Analysis Of Organic Air Pollutants In The Kanawha Valley, WV and The Shenandoah Valley, VA

                                    EPA-903/9-78-007


                                         ANALYSIS OF ORGANIC AIR POLLUTANTS
                                             IN THE KANAWHA VALLEY, WV
                                            AND THE SHENANDOAH VALLEY, VA


                                       7

                                                Mitchell D.  Erickson

                                                          and

                                                  Edo D.  Pellizzari



                                                     June,  1978
EPA

903/9-

78~007                                                     EPA Report Collection
     o                                                   Information Resource Center
C°P"7 L                                                       US EPA Region 3
                                                          Philadelphia, PA  19107

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                                 DISCLAIMER

     This report has been reviewed by the Region III U. S. Environmental
Protection Agency, and approved for publication.  Approval does not
signify that the contents necessarily reflect the views and policies of
the U. S. Environmental Protection Agency, nor does mention of trade
names of commercial products constitute endorsement or recommendation
for use.

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                                  ABSTRACT

     Recently developed techniques for sampling and analysis of ambient air
by GC/MS/COMP were applied to the Kanawha Valley, WV and Shenandoah Valley,
VA to assess the levels of organic pollutants,  Volatile and very volatile
compounds were concentrated on Tenax GC and carbon sorbent cartridges, re-
spectively, then thermally desorbed directly into the capillary column
GC/MS/COMP system for analysis.  Semivolatiles were collected on the
electrostatic precipitator plates of a Massive Air Sampler, extracted,
fractionated, and then analyzed by GC/MS/COMP.  The Kanawha Valley con-
tained a broad range of halogenated, ketone, aldehyde, ester, aromatic,
aliphatic and polynuclear aromatic compounds.  The Shenandoah Valley
contained a narrower range of organics, but generally higher observed
levels of the compounds quantitated.
                                     111

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iv

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                                   CONTENTS
                                                                          Page
Abstract	    iii
Figures	    vi
Tables	    viii
Acknowledgements	    xii

     1.   Introduction 	      1
     2.   Summary and Conclusions	      2
     3.   Recommendations  	      5
     4.   Objectives	      7
     5.   Sampling	      8
     6.   Sample Analysis	     33
     7.   Results	     38
     8.   Quality Control	     71
References	     76
Appendix
     A.   Sampling and Analysis for Volatile Organics in Ambient Air  .     78
     B.   Sampling and Analysis for Very Volatile Organics  (e.g.,
          Methyl Chloride, Methyl Bromide, Vinyl Chloride and Vinyl
          Bromide) in Ambient Air	    106
     C.   Volatile and Very Volatile Organic Compounds Identified
          in Air in the Kanawha Valley, WV	    118
     D.   Semivolatile Compounds Identified in Air Particulate
          Collected in Kanawha Valley, WV  	    146
     E.   Volatile and Very Volatile Organic Compounds Identified in
          Ambient Air in Front Royal, VA	    156
     F.   Semivolatile Compounds Identified in Air Particulate
          Collected in Shenandoah Valley, VA 	    173

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                                    FIGURES
Number                                                                Page
  1   Collection system for concentrating high and medium
          volatility organic compounds from ambient air .  	    9
  2   The Kanawha River Valley, West Virginia 	   14
  3   Map of area around Nitro, WV showing LA, L6, L7, and L9
          (See Table 1)	   20
  4   Map of area around St. Albans and Institute, WV showing L3 and
          L8 (See Table 1)	   21
  5   Map of area around Charleston and South Charleston,  WV showing
          LI and L2 (See Table 1)	   22
  6   Map of area around W. Belle, WV showing L5 (See Table 1). . .  .   23
  7   Front Royal, VA	   25
  8   Map of Front Royal, VA showing locations described in
          Table 5	   30
  9   Fractionation scheme used for fractionating air particulate
          collected in Charleston, WV (Trip 3, PI/LI) 	   35
 10   Extraction scheme for particulate collected in Front Royal, VA.   37
 11   Field Sampling Protocol Data Sheet  	   72
A-l   Vapor collection and analytical systems for analysis of
          organic vapors in ambient air	   80
A-2   Sampling head for housing cartridge sampling train  	   88
A-3   Profile of ambient air pollutants for Wood River, IL using
          high resolution gas chromatography/mass spectrometry/-
          computer	   95
A-4   Background profile for Tenax GC cartridge blank ...  	   96
A-5   Schematic diagram of gc-ms computer system  ....  	   97
A-6   Mass fragmentograms of characteristic ions representating
          carbon tetrachloride (m/e 117), tetrachloroethylene (m/e
          166) and m-dichlorobenzene  (m/e 146) in ambient air ....  101
                                      VI

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                               FIGURES (cont'd.)
Number                                                                     Page
A-7   Mass fragmentograms of characteristic ions representating
          methylene chloride (m/e 49) and chloroform (m/e 83) in
          ambient air	   102
B-l   Nutech Model 221-A AC-DC Sampler  	   108
D-l   Total ion current chromatogram of GC/MS/COMP analysis of polar
          neutral fraction of <1.7 ]i air particulate collected in
          Kanawha Valley, WV (Trip 3, PI/LI). . .-	   152
D-2   Total ion current chromatogram of GC/MS/COMP analysis of PNA
          fraction of <1.7 y air particulate collected in Kanawha
          Valley, WV (Trip 3, PI/LI)	   153
D-3   Total ion current chromatogram of GC/MS/COMP analysis of paraffin
          fraction of <1.7 y air particulate collected in Kanawha
          Valley, WV (Trip 3, PI/LI)	   154
D-4   Total ion current chromatogram of GC/MS/COMP analysis of base
          fraction of < 1.7 y air particulate collected in Kanawha
          Valley, WV (Trip 3, PI/LI)	   155
F-l   Total ion current chromatogram of GC/MS/COMP analysis of
          methanol extract of <1.7y air particulate collected in
          Front Royal,  VA (Trip 3, P1/L4)	    174
F-2   Total ion current chromatogram of GC/MS/COMP analysis of toluene
          extract of <1.7y  air particulate collected in Front Royal,
          VA (Trip 3, P1/L4)	   176

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                                    TABLES
Number                                                                Page
  1   Sampling Locations in the Kanawha Valley,  WV 	    16
  2   Sampling Protocol for Organic Compounds in Ambient Air in
          Kanawha Valley, WV	Trip 1	    17
  3   Sampling Protocol for Organic Compounds in Ambient Mr in
          Kanawha Valley, WV	Trip 2	    18
  4   Sampling Protocol for Organic Compouns in Ambient Air in
          Kanawha Valley, WV	Trip 3	    19
  5   Sampling Locations in the Shenandoah Valley, VA  	    26
  6   Sampling Protocol for Organic Compounds in Ambient Mr in
          Shenandoah Valley, VA	Trip 1	    27
  7   Sampling Protocol for Organic Compounds in Ambient Air in
          Shenandoah Valley, VA	Trip 2	    28
  8   Sampling Protocol for Organic Compounds in Ambient Air in
          Shenandoah Valley, VA	Trip 3	    29
  9   Summary of Particulate Sampling with MAS for Shenandoah and
           Kanawha Valleys	    32
 10   Recoveries of Selected Organic Vapors from Tenax Cartridges
          Subjected to Sample Transportation and Storage 	    39
 11   Volatile Organics Identified in Ambient Air in the Kanawha
          Valley, WV	    41
 12   Estimated Levels of Halogenated Organic Vapors in Ambient Air
          from the Kanawha Valley, WV	Trip 1	    51
 13   Estimated Levels of Halogenated Organic Vapors in Ambient Air
          from the Kanawha Valley, WV	Trip 2	    52
 14   Estimated Levels of Halogenated Organic Vapors in Ambient Mr
          from the Kanawha Valley, WV	Trip 3	    53
 15   Estimated Levels of Volatile Organics in Ambient Air from the
          Kanawha Valley, WV	Trip 1	    54
                                    viii

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                               TABLES (cont'd.)
Number                                                                     Page
 16   Estimated Levels of Volatile Organics in Ambient Air from the
          Kanawha Valley, WV	Trip 2	      55
 17   Estimated Levels of Volatile Organics in Ambient Air from the
          Kanawha Valley, WV	Trip 3	      56
 18   Volatile Organics Identified in Ambient Air in the Shenandoah
          Valley, VA (Front Royal)  	      58
 19   Estimated Levels of Halogenated Organic Vapors in Ambient Air
          from Front Royal, VA	Trip 1	      63
 ?0   Estimated Levels of Halogenated Organic Vapors in Ambient Air
          from Front Royal, VA	Trip 2	      64
 21   Estimated Level of Halogenated Organic Vapors in Ambient Air
          from Front Royal, VA	Trip 3	      65
 22   Estimated Levels of Volatile Organics in Ambient Air from
          Front Royal, VA	Trip 1	      66
 23   Estimated Levels of Volatile Organics in Ambient Air from
          Front Royal, VAa	Trip 2	      67
 24   Estimated Levels of Volatile Organics in Ambient Air from
          Front Royal, VAS	Trip 3	      68
 25   Control Samples for each Field Sampling Trip	      74
A-l   Overall Theoretical Sensitivity of High Resolution Gas Chromato-
          graphy/Mass Spectrometry/Computer Analysis for Atmospheric
          Pollutants	      81
A-2   Breakthrough Volumes for Several Atmospheric Pollutants 	      89
A-3   Operating Parameters for GLC/MS/COMP System 	      94
B-l   Estimation of Breakthrough Volumes for Vinyl Chloride and Vinyl
          Bromide on SKC Carbon (104)	    109
B-2   Estimation of Breakthrough Volumes for Methyl Chloride and Methyl
          Bromide on SKC Carbon (104)	    109
B-3   Approximate Limit of Detection for Methyl Chloride, Methyl
          Bromide, Vinyl Chloride and Vinyl Bromide   	    Ill
                                     ix

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                               TABLES (cont'd.)
Number                                                                Page
B-4   Parameters for Removing Water and Transferring Vapors to Tenax
          GC	   115 -
B-5   Operating Parameters for GLC/MS/COMP System  . .-	   116
C-l   Very Volatile Organic Compounds Identified in Air in the Kanawha
          Valley, WV (Trip 1, P2/L2)	   119
C-2   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 1, P2/L2)	   120
C-3   Very Volatile Organic Compounds Identified in the Kanawha Valley,
          WV (Trip 1, P2/L5)	   123
C-4   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 1, P2/L5) 	   124
C-5   Very Volatile Organic Compounds Identified in Ambient Air in
          the Kanawha Valley, WV (Trip 1, P2/L6) 	   126
C-6   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 1, P2/L6) 	   127
C-7   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 2, P2/L3) 	   129
C-8   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 2, P2/L4) 	   132
C-9   Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 2, P2/L5) 	   135
C-10  Very Volatile Organic Compounds Identified in Ambient Air in
          the Kanawha Valley, WV (Trip 3, P1/L8)	   137
C-ll  Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 3, P1/L8)	   138
C-12  Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 3, P2/L1) 	
C-13  Volatile Organic Compounds Identified in Ambient Air in the
          Kanawha Valley, WV (Trip 3, P2/L2) 	
C-14  Very Volatile Organic Compounds Identified in Ambient Air in
          the Kanawha Valley, WV (Trip 3, P2/L9) 	    145

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                               TABLES (cont'd.)
Number                                                                     Page
D-l   Compounds Identified in Polar Neutral Fraction of <1.7u Air
          Particulate Collected in Kanawha Valley, WV (Trip 3,
          LI/LI)	    147
D-2   Compounds Identified in PNA Fraction of <1.7 y Air Particulate
          Collected in Kanawha Valley, WV (Trip 3, PI/LI)  	    148
D-3   Compounds Identified in Paraffin Fraction of <1.7y Air
          Particulate Collected in Kanawha Valley, WV (Trip 3, PI/LI)   .    15°
D-4   Compounds Identified in Base Fraction of < 1.7 y Air Particulate
          Collected in Kanawha Valley, WV (Trip 3, PI/LI)  	    151
E-l   Very Volatile Organic Compounds Identified in Ambient Air in
          Front Royal, VA (Trip 1, P1/L4)	    157
E-2   Very Volatile Organic Compounds Identified in Ambient Air in
          Front Royal, VA (Trip 1, P2/L5)	    158
E-3   Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip 1, P3/L2)   	    159
E-4   Very Volatile Organic Compounds Identified in Ambient Air in
          Front Royal, VA (Trip 1, P3/L6)  	    161
E-5   Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip .1, P3/L6)	    162
E-6   Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip 2, P2/L3)   	    164
E-7   Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip 2, P3/L5)   	    166
E-8   Very Volatile Organic Compounds Identified in Ambient Air in
          Front Royal, VA (Trip 3, P1/L9)	    168
E-9   Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip 3, P2/L8)   	    169
E-10  Volatile Organic Compounds Identified in Ambient Air in Front
          Royal, VA (Trip 3, P2/L9)   	    171
F-l   Compounds Identified in Methanol Extract of <1.7y  Fraction of Air
          Particulate Collected in Front Royal, VA (Trip 3, PI/14) . .  .    175
F-2   Compounds Identified in Toluene Extract of  <1.7y  Fraction of Air
          Particulate Collected in Front Royal, VA (Trip 3, P1/L4) ...    177
                                      xi

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                                ACKNOWLEDGEMENTS

     The valuable assistance in sample collection,  workup,  method develop-
ment, and data interpretation by Ms.  S.  P.  Parks is gratefully acknow-
ledged.  Also, field assistance by Mr. C.  A.  Billings,  advice from Dr.
C. M. Sparacino, and mass spectral support from Ms. D.  Smith, Dr. K.
Tomer, Dr. J. T. Bursey, and Ms. N. P. Castillo are greated appreciated.
     The sampling of ambient air in the Kanawha Valley  was  assisted by
advice from Mr. Ronald Engle of the West Virginia State Air Pollution
Control Commission and the individuals who provided sampling locations.
     Sampling in the Shenandoah Valley was assisted by  suggestions from
Mr. Nick Kappel of the Virginia State Air Pollution Board and the indivi-
duals who provided sampling locations.
     We wish to thank Messrs. Robert Burton,  William Bernard, and Randy
Baxter of Environmental Assessment Branch, Health Effects Research
Laboratory, EPA, RTP, N. C. for the use of the Massive  Air Sampler and
the plate scraping facilitites.
     Finally, the encouragement and advice from Messrs. Daniel FitzGerald
and Ted Erdman of Region III, EPA are deeply appreciated.
                                    xii

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                                  SECTION 1
                                INTRODUCTION

     This study is an outgrowth of a long-term research program to develop
and perfect a comprehensive and systematic approach to the measurement of
organic compounds in ambient air.   Previous research has demonstrated that
a wide range of atmospheric contaminants may be readily measured by this
technique.  Until this technique was developed, the ability to collect and
analyze a wide variety of chemical classes from the atmosphere containing
toxic and/or carcinogenic compounds was not possible.  Thus, the health
impact of these compounds had not been thoroughly studied.  The techniques
used in this study enable the characterization of a wide profile of organic
compounds in ambient air.  These profiles provided a panoramic view of the
pollution at specific sites and times.
     Organic compounds are present in the atmosphere at widely varying
levels and may be either site-specific or ubiquitous.  Sources of these
compounds include natural emissions, manufacturing, automobile exhaust,
dry cleaning, combustion sources and others.  To complicate the milieu,
atmospheric reactions degrade some compounds and form others.
     The data generated by this technique will allow researchers to identify
and quantitate a complex mixture of organic air pollutants in order to
begin studing the sources, health effects and environmental effects of
the s e c omp ounds.

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                                  SECTION 2
                           SUMMARY AND CONCLUSIONS

     This study was designed to measure a wide range of organic pollutants"
in two industrialized valleys: the Kanawha Valley, WV and the Shenandoah
Valley, VA.  The Kanawha is heavily industrialized with a wide variety of
chemical industry stretching for roughly 40 km.  The valley is narrow with
high hills providing a well-defined emission reservoir.  The metropolitan
population is roughly 150,000.  Sampling locations were selected at various
sites throughout the valley to assess the general levels of organic compound
In contrast, the Shenandoah is heavily reliant on tourists and its only
major chemical industries are a viscose rayon plant and an allied sulfuric
acid plant.  The valley is broad and ill-defined near Front Royal (populatio;
about 10,000) and would not be expected to trap pollution to any great
extent.  Sampling sites were selected both upwind and downwind of the
industrialized area, and in the center of town in order to assess pollution
levels in the area.
     Very volatile organic compounds in ambient air (e.g., vinyl chloride)
were concentrated on carbon cartridges.  Volatile organics (e_.g_. , acetone
through naphthalene) were collected on Tenax GC sorbent cartridges.  Typical
sampling volumes for both carbon and Tenax GC samples were 200-600 £ of
air.  Semivolatiles (e.g., polynuclear aromatics) were collected as particu-
late using a Massive Air Sampler which collected the <1.7 |J respirable
particulate fraction of interest on electrostatic precipitation plates.
                                                         3
Typical particulate sampling volumes were 20,000-90,000 m .
     The volatile and very volatile compounds collected on the sorbent car-
tridges were analyzed by thermal desorption in line with a gas chromatograph,
mass spectrometer/computer (GC/MS/COMP).  High resolution was achieved
using an SE-30 SCOT capillary column.  The semivolatile compounds were
extracted from the particulate, fractionated and then analyzed by capillary

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column GC/MS/COMP.  Data were interpreted by comparison with known mass
spectra from spectral libraries.  Selected compounds in the volatile
fraction were quantitated using the intensities of selected mass ions.
     The volatile compounds identified in the Kanawha Valley (with the
number of times observed out of ten samples interpreted) include: vinylidene
chloride and/or the dichloroethylene isomer (8), methylene chloride (10),
chloroform (10), 1,2-dicixloroethane (2), 1,1,1-trichloroethane (8), 1-
chlorobutane (1), carbon tetrachloride (8), dichloropropene (1), trichloro-
ethylene (6), 1,2-dibromoethane (2), tetrachloroethylene (9), chlorobenzene
(1), dichlorobenzene (8), acetaldehyde (9), benzaldehyde (9), aliphatic
aldehydes (11), acetone  (10), acetophenone (7), benzophenone (4), 21 other
ketones, ethyl acetate (6), seven other esters, isopropanol (2), phenol
(7), six other alchols, diethyl ether (5), diphenyl ether (4) and eight
other ethers, benzene (9), alkyl benzene, indan (7), indene (1), naphthalene
(8), alkyl naphthalenes, biphenyl (7), CS  (6), other sulfur-containing
compounds, cyanobenzene  (1), C -alkyl pyridine  (1), and many alkanes.
                                                     3
Quantitative results included high values of 334 ng/m  for methylene
                   3                                         3
chloride, 1536 ng/m  for tetrachloroethylene, and 71,778 ng/m  for benzene.
Compounds identified in the particulate fraction included long-chain
alkanes, polycyclic aromatic hydrocarbons (PAH) from naphthalene through
anthanthrene (or an isomer), alkyl-PAH derivatives, and nitrogen-
containing heterocycles.
     In the Shenandoah Valley, VA, the volatile compounds identified  (with
the number of times observed out of nine samples interpreted) include:
vinylidene chloride and/or the dichloroethylene isomer (9), methylene
chloride (9), chloroform (9), 1,2-dichloroethane (1), 1,1,1-
trichloroethane (3), carbon tetrachloride (6),  trichloroethylene (3),
tetrachloroethylene (6), dichlorobenzene (5), acetaldehyde (9), benzaldehyde
(6), nine aliphatic aldehydes, acetone (9), acetophenone (6), benzophenone
(2), three other ketones, ethyl acetate (4), phenol (5), five alkyl phenols,
diethyl ether (8), benzene (8), alkyl benzenes, indan (5), naphthalene
(6), alkyl naphthalenes, biphenyl (3), and alkanes.  Quantitative results
                                   3                                    3
include high values of 238,000 ng/m  for methylene chloride, 14,500 ng/m
for chloroform, 2,933 ng/m , 1,1,1-trichloroethane, 2,994 ng/m  for

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                                3                            3
tetrachloroethylene, 24,000 ng/m  for benzene, and 3,721 ng/m  for aceto-
phenone.  Semivolatile compounds identified included polycyclic aromatic
hydrocarbons (PAH) from naphthalene through C~~H,2, alkyl-PAH derivatives,
oxygenated PNAs, (ketone and anhydrides), sulfur heterocyclic PNAs,  and
aliphatic hydrocarbons.
     Many more compounds were identified with greater frequency in the
Kanawha Valley than in the Shenandoah Valley.  This is especially noticeabl
in the pollutants potentially arising from industrial activity (halogenated
and oxygenated compounds).  Many compounds, including the aromatics,
result from combustion (e_.£. , automobile exhaust) or other sources which
could be considered ubiquitous.  This qualitative comparison is in keeping
with the greater industrial diversity and higher population density of the
Kanawha Valley.
     In contrast to the qualitative data, the quantitative data showed
much higher levels of most organic pollutants in the Shenandoah Valley
than in the Kanawha Valley.  This is espeically noteworthy, since the
Shenandoah Valley is broader and well-defined and is therefore not expected
be as good an emission reservoir as the Kanawha Valley.  The high levels
in the Shenandoah Valley were found on both Trips 1 and 2, implying that
the levels found are not fortuitous.

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                                  SECTION 3
                               RECOMMENDATIONS

     The results of this study indicate the widespread occurrence of organic
compounds in ambient air in these two valleys, sometimes at higher levels.
Further research may be directed along eight major fronts:
     (1)  More vigorous sampling protocols could hopefully identify point
source polluters for possible regulatory action.
     (2)  Long-term monitoring of these valleys may provide both mean
concentration data and show any trends in levels of compounds.  This data
could be useful in identifying industrial pollutants and in establishing a
data base for future epidemiological studies.
     (3)  Future studies could integrate this type of air monitoring with
sampling and analysis of other media including water, sediment, soil, vege-
tation, human tissue, mothers milk, etc.
     (4)  Future studies should more comprehensively study the correlation
of meteorology with pollutant levels (i.e_. , Do concentrations of specific
pollutants rise during an inversion?).
     (5)  Epidemiological studies could begin to attempt to correlate
disease incidence (e_.g. , cancer) with levels of toxic and/or carcinogenic
compounds in air and other media to which humans are exposed.
     (6)  Expansion and perfection of the techniques reported herein could
present a more complete picture of the pollution in these valleys.
     (7)  More research along the lines of this study and the recommendations
given above is needed to fully characterize the air pollution associated
with industrialized valleys.  Future studies should include both industri-
alized, residential/commercial, and uninhabited valleys.  In addition, more
samples taken over longer time periods are needed to accurately assess
pollutant levels.

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     (8)  Since it appeared that the highest concentrations of some pollu-
tants may have occurred at night, it may be important in future studies to
integrate the samples for at least 24 hr and/or take consecutive samples
which cover entire 24 hr periods.

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                                  SECTION 4
                                 OBJECTIVES

     This study was designed to provide information on the general organic
air pollutant levels in two industrialized valleys.  In specific:
     (1)  Samples were to be collected at three monthly intervals to assess
          changes of pollutant levels with time.
     (2)  Samples were to be collected at locations selected to show general
          pollutant levels in the valley, especially the levels effecting
          the human population.
     (3)  Samples were to be analyzed by gas chromatography/mass spec-
          trometry/computer to provide accurate and positive identification
          of the compounds present.
     (4)  Qualitative and quantitative data were to be presented such that
          EPA, Region III personnel could determine the extent to which
          organic chemicals may affect the human population in the areas
          sampled.

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                                  SECTION 5
                                  SAMPLING
SAMPLING EQUIPMENT
     Due to the wide range of compounds sought, it was necessary to use
more than one collection method.  Highly volatile compounds were collected
on carbon cartridges.  Compounds of medium volatility were collected on a
polymeric sorbent cartridge (Tenax GC).  Particulates were collected on
impactor and electrostatic precipitation plates using an ultra-high volume
Massive Air Sampler (MAS).
Collection of High- and Medium-Volatility Organics on Carbon and
Tenax GC
     High and medium volatility materials were concentrated from ambient
air on a sampling train consisting of (1) a glass fiber filter (GFF),  (Z) a
cartridge of Tenax GC, and (3) a cartridge of carbon, sequentially.
Glass Fiber Filter (GFF)—
     As illustrated in Figure 1, the glass fiber filter (GFF) was placed at
the front end of the sampling train, held in place by a 25 mm Delrin filter
holder.  Gelman Type A-E 25 mm diameter filters were used.  These filters
are rated at 99.7% efficiency for particles greater than 0.3 pm by the
dioctyl phthalate permeation test, and at 98% efficiency for particles of
0.05 (Jm diameter or larger.  The filter was used primarily to exclude
particulate containing non-desorbable compounds which would contaminate the
Tenax GC.
     A series of experiments were conducted to determine whether the GFF
excluded chromatographable compounds from the Tenax GC cartridge.  Parallel
cartridges, with and without the GFF, were sampled near a highway intersec-
tion with a large number of diesel trucks starting and stopping  (U. S. 70
and Old U. S. 70, Bethesda, NC).  Gas chromatographic analysis with flame
ionization detection  (GC/FID) of these two cartridges yielded similar  gas

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                       GLASS CARTRIDGE SAMPLER
                                              GLASS
                                              V/OOL
                        VAPOR COLLECTION SYSTEM
      GAS
     METER
                       FLOW
                       METER


PUMP



A
CARTRIDGE

\|
GLASS
FIBER
FILTER
NEEDLE
VALVE
Figure 1.  Collection system for  concentrating high and medium
           volatility organic  compounds from ambient air.

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chromatograms,  indicating no desorbable compounds were being excluded from
the Tenax GC cartridge by the GFF.   Based on these results, the GFF was
retained in the sampling train, since its use allowed recycling of the
Tenax GC resin.
Tenax GC Sampling Cartridges—
     The sampling tubes were prepared by packing a 10 cm x 1.5 cm i.d.
glass tube containing 6.0 cm of 35/60 mesh Tenax GC (1.6 g) with glass wool
                               (1-3)
in the ends to provide support.       Virgin Tenax GC was extracted in a
Soxhlet extractor for a minimum of 18 hours with acetone prior to prepara-
                           (1 21
tion of cartridge samplers.  '    In those cases where sampling cartridges
of Tenax GC were being recycled, the sorbent was extracted in a Soxhlet
apparatus with acetone, as described for the virgin material, and also
extracted with a non-polar solvent, hexane, in order to remove the relative]
non-polar and non-volatile materials which might have accumulated on the
sorbent bed during previous sampling periods.
     After purification, the Tenax GC was meshed to provide a 35/60 particle
size range.  Cartridges were then prepared and conditioned at 270°C with
helium flow at 30 ml/min for 20 minutes.  The conditioned cartridges were
transferred to Kimax  (2.5 cm x 150 cm) culture tubes, immediately sealed
using Teflon-lined caps, and cooled.  This procedure was performed in order
                                            (1 2)
to avoid recontamination of the sorbent bed.  '    One or more cartridges
selected at random from each batch were checked for background using GC/ITD.
If the background was unacceptable, the cartridges were redesorbed and
checked again.
     For large sample volumes it is important to realize that elution of
certain organic compounds through the sampling tube will occur if their
breakthrough volume is exceeded.  The breakthrough volume is defined as
that point at which 50% of a discrete sample introduced into the cartridge
is lost.  The breakthrough volumes of some representative compounds are
shown in Appendix A.   »>»>•'  These breakthrough volumes have been
                                               (1 4)
determined by a previously described technique.  '    Although the identity
of a compound during ambient air sampling is not known  (therefore, also its
breakthrough volume) the compound can still be quantitated after identifi-
cation by GC/MS/COMP once the breakthrough volume has been established.
                                     10

-------
Thus, the last portion of the sampling period represents the volume of air
sampled prior to breakthrough.  For cases when the identity of the compound
is not known until after GC/MS/COMP analysis, the breakthrough volume is
determined after the fact and the quantitation accomplished as above.
     Previous experiments have shown that organic vapors collected on Tenax
GC sorbent are stable and can be quantitatively recovered from the cartridge
samplers up to four weeks after sampling when they are tightly closed in
cartridge holders, protected from light, and stored at 0°C.
Carbon Cartridges—
     High purity charcoal (SKC, Inc., Pittsburgh, PA) was packed into a
bed, 3 x 0.3 cm, in a glass tube.  Carbon from this source has been shown
to be pure for these applications and was used without solvent purification.
Carbon cartridges were thermally stripped of organic vapors by heating to
400°C under He flow for 30 min.
     These cartridges efficiently trap the organic compounds which pass
through the Tenax GC cartridge (vinyl chloride, vinyl bromide, methyl
chloride, and methyl bromide).  They have been successfully used to analyze
vinyl chloride and the other highly volatile halocarbons (b.p. <30°) which
are not retained on Tenax GC to any significant extent.     The breakthrough
volume for vinyl chloride, and thus the amount collectable, on the carbon
cartridges is about 20 times that of Tenax GC.
Sampling Apparatus--
     Continuous sampling of ambient air was accomplished using a Nutech
Model 221-A portable sampler  (Nutech Corp., Durham, NC, see Figure 1).  The
flow was monitored through a calibrated rotameter, and the total flow
registered by a dry gas meter.  Concomitant with these parameters, the
temperature was also noted, since it was important for establishing the
breakthrough volume and therefore the total sampling volume which can be
used for quantitation.  This portable sampling unit operated on a 12-volt
storage battery and was operated from 4-12 hrs, depending on the sampling
conditions and flow rates used.  Duplicate cartridges were deployed on each
sampling unit.  A total of four portable sampling units were available for
sampling.
                                     11

-------
     At the same location as the MAS (vide infra),  a duPont Model P-200
personnel sampler was used to continuously sample air onto carbon and Tenax
GC cartridges over the entire period that the MAS was operated.  The duPont
personnel sampler, operated at about 200 cc/min, was powered by a 6V lantern
battery and the entire sampler housed in a chrome-plated aluminum box.
                                                                          *
Collection of Low-Volatility Organics Using a Massive Air Sampler
(MAS)
 —p.iia.i f                                                                      m
     A Massive Air Sampler (MAS) manufactured by Battelle Memorial Institute,
            (8 9)
Columbus, OH  '   was used for collecting particulate fractions in the
3.5 - 20, 1.7 - 3.5 and <1.7 micron ranges.  Preliminary studies (personal
communication R. Burton, Environmental Assessment Branch, HER1, USEPA, RTP,
NC) indicated that the larger particle range yielded greater than 1 g in a
                                   3
100 hr collection period at an 18 m /min sampling rate.  The middle sized
particle range was found to be approximately 0.8 g while the smallest
particles were well over 3 g for this collection period and rate.
     The sampler, about 140 cm tall and 60 cm square, is a large cascade
impactor with electrostatic precipitation for collection of the fine
particulate which is not impacted.  Air is sampled at a rate of 630 cfm  (18
m /min) by a blower using a 750j/sec motor (115 V,  12 amps).  The air enters
the sampler over a lip enclosed by the cover which serves as a scalping
stage with a cutoff of about 20 [J.  The air then enters the impactor assembly
stages consisting of four Teflon-coated plates  (28 x 43 cm).  The first  and
third plates have slots which serve as impactor jets.  The second and
fourth plates are the collection target plates  located about 1 cm below  the
jet plates.  Below the impactor sections is the electrostatic precipitator,
consisting of ionizing wires (-10 kV) and 55 Teflon-coated collection
plates (28 x 43 cm).  The plate potential is adjusted to the maximum achiev-
able without excessive arcing (generally 5-7 kV, depending on the humidity).
From the electrostatic precipitation section, the air is drawn to the
blower and then to exhaust.  The control panel  consists of a magnahelic
vacuum gauge to register the flow, a run time meter  (in hours), a volt
meter to indicate the voltage applied across the precipitator plates, and a
red flashing light to indicate malfunctions.
                                       12

-------
     For the purpose of this study, the MAS was chained into a pickup truck
for transportation and left in situ during sampling.
     Upon return from the field, the impactor and electrostatic precipitator
plates were scraped into glass vials, kept in the dark, and stored under
nitrogen at -5° to retard chemical reactions.  The plates were scraped in a
specially designed glove box to prevent contamination of the sample and for
protection of personnel.
METEOROLOGY
     Continuous measurements of temperature, wind direction and wind run
were recorded on a MRI (Meteorological Research, Inc.  Altadena, California)
Mechanical Weather Station (MRI) at a central location through the sampling
period.  The strip chart record allowed subsequent reference to calm periods,
wind direction shifts, etc., which could affect sampling results.  Intermit-
tent measurements were made at each sampling location.  Humidity, tempera-
ture, wind speed, and wind direction were measured and noted along with
general conditions (rain, snow, cloud cover, odors, etc.).  Measurements at
each location provided a cross-check with the MRI record.
     Pertinent meteorological data for the sampling period were obtained
from the nearest National Weather Service office.  This data was used to
augment that obtained at the sampling location.
SAMPLING PROTOCOLS
     Samplers were set out at locations designated in a numercial sequence
(e.g. LI) for a sampling period (e.g. PI).  Thus, each sample is designated
by a unique Trip/Period/Location (e.g. Trip 1, P2/L6) code.  This code is
presented in the sampling protocol tables and then used to identify samples
in the analytical results.
SAMPLING LOCATIONS
     Kanawfaa Valley
     Many manufacturers of organic chemicals which, along with the by-
products, are potentially toxic, carcinogenic and/or teratogenic are located
in the Kanawha Valley, W.V. (Figure 2).  DuPont, near Belle, has a large
chemical complex for the synthesis of substances such as methyl-methacry-
late, methylamines, ammonia, hydrogen cyanide, herbicides, and insecticides.
In South Charleston are production and consumption plants (Union Carbide,

                                      13

-------
and FMC).  Plastics, PVC, antifreeze, chlorine, halogenated organics,
carbon disulfide, peroxides, etc.  are the predominant chemicals produced
here.  The major facility in the town of Institute is Union Carbide which
also processes a broad spectrum of compounds, e. g.,  viscose rayon, and
phthalate esters.  There is also a large scale olefin processing complex
and a rubber accelerator plant.  A major terminal loading facility in South
Charleston handles large quantities of a variety of organic compounds.
Monsanto, FMC, Allied, and Fike have plants near Nitro for the production
of antioxidants, rubber accelerators, industrial chemicals, and other
materials.  Several other chemical manufacturers, consumers, and transporters
are located in the Kanawha Valley, some or all of which may contribute to
the presence of organic materials in the ambient air.
     Previous sampling and analysis efforts have found a wide variety of
organic compounds in ambient air.   '  '     These results were used in part
to select locations for sampling during this study.
     The rationale for selection of the locations in the Kanawha Valley was
to place samplers at several points along the valley floor throughout the
industrialized, metropolitan Charleston, WV area.  The location was selected
within a general area by sampling personnel on the basis of estimates on
where high concentrations of air pollutants might be detected, the potential
for human exposure, security of personnel and equipment, and also approval
of property owners where applicable.
     The MAS, duPont sampler, and MRI weather station were located at the
North Charleston Community Center (21st St. W. and 7th Ave., W.) based on
recommendations from personnel in the Environmental Assessment Branch,
HEEL, EPA, RTP, NC who had sampled there previously with the MAS.  This
location provided not only power,  but fenced-in areas for security.  Cen-
trally located in the valley, this location was judged to provide "average"
meteorology and air samples.
     The other four samplers were located up and down the valley at locations
in Belle, South Charleston, St. Albans or Institute,  and Nitro.
     The sampling locations, times, volumes, and meteorology are summarized
in Tables 1-4.  The location numbers are shown on detailed maps (Figures 3-
6).
                                    15

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Figure 3.  Map of area around Nitro,  WV showing L4, L6,  L7,
           and L9 (See Table 1).

                          20
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Figure 6.  Map of area around W. Belle, WV showing L5  (See
           Table 1).
                           23
-------
     Shenandoah Valley
     The Shenandoah Valley, near Front Royal, Virginia,  is less higiily
industrialized than the Kanawha Valley.  However,  the potential for man-
made pollution above and beyond that of day-to-day human activity does
exist.  In Front Royal, Allied Chemical Corporation operates an organic
chemicals plant and Avtex, Inc. produces cellulosic man-made fibers.  The
                          (12)
other manufacturers listed     in Front Royal and the small towns in the
vicinity include fabric mills, clothing manufacturers, canneries, producers
of crushed rock, and printers.  Because of its size (2200 employees), the
Avtex plant may be assumed to be the primary industrial source of organic
compounds in ambient air.
     The rationale for selection of sampling locations in the Shenandoah
Valley, VA was completely different from that in the Kariawha Valley, WV.
The only large industrial area of interest to this study (by direction of
the project officer) was in Front Royal, where Avtex fibers and Allied
Chemical Co. are located on adjoining plant sites.  Since the sampling area
was relatively small (Figure 7) and organic pollutants of interest were
suspected of coming from a point source, sampling locations were chosen in
a general array surrounding this point source.  During each sampling period,
locations were selected generally downwind (as determined by smell and the
direction of stack emission plumes) and upwind for control.  As with the
Kanawha Valley, personnel determined sampling locations based on estimates
of where high concentrations of pollutants might be detected, potential for
human exposure, security of personnel and equipment, and other factors as
necessary.
     The MAS, duPont sampler, and MRI weather stations were located in
downtown Front Royal at the fire department.   With personnel on duty full
time, this represented the safest location available in the area which also
fulfilled the power requirements of the MAS.  The duPont sampler and the
                                                                         *
MRI weather station were placed atop the fire station (about 10 m elevation^
     The sampling locations, times, volumes, and meteorology are summarized
in Tables 5-8.  The location numbers in Tables 5-8 are shown on a detailed
map (Figure 8).
                                      24
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   \*	1 km	»j
Figure  7.  Front  Royal, VA.
                            25
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30
-------
PARTICULATE COLLECTED WITH MAS
     Table 9 summarizes the amounts of particulate scraped from the collec-
tion plates of the MAS.  During the first trip to both locations the ionizing
wires were broken and the collection of < 1.7 M particulate was very poor.
The second trip to Charleston resulted in low collection due to high humidity
and occasional rain which forced operation of the sampler at a lower plate
voltage (and concomitant lower collection efficiency).  In addition, the
rain scrubbed most of the particulate of interest out of the air.  No
particulate was collected on the second trip to Front Royal due to a
steady rain throughout most of the sampling period.  The rain not only
scrubbed most of the particulate of interest from the air but also prevented
operation of the MAS with any voltage supplied to the electrostatic precipi-
tator plates due to excessive arcing.  During the third trip to both Front
Royal and Charleston, cool, dry weather permitted long collection periods
at high plate voltages.  These conditions allowed collection of more than
one gram of < 1.7 p particulate from both locations.  Only the samples from
Trip 3 were sufficient for GC/MS/COMP analysis.
                                      31
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-------
                                  SECTION 6
                               SAMPLE ANALYSIS
ANALYSIS OF TENAX GC CARTRIDGES BY GC/MS/COMP
     Air samples collected on Tenax GC cartridges were analyzed by capillary
column GC/MS/COMP.  The whole sample was introduced to the analytical
system by thermal desorption into a cryogenic capillary trap and thence
rapidly swept onto the chromatographic column.  Each cartridge was loaded
with a known amount of perfluorobenzene and perfluorotoluene for use in
quantitation.  Qualitative data interpretation was done by visual inter-
pretation of the spectra and comparison with standard reference spectra.
Quantitation was achieved by integration of a characteristic mass for a
compound over the chromatographic peak.  The amount of compound in the
sample was then calculated using the relative molar response factor and the
integrated area for a standard.  The concentration in ambient air was then
calculated using the volume sampled or the breakthrough volume, whichever
was larger.  Complete details of the sample analysis are in Appendix A.
ANALYSIS OF CARBON CARTRIDGES BY GC/MS/COMP
     Carbon backup cartridges contained the very volatile compounds which
have very low breakthrough volumes on Tenax GC (and thus would have high
detection limits).   The cartridges were not amenable to direct thermal
desorption/analysis due to high background (notably water).  However, the
compounds of interest (methylene chloride, vinyl chloride, acetaldehyde,
etc.) were eluted from the carbon cartridge at 270° onto a Tenax GC cartridge
using helium.  These Tenax GC transfer cartridges were then analyzed in the
manner described for the Tenax GC cartridges collected in the field.  This
procedure was fully validated on previous contracts.  Complete details of
the sample analysis are in Appendix B.
                                     33
-------
ANALYSIS OF SEMIVOLATILE ORGANICS COLLECTED BY MAS SAMPLES
Extraction/Partition Scheme
     Two extraction/partition schemes were used for extraction of the
semivolatile organics from air particulate.  The first scheme, used on
the < 1,7 (J fraction collected in Charleston, WV during Trip 3, yielded
six fractions.  This extent of fractionation resulted in concentrations
which were too low for effective GC/MS/COMP analysis.  A second scheme,
employed for the < 1.7 |J fraction for Front Royal, VA during Trip 3,
resulted in two fractions and yielded much more concentrated samples.
The GC/MS/COMP data from this sample were easier to interpret.
     Analysis efforts were directed toward the < 1.7 n fraction, as this
size particle is the most easily lodged in the respiratory system and is
therefore most significant with respect to potential human health effects.
For reasons discussed in the Sampling Section, only the samples collected
on Trip 3 were of sufficient volume to warrant extraction and analysis.
     The <1.7 |J fraction, scraped from the electrostatic: precipitator
plate of the MAS, was extracted by repeated sonication with cyclohexane
and then with methanol.  The methanol was effective in removing the more
polar compounds.  The extracts were then combined and fractionated
according to the scheme presented in Figure 9.  The individual fractions
were then concentrated for GC/MS/COMP analysis.  This extraction scheme
                                     (13)
was developed under another contract.
     The efficacy of the scheme was assessed by subjecting a mixture
containing known amounts of compounds to the partition procedure.  The
mixture consisted of benzoic acid, phenol, quinoline, hexadecane, phenan-
threne and ethylene glycol.  The compounds were chosen to represent the
five classes of materials produced by the partition scheme (all these
materials have been found in air particulate samples, except ethylene
glycol).  No information on the composition of the polar neutral fraction
was available, therefore ethylene glycol was included as a likely component
of this fraction based on its known chemical properties.,  The experiment -
was conducted using both large and small mass samples.  Recoveries were
determined gravimetrically.
     As a further check on the procedure, thin layer chromatography  (TLC)
scans were conducted on each fraction to ascertain the extent, if any, of
                                      34
-------
                            PARTICULATE
              ACIDS
                      INSOLUBLES
            NON-POLAR
             NEUTRALS
             BASES
PNAs
POLAR
NEUTRALS
Figure 9.   Fractionation scheme used for fractionating air
           particulate collected in Charleston, WV (Trip 3,
           PI/LI).
                                  35
-------
compound spillover into other fraction(s).   No such spillover was
detected.
Scheme Used for Front Royal, VA Sample —
     The sample was weighed, 102 (Jg d10-pyrene (Merck & Co., Rahway, NY)
added as an internal standard, and allowed to equilibrate overnight.  The"
sample was then extracted with toluene and methanol as shown in Figure 10.
The two fractions thus generated were analyzed by GC/MS/COMP.
GC/MS/COMP Analysis
     Samples were analyzed using a 1KB 2091 gas chromatograph/mass spectrom-
eter with a dedicated PDP-11/34 data system.  The samples were chromato-
graphed on an OV-101 capillary column (25 m, WCOT, obtained from LKB).  The
column was held at 100°C for 2 minutes after injection, and then heated to
265°C at a rate of 8°/min.  Carrier gas flow rate was 2.0 ml/min with a
split ratio of 10:1.  Injector temperature was 240°C.  Mass spectral scans
were taken every 3 sec scanning from 5-492 amu.  The ion source temperature
was 200°; electron energy, 70 eV; trap current, 50 |iA; accelerating voltage
3500 V; and multiplier setting 425-450.  Total ion current and mass spectra
plots were generated for interpretation.
     Data were interpreted by comparison of the unknown spectra with standa:
reference collections.  Where no reference spectrum was available, or where
spectral quality was not sufficient for positive identification, the com-
pounds were labeled "tentative."  All interpretations were made independent!
by two chemists and then correlated.  Further validation of equivocal
identifications was made by consultation with other chemists and spectros-
copists experienced in similar research.  This mass spectral interpretation
protocol was established to extract the maximum information from the data
and to guard against misidentification.  Quantitation of the compounds
identified in the semivolatile fractions was not feasible due to a lack of
available standards to generate relative molar response factors.  Rough
quantitation may be made by comparison of peak heights on the total ion
current chromatograms.
                                     36
-------
                             PARTICULATE
   Sonicate 30 min. under
   4 ml toluene ^ 60° —
   Repeat 4 x
       Centrifuge
   Concentrate Supernatants
   under N- stream
   GC/MS Analysis:
   "Toluene Fraction"
Sonicate 30 min
under 3 ml methanol
— Repeat 4 x
   Centrifuge
Concentrate Supernatants
under N  stream
Add 1 ml Water
                                                Extract with 1 ml
                                                methylene chloride
                                                — Repeat 3 x
                                                Dry over Na.SO,
                                                Concentrate under
                                                N- stream
                                                GC/MS Analysis:
                                                "CH2C12 Fraction"
Figure 10.  Extraction scheme used for fractionating air particulate
            collected in Front Royal, VA.
                                   37
-------
                                  SECTION 7
                                   RESULTS

     All of the samples were analyzed for volatile and very volatile
compounds.  The GC/MS/COMP data were stored on magnetic tape for subsequent
processing as discussed below.
     Data from about one-quarter of the sampling locations were selected
for qualitative interpretation.  The selection of samples was based on
knowledge obtained during sampling (e.g. meteorology, odor, observation of
plumes, etc.) and inspection of the total ion current chromatogram from
the GC/MS/COMP analysis.  Only selected samples were interpreted because
the compounds found in the area are not likely to be unique to a particular
sample.  Thus, interpretation of all data would have been redundant.
     A number of compounds were selected for quantitation from the lists
of compounds identified.  Quantitation was performed on all samples.  All
halogenated compounds found were quantitated and only representative com-
pounds from other classes were quantitated.  The values presented in the
tables below were not corrected for recoveries.  The recoveries of standard:
loaded onto cartridges are presented in Table 11.  Since recovery correctioi
were not made, all concentrations must be regarded as minima.  Where trace
(not quantitated) levels were observed, the designation "T" is followed by
the detection limit in parentheses.  Where no compound was observed, the
detection limit is shown.  The detection limits varied widely and were
dependent upon the breakthrough volume  (which is temperature-dependent),
volume sampled, and relative molar response, as discussed above.  As these
parameters were not constant among the  samples, the detection limits
varied widely.  In some cases compounds were identififed in the qualitative
analysis scheme, but were reported below the detection Limit in the quant-i-
tation.  This is due to the threshold set during the quantitation to
prevent noise from being quantitated and reported.  Thus, trace quantities
which were observed in the qualitative  data interpretation were not detecte>
during quantitation.  These samples may be regarded as trace.
                                      38
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ORGANIC COMPOUNDS IN THE KANAWHA VALLEY, WV
Volatile Organics
     The volatile compounds identified on Tenax GC and/or carbon cartridges
at ten locations are presented in Table 11.   Alkanes and alkenes were
generally not listed in the summary tables due to their ubiquity and rela^
tively benign environmental effects.   Full lists of the compounds found in
each sample are contained in Appendix C.  The quantitative results for the
halogenated hydrocarbons and representative compounds in other chemical
classes are presented in Tables 12-14 and 15-17,  respectively.
Halogenated Hydrocarbons—
     The levels of halogenated hydrocarbons in the Kanawha Valley during
the first trip were generally low.  Significantly higher levels were observe
on the second trip, especially in South Charleston (P2/L2).  During the
third trip, significant levels of some compounds were observed at several
sites, including S. Charleston (P3/L2) Charleston (PI/LI), and Institute
(P2/L8).
     Trichloroethylene concentrations at L4 were consistently higher than
at other locations.  Similarly, higher concentrations of tetrachlorethylene
were observed occasionally in South Charleston (L2).  High levels of chloro-
form, methylene chloride, and carbon tetrachloride did not seem to be
correlated to any specific location and were often independent of each
other.
Volatile Organics - (Non-halogenated)—
     As with the halogenated compounds, the organic concentrations during
the first trip were generally low.  Very high concentrations were observed
during the second trip in St. Albans and, to a lesser extent in S. Charlesto
Moderately high levels of some compounds were observed in Institute during
both sampling periods of Trip 3.
     As expected, the levels of aromatics (benzene, toluene, and naphthalene
show a loose general correlation.  The acetophenone level on Trip 3, P2/L2
was more than ten times higher than any other observed level.  Similarly,
the ethyl acetate level on Trip 2, P2/L3 was 30 times higher than in any
other sample.
                                      40
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Correlation between Levels of Halogenated and Non-halogenated Organics —
     There are no general correlation between the levels of halogenated and
non-halogenated organics in the Kanawha Valley.  Two samples (Trip 2,
P2/L2 and P2/L3) contained high levels of both halogenated and non-halo-
genated compounds.
Semivolatiles
     The compounds  identified in the polar neutral, PNA, paraffin and base
fractions of the <1.7 p air particulate are shown in Appendix D.  The few
compounds identified in the acid fraction were contained in other fractions
also.  It should be noted that the computer scales the TIC plot to the
largest peaks.  Therefore quantitative comparisons between fractions are
not possible.
ORGANIC COMPOUNDS IN THE SHENANDOAH VALLEY, VA
Volatile Organics
     A summary of the volatile compounds identified on Tenax GC and/or
carbon cartridges at nine locations are presented in Table 18.  Alkanes and
alkenes were generally not summarized because of their ubiquity and rela-
tively benign environmental effects.  Full lists of the compounds found in
each sample are contained in Appendix E.  The quantitation results for the
halogenated hydrocarbons and representative compounds in other chemical
classes are presented in Tables 19-21 and 22-24, respectively.
     The highest concentrations of volatile organics found on Trip 1 was at
P2/L3 and P2/L5 which were night samples.  P2/L3 was downwind of the Avtex
plant at least part of the sampling period.  The other samples obtained on
this trip contained moderate amounts of volatile organics.  The samples
collected during Trip 2 contained high amounts of volatile compounds.  The
highest concentrations were again in the overnight samples (P1/L4, P2/L3,
and P2/L5).  L4 and L5 were in the downtown Front Royal area, which was in
the floor of the valley.  Thus, settling of pollutants in the lower areas
during a night-time atmospheric inversion may have contributed to these
high values.  The other location (L3), however, was on top of a hill, so
atmospheric inversion conditions would not explain high values at this
point.  The values  obtained for P1/L3 were also relatively high.  This
sample was collected during the late afternoon-evening, so some of the
                                      57
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night-time effects discussed above may have been applicable to this sample.
The volatile organic levels during Trip 3 were generally low.
     The most striking feature of the halogenated organic quantitation is
the high levels of the C, halocarbons (methylene chloride, chloroform and
carbon tetrachloride).  Levels of 1,2-dichlorethylene were significant in
two samples (Trip 2, P2/L3 and P2/L5) which were collected overnight.
Levels of vinylidene chloride were significant in two samples collected
during Trip 1 (P2/L3 and P3/L2).
Semivolatiles
     The compounds identified in the toluene and methanol extracts of the
<1.7 |J fraction of air particulate from Front Royal are presented in Appendix
F.  The corresponding peaks are shown in the total ion current (TIC) chromato-
grams in Appendix F.  The computer scales the TIC chromatograms to the most
intense peak, so quantitative comparison of the two fractions is not
possible,
DISCUSSION
     Many more compounds were identified with greater frequency in the
Kanawha Valley than in the Shenandoah Valley.  This is especially noticeable
in the pollutants potentially arising from industrial activity (halogenated
and oxygenated compounds).  Many compounds, including the aromatics, result
from combustion (e.g. automobile exhaust) or other sources which could be
considered ubiquitous.  This qualitative comparison is in keeping with the
greater industrial diversity and higher population density of the Kanawha
Valley.
     In contrast to the qualitative data, the quantitative data showed much
higher levels of most organic pollutants in the Shenandoah Valley than in
the Kanawha Valley.  This is especially noteworthy, since the Shenandoah
Valley is broader and less well-defined and is therefore not expected to be
as good an emission reservoir as the Kanawha Valley.  The high levels in
the Shenandoah Valley were found on both Trips 1 and 2, implying that the
levels found are not fortuitous.
     The origins of the high levels of pollutants in the Shenandoah and
Kanawha Valleys are not discernible from these data, since wind directions
were inconsistent during most of the sampling.
                                      69
-------
     It appears from the results presented here that the highest concen-
trations of pollutants in the Shenandoah Valley occur at night.  Therefore,
future sampling efforts should make more direct comparisons between day and
night levels at the same locations.
                                        70
-------
                                  SECTION 8
                               QUALITY CONTROL

     Quality control was recognized as an integral and primary component of
this program.  As such, a rigorous quality assurance program was estab-
lished to prevent contamination or loss of sample, mislabeling, and to
provide estimates on the accuracy of the data.  The essential features of
the quality control program are discussed below.
SAMPLING
     The quality control program used for the sampling of ambient air
included sample and data logging, reagent and glassware control, and control
samples as discussed below.
Sample Collection
     During sample collection, a sample data sheet (Figure 11) was maintained
for each sample.  The sampling locations for each sampling period were
recorded on a detailed area map.  The coded form contained information such
as date and time of sampling, locations, sampling parameters and meteoro-
logical information.  The alpha-numeric sample code was also fixed directly
to the sample container at that time.
     Following each day's sample collection, the protocol sheets and sample
labels were independently reviewed by two field personnel to assure that
all information was logged in, that the codes were self-consistent and that
there was no duplication.  Upon returning to the laboratory, the samples
were again checked for proper labeling.  Upon submission for analysis, the
samples were logged in by the GC/MS/COMP operator and a running account of
sample analysis and data output maintained.  When the sample analysis and
data output were completed, the data were returned to the Project Director
and logged in.
     Each sample was collected on duplicate cartridges in parallel.  Thus,
additional quality assurance was provided not only in case of sample damage,
but also for confirmatory analysis if necessary.

                                        71
-------
                     FIELD SAMPLING PROTOCOL
Dace:
(	I
Project No.

Municipality
Location
Site
Sample Code
                Operator
                              Seq.
                   State
No.
           Dimensions
              (cm)
                            Sorbent
                                     M)
                                      M)
                                      M)
                                      M)
Date/Analytical  Procedure
DC Amps
                    Sampling Rate (LPM)_
Rationale:   Qual.  Anal  (F)	

Quant. Anal. (E)	Calibration  (C)_

Experimental:   Lab (L)	 Field  (X)_

Remarks   	
                                            End:

                                          Start:

                                          Total:
      _ Vacuum <"Hg)

       Tiaie
                                                               ft'
       Time
       (min).
                                                               ft'
                                            Volume Air/Cartridge:

                                        0.0283
                                        No. Split
            MAP:
                                  Time
                                            Temp. Wet.
                                  Rel. Humid
                                  Cloud	^
                                  Remarks
                                                Z Wind Dir./Speed	l__
                                                     Odor
                                                            Dry_
                                  Time	 Temp. Wet.	        	
                                  Rel. Humid	Z Wind Dir'. /Speed   T
                                  Cloud	 Odor	
                                  Remarks	
                                  Time	 Temp. Wet.	    	
                                  Rel. Humid	Z Wind Dir./Speed	/_
                                  Cloud	Odor	
                                  Remarks        	   	
                                  Tine
                                  Rel. Humid
                                  Cloud	
                                  Remarks
                                            Temp. Wee.
                 Dry_
                                                Z Wind 'Dir. /Speed   /~~_
                                                     Odor
       Figure  11.   Field Sampling  Protocol Data  Sheet.
                                   72
-------
Reagent and Glassware Control
     Reagent and glassware control was required in order to minimize
                                                                             ®
contamination.  Sample containers, glassware, etc. were cleaned with Isoclean ,
rinsed with, deionized-distilled water and heat treated at 450-500°C to
insure the removal of all traces of organic compounds.  Solvents were
redistilled in glass in our laboratories prior to their use.
Quality Control Samples
     Blank sampling cartridges and control cartridges loaded with known
amounts of standards were prepared for each sampling trip.  Half of the
samples were designated "lab blanks/controls" and remained in the laboratory,
the other half were designated "field blanks/controls", and were carried to
the field in the same containers as the sampling cartridges.  The quality
control scheme is outlined in Table 25 .  This procedure not only provided a
check of possible contamination during transportation and storage, but also
allowed calculation of overall recoveries during the storage and analysis
phases.
SAMPLE WORKUP AND ANALYSIS
Volatiles Collected on Tenax GC Cartridges
                                        *
     The quality assurance program consisted of analysis of controls and
blanks, cross-checking data interpretation, and validation of methodology.
     The results of the blank analyses are included with the quantitation
results (Tables 15, 16, 19, 21-24).  The recoveries of selected organic
compounds from Tenax GC cartridges are listed in Table 10.  The results
from Trip 3 are not included because the standards were improperly loaded
onto the cartridges.  The recoveries shown are very good, considering that
each cartridge was stored at ambient temperature for up to one week during
sampling.  These results indicate that sample loss from the cartridges
during storage is minimal.
     The qualitative data presented in Appendices C-F were independently
checked after interpretation.
     The entire method has been previously validated.    '  '
Highly Volatile Compounds Collected on Carbon Cartridges
     The quality control program for these samples was essentially the same
as for the samples collected on Tenax GC.  The recoveries of compounds on

                                    73
-------















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74
-------
the controls were not quantitated since no compounds of interest were found
in the field samples.  The method has been thoroughly validated on previous
   ^   _  (7,H,12)
contracts.  '   '
Particulate Collected on MAS
     Since there was no suitable method of preparation of control and blank
samples and quantitation was not attempted, no quality control samples were
used.
     As discussed above, the extraction method was validated for a broad
range of organic compounds.
     The data interpretation is described above.  It was necessary to
employ two independent interpreters to assure that identifications were
correct.  This procedure was especially critical for the semi-volatiles
(vis a vis the compounds collected on Tenax GC) due to the large number of
possible compounds present, and the relative state of the art.
Summary
     In summary,  measures were taken to assure that both the qualitative
and quantitative data generated under this study are accurate and complete.
                                      75
-------
                                REFERENCES
 1.   Pellizzari, E. D., Development of Analytical Techniques for Measuring
     Ambient Atmospheric Carcinogenic Vapors.  Publication No. EPA-600/2-
     75-076, Contract  No.  68-02-1228, 185 pp., November, 1975.
 2.   Pellizzari, E. D., The Measurement of Carcinogenic Vapors in Ambient
     Atmospheres,  Publication No. EPA-600/7-77-055, Contract No. 68-02-1228,
     288  pp.,  June, 1977.
 3.   Bursey, J.  T., D. Smith, J. E. Bunch, R. N. Williams, R. E. Berkley,
     and  E. D. Pellizzari, Amer. Lab., December, 1977, 35-41.
 4.   Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
     Lett., 9, 45  (1976).
 5.   Pellizzari, E. D., Analysis of Organic Air Pollutants by Gas Chroma-
     tography  and  Mass Spectroscopy, Publication No. EPA-600/2-77-100,
     Contract  No.  68-02-2262, 104 pp., June,  1977.
 6.   Zweidinger, R. A., Analysis of Organic Emissions of Automobile  Interior
     and  Quantitation  of Vinyl  Chloride Monomer, Interim Report, EPA
     Contract  No.  68-02-1325, Task 63, in preparation.
 7.   Pellizzari, E. D., Development of Method for  Carcinogenic Vapor
     Analysis  in Ambient Atmospheres.  Publication No. EPA-650/2-74-121,
     Contract  No.  68-02-1228, 148 pp., July,  1974.
 8.   Mitchell, R.  I.,  W. M. Henry, N. C. Henderson, R. J. Thompson  and  R.  M.
     Burton, N.  C. Henderson, "Massive Volume Sampler for Gram Quantities
     of Respirable Aerosols  (Mark II)".  Presented at Meeting of the Air
     Pollution Control Association, June 22-24,  1977, Toronto, Ont.
 9.   Henry, W. M.  and  R.  I. Mitchell, "Collection  and Analysis of Airborne
     Suspended Particulate Matter Respirable  to Humans for Sulfonates
     and  Polycyclic Organics",  Final Report,  EPA Contract No. 68-02-0752,
     May, 1975.
10.   Pellizzari, E. D., The Measurement of  Carcinogenic Vapors in Ambient
     Atmospheres,  EPA-600/7-77-055, June, 1977.
                                        76
-------
11.  Pellizzari, E.  D.,  Analysis of Organic Air Pollutants  by Gas Chroma-
     tography and Mass  Spectroscopy,  EPA-60Q/2-77-100,  June,  1977.
12.  Virginia State Chamber of Commerce, Industrial Directory of Virginia,
     10th ed., Richmond, 1969-70.
13.  L.  W.  Little, "Application of Salmonella typhimurium Histidine-
     Deficient Strains  to the Screening of Selected Air Pollutants for
     Potential Carcinogenicity," EPA  Contract No.  68-02-2724,  Quarterly
     Technical Progress  Report No. 2,  January, 1978.
                                       77
-------
                        APPENDIX A




SAMPLING AND ANALYSIS FOR VOLATILE ORGANICS IN AMBIENT AIR
                           78
-------
                                 APPENDIX A
         SAMPLING AND ANALYSIS FOR VOLATILE ORGANICS IN AMBIENT AIR

1.0  Principle of Method
     Volatile organic compounds are concentrated from ambient air on Tenax
GC in a short glass tube (1-3).  Recovery of the volatile organics is accomp-
lished by thermal desorption and purging with helium into a liquid nitrogen
cooled nickel capillary trap (1,2,4) and the vapors then introduced onto a
high resolution glass gas chromatographic column where the constituents are
separated from each other (2,5).  Characterization and quantitation of the
constituents in the sample are accomplished by mass spectrometry, either by
measuring the intensity of the total ion current signal or mass fragmen-
tography (2,6).  The collection and analysis systems are shown in Figure
A-l.
2.0  Range and Sensitivity
     The linear range for the analysis of volatile organic compounds depends
upon two principal features.  The first is a function of the breakthrough
volume of each specific compound trapped on the Tenax GC sampling cartridge,
and the second is related to the inherent sensitivity of the mass spectrom-
eter for each organic compound (2,7).  Thus, the range and sensitivity is a
direct function of each compound which is present in the original ambient
air.  The linear range for quantitation on the gas chromatograph/mass spectrom-
eter/computer (GC/MS/COMP) is generally three orders of magnitude.  Table A-
1 lists the overall theoretical sensitivity for some examples of volatile
organics which is based on these two principles (7).
     The sensitivity of this technique for the very volatile compounds (C,
to Ce) is inadequate for the purpose of this study.  Alternate methods for
their collection and analysis are suggested.
                                      79
-------

0
GAS
METEH


/
r

rLOW
vttTEH
carbon „ /
-0— PUMP 	
4
NEEDLE
VALVE
_«; 	 CARTRIDGE

GLASS
FIBER
FILTER
                      VAPOR COLLECTION  SYSTEM
                    GLASS
                     JET
                   SEPARATOR
                                                        PURGE
                                                         GAS
  TV/0
POSITION
 VALVE

                                                               THERMAL
                                                               DESORPTiCK'
                                                               CHAMBER
                     HEATED
                     SHOCKS
                                                               EXHAUST
                           ANALYTICAL  SYSTEM
Figure A-l.  Vapor collection  and analytical  systems  for analysis'
              of  organic  vapors  in ambient air.
                                  80
-------








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3.0  Interferences
     The potential difficulties with this technique are primarily associated
with those cases where isomeric forms of a particular substance cannot be
resolved by the high resolution chromatographic column and the mass cracking
pattern of each of the isomers is identical.  An example of such a problem
is seen with the C_-alkyl aromatics of which there are 53 isomers.  As the
number of carbon atoms increase in the hydrocarbons and aromatics, the
number of potential isomers become increasingly large aad difficult to
completely resolve by gas chromatography and/or by their corresponding mass
cracking patterns.  However, differentiation between the hydrocarbons, that
is alkanes, alkenes, aromatics, oxygenated, etc. can be made.  Known back-
ground compounds include phthalate esters; silanes, phosphines and thio-
phosphines (from the SCOT column); 2,2,4-trimethylpenta-l,3-diol-diisobuty-
rate ("SNOOP"); fluorocarbon refrigerants; and acetic acid. (Tenax GC decompc
sition product).
     Interferences in quantitation can usually be avoided by properly
setting the computer S/N threshold.
4.0  Reproducibility
     The reproducibility of this method has been determined to range from
±10 to ±30 percent of the relative standard deviation for different sub-
stances when replicate sampling cartridges are examined  (5).  The inherent
analytical errors are a function of several factors:  (1) the ability to
accurately determine the breakthrough volume for each of the identified
organic compounds,  (2) the accurate measurement of the ambient air volume
sampled, (3) the percent recovery of the organic from the sampling cartridge
after a period of storage, (4) the reproducibility of thermal desorption
for a compound from the cartridge and its introduction into the analytical
system, (5) the accuracy of determining the relative molar response ratios
between the identified substance and the external standard used for cali-
brating the analytical system, (6) the reproducibility of transmitting the
sample through the high resolution gas chromatographic column, and (7) tht;
day-to-day reliability of the ms-comp system (1-8).
     The accuracy of the analysis is generally ±30%, however, the accuracy
is dependent on the chemical and physical nature of the  compound  (2,8).
                                         84
-------
5.0  Advantages and Disadvantages of the Method
     The gas chromatograph/mass spectrometer, interfaced with a glass jet
separator is extremely sensitive and specific for the analysis of many
organic compounds in ambient air.  High resolution gas chromatographic
separation provides adequate resolution of the substances found in ambient
air for their subsequent quantification.  The combination of high resolution
gas chromatographic column and the selection of specific or unique ions re-
presenting the various compounds identified in air samples yields a relatively
specific assay method for these compounds (1-8).
     Collected samples can be stored up to one month with less than 10%
losses for most of the chemical classes (2,8).  Because some of the compounds
of interest may be hazardous to man, it is extremely important to exercise
safety precautions in the preparation and disposal of liquid and gas standards,
cleaning of used glassware, etc. and the analysis of air samples.
     Since the mass spectrometer cannot be conveniently mobilized, sampling
must be carried out away from the instrument.
     The efficiency of air sampling increases as the temperature of ambient
air decreases (i.e., sensitivity increases)  (8).
     The retention of water by Tenax is low, its thermal stability is high
and its background is negligible allowing sensitive analysis (1,2,5,8).
6.0  Apparatus
6.1  Sampling Cartridges
     The sampling tubes are prepared by packing a 10 cm long x 1.5 cm i.d.
glass tube with 6.0 cm of 35/60 mesh Tenax GC , placing glass wool in the  ends
to provide support (2,5).  Virgin Tenax (or material to be recycled) is
extracted in a Soxhlet extractor for a minimum of 48 hours with methanol  and
pentane prior to preparation of cartridge samplers (2,5).  After purification
of the Tenax GC sorbent and drying in a vacuum oven at 100°C for 16 hr at a
vacuum of 28 inches of water, all the sorbent material is meshed to provide
a 35/60 particle size range.  Cartridge samplers are then prepared and
conditioned at 270°C with helium flow at 30 ml/min for 30 minutes.  The
                                               ®
conditioned cartridges are transferred to Kimax  (2.5 cm x 150 on) culture
tubes, immediately sealed using Teflon lined caps, and cooled.  This procedure
is performed in order to avoid recontamination of the sorbent bed (2,5).
                                          85
-------
     Cartridge samplers with longer beds of sorbent may be prepared using a
proportional increase in the amount of Tenax GC in order to achieve a larger
breakthrough volume for each compound and thus increasing the overall sens it
ity of the technique (8).
6.2  Gas Chromatographic Column
     A 0.35 mm i.d. x 100 m glass SCOT capillary column coated with SE-30
stationary phase and 0.1% benzyltriphenylphosphonium chloride is used for,,
effecting the resolution of the volatile organic compounds (5).  The capilla
column is conditioned for 48 hr at 245°C at a 2.25 ml/min helium flow.
     A glass jet separator on a Varian-MAT CH-7 GC/MS/COMP system is employe
to interface the glass capillary column to the mass spectrometer.  The glass
jet separator is maintained at 240°C (2.5).
6.3  Inlet Manifold
     An inlet manifold for thermally recovering vapors trapped on Tenax
sampling cartridges is employed and is shown in Figure A-l (1,2,4,5).
6.4  Gas Chromatograph
     A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet manifold (Fig A-l).
6.5  Mass Spectrometry/Computer
     A Varian-MAT CH-7 mass spectrometer with a resolution of 2,000 equippec
with a single ion monitoring capability is used in tandem with the gas
chromatograph (Fig. A-l).  The mass spectrometer is interfaced to a Varian
620/L computer (Fig. A-l).
7.0  Reagents and Materials
     All reagents used are analytical reagent grade.
8.0  Procedure
8.1  Cleaning of Glassware
     All glassware, sampling tubes, cartridge holders, etc. are washed in"
        ®
Isoclean /water, rinsed with deionized distilled water, acetone and air
dried.  Glassware is heated to 450-500°C for 2 hours to insure that all
organic material has been removed prior to its use.
                                         86
-------
8.2  Collection of Halogenated Hydrocarbons in Ambient Air
     Continuous sampling of ambient air is accomplished using a Nutech
Model 221-A portable sampler (Nutech Corp., Durham, NC, see Fig. A-l, ref.
2).  Flow rates are maintained at 1-10 £/min are available with the system.
Flow rates are generally maintained at 1 Ji/min using critical orifices, and
the total flow is monitored through a calibrated flow meter.  The total
flow is also registered by a dry gas meter.  Concomitant with these param-
eters the temperature is continuously recorded with a Meteorology Research
Incorp. Weather Station since the breakthrough volume is important in order
to obtain quantitative data on the volatile organics.  This portable sampling
unit operates on a 12 volt storage battery and is capable of continuous
operation up to a period of 24 hours.  However, in most cases, the sampling
period will consist of 1 to 3 hours at the rates which will be employed in
the field.  This portable sampling unit will be utilized for obtaining
"high volume" samples.  Duplicate cartridges are deployed on each sampling
unit utilizing a sampling head as shown in Figure A-2.
     In addition to the Nutech samplers five duPont personnel samplers are
used to sample "low volumes" of ambient air as well as long term integrated
samples (12-36 hr).  Identical Tenax GC sampling cartridge are employed in
this case, and sampling is conducted in duplicate.  The flow rate is balanced
between duplicate cartridges using critical orifices to maintain a rate of
25 or 100 ml/min/cartridge.
     For large sample volumes it is important to realize that a large
volume of air may cause elution of compounds through the sampling tube if
their breakthrough volume is exceeded.  The breakthrough volumes of some
volatile organics are shown in Table A-2  (2,4,7,8).  These breakthrough
volumes have been determined by a previously described technique (2).  The
breakthrough volume is defined as that point at which 50% of a discreet
sample introduced into the cartridge is lost.  Although the identity of a
compound during ambient air sampling is not known  (therefore also its
breakthrough volume) the compound can still be quantified, after identi-
fication by GC/MS/COMP, once the breakthrough volume been been established.
Thus the last portion of the sampling period corresponding to the break-
through volume is selected for calculating their concentration.
                                       87
-------
Figure A-2.   Sampling head for housing cartridge
             sampling train.
                         88
-------







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92
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     Previous experiments have shown that organic vapors collected on Tenax
GC sorbent are stable and can be quantitatively recovered from the cartridge
samplers up to four weeks after sampling when they are tightly closed in
cartridge holders and placed in a second container that can be sealed,
protected from light, and stored at 0°C (1,2).
8.3  Analysis of Sample
     The instrumental conditions for the analysis of volatile organics on
the sorbent Tenax GC sampling cartridge are shown in Table A-3.  The thermal
desorption chamber and the six-port valco valve are maintained at 270° and
240°C, respectively.  The glass jet separator is maintained at 240°.  The
mass spectrometer is set to scan the mass range from 25-350.  The helium
purged gas through the desorption chamber is adjusted to 15-20 ml/min.  The
nickel capillary trap at the inlet manifold is cooled with liquid nitrogen.
In a typical thermal desorption cycle a sampling cartridge is placed in the
preheated desorption chamber and helium gas is channeled through the cartridge
to purge the vapors into the liquid nitrogen cooled nickel capillary trap
[the inertness activity of the trap has been shown in previous studies
(5)].  After the desorption has been completed, the six-port valve is
rotated and the temperature on the capillary loop is rapidly raised (greater
than 10°/min); the carrier gas then introduces the vapors onto the high
resolution glc column.  The glass capillary column is temperature programmed
from ambient to 240°C at 4°C/min and held at the upper limit for a minimum
of 10 mln.  After all of the components have been eluted from the capillary
column, the analytical column is then cooled to ambient temperature and the
next sample is processed (2).
     An example of the analysis of volatile organics in ambient air is
shown in Figure A-3 and the background from a blank cartridge in Figure A-
4.  The high resolution glass capillary column was coated with SE-30 sta-
tionary which is capable of resolving a multitude of compounds for subsequent
identification by ms-comp techniques; in this case over 120 compounds were
identified in this chromatogram.
     8.3.1  Operation of the MS-COMP System (Fig. A-5)
     Typically, the mass spectrometer is initially set to operate in the
repetitive scanning mode.  In this mode the magnet is automatically scanned
                                      93
-------
       Table  A-3.   OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
    Parameter                                       Setting


Inlet-manifold
     desorption chamber                              270°C
     valve                                           220°C
     capillary trap - minimum                       -195°C
                      maximum                       +180°C
     thermal desorption time                         4 min

GLC 100 m glass SCOT-OV101
     50 m glass SCOT-Carbowax 20M                    20-240°C, 4/C8 mi:
                                                     80-240°C
     carrier (He) flow                              -3 ml/min
     transfer line to ms                             240°C
MS
     scan range                                      m/e_ 20 •»• 300
     scan rate, automatic-cyclic                     1 sec/decade
     filament current                                300 uA
     multiplier                                      6.0
     ion source vacuum                              ~4 x 10   torr
                                   94
-------
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exponentially upward from a preset low mass to a high, mass value.  Although
the scan range may be varied depending on the particular sample, the range
is typically set from m/e 25 to m/e 300.   The scan is completed in approxi-
mately 1.8 seconds.  At this time the instrument automatically resets
itself to the low mass position in preparation for the next scan, and the
information is accumulated by an on-line 620/L computer and written onto "
magnetic tapes or the dual disk system.  The reset period requires approxi-
mately 20 seconds.  Thus, a continuous scan cycle of 3.8 seconds/scan is -
maintained and repetitively executed throughout the chromatographic run.
The results is the accumulation of a continuous series of mass spectra
throughout the chromatographic run in sequential fashion.
     Prior to running unknown samples the system is calibrated by intro-
ducing a standard substance, perfluorokerosene, into the instrument and
determining the time of appearance of the known standard peaks in relation
to the scanning magnetic field.  The calibration curve which is thus gene-
rated will be stored in the 620/L computer memory.  This calibration serves
only to calibrate the mass ion over the mass scanning range.
     While the magnet is continuously scanning the sample is injected and
automatic data acquisition is initiated.  As each spectrum is acquired by
the computer, peaks which exceed a preset threshold are recognized and
reduced to centroid time and peak intensity.  This information is stored in
the computer core while the scan is in progress.  In addition, approximatel
30 total ion current values and an equal number of Hall probe signals are
stored in the core of the computer as they are acquired.  During the two-
second period between scans this spectral information, along with the
spectrum number,  is written sequentially on disks, and the computer is
reset for the acquisition of the next spectrum.
     This procedure continues until the entire gc run is completed.  By
this time there are from 800-1,400 spectra on the disk which are then
subsequently processed.  Depending on the information required,  the data -
may then either be processed immediately or additional samples may be run,
stored on magnetic tape and the results examined at a later time.
     The mass spectral data are processed in the following manner.  First,
the original spectra are scanned and the total ion current  (TIC) informatic
                                      98
-------
is extracted.  Then the TIC intensities are plotted against the spectrum
number on the Statos 31 recorder.  The information will generally indicate
whether the run is suitable for further processing, since it will give some
idea of the number of unknowns in the sample and the resolution obtained
using the particular glc column conditions.
     The next stage of the processing involves the mass conversion of the
spectral peak times to peak masses which is done directly via the dual disk
system.  The mass conversion is accomplished by use of the calibration
table obtained previously using perfluorokerosene.  Normally one set of the
calibration data is sufficient for an entire day's data processing since
the characteristics of the Hall probe are such that the variation in cali-
bration is less than 0.2 atomic mass units/day.  A typical time required
for this conversion process for 1,000 spectra is approximately 30 min.
     After the spectra are obtained in mass converted form, processing
proceeds either manually or by computer.  In the manual mode the full set
of spectral from the gc run are recorded on the Statos 31 plotter.  The TIC
information available at this time is most useful for deciding which spectra
are to be analyzed.  At the beginning of the runs where peaks are very
sharp nearly every spectrum must be inspected individually to determine the
identity of the component.  Later in the chromatographic run when the peaks
are broader, only selected scans need to be analyzed.
     Identification of resolved components is achieved by comparing the
mass cracking patterns of the unknown mass spectra to an eight major peak
index of mass spectra (9).  Individual difficult unknowns are searched
through the use of the Cornell University STIRS and PBM systems.  Unknowns
are also submitted to the EPA MSSS system for identification.  When feasible,
the identifications are confirmed by comparing the cracking pattern and
elution temperatures for two different chromatographic columns (SE-30 and
Carbowax SCOT capillaries) for the unknown and authentic compounds.  The
relationship between the boiling point of the identified halogenated hydro-
carbon and the elution temperature on a non-polar column (the order of
elution of constituents is predictable in homologous series since the SE-30
SCOT capillary separates primarily on the basis of boiling point) is care-
fully considered in making structure assignments.
                                       99
-------
     Mass spectra search programs are operational at the Triangle Univer-
sities Computation Center (TUCC).  RTI maintains twice daily service to
TUCC, which is one-quarter mile distance from the RTI campus.  Additional
information about each magnetic tape containing the mass spectra of halo-
genated hydrocarbons is entered directly into the TUCC job stream using a
remote job entry processing.  This is normally done using one of the five
terminals located within the Analytical Sciences Laboratory.  The control
program contains instructions for processing selected spectra or entire gc
runs.  The computer program compares simultaneously either the entire
library of 25,000 compounds or some subset of this library.  The complete
report showing the best fits for each of the unknowns is produced at TUCC
and printed out at the high speed terminals located on the RTI campus.
     8.3.2  Quantitative Analysis
     In many cases the estimation of the level of pollutants by capillary
gas chromatography in combination with mass spectrometry is not feasible
utilizing only the total ion current monitor (see Fig. A-3 for example).
Since baseline resolution between peaks is not always achieved, we employ
techniques (previously developed under contract) whereby full spectra are
obtained during the chromatographic separation step, and then selected ions
are presented as mass fragmentograms using computer software programs which
allow the possibility of deconvoluting constituents not resolved in the
total ion current chromatogram  (6).  Examples are depicted in Figures A-6
and A-7 which represent an ambient air sample with a TIC profile as in Fig.
A-3.
     In our GC/MS/COMP system we request (from the Varian 620/L) dedicated
computer mass fragmentograms for any combination of m/e ions when full mass
spectra are obtained during chromatography; thus selectivity is obtained by
selecting the unique ion for that particular organic substance, and this is
represented versus time with subsequent use of that ion intensity for
quantitation.  Also, quantitation with external standards is easily achieve
using the intensity of the total ion current monitor or the use of a unique
mass cracking ion in the mass spectrum of that external standard.  Thus, we
use mass fragmentography for the quantitation of organics in ambient air
when the total ion current is inadequate due to lack of complete resolution
between components.

                                       100
-------
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     As described previously, the quantitation of constituents in ambient
air samples is accomplished either by utilizing the total ion current
monitor or, when necessary, mass fragmentograms.  In order to eliminate the
need to obtain complete calibration curves for each compound to be  quantitated,
we use the method of relative molar response  (RMR) factors  (10) .  Successful
use of this method requires information on the exact amount of standard
added and the relationship of RMR (unknown) to the RMR  (standards).  The
method of calculation is as follows:
     /-,\ r«»m                   A  ,  /Moles  ,
     (1) RMR  .      / „   ,   , =  unk/ _ unk
            unknown/ standard   - - — q -
                               A t , /Moles ^ ,
                                std/     std
          A = peak area, determined by integration or triangulation.
     The value of RMR is determined from at least three independent analysis.

                       A  . /g  . /GMW
                        unk
          A = peak area, as above
          g = number of grams present
        GMW = gram molecular weight
Thus, in the sample analyzed:
                 A  .  GMW  . g   ,
      ,,,       _  unk*   unk* std _
      (  '  gunk ~ A ^ , GMW   , RMR , ,   ,
                  std*   std*    unk/std

The standard  can be added  as  an internal standard during sampling;
however, since the volume  of air taken  to  produce a  given sample is  accu-
rately  known, it is also possible and more practical to  use  an  external
standard whereby the standard is introduced into  the cartridge  just  prior
to its  analysis.  Two standards, hexafluorobenzene and perfluorotoluene are
used  for the purpose of calculating RMR's.   From  previous research,  it  has
been  determined that the retention times for these two compounds are such
that  they elute from the glass  capillary column  (SE-30)  at a temperature
and retention time which does not interfere with  the analysis of unknown
compounds in ambient air samples.
      Since the volume of air taken to produce a given sample is accurately
known and an external (or  internal) standard is added to the sample, then
the weight can be determined per cartridge (hence the concentration  of  the
unknown) .  This approach for quantitating  ambient air pollutants requires
                                        i n-a
-------
that the RMR be determined for each constituent of interest.   Thus,  when an
ambient air sample is taken,  the external standard is added during the
analysis at a known concentration.   It is not imperative; at this point to
know what the RMR of each of  the constituents in the sample happens  to be;
however, after the unknowns are identified,  the RMR can be subsequently
determined and the unknown concentration calculated in the original  sample.
In this manner it is possible to obtain qualitative and quantitative inforcu
tion on the same sample with a minimum of effort.
9.0  References
1.   Pellizzari, E. D., Development of Method for Carcinogenic Vapor Analys:
     in Ambient Atmospheres.   Publication No. EPA-650/2-74-121, Contract
     No. 68-02-1228, 148 pp., July, 1974.
2.   Pellizzari, E. D., Development of Analytical Techniques for Measuring
     Ambient Atmospheric Carcinogenic Vapors.  Publication No. EPA-600/2-
     76-076, Contract No. 68-02-1228, 185 pp., November, 1975.
 3.  Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Sawicki, Enviro
     Sci. Tech., 9, 552 (1975).
 4.  Pellizzari, E. D., B. H. Carpenter, J.  E. Bunch and E. Sawicki, Enviro
     Sci. Tech., 9, 556 (1975).
 5.  Pellizzari, E. D., The Measurement of Carcinogenic Vapors in Ambient
     Atmospheres.  Publication No.  EPA-600/7-77-055, Contract No. 68-02-
     1228, 288 pp., June, 1977.
 6.  Pellizzari, E. D., J. E. Bunch, R. E. Berkeley and J. McRae, Anal.
     Chem., 48, 803 (1976).
 7.  Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No. 68-02-
     2262, February, 1976.
 8.  Pellizzari, E. D., J. E. Bunch, R. E. Berkeley and J. McRae, Anal.
     Lett., 9, 45  (1976).
 9.  "Eight Peak Index of Mass Spectra", Vol. 1,  (Tables 1 and 2) and II
     (Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
     RT74PR, UF, 1970.
                                       104
-------
10.  Pellizzari, E.  D.,  Quarterly Report No.  3, EPA Contract No.  68-02-
     2262, in preparation.
Analytical protocol revised 5/31/78.
                                       105
-------
                              APPENDIX B

SAMPLING AND ANALYSIS FOR VERY VOLATILE ORGANICS (e.g., METHYL CHLORIDE
   METHYL BROMIDE, VINYL CHLORIDE AND VINYL BROMIDE) IN AMBIENT AIR
                                106
-------
                                 APPENDIX B
  SAMPLING AND ANALYSIS FOR VERY VOLATILE ORGANICS (E.G., METHYL CHLORIDE,
      METHYL BROMIDE, VINYL CHLORIDE AND VINYL BROMIDE) IN AMBIENT AIR

1.0  Principle of Method
     Very volatile compounds (e.g., methyl chloride, methyl bromide, vinyl
chloride and vinyl bromide) are concentrated from ambient air on SKC carbon
in a short, glass tube (1).  Recovery of these volatile halogenated hydro-
carbons is accomplished by thermal desorption and purging with helium to
transfer the trapped vapors from the carbon cartridge to a Tenax GC cartridge
through a calcium sulfate drying tube to remove excessive amounts of water.
The vapors are then transferred from Tenax into a liquid nitrogen-
cooled nickel capillary trap by thermal desorption and purging with helium
(2), and the vapors are introduced onto a high resolution glass, gas chromato-
graphic column where the constituents are separated from each other (2).
Identification and quantification of very volatile compounds in the sample
are accomplished by mass spectrometry, either by measuring the intensity of
the total ion current signal or mass fragmentography (3).  The collection
and analysis systems are shown in Figure B-l.
2.0  Range and Sensitivity
     The linear range of the mass spectrometric signals for organic compounds
depends upon two principle features.  The first is a function of the break-
through volume of each specific compound trapped on the SKC carbon sampling
cartridge and the second is related to the inherent sensitivity of the mass
spectrometer (3,4).  Thus, the range and sensitivity is direct function of
each compound.  The linear range for quantification on the gas chromato-
graph/mass spectrometry/computer (GC/MS/COMP) is generally over three
orders of magnitude.  Tables B-l and B-2 lists the breakthrough volumes for
methyl chloride, methyl bromide, vinyl chloride and vinyl bromide on SKC
carbon.
                                      107
-------
      POWER SWITCH
             VALVE
             VAC.
                                           PUMP
                                                        GAS VOLUME
                                                                 REMOVABL
                                                                 AND REAR
                                      BATT. TERMINAL
AIR IN
          no
         I/A QC
AC SWITCH

    \
                                               12 VDC (AUXILLiARY)
                                    DC
                                  POWER
                                   SUPPLY
                         VALVE
                                       PUMP SWITCH
                                       FLOW
                                       METER
                PUMP
                   DRYING
                    TUBE
 BAFFLE'
3CHAMB-
'
                                                   GAS
                                                  METER
              Figure 3-1.  Nutech Model 221-A AC-DC  Skimpier
                                      108
-------
           Table B-l.  ESTIMATION OF BREAKTHROUGH VOLUMES FOR
                       VINYL CHLORIDE AND VINYL BROMIDE ON SKC
                       CARBON (104)
Temperature
°C (°F)
10
15.5
21.1
26.7
32.2
37.8
(50)
(60)
(70)
(80)
(90)
(100)
Vinyl
1/R
104
81
63
49
38
30
Chloride
*/2.52 lta
262
204
159
123
96
76
Vinyl
Us
388
306
241
190
150
118
Bromide
572.52 ga
978
771
608
479
378
298
a
 A 1.5 cm i.d. x 4.0 cm bed of carbon weighs 2.52 g.
         Table B-2.  ESTIMATION OF BREAKTHROUGH VOLUMES FOR
                     METHYL CHLORIDE AND METHYL BROMIDE ON
                     SKI CARBON (104)
Temperature
°C (PF)
10
15.5
21.1
26.7
32.2
37.8
(50)
(60)
(70)
(SO)
(90)
(100)
Ketby] Chloride
A/fi
14.3
11.1
8.7
7.5
5.6
4.4
?-/2.52 g
36
28
22
19
14
11
llothyl Broride
A/£
98
75
57
43
32
25
A/2.52 s
248
188
143
108
82
62
                                   109
-------
     Table B-3 lists the approximate limits of detection for methyl chloride,
methyl bromide, vinyl chloride and vinyl bromide based upon these break-
through volumes.  As it might be expected, the highest sensitivity is
observed for vinyl bromide, and the lowest for methyl chloride.  Never-
theless, the limits of detection are in the parts per trillion range.
3.0  Interferences
     Because of the unique isotopic clusters for chlorine: and bromine in  .
these compounds, the background that is generally observed at their retentioi
times on a glass capillary column will not interfer with their qualitative
and quantitative analyses.
4.0  Reproducibility
     The reproducibility of this method has been determined to be approxi-
mately +20% of the relative standard deviation for the four compounds when
replicate samples are examined (3).  The reproducibility is a function of
several factors.  (1)  The ability to acurately determine the breakthrough
volume for each compound;  (2)  The accurate measurement of the ambient air
volume sampled; (3) The percent recovery of the compound from the carbon
sampling cartridge after a period of storage; (4)  The reproducibility of
thermally recovering each  compound from the carbon cartridge and of sample
introduction into the analytical system;  (5)  The accuracy and determination
of the relative molar response ratios between the compounds of interest and
the external standards used for calibrating the analytical system;  (6) The
relative efficiency and reproducibility of transferring the trapped vapors
from the carbon sampling cartridge to the Tenax GC cartridge prior to
analysis in order to remove the excessive amounts of water using calcium
chloride; (7) The reproducibility of transmitting the sample through the
high resolution gas chromatographic column, and (8) The day-to-day reli-
ability of the tns/comp system  (2-4).
                                                                          V
     The accuracy of analysis  is generally +15% of the amount determined as
shown by repeated analysis of  the halogenated hydrocarbons.  The accuracy
of the analysis is dependent upon the storage period.
                                       110
-------
Table B-3.  APPROXIMATE LIMIT OF DETECTION FOR METHYL CHLORIDE,  METHYL
            BROMIDE,  VINYL CHLORIDE AND VINYL BROMIDEa

Methyl chlorideb
Methyl bromide
Vinyl chloride
Vinyl bromide
Ambient Air Temperature °C (°F)
10 (50)
138 (69)
8 (2.1)
48 (20)
5 (1.2)
15.5 (60)
178 (89)
11 (2.8)
62 (26)
6.5 (1.5)
21.1 (70)
227 (114)
14 (3.6)
79 (33)
8.2 (1.9)
26.7 (132)
253 (132)
18 (4.8)
102 (42)
10.5 (2.5)
32.2 (90)
357 (178)
24 (6.3)
131 (55)
28 (6.7)
  /Values are in ng/m  (ppt)
   Estimation of L.O.D.  based on 2.52 g carbon
  Estimation of L.O.D.  based on 1.0 g carbon
                                      111
-------
5.0  Apparatus
5.1  Sampling Cartridges
     The sampling tubes are prepared by packing a 10 cm long x 1.5 cm id
glass tube with 2-4 cm of SKC carbon Lot No.  104, with glass wool in the
ends to provide support (3,4).  The carbon cartridges are conditioned at .
400°C with a helium flow of approximately 30 ml/min for 30 min.  The condi-
                                          ®
tioned cartridges are transferred to Kimax  culture tubes, immediately
sealed using Teflon lined caps, and cooled.  This procedure is performed in
order to avoid recontamination of the sorbent bed (3,4).
     Cartridge samplers with longer beds of sorbents may be prepared using
a proportionally increased amount of carbon in order to achieve a larger
breakthrough volume for each compound, thus increasing the overall sensitiv-
ity of the technique.  However, it must be noted that the percent recovery
of the organic compounds significantly decreases when the amount of carbon
is increased and/or when an excessive length of storage period is employed
(more than a week).
5.2  Gas Chromatographic Column
     A 0.35 mm i.d.  x 100 m glass SCOT capillary column coated with OV-101
stationary phase and 0.1% benzyltriphenylphosphonium chloride is used for
effecting resolution.  The capillary column is conditioned for 48 hrs at
230°C at 1.5 - 2.0 ml/min of helium flow.
     A Finnigan type glass type jet separator on a Varian MAT CH-7 GC/MS/
COMP system is employed to interface the glass capillary column to the mass
spectrometer.  The glass jet separator is maintained at 240°C.
5.3  Inlet-Manifold
     An inlet-manifold for thermally recovering compounds of interest
trapped on SKC carbon sampling cartridges is employed and is shown in
Figure
                                                                         »-
5.4  'Gas Chromatograph
     A Varian 1700 gas chromatograph is used to house the glass capillary
column and is interfaced to the inlet-manifold (Figure  B-l).
                                    112
-------
5.5  Mass Spectrometry/Computer
     A Varian MAT CH-7 mass spectrometer with a resolution of 2000 equipped
with single ion monitoring and mass fragmentography capabilities is used in
tandem with the gas chromatograph (Figure B-l).  The mass spectrometer is
interfaced to Varian 620/L computer (Figure B-l).
6.0  Reagents and Materials
     SKC carbon Lot No. 104 is from SKC Carbon Company, Boston, MA.  All
reagents used are analytical reagent grade and distilled in glass prior to
use.
7.0  Procedure
7.1  Cleaning of Glassware
     All glassware, sampling tubes, cartridge holders, etc. are washed in
        ®
Isoclean /water, rinsed with deionized distilled water, acetone and air
dried.  Glassware is heated to 450-500°C for two hours to insure that all
organic material has been removed prior to its use.
7.2  Preparation of Carbon
     Virgin carbon is packed into glass sampling tubes without further
purification.  Used carbon cartridges are not recycled.
7.3  Collection of Very Volatile Compounds in Ambient Air
     Continuous sampling of ambient air is accomplished using a Nutech
Model 221-A portable sampler (Nutech Corp., Durham, NC, see Figure 1).
Flow rates are maintained at 1 £/min using critical orifices and the total
flow is monitored through a calibrated rotameter.  The total flow is also
registered by a dry gas meter.  Concomitant with these parameters the
temperature is continuously recorded with a Meteorology Research Incorpora-
ted weather station since the breakthrough volume is important in order to
obtain quantitative data on these compounds.   This portable sampling unit
operates on a 12-volt storage battery and it is capable of continuous
operation up to a period of 24 hours.  However, in most cases the sampling
period consisted of one to two hours at the rates which were employed in
the field.  This portable sampling unit is utilized for obtaining "high
volume" samples.  Duplicate cartridges are deployed on each sampling unit
and are in tandem with Tenax GC cartridges.  The carbon cartridges serve as
a backup to the Tenax GC cartridge for collecting the more highly volatile
-------
constituents which have a low breakthrough volume on Tenax GC.   A total of
four portable sampling units are available for sampling ambient air surround-
ing the bromine industry.
     In addition to the Nutech samplers,  five duPont personal samplers are
used to sample "low volumes" of ambient air as well as long term integrated
samples (12-36 hrs).  An identical SKC carbon sampling cartridge is employed
in this case and sampling is conducted in duplicate.  The flow rate is
balanced between duplicate cartridges using critical orifices to maintain a
rate of 25 or 100 ml/min per cartridge.
7.4  Analysis of Sample
     The conditions for transferring very volatile organic compounds from
SKC carbon sampling cartridges to Tenax GC sampling cartridges prior to
instrumental analysis is shown in Table B-4.  A 1.5 x 2 cm bed of calcium
sulfate is used to remove the water vapor prior to retrapping of the compo-
nent vapors on the Tenax GC sampling cartridge.
     The instrumental conditions for the analysis of the volatile components
on the sorbent carbon sampling cartridge is shown in Table B-5.
     7.4.1  Operation of the MS/Comp System (Figure B-l)
     The operation of the ms/comp system is identical to as that described
for the Analytical Protocol under Appendix A entitled, "Sampling and Analysi
for Volatile Organic Compounds in Ambient Air."
     7.4.2  Quantitative Analysis
     The procedure for the estimation of the level of very volatile compound
by capillary gas chromatography in combination with mass spectrometry is
identical to that described for the analytical protocol entitled, "Sampling
and Analysis for Volatile Organics in Ambient Air".
8.0  References
                                                                          *
1.   Pellizzari, E. D.  Development of Method for Carcinogenic Vapor
     Analysis in Ambient Atmospheres.  EPA Contract No. 68-02-1228,
     EPA-650/2-74-121, July 1974, 148 pp.
2.   Pellizzari, E. D.  Development of Analytical Techniques for
     Measuring Ambient Atmospheric Carcinogenic Vapors.  EPA Contract
     No. 68-02-1228, EPA-600/2-75-076, November 1975, 187 pp.
                                       114
-------
Table B-4.  PARAMETERS FOR REMOVING WATER AND TRANSFERRING
            VAPORS TO TENAX GC
          Parameters                             Condition

Inlet-manifold
   desorption chamber                               295°C
   valve                                            200°C
   CaSO, drying tube (1.5 x 2.0 cm)          ambient temperature
   transfer line                             ambient temperature
   Tenax GC cartridge (1.5 x 6.0 cm)         ambient temperature
Desorption time                                  10 minutes
He purge rate                                    10 ml/min
                                 115
-------
     Table B-5.   OPERATING PARAMETERS FOR  GLC-MS-COMP  SYSTEM
    Parameter
Setting
Inlet-manifold
     desorption chamber
     valve
     capillary trap - minimum
                      maximum
     thermal desorption time
GLC
MS
     100 m glass SCOT-OV-101

     carrier (He) flow
     transfer line to ms
     scan range
     scan race, automatic-cyclic
     filament current
     multiplier
     ion source vacuum
 270°C
 220°C
-195eC
+180°C
 4 min
 20-240°C, 4/C° mi;

 -3 ml/min
 240°C
 m/e 20 -»• 300
 1 sec /decade
 300 yA
 6.0
-4 x 10~° torr
                              116
-------
3.   Pellizzari,  E.  D.   Development of Analytical Techniques for Measuring
     Ambient Atmospheric Carcinogenic Vapors.   EPA Contract No.  68-02-1228,
     1976, in preparation.
4.   Pellizzari,  E.  D.   Identification of Atmospheric Pollutants by the
     Combined Techniques of Gas Chromatography/Mass Spectrometry.   EPA
     Contract No. 68-02-2262, 1976, in preparation.
Analytical protocol revised 1/31/77.
                                        117
-------
                        APPENDIX C
VOLATILE AND VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN
               AIR IN THE KANAWHA VALLEY, WV
                                118
-------
Table C-l.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN
            AIR IN THE KANAWHA VALLEY, WV (TRIP 1, P2/L2).
Chromato-
grapnic
Peak No.
1
2A
2B
3
3A
4
4A
' 4B
5
6A
7
7A
8
8A
9
Elution
Temp.
CO
49
55
55
57
60
61
62
64
65
67
69
71
72
74
75
Compound
co2
C,HQ isomer
J O
ji-butane
acetaldehyde
isopentane
acetone
furan (cent.)
vinylidene chloride (tent.)
methylene chloride
cs2
C^HjO isomer
methyl vinyl ketone (tent.)
2-methylpentane
C^HgO isomer
3-methylpentane
Chromato-
graphic
Peak So.
10
11
11A
12
12A
13
13A
13B
14
15
16
17
17A
18

Elucion
Tenp.
CC)
76
77
78
82
83
88
89
94
97
109
148
151
151
165

Compound
hexaf luorobenzene (el)
£-hexane
chloroform
perfluorotoluene (el)
methylcyclopentane
benzene
cyclohexane
ji-pentanal
n-heptane + acetic acid
toluene
benzaldehyde
phenol
C, H. isomer
ace tophenone

                            119
-------
Table C-2.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN
            AMBIENT AIR IN THE KANAWHA VALLEY,  WV (TRIP 1, P2/L2
Chromato-
graphic
Peak No.
1
2A
3

3A
3B
4
4A

4B
4D
5B
6
6A
6B
7
8
3A
9
10
10A
10B
11
11A
12
12A
12B
13
13A
14
14A
15
16
16A
17
17A
18
ISA
19
20
21
22

22A
23
23A

24
24A
Elution
Temp.
CO
48
54
55

55
59
61
61

62
64
70
71
72
73
74
75
76
77
81
82
83
84
36
87
88
89
90
91
92
93
94
95
96
97
98
101
102
103
108
109
110

111
112
113

114
115
Compound
co2
C.H- isomer
4 3
acetaldehyde +• ^-butane
(tent.)
C4Hj isomer
isopentane
acetone
C,H, - isomer
5 10
n-pentane
mechylene chloride
C.H,0 isomer
4 6
2-methy Ipentane
methyl isopropyl ketone
butanal (tent.)
3-methy Ipentane
hexafluorobenzene (e$)
ji-hexane
chloroform
perfluoro toluene (eS)
methylcyclopentane
1,2-dichloroethane (tent.)
1,1,1-trichloroethane
C,H_ isomer
benzene
carbon tetrachloride
cyclohexane
2-methy Ihexane
acetic acid
3-me thy Ih exane
C-Hj, isomer
C7H14 * C5H10° isomers
trichloroethylene
C?H14 isomer
n-heptane
C7H14 isomer
methylcyclohexane
4-mechyl-2-pentanone
C-H . isomer
o io
C.H,, isomer (tent.)
9 lo
toluene
C.H . isomer
8 IS
C8H18 iSOner
C8H18 isomer
C.H.. , isomer
0 ID
^6^12 *-soner
C.H,, isomer
0 ID
hromato-
raphic
eak No.
24B
25
26
26A
27
28
29
29A

30
30A
30B
31
32
32A
32B
33
34
35
35A
36
36A
37
37A
38
39

39A
40
40A
40B
41
4IA
413
42
42A
43
44
44A
44B
45
45A

46
47
48

48A

Elution
Temp.
CO
116
117
118
120
121
122
123
124

125
125
126
128
130
130
131
132
133
134
134
' 135
136
137
138
140
141

142
142
143
144
144
145
146
146
146
147
148
148
149
150
150

151
152
153

153

Compound
C.H,, a.somer
0 -LO
^-octane
tetrachloroethylene
C.H, isomer (tent.)
C-H, 0 isomer
7 14
C8H16 Ls°oer
C9H2Q Lsomer
C-H-,. Lsomer
9 20
ethylcyclohexane
C9H2Q isomer
C9Hlg isomer
ethylbensene
xylene isomer
C9H20 isomer
C9H18 isomer
C9H2Q isomer
C9H2Q isomer
styrene
»-heptanal (tent.)
o^-xylene
C9H18 isomer
^-nonane
CjH^g isomer
C9Hlg isomer
isopreipylbenzene +
C10H22 lsOInerS
C10H2;, isomer
C9H16 isomer
cioH2:i isomer
C--al!cyl cyclohexane isomer
C10H27 Corner
C10H2() l30mer
C10H22 is°mer
benzaldehyde
C10H20 isollier
n^-propylbenzene
ethyltoluene isomer
C1(JH22 isomer
C,.H22 isomer +• phenol
1 , 3 , 5- trimethy Ibenzene
C,-H-« isomer
10 20
C10H22 isomer
o_-ethy 1 to luene
C.-H-- isomer
10 20
C10H13 lsomer

                         (continued)
                           120
-------
Table C-2.  (cont'd.)
Chromato-
graphic
Peak No.
49


50
50A
51
52
52A
52B
52C
53

54
55

56
56A

56B
56C
57
57A
57B
58
59
59A
59B
60
61
62
62A
62B

53
63A
64
65
65A
65B
66
66A
67
67A
67B

68
69
69A
70
71


Elution
Temp.
154


154
155
156
157
157
148
148
149

160
160

161
162

162
162
163
163
164
164
165
165
166
166
167
167
168
168

169
170
170
171
171
172
173
173
176
174
175

176
177
178
179
180


Compound
C,nH,_ isomer + n-octanal
10 20 —
(tent.)
1,2, 4-trimechylbenzene
C10H20 i30Ber
ti-decane
dichlorobenzene isomer
C10H20 lsomer
C.-alkyl benzene isomer
C1 H._ isomer
C.-alkyl benzene +
CnH24 isomers
1,2, 3-trimethylbenzene
C...H,. isomer
11 24
C11H22 isoner
C.-H,, isomer
10 16
indan
C.,H-. isomer
11 24
C^-alkyl cyclohesane isomer
C11H22 isOTer
C.-alkyl benzene isomer
C4-alkyl benzene isomer
acetophenone
C.-alkyl benzene isomer
C11H22 isoaer
C11H24 isomer
C11H24 isomer
C.-alkyl benzene isomer
C10H18 isoner
C.-H,. isomer
11 24
C,-alkyl benzene isomer
C11H22 1SOT>er
C,-alkyl benzene isomer
C,H7~benzene + C.^H^, isoaers
C.-alkyl benzene isomer
C..H-- isomer
n-undecane
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C, H isomer
11 22
tetramethylbenzene isomer
C.-alkyl benzene isomer
C.-alkyl phenol isomer
C.-alkyl benzene isomer
C.-alkyl benzene +
C.H_-benzene isomers
4 /
Chromato-
graphic
Peak No.
7U

71B
71C
71D
7 IE
72
73
74
74A

75
75A
7 SB

76
76A

76B
77
78
79
80

80A
81
81A
81B
82
82A
83
85

86
86A
36B
87
88
89
90
90A
90B
90C


91
91A
92
93
93A
94
(continued)
Elution
Temp .
CO
180

181
181
181
182
182
183
184
184

185
186
186

187
188

189
189
191
192
193

194
195
195
197
198
198
199
203

204
205
206
207
211
213
214
215
216
217


218
220
223
226
227
230

Compound
C,-H,. isomer
12 24
C11H20 isomer
C.-alkyl benzene isomer
Cj-alkyl phenol isomer
C.H, -benzene isomer
4 7
C.-alkyl benzene isomer
C.-alkyl benzene isomer
1,2,3, 4-tetrahy dronaph thalene
C.-alkyl benzene +•
C13H28 isome"
C.-alkyl benzene isomer
C10H16 + C13H26 i3omers
C,_H-, isomer
12 24
naphthalene
C, ,H... isomer
12 24
C.-alkyl benzene isomer
ji-dodecane
C.-alkyl benzene isomer
C13H28 iacm'r
C,-alkyl benzene isomer
(tent.)
C -H_, isomer
C13H28 lsomer
C.-alkyl benzene isomer
C13H28 isooer
C.Hg-benzene isomer
C.-alkyl benzene isomer
0
C,-H,, iscaer (tent.)
13 26
C.nH... isomer
13 26
n_-tridecane
S-niethylnaphthalene
C, ,H_, isomer
XJ ^0
a-methylnaphthalene
sat. hydrocarbon (tent.)
C14H30 isomer
alkyl butyrate
biphenyl
C14H28 isoner
diphenyl ether or
C. 0H. _0 isomer
12 10
n_-tetradecane
dimethylnaphthalene isoaer
dimethylnaphthalene isomer
C15H32 isomer (tent.)
C. .H,Q isoner
ti-pentadecane

         121
-------
Table C-2.  (cont'd.)
Chromaco- Elucion
graphic Temp- Compound
Peak No. (°C)
95 233 unknown
96 239 diechyl phthalace
99 240 unsar.. hydrocarbon
Chromaco- Elution
graphic Temp . Compound
Peak No. (°C)
100 240 n-heptadecane
101 240 unsac. hydrocarbon
102 240 sat. hydrocarbon
            122
-------
Table C-3.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED
            IN THE KANAWHA VALLEY, WV (TRIP 1, P2/L5).
Chromaco-
graphic
Peak No.
1
4
4A
5
5A
6
7
8
9
9A
10
IDA
12
13
13A
Elucion
Temp.
<°C)
48
52
53
53
54
55
57
58
59
60
61
61
63
66
68
Compound
co2
n-propane (cenc.)
bucene isomer
n— bucane
bucene (cenc.)
acecaldehyde
isopencane
acecone
n-pencane
diechyl echer
vinylldene chloride
methylene chloride
cs2
2-mechylpencane
n-bucanal
Chromaco-
graphic
Peak No.
14
15
16
16A
17
18
ISA
18B
18C
18D
19
19A
20
20A
Elucion
Temp.
(°C)
68
70
71
72
75
76
77
78
79
80
103
107
145
146
Compound
3-me thy Ipen c ana
hexafluorobenzene (eS)
fr-hexane
chloroform
perfluorocoluene (el)
mechylcyclopencane
C6H1Q isomer
benzene
carbon cecrachloride
cyclohexane
coluene
acecic acid (cent.)
phenol
C11H24 isomer
                             123
-------
Table C-4.  VOLATILE ORGANIC COMPOUNDS•IDENTIFIED IN AMBIENT
            AIR IN THE KANAWHA VALLEY, WV (TRIP 1, P2/L5).
Chromato-
graphic
Peak No.
1
2A
2B
2C
2D
2E
3
3A
4
6
6A
6B
7
8
8A
SB
8C
9
9A
9B
9C
10
10A
10B
11
12
13
13A
14
15
16
17
18
19
20
20A
2QB
20C
21
22
22A
22B

23
24
25
25A


Elution
Temp.
CO
49
54
55
55
60
60
61
65
66
74
75
76
78
79
80
81
82
83
34
86
88
89
90
91
91
93
95
96
96
98
102
104
109
110
112
113
114
115
117
118
122
123

125
128
130
130


Compound
co2
propane
butane
acecaldehyde
dimethyl ether
isopencane
acetone
vinylidene chloride
dichloromethane
2-methylpeneane
C,H.. _ isomer
0 1Z
3-methylpentane
hexafluorobenzene (e§)
n-hexane
chloroform
C,HgO isomer
ethyl acetate
perfluorocoluene (el)
methylcyclopentane
1,1,1-trichloroechane
C,H, isomer
0 1U
benzene
carbon tetrachloride
acetic acid (cent.)
C7Hlfi isomer
C_H., isomer
CTH14 isomer
trichloroethylene (tent.)
C-H, . isomer
S 10
it-heptane
methylcyclohexane
C3H18 + C7H14° iSOmer
coluene
C8Hlg isomer
CSH18 isomer
C-H , isomer
_o ID
hexanal (tent. )
C-H,, isomer
0 .to
^-octane
tetrachloroethylene
C8H1& isomer
C_H_A isomer
9 20
CgH2Q isomer (tent.)
ethylbenzene
xylene isomer
C.H,,. isomer
Chroma to-
graphic
Peak No.
26
26A
26B
27
27A
28
28A
29
30
31
31A
31B
32
33

34
34A
35

36
36A
37
37A
38
39
39A
40
41
41A
41B

42
43
43A
44
44A
44B
45
46
47
47A
48

49

50
50A
9 20
(continued)
Elucion
Temp.
CO
132
133
133
134
135
137
140
140
142
143
144
145
145
146

147
148
149

150
151
151
152
153
153
154
155
156
157
158

159
159
160
160
161
162
162
163
164
165
165

166

168
169


Compound
C9H2Q isomer
CylL^O isomer (tent.)
styrene
o-xylp.ae
C9H18 isomer
ji-noniine
C9H18 iaom"
isopropylbenzene
C10H22 iso*"
C10H22 is0mer
C,-altyl cyclohexane isomer
C10H22 i30mer
benzaldehyde
n_-propylbenzene + ^10^20
isomer
ethyl toluene isomer
C10H22 isomer * Pnen°l
1,3,5-trimethylbenzene +
C11H24 ia°*SI
C10H22 isotner
o-ethyltoluene
C10H22 I30mfir
CIOH;:O lsomer
£-00: anal
1,2,4-trimethylbenzene
CIOH:;O isoiner
ii-de
-------
Table C-4.  (cont'd.)
Chromaco-
graphic
Peak No.
51
52
52A
53
53A
53B
54
55
55A
55B
55C
55D
56
56A
56B
56C
560

56E
57
57A
57B
57C
58
Elucion
Temp.
CO
169
170
171
172
173
174
175
177
178
178
179
179
180
181
181
183
184

185
186
187
187
188
188
Compound
C.-alkyl benzene isomer
nr-nonanal
C11H22 isonier
n— undecane
C.-alkyl benzene isomer
C11H22 i3omer
C.-alkyl benzene isomer
C2-alkyl phenol isomer
C.-alkyl benzene isomer
C -H_. isomer
12 24
C,H7-benzene isomer
C, -alkyl cyclohexane isomer
C^-alkyl phenol isomer
C.H^-benzene isomer
C,-alkyl benzene isomer
C.-alkyl benzene isomer
C12H26 + C5~al!cy1 benzene
isomers
C,- alkyl phenol isomer
naphthalene
n-decanal
C12H24 isooer
C.-alkyl benzene isomer
n-dodecane
Chromato-
graphic
Peak No.
58A
58B
58C
58D
59A
59B
59C
59D
60
60A
61
62
63
64
64A
65

65A
66
66A
67
68
71
72
• Elucion
Temp.
CO
189
190
190
191
195
199
201
201
202
203
205
211
212
213
215
216

220
225
228
229
231
240
240
Compound
C.-alkyl benzene isomer
C.-H-, isomer
Cj-alkyl phenol isomer
C13H28 isoner
unsacurated hydrocarbon
saturated hydrocarbon
C11H22° isomer
ri-undecanal (tent.)
ii-cridecane
S-methylnaphchalene
o-mechylnaphthalene
alkyl bucyrate (tenc.)
alkyl butyrate (tent.)
biphenyl
C, ,H,0 isomer (tent.)
14 28
n_-tetradecane + diphenyl echer
(tent.)
C.-alkyl naphthalene (cent.)
saturated hydrocarbon
C,CH,_ isomer (tent.)
15 30
ri-pencadecane
unknown
C17H36 isomer
^n-hep tadecane
     125
-------
Table C-5.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN THE KANAWHA VALLEY, WV (TRIP 1, P2/L6).
Chromato-
graphic
Peak No.
1
3
3A
4
4A
4B
5 .
7
3
8A
3B
9
11
Elucion
Temp.
(°C)
49
53
53
54
55
55
57
58
59
59
60
61
63
Compound
co2
propane
C HR isomer
ii-butane
butene isomer
acetaldehyde
isopentane
acetone
n-pentane
C-H „ isomer
vtnylidene chloride
methylene chloride
CS,
Chromato-
graphic
Peak No.
11A
12
13
14
15
ISA
16
17
17A
17B
17C
17E
18
Elucion
Temp.
("C)
66
67
70
71
72
73
76
77
79
82
84
96
104
Compound
C.Hj- isomer (cent.)
2-methylpencane
3-methylpentane
hexafluorobenzene (el)
£-hexane
chloroform
perfluorobenzene (el)
mechylcyclopencane
1,1,1-trichloroechane (tent.)
benzene
cyclohexane
methyl cyclohexane
to lues e
                                126
-------
Table C-6.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN THE  KANAWHA VALLEY, WV  (TRIP  1,  P2/L6).
Chromato-
graphic
Peak No.
1
2A
2B
2C
2D
2E
3
3B
4
5
6A
7
3
8A
SB
9
10
IDA
108
11
11A
12
13
14
15
ISA
16
16A
17
IS
19

19A
20
20A
21
22
23
24
25
26
26A
27
28
28A
28B
Elution
Temp.
CC)
49
53
54
54
56
59
60
63
64
65
70
71
74
74
75
75
76
77
78
79
80
81
82
83
86
88
39
90
91
93
94

95
96
97
101
103
105
107
108
109
110
111
113
114
114
Compound
co2
propane
C4Hg isomer
ji-butane
acetaldehyde
dimethyl ether
acetone
diethyl ether
vinylidene chloride
dichloromethane
C,H,0 isomer (tent.)
4 6
2-methylpentane
3-methylpentane
n-butanal
CgH.,- isomer
hexafluorobenzene (eZ)
o-hexana
chloroform
methyl ethyl ketone
ethyl acetate
CgH12 isomer
perfluoro toluene (el)
methylcyclopentane
1,1,1-trichloroethane
benzene
cyclohexane
2-methylhexane
2, 3-dimechylpentane
3-methylhexane
C-IL, isomer
trichloroethylene (tent.) +
CaH1a isomer
5 io
acetic acid
n-hepcane
CyH14 isomer
me thy Icyclohexane
C8H18 isoner
C8H16 isomer
C8H18 Is0mer
toluene
CgHlg isomer
CaH. , isomer
0 ID
CaH,a isomer
a io
C3H16 isomer
CaH. - isomer
9 10
C,H,-0 isomer
0 1Z
Chromaco-
graphic
Peak No.
28C
29
30
30A
31
32
33
34
34A
35
35A
36
36A
37
37A
38
38A
39
40
40A
41
41A
42
43

44
44A
45
45A
45B
46
47
48
48A
49
49A
50
51
52
52A
53

54
54A
55
55A
Elution
Temp.
CO
115
115
116
117
118
120
121
123
123
124
125
128
128
129
130
131
132
133
134
135
136
138
139
140

141
142
143
144
145
145
146
147
148
149
150
150
151
152
153
153

154
153
155
156
Compound
C8H16 isomer
C8H16 isomer
n-octane
C8H16 isomer
tetrachloroethylene
C9H20 isomer
C9H20 lsom
-------
Table C-6.  (cont'd.)
Chromaco-
graphic
Peak No.
56
57
57A
58
59
60

60A
61
61A
62
62A
63

63A
64
65
66
66A
66B
67
67A
67B
63
69
70
71
71A
72
73

74
74A

74B

Elucion
Temp.
156
158
158
159
160
161

161
162
163
163
163
164

164
165
165
156
166
167
167
168
168
169
170
171
172
173
174
176

177
178

179

Compound
C,-alkyl benzene isomer
C11H24 isomer
C4-alkyl benzene isomer
1,2, 3-crimechylbenzene
C^ H-4 isomer
CUH24 "*" dichlorobeslzen6
isomers (cenc.)
indan +• C. .H__ isoraer
C,-alkyl cyclohexane isomer
C4-alkyl benzene isomer
C, -alkyl benzene isomer
°11H24 isomer
C4~alkyl benzene isomer -t-
acecophenone
o-bucylbenzene
C11H22 isaa"
C,,H24 isomer
C4~alkyl benzene isomer
CUH22 isomer
C10H18 is0mer
C11H24 isomer
C4-allcyl .benzene isomer
C11H22 isomer
C4-alkyl benzene isomer
C. H._ isomer
tj-nonanal
ii— undecane
C4~alkyl benzene isomer
C11H22 isomer
C.-alkyl benzene +
C12H26 is°mers
C12H24 isomer
C.-alkyl benzene + C.-alkyl
phenol isomers (cent.)
C4~benzene +• C.-alkyl
benzene isomers
Chromaco-
graphic
Peak Jfo.
75
75A
75B
76
76A
76B
77
77A
77B
78
78A
79
79A
79B
30
80A
81
81A
81B
82
82A
83

84
85
86
36A
36B
S6C
38
89
89A
90
91A


Elucion
Temp.
179
180
180
181
181
182
183
184
184
186
187
188
189
195
199
202
203
204
204
206
208
211

212
213
217
219
221
225
229
232
237
238
240


Compound
C.-alkyl cyclohexane isomer «
C12H24 isomer
C.-alkyl benzene isomer
C4H. -benzene isomer
C4-alkyl benzene isomer
Cj-alkyl benzene isomer
^12^26 ^somer
C1,H26 isomer
C.-alkyl benzene isomer
naphathalene
C12H24 isolner
3-d ode cane
C.-alkyl benzene isomer
C12H24 isonler
sac. hydrocarbon
C13H26 isomer
n_-crid.ecane
S-meth.ylnaphchalene
C13H26 i30mer
o-mechylnaphchalene
C..H2, isomer
C_-alkyl cyclohexane or
C1.-|H26 lsomer
alkyl butyrate
alkyl bucyrate
n-cetradecane
Cj-alkyl naphthalene isoner
C,-allcyl naphthalene isomer
C15H30 isomer
^-pencadecane
unkncnm
C16H32 isomer
diechvl phthalace
£-hexadecane


       128
-------
Table C-7.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN  THE KANAWHA VALLEY, WV  (TRIP  2,  P2/L3).
Chroma to-
graphic
Peak No.
1
3A
4
4A
4B
5
5A
6
6A
6B
7
8
8A
SB
8C
9
9B
10
10A

10B
11
11A

12
13
13A
14
15
ISA
15B
15C
16
16A

16B

17
18
ISA
18B
19
19A

20
20A
21
22

23
Elution
Temp.
49
53
54
54
55
58
58
59
59
60
60
61
62
62
62
63
64
66
67

68
68
69

70
71
71
72
73
73
74
74
75
75

76

77
78
79
79
30
32

32
33
33
84

35
Compound
co2
C.H. isomer
4 8
acetaldehyde
n-butane
methyl formate (tent.)
isopentane
dimethyl ether (tent.)
acetone
furan (tent.)
C.H1(, isomer
nr-pentane
C.H^. isomer
isopropanol (tent.)
C,HIQ isomer
methylene chloride
methyl acetate
carbon disulfide
2-methylpropanal
C.H, . isomer
6 12
C,H,0 isomer
4 6
2-methylpen cane
methyl isopropyl ketone
(tent.)
3-methylpentane
methyl ethyl ketone
C,Hn , isomer
0 LL
hexafluorobenzene (eS)
n-hexane
isopropyl ether
chloroform
CgHj- isomer
ethyl acetate
C,H, , isomer
5 12
C.H, _ isomer
6 12
perfluorotoluene (ef)
methylcyclopentane
1,2-dichloroechane (tent.)
1,1, 1- trichloroethane
unknown
C,H1n isomer
6 10
isopropyl acetate
benzene
carbon tetrachlorlde
isopropenyl acetate +•
hexane
2-oethylhexane
Chromato-
graphic
Peak No.
24
24A
25
26
26A
27
27A
28
28A
28B
29
30
30A
31
32
33
33A
34
34A

35
36
36A
37
37A
38
38A
38B
39
40
40A
41
41A
42

43

44
44A
44B
45
45A
45B

46
46A
47
47A
48
49
Elution
Temp.
CC)
36
86
87
38
39
90
91
92
92
93
94
97
98
98
99
101
102
103
104

104
106
107
107
109
109
110
111
112
113
113
114
115
117

118

119
120
120
121
122
123

124
124
126
126
128
129
Compound
2 , 3-dime thy Ipentane
alkyl ether (tent.)
3-ne thy Ihexane
3-pentanone
C-H-4 isomer
1,1,1-trichloroethylene
C.H . isomer
7 14
ii-heptane
ti-propyl acetate
C7H14 lsomer
C-H^, isomer
methylcyclohexane
4-methyl-2-pentanone
C8H18 isomer
CBHn „ isomer
O 10
C8H16 lsotner
2-ethylbutanal
C8H18 i30IBer
C.H, , isomer
8 16
toluene
C,Hia isomer
5 lo
alkyl ether (tent.)
C,H.H isomer
o lo
dimethylcyclohexane isomer
CgHlg isomer (tent.)
1,2-dibromoetha.ne (tent.)
alcohol isomer (tent.)
C8H16 isolner
n-octane
nj-butyl acetate
tetrachloroethylene
C.B., isomer
0 lo
C-H-- isomer
9 20
C..H-- isomer
9 20
C9H20 is0mer
C.H. , isomer
C.H.g isomer
C9H20 isooler
CgH18 isomer
CnH, „ isomer
9 18
ethylbenzene
C H,0 isomer
7 10
xylene isomer
C-H,,, isomer
CgH20 isomer
C H140 isomer (tent.)
                               (continued)
                                  129
-------
Table  C-7.   (cont'd.)
Chromato-
grapnic
Peak No.
50
50A
51
52
53

54
54A
55
55A
56
56A
56B
57
57A
58

58A
59
59A
60
60A
61
61A
62
62A
62B
63
63A
64
65
65A
66
66A
67
57A
58
68A
69
59A
70

70A
70S
71

Elution
Temp . Compound
130
130
131
132
133

133
134
136
137
137
137
138
139
140
140

141
141
142
142
142
142
143
144
145
145
146
146
147
148
148
149
149
150
150
151
152
152
153
153

154
155
155

styrene
hep canal
o-xylene
CqH^g isomer
cyclohexyl acetate or
C,H, , acetate isomer
a 1.1
n-nonane
^10^20 *-somer
C_H. - isomer
C1QH22 isomer
isopropylbenzene
C10H22 isomer
C10H20 isoner
C9H16 + C10H22 isomer
C10H20 lsomer
C3-alkyl cyclohexane +
C10H22 isomers
C10H22 isomer
C10H16 + C8H16° isolners
C^-H.,- isomer
benzaldehyde
t* TJ T BnmAT.
C10H20 1S°mer
n-propylbenzene
C10H20 isomer
ethyltoluene isomer
C10H22 isomer
phenol (tent.)
1,3,5-triaethylbenzene
C-_H-_ isomer
10 22
o-ethyl toluene
C10H18 * C11H24 ismie«
C10H20 1SOmer
C10H18 is0a"
C^ H,- isomer
C,H. -benzene isomer
1,2, 4-trimethylbenzene
C10H20 isolner
tt-decane
dichlorobenzene isomer
C10H20 lscmer *
isobucylbenzene
sec-bucylbenzene
C.^H,, isomer
C H- + C.-alkyl
L± L<4 <4
benzene isomers
Chromaco-
graphic
Peak No.
72
73
74

74A
74B
75
75A
76
77
78
78A
79
80
30A
81
81A
SIB
82
83
83A
84
85
85A
85B
85C
86

87
87A
88

89
89A
90

91
91A
9 IB
92

93
93A
94
95

Elution
Temp.
C°C)
156
156
157

158
158
159
159
160
161
162
162
163
163
164
154
165
166
167
167
168
169
170
170
171
171
172

173
174
174

175
175
176

176
177
177
177

178
178
179
180

Compound
1 , 2, 3-crimethy Ibenzene
C-.Hj, Lsomer
dichlorobenzene -t-
C11HZ4 isomars
indan + <-inS20 ^sonier
Cn.H.. isoner
11 24
C,-alkyl cyclohexane isomer
C4-alkyl benzene isomer
propyltsluene isomer
C4-alkyl benzene isotner
C^.H-, isomer
C11H22 isomer
C11H24 isomer
C4-alkyl benzene isomer
C10H18 isooer
C11H24 isomer
C^-alkyl benzene isomer
C4Hy-benzene •*• C^H-. isomers
C4-alkyl benzene isomer
C4H^-b«nzene + C._H__ isomers
C.^.. isomer
n-undecane
C4-alkyl benzene isomer
CUH22 isonieT
C4-alkyl benzene isomer
C12H26 isomer
tecrame-chylbenzene -t-
C H isomers
C4-alk5'l benzene isomer
C11H20 is°mer
C H-, -I- C -alkyl
LjL ^D L
phenol isomers
Cj-alkyl benzene isomer
C12H24 isomer
C, -alkyl benzene +
C4H.-benzene isomers
C, -alkyl cyclohexane isomer
C11H20 + C12H24 isofflers
Cj-alkyl phenol isomer
C H -benzene + C -alkyl
benzene isoners
C4-alkyl benzene isomer
Cj-H_, isomer
C.-alkyl benzene isomer
1,2,3,4-tecrahydronaphthalene +
C,-alkyl benzene isomer
      (continued)
        130
-------
Table C-7.  (cont'd.)
Chromato-
graphic
Peak No.
95A
96
96A

96B
96C
97
97A
97B

98
99

100
101
101A
1013

102
102A
103
103A
104
104A
105
106
107
107A
108
10SA
108B
109
109A
109B
110
Elution
Temp.
CO
180
181
182

182
183
183
184
184

185
186

187
188
189
190

190
191
192
193
193
193
194
195
196
198
200
200
202
203
204
206
207
Compound
C12H24 isomer
C.-alkyl benzene isomer
C, -H,, isomer
12 24
C,-alkyl benzene Isomer
0
C.H.-benzene + cj_2H24 isomers
naphthalene
C.-alkyl benzene Isomer
C.-alkyl benzene +•
C12H24 isomers
ii-dodecane
C.-alkyl benzene +•
C12H24 isomers
C13H2g Isomer
C,-alkyl benzene isomer
D
C13H28 is°mer
C. ,H_ , isomer
13 26
Cg-alkyl benzene isomer
C H isomer
lo 2o
C,-alkyl cyclohexane isomer
0
C.-alkyl benzene isomer
C13H28 isomer
C.Hg-benzene isomer
C.-alkyl benzene isomer
0
C13H28 isoffler
C14H30 lsomer
C13H26 isooer
ci-tridecane
B-methylnaphthalene
C.-alkyl benzene isomer
a-mechylnaphthalene
C14H28 Is00er
C14H28 isomer
C14H30 iS°mer
Chromato-
graphic
Peak No.
110A
HOB
111

112
113
U3A
113B
114
114A
115
115A
116
116A
116B
117
118

119
120
121
122
122A
Elution
Temp.
(°C)
207
208
209

210
211
211
212
213
214
216
217
218
219
219
220
222

224
225
226
228
233
Compound

C,-alkyl benzene isomer
C13H26 l30mer
C..H,. isomer
14 30
alkyl butyrace
C.. ,H,_ isomer
biphenyl
Cj,H... isomer
n-cetradecane
C.-alkyl naphthalene
C.-alkyl naphthalene
C15H30 isomer








isomer
isomer

dimethylnaphchalene isomer
C15H30 isomer
C15H32 isomer
C.-alkyl naphthalene
C.,H.. isomer
16 34
C13H26° isomer 
-------
Table C-8.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN THE KANAWHA VALLEY, WV (TRIP 2, P2/L4).
Chromato-
graphic
Peak No.
1
2A
2B
2C
2D
2E
3
4
4A
5
5A
5B
5C
6
6A
6B
6C
5D
7
8
8A

9
10
10A
11
12
12A
12B
13
14
14A
15
16
16A
17
17A
17B
17C
18
ISA
19
19A
19B
19C
20

Elution
Temp.
48
53
53
54
54
56
53
59
59
60
60
61
62
63
64
64
66
67
68
70
71

72
73
73
74
75
75
76
76
77
78
80
81
82
82
83
83
84
84
85
86
87
88
88
88

Compound
C°2
C.H. isomer
n-butane
acetaldehyde (tent.)
C,Hg isomer
C5H10 isomer
isopentane
acetone
CjH.Q isomer
it-pen tane
CjH . isomer
isopropanol
dichloromethane +• '-C^^Q isomer
methyl acetate
C.H, isomer
J 0
cs2
2-methy Ipropana ]
C.H. isomer
3 o
2-methylpentane
3-methylpentane
CgH. . isomer + methyl ethyl
ketone (tent.)
hexafluorobenzene (eS)
tt-hexane
isopropyl ether
chloroform + C,H, - isomer
0 Ij.
C6H12 isomer
ethyl acetate (tent.)
C,H, _ isomer
b 12
per fluoro toluene (e$)
C,H.,- isomer
1,1,1-trichloroethane
1-chlorobucane
unknown
C,H, - isomer
b 10
benzene
isopropyl acetate (tent.)
carbon tatrachloride
cyclohexane
2-methylhexane
2, 3-dimethylpentane
3-oe t hy Ihexane
C6H10 isolner
C5H10° isomer
C,H. , isomer
7 14
dichloropropene
Chromato-
graphic
Peak No.
20A
21
21A
22
22A
22B
23
23A
24
24A
24B
24C
25
26
27
28
29
30
31
32
32A
32B
33
34
34A
35
35A
36

37
37A
38
39
39A
39B
40

41
41A
41B
41C
42
43
43A
44
44A
(continued)
Elution
Temp.
CC)
89
89
90
91
92
93
94
94
96
97
98
98
98
100
102
104
105
107
108
109
110
110
in
112
113
114
U.4
116

117
118
118
119
U9
120
120

121
128
123
123
124
124
125
125
126

Compound
C-,H, , isomer >
7 16
trichloroethylene
C7H14 j-sooer
^-heptane
C7H14 lsomer
ja-propyl acetate
C.H, . isomer
7 14
C7H_2 Isomer
me thy lc:y clohexane
4-methyl- 2-pentanone
C8H18 isomer
dimethyl disulfide
C8H18 isomer
CgH.g :.somer
CgHlg - C7H12 isomers (tent.)
toluetus
C8H18 isomer
C.H... isomer
o lo
CgH,6 isomer
C8H18 :Lsomer
CgH,6 isomer
1,2-dibromoethane (tent.)
C,H1(; isomer
O J.O
o-octane
CgH 6 isomer
tetrachloroethylene
CgH16 :Lsomer
dimethylpentanal or
CyH.. 40 isomer
C.H.. 'Lsomer
C.H,, isomer (tent.)
CgH2Q Lsomer
4-viny.Lcyclohexene
C.H. , Lsomer
o 10
C9H18 Lsomer
C-H2Q .Lsomer •(•
echylcyclohexane
trimethylcyclohexane isomer
C5H18 Lsomer
C9H16 Lsomer
C-H „ Lsomer
ethylbanzene "
C9H18 Lsomer
C9H2Q Lsomer
xylene isomer
C9H20 U°mar

                               132
-------
Table C-8.  (cont'd.)
Chromaco-
graphic
Peak No.
45
46
46A
47
47A

48 .
48A
49
50
50A
SOB
50C
51
51A
52

52A
53
53A
53B
54
54A
55
55A
56
57
57A
58
58A
59

59A
60
61
62
63
63A
64
64A
65
65A
66
66A
66B

Elution
Temp.
CO
127
128
129
129
129

130
130
131
133
134
135
135
136
136
137

138
138
139
140
140
141
141
142
142
143
143
144
145
145

146
147
148
148
149
150
150
151
152
153
153
154
154

Compound
C9H2Q isomer
C?H140 + C9H1S isooers
C9Hlg isomer
styrene
cetrahydroindene or
C9H12 isomer
o^xylene
C9H18 1SOnier
mechylethylcyclohexane isomer
n— nonane
anisole
C10E20 isomer
C10H22 iacmK
C,-alkyl cyclohexane isomer
C9H12 isomer
isopropylbenzene +•
C10H22 tsomer
C10H20 isomer
C9H16 is0m"
C10H22 isomer
C10H20 lsomer
propylcyclohexane
C10H22 lsollier
C10H16 **»*
C10H22 isolner
C10H20 isomer + benzaldehyde
n_-propy Ibenzene
C10H20 lsomer
ethyltoluene isomer
C10H22 isomer
1 , 3 , 5- crime thy Ibenzene +•
C10H22 isomer
C10H20 isooer
C10H22 isomer
oj-ethyl toluene
C10H18 is00>6r
C10H20 iscaier
C,H,-benzene Isoner
1, 2, 4-crimechylbenzene
C1QH20 isooer
tt-decane
dichlorobenzene isomer (cent.)
C10H20 is0mer
C4-alk,yl benzene isomer
C H22 isomer (cent.)
Chromaco-
graphic
Peak No.
67

68
69
70

70A
71
71A

72
73

74
75
75A
76
76A
76B
77

78
78A
7 SB
79
79A
80
81
81A
82
82A
33
83A
83B
83C
34
34A
35
85A
36
36A
86B

87
87A
(continued)
Elation
Temp.
CO
155

156
156
157

158
159
160

160
161

162
162
163
163
163
164
164

165
165
165
166
166
167
168
168
169
170
170
171
171
171
172
173
174
174
175
175
176

177
177

Compound
C11H24 + C4~all!:y1 bsazeae
isomers
1,2, 3- trimechy Ibenzene
CUH24 isomer
C, ,H,, Isomer +
11 24
^•dichlorobenzene
indan
C4-alkyl cyclohexane isomer
CUH22 + C4~alkyl benzene
isomers
C4~alkyl benzene isomer
C,-alkyl benzene isomer +
tt-bucy Ibenzene
CUH24 isomer
CUH22 isomer
C4-alkyl benzene isomer
C11H22 i3omer
C,-alkyl benzene isomer
C10H18 i300er
C4~alkyl benzene +
C11H24 isomers
C4~alkyl benzene isomer
CUH2Q isomer
CUH22 isomer
C4~alkyl benzene isomer
C12H22 I30mer
C11H22 lsomer
CUH22 isomer
C12H24 isomer
ti-undecane
C4~allc7l benzene iaooer
CUH22 isomer
C12H24 isomer
C12H26 "omer
C4-alkyl benzene isomer
C12H26 i30nier
CUH2Q isomer
C12H26 ls°mer
C.-alkyl phenol isomer
C--alkyl benzene isomer
C, -H-. isomer
12 24
C.-alkyl benzene i- C,H,-
benzene isomers
C.-alkyl cyclohexane isomer
CUH20 isomer

           133
-------
Table C-8.  (cont'd.)
Chroroaco-
graphic
Peak No.
87B

87C
88

89
90

90A
91

91A
92
92A

92B
93
94
95
96
96A
97
98
98A
99
100
100A
101
101A
102

103
103A
104

105
Elucion
Temp.
177

178
178

179
180

180
181

182
183
184

184
185
186
187
188
190
191
192
192
193
194
195
196
197
198

199
200
201

202
Compound
C.-alkyl benzene -t- C--alkyl
phenol isomer
C,H--benzene +• C, ,H_. isomers
47 12 24
C, ,H,, +• cecramechylbenzene
xz zo
isomers
Cj-alkyl benzene isomer
1,2,3,4-cetrahydronaphchalene +•
C.-alkyl benzene isomer
C,-alkyl benzene isomer
C.-alkyl benzene +
C,,H-, isomers
J.Z Zo
C12H24 isooer
naphthalene
C,_H_. isomer
12 24
C,-alkyl benzene isomer
n-dodecane
C.-alkyl benzene isomer
C13E28 isomer
C,-alkyl benzene isomer
C,-alkyl benzene isomer
0
C13H26 is0ner
C,-alkyl cyclohexane isomer
Q
C^ H., isomer
C13H28 iSOn«
C.-alkyl benzene isomer
C13H28 iSOmer
C14H30 iSOmer
C11H22° l30mer
C H-, isomer
13 26
n-cridecane
3-mechylnaphchalene
C.-alkyl benzene +•
C13H26 iso»ars
a-mechy Inaph thalene
Chromaco—
grapnic
Peak No.
10 5A
105B
105C
106

106A
107
107A
108
108A
109
110
111
111A

112
113
113A
113B
114
115
115A
115B
116
117
117A
USA
119
119A
120

12 OA
121
122
123
124
Elucion
Temp .
203
205
206
207

208
209
210
211
211
213
215
217
218

220
222
224
225
226
228
231
232
235
237
237
239
240
240
240

240
240
240
240
240
Compound
C,H, ,-oenzene isomer (tent.)
o 11
C^-alkyl benzene isomer
C14H28 1SOmer
C^-alkyl cyclohexane or
C,,H-, isomer
lj /o
C15H32 isotner
C,QH 1Q0 kecone isomer
C15H30 iso0er
biphenyl
C14H28 isomer
n-cetradecane •*• diphenyl echer
dimethylnaphchalene isomer
dimechylnaphchalene isomer
C, .H-. isomer
15 30
C15H32 iSOner
C16H34 is0mer
C15H30 isomer
C15H30 isomer
n-pent.adecane
unknov-n
C15H30 isomer
C,-allr7l naphthalene isomer
diethyl phchalate
C^.H-gO isoner
C16H,., isomer
ji-hexadecane
unknown
beniophenone
C. _H, , isomer
17 3'+
C17H3S Is0mer
sac. 'lydrocarbon
C15H30° iSOaeZ
n-hep cadecane
C19H40 is°mer
         134
-------
Table C-9.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN THE KANAWHA VALLEY, WV  (TRIP 2, P2/L5).
Chroma to-
graphic
Peak No.
1
4
4A
5
6
7
7A •
8
3A
9
10A
10B
11
12
13
14
14A
15
15A
16
16A
17
17A
17B
17C
18
ISA
19
20
20A
20B
20C
20D
20E
21
21A
21B
22
23
23A
23B
24
24A

24B
24C
25

Elution
Temp.
CC)
49
52
53
53
55
58
58
59
61
62
65
68
68
70
72
73
73
74
75
77
78
83
34
94
95
87
39
90
92
93
97
99
102
102
104
105
107
110
113
115
124
126
129

130
131
131

Compound
CO,
n-propane (tent.)
butene
n-butane
acetaldehyde
isopentane
dimethyl ether
acetone
dichloroethylene isomer
dichloromethane
C.H.O isomer
4 8
C,H.2 isomer (tent.)
2-methylpentane
3-methylpentane
hexai luorobenzene (eS)
u-hexaae
diisopropyl ether
chloroform
ethyl acetate (tent.)
perfluoro toluene (el)
methylcyclopentane
benzene
carbon tecrachlorlde
cyclohexane
2 -me t hy Ih exane
C7H16 iscnler
C-H.4 isomer (tent.)
acetic acid
n-hep tane
C?H14 + C5H10° isomers (cent.)
methylcyclohexane
C-H,. isomer (tent.)
C.,HI , isomer
CgH.g isomer
toluene
C8?13 is0mer
C3H18 lsomer
rfhexanal
o-octane
tetrachloroechylene (tent.)
ethylbenzene
xylene isomer
C.H.n isomer
9 20
styrene
n-hep tanal
o-xylene + C_H,Q isomer
Chromato-
graphic
Peak Ho.
26
27
27A
27B
27C
28
28A
28B
29
29A
29B
30
31
31A
31B
32
32A

33
33A
34
34A
35
35A
35B

35C
35D
35E
36
36A
37
37A
37B
38
38A
38B
39
39A

39B
40
40A

41
41A
41B
(continued)
Elution
Temp .
133
137
140
141
142
143
143
144
146
147
148
149
150
150
151
152
155

157
159
160
161
162
163
164

165
166
166
167
168
169
172
174
175
176
177
178
180

182
184
185

186
187
188

Compound
ji-nonane
C1QH22 isomer
C10H22 is°ner
C10H16 is0mer
C-H.,0 isomer
benz aldehyde
ri-propylbenzene
echyltoluene isomer
C11H24 i30mer
phenol
C.-alkyl benzene isomer
CUH24 isomer
a-octanal
C10H20 iS°mer
1,2,4-trimethylbenzene
ri-decane
1,2,3-trimethylbenzene +
C11H24 lsoner
C1?H,. isomer
11 24
unsac. hydrocarbon
sat. hydrocarbon
C.-alkyl benzene isomer
acetophenone
cresol isomer
C4-alkyl benzene +
C11H24 isoniers
C4-allcyl benzene isomer
CnH22 isomer
C4-alkyl benzene isomer
n— nonanal
C H,_ isomer
n— undecane
C4-alkyl benzene isomer
C12H24 iSOmar
dimethylphenol isomer
C12H24 isomer
C^jHjg isomer
C2-alkyl phenol isomer
C.-alkyl benzene + ci_2H24
isomers
C,-alkyl phenol isomer
n^decanal + naphthalene
C..H., isomer
12 24
D— dodecane
C,-alkyl phenol isomer
C,-H.. isomer
12 24

                                 135
-------
Table C-9.  (cont'd.)
Chromaco-
graphic
Peak No.
41C
41D
41E
42
43
43A
43B
Eludon
Temp.
CO
193
197
198
199
200
201
205
Compound
C12H24 isomer
C11H'>00 isomer (cenc->
C13H26 isomer
n-undecanal
ii-cridecane
8-mechylnaphchalene
C14H30 iSOmer
Chromaco-
graphic
Peak No.
44
44A
44B
45
47
47A

Elucion
Temp.
(°C)
207
208
209
210
222
223

Compound
alkyl aucyrace
biphenyl (cent.)
C14H28 isomer
£-cecradacane
sac. hydrocarbon
C15H30 isomer

           136
-------
Table C-10.
VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
IN THE KANAWHA VALLEY, WV (TRIP 3, P1/L8).
Chroraato-
graphic
Peak No.
1
3
3A
4
4A
4B
5
5A
6
6A
Elucion
Temp.
CO
48
51
52
53
54
55
56
56
57
59
Compound
co2
acetaldehyde
C^Hg isomer
isobutane
C4H8
C4H8
tr-butane
C5H10
isopentaoe
acetone
Chromaco-
graphic
Peak No.
7
7A
7B
7C
9
10
11
12
13
14
Elucion
Temp.
CO
60
60
61
61
67
69
70
71
75
76
Compound
nj-pentane
dichloroethylene iaoner
nethylene chloride
C,H, „ isomcr
5 10
2-mechylpencane
3-methylpencane
haxaf luorobenzene (el)
n^hexane
perf luorotoluene (eS)
nethyleyelopentane
                                  137
-------
Table C-ll.
VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
IN THE KANAWHA VALLEY, WV (TRIP 3, P1/L8).
Chroma to-
graphic
Peak No.
1
3
3A
3B
3C
4
5 -
5A
5B
6
6A
7
7A
7B
10
10A
11
11A
11B
12
12A
13
13A
13B
14
14A
15
16
16A
16B
17
17A
18
19
19A
20
20A
20B
21
22
22A
23
24
25
26
27

Elucion
Temp.
48
53
55
56
56
58
59
60
60
62
63
63
69
69
70
71
73
73
73
75
75
76
76
78
80
81
83
86
87
87
88
89
90
92
93
95
97
100
101
104
106
108
110
113
115
117

Compound
co2
propane
C4H10 isomer
acetaldehyde
butane
isopentane
methyl acetate (tent)
dimethyl ether
acetone
n-pentane
C.H--0 isomer (tent)
methylene chloride
C6H12 isomer
CjH^Q isomer
2-methylpentane
C6H12 isomer
3-methylpentane
butanal (tent)
C,H-2 isomer
hexafluorobenzene (el)
n-hexane
isopropyl ether
chloroform
























methyl ethyl ketone (tent)
perfluorotoluene (eS)
CgH-_ isomer (tent)
1, 1, 1-trichloroe thane
benzene
carbon tetrachloride
cyclohexane
2-me thy Ihexane
2, 3-dimethylpentane
3-me thy Ihexane
C7H14 isomer
C,H-nO isooer
n_-h«ptane
C,H,_0 isooer (tent)
o 12
methylcyclohexane
4-raethyl-2-pentanone
C,H, nO ketone isooers
0 1U
2-hexanol
toluene
C-H, . isomer
o lo















(tent)



4-methyl-3-penten-2-one
n— octane
tetrachloroechylene



Chroma to-
graphic
Peak Ho.
27A
28
28A
29
29A

29B
30
31
31A
32
32A
33
34
34A
35
36
37

37A
38

38A
39
40
40A
41
41A
41B

42
42A
42B
42C
43
43A
43B
44
45
46
46A
46B
46C
-
46D
47
(continued)
Elucion
Temp.
118
119
122
123
124

125
127
129
129
130
130
132
133
134
135
138
139

140
142

143
143
144
145
146
147
147

147
148
148
149
149
150
151
152
153
154
155
155
156
-
157
157

Compound
C.E., isooer
2-methoxy-2h-dihydro-pyran
C9H20 tsoner
C.H., isooer
chlorobenzene + ethylcyclo-
hexane
C,,lLg isomer
ethylbenzene
xylene isomer
C^HjQ iaomer
C9H20 is0n*r
heptanone isomer
styrene
o_-xylene
C9H18 ls°mer
n— nonane
C.H- „ isomer
isopropylbenzene + C.-H-2
isomer
C10H22 i30Mr
C1QH,2 +• C,-alkyl cyclohexane
isomers
C10H16 isomer
benzadehyde
n_-propylbenzene
ethyltoluene isomer
C-H-gO ketone isomer
pheno 1
cyancbenzene + 1,3,5-trimethyl-
benzene
C10H22 iSOmeT
C10H20 i30Tner
C10H22 1SOIBer
o^etfcyltoluene
C.Hn ,,0 ketone isomer
7 J.O
C^-H.., isomer
benzofuran -t- C.-H-- isomer
1,2, 4-trimethylbenzene
th-decane
dichlorobenzene isomer
C^gHyg isomer
C,-alkyl benzene isomer
C^-jH.,, +• C,-alkyl benzene
isomers
CIOH::O isomer
1,2,3- crimethy Ifaenzene

                                  138
-------
Table C-ll.  (cont'd.)
Chromaco-
graphic
Peak No.
47A

48
48A

48B
48C
48D
48E
48F
49
49A
50

51
51A
51B
52
52A
53
53A
53B
54
54A
55

55A
55B
55C
55D

55E
Elution
Temp .
(°C)
157

159
159

160
161
161
161
162
162
163
165

166
166
167
168
168
169
169
170
171
172
173

174
175
175
175

176
Compound
C, ,H_, + C.-alkyl benzene
11 24 4
isomers
£-dichlorobenzene
C4-alkyl cyclohexane isomer +•
indan
C11H24 isomers
indene + C-.H-. isomers
C,-alkyl pyridine isomer (tent)
C4-alkyl benzene isomer
Chalky! benzene isomer
acetophenone
C4-alkyl benzene isomer
C11H''4 + C4~alkyl benzena
isomers
C11H24 is0msr
C4-alkyl benzene isomer
C4H^-benzene isomer
C4-alkyl benzene isomer
C11H22 iso'ner
n_-nonanal
C4H^-benzene isomer
C..H._ isomer
n— undecane
C,-alkyl benzene isomer
3,5 ,5-trimethyl-2-cyclohexen-
one
C4alkyl benzene isomer
2-pyrone (tent)
C. ,H „ isomer
C..H.,., isomer
11 22
C.-alkyl benzene isomer
Chrociaco-
graphic
Peak No.
55F
55G
56
56A
57
57A
58
58A
59
60
60A

60B
60C
60D
61
51A
61B
61C
62
63
64
64A
64B
64C
64D
65
65A
68
68A


Elucion
Temp.
178
178
180
180
181
183
185
186
137
188
192

196
198
200
202
203
205
209
213
214
216
217
218
220
228
229
231
240
240


Compound
C,H, -benzene isomer
4 7
unsat. hydrocarbon
C12H26 iaonler
C,-alkyl benzene isomer
1,2,3, 4-te trahydronaphthalene
C.-alkyl benzene isomer
naphthalene
2,3-benzothiophene (tent)
n-dodecane
2, 6, 8-trimethylnonanone-4
nethyldihydronaphthalene
isomer (cent.)
C^.H.,0 isomer (tent)
12 24
C13H28 i3omer
unsat. hydrocarbon
ti-tridecane
S-methylnaphthalene
a-methylnaphthalene
C^.H,, isomer (tent)
a-tetralone
biphenyl
diphenyl ether~'f n_-tetradecane
C14H28 is0mer
C.-alkyl naphthalene isomer
C.-alkyl naphthalene isomer
C15H30 isoael
n-pentadecane
'"14^12 ^somer
benzophenone
C ,H,, isomer
17 36

         139
-------
Table C-12.
VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
IN THE KANAWHA VALLEY, WV (TRIP 3, P2/L1).
Chromaco-
graphic
Peak No.
1
3
4
5
6
7
9
9A
10
10A
11
13
14A
15
16
ISA
17
18
19
20
20A
21
22
23
24
24A
24B
25
26
26A
27
27A
28
29
30
30A
31
31A
32
33
34
34A
35
35A
36
36A

Elution
Temp.
48
51
52
53
56
58
60
61
61
61
62
65
68
69
71
72
73
74
75
76
77
78
79
80
31
82
83
84
85
86
86
87
87
38
90
91
91
92
93
94
99
100
101
102
103
104

Compound
co2
propane (tent)
C.1L. isomer (tent)
acecaldehyde
n-butane
isopentane
acetone
diethyl ether
n^pencane
Background peak
aethylene chloride
CglL, isomer (tent)
=5*10 i30m"
2-methylpentane
3-methylpentane
C6H12 Is0°er
hexafluorobenzene (ef)
n-hexane
chloroform
ethyl acetate
C6H12 I30mer
perfluorocoluene (el)
methylcyclopentane
unsat. hydrocarbon (tent)
1 ,1 , 1-trichlo roe thane
C7*U isoner
CfiH10 isomer
benzene
carbon tetrachloride
cyclohexane
2-methylhexane
2, 3-dimethylpentane
acetic acid
3-methylhexane
C7HU isomer
C7H14 i30mer
C8H18 isomer
C^IL , isomer
ti-hep tane
SH14 iSOMr
methylcyclohexane
CgtL, isomer
C8H18 is°mer
C,Hn,0 isomer
D J.Z
C8Hlg isomer
C.H,.. isomer
5 J.O
Chromato-
graphic
Peak No.
37
38
39
40
40A
41
41A
42
43
43A
43B
43C
4 3D
43E
44

44A
44B
45
45A
46
46A
47
47A
48
49
49A
49B
50
50A
51

51A
52
53
53A
54
55
56
57
57A
57B
57C
58
58A
58B
continued
Elution
Temp.
CO
105
106
108
109
111
112
113
115
116
117
119
120
121
122
123

124
125
127
127
128
129
130
132
132
133
134
134
136
138
139

140
141
143
143
144
144
145
146
147
148
148
148
150
150

Compound
CgH^8 isomer
toluene
C,jH- 8 isomer
CgHlg isomer
CgH. , isomer
C9H20 i30mer
C8H16 lsomer
n-octane
tetrachloroethylene
C8H16 i801Der
C.H.. isomer
C9H20 isomer
SH20 l30ner
C8H16 isomer
ethylcyc lohexane + cgH2o
isomer s
C9H^g isomer
CgH^g isomer
ethylbetizene
C9H18 isomer
xylene Isomer
CgH20 isomer
C9H2Q iaomer
C9H20 laoaer
styrene
oj-jcylents
C10H22 isomer
CgH^g tiiomer
n-nonanis »
C9H18 i30mer
C.nH._ Lsomer + isopropyl-
1U L£
benzene
C10H20 Ls0mer
C10H22 *-somer
C10H22 1SOmer
C10H20 lsoiner
^10^16 ^sonier
benzaldehyde
n-p ropy Iben zene
ethyltoluene isoner
C. 0H_- isomer
phenol
1,3,5-crimethylbenzene
C11H24 isonler
C10H22 isomer
o-ethyl toluene

                                 140
-------
Table C-12.  (cont'd.)
C'nromaco-
graphic
Peak No.
58C
580
58E
59
59A
60
61
6LA
61B
6 1C

62
62A
63
63A
63B
63C
6 3D
64

63
65A
65B
65C
66

66A
66B
66C
66D
67
67A
68
68A

69
69A
69B
69C
70
70A
70B
70C
Elution
Temp.
CO
151
152
152
153
154
155
156
156
157
158

158
159
160
161
162
162
163
163

164
164
165
165
166

168
168
169
169
169
170
170
171

172
173
173
174
176
177
178
173
Compound
C10H22 isomer
C10H16 iSOTCr
C,H_-benzene + ciQH20 isomers
1,2, 4- trimethylbenzene
C10H20 1SOmer
n-decane
dichlorobenzene isomer
C10H20 isomer
C.-alkyl benzene isomer
C,.H,, + C4-alkyl benzene
isomers
1,2, 3- trimethylbenzene
C11H24 isomer
C12H26 isomer
in dan
C.-alkyl cyclohexane isomer
CUH22 isomer
C4-alkyl benzene isomer
C,-alkyl benzene + ciiH24
isomers
acetophenone
C4~alkyl benzene isomer
^11^24 ^somer
C,,H_ isomer
C11H24 + C4~alkyl benzene
isomers
C,,H-4 isomer
C4-alkyl benzene isomer
Cj-H24 isomer
C, H,-benzene isomer
4 7
C4~alkyl benzene isomer
C12H26 isomer
iv-nonanal
C, ,H,_ isomer
11 22
n^undecane
C.-alkyl benzene isomer
C4~alkyl benzene isomer
C,,ft_2 isomer
C.-alkyl benzene isomer
C12H26 isoner
C,-alkyl phenol isomer
C.-alkyl benzene isomer
Chromato-
graphic
Peak No.
70D
70E
70F

70G
71

71A
71B
71C
71D
71E
71?
71G
72
72A
72B
73
73A
73B
73C
7 3D
73E
74
74A
74B
74C
75
75A
76
76A
76B
76C
76D

77
78
79A
80A
SOB



Elucion
Temp.
CO
179
180
180

181
182

182
183
183
184
184
185
186
187
187
188
189
190
190
196
200
202
204
204
205
206
211
216
218
220
222
224
230

231
235
240
240
240



Compound
C.-alkyl benzene isomer
C.-alkyl cyclohexane isomer
^12^24 + C^-alky! benzene
isomers
C.lU-benzene isomer
C12H26 * C5"alky1 benzene
isomers
C12H24 isorner
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C12H26 is0mer
C.-alkyl benzene isomer
C10H20° 1SOtner
naphthalene
n-decanal
C^-H_4 isomer
C.-alkyl benzene isomer
n^-dodecane
C.-alkyl benzene isotner
C^-H.j isomer
CUH28 isomer
C13H28 isomer
C12H24 isomer
n_-tridecane
S-ffle thy Inap h thalene
C13E26 isooer
a-oethylnaph thalene
C.-alkyl cyclohexane isomer
C14H28 isomer
_n-cetradecane
dimethylnaphthalene isomer
dimethylnaphthalene isomer
C..H. isomer
C, .H,- isomer
15 30
n-pentadecane
unknown
C16H32 isomer
nj-hexadecane
benzophenone



          141
-------
Table C-13.
VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
IN THE KANAWHA VALLEY, WV (TRIP 3, P2/L2).
Chrooato-
graphic
Peak No.
1
3A
3B
4
4A
48
4C
4D
5
5A
SB

6
?A
8
8A
9
9A
9B
10
U
12
12A
13
14
14A
14B
15
ISA
15B
16
ISA
17
18
ISA
18B
19
19A
20
21
Z1A
215
21C
22
23
24

Elution
Temp.
48
52
52
53
54
59
61
61
62
63
64

64
71
71
73
74
74
75
76
77
77
80
81
82
84
86
87
38
38
89
90
91
93
94
94
96
98
101
103
103
105
106
107
108
109

Compound
CO
propane (tent)
C4H_ isomer
C4H10 isomer
acetaldehyde
isopentane
C.H.. isomer
furan (cent)
acetone +• £-pentane
diethyl ether (tent)











dichloroethylene isomer
(traces)
methylene chloride
C,H-Q iaomer
2-me thy Ipentane
C_H1nO isomer
3-me thy Ipentane
butanal
C,H_ - isomer








hexafluorobenzene (el)
^hexane
chloroform
CgH-_ Isomer
perfluorotoluene (e!)
me thy Icy c lopen tane
1 , 1, 1-trlchloroethane
C-R-g isomer (tent)
benzene
carbon tetrachloride
cyclohexane
2-methylhexane








(traces)


2,3-dimethylpentane (tent)
3-me thy Ihexane + acetic acid
C7H14 lsomer
trichloroethylene
C3H18 isoner
ii-heptane
C.EL , isomer
oechylcyclohexane
C Hia isomer
a lo
CglL-0 kecone isomer
C.H, , isomer
3 16
C3H16 isomer
CgH^g isomer
toluene
= 8*18 1SOraer














Chroma to-
jraphic
Peak No.
25
25A
25B
26
26A
27
28
28A
28B
29
29A
29B
30
30A
31

31A
31B
32
32A
33
33A
34
34A
35
35A
35B
36
36A
37
38
39

39A
40
40A
40B
41
41A
42
42A
43
44
44A
45
45A
(continued)
Elucion
Temp .
Ill
112
112
113
114
116
117
118
119
119
121
121
122
123
124

125
126
127
128
129
129
130
131
132
132
133
133
134
136
138
139

140
141
141
142
142
143
144
145
145
146
147
148
148

Compound
CgH.g Lsomer
C.R.,0 isomer
C3H16 U°mer
n_-hexanal +• CgH-- isomer
C-H.., Lsomer
o lo
n_-octane
tetrachloroethylene
C.H.., isomer
C_H-n isomer (tent)
C9H20 Uomer
C9H20 lsollier
C.,^, Isomer
o 10
C9H,,. Isomer
CgH^g Isomer
CgH20 isomer + ethylcyclo-
hexane
C9H18 1SOmer
C,H, ,0 isomer (tent)
7 14
ethylbenzene isomer
CjH^g isomer
xylene Isomer
CgH,- Isomer
CgH.ft isomer
C-IL ,0 isomer
C10322 isoner
styrene
S^s lsomer
o_-xylene
CgE^g isomer
n^nonsine
CgH^ isomer
C-0H2., isomer + isopropyl-
beitzene
C10H20 1SOmer
cioH::2 isomer
C0H-C isomer (tent)
9 lo
C. -H_ ,_ isomer
C- n^<7 •* isotosr1
C,-ai;tyl cyclohexane isomer
benzaldehyde
C^..H-- isomer
n-propylbenzene
ethylcoluene isomer
C10H22 iSOner
1,3,5-trimethylbenzene
C11H24 isomer

                                 142
-------
Table C-13.  (cont'd.)
Chromato—
graphic
Pea* No.
45B
46
47
47A
47B
48
49
49A
50
51
51A
51B
52

53
53A

54
55
55A
55B
55C
55D
56
57

57A
57B
58
58A
59
59A
60
60A

61
61A

62

63
63A
63B
63C
6 3D
64
65
65A

Elution
Temp.
149
149
150
151
151
152
153
153
154
155
155
156
157

158
158

159
160
161
161
161
162
162
163

164
164
166
167
167
168
169
169

170
170

171

172
173
173
173
174
174
175
176

Compound
phenol (tent) +• C1QH,0 isomer
C10H22 1SOmer
o^-ethyltoluene
C10H-_ isomer
C11H24 isomer
n_-octanal
1,2, 4- trimethy Ibenzene
C10H20 I30ner
n_-decane
dichlorobenzene isomer
isobutylbenzene
sec-buty Ibenzene
C4-allcyl benzene +• C..H_4
isomers
1,2 , 3- trimethy Ibenzene
C, -H-, isomer
11 24
Cj.H_4 isomer
C-H.-benzene isomer
C11H24 isomer
C4-alkyl eyclohexane isomer
C11H22 isomer
C4-alkyl bencene isomer
p-propyl toluene
C4-alkyl benzene isomer +
acetophenone (tent . )
C4~alkyl benzene isomer
C1,H-4 isomer
£-propyl to luene
CUH24 isomer
C.-alkyl benzene isomer
C11H24 Is0ncr
C4-alkyl benzene Isomer
n_-nonanal + C4H_-benzene
isomer
C4-alkyl benzene isomer
C, ,H-- isomer
11 22
ii-undecane •+• C.-alkyl benzene
isomer
C.-alkyl benzene isomer
C11H22 iSOiner
C.-alkyl benzene isomer
C12H24 isomer
C12H26 is0mer
tetramethylbenzene isomer
C.-alkvl benzene isoraer
4
C12H26 Is0mer
Chromaco-
graphic
Peak No.
66
66A
67
67A
67B
68
69
70
70A
70B
71
71A
72
72A
72B
72C


73
73A
73B
74

74A
75
75A
76
76A
76B
77
77A
77B
77C
77D
77E
77T
77G

77H
78
78A
78B
78C
79
79A
80
80A
81
(continued)
Elution
Temp.
CC)
177
178
178
178
179
179
180
181
181
182
182
182
183
184
185
185


186
186
186
187

188
189
190
191
192
193
194
195
195
195
196
196
196
197

197
199
200
200
201
202
203
204
205
205

Compound
C.-alkyl benzene isomer
C.H,-benzene isomer
4 7
C.-alkyl benzene isomer
C.H.J— benzene isomer
C12H24 isolner
C.-alkyl benzene isomer
C.H,-benzene isomer
4 7
C,-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl benzene isoraer
1,2, 3,4-tetranydronaphthalene
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C,-alkyl benzene isomer
C.HQ-benzene + C.-alkvl
59 3
benzene isomers
naphthalene
C,H9~benzene isomer
C.-alkyl benzene isomer
Cj-alkyl benzene isomer +•
ii-dodecane
C,-alkyl benzene isomer
0
C.-alkyl benzene isomer
C-,H,., isomer
C,-alkyl benzene isomer
0
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C^-H., isomer
C,-alkyl benzene isooer
0
C.-alkyl benzene Isomer
C13H28 l30Tner
C.H_-benzene isomer
C,-alkyl benzene isomer
C.-alkyl benzene isomer
Cn ,H - isomer
13 28
C.-alkyl benzene isomer
C14H30 isonier
C. ,H., isomer
C.-alkyl benzene isomer
C13326 isoiner
n_-tridecane
S-methylnaphthalene
C.-alkyl benzene isomer
C,-alkyl benzene isomer
0
a-raethylnaphthalene

            143
-------
Table C-13.  (cont'd.)
Chromaco-
graphic
Peak No.
SLA
82
83

83A
33B
83C
84 .
84A
34B
84C
Elucion
Temp.
(°C)
209
210
213

214
214
215
216
218
219
220
Compound
C,H--benzene + C^-alkyl
benzene isomers
C.-alkyl benzene isomer
o
1 , 2 , 3 , 4- ce trahy dronaph chalen-
1-one
biphenyl
C14H30 i30W**
C14H28 is°mer
n_-te trade cane
C10H10° lsoner (tent)
dimechylnaphthalene isomer
dimethylnaphthalane isomer
Chroma co-
graphic
Peak No.
84D
84E
84F
84G
85
86
88A
88B
88C
88D
88E

Elucion
Temp.
(°C)
223
225
227
228
229
233
240
240
240
240
240

Compound
C15H30 1SOmer
C15H32 isomers
C13H26° isoroer
C15H30 isomer
ir-penc adecane
unknown
ii-hexadecane
benzophenone
C17H36 isomer
alkyl ketone
ti-heptadecane

             144
-------
Table C-14.
VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
IN THE KANAWHA VALLEY, WV (TRIP 3, P2/L9).
Chromato-
graphic
Peak No.
1
3
4
4A
5
6
7
8
8A
SB
9
Elution
Temp.
47
51
53
54
56
58
59
60
61
62
62
Compound
co2
propane
isobutane
C4H2 isomer
n_-butane
isopentane
acetone
ti-pentane
diethyl ether
vinylidine chloride
methylene chloride
Chronato-
graphic
PeaK No.
11
12
13
13A
14
15
ISA
16
17
18

Elution
Temp.
(°C)
64
69
71
72
73
74
75
76
78
79

Compound
cs2
2-m«thylpentane
3-methylpentane
CjH12 isomer
hexafluorobenzene (el)
tv-hexane
chloroform
CyH., isomer (tent.)
p«rfluorotoluene (ei)
methylcyclopentane

                              145
-------
                          APPENDIX D

SEMIVOLATILE COMPOUNDS IDENTIFIED IN AIR PARTICULATE COLLECTED
                    IN KANAWHA VALLEY, WV
                              146
-------
Table  D-l.   COMPOUNDS  IDENTIFID  IN  POLAR  NEUTRAL  FRACTION  OF  <1.7  u
              AIR PARTICULATE COLLECTED  IN KANAWHA VALLEY,  WV
                                   (Trip 3,  PI/LI)
Chroma to-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

i. c13
2. Cu
3- C16
4. Clg
Elution
Temp . Compound
(°C)
124 naphthalene
135 benzothiazole (tent.)
161 Si compound (bkg.)
167 C^ alkyl benzene
168 naphthol + unknown
182 unknown
196 p-nonyl phenol
202 ci4Hin isoloer
212 a phthalate (bkg.)
213 CT,HON isomer1 (tent.)
2
216 C, ,H.O isomer (tent.)
1J o
217 C2 alkyl fluorene (tent.)
221 methyl hexadecanoate
222 a phthalate (bkg.)
234 C..,H.- isomer3
10 1U _
239 C.,Hn.. isomer
10 lu
243 methyl octadecanoate +
unknown (s)
Chromato-
graphic
Peak No.
18
19
20
21
22
23
24
25
26

27

28
29
30
31
32
33
H H isomers include benzoquinoline isomers and acridine.
HgO isomers include fluorenones and perinaphthindenones and
H isomers include pyrene and fluoranthene.
H isomers include 1,10-benzfluoranthene, 3,4-cyclopentapyi
Elution
Temp .
(°C)
259
263
265
265
265
265
265
265
265



265
265
265
265
265
265


Compound

a phthalate
a phthalate
C18H10 isoner* <""•>
C18H14 Isoner4
C^.H^jj isomer (tent.)
C18H12 isomer
benzanthrone
a phthalate (bkg.)
methylbenzanthracene isomer or
methylbenzophenanthrene isomer
triphenylphospine sulfide
(bkg.)
unknown
8
C..-H.. . isomer
/u 1^ g
C20ai2 isoBler (^ent.)
C20H12 lsoner8
binaphthyl isomer + unknown
unknown

benzoindenones .

•ene and

1 , 10-benzoaceanthrylene .
  5.  C, a^-iL  isomers include terphenyl isomers.
  6.  '•TS^I?  ^someIB include benzanthracene isomers (naphthacene et_ a^.) and benzophenanthrene isomers  (triphenylene,
     chrysene et al.)
  7.  This compound is not a methylchrysene or a nethyltriphenylene.
  8.  Ca   isoners include perylene, benzpyrene isomers, and benzfluoranthene isomers.
                                       147
-------
Table-D-2.  COMPOUNDS IDENTIFIED IN PNA FRACTION OF <1.7 y
      AIR PARTICIPATE COLLECTED IN KANAWHA VALLEY, WV
                      (Trip 3, PI/LI)
Chroma to-
graphic
Peak Mo.
1

2
3
4
5
6
7
8
9
10
11
12

13
14
15
16
17
18

19
20
21

22
23
24
25
26
27
28

29
30
31
32
33
34
35
36

37
38
39
40
Elucion
Temp.
CO
111

116
122
123
124
125
132
143
144
151
155
156

159
160
162
168
169.5
173

175
177
181

184
191
193
195
201
208
211

212
216
217
219
211
222
229
230

231
233
236
239
Compound
unknown + dichloromethane
(solvent)
Si compound (bkg.)
unknown
naphthalene
Si compound (bkg.)
unknown
unknown
unknown
nethylaaphthalene isomer (tent.)
C12H1Q isomer
unknown
dimethylnaphthalene isomer +
unknown
biphenylene (tent.)
unknown
di-t-butylbenzoquinone (bkg.?)
dibenzofuran (tent.)
unknown
trimethylnaphthalene isomer
(tent.) +• a phthalate (bkg.)
C, alkyl naphthalene (tent.)
fluorene
2,2, 4-trinethylpenta-l, 3-diol
di-isobutyrate (bkg.)
hydroxyfluorene (tent.)
C, alkyl naphthalene (tent.)
oethylf luorene isomer (tent.)
unknown
C14H10 iam"2
dimethylfluorene + unknown
methyldibenzothiophene isomer
(tent.)
a phthalate (bkg.)
methyl C^H^ isomer
4 , 5-methy lenephenanthrene
methyl C ,H.- isomer
14 1U
unknown (s)
a phthalate (bkg.)
dimethylpbenanthrene isomer
diphenyloxazole isomer (s)
(tent.)
diaethylphenanthrene isomer
C ,SL isomer3
16 10 -
^e'lo isoner:
ci6Hio isooer
Chroma co-
graphic
Peak No.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
51
62
63
64

65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
Elution
Temp.
CO
243
244
246
247
249
251
252
255
261
264
265
265
265
265
265
265
265
265
265
265
265
265
265
265

265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
Compound
trimethylphenanthrene isomer
trimethylphenanthrene isomer.
tximethylphenanthrene isomer
benzof luorene isomer
C17H12 isomer4
methylpyrene isomer (tent.)
methylpyrene isomer (tent.)
methylpyrene isomer
C4 alkyl C14H10 isomer (tent.)
a phthalate
terphenyl isomer (tent.)
terphenyl isomer (tent.)
cisaio isooer5
cerphenyl isomer
C18H10 iS°me%
C18H12 isoffler
ii phthalate (bkg.)
unknown
unknown
C19H14 isomer7 (tent.)
•phthalate(s) (bkg.)
phthalate(s) (bkg.)
7
C, aH, , isomer (tent.)
1 J 14 _
methyl C.gH1Q isomer (tent.)
+• C, alkyl terphenyl (tent.)
' A
C, alkyl CiaH.., isomer
^ io XX ,.
C2 alkyl C-.H^ isomer
C2 ilkyl ClgH12 isomer6
C 22*12 isomer (cent.)
C20H12 isomer'
C,,^, isomer (tent.)
10
C21H20 isoIBer (tent.)
°20H12 isonier (cent.)
C2 alkyl ClgH12 isomer (tent.)
C-.H,, isomer (s) (tent.)
11
C-..H,, isomer (tent.)
11
C,,H-, isomer (tent.)
A
CjjH^ isomer (tent.)
C20H14 i^0""12 (tent-)
C2QH12 isomer (tent.)
C22E12 isOTer" 
C..H. , isomer (tent.)
i 7
C,.£L. isomer (tent.)
14
C,,H, . isomer (tent.)
ij 14 Q
C2QH12 isomer (teat.)
C2iai6 iso>ner (tent.)
                             (continued)
                                148
-------
                                Table  D-2.    (cont'd)
Chromato- Elution
graphic Temp .
Peak No. (°C)
Compound
Chromato- Elution
graphic Temp .
Peak No. (°C)
Compound
86
87
88
89
90
91
     265
     265
     265
     265
     265
     265
       isomer(s)
             13
C21H18 isooer
C21H14 isomer
C21»16
C4 alkyl
13 (tent.)
(tent.)
(tent.)
(tent.)

isomer  (tent.)
92
93
94
95
96

       isomer"* (tent.)
C22H18 lsomer   (tent.)
265
265
265    unknown
                           a
265    methyl C20H12 isomer  (tent.)
265    unknown
 1.
 2.
 3.
 4.
 5.
 6.
 7.
 8.
 9.
10.

11.

12.

13.

14.
15.
16.
17.
C.-H... isomers include biphenyl and acenaphthene.
C..H... isomers include diphenylacetylene,  phenanthrene and anthracene.
C,,H,„ isomers include fluoranthene, pyrene,  benz[a]acenaphthene and benz[e]  acenaphthene.
 ID 1U
CI,HI,, isomers include benzofluoretie isomers  and methyl C-,Hj- issuers.
C.-H,- isomers include 1,10-benzfluoranthene, 3,4-cyclopentapyrene and  1,10-benzoaceanthrylene.
 iO 1U
C^gH,. isomers include benzanthracene isoners,  benzophenanthrene isomers,  triphenylene and  chrysene.
Cj_H   isomers include methyl C.glL, isomers.
C,.H   isomers include 1,12-benzperylene;  2,3-o-phenylenepyrenej anthanthrene and indeno[l,2,3—cd]pyrene.
C-.H . isomers include perylene; benzfluoranthene  isomers; benzpyrene isomers and benzaceanthrylene isomers.
C, H.Q isomers include C, alkyl terphenyl  isomers;  C, alkyl styrylnaphthalene isomers and triphenyl C, ali;ane
isomers.
C,,H,, isomers include diphenylindene isomers;  methylbenzaceanthretie isomers; methylbenzilidine  fluorene
 xi. i.b
isomers and dinaphthylmethane isomers.
<"20H14 is°i°ers include acenaphthanthracene;  phenylanthracene isomers; binaphthyl isomers; benzaceanthrene
isomers;  indenofluorene isomers and 9-benzylidene  fluorene.
C-.H.a isomers include dihydromethyl C..L,  isomers,  tetrahydrocyclohepta-C.^H . isomers and methyl C20ai6
isomers.
C2,H,4 isomers include methyl C^HT? isomers.
C_ Hj, isomers include methyl C_-.H   Isomers.
C.-H,_ isomers include triphenylbenzene isomers (quaterphenyls)
 t-£ i.O
C22H18 isomers include dihydromethylcyeloheptapyrene  isomers;  C-2 alkyl  C-0H-4 isomers and  methyl C21Hlfi
isomers.
                                                       149
-------
Table D-3.  COMPOUNDS  IDENTIFIED  IN PARAFFIN FRACTION OF <1.7
       AIR PARTICULATE  COLLECTED IN KANAWHA VALLEY,  WV
                         (TRIP  3, PI/LI)
Chromato- Elucion
graphic Temp.
Peak No. (°C)
1
2
3
4
5
6
7
8


9
10
11
12
13
14
15
115
118
123
124
125
129
131
165


176
^215-250
265
265
265
265
265
Compound
undecane (tent.)
dimethylundecane (tent.)
an alkane
an alkane
an alkane
n-dodecane
an alkane
di-t-butyl-o-benzoqulnone
isomer + di-t-butyl-p-benioqui-
none isomer
an alkane
alkanes + alkenes
a phthalate (bkg.)
C26H54 alkane
C27H48 8lkene
C--H- alkane
C28H50 alkene
Chromato-
graphic
Peak No.
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31

Elution
Temp.
CO
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265

Compound
unknown
C29H52 *rene
C30H34 arene
mixture of alkanes and alkenes
C29H52 *reM
C29H52 arene
C30H54 areoe
a phthalate (bkg.)
C29H60 alkan« « C30H48 alkene
C30H54 arene
C-,H,, alkene (tent.)
a phthalate (tent.)
unknown
C30H62 alkane
C30H30 arene 
areae(s)

                                 150
-------
     Table-D-4.   COMPOUNDS  IDENTIFIED IN BASE FRACTION OF <1.7  y
          AIR PARTICULATE COLLECTED  IN KANAWHA VALLEY,  WV
                            (TRIP 3, PI/LI)
Chromato-
graphic
Peak No.
1
2
3
4
5
6

7
8

9
Elution
Temp.
CO
125
143
156
164
170
183

191
195

196
Compound
naphthalene ( tent . )
qu incline (tent.)
nicotine (tent.)
C. alkyl quinoline (tent.)
di-t-butylphenol
2,2, 4-trimethylpenca-l , 3-diol
di-isobutyrate (bkg.)
C. alkyl phenol (tent.)
unknown

Cg alkyl phenol
Chroma to-
graphic
Peak No.
10
11
12
13
14
15
16
17
18
*
19
Elution
Temp.
CO
198
201
203
206
210
211
213
225
233

265
Compound
p-nonylphenol
Cg alkyl phenol
C alkyl phenol
C HgN isomer
C. ~HgN isoiser
caffeine (tent.)
a phthalate (bkg.)
a phchalate ester (bkg.)
2,5-diphenyl oxazole

dioctyladipate (bkg?)
Onlabelled peaks beyond file position 400 are phthalates (bkg.)
                                 151
-------
                                                                                 -008
                                                                                                 1-1

                                                                                                 3

                                                                                                Z
                                                                                                 O  r-l
                                                                                                (X   CO
                                                                                                •H   CO
                                                                                                 CO   C
                                                                                                 >">  CO
                                                                                                f™^  "sX
                                                                                                 CO
                                                                                                 C   C
                                                                                                <  T-I
                                                                                          g
                                                                                 -002
                                                                                 loo?
S   v
O  J-i
a   o
-^  a)
C/l  rH

^  o
u   o
Ed
     QJ
14-1  U
 O   CO
    rH
 S   3
 CO   O
 ^1  T-l
 oo -u
 O   5-1
 4-1   CO
 CQ   a*

 o   M
                                                                                                 C r-
                                                                                                 0)   •
                                                                                                 W rH
                                                                                                 }-l
                                                                                                 3
                                                                                                 CJ
                                                                                                 C
                                                                                                 O
                                                                                                 O
                                                                                                 H
                                                                                                     O  OH
                                                                                                     C   •
                                                                                                     O  
-------
                                                     Loo3
                                                     Loo9
                                                     -003
                                                    -Loo*   3
                                                     Loot
                                                      OOT
89
                 Of
                                                                   C >H
                                                                   O OH

                                                                   4-J  -
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                                                                   2
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                                                                   O

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    CO
   J3

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o
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                            153
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C3
                     155
-------
                 APPENDIX E
VOLATILE AND VERY VOLATILE ORGANIC COMPOUNDS
IDENTIFIED IN AMBIENT AIR IN FRONT ROYAL, VA
                      156
-------
Table E-l.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN FRONT ROYAL, VA (TRIP 1, P1/L4).
Chromato-
graphic
Peak No.
1
2A


3

4

5
6
7
7A
8
9
10A
10B

IOC
11
Elution
Temp.
49
52
52
52
53
54
54
56
57
58
59
60
61
61
63
65

67
68
Compound
co2
propane (cent.)
isobutane (tent.)
butene isomer
^-butane
butene isomer
acetaldehyde
C.H,Q isomer (tent.)
isopentane
acetone
n-p entane
diethyl ether
vinylidene chloride
methylene chloride
cs2
C.H-0 isomer
4 8
C5H10 i3OTer
2-methylpentane
Chromato-
graphic
Peak So.
12
13
14
15
16
16A
16B
16C
16D
16E
17
18
19
19A
20
21

22

Elution
Temp .
<"C>
70
71
72
73
76
78
82
84
85
86
89
94
103
107
109
111

113

Compound
3-me thy Ipen cane
hexafluorobenzene
ti-hexane
chloroform

(el)


perfluorotoluene (el)
methylcyclopemcane
benzene
cyclohexane
C7Hlfi isomer
C.H., isomer
7 10
CgH18 isomer
acetic acid
toluene
C8H18 lsoner
C_H,, isomer
o 10
C.H , isomer
8 16
C8H16 isomer















                               157
-------
Table E-2.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED  IN AMBIENT  AIR
            IN FRONT ROYAL, VA (TRIP 1, P2/L5).
Chromato-
graphic
Peak No.
1
2A
3
3A
38
4
4B
4C
4D
4E
4F
5
6A
6B
7
7A
S
9
Elution
Temp.
49
52
53
54
55
58
59
59
60
60
61
62
64
67
68
70
71
72
Compound
co2
C.H0 isomer +• propane (cent.)
H O
n_-butane
C^Ha isomer
acetaldehyde
isopentane
propanal
acetone
n_-pentane
diethyl ether
vinylidene chloride
methylene chloride
CS,
C,H,0 isomer
2-methylpentane
ti-butanal
3-methylpentane
hexafluorobenzene (eS)
Chromato-
graphic
Peak No.
10
10A
10B
11
12
13
14
15
16A
16B
17
17A
17B
18
ISA
19
20

Elution
Temp.
73
74
75
77
79
83
85
88
92
95
105
106
109
110
111
113
117

Compound
ii-hexane
chloroform
C,.H 0 isomer
perfluorotoluene (ef)
methylcyclopentane
benzene
cyclohexane
ii-pentanal
n_-heptane
C7H14 isomer
toluene
C.H1fl isomer (tent.)
o lo
C,H, ,0 isomer
0 Li.
n_-hexanal
CgH., isomer
ij-octaae
CgH^g isomer (tent.)

                               158
-------
Table E-3.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN FRONT ROYAL, VA (TRIP 1, P3/L2).
Chromato-
graphic
Peak No.
1
2A

2B
2C
2D
3
4
5
6
8
9
9A
10
11
12
13
14
14A
15
15A
15B
ISC

16
17
18
ISA
19
19A

19B
19C
20
20A

21
22
22A
22B
23
23A
24
24A
24B
25
25A
25B
26
27

Elution
Temp.
CC)
49
54

56
57
60
61
63
64
65
71
74
75
76
77
78
79
81
82
87
87
88
90

91
93
96
101
109
no

111
113
114
115

117
119
123
126
129
130
131
134
134
135
136
137
138
141

Compound
co2
C.Hn isomer
4 8
n_-butane
acetaldehyde
isopentane ( tent . )
acetone
diethyl ether
vinylidene chloride
dichlorooethane
2-methylpentane
3-methylpentane + ti-butanal
C6H12 isomer
hexafluorobenzene (eZ)
^-hexane
chloroform
ethyl acetate
perfluorotoluene (el)
me thy Icy c lop en Cane
benzene
carbon tetrachloride
cyclohexane
C.Hn. isomer (tent.)
7 14
acetic acid
pentanal (tent.)
ti-heptane
C,H isomer
7 14
toluene
C0H isomer
8 18
C8H18 1SOTier
C8H16 isomer
n_-hexanal
C.H isomer
S 16
ii-octane
tetrachloroechylene
C8H16 isOTner
unsat. hydrocarbon
ethyibenzene
C9H18 isomer
xylene •*• CgH,,, isomers
CqH.- isomer
styrene
£-xylene +• n-heptanal
CgH. isomer
CgH. „ isomer
n-nonane
C10H22 lsomer
Chromaco-
graphic
Peak No.
28
28A

29
29A
30
30A
30B
31
31A
31B
32
33
34
34A
35
35A
35B
35C
36
36A
37


38
38A
38B
38C
38D
38E

38F
39
40
40A

41
42
43
43A
43B
44
44A
45
45A
46
46A
46B
46C
47
(continued)
Elution
Temp.
CC)
145
148

146
147
148
149
149
150
151
151
152
153
154
155
156
157
159
160
160
162
164


165
166
166
168
159
170

170
171
173
174

178
181
183
185
185
186
187
188
189
189
190
191
193
194

Compound
C10H22 is°mer
CinH. , isomer
10 16
benzaldehyde
n-propy Ibenzene
ethyltoluene isomer
C-H, ,0 isomer
a XO
phenol
CUH24 isOTU!r
C10H20 1SOIner
CQH,,0 isomer
a 10
CUH24 isomer
n_-octanal
1,2,4- trime thy Ibenzene
C10H20 lsomer
n_-decane
dichlorobenzene isomer (tent.)
C11H24 isomer
1,2, 3-trime thy Ibenzene
CUH24 isomer
indan
C.-alkyl benzene +
C, ,H,, isomers
12 26
acetophenone
cresol isomer
C-JLgO isomer
sat. hydrocarbon
C,-alkyl benzene isomer
C, , H-- isomer
11 22
C.-alkyl benzene isomer
ii-nonanal
n_— undecane
C. ,H,_ isomer (tent.)
11 20
dlinethylphenol isomer
Cj-alkyl phenol isoowr
C-j-alkyl phenol isomer
C.-alkyl benzene isomer
C10H20° isoiner
C^-alkyl phenol isomer
naphthalene
o-decanal
C12H24 isomer
n-dodecane
C,-alkyl phenol isomer
C,-alkyl phenol isomer
C,-alkyl phenol isomer
unknown

                               159
-------
Table E-3.  (cont'd.)
Chromaco-
graphic
Peak No.
48
48A
49
49A
50
50A
51
52
Elution
Temp.
195
201
203
204
204
205
206
211
Compound
unknown
C11H22° isomer
ti-undecanal
C ,H.j, isomer
ti-tridecane
8-methylnaphthalene
unknown
C.. H,_ isomer (cent.)
Chromato-
grapnic
Peak No.
53
54
54A
55
55A
56
57
58
Elution
Temp.
213
214
216
217
228
229
230
232
Compound
alkyl bucyrate (BKG) «
alkyl isobutyrate (BKG)
C -alkyl phenol
0
n-tetradecane
C,,H,.0 isomer (tent.)
12 24
C15H30 isomer
n^-pentadecane
unknova
            160
-------
Table E-4.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT
            AIR IN FRONT ROYAL, VA (TRIP 1, P3/L6).
Chromato-
graphtc
Peak No.
1
2A
3
4
5
6A
7
3
9
11
12
12A
Elution
Temp.
CO
48
52
53
54
57
58
59
61
61
63
67
69
Compound
co2
C.H0 isoner
4 8
nt-butane
C.H0 isotner
4 8
Isopencane
acetone
n-pentane
vinylidene chloride
methylene chloride
cs2
2-methylpentane
£-butanal
Chroma to-
graphic
Peak No.
12B
13
13A
14
15
ISA
16
17
17A
18
19
19A
EluCion
Temp.
CO
69
70
70
71
72
73
76
77
81
32
34
36
Compound
methyl vinyl ketone
3-methylpentane
methyl ethyl ketone
hexafluorobenzene (el)
ri-hexane
chloroform
perfluorotoluene (el)
methylcyclopentane
CjHj-0 isomer (tent.)
benzene
cyclohexane
n-heptane (tent.)
                             161
-------
Table E-5.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN FRONT ROYAL, VA (TRIP 1, P3/L6).
Chromato-
graphic
Peak No.
1
5
5A
SB
6
6A
7
7A
3
9A
10
11
11A
1.2
13
14
15
15A
L5B
15C
16
16A
16B
17
18
ISA
19
19A
20
20A

20B
20C
20D
21
22

23
23A
24
24A
25
26
26A

26B
26C
26D
27

Elucion
Temp.
CO
49
53
54
54
56
59
61
65
65
71
72
75
76
76
77
78
82
83
85
87
88
88
89
90
92
94
95
96
97
100

103
104
105
UO
111

113
114
115
116
118
119
124

126
128
128
129

Compound
co2
propane
butene isomer
^-butane
acetaldehyde
isopentane
acetone
dichloroethylene isoraer (tent.)
dichloromethane
C H,0 isomer
2-methylpentane
3-methylpentane
C,E. , isomer
o 12
hexafluorobenzene (e5)
n-hexane
chloroform
perfluorotoluene (eS)
methylcyclopentane
1,1,1- crichloroethane
C6H10 lsonier
benzene
carbon tetrachloride (teoc.)
cyclohexane
acetic acid +• C-,H. , isomer
/ ID
3-methylhexane
&-pencanal
CaH?a isomer
o lo
C_H, . isomer
7 14
n— hep tane
C.H.. isomer
o IS
methylcyclohexane
C.H. „ isomer
o J.O
C.H, -0 isomer
0 1Z
toluene
C.H isomer
o 1.Q
c8Hia lsomer
C-H,, isomer
o J.O
ji-hexanal
C_Hn . isomer
o J.O
n^octane
tecrachloroechylene
o^on isomer
9 20
C8H16 * C9H20 isolners
CqH,g isomer
C,H 0 aldehyde isomer
echylbenzene
Chromato-
graphic
Peak No.
28
29
29A
29B
29C
30
30A
31
31A
32

33

33A
34
34A
35
35A
36

36A
36B
36C
37
38
38A
39
39A
39B
39C

39D
40
40A
40B
40C

40D
40E
41
41A
41B
41C
41D

41E
4 IF
410
41H
(continued)
Elution
Temp.
CO
131
133
134
134
135
136
137
138
140
142

145

146
147
148
149
150
150

151
152
152
154
155
156
157
158
158
159

160
161
161
163
164

165
165
166
166
167
167
168

168
170
170
171

Compound
xylena isomer
CgH2_ isomer
C^H^.O isomer
£-hepcaldehyde (tent.)
styrene
Oj-xylene
CgiL- isomer
n-nonane
CgHlg isomer (tent.)
isopropylbenzene +
C10H22 ls°mer
C,-allcyl cyclohexane +
C10H22 lsomers
C10H16 iS°mer
benz aldehyde
ji-propylbenzene
ethylcoluene isomer
C10H22 isomer
1,3,5-triaethylbenzene •*•
phenol
C11H24 i30ner
C10H22 1SOmer
o_-echyltoluene
n-octanal
1,2, 4-trimethylbenzene
C10H20 iaraer
n— decline
dichlorobenzene isomer
C.-all^l benzene isomer
C.-H.,. isomer
10 20
C,-alkyl benzene isomer
1,2,3- trimethy Ibenzene
C11H24 isomer
indan
C..H., isomer
10 20
C,-all:yl benzene isomer
C,-alkyl benzene isomer
acecophenone
C.-alkyl benzene isomer
cresol Isomer
*"11^24 ^somer
C,,H_,, isomer
11 22
C, , H2i isomer
C,-all!.yl benzene isomer
C0H.-0 isomer
C.-ali^rl benzene isomer

                                162
-------
Table E-5.  (cont'd.)
Chromato-
graphlc
Peak No.
42
42A
43
43A
43B
43C
430
43E
44
44A

44B
45
45A
46
46A
47
47A
47B
48
48A
49
Elution
Temp.
172
171
174
175
176
177
177
178
179
181

181
182
183
184
185
186
136
187
188
189
190
Compound
ji-nonanal
cnH22 lsffl"r
n-undecane
C.-alkyl benzene isomer
CUH22 isomer
C.-alkyl benzene isomer
tetramethylbenzene isomer
C12H26 isoner
dimethylphenol isomer
C^H^-benzene + C.-alkyl
benzene isomers
C..H-, isomer
ethylphenol isomer
C.-alkyl benzene isomer
dimethylphenal isomer
C.-alkyl benzene isomer
C.-alkyl phenol isomer
C12H24 isomer
naphthalene
D-decanal
C.-alkyl benzene isomer
a-dodecane
Chromato-
graphic
Peak No.
49A
49B
49C
50
51
51A
51B
51C
52
53
53A
53B
54
54A

54B
55
56
57
57A
58A
58B
Elution
Temp.
191
193
198
204
205
205
206
208
213
215
216
217
218
221

230
231
233
240
240
240
240
Compound

C,-alkyl phenol isomer
C.-alkyl phenol isomer
C13H28 iSOmet
n-uodecanal
a-cridecane
S-methylnaphthalene
unsat. hydrocarbon
a-methylnaphthalene
alkyl butyrate
alkyl butyrate
biphenyl









C,-alkyl phenol isomer
n-tetradecane
C.-alkyl naphthalene
(tent.)
C.,H,Q Isomer
n-pentadecane
unknovn
diethyl phthalate
CI,H-. isomer
n-hexadecane
benzophenone

isomer








          163
-------
Table E-6.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT
            AIR IN FRONT ROYAL, VA (TRIP 2, P2/L3).
Chroraato-
graphic
Peak Ho.
1
2A
2B
3
3A
3B
4
6
6A
7
7A
7B
7C
7T>
7E
8
9
10
IDA
10B
11
12
12A
13
14
14A
14B
15
15A
16
16A
16B

17
17A
18
ISA
18B
19
20
20A
20B
21
22
23
23A
23B


- Elution
Temp.
CO
49
55
57
59
61
62
63
65
69
70
71
71
72
72
73
73
74
75
76
77
78
79
80
81
83
84
85
85
86
87
88
89

90
90
92
93
96
97
97
98
101
103
105
106
107
108


Compound
C°2
aceealdehyde
tt-bucane
acetone
diechyl echer (cent.)
dichloroethylene isomer
diehlorome thane
CS2
C5H10 isomer
2-methylpentane
C,H00 isomer
J O
C^HgO isomer
3-methylpentane
C,H, . isomer
o 12
methyl ethyl ketone
hexafluorobenzene (eS)
j3— hexane
chloroform
ethyl acetate
C,H_, isomer
perfluorotolueae (el)
methylcyclopencane
1,2-dichloroethane (tent.)
1,1,1-trichloroechane
benzene
carbon tecrachloride
cyclohexane
2-methylhexane
2, 3— dimethylpencane
3-mechylhexane
pentanal
C,H, , isomer
7 14
crichloroethylene
C.H. 0 isomer (cent.)
o lo
n-heptane
C7H14 lsomer
C.H, , isomer
0 lo
methylcyclohexane
acetic acid
C.H.,0 isomer (tent.)
C0H, , isomer
0 10
coluene
C8H18 lsomer
C.H., „ isomer
u IS
C0H, - isomer
0 10
C.H,, iaomer
Chromaco-
graphic
Peak No.
24
24A
25
25A
26
26A
27
28

28A
28B
28C
29
29A
29B
30
30A
31
31A
32
32A
32B
33
33A
34
34A
35
36

37
37A
38


39
40
40A
40B
41
41A
42
42A
42B
43
44
45
45A
a 16
(continued)
Elucion
Temp.
CC)
109
111
112
113
113
117
118
119

120
120
122
123
124
124
125
125
127
127
128
129
129
130
131
132
134
135
136

137
138
139


140
141
141
142
143
144
144
145
145
146
147
147
148


Compound
C9H20 iS°mer
C8H16 l30mer
n,-octane
C.H,.. isomer
o 10
tetrachloroethylene
C9H20 lscmer
CgH20 isomer
ethylcyclohexane or
C,S., isomer
0 lo
C9H20 isoniar
C9H18 isomer
C9H18 ±somi*
ethylbenzene
CgHlg isomer
C9H20 lsomer
xylene isomer
C9H20 1S°mer
CgH2Q isomer
C7H140 isomer (tent.)
CgH2Q isomer
styrene
CgH18 isomer
o_-xylene
CgHlg isomer
n-nonaae
CgHlg isoopr
C10H22 isomer
C10H22 isomer *
isopropylbenzene
C10H22 is°mer
C10H20 1SOmer
C H._ +• C -alkvl
10 22 3 aJ-K'J-
cyclohexane isomers
C10H16 iSOm"
benzaldehyde
n-propylbenzene
C10H20 iS001er
ethylcaluene isomer
1,3,5- crime chy Ib enz ene
C11H24 isomer
phenol
C10H22 isonler
£-echyltoluene
sac. hydrocarbon
C10H16 is°ffler
C, -H__ isomer
10 20

                               164
-------
Table E-6.  (cont'd.)
Chromato-
graphic
Peak No.
46
46A
47
47A
48
48A
48B
48C
49

50
50A
SOB
51
51A
52
52A
53
53A
53B

54
54A-
54B
54C
55
55A
56
56A
57
57A
57B
58
59
59A
59B
60
Elution
Teop.
148
149
150
151
151
152
153
153
154

155
156
156
157
157
158
158
159
160
160

161
161
163
163
164
165
165
166
167
167
168
170
172
173
173
174
Compound
1,2,4-trimethylbenzene
C10H20 iSOmer
n-decane
dichlorobenzene isomer
C,,H,, isomer (tent.)
11 24
C.-alkyl benzene isomer
C -alkyl benzene isomer
1, 2, 3-trimeChylbenzene
C4-alkyl benzene +•
C11H24 isoners
C11H24 iam"
C10H16 1SOmer
indan
C11H24 is°m"
C10H20 l30Ber
C11H24 iS°mer
C4-alkyl benzene isomer
acetophenone
cresol isomer
C11H24 +
C.-alkyl benzene isomers
C H24 isomer
C11H22 isomer
C4-alkyl benzene isomer
CUH22 isomer
C.-alkyl benzene isomer
C H,-benzene isomer
4 7
n--nonanal
C11H22 isomer
n-undecane
C--alkyl benzene isomer
C11H22 isomer
C -alkyl benzene isomer
dimethylphenol isomer
C -alkyl benzene isomer
C.H, -benzene isomer
4 7
C2-alkyl phenol isomer
Chromato-
graphic
Peak No.
60A
60B
60C
61
61A
6 IB
62
63
64
64A
65
66
66A
66B
67
67A
67B
67C
67D
68
69
69A
69B
69C
70
71
71A
73
73A
73B
74
75
76
76A
77A
77B
78
Elution
Temp.
CO
175
176
176
176
177
179
179
181
183
183
184
187
189
195
196
197
198
199
204
205
207
208
208
209
209
210
212
219
221
222
223
225
232
234
236
240
240
Compound
C.H, -benzene isomer (tent.)
4 7
C.-alkyl benzene isomer
C.-alkyl benzene isomer
C--alkyl phenol isomer
C.-alkyl benzene isomer
C -alkyl phenol isomer
C.-alkyl phenol isomer
naphthalene + Ci2H24 isomer
n-dodecane
C13H26 isomer
C,-alkyl phenol isomer
unknown
C13H26 isomer
C. ,H,, isomer
n-tridecane
8-methylnaphthalene
C13H26 ison"
a-methylnaphthalene
C13S26 isooer
alkyl butyrate
alkyl butyrate
C12H24° isoiner
biphenyl (tent.)
C, -alkyl phenol isooer
o
C14H28 1SOTer
sat . hydrocarbon
C2-alkyl naphthalene isomer
unsat. hydrocarbon
C, ,H-,0 isomer (tent.)
13 26
C _H,- isomer
o-pentadecane
unknown
diethyl phthalate
C14H28° lsomer
C.,H_2 isomer
C15H30° isoner («nt-)
n-hcp tadecane
         165
-------
Table E-7.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT
            AIR IN FRONT ROYAL, VA (TRIP 2, P3/L5).
Chromato-
graphic
Peak No.
1
4
4A
5
6
6A
7
7A
3
9
10A
11
11A
11B
12
12A
13
14
14A
15
16
17
18
ISA
19
19A
19B
20
20A
21
22
22A
22B
23
23A
24
24A
24B
25

26
27
27 A
28
28A
28B

Elution
Temp.
CO
48
51
51
52
53
55
58
60
51
62
66
68
68
69
70
71
72
73
74
75
77
78
83
84
84
85
86
87
88
90
91
93
96
97
99
104
105
107
109

112
113
123
125
126
128

Compound
CO,
n_-propane (tent.)
butene isomer
tt-butane
acetaldehyde
isopentane
acetone
diethyl ether (tent.)
vinylidene chloride
dichioromethane
C.H.,0 isomer
4 8
cyclopentane
2-me thy Ip en tane
methyl isopropyl ketone (tent.)
tJ-butanal
3-methylpentane
hexafluorobenzene (eS)
n.-hexane
chloroform
ethyl acetate
perfluorotoluene (eS)
methylcyclopentane
benzene
carbon tetrachloride
cyclohexane
2-methylhexane
2, 3— dimethylpentane
3-methylhexane +• CyH.. , isomer
acetic acid (tent.)
C.H isomer
o ID
ji-heptane
C-.H, . isomer (tent.)
7 14
C_H, 0 isomer
3 lo
methylcyclohexane
Cgli^g isomer
toluene
C3H18 isooer
C8H18 isomer
^i-nexanal (tent.) +
CgH , isomer
r>- octane
tetrachloroethylene
ethylbenzene
xylene isomer
CgH2Q isomer (tent.)
C7H 0 isomer (tenc.)
Chromato—
graphic
Peak No.
28C
29
29A
30
31
32
33
34
34A
34B
34C

35
35A
36
36A
37
37A
38
38A
38B
38C
39
40
41
41A
4 IB
41C
41D
42
42A
43
44
45
45A
45B
46
46A
47
48
48A
43B
48C
48D
48E
49
(continued)
Elution
Temp.
CO
129
130
131
132
136
139
140
141
143
144
144

145
146
147
148
149
149
150
151
152
154
156
159
160
161
162
164
165
166
167
168
173
176
178
179
180
181
182
183
185
186
137
191
195
197

Compound
styrene
£-xylene +• C.H-., isomer
CgH,_ Lsooer (tent.)
ti-nonane
C10H22 isomer
C10H22 isomer
C10H16 isomer
benzaldehyde
ethyltoluene isomer
C,H.,0 isomer
0 10
phenol •*• C,-alkyl
benzene isomer
C11H24 isomer
C,-alkyl benzene isomer
C10H22 ls°mer
C11H24 ls°mer
p/-octanal
trimethylbenzene isomer
n-decane
C11H24 isomer
C10H20 i30mer 
-------
Table E-7.  (cont'40
Chromaco-
graphic
Peak No.
50
50A
SOB
50C
SOD
51
51A
SIB
52
53
53A
Elucion
Temp.
198
198
201
204
205
208
209
211
212
217
221
Compound
£-cridecane
3-mechylnaphchalene
a-mechylnaphchalene
unsac . hydrocarbon
unsac. hydrocarbon
alkyl bucyrace
C12H24° isooer
unsac. hydrocarbon
ti-cecradecane
unknown
unsac. hydrocarbon
Chromaco—
graphic
Peak No.
53B
54
55
56
57
57A
58A
58B
58C
58D
58E
Elucion
Temp.
CO
222
223
224
226
233
235
236
240
240
240
240
Compound
C13H26° isomer
C15H30 i300er
n-pencadecane
unknown
diethyl phchalace
C,,H,, isomer
10 Jt
n-hexadecane (cent.)
benzophenone
C15H30° is°Mr
C17H34 isomer
n-hep cadecane
          167
-------
Table E-8.  VERY VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT
            AIR IN FRONT ROYAL, VA (TRIP 3, P1/L9).
Chromaco-
graphic
Peak. No.
1
3A
3B
4
4A
5
5A '
6
7
Elucion
Temp.
CO
48
53
53
54
55
56
57
58
60
Compound
co2
propane
propylene
isobutane
C,H. isomer
acetaldehyde
C.Hj isomer
n— butane
isopentane
Chroma co-
graphic
Peak No.
8
3A
9
10A
12
13
14
15
15A
Elucion
Temp .
CO
61
64
55
67
72
75
76
77
78
Compound
i
acetone
diethyl ether (tent.)
oethylene chloride
CS2
2-mechylpentane
3-me thylpentane
hexaf luorobenzene (eS)
n_-hexane
chloroform
                                168
-------
Table E-9.  VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT AIR
            IN FRONT ROYAL, VA (TRIP 3, P2/L8).
Chromato-
graphic
Peak No.
1
3A
5
6
7
8
9
10
11
12
13
16
16A
17
18
19
20
20A
21
21A
22
23
24
24A
24B
25
25A
26
27
27A
27B
28
29
29A
30

31
32
33
34
35
36
37
38
39
39A

Elucion
Temp.
CO
48
51
53
55
56
58
59
60
51
62
63
67
69
70
72
74
75
76
77
78
79
30
81
83
84
85
86
87
87
88
88
39
91
91
92

94
95
97
99
101
105
106
108
109
111

Compound
co2
propane (tent)
C,1L- isomer
acetaldehyde
^-butane
isopencane
acetone
ii-pentane
diethyl ether
Background peak
methylene chloride
C.H, . isomer (tent)
6 14
Cjl^g isomer
2-me thy Ipentane
3-me thy Ipentane
hexafluorobenzene (e
ii-hexane
chloroform
methyl ethyl ketone
ethyl acetate (tent)















i)


(tent)

perf luoiotoluene (ej)
methylcyclopentane

1,1, 1-trichloroethane
C,H. . isomer
7 14
C6H1Q isomer
benzene



carbon tetrachloride (tent)
cyclohexane
2-methylhexane
2, 3-dimethy Ipentane
acetic acid
3-ne thy Ihexane
n-pentanal
C7H14 iSOTer







C0H, „ isomer + trichloro-
S -LO
ethylene
n_-heptane
C-H. - isomer
unsat. hydrocarbon
methylcyclohexane
C8H18 + C6H12° isom
C H isoner
3 19
toluene
C_H _ isooer
o 19
C3Hlg isomer
C8H16 lsomer






rs





Cinemato-
graphic
Peak No.
39B
40
40A
41
41A
42
43
43A
43B
43C
44

44A
45
45A
45B
46
46A
47
47A
43
48A
49
49A
50
50A
SOB
51

52
53
54
55
56
57
57A
57B
58
59
59A
59B
60
60A
61
61A
62
('continued)
Elution
Temp.
CC)
111
112
113
114
115
116
118
119
121
121
122

123
126
126
127
127
128
129
130
131
131
132
133
134
135
137
138

139
141
142
143
144
145
146
146
147
148
149
149
150
151
151
152
153

Compound
C6H12° isomer
hexanal
C8H16 i30Iner
n-octane
C8H16 isomer
tettachloroethylene
C.H, , isomer
C9H20 isomer
C9H20 isomer
C.H, , isomer
8 16
C9H20 isooer *
ethylcyclohexane
C.H-g isomer
ethylbenzene
C9H18 isolner
C9H20 lsoner
xylene isomer
CjHjg isomer
C9H20 isomer
C-H^,0 isomer
styrene
n-hep canal
o-xylene
S^s isoner
n-nonane
C10H22 isoner
CgH.- isomer
^10^22 ^•so"ler * isopropyl-
benzene
CgH^gO isomer
C10H22 lsomer
C--H-, isoner
benzaldehyde
iv-propylbenzene
ethyltoluene isomer
phenol
1,3,5-trimethylbenzene
C10H22 isomer
£-ethyltoluene
C10H22 ia°MI
C11H24 isomer
ii-octanal isomer (tent)
C.nH.n isoner
1,2, 4-trime thylbenzene
C10H20 isooer
n-decane

                                169
-------
Table E-9.  (cont'd.)
Chromato-
graphic
Peak No.
62A
62B
62C
62D
63
63A
63B
63C
64
64A
65

65A
65B
66
66A
66B
67
67A
68
69
69A
70
70A
70B
70C
71
72
72A
72B

Elution
Temp.
154
154
155
156
156
157
159
150
161
161
162

163
163
164
164
165
166
167
168
169
170
171
172
172
174
175
176
177
178

Compound
dichlorobenzene isomer
C4~alkyl benzene isomer
C11H24 lsomer
C4-alkyl benzene isomer
1,2 , 3-trimethylbenzene
C^ H isomer
indan
C.-alkyl cyclohexane isomer
C4~alkyl benzene isomer
C.-alkyl benzene isomer
acetophenone -I- C.-alkyl
benzene isomer
cresol isomer
CUH22 isomer
C-^H24 isomer
C4-alkyl benzene isomer
C10H1S isomer
C. H_, isomer
C.-alkyl benzene isomer
C4~alkyl benzene isomer
n_-nonanal
C11H22 isolller
n— undecane
C4~alkyl benzene isotner
C-jH,. isomer
C4~alkyl benzene isoraer
C12H24 Is0tner
Cj-alkyl phenol isomer
C.-alkyl benzene isomer
C.-alkyl benzene + C.H,
benzene isomers
Chromato-
graphic
Peak No.
72D
72E
73

73A
73B

73C
73D
74
74A
75
75A
75B
76
76A
76B
77
78
78A
79
79A
80
80A
SOB
80C
81
81A
81B
SIC
82A
Elucion
Temp.
179
179
180

181
183

183
184
185
186
187
189
190
192
197
199
200
201
202
204
204
215
228
229
230
232
237
238
239
240
Compound
*
C.-alkyl benzene isomer
Cj-alkyl phenol isomer
C.-alkyl benzene +• C...H-,
isomers
C12R26 isomer
C.-alkyl benzene + C.-H_
isoners
C.-alkyl phenol isomer
C,-alkyl phenol isomer
naphthalene + n-decanal
C12H24 is0mer
n-dodecane
C.,H2g isomer
C,-alkyl phenol isomer
unknown
^14^30 ^somer
unsat . hydrocarbon
n-undecanal
£- tridecane
8-methylnaphthalene
unknown
o-methylnaphthalene
n- tetradecane
unsat. hydrocarbon
n_-pentadecane
C15H30 isomer
unknown
unsat. hydrocarbon
diethyl phthalate
C.,H,, isomer
C16H34 isomer
           170
-------
Table E-10.
VOLATILE ORGANIC COMPOUNDS IDENTIFIED IN AMBIENT
AIR IN FRONT ROYAL, VA (TRIP 3, P2/L9).
Chromato-
graphic
Peak No.
1
3
3A
3B
3C
4
4A
4B
4C
5
6A
6B

7
8
8A
9
10
10A
10B
11
12
12A
13
13A
13B
14
14A
15
15A
16
16A
17

18
ISA
18B
18C
19
19A
19 B
20
20A
21
22
23
24


Elucion
Temp.
CO
47
52
53
55
57
59
60
61
61
62
64
68

69
71
72
73
74
74
77
78
79
81
84
85
85
86
87
38
89
90
90
91

93
94
96
97
98
99
100
100
101
104
105
106
108


Compound
CO,
C4H10 isomer (tent)
acetaldehyde
so2
isopentane
acetone
n-pentane
diethyl ether
Background peak
methylene chloride
cs2
C.H. - isomer
5 10
2-methylpentane
3-me thy Ipentane
C6H12 iactner
hexafluorobenzene (eS)
n-hexane
chloroform
C,Hj, isomer
perfluorotoluene (el)
methylcyclopentane
1,1,1-trichloroethane
benzene
carbon tetrachloride
cyclohexane
2-met hy Ihexane
2, 3-dimethylpentane
3-methy Ihexane
acetic acid
C,H, . isomer
7 14
C7H14 lsomer
trichloroethylene + ciAg
isomer
n_-heptane
C7H14 isomer
C7H14 isomer
CgH.g isomer
me thy Icyclohexane
C-H . isomer
o la
C6H12° isomer
C8H1S isomer
CSH16 isomer
C8H18 lsomer
toluene
CgH isomer
CjH18 isomer
Chromaco-
graphic
Peak No.
24A
25
25A
25B
26
26A
27
27A
27B
28
28A
29

29A
30
30A
31
31A
32
32A
33
33A
34
34A
35
35A
35B
36

37
37A
37B
38

38A
39
40
41
41A
42
42A
42B
43
43A
43B
43C
4 3D
continued
171
Elucion
Temp.
CC)
110
110
111
113
113
114
115
115
117
119
120
121

122
124
125
126
126
127
128
129
129
130
131
132
134
135
136

137
138
138
139

140
141
142
143
144
144
145
145
146
147
148
148
149


Compound
CRHlfi isomer
CgHig isomer
C-H., Isomer
8 lo
C8H16 isoIBer
ri-octane
C.H, , isomer
tetrachloroethylene
CgH. , isomer
C^HJQ isomer
C9H20 isonar
C..H, ,. isomer
C.H.- isomer
9 20
C9H1S lsomer
ethylbenzene
C— H^ _ isomer
xylene
C9H2Q isomer
CgH2Q isomer
C.H,4n isomer (tent)
styrene
C9H18 isolBer
o_-xylene
CjHjg isomer
n-nonane
C10H20 isomer
Cg^g isomer
isopropylbenzene + <"io^22
isomer
C10H22 isoner
CgH16 isomer (tent)
C1QH2, isomer
C^.H2- +• C,-alkyl cyclohexane
isomer
C10H16 Is0mer
benzaldehyde
n^-propylbenzene
eChyltoluene isomer
C^.H, isomer
1,3,5-trimethylbenzene
C10H22 is0mer
C10H20 is0mar
o_-ethyltoluene
C,.H- isomer
11 24
C.-H. isomer
n_-octanal
C.H, -benzene isomer


-------
Table E-10.  (cont'd.)
Chromato-
graphic
Peak No.
44
44A
45
45A
45B
45C
45D
46
46A
46B
46C
46D
46E

47
48

48A

48B
49

49A

50
50A
SOB
51
52

52A

52B

53
53A
53B
53C
5 3D
54
54A
Elucion
Temp.
149
150
151
152
152
153
154
154
155
156
157
158
158

159
160

161

162
162

163

164
164
165
165
166

166

167

168
163
169
169
170
171
172
Compound
1,2, 4-trimethylbenzene
C10H20 isoner
n-decane
dichlorobenzene isomer
C.-alkyl benzene isomer
Cj-ELg isomer
C.-alkyl benzene isomer
1,2, 3-trimethylbenzene
C11H24 lsomer
C11H24 isooer
indan
C.-alkyl cyclohexane isomer
C.,,H«,, -t- C.-alkyl benzene
11 22 4
isomers
C,-alkyl benzene isomer
acecophenone +• C, -alkyl
benzene isomer
C11H24 i30iner
J.J. -i**
C11H22 isoTner
C,~aikyl benzene iscraer
^
C, ,H,, isomer
11 24
C,-alkyl benzene isomer
Cn1H__ isomer
XX H.
C , H-,-benzene isomer (cent)
H /
C.-alkyl benzene isomer
n-nonanal

C.-alkyl benzene isomer

C, , H, . isomer
11 22
n-undecane
C.-alkyl benzene isomer
C, .H,- isomer
11 22
Cc-alkvl benzene isomer
5
C.-alkyl benzene isomer
tetranethylbenzene iaomer
C12H26 isomer
Chromaco-
graphic
Peak No.
54B
54C
54D
54E
54F
SAG
55

55A
55B
55C
55D
56
56A
56B
56C
57
57A
57B

57C
57D

57E

58
58A
S8B
58C
59

59A

59B

59C
59D
59E
60


Elution
Temp.
172
173
174
175
175
176
177

177
178
179
180
182
182
183
183
184
185
186

187
190

192

198
199
201
206
208

210

216

217
220
221
239


Compound
C.. jH-g isomer
C -alkyl benzene isomer
C.-alkyi benzene isomer
C.H, -benzene isomer *
4 7
C -alkyl. cyclohexane isomer
C.-alkyl. benzene isomer
C, -H-, + C.-alkyl benzene
12 26 4
isomers
C.-alkyl. benzene isomer
C.alkvl benzene + C. .H
C.-alkyl benzene isomer
C..-H-, +• alkvl benzene isomers
naphthalene
t^-de canal
C12H,4 isomer
C.-alkyl benzene isomer
n— dodecane
C, -alkyl benzene isomer
C^-H,- Isomer

C,-alkvl benzene isomer (tent)
0
C 1? i^OTB^T
13 26
C H isomer

ti-tridecane
8-methylnaphthalene
a-me thylnaphthalene
biphenyl (tent)
n— ce trzidecane

C H jLsoiner
14 28 J-someI:
C W 1 an-me T
16 34 isDIIEt
unsat. hydrocarbon
n_-pentadecane
C15H30 isomer
C16H34 lsomer


           172
-------
                    APPENDIX F
SEMIVOLATILE COMPOUNDS IDENTIFIED IN AIR PARTICULATE
        COLLECTED IN SHENANDOAH VALLEY, VA
                        173
-------
                                     o
                                     CO
i:
t
i
"_00 6
L
r
" -
'_
r
r

.
.*
J-23J
.,

t
L
'_

1003
i. c
h 5
r "
f 1
E *
•;_oos 3
j_ [fa
r
'r
f
n*
«•
^.33*
(

S"
J--
"^<_
C
£.301

_
t
\
r
ilaos
'-
3
-*
0 «
C fl
M
•C 0.
4J -H
^
U-l
0 <
CQ
•rH ^
CO tH
^ CO
iH >,
CO O

CO
a c
e o
O (-*
O pt.

en c
6 "^
a -a
00 0)
4-1
4-1 CJ
O 0)
e rH
cfl O
I-I CJ
00
O Q)
4J 4-1
CO CO
3 r-4
0 3
W 0
-C -H
CJ 4-1
M
4J CO
C 0.
0)
!-< i-(
3 CO
O
a
O r-»
•H •
r-i
CO V
o y-i
H 0
                                     oo
174
-------
             Table F-l.    COMPOUNDS  IDENTIFIED IN METHANOL  EXTRACT OF  <1.7y
                              FRACTION OF AIR PARTICIPATE  COLLECTED  IN FRONT  ROYAL,
                              VA  (TRIP 3. P1/L4)
Chromato-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
10

11

12
13
14
15

16
17
18

19
20
21
22
23
24
25
26
27

Notes:
lr u
Elution
Temp .
CO
100-107
104-106
108
108.5
113
120.5
129
134.5
140-142
145

170.5

171
175
177
181

185
189
195

202
204
207
211
212
216
224
225
231




Compound

dichlorome thane (solvent)
toluene (solvent)
benzaldehyde
phenol
methylacetophenone isomer (tent.)
unknown
naphthalene (tent.)
benzothiazole (tent.)
unknown
methylnaphthalene (tent.) +
phthalic anhydride
(C.UQ). beczoquinone isomer
(tent.) + Si cmpd. (bkg.)
dibenzoiuran (tent.)
unknown
di-butylcresol isomer (bkg.)
C_ alkyl biphenyl isooer +
Si cmpd. (bkg.)
a phthalate (bkg.)
unknown
4-hydroJty- 3 ,5-dioethoxybenz-
aldehyde
unknown
methylxanthene isomer (tent.)
methylxanthene isooer (tent.)
C, .H,,, isomer(s)
14 10
phenothiazine (tent.)
C2 alkyl xanthene
9- f luorenone ( t ent . )
C., ,H 2 isomer (tent.)
unknown

Chromato-
graphic
Peak No.
28
29
30
31
32
33
34
35
36
37
38
39
40

41
42
43
44
45
46
47
48
49
50
51

52
53
54
55
56
57


Elution
Temp.
(°C)
232
238
239
241
244
249
252
254
255
265
265
265
265

265
265
265
265
265
265
265
265
265
265
265

265
265
265
265
265
265

v 1 0na .

Compound

a phthalate (bkg.)
naphthalic anhydride
C2 alkyl cigH12 iaomer (tent.)
methylphenylindole isooer (tent.)
C16H10 lsooer4
pyrene + pyrene-d,. (ext. std.)
Si cmpd. (bkg.)
Si ospd. (bkg.)
Si cmpd. (bkg.)
Si cmpds. (bkg.) •*• phthalates (bkg.)
, „ ,«„_._ 5
C18H10 1S01a<":(.
C18H14 iSoner
C, ..H, , isomer + C, 0H - isooer
iO i.£ Xo J.W
(tent.)
benz an throne
a phthalate (bkg.)
C19H14 i90TO%
C.-H 2 isomer (tent.)
bkg.
unknown
C. alkyl Cjaai2 isooer (tent.)
C. alkyl ClgH1Q isomer (tent.)
C20H12 iSOOer9
C2QH12 isoner
C20H12 isomer + C2 alky1 C18H10
isomer
•s
C3 alkyl C18H 2 iaooerJ (tent.)
C...H. - i«omer (tent.)
20 12 7
C19ai4 isomer (tent.)
bkg.
C..H.. isomer10
10
C22H12 lsomer


 C.,H . isooers include methylphenanthrene and methylanthracene.

 C .H   isomers include chrysene, benzophenanthrene isomers, triphenylene, naphthalene, and benzanthracene isomers.

 C,,H,„ isooers include pyrene, fluoranthene,  and diphenyldiacetylene.
e 15 10
 C.0H,. isomers include 1,10-benzfluoranthene  and 3,4-cyclopentapyrene.
£ ID 10
   0^, isooers  include terphenyl is<

    isooers.
,  styrylnaphthalene isomers, and
 C -H., isomers  include oethyltriphenylene isooers, methylbenzanthracene isooers, methylchrysene isooers,

   methylbenzophenanthrene isomers, and 9-phenylfluorene.
o
 CiqH  . isomers  include oethyl-l,10-benzfluoranthene isooers.
q   ^^
 C. H   isomers  include perylene, benzpyrene isomers, and benztluoranthene isomers.


 C..H  , isomers  include 1,12-benzperylene, anthanthrene,  and  2,3-o-phenylenepyrene.
                                                    175
-------
                                                 v
                                                 M-I
                                                  o
                              r J a-
                                 ••5:


                                 «'•?"
                                "J-IJOI
                                                  o
                                                  C8
                                                  l-i
                                                  4J
                                                  X
                                                  0)

                                                  0)

                                                  (1)

                                                 jH
                                                  O
                                                  4J

                                                 %
                                                 iH
                                                  58
                                                  C
                                                  CO

                                                  a.
                                                  B
                                                  o
                                                  u
                                                  o
                                                  00

                                                 u-<
                                                  o

                                                  e
                                                  58
                                                  U
                                                  00
                                                  O
                                                 J_l
                                                  aj

                                                  O
                                                  J^
                                                 J=
                                                  u

                                                 4-1
                                                  C
                                                  ,
                                                      o
                                                     Pi
    o
    M
    PSH
    -O
    0)
    4-1
    CJ
    0)
    iH
    iH
    O
    O

    0)
    4-1
    58
    r-l
    3
    O
    •H
    4J
    i-l
    03
    PU
-i   M
O  -rl
H   CB
                                                 C^J

                                                 fc-

                                                  0)
                                                  M
                                                  3
                                                  00
                                                 T-l
176
-------
             Table  F-2.   COMPOUNDS IDENTIFIED  IN TOLUENE EXTRACT  OF <1.7y
                              FRACTION  OF AIR  PARTICULATE  COLLECTED  IN FRONT  ROYAL,
                              VA  (TRIP  3, P1/L4).
Chromato-
graphic
Peak No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

20
21
22
23
24
25
26
27
28
29
30
31
32
33
Notes:
l»
Elution
Teop.
CC)
100-112
109
110.5
112
113
116
120
122
127
128
136-139
141
142
167
172
173
177
187
191

198.5
201
206
207
208
212.5
220.5
222
234.5
241
244
247
248.5
251

isooers ii

Compound

toluene (solvent)
trimethylbenzene isooer
trimethylbenzene isomer
C,H7 benzene isomer
C,H. benzene isooer
C.H- and C.H^ benzene isooers
C,H. benzene isooer (tent.)
C.H7 benzene isomer
naphthalene (tent.)
C.H. benzene isooer
mixture of alkanes
phthalic anhydride
methylnaphthalene isomer
dibutylcresol isomer (bkg.)
unknown
dibutylcresol isooer (bkg.)
C, alkyl biphenyl (tent.)
Si copd. (bkg.)
4-hydroxy-3 , 5-dimethoxy-
benzaldehyde
C. alkyl fluorene isooer (tent.)
C, ,H, , isooer
15 16
unknown
C14H10 1SOm8r2
phenothiazine (tent.)
xanthene (tent.)
naphthindenone isomer (tent.)
methyl C. ,H1Q isomer
Si caipd. (bkg.)
C,,H - isomer (not pyrene)
C..,H „ isomer (not pyrene)
ID 1U
pyrene •*• pyrene-d (ext. std.)
C18H10 1SOMr4
unknown
Chromato-
graphic
Peak No.
34
35
36
37
38
39

40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60







Elution
Temp.
CO
258
260
263
264
265
265

265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265
265







elude diphenylpropane isooers, ditolymethane isoaers, and C,

Compound

methylpyrene isomer
C..-H..2 isooer (tent.)
unknown
methylpyrene isomer
unknown
terphenyl isomer (tent.)
phenyl phosphate (bkg
terphenyl isooer (tent.)
4
C18H10 Uoner
C18H14 iaomer
C18H10 i8ome%
C18H12 iaraer7
C18H12 isc"Ber
C.gH._ iaomer
benz an throne
di-2-ethylhexylphthalate
0
C.-Hj, isomer (tent.)








+• tri
)








(bkg.)

long-chain saturated hydrocarbon
C20H12 I3oner'
C20H12 iSOnar10
C20H14 isoo>er
C2QH12 isomer




long-chain saturated hydrocarbon
long-chain saturated hydrocarbon
C22HT9 isomer
C22H12 isomerU
C22H12 lsomer
C..B.. isomer







alkyl biphenyl isomers.












  C,,H,- isooers include pyrene, fluoranthene, and diphenyldiacetylene.
 4 16 10
  C,0H1n isoaers include 1,10-benzfluoranthene and 3,4-cyclopentapyrene.
 5 18 10
  C 7H _ isomers include methylpyrene isooers and benzofluorene isomers.

  C1gH 4 isooers include terphenyl isomers, styrylnaphthalene  isomers,  diphenylbenzene isomers,  and dihydro-

    benzathracene isooers.

  C.gH.. isooers include chrysene, benzophenanthrene isomers,  triphenylene, naphthacene, and benzanthracene isomers.

  C.-H,, isooers include methyltriphenylene isomers, methylbenzanthracena  isoaers,  methylchrysene  isomers,

    and phenylfluorene.
 Q
        isomers include perylenebenzpyrene isoaers, and benzfluoranthene  isomers.
10-.*
11
C20H14 isomers  include binaphthyl isomers, anthracene benzyne adduces,  6,7-acechrysene, and tripcycene.
C  H._ isooers  include 1,12-benzperylene, anchranthrene, and 2,3-o-phenylenepyrene.


                                                 177
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-903/9-78-007
4. TITLE AND SUBTITLE
ANALYSIS OF ORGANIC AIR POLLUTANTS IN THE KANAWHA
VALLEY, WV AND THE SHENANDOAH VALLEY, VA
7. AUTHOR(S)
Edo D. Pellizzari
Mitchell D. Erickson
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, NC 27709
12. SPONSORING AGENCY NAME AND ADDRESS
U. S. Environmental Protection Agency
Region III
6th and Walnut Streets
Philadelphia, PA 19106
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
June 1978
6. PERFORMING ORGANIZATION
8. PERFOFIMING ORGANIZATION
RTI/1401/00-01F
CODE
REPOF
<
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
BOA 68-02-2543, Order
Jt
No.
13. TYPE OF REPORT AND PERIOD COV
FINAL, Aug. 10 '77-Dec. 9
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
     Project Officer is Daniel FitzGerald
16. ABSTRACT
      Recently developed techniques for sampling and analysis of ambient air
 fay GC/MS/COMP were applied to the Kanawha Valley, WV and Shenandoah Valley,
 VA to assess the levels of organic pollutants.   Volatile and very volatile
 compounds were concentrated on Tenax GC and carbon sorbent cartridges, re-
 spectively,  then thermally desorbed directly into the capillary column
 GC/MS/COMP system for analysis.  Semivolatiles were collected on the
 electrostatic precipitator plates of a Massive Air Sampler, extracted,
 fractionated, and then analyzed by GC/MS/COMP.   The Kanawha Valley con-
 tained a broad range of halogenated, ketone, aldehyde, ester, aromatic,
 aliphatic and polynuclear aromatic compounds.  The Shenandoah Valley
 contained a narrower range of organics, but generally higher observed
 levels of the compounds quantitated.
17.
KEY WORDS AND DOCUMENT ANALYSIS ~~~
a. DESCRIPTORS
GC/MS/COMP
Air Pollution
Air Pollution Sampling
Kanawha Valley, WV
Shenandoah Valley, VA
Charleston, WV
Front Royal, VA
Air Sampling
Gas Chromato-
graphy
Mass Spectro-
metry
Organic Com-
pounds
18. DISTRIBUTION STATEMENT
UNLIMITED
b.lOENTIFIERS/OPEN ENDED TERMS

19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS /This page)
UNCLASSIFIED
c. COSAT! Fieid/G
f
21. NO. OF PAGES
178
22. PRICE
SPA Form 222D-1 (Rev. 4-77)
                      PREVIOUS EDITION IS OBSOLETE
                                                178
-------