United States
Environmental Protection
Agency
Off ice of Air Quality EPA-450/4-91-001
Planning and Standards October 1990
Research Triangle Park NC 27711 .,
Air
v'/EPA
1989 URBAN AIR TOXICS
MONITORING PROGRAM
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EPA-450/4-91-001
1989 URBAN AIR Toxics
MONITORING PROGRAM
By
Robert A. McAllister
Wendy H. Moore
JoaimRice
Emily Bowles
Dave-Paul Dayton
Robert F. Jongleux
Raymond G. Merrill, Jr.
Joan T. Bursey
Radian Corporation
Research Triangle Park, NC 27709
EPA Contract No. 68D80014
EPA Contract Officers:
Neil J. Berg, Jr.
Office Of Air Quality Planning And Standards
And
Frank F. McElroy and Vinson L. Thompson
Atmospheric Research And Exposure Assessment Laboratory
Office Of Air Quality Planning And Standards
Office Of Air And Radiation
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
U.S. Environmental Protection Aeencv
October 1990 Region 5, Library (PL-12J)
77 West Jackson Boulevard l?th ci
Chicago, !L 60604 3590 h Floqr
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This report has been reviewed by the Office Of Air Quality Planning And Standards, U. S. Environmental
Protection Agency, and has been approved for publication as received from the contractor. Approval does
not signify that the contents necessarily reflect the views and policies of the Agency, neither does mention
of trade names or commercial products constitute endorsement or recommendation for use.
EPA-450/4-91-001
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TABLE OF CONTENTS
Section Page
List of Figures iv
List of Tables vi
Symbols and Abbreviations ix
1.0 SUMMARY 1-1
2.0 INTRODUCTION 2-1
3.0 URBAN AIR TOXICS TECHNICAL NOTES 3-1
3.1 Sampling Equipment 3-1
3.2 Sample Preseason Preparation and Certification . . . 3-4
3.3 Sample Interface System 3-5
3.4 Calibration Standards Generation 3-5
3.5 Analysis . .' 3-9
3.5.1 GC/MD Instrumentation 3-9
3.5.2 GC/MS Instrumentation 3-9
3.6 Canister Cleanup 3-13
4.0 RESULTS 4-1
4.1 Data Summary 4-1
4.1.1 Overall Data Summary by Compound 4-3
4.1.2 Site Specific Overall Data Summary 4-5
4.2 Precision 4-21
4.3 Accuracy 4-27
4.4 GC/MS Compound Identification Confirmation
Results 4-33
4.5 Sample Completeness 4-33
4.6 Calibration Results 4-37
4.7 Canister Pressure 4-37
cah.!92f
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TABLE OF CONTENTS (Continued)
Section Page
5.0 DISCUSSION 5-1
5.1 Concentration Distributions 5-1
5.2 Correlation of Compound Concentrations 5-9
5.3 Ratios of Compound Concentrations 5-24
6.0 RECOMMENDATIONS 6-1
6.1 Canister Pressure and Elapsed Time Acceptance
Criteria 6-1
6.2 Canister Cleanup Study 6-1
6.3 Instrument Detection Limit Study 6-1
6.4 Additional Target Compounds 6-1
6.5 Presampling Canister Data 6-2
7.0 REFERENCES : 7-1
APPENDICES
APPENDIX A: Urban Air Toxics Monitoring Program Site Data
Summaries for GC/MD Analyses Al
APPENDIX B: Urban Air Toxics Monitoring Program AIRS Site Data . Bl
APPENDIX C: Urban Air Toxics Monitoring Program Concentration
Correlation Graphs Cl
iv
cah.!92f *
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LIST OF FIGURES
Figure Pass
3-1 Perspective view of UATMP sampler 3-2
3-2 Sampling assembly for the UATMP 3-3
3-3 Gas chromatographic multidetector system 3-6
3-4 Interface sample valve configuration 3-7
3-5 Dynamic flow dilution apparatus 3-8
3-6 UATMP multiple detector configuration 3-11
3-7 Canister cleanup apparatus 3-14
5-1 Stem-and-leaf plot of 1,1,1-trichloroethane 5-2
5-2 Stem-and-leaf plot of carbon tetrachloride 5-3
5-3 Stem-and-leaf plot of toluene 5-4
5-4 Stem-and-leaf plot of styrene/o-xylene 5-5
5-5 Stem-and-leaf plot of m,p-xylene 5-6
5-6 Stem-and-leaf plot of ethylbenzene 5-7
5-7 Stem-and-leaf plot of benzene 5-8
5-8 Pearson correlation matrix for BRLA 5-10
5-9 Pearson correlation matrix for C4IL 5-11
5-10 Pearson correlation matrix for CANJ 5-12
5-11 Pearson correlation matrix for DLTX 5-13
5-12 Pearson correlation matrix for FLFL 5-14
5-13 Pearson correlation matrix for H1TX 5-15
5-14 Pearson correlation matrix for MIFL 5-16
5-15 Pearson correlation matrix for S2MO 5-17
cah.!92f
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LIST OF FIGURES (Continued)
Figure Page
5-16 Pearson correlation matrix for SAIL 5-18
5-17 Pearson correlation matrix for W1DC 5-19
5-18 Pearson correlation matrix for W2DC 5-20
5-19 Pearson correlation matrix for W1KS 5-21
5-20 Pearson correlation matrix for W2KS 5-22
cah.!92f VI
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LIST OF TABLES
Table Pagi
1-1 1989 Urban Air Toxics Monitoring Program Sites 1-2
1-2 1989 UATMP Estimated Instrument Detection Limits,
GC/MD and GC/MS 1-3
1-3 1989 UATMP Compound Identifications with GC/MD for
3-1
3-2
4-1
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
4-10
4-11
All Sites
1989 UATMP GC/MD Operating Conditions
1989 UATMP GC/MS Operating Conditions
1989 UATMP Ambient Air Samples and Analyses
1989 UATMP Compound Identifications with GC/MD
for All Sites
1989 UATMP Frequency of Occurrence of Target Compounds . .
1989 UATMP Compound Identifications with GC/MD
for BRLA
1989 UATMP Compound Identifications with GC/MD
for C4IL
1989 UATMP Compound Identifications with GC/MD
for CANJ
1989 UATMP Compound Identifications with GC/MD
for DLTX
1989 UATMP Compound Identifications with GC/MD
for FLFL
1989 UATMP Compound Identifications with GC/MD
for H1TX
1989 UATMP Compound Identifications with GC/MD
for MIFL
1989 UATMP Compound Identifications with GC/MD
for PEFL
1-4
3-10
3-12
4-2
4-4
4-6
4-7
4-8
4-9
4-10
4-11
4-12
4-13
4-14
cah.!92f
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LIST OF TABLES (Continued)
Table Page
4-12 1989 UATMP Compound Identifications with G
for S2MO ........................ 4-15
4-13 1989 UATMP Compound Identifications with GC/MD
for SAIL ........................ 4-16
4-14 1989 UATMP Compound Identifications with GC/MD
for W1DC ........................ 4-17
4-15 1989 UATMP Compound Identifications with GC/MO
for W2DC ........................ 4-18
4-16 1989 UATMP Compound Identifications with GC/MD
for W1KS ........................ 4-19
4-17 1989 UATMP Compound Identifications with GC/MD
for W2KS ........................ 4-20
4-18 1989 UATMP Overall Precision for Replicate Pairs ..... 4-22
4-19 1989 UATMP Replicate Statistics by Compound ........ 4-23
4-20 1989 UATMP Replicate Statistics ...... ......... 4-24
4-21 1989 UATMP Overall Precision for Duplicate Pairs ..... 4-25
4-22 1989 UATMP Duplicate Statistics by Compound ........ 4-26
4-23 1989 UATMP Duplicate Statistics .............. 4-28
4-24 1989 UATMP GC/MD Audits .................. 4-29
4-25 1989 UATMP GC/MS Audits .................. 4-31
4-26 1989 UATMP Compound Identification Confirmation ...... 4-34
4-27 1989 UATMP Completeness .................. 4-35
4-28 1989 UATMP Invalidated Samples .............. 4-36
4-29 1989 UATMP Calibration Data for Flame lonizaticn
Detector ........................ 4-38
cah.!92f
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LIST OF TABLES (Continued)
Table Page
4-30 1989 UATMP Calibration Data for Photoionization
Detector 4-39
4-31 1989 UATMP Calibration Data for Electron Capture
Detector 4-40
4-32 1989 UATMP Canister Pressures After Sampling 4-42
5-1 1989 UATMP Ratios for Benzene, Toluene, and Xylenes
to Ethyl benzene 5-25
cah.!92f
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SYMBOLS AND ABBREVIATIONS
AC, A.C., or
a.c.
A/D
ADELTA
AIRS
a.m.
Apr
AREAL
Laboratory
Aug
BRLA
BTX
C4IL
Cal., or
Calib.
CANJ
cm
DLTX
DNPH
Dup.
e
ECD
EPA
F
FID
FLFL
GC/ECD
GC/FID
GC/MD
GC/MS
H
H1TX
Hi-Vol
Hg
HPLC
Hr
i.d.
ID
IDL
in.
INST.
area counts, generated from a gas chromatograph
analog to digital
absolute value of DELTA
Aerometric Information Retrieval System
ante meridiem
April
Atmospheric Research and Exposure Assessment
August
Baton Rouge, Louisiana (AIRS No. 22-033-0004)
benzene, toluene, m/p-xylene
Chicago, IL (AIRS No. 17-031-0060)
calibration
Camden, NO (AIRS No. 34-007-0003)
centimeter
Dallas, Texas (AIRS No. 48-113-0069)
di ni trophenylhydrazi ne
duplicate
base of natural logarithm, 2.71828...
electron capture detector
United States Environmental Protection Agency
Friday
flame ionization detector
Fort Lauderdale, Florida (AIRS No. 12-011-1003)
gas chromatograph/electron capture detector
gas chromatograph/flame ionization detector
gas chromatograph/multiple detector
gas chromatograph/mass spectrometer
high level of confidence
Houston, Texas (AIRS No. 48-201-1034)
High-Volume (filter)
mercury
high performance liquid chromatography
hour
inside diameter
identification
instrument detection limit
inches
instrument
can.!92f
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Jul July
Jim June
L liter
L low level of confidence
Lpm liters per minute
m meter
M medium level of confidence
MAX maximum
mb megabyte
MDL method detection limit
MID multiple ion detection
MIFL Miami, Florida (AIRS No. 12-025-4002)
MIN minimum
min. minute
ml mill il Her
mm millimeter
NC North Carolina
NMOC Nonmethane organic compound
No. Number
Oct October
o.d. outside diameter
Off. Office
PDFID cryogenic preconcentration and direct flame ionization
detection
PEFL Pensacola, Florida (AIRS No. 12-033-0004)
PID photoionization detector
p.m. post meridiem
ppb parts per billion
ppbv parts per billion by volume
ppm parts per million
ppmC parts per million by volume as carbon
ppmv parts per million by volume
psi pounds (force) per square inch
psig pounds (force) per square inch gauge
QA quality assurance
QAD Quality Assurance Division (EPA)
QAPP Quality Assurance Project Plan
QC quality control
RT retention time
RTP Research Triangle Park
cah.!92f XI1
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S2MO St. Louis, Missouri (AIRS No. 29-510-0072)
SAIL Sauget, Illinois (AIRS No. 17-163-1010)
SAROAD Storage and Retrieval of Aerometric Data
Sep September
SOP standard operating procedure
STD standard deviation
T Tuesday
UATMP Urban Air Toxics Monitoring Program
U.S. United States
W1DC Washington, DC (AIRS No. 11-001-0025)
W1KS Wichita, Kansas (AIRS No. 20-173-0010)
W2DC Washington, DC (AIRS No. 11-001-0039)
W2KS Wichita, Kansas (AIRS No. 20-173-0007)
W Wednesday
"C degrees Celsius
°F degrees Fahrenheit
%CV percent coefficient of variation
%Diff percent difference
microgram per standard cubic meter (at 25*C and 1.0
atmosphere)
micrometer
cah.!92f Xlii
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XIV
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1.0 SUMMARY
The Urban Air Toxics Monitoring Program (UATMP) was developed in 1987 by
the United States Environmental Protection Agency (U.S. EPA). The data
discussed in this report are from the analyses of samples collected during the
1989 program, from January 1989 through January 1990. During the 1989
program, 397 valid samples were collected in 6-liter (L) SUMMA*-treated
canisters. These samples were collected from 14 sites in the United States
every 12 days, for a 24-hour collection period.
Table 1-1 lists the 1989 UATMP sites, along with the EPA Region, the
city in which the site is located, the Radian site code, the site numbers of
the Storage and Retrieval of Aerometric Data (SAROAD) set, and the Aerometric
Information Retrieval System (AIRS) number for the site. Six of the 1989
sites also participated in the 1988 UATMP: MIFL, C4IL, SAIL, DLTX, H1TX, and
BRLA.
UATMP canister samples were analyzed by a gas chromatograph/multiple
detector (GC/MD) system for 38 target organic compounds. The estimated
instrument detection limits (IDLs) for each of the 38 compounds are listed in
Table 1-2. A portion of the samples were also analyzed using a gas
chromatograph/mass spectrometer (GC/MS) as identification confirmation of the
GC/MD results. The estimated IDLs for GC/MS are also listed in Table 1-2.
These estimated IDLs were used as guidelines for precision and quantitation
only. Data were not excluded as a result of being below the estimated IDL.
Table 1-3 presents summary statistics for the 1989 UATMP compound
identifications pooled for all the sites. Compound identifications and
quantitation included all cases in which identification criteria of retention
time and detector response ratio(s) were met, regardless of whether the
compound concentration was above or below the IDLs given in Table 1-2.
Several target compounds were identified in 100% of the samples analyzed--
benzene, toluene, m/p-xylene, styrene/o-xylene, and ethylbenzene. Carbon
tetrachloride and 1,1,1-trichloroethane were identified in 99.5% of the
samples analyzed. The frequency of occurrence of target compounds dropped to
44.1% for tetrachloroethylene, and 40.3% for 1,3-butadiene. The remainder of
the target compounds were identified less frequently.
The concentration ranges for target compounds, presented in Table 1-3 as
minima and maxima, ranged from 0.01 parts per billion by volume (ppbv) to
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TABLE 1-1. 1989 URBAN AIR TOXICS MONITORING PROGRAM SITES
EPA
Region
II
III
IV
V
VI
VII
City
Camden, NJ
Washington, DC
Washington, DC
Miami, FL
Ft. lauderdale, FL
Pensacola, FL
Chicago, IL
Sauget, IL
Dallas, TX
Houston, TX
Baton Rouge, LA
Wichita, KS
Wichita, KS
St. Louis, MO
Radian
Site Code
CANJ
W1DC
W2DC
MIFL
FLFL.
PEFL
C4IL
SAIL
DLTX
H1TX
BRLA
W1KS
W2KS
S2MO
SAROAD
Number
31-0720-003
09-0020-025
09-0020-039
10-2700-002
10-1260-003
10-3540-004
14-1220-060
14-6900-010
45-1310-069
45-2560-034
19-0280-004
17-3740-010
17-3740-009
26-4280-072
AIRS
Numoer
34-007-0003
11-001-0025
11-001-0039
12-025-4002
12-011-1003
12-033-0004
17-031-0060
17-163-1010
48-113-0069
48-201-1034
22-033-0004
20-173-0010
20-173-0007
29-510-0072
cah.!92f . 1-2
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TABLE 1-2. 1989 UATMP ESTIMATED INSTRUMENT DETECTION LIMITS, GC/MD AND GC/MS
Compound
Acetylene
Propylene
1,3 -Butadiene
Vinyl chloride
Chloromethane
Chloroethane
Bromomethane
Methyl ene chloride
trans- 1 , 2-Di chl oroethyl ene
1,1-Di chl oroethane
Chloroprene
Bromochl oromethane
Chloroform
1,1,1 -Tri chloroethane
Carbon tetrachloride
1, 2-Di chloroethane
Benzene
Tri chl oroethyl ene
1, 2-Di chl oropropane
Bromodichl oromethane
trans-l,3-Dichloropropylene
Toluene
n-Octane
ci s- 1 , 3-Di chl oropropyl ene
1 , 1 , 2-Trichl oroethane
Tetrachl oroethyl ene
Di bromochl oromethane
Chlorobenzene
Ethyl benzene
m/p-Xylene
Styrene
o-Xylene
Bromoform
1,1,2 , 2-Tetrachl oroethane
m-Di chlorobenzene
p-Di chlorobenzene
c-Di chlorobenzene
GC/MD
ppbv
1.00
0.10
0.10
0.20
0.20
0.10
0.20
0.11
0.04
0.04
0.06
0.003
0.006
0.001
0.001
0.04
0.04
0.004
0.04
0.001
0.04
0.02
0.03
0.04
0.04
0.07
0.001
0.02
0.02
0.04
0.02
0.02
0.001
0.002
0.02
0.09
0.02
GC/MS'
ppbv
b
0.40
0.57
0.43
0.56
0.38
0.25
0.31
0.39
0.53
0.57
0.48
0.27
0.70
0.37
0.59
0.34
0.37
0.44
0.22
0.50
0.50
0.29
0.80
0.22
0.32
0.25
0.57
0.72
0.46
0.46
0.39
0.27
0.37
0.28
0.56
0.37
GC/MS operated in the multiple ion detection (MID) mode using a
512-miTMliter (mL) sample, twice the volume of GC/MD samples.
Below GC/MS scan range.
cah.lSZf 1-3
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TABLE 1-3. 1989 UATMP COMPOUND IDENTIFICATIONS WITH GC/MD FOR ALL SITES
Cases'
Compound No.
Acetylene
Propylene
1.3-Butadiene
Vinyl chloride
Chloromethane
Chi oroethane
Bromomethane
Methyl ene chloride
trans-l,2-01ch1oroethylene
1,1-Oichloroethane
Chi oroprene
Bromochl oromethane
Chloroform
1 , 1 , 1 -Tri chl oroethane
Carbon tetrachlonde
1.2-Oichl oroethane
Benzene
Tri chl oroethy 1 ene
1,2-01 chl oropropane
Bromodi Chloromethane
t-1.3-0ichloropropylene
Tol uene
n-Octane
n-Octane/trans-
1 , 3-di chl oropropy 1 ene
cis-l,3-Dichloropropylene
1,1.2-Trichl oroethane
Tet rachl oroethy 1 ene
Oi bromochl oromethane
Chlorobenzene
Ethyl benzene
m/p-Xylene
Styrene/o-xylene
Bromoform
1.1.2. 2-Tetrachl oroethane
m-Oi Chlorobenzene
p-Di chl orobenzene
o-Oi chl orobenzene
52
51
160
7
2
18
9
35
14
12
120
6
56
395
395
7
397
174
90
14
7
397
48
36
13
76
175
1
98
397
397
397
2
13
63
153
78
%
Freq
13.
12.
40.
1.
0.
4.
2.
8.
3.
3.
30.
1.
14.
99.
99.
1.
100.
43.
22.
3.
1.
100.
12.
9.
3.
b
l
8
3
8
5
5
3
a
5
0
2
5
1
5
5
8
0
8
7
5
,8
0
.1
.1
,3
19.1
44,
.1
0.3
24
.7
100.0
100
100
0,
3
15
38
19
.0
.0
.5
.2
.9
.5
.6
Min.
ppbv
0.45
0.07
0.04
0.35
0.03
0.03
0.03
1.06
0.03
0.03
0.01
0.01
0.02
0.18
0.11
0.04
0.05
0.01
0.04
0.02
0.02
0.08
0.02
0.01
0.01
0.01
0.01
0.02
0.01
0.02
0.09
0.03
0.02
0.03
0.01
0.02
0.01
Max.
ppbv
36.82
72.76
4.78
48.89
12.10
0.47
2.92
17.26
2.06
0.48
4.91
0.16
80.76
65.57
1.78
0.21
27.66
5.60
3.63
0.11
0.45
217.89
4.46
1.22
1.30
4.08
5.81
0.02
11.72
9.77
50.50
16.61
0.03
0.75
1.08
15.72
2.85
Mean'
ppbv
6.17
7.75
0.46
7.76
6.06
0.19
0.63
6.27
0.59
0.14
0.31
0.08
1.71
1.14
0.19
0.08
1.96
0.55
0.76
0.05
0.11
4.56
0.34
0.19
0.29
0.29
0.35
0.02
0.49
0.57
3.16
1.09
0.02
0.16
0.12
0.75
0.21
Mean*
ppbv
1.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
1.
0.
0.
0.
0.
4.
0.
24
04
21
24
13
06
11
60
04
02
11
003
24
13
19
02
96
24
19
002
02
56
05
0.04
0.03
0.07
0.18
0.001
0.
0.
3.
,13
,57
.16
1.09
0.
0.
,001
,01
0.03
0.32
0,
.05
Mean* Medi an
ppbv ppov
0.81
1.00
0.18
0.14
0.03
0.01
0.01
0.55
0.02
0.004
0.09
0.001
0.24
1.13
0.19
0.001
1.96
0.24
0.17
0.002
0.002
4.56
0.04
0.02
0.01
0.06
0.16
0.0001
0.12
0.57
3.16
1.09
0.0001
0.01
0.02
0.29
0.04
2.55
5.37
0.27
0.59
6.06
0.15
0.11
4.98
0.20
0.08
0.12
0.08
0.18
0.50
0.15
0.06
1.38
0.23
0.48
0.05
0.05
2.50
0.15
0.11
0.23
0.04
0.20
0.02
0.20
0.36
1.95
0.68
0.02
0.08
0.04
0.22
0.10
STD'
ppov
8.71
11.23
0.55
18.15
8.53
0.12
0.96
4.23
0.66
0.15
0.55
0.06
10.76
3.75
0.15
0.06
2.23
0.81
0.78
0.03
0.16
12.52
0.70
0.25
0.33
0.79
0.59
0.00
1.37
0.88
4.56
1.58
0.01
0.20
0.19
1.65
0.42
'A total of 397 samples were analyzed by GC/MO.
'Percent of the total samples analyzed in which the compound was identified.
'The arithmetic average concentration of all cases in which the compound was identified.
'The arithmetic average concentration of all samples, using half the IOL value for samples in which
the compound was not identified.
The arithmetic average concentration of all samples, using zero for samples in which the compound
was not identified.
'The standard deviation (STD) of all cases in which the compound was identified.
cah.!92f
1-4
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217.89 ppbv. The maximum overall concentration of 217.89 ppbv was for
toluene. Nine compounds had maximum concentrations below 1.0 ppbv. Table 1-3
also gives the medians, standard deviations, and three types of means, or
averages, for the target compounds. Column six of Table 1-3 lists the mean,
or the arithmetic average concentration, for each compound identified in each
sample. In the next column, the mean is calculated using one-half the IDL
(Table 1-2) for samples in which the compound was not identified. Finally,
column eight of Table 1-3 gives the mean concentrations, using zero for
samples in which the compound was not identified.
Although concentrations of air toxic pollutants have been shown to be
approximately lognormally distributed1"3, arithmetic averages (or means) have
been used in this study. Means calculated in columns seven and eight may be
viewed as annual means, because the overall time period of the data span about
one year. Standard deviations given in Table 1-3 are calculated using only
the cases in which the compound was identified.
Analytical precision was measured in terms of percent coefficient of
variation (% CV) for repeated analyses of the same sample, and ranged from
-23.1% to 41.8%, averaging -0.44 percent. Sampling and analysis precision was
determined from analyses of duplicate samples. Percent CV for duplicates
ranged from -14.1% to 57.9%, averaging -0.62 percent.
Accuracy was determined from six external audits conducted by the
Quality Assurance Division (QAD) of the Atmospheric Research and Environmental
Assessment Laboratory (AREAl) of the USEPA. The average bias calculated for
each audited compound, ranged from -14.6% for ethyl benzene and bromomethane,
to 21.5% for methylene chloride. The overall average bias for all audited
compounds was -1.2 percent. Compound concentrations in the audit samples
ranged from about 2 to 8 ppbv.
About 15% of the UATMP samples were analyzed by GC/MS to confirm the
GC/MD analyses. Identifications were confirmed if both GC/MD and GC/MS
identified, or did not identify, the compound. GC/MS confirmed 94.1% of the
GC/MD results in the 1989 UATMP sample analyses.
The replicate and duplicate precision results, along with the audit
bias results for determining accuracy, reflect the quality of the data
presented in this report. The high percentage of GC/MS confirmed results
indicates the reliability and the representativeness of the compound
identifications and concentrations reported for UATMP.
cah.!92f . 1-5
-------
-------
2.0 INTRODUCTION
The UATMP was developed In 1987 to help state and local agencies
determine if an air toxics problem existed and, if one existed, what was the
nature and extent of it. Data from the UATMP are used in risk assessment
models associated with toxic organic compounds. From its origin, the UATMP
has been regarded as a screening program. That is, to assess the kinds of
metals and organic compounds, and their relative concentrations, which may be
in urban atmospheres. Because there may be hundreds of these substances in
urban environments, and because it is not possible to measure all of them in
small samples, the UATMP was deliberately structured to confine analysis of
the samples to a limited number of compounds which were of special concern to
health professionals.
Nonmethane organic compound (NMOC) and 3-hour air toxics monitoring
programs for 1989 are companion programs to UATMP. Sampling for the NMOC and
3-hour air toxics monitoring programs began on June 6, 1989, and completed on
September 29, 1989. The results of the NMOC and 3-hour air toxics monitoring
programs are presented in a separate report.1
The UATMP consists of three analytical fractions: filter samples to be
analyzed for selected metals and benzo(a)pyrene, dinitrophenylhydrazine (DNPH)
cartridges samples for collection of carbonyl compounds, and canister samples
to be analyzed for 38 gaseous organic compounds. The DNPH cartridges are also
called "aldehyde cartridges," although both aldehydes (formaldehyde and
acetaldehyde) and a ketone (acetone) are quantitatively derivatized.
Throughout the remainder of this report, the DNPH cartridges will be referred
to as the aldehyde cartridges. The results from canister samples will be
presented and discussed in this report. The results from the aldehyde
cartridge samples and the high-volume (Hi-Vol) filter samples will be
presented in separate reports.
The samples for each analytical fraction were collected simultaneously,
i.e., timers were programmed to start Hi-Vol filters, to start pumps that draw
air through cartridges that trap carbonyl compounds, and to open a valve to
start the canister sampling—all beginning at midnight on each scheduled day.
Samples were collected from January 16, 1989, through January 23, 1990, on a
12-day cycle, for the 1989 UATMP. Hi-Vol filter samples were sent by site
personnel directly to the U.S. EPA for analysis. Aldehyde cartridges and the
-------
UATMP 6-L canisters were returned to Radian's Research Triangle Park (RTF),
NC, laboratory. The aldehyde cartridges were transported to the U.S. EPA for
analysis, and the UATMP samples were analyzed by Radian.
Section 3.0 presents the descriptions of the UATMP fie id sampling
equipment, the GC/MD and GC/MS analytical equipment, the standards preparation
apparatus, and the canister cleanup system. Section 4.0 summarizes the
analytical results obtained for the 1989 UATMP, and Section 5.0 discusses the
data characterizations for the UATMP results. Section 6.0 gives
recommendations for future programs, and Section 7.0 provides the references
cited.
cah.!92f 2-2
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3.0 URBAN AIR TOXICS TECHNICAL NOTES
This section presents descriptions of the equipment and procedures used
in the 1989 UATMP. The sampling equipment, sample interface, analytical
systems, compound identification and confirmation procedures, calibration
standard generation apparatus, and the canister cleaning system are detailed
in this section.
3.1 SAMPLING EQUIPMENT
A perspective view of the UATMP sampler is given in Figure 3-1, and
Figure 3-2 shows the detailed layout of the sample lines, flow controller, and
the other components of the UATMP sampler. The sampler was designed to obtain
a 24-hour integrated ambient air sample in an evacuated stainless steel
canister. Separate sample lines are used for the ambient air sample and for
the aldehyde sample cartridges. The aldehyde sample lines are heated from the
inlet to the aldehyde cartridges.
The aldehyde sample cartridges were prepared by an EPA Mobile Source
Branch on-site contractor and sent to Radian Corporation's RTP laboratory for
shipment to the UATMP sites. Each aldehyde cartridge was given a unique
serial number. Three cartridges, one blank and two duplicates, were enclosed
with each canister sent to the sites. After ambient air sample collection was
complete, site operators returned the aldehyde cartridges to the Radian
laboratory in the canister shipment container along with sample canisters and
sample custody records. The aldehyde cartridges were transferred to the
U.S. EPA AREAL for analysis. The aldehyde results have been reported in a
separate report.
The UATMP samplers were set to begin drawing air at a flow rate of
150 mL/minute (min.) through the sample inlet and sample lines about six hours
before the air was directed into the evacuated sample canister(s). This
procedure ensured that once the flow in the sample line was directed into the
canister, the sample line had been well conditioned with ambient air. The
sample flow rate into the 6-L canister was controlled at approximately
3.5 mL/min. The resulting pressure in the canister after 24 hours was
approximately 1.0 to 5.0 inches (in.) mercury (Hg) vacuum. Section 4.7
presents and discusses the actual canister pressure distribution after the
canisters were received in Radian's RTP laboratory. The method of sampling
-------
Figure 3-1. Perspective view of UATMP sampler.
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Heated inlet bne
A
/ /
/ /
/ /
/ /
/ /
/ /
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Cartridges
FiKer/Ni
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Figure 3-2. Sampling assembly for the UATMP.
3-3
-------
operated on a slip-stream approach with the canister under vacuum (about
29.72 in. Hg vacuum) to avoid potential contamination from the pump.
3.2 SAMPLER PRESEASON PREPARATION AND CERTIFICATION
The UATMP samplers were cleaned and prepared for deployment to the field
sites prior to the 1990 season. The samplers used in the 1988 program were
returned from the field sites to the Radian RTP laboratory for refurbishment.
The refurbishment involved cleaning and extensive checks of the electrical and
mechanical components of the sampler. Any worn or damaged parts were
replaced. The samplers were then reassembled and leak checked. Flow rates
for the aldehyde and canister subsystems were checked against a primary flow
standard.
All samplers were cleaned through an extended purge with humidified zero
air following the TO-14 procedure for humid zero air certification.4 Because
of the large air volume required to purge the samplers, a temporary dedicated
zero certification manifold was utilized. After the samplers were prepared
and purged, a final analysis of the humid zero purge air was performed to
serve as part of the permanent record of any residual contaminant levels for
the UATMP target compounds. Background levels from zero air and the canister
were measured and subtracted from the certification samples collected through
each sampler unit. All analyses were performed on the GC/MD analytical system
dedicated to the UATMP program. Each sampler collected a 24-hour sample in
its standard operating mode from the zero air manifold.
Acceptance criteria for the cleaned and blanked canisters used for the
sampler zero check were approximately 0.2 ppbv per target compound or the
compound IDL, whichever was higher. The majority of the samplers deployed to
the field met the criteria of 0.2 ppbv per target analyte and 25 ppbv total
for all species as measured by the flame ionization detector (FID) of the
GC/MD analytical system. The total of 25 ppbv was based on total area counts,
including target compounds arbitrarily using an average response factor of
0.001 ppbv/area count. Some of the samplers exhibited residual peaks that
were attributed to acetonitrile contamination from the aldehyde subsystem.
Because the residual peak(s) did not interfere with the UATMP target analytes,
field deployment was recommended and implemented by the project team.
cah.!92f 3-4
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3.3 SAMPLE INTERFACE SYSTEM
Figure 3-3 shows the UATMP GC/MD system that includes the Sample
Interface System, the Analytical System, and the Data System. Figure 3-4
diagrams the sample valve configurations of the interface system. The upper
half of Figure 3-4 shows the configuration of the interface system valve for
the loading of sample through Trap 1 in which the organic compounds in the
sample are condensed (trapped) by flowing through a 1/8-in. stainless steel
glass-head-filled trap that is immersed in liquid argon. The lower half of
Figure 3-4 shows the sample interface system valve in the position for
injecting the cryogenically trapped sample onto the column in the GC/MD. In
the latter mode, the argon is removed from around the trap, and the trap is
heated to about 200 degress eel si us (*C).
The sample interface withdraws a constant sample volume of 256 ml from
the sample canister and preconcentrates the sample by cryogenic trapping (see
Load Trap 1 in Figure 3-4). Following sample preconcentration, the eight-port
sampling valve is placed in the inject position (Inject Trap 1 in Figure 3-4)
and the sample trap is rapidly heated. Helium carrier gas transports the
trapped sample directly onto the column.
Initial calibration of the GC/MD system showed that the sample interface
system provides a consistent sample volume with a precision (percent
coefficiency of variation, % CV) of less than 3.0 percent.
3.4 CALIBRATION STANDARDS GENERATION
Calibration standards were generated with a dynamic flow dilution
apparatus shown in Figure 3-5. The flow dilution system uses vendor-certified
gases (±5%) and dilutes them with zero-grade air that has been routed through
a catalytic oxidizer and then humidified with HPLC-grade water. The gases are
mixed in a SUMMA*-treated mixing sphere prior to flowing into an evacuated
canister. One dilution stream of the zero-grade air is routed through a
SUMMA«-treated bubbler containing HPLC-grade water to humidify it, and the
other stream is not humidified. The dilution air streams are then brought
together for mixing with the streams from three certified standard cylinders.
Flow rates from all streams are gauged and controlled by mass flow
controllers. The split air dilution streams are metered by wet and dry
cah.!92f 3-5
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Vent
Sample Gas In
To Analytical System
Helium Carrier Gas In
Conduit
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Inject Trap 1
Cryogenic
Trap 1
Vent
Sample Gas In
To Analytical System
Helium Carrier Gas In
Conduit
Loop
Valve viewed from handle
Figure 3-4. Interface sample valve configuration.
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Mass Flow
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Mass Flow
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rotameters from the humidified and unhumidified dilution air streams,
respectively. The lines and the mixing flask containing the diluted gases are
heated to 100'C to prevent condensation of liquids on the surfaces and to
reduce adsorption of organic compounds on the surfaces.
The system is evacuated with a vacuum pump while the closed canister is
connected. A precision absolute pressure gauge measures the canister pressure
before and after filling. The lines leading to the canister and to the mixing
sphere are flushed for at least 15 minutes with the diluted standard gases
before being connected to the canister for filling.
3.5 ANALYSIS
UATMP samples are analyzed for 38 target compounds by the GC/MD system.
Having simultaneous detector responses from the electron caputre detector
(ECD), photoionization detector (PID), and the FID allows the analyst to
identify target compounds with greater accuracy. Quantitation is done
primarily using the FID response, although the ECD is used for quantitation of
most halogenated compounds. About 15% of the 1989 UATMP samples were also
analyzed for compound identification confirmation by GC/MS, operating in the
MID mode.
3.5.1 GC/MD Instrumentation
The gas chromatograph used with the multiple detector system is a
VARIAN 3700. The operating conditions for the GC/MD system are given in
Table 3-1. Figure 3-6 shows the multiple detector system arrangement.
The oven of the gas chromatograph, which contains the DB-624 capillary column,
is cooled to -30*C with liquid nitrogen at the beginning of the sample
injection. The -30*C temperature remains constant for one minute, and then
the temperature is increased at the rate of 3*C per minute, to a final
temperature of 200*C. The column effluent is routed through a 1:10 fixed
splitter that divides the flow to the ECD and the PID/FID. The smaller gas
stream from the splitter goes to the ECD, and the larger fraction goes first
to the PID and then the FID.
3.5.2 GC/MS Instrumentation
A total of 53 UATMP samples were analyzed by GC/MS using a FINNIGAN 4500
operating primarily in the MID mode. The GC/MS operating conditions are given
in Table 3-2. The full-scan mode was used occasionally to detect non-target
cah.!92f 3-9
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TABLE 3-1. 1989 UATMP GC/MD OPERATING CONDITIONS
Parameter
Operating Value
Sample Volume
256 ml
J&W Megabore* DB-624 Capillary Column
Length
Inside Diameter
Oven Temperature
Film Thickness
30 m
0.53 mm
-30*C for 1 min.
Temperature programmed at
3'C/min. to 200'C
3 »m
Injector Oven Temperature
200'C
Detector Temperatures
FID
PID
ECD
250'C
225-C
250*C
Gas Flow Rates
Helium Carrier Gas
N2 Make-up
H2 to FID
Air to FID
5 mL/min.
25 mL/min.
30 mL/min
300 mL/min.
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TABLE 3-2. 1989 UATMP GC/MS OPERATING CONDITIONS
Parameter
Operating Value
Sample Volume
512 ml
JiW Megabore« DB-624 Capillary Column
Length
Inside Diameter
Oven Temperature
Film Thickness
30 m
0.53 mm
10'C for 5 min.
Temperature programmed at
6'C/min. to 220'C
3 urn
Injector Oven Temperature
Separator Temperature
Manifold Temperature
110'C
220*C
100'C
Gas Flow Rates
Helium Carrier Gas
Helium Make-up
10 mL/min.
20 mL/min.
cah.!92f
3-12
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compounds when an Interference was suspected or apparent. The MID mode was
used for all other confirmation analyses.
3.6 CANISTER CLEANUP
The sample canister cleanup system used for the 1989 UATMP is the same
as the one described in the 1989 NMOC and 1989 UATMP Quality Assurance Project
Plans (QAPPs)2-3 and the 1989 NMOC Monitoring Program.1 The canister cleanup
apparatus diagram is shown in Figure 3-7.
To clean the UATMP canisters, a bank of eight canisters is connected to
each manifold shown in Figure 3-7. The valve on each canister is opened, with
the shutoff valves and the bellows valves closed. The vacuum pump is started
and one of the bellows valves is opened, drawing a vacuum on the canisters
connected to the corresponding manifold. After reaching 5-mm Hg absolute
pressure as indicated on the absolute pressure gauge, the vacuum is maintained
for 30 minutes. The bellows valve is then closed. Next, air that has been
filtered, dried, and cleaned, and then humidified at about 80% humidity is
introduced to the evacuated canisters until the pressure reaches 20 pounds
(force) per square inch gauge (psig). The canisters are filled from the clean
air system at the rate of 12.0 L/min. This flow rate is the result of
6.0 L/min. passing through each catalytic oxidizer. A flow rate of 6.0 L/min.
is recommended by the manufacturer as the highest flow rate at which the
catalytic oxidizers eliminate hydrocarbons with a minimum 99.7% efficiency.
When the first manifold has completed the evacuation phase and is being
pressurized, the second manifold is then subjected to vacuum by opening its
bellows valve. After 15 min., the second manifold is isolated from the vacuum
and connected to the cleaned, dried, and then humidified air. The first
manifold of canisters is then taken through a second cycle of evacuation and
pressurization. Each manifold bank of eight canisters is subjected to these
cleanup cycles.
During the third vacuum/pressurization cycle, the canisters are
pressurized to 20 psig with air that has been filtered, dried, cleaned, and
then humidified air. Each UATMP canister is blanked by the cryogenic
preconcentration and direct flame ionization detection (PDFID) method. If the
total NMOC determined by PDFID is less than 0.020 parts per million by volume
as carbon (ppmC), the eight canisters on the manifold are considered clean.
cah.!92f 3-13
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Finally, the canisters are again evacuated to 5-mm Hg pressure absolute,
capped under vacuum, and packed into containers to be shipped to the field
sites.
The UATMP canisters were designated from the start of the program for a
specific site. UATMP canisters from a given site are returned after analysis
and cleanup to the same site for the next sample.
cah.!92f 3-15
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4.0 RESULTS
4.1 DATA SUMMARY
This section summarizes the GC/MD analytical results. Data for each
sample, including site code, sample date, compounds identified, concentrations
for each identified compound, and the identification confidence level, are
tabulated in Appendix A. The site code descriptions, as listed in the AIRS
database, are given in Appendix B.
Table 4-1 summarizes the number of 1989 UATMP canister samples for each
site and the analyses performed. The second column of Table 4-1 is the number
of valid canister samples taken at each UATMP site. The third and fourth
columns show the number of duplicate pairs and replicate analyses pairs for
each site, respectively. At least one pair of duplicate canisters was
attempted each quarter for each site, excluding Pensacola, FL (PEFL).
Sampling at the PFEL site was unable to begin at the same time as the other
1989 UATMP sites, and it was not sampling a sufficient period of time in 1989
to have a GC/MS confirmation analysis scheduled. As observed in Table 4-1,
the duplicate samples were not always valid, therefore, the number of
duplicates is lower for some sites. Replicate analyses were performed-on each
duplicate canister sample to measure sampling and analysis precision. The
total number of GC/MS analyses are shown in column five of Table 4-1.
Finally, the total number of GC/MS confirmation analyses are shown in the last
column of the table.
The reported concentrations were frequently below the IDLs listed in
Table 1-2. However, each identified compound was reported and quantified,
even if the concentration was below its estimated IDL. All the compound
identifications in the tables of Appendix A show the level of confidence in
the identification — low (L), medium (M), and high (H). Compounds were
identified in the UATMP study by retention times and detector response ratios.
If a compound in the sample was within a retention time window (average
retention time ± about 10%) for a target compound, the response ratio for the
target compound in the sample was compared to an average response ratio for
the target compound in the standard. The response ratios are the ratios of
area count responses from two detectors, e.g., ECD and the FID in the GC/MD
analytical instrument. The precision (percent coefficient of variation, % CV)
was calculated for the compound response ratio in the sample and the compound
-------
TABLE 4-1. 1989 UATMP AMBIENT AIR SAMPLES AND ANALYSES
Site
Code
BRLA
C4IL
CANJ
DLTX
FLFL
H1TX
MIFL
PEFL
S2MO
SAIL
W1DC
W2DC
W1KS
W2KS
No. of
Valid
Samples
31
27
32
25
31
34
33
7
30
31
27
27
31
31
Total 397
GC/MD
Duplicate
Pairs
4
1
4
4
3
3
6
1
3
4
4
4
4
3
48
Analyses
Replicate
Pairs
4
1
4
4
3
3
6
1
3
4
4
4
4
3
48
Total
GC/MD
Analyses
39
29
40
33
37
40
45
9
36
39
35
35
39
37
493
Total
GC/MS
Analyses
5
4
4
1
6
4
6
0
5
4
2
3
5
4
53
cah.!92f
4-2
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response ratio in the standard. If the precision was within ±20 % CV, the
compound was identified with a high level of confidence (H). If the precision
was between ±20 and ±35 % CV, the compound was identified with a medium level
of confidence (M). If the precision was between ±35 and ±40 % CV, the
compound was identified with a low level of confidence (L). Compounds with
response ratios outside ±40 % CV were usually not identified, unless there was
additional evidence to indicate the compound was actually in the sample.
Sample concentration results are grouped in two ways, by compound and by
site, and are discussed in the following subsections, 4.1.1 and 4.1.2,
respectively. For each target compound identified at all of the 14 sites,
summary concentrations are given as minima, maxima, and means. Site-specific
data summaries show which target compounds were identified in samples from
each site, and give minimum, maximum, and mean concentrations.
4.1.1 Overall Data Summary by Compound
Table 4-2 presents the UATMP target compounds identified for all the
sites. The number of cases of identification for each compound is given,
along with the frequency at which they were identified. The frequency of
occurrence is expressed as a percent of the 397 total GC/MD analyses. Samples
collected in duplicate actually reflect only one sampling event, but result in
two analyses. Since duplicate samples were also analyzed in replicate, this
results in a total of four analyses from one sampling event. To avoid any
bias in the data by counting four results from one sampling event, the
duplicate and replicate results for each compound identified were averaged.
This average result was used in the statistical summaries and the frequency
calculations. If a compound was identified in less than all four analyses,
the results were averaged for the analyses in which it was identified.
Benzene, toluene, m/p-xylene, styrene/o-xylene, and ethyl benzene were
identified in each of the 397 GC/MD samples. In addition, 1,1,1-tri-
chloroethane and carbon tetrachloride were reported in 395 out of the 397
total samples. m-Xylene and p-xylene coelute on the analytical column used in
the GC/MD system. These compounds were reported together, because it was not
possible to distinguish whether one or both compounds were present in the
sample. This was also the situation with o-xylene and styrene. n-Octane and
trans-l,3-dichloropropylene were coeluted only during the third and fourth
cah.!92f 4-3
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TABLE 4-2. 1989 UATMP COMPOUND IDENTIFICATIONS WITH GC/MD FOR' ALL SITES
Cases'
Compound No .
Acetyl ene
Propyl ene
1,3-Butadiene
Vinyl chloride
Chloromethane
Chi oroethane
Bromomethane
Methyl ene chloride
trans-1 , 2-Oi chl oroethy 1 ene
1,1-Dlchl oroethane
Chl oroprene
Bromochl oromethane
Chloroform
1.1.1 -Tr i chl oroethane
Carbon tetrachl ori de
1 , 2-01 chl oroethane
Benzene
Tr i chl oroethyl ene
1 , 2-Oi chl oropropane
Bromodi chl oromethane
t-l,3-Dichloropropylene
Tol uene '
n-Octane
n-Octane/trans-
1 . 3-di chl oropropyl ene
ci s-1 . 3-01 chl oropropyl ene
1,1,2-TricW oroethane
Tetrachl oroethyl ene
01 bromochl oromethane
Chlorobenzene
Ethyl benzene
m/p-Xylene
Styrene/o-xyl ene
Bromoform
1 , 1 , 2 , 2-Tetrachl oroethane
m-Oi chl orobenzene
p-Oi chl orobenzene
o-Oi chl orobenzene
52
51
160
7
2
18
9
35
14
12
120
6
56
395
395
7
397
174
90
14
7
397
48
36
13
76
175
1
98
397
397
397
2
13
63
153
78
%
Freq.°
13.1
12.8
40.3
1.8
0.5
4.5
2.3
8.8 .
3.5
3.0
30.2
1.5
14.1
99.5
99.5
1.8
100.0
43.8
22.7
3.5
1.8
100.0
12.1
9.1
3.3
19.1
44.1
0.3
24.7
100.0
100.0
100.0
0.5
3.3
15.9
38.5
19.6
Min.
ppbv
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
45
07
04
35
03
03
03
06
03
03
01
01
02
18
11
04
05
01
04
02
02
0.08
0.02
0.01
0.01
0.01
0.01
0.02
0.01
0
.02
0.09
0
0
0
0
0
Q
.03
.02
.03
.01
.02
.01
Max.
ppbv
36.82
72.76
4.78
48.89
12.10
0.47
2.92
17.26
2.06
0.48
4.91
0.16
80.76
65.57
1.78
0.21
27.66
5.60
3.63
0.11
0.45
217.89
4.46
1.22
1.30
4.08
5.81
0.02
11.72
9.77
50.50
16.61
0.03
0.75
1.08
15.72
2.85
Mean'
ppbv
6.17
7.75
0.46
7.76
6.06
0.19
0.63
6.27
0.59
0.14
0.31
0.08
1.71
1.14
0.19
0.08
1.96
0.55
0.76
0.05
0.11
4.56
0.34
0.19
0.29
0.29
0.35
0.02
0.49
0.57
3.16
1.09
0.02
0.16
0.12
0.75
0.21
Mean'
ng/m'
6.68
13.55
1.03
20.16
12.73
0.50
2.48
22.14
2.37
0.57
1.14
0.45
8.49
6.32
1.21
0.34
6.35
2.99
3.58
0.36
0.53
17.49
1.62
0.87
2.69
1.61
2.44
0.17
2.28
2.52
27.89
9.56
0.24
1.13
0.75
4.60
1.28
Mean" Mean* Median
ppov ppov rf)1;.
1.24
1.04
0.21
0.24
0.13
0.06
0.11
0.60
0.04
0.02
0.11
0.003
0.24
1.13
0.19
0.02
1.96
0.24
0.19
0.002
0.02
4.56
0.05
0.04
0.03
0.07
0.18
0.001
0.13
0.57
3.16
1.09
0.001
0.01
0.03
0.32
0.05
0.81
1.00
0.18
0.14
0.03
0.01
0.01
0.55
0.02
0.004
0.09
0.001
0.24
1.13
0.19
0.001
1.96
0.24
0.17
0.002
0.002
4.56
0.04
0.02
0.01
0.06
0.16
0.0001
0.12
0.57
3.16
1.09
0.0001
0.01
0.02
0.29
0.04
2.55
5.37
0.27
0.59
6.06
0.15
0.11
4.98
0.20
0.08
0.12
0.08
0.18
0.50
0.15
0.06
1.38
0.23
0.48
0.05
0.05
2.50
0.15
0.11
0.23
0.04
0.20
0.02
0.20
0.36
1.95
0.68
0.02
0.08
0.04
0.22
0.10
STO'
r-iiOV
8.71
11.23
0.55
18.15
8.53
0.12
0.96
4.23
0.66
0.15
0.55
0.06
10.76
3.75
0.15
0.06
2.23
0.81
0.78
0.03
0.16
12.52
0.70
0.25
0.33
0.79
0.59
0.00
1.37
0.88
4.56
1.58
0.01
0.20
0.19
1.55
0.42
A total of 397 samples were analyzed by GC/MD.
Percent of the total samples analyzed in which the compound was identified.
The arithmetic average concentration of all cases in which the compound was identified.
The arithmetic average concentration of all samples, using half the MOL value for samples
which the compound was not identified.
The arithmetic average concentration of all samples, using zero for samples in which the
compound was not identified.
The standard deviation of all cases in which the compound was identified.
cah.!92f
4-4
-------
quarters of 1990. On July 25, 1990, the chromatography column (DB-624) was
replaced because bleeding from the column was causing excess coating on thePID
with concomitant loss of sensitivity. The new column (another DB-624)
eliminated the bleeding problem on the PID but resulted in coelution of
n-octane and trans-l,3-dichloropropylene. These two compounds, therefore, are
listed separately and as coeluters, since they could be distinguished from one
another for part of the year. Dibromochloromethane was identified in only one
of the 1989 UATMP samples, and chloromethane and bromoform were seen only
twice. Reported concentrations of the target compounds ranged from 0.01 ppbv
for 10 compounds to 218 ppbv for toluene. Average concentrations ranged from
0.02 ppbv for dibromochloromethane to 7.76 ppbv for vinyl chloride. The
concentration range for each compound is given as minimum and maximum. The
average concentration for each compound identified is expressed in parts per
billion by volume and micrograms per standard cubic meter (jig/m3) at 20"C. In
the latter dimensions, the cubic-meter term is a "standard" cubic meter
calculated at 25*C and 1.0 atmosphere pressure.
Table 4-3 groups the compounds by frequency of occurrence for the target
compounds in the UATMP samples. The most obvious feature of these results is
the large gap in frequency of occurrence between 99.5% for 1,1,1-tri-
chloroethane and carbon tetrachloride, and 44.1% for tetrachloroethylene.
This phenomenon may suggest that the target compounds in the 99.5 to 100%
group are significantly more stable in ambient air than all the other UATMP
target compounds. All the halogenated methane compounds containing bromide
radicals fall in the frequency-of-occurrence range of less than 3.5 percent.
This may be a reflection of the low concentrations of bromine and bromine
derivatives in ambient urban air.
4.1.2 Site-Specific Overall Data Summary
Site-specific compound identifications by GC/MD are presented in
Tables 4-4 through 4-17. The "cases" column is the number of samples in which
the compound was identified at a particular site. Concentration ranges are
given in terms of minima and maxima for each compound. The mean, or average,
concentrations are reported in the fifth through eighth columns of each
table. Means are calculated in the same way as discussed in Table 4-3.
Medians and standard deviations of the identified concentrations found in the
cah.!92f 4-5
-------
TABLE 4-3. 1989 UATMP FREQUENCY OF OCCURRENCE OF TARGET COMPOUNDS
Range for
Frequency of
Occurrence
Target Compounds
100 to 99.5%
45 to 20%
19 to 8%
7 to >0%
1,1,1-Tri chloroethane
Carbon tetrachloride
Benzene
Toluene
1,3-Butadiene
Chloroprene
Trichloroethylene
1,2-Dichloropropane
Acetylene
Propylene
Methylene Chloride
Chloroform
n-Octane/trans-1,3-
dichloropropylene
Vinyl Chloride
Chloromethane
Chloroethane
Bromomethane
trans-1,2-Di chloroethylene
1,1-Dichloroethane
Bromochloromethane
Ethyl benzene
m/p-Xylene
Styrene/o-xylene
Tetrachloroethylene
Chlorobenzene
p-Dichlorobenzene
n-Octane
1,1,2-Tri chloroethane
m-Dichlorobenzene
o-DiChlorobenzene
1,2-Dichloroethane
Bromodi chloromethane
trans-l,3-Dichloropropylene
cis-l,3-Dichloropropylene
Di bromochloromethane
Bromoform
1,1,2,2-Tetrachloroethane
cah.!92f
4-6
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