , 3- Di chloropropylene
,2-Trichloroethane
jene
romoch I oromethane
:tane
rachloroethylene
orobenzene
/I benzene
•Xylene/Bromoform
rene
)flene/1,1,2,2-Tetrachloroethane
ich I orobenzene
ich I orobenzene
ich I orobenzene
6/17/93
1086
6/24/93
1151
7/12/93
1314
Concentration,
<1.00
1.26
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.04
<0.04
1.23
0.27
0.36
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.63
<0.001
0.07
0.26
<0.02
0.21
1.04
0.05
0.50
<0.02
<0.09
<0.02
U)
(L)
(L)
(H)
(L)
(H)
(H)
(L)
CH)
(L)
(H)
(L)
<1.00
2.70
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.17
<0.04
1.84
0.51
0.39
<0.04
<0.001
0.61
<0.04
<0.04
<0.04
2.89
<0.001
0.13
0.40
<0.02
0.31
1.47.
0.07
0.74
<0.02
<0.09
<0.02
CD
CL)
CD
CH)
CD
CM)
CH)
CM)
CD
. CM)
CD
CD
CD
<1.00
2.75
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.04
<0.04
1.39
0.77
0.36
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
2.87
<0.001
0.20
0.20
<0.02
0.47
2.25
0.08
1.04
<0.02
0.16
<0.02
ppbv
(L)
(L)
(M)
(H)
-------
TABLE H4. NWNJ (Continued)
Sample Date
Sample ID
Compound
Acetylene
Propylene
Chi oromethane
Vinyl Chloride
1,3-Butadiene
Bromomethane
Chloroethane
Methylene Chloride
trans-1,2-Dichloroethylene
1, 1-0 i chloroethane
Chloroprene (A)
Bromoch I oromethane
Chloroform
1, 2 -Di chloroethane
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
1 ,2-Dichloropropene
B romod i ch I oromethane
Trichloroethylene
cis-1 , 3-D ich I oropropy I ene
t rans • 1 , 3 - D i ch I oropropy I ene
1,1,2-Trichloroethane
Toluene
0 i bromoch I oromethane
n-Octane
Tetrachloroethylene
Chi orobenzene
Ethyl benzene
m/p- Xy 1 ene/Bromof orm
Styrene
o-Xylene/1 , 1 ,2,2-Tetrachloroethane
m-D i ch I orobenzene
p- D i ch I orobenzene
o-D i ch I orobenzene
8/20/93
1715
8/27/93
1754
9/08/93
18390
9/08/93
1839R
9/08/93
18400
Concentration, ppbv
<1.00
2.82
<0.20
<0.20
0.11
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.06
<0.04
1.64
0.89
0.24
<0.04
<0.001
0.42
<0.04
<0.04
<0.04
3.62
<0.001
0.14
0.22
0.05
0.48
2.37
0.18
1.03
<0.02
<0.09
<0.02
(L)
(M)
(L)
(L)
(H)
(L)
(H)
(H)
(L)
(L)
(H)
(M)
(L)
(H)
(L)
<1.00
11.03
<0.20
<0.20
0.30
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.20
<0.04
4.24
2.11
0.27
<0.04
<0.001
0.33
<0.04
<0.04
<0.04
10.04
<0.001
0.57
1.33
<0.02
1.67
8.41
0.52
3.92
<0.02
<0.09
<0.02
(L)
(H)
(L)
(H)
(H)
(L)
(H)
(H)
(H)
(L)
(H)
(L)
(L)
(L)
<1.00
1.11
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.04
<0.04
4.59
0.30
0.31
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.99
<0.001
0.05
0.35
<0.02
0.27
1.23
0.18
0.64
<0.02
0.16
<0.02
(L)
(L)
(M)
(H)
(L)
(H)
(L)
-------
TABLE MS. MULTIPLE DETECTOR SPECIATED UATMP DATA SUMMARY FOR P1PA
Sample Date
Sample ID
Compound
stylene
jpylene
.oromethane
lyt Chloride
i-Butadiene
xnomethane
.oroethane
:hylene Chloride
ins-1,2-0ichloroethylene
-Dich I oroethane
oroprene (A)
moch I oromethane
oroform
-Dich I oroethane
, 1 • T r i ch loroethane
zene
bon tetrachtoride
-D i ch I oropropane
nod i ch I oromethane
:hloroethylene
•1,3-Dichloropropylene
-is-1,3-0ichloropropylene
,2-Trich loroethane
jene
•omoch I oromethane
:tane
•achloroethylene
jrobenzene
'I benzene
Xylene/Bromoform
•ene
'lene/1 , 1 , 2, 2-Tetrach I oroethane
ch I orobenzene
ch I orobenzene
ch I orobenzene
6/24/93
1159
<1.00
2.60
<0.20
<0.20
0.11
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.08
<0.04
3.28
0.96
0.37
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
3.18
<0.001
0.10
0.48
<0.02
0.40
2.15
0.42
1.11
<0.02
<0.09
<0.02
6/29/93
1209
<1.00
(L) 1.16
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
(L) 0.26
<0.04
(H) 4.00
(H) 0.64
(M) 0.38
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.37
<0.02
<0.09
0.11
ppbv
CD
CD
CM)
(H)
CD
CH)
CH)
CD
CH)
CD
CL)
CD
8/02/93
1488
<1.00
• 0.55
<0.20
<0.20
0.07
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.06
<0.04
0.56
0.42
0.31
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.04
<0.001
0.04
0.11
<0.02
0.14
0.63
<0.02
0.30
<0.02
<0.09
<0.02
CD
CD
CD
CD
CH)
CH)
CH)
CD
CD
CD
CD
CD
8/09/93
1551
<1.00
0.92
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.04
<0.04
0.39
0.60
0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
5.82
<0.001
<0.03
0.18
<0.02
<0.02
1.27
<0.02
<0.022
<0.02
<0.09
<0.02
CL)
CL)
CD
CD
CD
CH)
CD
CL)
High confidence level (M) Medium confidence level
Present but not quantitated due to interference
(L) Low confidence level
(Continued)
H9
-------
TABLE H5. P1PA (Continued
Sample Date
Sample 10
Compound
Acetylene
Propylene
Chloromethane
Vinyl Chloride
1,3-Butadiene
Bromomethane
Chloroethane
Methylene Chloride
trans- 1,2-Oichloroethylene
1,1-Di chloroethane
Chloroprene (A)
Bromoch loromethane
Chloroform
1 , 2-0 i ch loroethane
1,1,1-Trichloroethane
Benzene
Carbon tetrachloride
1 , 2 - D i ch I oropropane
Bromodi ch I oromethane
Trichloroethylene
cis-1,3-Dichloropropylene
trans-1,3-0ichloropropylene
1,1,2-Tri chloroethane
Toluene
D i bromoch I oromethane
n-Octane
Tetrachloroethylene
Ch I orobenzene
Ethyl benzene
m/ p- Xy 1 ene/B rornof orm
Styrene
o-Xylene/1 , 1 ,2,2-Tetrachloroethane
m- 0 i ch I orobenzene
p- D i ch I orobenzene
o-Oichlorobenzene
8/25/93
1739
8/27/93
1752
9/21/93
19650
9/21/93
1965R
9/21/93
19660
Concentration, ppbv
<1.00
1.52 (L)
0.79 (L)
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.06 (L)
<0.04
0.56 (L)
0.55 (H)
0.23 (L)
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.16 (H)
<0.001
<0.03
0.15 (L)
<0.02
<0.02
0.53 (L)
<0.02
<0.022
<0.02
<0.09
<0.02
<1.00
3.08
<0.20
<0.20
0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.24
<0.04
1.70
1.26
0.25
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
4.59
<0.001
0.17
0.44
0.04
0.61
2.92
0.18
1.49
<0.02
<0.09
<0.02
(L)
(M)
CL)
(M)
(H)
(L)
(H)
(H)
(L)
(L)
(H)
(L)
(H)
(D
<1.00
0.61
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.02
<0.04
0.26
0.26
0.20
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.70
<0.001
<0.03
0.20
<0.02
0.09
0.45
<0.02
0.31
<0.02
<0.09
<0.02
<1.00
CL) 0.57
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
(L) 0.02
<0.04
(L) 0.30
(H) 0.26
(D 0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 0.77
<0.001
0.03
(L) 0.28
<0.02
CM) 0.10
(L) 0.51
<0.02
CD 0.33
<0.02
<0.09
<0.02
<1.00
(L) 0.59
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
(D 0.04
<0.04
(D 0.35
(H) 0.26
CD 0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 2.28
<0.001
CL) <0.03
(D 0.26
<0.02
(D 0.16
(D 0.67
0.04
CD 0.32
<0.02
<0.09
<0.02
(D
CD
CD
CH)
CD
(H)
CD
CD
CD
CD
CD
(H) High confidence level Medium confidence level
R Replicate analysis D Duplicate sample
(A) Present but not quantitated due to interference
(L) Low confidence level
(Continued)
H10
-------
TABLE H6. MULTIPLE DETECTOR SPECIATEO UATMP DATA SUMMARY FOR P2PA
Sample Date
Sample ID
Compound
stylene
spy I ene
.oromethane
lyl Chloride
!-Butadiene
momethane
oroethane
:hylene Chloride
ins-1,2-Dichloroethylene
-Dich I oroethane
oroprene (A)
moch I oromethane
oroform
•Dich I oroethane
,1-Trichloroethane
zene
bon tetrachloride
• D i ch I oropropane
nodi ch I oromethane
:hloroethylene
•1,3-Dichloropropylene
is -1,3-Diehloropropylene
,2-Tricht oroethane
jene
•omoch I oromethane
:tane
•achloroethylene
>robenzene
'I benzene
•Xylene/Bromoform
•ene
'lene/1 , 1 ,2,2-Tetrachloroethane
chlorobenzene
chlorobenzene
chlorobenzene
6/24/93
1142
6/29/93
1210
7/12/93
1321
Concentration,
<1
1
<0
<0
0
<0
<0
<0
<0
<0
<0
<0
0
<0
1
0
0
<0
<0
0
<0
<0
<0
2
<0
0
0
<0
0
1
0
0
<0
0
0
.00
.24
.20
.20
.08
.20
.10
.11
.04
.04
.06
.003
.09
.04
.10
.58
.33
.04
.001
.35
.04
.04
.04
.20
.001
.05
.30
.02
.32
.50
.06
.78
.02
.25
.10
(L)
(H)
(L)
(M)
(H)
CM)
(H)
(H)
(L)
(H)
(L)
(L)
(L)
(L)
(L)
<1.00
0.46
<0.20
<0.20
0.03
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.07
<0.04
1.02
0.34
0.38
<0.04
<0.001
0.53
<0.04
<0.04
<0.04
1.05
<0.001
0.03
0.22
<0.02
0.13
0.73
0.04
0.40
<0.02
0.19
<0.02
(LX
(H)
(L)
(L)
(H)
(L)
(H)
(H)
(L)
(L)
(H)
(L)
(H)
(L>
(H)
<1.00
1.02
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.08
<0.04
0.45
0.55
0.35
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.16
<0.001
0.03
0.18
<0.02
0.15
0.75
0.02
0.41
<0.02
0.14
<0.02
7/28/93
1453
ppbv
<1
(L) 0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
(L) 0
<0
(L) 1
(H) 0
(M) 0
<0
<0
0
<0
<0
<0
(H) 0
<0
(H) 0
(L) 0
<0
(H) 0
CD 0
(D <0
(D 0
<0
(M) 0
<0
.00
.33
.20
.20
.10
.20
.10
.11
.04
.04
.06
.003
.06
.04
.50
.29
.33
.04
.001
.19
.04
.04
.04
.65
.001
.02
.09
.02
.10
.44
.02
.30
.02
.10
.02
(D
(D
(M)
(H)
(L)
(D
(H)
(L)
(L)
(H)
CD
(L)
(M)
8/02/93
1487
<1.00
3.73
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.04
<0.04
0.45
0.59
0.35
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.19
<0.001
0.04
0.11
<0.02
0.14
0.54
<0.02
0.39
<0.02
0.43
0.19
(D
(L)
(L)
(H)
(H)
(H)
CM)
CD
(H)
CD
(L)
CH)
(D
High confidence level (M) Medium confidence level
Present but not quantitated due to interference
(L) Low confidence level
(Continued)
K11
-------
TABLE H6. P2PA (Continued)
Sample Date
Sample ID
Compound
Acetylene
Propylene
Chi oromethane
Vinyl Chloride
1,3-Butadiene
Bromomethane
Chloroethane
Methylene Chloride
trans- 1,2-Dichloroethylene
1 , 1-Di chloroethane
Chloroprene (A)
Bromoch I oromethane
Chloroform
1 , 2-D i ch I oroethane
1,1, 1 -Tri chloroethane
Benzene
Carbon tetrachloride
1 ,2-Dichloropropane
B romod i ch I oromethane
Trichloroethylene
cis-1,3-Dichloropropylene
trans -1 ,3-Dichloropropylene
1,1,2-Tri chloroethane
Toluene
D i bromoch I oromethane
n-Octane
Tetrachtoroethytene
Chlorobenzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/1 , 1 ,2,2- Tetrach I oroethane
m-Di chlorobenzene
p-0 i ch I orobenzene
o-Di chlorobenzene
8/27/93
1705
:asaaaaBBaaaaaaaaaaaaa*saaca»saa«*
8/23/93 9/09/93
1709 1870D
Concentration,
<1
0
<0
<0
0
<0
<0
<0
<0
<0
<0
<0
0
<0
0
0
0
<0
<0
<0
<0
<0
<0
1
<0
0
0
0
0
1
<0
0
<0
<0
<0
.00
.78
.20
.20
.05
.20
.10
.11
.04
.04
.06
.003
.07
.04
.91
.63
.27
.04
.001
.004
.04
.04
.04
.64
.001
.07
.14
.04
.23
.10
.02
.78
.02
.09
.02
(L)
(L)
(L)
(M)
(H)
(L)
(H)
(H)
(L)
(M)
(H)
(L)
(L)
<1
1
0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
<0
0
0
0
<0
<0
<0
<0
<0
<0
4
<0
<0
0
<0
0
0
<0
0
0
<0
<0
.00
.71
.42
.20
.10
.20
.10
.11
.04
.04
.06
.003
.10
.04
.59
.52
.25
.04
.001
.004
.04
.04
.04
.40
.001
.03
.41
.02
.20
.90
.02
.57
.52
.09
.02
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
(L)
<1.00
1.75
<0.20,
<0.20
0.07
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.05
<0.04
0.69
0.79
0.25
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
2.38
<0.001
0.09
0.73
0.02
0.29
1.46
0.10
0.75
<0.02
<0.09
<0.02
aBBsaacnaaaasasasssasaaaaszaaazszaans
9/09/93 9/09/93
1870R 1871D
ppbv
<1
(L) 1
<0
<0
(H) 0
<0
<0
<0
<0
<0
<0
<0
(L) 0
<0
(L) 0
(H) 0
(M) 0
<0
<0
<0
<0
<0
<0
(H) 2
<0
(M) <0
(L) 0
(M) <0
(H) 0
(L) 1
(M) <0
(L) 0
<0
<0
<0
.00
.45 (L)
.20
.20
.08 (H)
.20
.10
.11
.04
.04
.06
.003
.04 (L)
.04
.63 (L)
.85 (L)
.24 (L)
.04
.001
.004
.04
.04
.04
.30 (M)
.001
.03
.50 (L)
.02
.33 (H)
.44 (L)
.02
.58 (L)
.02
.09
.02
<1.00
1.41
<0.20
<0.20
0.08
<0. 20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.07
<0.04
0.67
0.77
0.24
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
2.32
<0.001
0.05
0.72
<0.02
0.28
1.40
0.12
0.72
<0.02
<0.09
<0.02
(L)
(H)
(L)
(L)
(H)
(M)
(H)
(L)
(H)
(L)
-------
TABLE H7. MULTIPLE DETECTOR SPECIATED UATMP DATA SUMMARY FOR PLNJ
Sample Date
Sample ID
Compound
ttylene
>pylene
oromethane
lyl Chloride
>-Butadiene
roomethane
oroethane
hylene Chloride
ns-1,2-Dichloroethylene
-Dich I oroethane
oroprene (A)
moch I oromethane
oroform
-Dichloroethane
,1-Trichloroethane
zene
Don tetrachloride
-Dichloropropane
nod i ch I oromethane
:hloroethylene
•1,3-Dichloropropylene
is - 1 , 3 - D i ch I oropropy I ene
,2-Trichloroethane
jene
•omoch I oromethane
:tane
•achloroethylene
)robenzene
'I benzene
Xy I ene/B romof orm
•ene
'lene/1,1,2,2-Tetrachloro«thane
chlorobenzene
chlorobenzene
chlorobenzene
6/17/93
1127
6/24/93
1186
7/15/93
1360
Concentration,
<1.00
0.85
0.47
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.74
0.33
0.28
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
1.41
<0.001
0.05
0.16
<0.02
0.12
0.54
<0.02
0.33
<0.02
<0.09
<0.02
•0.00-
0.33
(L) 1.50
0.10
(L) 0.78
<0.02
<0.09
0.06
CL)
CL)
CL)
CH)
(L)
CH)
CL)
CL)
CH)
CL)
CM)
CL)
CL)
<1.00
0.46
0.70
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.42
0.26
0.30
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.63
<0.001
0.03
0.15
<0.02
0.08
0.37
<0.02
0.25
<0.02
<0.09
<0.02
ppbv
(L)
(L)
(L)
(M)
(H)
(L)
(H)
(M)
(L)
(H)
(L)
(L)
7/23/93
1437
<1.00
<0.10
<0.20
<0.20
<0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.03
<0.04
0.30
0.18
0.28
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
0.45
<0.001
<0.03
0.11
<0.02
0.07
0.28
<0.02
0.16
<0.02
<0.09
<0.02
8/02/93
1506
<1.00
3.16'
<0.20
<0.20
0.10
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06 '
<0.003
(L) 0.08
<0.04
(L) 0.80
(H) 1.21
(L) 0.32
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
-------
TABLE H7. PLNJ (Continued)
Sample Date
Sample 10
Compound
Acetylene
Propylene
Chloromethane
Vinyl Chloride
1,3-Butadiene
Bromomethane
Chloroethane
Methyl ene Chloride
trans-1,2-Dichloroethylene
1,1-Di Chloroethane
Chloroprene (A)
Bromoch I oromethane
Chloroform
1,2-Di Chloroethane
1,1,1-Tri Chloroethane
Benzene
Carbon tetrachloride
1 , 2-0 i ch I oropropane
Bromodi chloromethane
Trichloroethylene
c i s- 1 , 3-D i ch loropropy I ene
trans- 1,3-0 ich loropropy I ene
1 , 1 ,2-Tri Chloroethane
Toluene
D i bromoch I oromethane
n-Octane
Tet rach I oroethy I ene
Chi orobenzene
Ethylbenzene
m/p-Xylene/Bromoform
Styrene
o-Xylene/1,1,2,2-Tetrachloroethane
m- D i ch I orobenzene
p- D i ch I orobenzene
o-O ich I orobenzene
8/24/93
1721
8/27/93
1751
9/10/93
19000
9/10/93
1900R
9/10/93
19010
Concentration, ppbv
<1.00
5.60
<0.20
<0.20
0.22
<0.20
<0.10
<0.11
•(0.04
<0.04
<0.06
<0.003
0.09
<0.04
1.73
1.40
0.26
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
4.63
<0.001
<0.03
0.19
<0.02
0.50
2.52
<0.02
1.58
<0.02
<0.09
<0.02
<1.00
(0 7.52
<0.20
<0.20
(M) 0.31
<0.20
<0.10
3.28
<0.04
<0.04
<0.06
<0.003
CD 0.28
<0.04
CO 4.07
(0 3.09
CO 0.26
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(0 15.18
<0.001
<0.03
CO 0.74
<0.02
CO 1.47
(0 7.08
0.55
(0 3.16
<0.02
<0.09
<0.02
(L)
(H)
CM)
CO
CH)
CH)
CO
(H)
CM)
(H)
CO
CH)
CO
<1.00
3.29
<0.20
<0.20
0.11
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
0.05
<0.04
0.60
1.20
0.26
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
4.69
<0.001
0.09
0.15
<0.02
0.49
2.32
0.22
1.20
<0.02
<0.09
<0.02
<1.00
CO 3.12
<0.20
<0.20
CH) 0.09
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
CO 0.02
<0.04
(H) 0.48
CH) 1.06
CO 0.23
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(H) 3.80
<0.001
CO <0.03
CO 0.11
<0.02
CO 0.34
CO 1.61
(0 0.28
CO 1.98
<0.02
<0.09
<0.02
<1.00
CO 3.62
<0.20
<0.20
CM) 0.15
<0.20
<0.10
<0.11
<0.04
<0.04
<0.06
<0.003
CO 0.05
<0.04
CO 0.52
CH) 1.02
CM) 0.22
<0.04
<0.001
<0.004
<0.04
<0.04
<0.04
(M) 4.03
<0.001
0.10
(0 0.14
<0.02
CO 0.38
(0 1.83
CH) 0.17
CO 0.88
<0.02
<0.09
<0.02
CO
CH)
(L)
(M)
(H)
CO
(H)
CO
CO
CO
CO
CO
CO
(H) High confidence level (N) Medium confidence level
R Replicate analysis D Duplicate sample
(A) Present but not quantitated due to interference
(L) Low confidence level
(Continued)
H14
-------
APPENDIX I
AUDIT RESULTS
-------
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
ATMOSPHERIC RESEARCH AND EXPOSURE ASSESSMENT LABORATORY
RESEARCH TRIANGLE PARK
NORTH CAROLINA 27711
November 15, 1993
MEMORANDUM
SUBJECT: NMOC Project Audit Results
FROM: Howard L.
Quality Assurance Support Branch (MD-77B)
TO: Neil 3. Berg, Jr.
OAQPS (MD-14)
The results of the audit canisters analyses by the Radian Corporation for the
NMOC Program are listed in the attached tables. The results for the propane samples
appear in Table No. 1. The percent difference (using means of reported data) for
both samples are 3.6% and 4.5* from the expected concentrations. The results for
the two multi- component hydrocarbon audit canisters are listed in Table No. 2. The
percent differences for the two samples were similar ranging from -16* to 17* for
NO. 1862 and -20* to 17* for NO. 1863. The data had a consistent negative bias.
The analyses for the same compound at different concentrations in the two canisters
showed good reproducibility and the overall results of the analyses of the audit
samples indicated good relative accuracy.
Attachments
cc: William J. Mitchell (MD-77B)
-------
Table No. 1 NMOC Project Audit Results
ppmC
Audit
Sample No. Reported1 Expected Difference. *
1863 • 1.16 1.12 3.6
1864 0.69 0.66 4.5
1 - Mean of data reported for four GC channels.
-------
Table No. 2 NMOC Project Audit Results
ppbC
Reported Expected
Ethylene -
Ethane
Propane
1-Butene
t-2-Butene
3-Methyl-1-Butene
1-Pentene
Isoprene
C-2-Pentene
2,2 Dimethyl butane
4-Methyl-l-Pentene
2,3-Dimethyl butane
3-Methyl pentane
n-Hexane
C-2-Hexane
2,4 -Di methylpentane
Cyclohexane
2-3-Dimethylpentane
2,2,4-trimethylpentane
methylcyclohexane
2,3,4 Trimethylpentane
2-Methyl heptane
Ethyl benzene
p-Xylene
o-Xylene
Isopropylbenzene
1,3,5 -Tri methyl benzene
1862
14.7
14.5
21.9
32.0
29.5
38.2
35.7
32.6
33.8
53.4
45.6
48.5
48.8
48.4
45.8
58.2
50.4
61.2
71.0
61.2
65.5
69.9
67.0
68.0
66.0
73.6
72.1
1865
27.8
23.2
41.6
58.6
55.1
70.7
65.5
60.4
61.7
96.4
83.3
89.1
90.8
89.4
84.3
108
92.9
113
131
112
121
128
125
128
124
139
138
1862
16.8
15.8
23.5
27.4
30.4
42.1
37.8
38.2
37.0
53.5
50.3
53.5
57.8
51.3
49.0
63.8
55.2
70.5
76.9
66.3
71.9
75.4
74.3
74.5
72.3
82.4
84.2
1865
30.9
29.1
43.2
50.4
55.8
77.4
69.6
70.4
68
98.4
92.5
98.4
97.0
94.3
90.0
117
102
130
141
121
132
139
137
137
133
152
155
Differences. *
1862
1865
-12
-8.2
•6.8
17
-3.0
-9.3
-5.6
•15
-8.6
•0.2
-9.3
-9.4
•16
-5.6
-6.5
-8.8
-8.7
•13
-7.7
•7.7
-8.9
-7.3
•9.8
•8.7
-8.7
-11
-14
-10 -
-20 -
-3.7
16
-1.2
-82
-5.9
-14
-9.3
-2.0
-10
-9.4
-6.4
-5.2
-6.3
-7.7
-8.9
-13
-7.1
-7.4
-8.3
-7.9
-8.8
-6.6
-6.8
-8.6
-11
NOTE: The following compounds were reported in the audit gas mixture but have not
been verified by ManTech: m-ethyl toluene and 1,2,3-trimethyl benzene.
-------
APPENDIX J
SPECIATED NMOC ANALYSIS METHOD
-------
RESEARCH PROTOCOL METHOD FOR
ANALYSIS OF C.-C., HYDROCARBONS IN AMBIENT AIR
3Y GAS CHROMATOGRAPHY WITH CRYOGENIC CONCENTRATION
P'repared by
Robert L. Se11 a
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
and
Dona Id A. Cox
Quality Assurance Data Services, Inc.
Boone, North Carolina 26807
Prepared for
U.S. Environmental Protection Agency
Atmospheric Chemistry and Physics Division
Atmospheric Sciences Research Laboratory
Research Triangle ParK, North Carolina 27711
SEPTEMBER 1988
-------
Revision No.
Date: 9/21/d3
Page:1 of 41
RESEARCH PROTOCOL METHOD FOR
ANALYSIS OF C2~C12 HYDROCARBONS IN AMBIENT AIR
BY GA3 CHROMATOGRAPHY WITH CRYOGENIC CONCENTRATION
Robert L. Seila
Author - User
William A. Lonneman
Author - User
Ronald K. Patterson
ASRL QA Officer
Approva 1s
Date
St.
Date
Date
-------
Date : 9/21/Ss
Page: 2 of 41
DISCLAIMER
The Research Protocol/Method ( R P M } described herein s n o u 1 a
not se interpreted as a generally accepted, standard or
equivalent method or procedure. This RPM was developed for
use within the Atmospneric Sciences Researcn Laboratory of
EPA and m.ay not be applicable to the needs of other
organizations.
-------
A 3 .1 ** - .-. _ r «, - ?. ? M - ~ ; 2
Revision No. 1
Sate : 9/21/88
Page : 3 of 41
1.0 SCOPE AND APPLICATION
This recommended method is intended for analysis of
C_-C12 hydrocarnons (HC) in ambient air. The metncc's
minimum quantification limit (MQL) is 0.12 ppb carbon; tne
metnod's minimum detection limit (MDL) is 0.04 ppb caroon.'
The MQL and y.DL were determined by the method described cy
Knoll (reference 1).
2.0 SUMMARY OF METHOD
A known volume . of gaseous sample is passed throuqr. a
cryogenicaly cooled trap, cooled with liquid oxygen or
liquid argon, cryogenicaly cooling traps out C and heavier
hydrocarbons without trapping methane. The trap containing
the condensed HC's is warmed with hot water and its contents
injected into a gas chromatograph (GC) capillary column
where separation of the C -C . hydrocarbons takes place.
Detection of the hydrocarbon is by flame-ionization detector
(FID), and the resultant peaks are quantified and
by an electronic integrator.
recorded
3.0 DEFINITIONS
3.1 Accuracy - The degree of agreement of the measurements
with the true value of the propane Standard
Reference Material (SRM) measured.
3.2 Precision - The repeatability of propane measurements
from the same canister under essentially
the same conditions.
4.0 INTERFERENCES
Any hydrocarbon compound that elutes with the same
retention times as any of the C2~Ci2 hydrocarbons and
responds to flame lonization detection will interfere in
this method.
5.0 PERSONNEL REQUIREMENTS
The researcher using this procedure is expected to be
familiar with gas chromatographic practices and able to
operated the instrument following the manufacturer's manual.
Operator requirements will include daily startup procedures,
instrument sensitivity adjustment, maintenance schedules,
and other manufacturer's recommendations.
-------
v * 5 * —
Date: 9/21/55
Page:4 of 41
6.0 FACILITIES REQUIREMENTS
No special laboratory facilities are required.
7.0 SAFETY REQUIREMENTS
The caliaration standards, collected sample, and most
laboratory reagents used in tnis method pose no hazard to
t r. e researcher if normal laooratory safety practices are
followed. Eye and hand protection are required wnen using
liquid nitrogen and argon or other cryogens. Comoustion is
possiole when using liquid oxygen, and its contact with all
flammable materials must be avoided. In addition, electrical
connections can also pose a hazard.
The American Chemical Society (ACS) guideline regarding
the safe handling of chemicals used in this method is
required.
7.1 EPA Safety Regulations
Information on EPA Safety Regulations are included in
text.
7.2 Vacuum Systems
See page G9 of the EPA/RTP Safety Manual (ref. 2) for
precautions.
7.3 Heated Surfaces
The GC infection ports, column, column oven, and
detectors are maintained at temperatures high enough to
cause burns. The researcher should exercise caution to
avoid contact with these surfaces.
7.4 Immersion Heater
WARNING - The immersion heater must always be immersed
in water, otherwise very high temperatures to be reached
with the possible ignition of combustible materials and
reduction of the operating life.
7.5 Compressed Gases
See pages F14 through F18 of the EPA/RTP Safety Manual
(ref. 2) for safety precautions. The following are specific
safety requirements for this method.
7.5.1 £££[££££.£
Hydrogen gas cylinders used for FID fuel are- not
permitted in the RTP Tech Center. Hydrogen cylinders and
tneir regulator must be secured outside the building, and a
stainless steel pressure line run into the laboratory.
-------
ASRL-AC?"-?. PM--22
Revision NO. 1
Dace: 9/21/33
P -e : 5 of 41
7.5.2 Cryogenc Liquids
See pages r 1 8 througn F20 of the EPA/RTP Safety Manual
(reference 2) for precautions.
7.5.2.1 Liquid Oxyoen_^i f _used|
£!£ " Strong oxidant. Vigorously promotes
comoustion. Avoid contact with all flammable materials.
Containers, lines, valves, and vents must" be free of oil and
grease. May cause severe frostbite. Wear eye and hand
protection .
7.5.2.2 LI cuid_N,i trogen and^L^gu^d^Ar oon^l^ f ^us eg )
WA = "!£JG - Cryogenic fl_ May cause E ?re fros- ?.
w o -i r e-. and hand protect n . Use witr. :dequate . z~
v tili .n. Keep contact -ith air to a m. .mum to /oi.
b _ . 1 d u :; : liquid oxygen (see above).
8.0 APPARATUS AND EQUIPMENT
T sect.on descries the instrument requirements for
this me..iod.
8.1 Gas Chromatograph
The gas chromatograph is equipped with a temperature
ogrammed oven that holds the separation column, flame-
nization detector (FID), and electronic integrator. This
.-thod uses an HP 5380A Gas Chromatograph with the following
^pacifications:
8.1.1 Gas Chromatograph Column
Type: fused silica capillary column.
Diameter: 0.32 mm ID.
Length: 60m.
Liquid Phase: DB-1 bonded liquid phase (J&w Scientific
Inc., Folsom, <~ '.if.)
d Phase Thic -ess; 1.0
-------
n e v -. s . 3 n NO.
Date: 9/21/sa
?age:6 of 41
8.1.2 Inlet Svstem
The inlet system is illustrated in Figure 1. The
automatic six-port gafe sampling valves ( V4 and V5, Figure 1)
are located on an aluminum block whicn is temperature
regulated. All other valves are at ambient temperature.
3.1.2.1 Conn ec 1 1 gn^o^^I^n^j.. e^ti_.S^s-t.emjii|t.o:_Co 1 umn
A 5" length of l/4in. x 0.75 mm OD glass tube
( Supe Ico , Inc . ) is used to connect the gas sampling valve -to
the column. At the value end of the glass tube, there is a
1/4-in to 1/16-in Swagelok S3 reducing union; at tne
column end is a 1/4-in to 1/16-in specially modified
reducing union (Supelco, Inc.). Grapni te /Vespel ferrules
are used .
8.1.3 T£££
The sampling trap is constructed of clean,
chromatographic grade, 3.2 mm (1/8 in) OD stainless steel
tubing, 16 cm in length, which is bent into a U-shape
approximately 7 cm from each end so that the U is approxi-
mately 2.2 cm in width. Clean, untreated 60/80 mesh glass
beads are poured in the U tube to a height of approximately
3 cm. Silanized glass wool is used as a plug to the last cm
of both ends. l/16"-l/8" unions are added to each end for
connection to the gas sampling valve.
8.2 Mass Flow Meter
A thermal conductivity mass flow meter (Ml, Figure 2!
(TYLAN Corp., model FM 360, 0 to 500 standard cm3/min or
equivalent) is used to measure the flow rate through the
cryogenic trap. See the following ASRL-ACPD-RPM- ? ? ? for mass
flow meter operation instructions.
8.3 Pressure Gauge
A precision Bourdon gauge (PI, Figure 1), with a range
of 0 to 200 Torr (absolute), is used. A gauge witn a range
of 0 to 400 Torr is also acceptable.
8 . 4 Vacuum Pump
An oil-less diaphragm pump (such as Thomas model
2106CA13-51 5-2 ) is used to evacuate the inlet system.
CAUTION ; Due to the possibility of contamination,
oil-sealed vacuum pumps should not be used.
8.5 Tubing and Connectors
All tubing is chromatographic grade stainless steel.
All connections are stainless steel compression tune
fittings (Swagelok ' or equivalent).
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A S R 1 - A C ? 0 - H ? M - : C 2
Revision No. 1
Date: 9/21/83
Page:? of 41
8.6 Regulators for compressed gases
Carrier c - s, hydrogen, and air delivery pressures are
controlled by wo-stage regulators mounted at the tank.
The H regulator is outside of the building
at R 7 ? . Other gases have regulators on tr.e
NOTE :
inside line.
CAUTION; Due to the possibility of contamination oy
organic materials, only regulators with
stainless-steel diaphragms should be used.
8.7 Immersion Heater
An immersion heater is used to heat a water oath -.at
heats tne trap, volatilizing the cryogenically tr pea
gases.
9. REAGENTS/MATERIALS
All gases used to o p - - a t e the GC system are high
quality grade and may vary in specifications witn
manufacture. Instrument calibration gases are obtained from
the National Bureau of Standards (NBS) and are referred to
as Standard Reference Materials (SRM). Use of reagent grade
chemicals for all dilutions and standards materials is
recommended.
9.1 Gases and Cryogens
The following is recommend for use with this method.
9.1.1 Helium Carrier Gas
High purity, minimum purity of 99.995 percent helium
carrier gas is best. Bureau of Mines.
9.1.2 Detector Air
Linde zero grade with total hydrocarbons <1 ppm, -r
equivalent.
9.1.3 Detector Hydrogen
Prepurified grade 99.99 percent pure or equivalent.
9.1.4 Detector Makeup Nitrogen
Prepurified grade 99.99 percent pure (or equivalent!.
9.1.5 LjLgujLd^Niitrogen_4_for GC oven cooling!
Commercial grade acceptable.
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Revision No.
Date : 9/21/88
Page: 3 of 41
9.1.6 LiQUi.dOx vgg.". __ L°g cooling)
Commercial grade acceptaole.
9.1.7 Liguid^Ar ggn _ (_,fqr trap cocking)
Liquid argon may be used instead of liquid oxygen for
trap cooling. Althougn liquid argon is more expensive,
it is inert, and its use eliminates tne oxidant hazard
associated with liquid oxygen. Commercial grade i-s
acceptaole.
9.1.8 ?ropane__in Air (for calibration)
NBS SRM 1665, 3 pprn (nominal) propane in air.
9.1.9 Instrument A ir_ Vacuum
The six-port gas sampling valves require clean filtereu
air at 350 kPa (35 psig) and a vacuum of approximately
20 in Hg for operation.
10.0 SAMPLE/SAMPLING PROCEDURE
This RPM is generally limited to the laboratory
analysis but could also be used for field analysis. Field
sampling and canister preparation procedures are coverea
separately (See reference 3.). Canister containing tne
sample are connected into the system as shown in Figure 1.
11.0 CALIBRATION AND STANDARDIZATION
11.1 Mass Flow Meter Calibration
For calibration see ASRL-ACPD-RPM XXX
11.2 Pressure Gauge Calibration
For calibration see ASRL-ACPD-RPM XXX
11.3 Gas Chroma tograpn Calibration
To perform a calibration in the parts per billion
carbon (ppbC) range, the following procedure is utilized:
11.3.1 Instrument Opt ini zat ion
A propane in air sample should be first analyzed and
adjustments made to the carrier gas linear velocity such
that the propane peak elutes at 3.105 mm (3 mm 6 sec)
following injection. Using the capillary column and
temperatures specified in this document, these C2~ci2 HC
compounds should elute in the order of the retention tines
-------
given in Table 1. (This assumes that
rate is pressure controlled). The
sr.ould be determined by preparing
sa.-ples of eacr. compound and depends
carrier flow rate, column temperature,
Revision No. i
Date: 9/21/88
Page:9 of 41
the carrier gas flow
actual eluting times
and analyzing known
upon column length ,
etc.
The flame-ionization detector and air flow rates
adjusted ac- rding to the manufacturer specifications
prope oper. .on and op-
flow- tes f r the HP5;
400 c /nun .for air.
are
for
-.urn signal to noise ratio. These
5 are . cm /nun for hydrogen . and
11.3.2 Calibration Using Propane
respon of the is assumed to be linear with
resp . o the number c rarbon atoms present in the
dete; compou:.^ (referer. 3). Thus, it is convenient to
measu. -ompound peak concentration (cone.) in terms of
parts- -billion-carbon (ppbC) where
Conc.,ppbC » (number of carbon atoms in compound)(Cone.,ppb)
For a fixed sample volume, the concentration is
proportional to the area under the chromatographic peak.
The area u-.ier the chroma tographic peak is converted to ppbc
concsntra ~ns by "he integrator by the following
ca.c-lati- .
Area
- e r i m e r.
same
c-.ibratiu
SRM propane
by :
Cone., ppbC
s given in
.y d -.ermined
»1ue of k i
ions .ant k is
(k) (Area)
•egrator counts and k is an
ibration constant (ppbC/count).
used for all compounds. The
Determined by analysis of an NBS
in air standard. The value of k is then given
oC/count)
3JCgnc.LtjBS Standard Prgpane^ppm ) ( 1000.
Median Area Count
Three to five concentration levels of the standard are
needed to generate a suitable calibration curve. Two to
three repeated sample injections per calibration level are
made. Averaged values of K are calculated and recorded in
the laboratory notebook, and the mean or median value taken.
Example are given in Exhibit 1. below.
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Date: 9 / 21/S6
Page : 10 of 41
EXHIBIT 1. LABORATORY NOTEBOOK RECORD
Calibration of the HP-5880A GC equipped with JSW DB-1
silica col umn
fused
Propane SRM: 2.83 ^ 0.03 urno le/mo 1 e ( ppm )
8490 ppb as caroon
Cylinder Number : FF18831, Sample Number 85-51-E
Sample Volume Equivalent
cm ,,_ . Propane Cone.
(ppbC)
la
Ib
1
2
c
a
2b
2
3
3
3
c
a
b
c
4a
4
4
b
c
4
4
4
3
3
3
2
2
2
1
1
1
20 f.
20
2
1
1
1
0
6
<
6
6
10
1
1
0
0
11
0
0
5 .
5 *
05
>, 8
'O
8
4
4
84
6
"e 6
6
4
4
4
2
°*-s2
2
3
3
3
2
90
90
90
6
6
6
4
24
2
1
1
1
4
2
2
2
7.
7.
7.
5
5
5
2.
2.
2.
5
5
5
5
5
5
Area of Response Factor
Propane Peak Cone/Area
28014.4
21191.7
14013.5
6361.1
0.303053
0. 300471
0.302922
0.309353
For this example: n-4 r2« 1.00 y-0.139 + 3.328X.
The mean (X) is 0.30395 and 0.30299 is the median and cone.
(ppoc) » 0.30048 x (area) * 0.042
where Y * cone, (ppbc), M « 0.30048, X - area, B « 0.042
and Y » M x + B
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Revision No. 1
Date: 9/21/86
Page:11 of 41
11.3.3 Call-ration_Quality Control
It is assume that the NBS propane standard is reliable
and valid for 2 years from date of purchase. Three to five
different concentrations of the NBS standard and one zero
standard are injected and the response factors are obtained,
as discussed above. _T_hep e r c e n t difference of the re_§_ponse
factor from the mean shall 5e~
d i f f erencfeis c ale tfl a t e d By :
"n~5more than 5%.The percent
% Diff. • ((Response - Mean)/Mean) x 100
For example:
Response Factor
.0.303058
0.300471
0.30292.2
0.309353
Mean Difference % Difference
0.29
1.14
0.34
1.78
0.30395
0.30395
0.30395
0.30395
0.000892
0.003479
0.001028
0.005403
Problems leading to a failure of the system to meet the
above requirement for the response factors must be corrected
before proceeding with the analysis. Minor variations from
the proper value are probably due to operator error.
However, large variations are probably attributable to
equipment problems.
It is assumed that the response of the FID is linea^
with respect to the number of carbon atoms present (i.e., r
should be _> .95). This assumption has been previously
verified ( ref . 3) for several hydrocarbon compounds. The
intercept should be not • s igni f i cantly different from zero at
a -0.05. A positive intercept implies propane contamination
Procedures for least-squares method
or nonlinear function to the calibration
in appendix J of reference 4. The
function is:
of fitting a 1 inear
data set are found
calculation for linear
b - n(£xy) - (£x)(£xy) - slope of fitted line
n(£x2) -
~ b(£x) " intercept of line
n-1
Where n - number of points,
- equivalent propane cone;
- area of propane peafc, and
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Revision No. .
Date: 9/21/33
Page:12 cf 41
Establishment of Standard Error of Estimate
After the calioration curve statistics has cee.n
calculated, the standard error of estimate or ( S e } can oe
calculated using:
3e
.Vnereas, a * y-intercept,
in tne calibration curve
=slooe and n* numner of ooints
A calibration will show variation in both slope and
intercept over tine and the SE will become larger. The Se"
has properties analogous to those of the standard deviation
and can be used as an indicator of curve degradation. For
data analysis, tn.e SE will be used to compute the upper and
lower limits for a single data observation (xoos) cased or.
tne calibration curve data using:
(a
(b xoos))
ta/2 x Se x
n(xobs - x)2
]2
Whereas ta/2 is obtained from the t distribution taale
at 95 % and the numoer of degrees of freedom is n-2.
11.3.3.2 £s ta b.11, shmen t of _ I,n 11 ^a 1 Wa r n_i ng_a^nd_Contr o lr_ 1,1,^1^ 1
After the initial calibration curve has been
constructed according to 11.3.2, reanalyze additional
samples of the low and high concentration standards.
Calculate the concentrations using the previously derived
calioration curve. Repeat this procedure until at least ten
determinations at each concentration level have been made.
Tnese additional high and low concentrations should as
collected on ten different days to provide a realistic
estimate of the method daily vanafii 11 ty. Calculate
standard deviation(s) at each concentration level (i.e.,
highest and lowest standard). Use the mean concentration as
the mean value (X) for determining the control limits. A
warning limit of X ^ 2s (95 %) and a control limit of X ^ 2s
(99 %) should be used.
-1.4 STANDARDIZATION
Information to be supplied at a later date.
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Revision :;o.
Date: 9/21/53
?age:13 of 41
12.0 ANALYSIS PROCEDURES
The analysis procedure is divided into two staaes:
Sample preparation and gas cnromatograpnic analysis.
12.1 Preparation Stage
The sample preparation steps are:
A. Adjust instrument gas flow rates.
1) Turn off the FID and FID heater - allow to cool
to room temperature.
2) Attach a soap film flow meter to the detector
chimney (see instrument instruction manual for
an illustration this apparatus.
3) Set the carrier gas (Helium) pressure to 20C
kPa
(29 psia).
4) Set the hydrogen pressure to 250 kPa (35 psia).
WARNING - Hydrogen delivery pressure should oe
less than detector air pressure.
Adjust the hydrogen flow to 2'8-30 cm /mm.
5) Set the detector air pressure to 300 kPa (,45
psia). Adjust the detector flow to 430 cm*/mm
+ 10 cm /mm.
6) Set the makeup nitrogen pressure to 300 k?a (45
psia). Adjust the nitrogen makeup and carrier
gas flow rate to a total flow of 30 cm /mm.
NOTE:The above flow rates were optimized for the given
column on an HP 5880A gas chromatograph with FID. If
another gas chromatograph is used, adjust tne flew
rates to obtain maximum sensitivity according to tne
manufacturers instructions for that instrument.
B. Adjustment of Carrier Gas Flow Rate
Verify that the carrier gas (Helium) pressure is
at 29 kPa. Refer to Section 1.11.1 for fine tunmg of
the carrier gas flow rate. Flow rate is dependent upon
the column head pressure.
C. Set Up Detector
With the flow rates adjusted as in Step A, remove
the adapter from the FID cnimney and reset tne detector
temperature to 250°C. Light the detector with tn?
ignitor and checK that comoustion is taking place.
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Date: 5/21/53
Page : 14 of -41
D. . Column and Value Temperatures
Detector * 250 C.
Initial Oven Temperature » -50 C.
Over. Temperature Programming Rate = 8 C/min
;13 mperature programming started 2 minutes after
tine of injection).
Final Oven Temperature * 200 C.
o
Six-Port Valve Temperature * 60 C.
12.2 Analysis Stage
.?reconcentration and injection of the sample is carries
out as follows. Initial conditions are these: V2 is
closed, vacuum pump is on, valves V3 and V6 are closed, gas
sampling valves V4 and V 5 are in the off position (Figure
1). Attacn the canister to be analyzed to tne inlet line.
Open, valves V3 and.V6 to evacuate the system. When the
vacuum gauge (PI) reaches 50 Torr or below, close valve v6.
The system should remain at or very near 50 Torr. A rising
pressure indicates a leak in the system.
The sample concentrating trap is immersed in a Dewar
flasK containing liquid oxygen (or liquid argon) sufficient
to cover most of tne "U" but placed so that the compression
fittings.are neither inside tne flask nor touching tne
liquid cryogen. If the fittings are inside tne f 1 a s .< ,
sample will condense in the fittings instead of on the trap.
This could result in either plugged carrier gas flow due to
ice forming in the fitting and/or improper sample plug
injection of the trapped hydrocaroons.
Open valve V2 and adjust valve VI to a flow of ICO
cm3/min, using mass flow-meter Ml. When the pressure gauge
(PI, Figure 2) is at 60 Torr, actuate valve V4 (V4 is
switcned to one direction, see Figure 2). Adjust flow rate
oack to 100 cm /mm, using valve VI, if necessary.
When PI reads 140 Torr, inject sample onto column cy
actuating valve V5 (Figure 3), removing liquid oxygen flas*
from trap, immersing the U-trap in the hot water bath, ana
pressing start button on electronic integrator (and GC, if
needed); deactivate valve V4 (Figure 3).
CAUTION: It is extreme 1y' important that V5 be closed before
removing the liquid oxygen flask from the trap.
Failure to observe this sequence will permit lignt
hydrocarbons to be vented before injection.
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3 e v i s i o r. s c . 1
Date : 9/21/35
Page : 15 of 41
At a time of 2 minutes into the run, deactivate valve
V5. Stop the run manually or automatically after
approximately 15 minutes or when the last compound of
interest elutes. Identify sample p e a * s c y their retention
tines, as determined in Section 11.3.2. An example
cr.ronatogram is shown as Figure 4.
At least one QC sample (Section 13.0) is run routinely.
Upon completion of the sample run, calculate and review the
2 C results to determine if there are any significant
differences. Any value falling out-side" the control limits
is indicative of a system proolem and r-equires corrective
action (Section 15.0) before continuing analysis of samples.
13.0 CALCULATIONS
Using the calibration constant (k) determined in
section 11.3.2, calculate the concentration of eacn compound
(peaiO as follows:
Concentration, ppoC « (k)(Area)
where the area is in integrator counts. Most integrators
may be programmed to perform this calculation and present
results directly in units of concentration.
13.1 AmbientiData
To calculate the upper and lower limits of the
concentration (i.e., Limits of prediction), the appropriate
formula to calculate the limits of prediction are given in
section 11.3.3.1
14.0 Data Reporting
The concentration of each C -C _ hydrocarbon snould se
reported. The Integra tor chart of sample and calibration
standard should be saved as a record of analysis. Data tape
from tne integrator computer system should be identified,
logged in the laboratory notebook, and stored. Sample run
report should be recorded in the laboratory notebook in tne
following format:
Day Month
Notes: (e.g., QC, Standard, Duplicate, Replicate, etc.)
12 !!!£ 2£Ii ££ii! PEAKS 21.il TAPS ( COMPARISONS!
Other forms of computer data storage should be noted
when they occur. It is recommended that all C2~C12
hydrocarcon pea* data be stored in a computer compatibil
format for ease of reporting and analysis.
-------
x e v i s i. z r. :,o. .
Date : 9/ 2 1 / o 3
Page : 1 6 of -. i
15.0 Corrective Action
Corrective action sr.ouid oe t a « e n whenever any of trie
following are ooserved:
o Internal 3 C cnecxs exceeding limits.
o Variation of response, as snown oy more than a * 15
percent cnange in calioration constant.
o Variation of ^0.2% of retention times for specific
peaKS .
o Poor or ill-shaped pea/:s (wide or snallow).
o Fused or comoined peaks.
o Presence of other pea*s wnicn elute with the compounds
of interest (C--C.. hydrocarnons ) .
o Integrator failure to correctly recognize start time,
stop time, or to correctly determine baseline and peak
areas.
Determination of tne proper corrective action requires
a Knowledge of chromatograpnic principles and instrumenta-
tion beyond the scope of tnis document.
Based on repeated analysis of NBS SRM propane in air
Standards over a one year period, the variation of the
calibration Constant (k) was found to be within ^ 15 percent
of tne initial value. Replicate analysis of ambient air
samples for total nonmethane organic compounds (NMOC) using
a similar technique (reference 2) showed an analytical
precision of approximately ^ 12 percent. The precision for
C -C12 hydrocarbons should be similar. Method precision
will* be determine from replicate analysis of the RTI
canister or duplicate measurements made at concentration
levels representative of the range experienced oy routine
samples. Operator and daily instrument precision will be
determined from duplicate analyses of ambient canisters.
17.0 .1ETHOD ACCURACY
Due to the lack of suitable NBS standards for the range
of hydrocarbons, the accuracy for analysis of all hydre-
caroons (C-C.) cannot be directly determined using tne
propane standard. For tnis method, the propane SRM will- ce
used to determine the accuracy. External audits are an
essential part of the method ^A program and performance
audits say oe used to determine instrument accuracy.
-------
^3 0 ^AT'Y ^'J A L ~ T v
*. w • w •• rt * •* i >/ U rt ^ * 1 *
ASRL-ACPD- .=.?.:•
Revision r; o . ;
Date: 9/21/83
?age:17 of 41
This section specif; -s the dai y QC program and aiscus-
ses responsibilities f evalua" on of the QC data.
Calinration QC is diSv.ssed i.- section 11.3. These
procedures require real-time 3 v i e w of analytical
performance oy the analyst, and QC review of all data
directly after input to the data case.
13.1 QC Checks and Frequency
One -sample -f NBS S"M propane • air should •= anal-/zed
attheoeginni ofeacr :ay that ample .sr One
moreQC cams: s will .e r-n ngth s = ng
Duplicates of tne QC canisters .1 be run ce-_
procedural or operator oias as .art or th= -eal-t
with in-day QC review. Replicates will be run .0 d e t e . .
variaoility in the instrument performance (day to day) ana
to determine the instrument precis
IB . 1 . 1 Duplicates
Positive or negative differences of duplicate measure-
ments are indicative of gross method error or procedural
in-run operator bias. The data obtained from duplicate
- =>asurements will be used to determine when the GC is out of
.atistical control. The percent difference of the results
-nould oe no more t n a n 10%.
The standard deviations used to generate the-initial QC
control limits (section 11.3.5) can be used to evaluate to
the duplicate differen ces initially. Duplicate measurenents
should agree within 2 %/2" s (or 2.83 times the s). After a
reasonaole period of time (i.e., ten or more duplicate mea-
surements), the following procedure for calculating new du-
plicate control limits should be performed.
For duplicate measurements x and y, where x and y arc
the ooservation in the order obtained, the difference d = x
-y is calculated and recorded. To determine duplicate con-
trol Limits after ten to fifteen sets of duplicates, tne
formula for s is:
d2/2k
where k is tne number of subgroups or pairs of duplicate
analyses. The average range (3) for duplicates is:
Control limits can be reestaolished based on the number
of duplicates performed over a period of time. Control
charts for differences and ranges can be constructed by ^ 3
k/"~2s with the central line being 0; the limit for the range
can be obtained from D4R (Ref. 4, Section H for 04 value).
-------
=t e v i 5 i c - .. - .
3 a t e : = / 2 1 / = =
41
? a g e : 1 a of
18.1.2 3e_pl. ia te Measurements
Positive or negative differences of analysis replicate
measurements with respect to tne initial value measured are
indicative of a nethod error or operator day to day cias.
T T. e data ootained from t n e s e measurements will be use to
determine w.-en the measurement system is out of statistical
control and to determine analytical precision.
Historical replicate data must first S3 conamed as
necessary to develop an assessment of precision that defin-es
tne expected standard deviation of replicates. The standard
deviations used to generate the QC. control limits (section
11.3.5) can oe used initially. Recent and historical pat-
terns are essential to evaluating the control status using
replicate r.easurenents. The number of replicate measurements
needed for an experiment will be determined on the Histori-
cal or recent variaoility of the system.
Given a series of repeated measurements (R1,R2, Sn),
the formula for s is:
D) 2/2k
where k is the number of replicate pairs and D is difference
between the pair values. It is important that all repli-
cates are determined under identical conditions and that tr.e
distribution of repeated results is approximately "r.ormal"
to estaolish the control limits. It is recommended tnat tr.e
standard deviation and range' charts be used and the Control
limits are set at 3s and 2s . A ratio greater than 1.3
between-run (replicates) and with in-run (duplicates) snouid
o e considered "statistically significant" and corrective
action taken. Reestaolish new control limits wnenever
instrumental operation conditions are varied, calibrations
performed, or QC constrictions are cnanged.
1 6.1 . 3 Control Chart for QC_Canisters/Samples
The measured value of the yC sample is plotted on tne
control enarts for the QC sample concentration differences
or as an percent difference. The measured value (ppoC)
snouid not differ by more than two times the standard devia-
tion of NBS-certifled value (ppb). If this occurs, -the
system should be cnecked for proper operation. If tne
condition persists, or if two successive QC measurements are
outside of tne * 2s limits, or if the measured value
exceeds tne upper or lower control limit (three standard
deviations, section 11.3.5), the detector should be cleaned
and checked for correct operation. If the response remain;
outside the upper or lower control limit, then the
instrument snouid be recalibrated and/or corrective action
taken. Plot the data obtained from the QC measurements on a
control chart for routine assessment of analytical aias anc
orecis i on .
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A 5 Ir L - A C ? D - ?, ? X - „ ~ 2
Revision :,' 3 . i
Date: 9 / 2 1 / s 3
Page:19 of 41
13.1.4 Control Chart fcr Zia_i ly__._;3£ .. SR.M
The measured value of the daily MBS SRM propane sarr.sle
is plotted on a control chart. The measured value (ppcC;
snould not differ oy .rr.ore than two tines the standard
deviation of NBS -cert i f led value (ppb) If t.iis occurs, the
systam snould oe cnecked for proper operation. If the
cor.aiticn persists or tne measured value exceeds the u 3 p e r
or lower control limit (three standard deviations, section
11.2.5), corrective action snould be performed before any
further sample analysis. This includes checking the sample
oreconcentration procedure and the GC analysis system for
proper operation. If the response remains outside the upper
or lower control limit), then the instrument sncald =e
recalibrated.
13.2 Performance Evaluations
P ticip :on . perfc rr.ance evaluation studies is
recomm ied : this -ethod. The samples used for tnese
performance audits should contain the species of interest at
concentrations within the normal working range of this
metnod. The true values should remain unknown to the
analyst until the end of the study to prevent operator bias.
IS.3 Systems Audits
This section contains the recommended procedure for
performing an system audit for this method. The need for
and scheduling of systems audits will be determine by t ne
Project Officer. The -asic scope of the system audit will
be:
1. to verify the adherence to this researcn
protoco1/method; and
2 . to verify the data flow and archiving process used
for the computerized data base.
Orga .zations performing systems audits should review
the follc~ing sections and the audit questionnaire (Appendix
A). It is recommended that the independent audit plan oe
comparea to this document and differences noted. In all
cases, methods for assessing the data quality for tr.is
method must be approved by tne organization being audited
prior to starting the audit.
18.3.1 Audit Plan
1. Meet with organizational personnel, identify *ey
personnel, identify the purpose of the audit, a r. ^
review audit plan and questionnaire.
2. Collect all QC Documentation (i.e., QC Charts,
forns, notebooks, etc.) and data oase print outc.
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.-. e v i 5 i c r. ., - . .
Date: 9/21/35
Page:; 2 3 of 41
2 . Perform audit of sample analysis.
4. Perform a u a 11 of sample data processing
activities.
5. Perform audit of data validation.
o . Perform audit of data case.
7. Complete audit questionnaire.
B. Hold audit review meeting and critique audit
findings. ;;a*e corrections to audit findings or
questionnaire if required. Discuss corrective
action plans, if appropriate.
It is suggested that data quality mignt be assigned zr.e
cf three levels according to t n e following guidelines:
1. Unknown quality - a vital piece of QC data is
missing or can not be verified.
2 . Questionacle quality - generally all data and
documents are in g'ood order, but a secondary iter.
needed to completely characterize t n e data is
missing, e.g., a control chart to demonstrate t n a t
the method was in control over a given tine
interval.
3. Known quality - all documentation is i r. order,
with data traceable from the final report to ine
date and time of the analysis.
18.3.2 Documents
The following documents will be reviewed at the tir.e of
the auait:
1. Laboratory notebooks or forms for method.
2. •" C charts for duplicates or replicates
3. At least five previous calibration curves.
4. Instruction manuals and related SOP's or RPM's
5. Documents relating to quality of materials used.
6. All documentation for GC computer, data
validation, and data storage
7. All documents related to compliance with ASRL f*A
plan requirements.
-------
ASRL-ACPD-RPM-3C2
Revision NO. 1
Date: 9/21/98
Page : 21 of 41
19.0 DATA VALIDATION
Data will be critically reviewed to identify and
isolate errors. Data validation occurs at each step of the
measurement process, beginning with the GC electronic.
integrator. Once data enters a computerized storage and
retrieval system, a more detailed screening process is
required.
20.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT
Laboratory QC data and aud; results are reported
quarterly. A report will be submitted to management anytime
for one or more of the following:
1. When a s: -. ificant discrep ry is noted and an
examinatic. of the analytica. procedure reveals
not apparent reason for the discrepancy;
2. v;hen the. analysis comparing the commercial and NBS
standards indicates serious deterioration of the
commercial standard; and
3. When audit results or out-of-control situations
are noted that indicate that the method is
producing data of unknown quality.
21.C PREVENTIVE MAINTENANCE
• o be de .ned at later •? a t e
-------
Revision No. 1
Date : 9/21/88
Page : 22 of 41
REFERENCES
1. Knoll, J. E., Journal of Chromatographic analyses.
Vol. 23, p. 422, September 1987.
2. EPA/RTP Safety Manual, Support Services Office,
Environmental Research Center, Research Triangle Park,
N C 27711.
3. Dietz, W. A., Journal of Gas Chromatography, Vol. 5,
pp. 68-71 (1967).
4. Quality Assurance Handbook for Air Pollution
Measurements, Volume 1. Principles (EPA-60Q/9-76- 005
Dec 1984).
GLOSSARY
BIAS
- An error in a method that systematically distorts results
REST TO BE DEFINED LATER
-------
ASRL-AC?D-S?M-::2
Revision No. 1
Date: 9/21/35
Page:23 of 41
APPENDIX A
TABLE OF
HYDROCARBON IDENTIFICATIONS AND RETENTION TMES
-------
TABLE 1.
Revision No. 1
Date: 9/21/88
Page:24 of 41
HYDROCARBON IDENTIFICATIONS AND RETENTION TIMES
HP5880 Calibration Table
CAL.
NO.
0
102
104
106
108
110
112
114
116
118
120
122
124
126
125
130
132
134
136
138
140
142
144
146
148
150
152
154
156
158
160
162
164
166
163
170
172
174
176
173
180
182
134
186
133
190
192
194
196
198
200
Ret.
Time
0.000
1.530
2.988
3.373
4.017
5.105
5.661
6.286
6.937
8.739
9.652
10.036
10.410
10.737
11.116
11.256
11.551
11.994
12.486
12.631
12.348
13.031
13.369
13.643
14.062
14.240
14.406
14.605
14.398
15.177
15.523
15.631
15.980
16.320
16.437
16.592
16.916
17.316
17.507
17.762
13.343
18.602
18.897
19.170
19.257
19.408
19.701
20.001
20.180
20.330
2C.47Q
REF
0
0
0
0
0
1
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0 i
CT:
0
Compound
Name
Uncalibrated
ETHYLENE
PROPENE
Unknown
OLEFIN
ISOBUTANE
Unknown
BUTENE-1
t-2-BUTENE
C4 OLEFIN
C5 OLEFIN
C5 OLEFIN
n-PENTANE
t-2-PENTENE
C5 OLEFIN
C5 OLEFIN
C6 PARAFFIN
C6 OLEFIN
C6 PARAFFIN
CYCLOPENTANE
C6 QLEFIN
C6 OLEFIN
C6 OLEFIN
C6 OLEFIN
1 n-HEXANE
C7 OLEFIN
C7 OLEFIN
C7 OLEFINH
METHYLCYCLOPENTANE
C7 PARAFFIN
C7 OLEFIN
- BENZENE
OTCLOHEXANE
2-METHYLHEXANE
C7 PARAFFIN
3-METHYLHEXANE
C7 PARAFFIN
C8 OLEFIN
C8 PARAFFIN
C8 OLEFIN
C8 PARAFFIN
C8 PARAFFIN
2,3,4-TRXMETHYLPENTANE
C8 PARAFFIN
C3 PARAFFIN
C8 PARAFFIN
C8 PARAFFIN
C8 PARAFFIN
C8 PARAFFIN
0* n-OCTANE
C9 PARAFFIN
CAL
NO.
101
103
105
107
109
111
113
115
117
119
121
123
125
127
129
•131
133
135
137
139
141
143
145
147
149
151
153
155
157
159
161
163
165
167
169
171
173
175
177
179
181
183
Ret.
Time REF
2.013
1.960
3.105
3.540
4.450
5.423
6.115
6.462
7.500
9.398
10.000
10.272
10.560
11.008
11.172
11.505
11.672
12.252
12.490
12.763
12.957
13.097
13.440
13.850
14.164
14.317
14.543
14.750
15.085
15.281
15.657
15.878
16.056
16.358
16.507
16.785
17.007
17.358
17.667
17.984
18.407
18.816
0
0
0
0
Q
0
0
1
0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Compound
Name
ETHANE
ACETYLENE -
PROPANE
PARAFFIN
OLCFIN
Unknown
2-METHYLPROPYLENE
n-3UTANE
C-2-BUTENE
ISOPENTANE
•1-PENTENE
2-METHYL-1-3UTENE
ISOPRENE
C5 OLEFIN
C-2-PENTENE
C6 PARAFFIN
2, 2-DIMETHYLa'JTANE
C6 OLEFIN
C6 OLEFIN
2. 3-DIXETHYL3UTANE
2-METHYLPENTANE
C6 OLEFIN
3-METHYLPE!.'TANE
C6 OLEFIN
C7 PARAFFIN
C7 OLEFIIJ
C7 OLEFIN
C7 OLEFIN
2,4-Di:iETHYL?E:,TANE
C7 OLEFIN
C7 PARAFFIN
3, 3-DI.1ETHYLPE.NTANE" -
C7 OLCFIN
2.3-DIMETHYLPENTANE
C7 OLEFIN
C7 PARAFFIN
2, 2, 4-TRIMETHYLPENTANE
n-HEPTANE
C8 OLEFIN
METHYLCYCLOHEXANE
C8 PARAFFIN
C8 PARAFFIN
185 19.022 -1 TOLUENE
187 19.202
189 19.361
191 19.585
193 19.905
0 C8 PARAFFIN
0 C3 PARAFFIN
0 C8 PARAFFIN
0 C8 PARAFFIN
195 20.109 0 C8 PARAFFIN
197 20.250 0 C8 PARAFFIN
199 20.377 0 C9 PARAFFIN
201 20.662 0 C9 PARAFFIN
-------
TABLE 1.
ASRL-ACPD-RPM-002
Revision No. 1
Date: 9/21/88
Page:25 of 41
HYDROCARBON IDENTIFICATIONS AMD RETENTION TIMES (Continued)
HP5880 Calibration Table
CAL
NO.
202
204
206
208
210
212
214
216
218
220
222
224
226
228
230
232
234
236
238
240
242
244
246
248
250
252
254
256
253
260
262
264
266
268
270
272
274
276
278
280
282
284
285
286
238
290
292
294
296
298
22
22
22
Compound CAL
REF Name NO.
0 C9 P#RAFFIN 203
C9 PARAFFIN 205
C9 PARAFFIN 207
C9-PARAFFIN 209
C9 PARAFFIN 211
C9 PARAFFIN 213
C9 PARAFFIN 215
C9 PARAFFIN 217
C9 PARAFFIN 219
C9 OLEFIN 221
O-XYLENE 223
C9 PARAFFIN 225
C9 PARAFFIN 227
n-»ONANE 229 23
CIO PARAFFIN 231 23
CIO PARAFFIN 233
CIO PARAFFIN 235
CIO PARAFFIN 237
CIO PARAFFIN 239
CIO OLEFIN 241
n-PROPYL3EHZENE- 243
p-ETHYLTOLUENE- 245
C9 AROMATIC 247
CIO PARAFFIN 249 24
C9 AROMATIC 251 25
CIO OLEFIN 253
C9 AROMATIC 255
n-DECANE — 257
C9 AROMATIC 259
1,2, 3-TRIMETHYL3E:iZENE261
Cll PARAFFIN 263
CIO AROMATIC 265
CIO AROMATIC 267
CIO AROMATIC 269
CIO AROMATIC 271
26.960 0 CIO AROMATIC 273 27
Ret.
Time
20.827
009
172
277
425
596
842
140 0
322 0
462
601
733
860
034
243
455
635
824
940
107 0
212 0
336 0
578 0
694 0
979
122
320
520
,661
,909
,043
,218
.497
26.710
26.842
21.
21.
21.
21.
21.
21.
22.
22.
22.
22.
22.
22.
23.
23.
23.
23.
23.
23.
24.
24.
24.
24.
24.
24.
25.
25.
25.
25.
25.
26.
26.
26.
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Re-_.
Time
20.949
21.123
21.I23
21.369
21.524
21.744
21.973
22.235
22.415
22.518
683
785
940
174
305
0
0
0
0
0
0
0
0
0
0
0
0
27
27
27
27
27
23
23
28
23
142
227
421
680
809
040
116
193
360
28.623
28.730
28.923
29.120
29.270
0 Cll PARAFF.IN
275 27
Compound
REF Name
0 C9 OLEFIN
C9 PARAFFIN
C9 PARAFFIN
C9 -PARAFFIN
C9 PARAFFIN
ETHYLBENZEME
1 m&p-XYLENE
0 C9 PARAFFIN
C9 PARAFFIN
C9 PARAFFIN
C9 PARAFFIN
C9 PARAFFIN
C9 PARAFFIN
CIO PARAFFIN
CIO PARAFFIN
540 0 CIO PARAFFIN
706 0 CIO PARAFFIN
0 CIO PARAFFIN
CIO OLEFIN
0 CIO PARAFFIN
CIO PARAFFIN
m-ETHYLTOLUENE-
C10 PARAFFIN
0-ETHYLTOLUENE
CIO PARAFFIN
0 1,2,4-TRIrfETHYLaENZENE
0 CIO PARAFFIN
o C9 A? :MATIC
770 0 C9 A3CMATIC
972 0 Cll PARAFFIN
103 0 Cll PARAFFIN
0 CIO. AROMATIC
567 0 CIO AROMATIC
26.807 0 CIO AROMATIC
26.877 0 Cll PARAFFIN
0 Cll PARAFFIN
0 CIO AROMATIC
23
23
23
24
24
24
24
24
25
25
25
883
007 0
177
310 0
,447
,632
,852
,051
,217
,408
,597
25
25
26
26.379
26
,023
,181
0--l,2-DIMETHYL-4-ETHYLBEKZENEx277 27.363 0 CIO AROMATIC
0 CIO AROMATIC 279 27.601 0 Cll PARAFFIN
0 CIO AROMATIC . 281 27.769 0 CIO AROMATIC
0 l,2-DIMETHYL-3-ETHYLBENZEHE-283 27.953 0 CIO AROvlATIC
O" 1, 2^4 . 5-TETRAMETHYLBENZENE
0> 1,27^-TETRAMETHYLBENZENE,
CIO A=3XJVTIC 287 28.
0
0 CIO ARCilATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
,244 0 Cll PARAFFIN
289 20.763 0 C9 PARAFFIN
291 28.662 0 Cll AROMATIC
293 28.845 0 Cll AROMATIC
295 29.056 0 Cll AROMATIC
297 29.199 0 Cll AROMATIC
299 29.350 0 Cll AROJIATIC
-------
TABLE 1,
Revision NC. 1
Date: 9/21/88
Page:26 of 41
HYDROCARBON IDENTIFICATIONS AND RETENTION TIMES (Continued)
HP5880 Calibration Table
CAL. Ret.
Compound
NO. Time REF Name
300 29.570
302 29.840
304 29.939
306 3C.159
308 30.233
310 30.598
312 30.770
314 30.908
316 31.162
313 31.305
320 31.471
322 31.667
324 31.983
326 32.210
328 32.380
330 32.623
332 32.823
334 33.060
336 33.147
338 33.802
340 36.057
342 8.227
344 13.673
346 16.156
348 17.196
350 17.560
352 19.472
354 20.543
1 Cll AROMATIC
0 Cll AROMATIC
0 C PARAFFIN
0 Cll AROMATIC
0 Cll AROMATIC
C Cll AROMATIC
0 C12 PARAFFIN
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C13 PRAFFIN
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROilATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C4 OLEFIN
0 C6 OLEFIN
0 C7 OLEFIN
0 C7 OLEFIN
0 C8 OLEFIN
0 C8 PARAFFIN
0 C9 OLEFIN
356 27.550 0 CIO AROMATIC
358 30.307 0 Cll AROMATIC
360 30.660 0 Cll AROMATIC
362 31.752 0 C12 AROMATIC
364 15.617 0 C7 OLCFIN
366 13.080 Q C3 PARAFFIN
368
370 28.970 0 CIO AROMATIC
372 22.150 0 C9 PARAFFIN
374 23.460 0 CIO AROMATIC
376 13.520 0 CG OLEFIN
373 35.220 0 C12 AROMATIC
330 29.032 0 Cll AROMATIC
382 3.293 0 C3 PARAFFIN
334 7.206 0 C4 PARAFFIN
386 14.953 0 C7 PARAFFIN
333 19.150 0 C8 PARAFFIN
390 34.410 0 C12 AROMATIC
392 6.850 0 C4 OLEFIN
394 10.120 0 C5 OLEFIN
396 12.150 0 C5 OLEFIM
39S 21.460 0 C9 PARAFFIN
CAL Ret.
NO. Time
301 29.695
303 29.883
305 30.077
307 30.210
309 30.367
311 30.727
313 30.821
315 31.-070
317 31.253
319 31.383
321 31.617
323 31.924
325 32.095
327 32.340
329 32.530
331 32.718
333 32.923
335 33.098
337 33.450
339 33.817
341 7.340
343 8.350
345 15.493
347 16.637
349 17.399
351 18.260
353 20.063
Compound
REF Name
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 Cll AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C12 ARO.'IATIC
0 C13 PARAFFIN
0 C12 AROMATIC
0 C12 AROMATIC
0 C4 OLEFIN
0 C4 OLEFIN
0 C7 OLEFIN
0 C7 PARAFFIN
0 C8 OLEFIN
0 C8 OLEFIN
0 C8 PARAFFIN
355 27.487 0 Cll OLEFIN
357 28.505 0 CIO AROMATIC
359 30.444 0 Cll AROMATIC
361 30.980 0 C12 AROMATIC
363 31.877 0 C12 AROMATIC
365 16.860 0 C7 PARAFFIN
367 22.170 0 C9 PARAFFIN
369 13.310 0 C6 PARAFFIN
371 15.020 0 C7 OLEFIN
373 27.125 0 CIO AROMATIC
375 3.926 0 C4 OLEFIN
377 29.413 0 Cll AROMATIC
379 28.550 0 Cll AROMATIC
381 33.376 0 C12 AROMATIC
383 4.377 0 C3 PARAFFIN
385 12.409 0 C6 PARAFFIN
3S7 15.780 0 C7 OLEFIN
389 20.760 0 C9 PARAFFIN
391 7.580 0 C4 PARAFFIN
393 9.700 0 C5 OLEFIN
395 11.790 0 C5 OLEFIN
397 18.650 0 C8 PARAFFIN
399 21.890 0 C9 PARAFFIN
-------
ASRL-ACPS-RPM-002
Revision No. 1
Date: 9/21/88
Page:27 of 41
TABLE 1. HYDROCARBON IDENTIFICATION'S AND RETENTION TIMES (Continued)
HP5350 Calibration Taole
CAL.
NO.
400
402
404
406
408
410
412
414
416
Ret.
Time
23.
27.
32.
35.
25.
33.
9.
31.
30.
770
310
460
370
830
270
580
710
280
Compound
REF Name
0 CIO PARAFFIN
0 CIO AROMATIC
0 C12 AROMATIC
0 C12 AROMATIC
0 C9 AROMATIC
0 C12 AROMATIC
0 C5 OLEFIN
0 C12 AROMATIC
0 Cll AROMATIC
CAL Ret. Compound
NO. Time REF Name
401 25.630 0 CIO AROMATIC
403 27.850 0 CIO AROMATIC
405 34.590 0 C12 AROMATIC
407 13.140 0 C6 PARAFFIN
409 30.530 0 Cll AROMATIC
411 34.310 0 C12 AROMATIC
413 10.890 0 C5 OLEFIN
415 15.480 0 C7 OLEFIN
-------
Re v i s i cn NO. ;
Date: 9/21/38
Page : 28 of 41
APPENDIX B
GAS CHROMATOGRAPY
AUDIT QUESTIONNAIRE
-------
A S R L - A C ? 2 - S ? M - 0 : 2
Revision No. 1
Date: 9/21/88
? -- •: e : 2 9 of 41
YES NO
1) Does the technicia- ave a c- rent cop .f
the RPM at or near ir.e bench? ^^ ^^
2) Are gases traceaole to, at a minimum.
Research reagent grade gases? ___
3) Are calibration results within 5% of the
mean?
4) Are outlying standards rejected? And is
the rejection:
a ) documented?
b) explained?
c) reviewed? _„__ ___
r \re da standar
i) r .mmediatc... following the
ci-.oration?
o) within 2. 10* °f known value?
6} Are repeated measurements made of:
a) tne highes standard? _____
b) the lowest standard?
7) Have the standard deviations for:
a) the highest standard been computed?
b) the lowest standard been computed?
3) Have the initial control limits been
computed for:
a) daily standard me:surer its?
b) duplicate measure.-ents?
c) replicate measurements? ___
9) Are standards reanalyzed periodically?
10) Are any samples analyzed in duplicate? j
11) Are replicate samples analyzed?
12) Are QC samples analyzed?
-------
R e visio n No. 1
Date: 9/21/88
Page : 30 of 41
YES NO
13) Are QC sample control charts current? _^_
14) Are blinds analyzed?
15) Are audit samples analyzed periodically? _
16) Are the following control samples analyzed:
a) spikes?
b) • i nterlaboratory?
c) intralaboratory?
d ) old samples?
e) other QC samples? _
17) Are NBS SRM samples analyzed regularly?
13) Are accuracy measurements:
a) made on scheduled basis?
b) within RPM specifications?
19) Are precision measurements:
a) made on scheduled basis? ____
b) within RPM specifications? _
20) Is GC preventive maintenance performed as
required by RPM?
21) Were corrective action procedures implemented
asrequired? '
22) Are control charts and other QC records:
a) filled in an organized manner? _.
b) recorded in laboratory notebook?
23) Are computer printouts and reports spot-
checked and validated?
24) Have any of the following audits been
performed in this laboratory?
a) Systems Audit? ___ ___
b) Performance audit? ___ .-
25) Are internal QC reports prepared on a
timely basis to management? _
-------
Revision No. i
Date: 9/21/53
Page : 3 1 of 41
APPENDIX C
FIGURES, -FORMS AND
EXAMPLES
-------
A a n — ~ « w r - - .-. r .•! - „ „ i
Revision No. 1
Date: 9/21/88
Page: 32 of 41
TABLE 2. LEGEND FOR FIGURES 1, 2, AND 2
VI = stainless steel needle valve
V2' V3' and V6 » shut-off valves (a)
V4 and V5 » 6-port electrically actuated gas
sampling valve
(attached to HP 5330A Gas Chromatograph ) .b)
Ml « 0 to 500 cn3/min.mass flow meter
PI * 0 to 200 Torr Wallace and Tierman
Bourdon Gauge
(a) V2 is a stainless steel bellows valve on the
canister. V3 and V 6 are toggle valves* they may be
stainless steel or brass.
(b) The gas sampling valve used should be capable of
holding a vacuum down to 10 Torr for proper operation.
-------
TOGO COLUMN
GAS (He)
TRAP
3-WAY
TOGGLE
VALVE
»»
. ft c
«•* a *•
(^ o ••
VAC
-------
TO QC COLUMN
CARRER GAS (He)
TRAP
DEWAR FLASK
3-WAY
TOGGLE
VALVE
.. o
VAC. PUMP
o -i
o
ri
-------
. I •
TOGO COLUMN
CARRER GAS (He)
DEWAR FLASK
•V l/» iff )»
•• A r* I/I
.0 -O *• t
VAC. PUMP
O -I -»» O
•* •*• '
-------
ASRL-ACPG-aPM :
Status: Draft
Rtvislon: 9
Stptemo«r 1386
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Rational J&urttm of
Certificate of
Standard Reference Material 1665b
Propane in Air
(Nominal Concentration 3 ppm)
(Mobile-Source Emission Gas Standard)
This Standard Reference Material is intended for use in the calibration of instruments used for the analysis of
hydrocarbon in mobile-source emissions. It is not intended as a working standard, but rather as a primary
standard to which the concentration of the daily working standards may be related.
Propane concentration: 2.83 ± 0.03 ^mole/mole (ppm)
Cylinder Number FF-18831 Sample Number 85-51-E
The concentration of propane is relative to all other constituents of the gas. The uncertainty shown is the
estimated upper limit of error of the propane concentration at the 95 percent confidence level. This uncertainty
includes the inaccuracy of the gravimetric primary standard and the imprecision of imercomparison with the
gravimetric standards. This sample is certified only for the concentration of propane. However, representative
samples from the lot have been examined for the presence of other hydrocarbons. The estimated concentration
of other hydrocarbons, expressed at propane, is 0.06 ^mole/mote (ppm).
Each cylinder is individually analyzed and the concentration appearing above applies to the cylinder number
and sample number identified on this certificate.
The original development and evaluation of the Propane in Air Series of these Standard Reference Materials
was performed at the National Bureau of Standards by W. P. Schmidt and W. D. Dorko.
The overall direction and coordination of technical measurements leading to certification were performed in the
Gas and Paniculate Science Division under the chairmanship of E. £. Hughes and H. L. Rook.
The technical and suppon aspects involved in the preparation, certification, and issuance of this Standard
Reference Material were coordinated through the Office of Standard Reference Materials by T. E. Gills.
Washington, D.C 20234 George A. Uriano. Chief
January 31, 1980 Office of Standard Reference Materials
(over)
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Project No..
. Book No..
41 of 41
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APPENDIX K
SPECIATED NMOC ANALYTICAL RESULTS
(Obtain from Neil Berg, U.S. EPA)
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TECHNICAL REPORT DATA
(PLEASE READ INSTRUCTIONS ON THE REVERSE BEFORE COMPLETING)
PORT NO.
'A-454/R-99-012
3. RECIPIENT'S ACCESSION NO.
LE AND SUBTITLE
93 Nonmethane Organic Compounds And Speciated Nonmethane
ganic Compounds Monitoring Program
5. REPORT DATE
1/1/94
6. PERFORMING ORGANIZATION CODE
THOR(S)
dian Corporation
search Triangle Park, N. C. 27709
8. PERFORMING ORGANIZATION REPORT NO.
RFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D2-0160
'ONSORING AGENCY NAME AND ADDRESS
rice Of Air Quality Planning And Standards
S. Environmental Protection Agency
search Triangle Park, N. C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
JPPLEMENTARY NOTES
5STRACT
CERTAIN AREAS OF THE COUNTRY WHERE THE NATIONAL AMBIENT AIR QUALITY STANDARD (NAAQS)
R OZONE IS BEING EXCEEDED, ADDITIONAL MEASUREMENTS OF AMBIENT NONMETHANE ORGANIC
IMPOUNDS (NMOC) ARE NEEDED TO ASSIST THE AFFECTED STATES IN DEVELOPING REVISED OZONE
'NTROL STRATEGIES. BECAUSE OF PREVIOUS DIFFICULTY IN OBTAINING ACCURATE NMOC
iASUREMENTS, THE U.S. ENVIRONMENTAL PROTECTION AGENCY (EPA) HAS PROVIDED MONITORING
D ANALYTICAL ASSISTANCE TO THESE STATES, BEGINNING IN 1984 AND CONTINUING THROUGH THE
)3 NMOC MONITORING PROGRAM.
KEY WORDS AND DOCUMENT ANALYSIS
5CRIPTORS
one Control Strategies
tional Ambient Air Quality Standards
nmethane Organic Compound
nitoring Analysis
)3 NMOC Monitoring Program
STRIBUTION STATEMENT
LIMITED
b. IDENTIFIERS/OPEN ENDED TERMS
C. COSATI FIELD/GROUP
21. NO. OF PAGES
424
22. PRICE
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