FINAL REPORT
AMBIENT MEASUREMENT METHODS AND PROPERTIES OF THE
         189 TITLE m HAZARDOUS AIR POLLUTANTS
                            by

Thomas J. Kelly, R. Mukund, Sydney M. Gordon, and Melinda J. Hays
                        BATTELLE
                      505 King Avenue
                   Columbus, Ohio 43201
                        March 1994
                 Contract Number 68-DO-0007
                  Work Assignment No. 44
                       Project Officer

                    William A. McClenny
     Atmospheric Research and Exposure Assessment Laboratory
             U.S. Environmental Protection Agency
                          MD-44
          Research Triangle Park, North Carolina 27711

-------
                      FINAL REPORT
AMBIENT MEASUREMENT METHODS AND PROPERTIES OF THE
         189 TITLE m HAZARDOUS AIR POLLUTANTS
                            by

Thomas J. Kelly, R. Mukund, Sydney M. Gordon, and Melinda J. Hays
                        BATTELLE
                      505 King Avenue
                   Columbus, Ohio  43201
                        March 1994
                 Contract Number 68-DO-0007
                   Work Assignment No. 44
                       Project Officer

                    William A. McClenny
     Atmospheric Research and Exposure Assessment Laboratory
             U.S. Environmental Protection Agency
                          MD-44
          Research Triangle Park, North Carolina 27711

-------
                                  EPA DISCLAIMER
      The information in this document has been funded wholly or in part by the United
 States Environmental Protection Agency under Contract 68-DO-0007 to Battelle Memorial
 Institute.  It has been subject to the Agency's peer and administrative review, and it has been
 approved for publication as an EPA document.  Mention of trade names or commercial
 products does not constitute  endorsement or recommendation for use.
                              BATTELLE DISCLAIMER
      This report is a work prepared for the United States Environmental Protection Agency
by Battelle Memorial Institute. In no event shall either the United States Environmental
Protection Agency or Battelle Memorial Institute have any responsibility or liability for any
consequences of any use, misuse, inability to use, or reliance upon the information contained
herein, nor does either warrant or otherwise represent in any way the accuracy, adequacy,
efficacy, or applicability of the contents hereof.
                                           11

-------
                                  FOREWORD
       Measurement and monitoring research efforts are designed to anticipate
environmental problems, to support regulatory actions by developing an in-depth
understanding of the nature of processes that impact health and the ecology, to provide
innovative means of monitoring compliance with regulations, and to evaluate the
effectiveness of health and environmental protection efforts through the monitoring of
long-term trends.  The Atmospheric Research and Exposure Assessment Laboratory,
Research Triangle Park, North Carolina, has responsibility for assessment of
environmental monitoring technology and systems for air, implementation of agency-
wide quality assurance programs for air pollution measurement systems, and  supplying
technical support to other groups in the Agency, including the Office of Air and
Radiation, the Office of Toxic Substances,  and the Office of Solid Waste.

       The 189 Hazardous Air Pollutants (HAPs) listed in the 1990 Clear Air Act
Amendments were so designated because of concerns about human health risks from the
presence of those HAPs in air.  Determination of human health risks, confirmation of
mandated reductions in those risks, and evaluation of emission control  efforts all
require ambient measurements of the  189 HAPs.  The survey of measurement methods
for HAPs  described in this report is an important resource with which  HAP
measurement methods may be identified and implemented.
                                  Jay J. Messer
                                  Acting Director
                                  Atmospheric Research and Exposure
                                   Assessment Laboratory
                                  Research Triangle Park,
                                  North Carolina  27711
                                       111

-------
                                   ABSTRACT

       This is the final report on a study conducted by Battelle to identify ambient air
 measurement methods for the 189 Hazardous Air Pollutants (HAPs) designated in Title
 in of the 1990 Clean Air Act Amendments.  The main objective of this work was to
 document the state of development of measurement methods for each of the 189 HAPs
 in ambient air.  This was accomplished by identifying and reviewing pertinent literature
 on applicable methods for each HAP.  A secondary objective of this work was to
 compile data on the chemical and physical properties of the HAPs, as the basis for
 selecting and evaluating measurement methods.  The results of both the HAP properties
 and HAP methods surveys are presented in this report.
       The 189 HAPs are an extremely diverse group of chemicals, including a few
 compounds unlikely to exist in ambient air, and several mixtures or chemical groups
 spanning wide ranges of physical and chemical properties. The physical  and chemical
 properties of the HAPs were surveyed by first distinguishing the  166 organic and 23
 inorganic chemicals on the HAPs list.  For all 189 HAPs, vapor pressure and boiling
 point data were compiled. Both the organic and inorganic HAPs were then separated
 into four volatility classes, based on quantitative vapor pressure criteria.  Listings of the
 HAPs assigned to each volatility class are provided in Appendix D of this report.  For
 the volatile and very volatile HAPs, further properties were then compiled, including
 water solubility, electronic polarizability, aqueous reactivity, and estimated lifetime in
the atmosphere.  These properties were used to assess the chemical and physical
characteristics of the HAPs, and the similarities and differences between  HAPs, as  a
guide in selecting measurement methods.  The data on HAPs properties are tabulated in
Appendices A and B of this report.
                                        IV

-------
       The survey of measurement methods for the 189 HAPs drew upon standard
 methods published by EPA, NIOSH, OSHA, and other organizations, and upon wide-
 ranging literature searches and reviews of recent publications. A total of 168 distinct
 measurement methods were identified, some applicable to several HAPs, and others
 applicable to a single HAP.  The identified methods were assigned to one of three
 categories according to their degree of development, i.e.:
       Demonstrated methods, established and documented to a reasonable degree for
 measurement of the target HAP in ambient air.  (This definition does not necessarily
 imply that all issues have been fully resolved regarding the sampling and analysis of the
 HAP in the atmosphere.  An overly optimistic view of the state of HAPs measurement
 methods could result if these reservations are overlooked.)
       Likely methods, established  for the target HAP or for a closely similar HAP  in
 (e.g.) workplace air, but needing further development before application  to ambient  air.
       Potential methods, needing extensive further development before measurements
 in ambient air could be considered.
       For each HAP, all  identified methods were tabulated, so that for many HAPs
 methods in more than one of the above-named categories were listed. Quantitative
 detection limits were also tabulated, for at least the most fully developed methods for
 each HAP. Pertinent literature was also cited, to allow the reader to obtain details of
 each method if needed.  The full data base resulting from the HAPs methods survey is
 presented in Appendix C of this report.
       For 126 of the HAPs, Demonstrated methods of measurement were identified.
 For 53 other HAPs, Likely methods, but no Demonstrated methods, were found.
 These two results combined suggest that ambient measurements should be achievable
 for most of the 189 HAPs, with a reasonable further method development effort.
However, that method development must include both Demonstrated and Likely
 methods, since methods currently identified as Demonstrated may not all be fully
proven for all ambient conditions and for the full range of HAPs properties and
reactivity. In addition, for 6 HAPs only Potential methods were found,  implying

-------
 extensive further development before ambient measurements are achievable, and for 4
 HAPs no methods were found at any stage of development.
       The primary recommendation of this study is that method development be
 focussed on the 53 HAPs for which Likely methods were found. This approach is
 likely to produce the greatest return for the resources invested.  The 10 HAPs with
 little or no current measurement capability should also be the subject of methods
 development, but that effort should be prioritized based on the likely presence and
 importance of these  HAPs in the atmosphere.
       This report is submitted in fulfillment of Contract No. 68-DO-0007 (Work
 Assignment 44) by Battelle under the sponsorship of the U.S. Environmental Protection
 Agency.  It covers the period from March  1, 1993 to  March 31, 1994, and all work
was completed as of March 31, 1994.
                                      VI

-------
                                 CONTENTS


 Foreword	iii

 Abstract	iv

 Figures  	,	viii

 Tables	  	ix

 Acknowledgment  	   x

  1.  Introduction  	1
  2.  Conclusions  	4
  3.  Recommendations	5
  4.  Survey Methods  	6
             HAPs Properties	6
             HAPs Measurement Methods	 7
  5.  Survey Results	13
             HAPs Properties  	13
             HAPs Measurement Methods  	16

References  	29

Appendices

      A.  Results of the Survey of Chemical and Physical Properties
          of the 189 HAPs	33

      B.  Physical and Chemical Properties of VOCs on the HAPs List	45

      C.  Results of the Survey of Ambient Air Measurement Methods
          for the 189 HAPs   	54

      D.  Listings of the 189 HAPs by Volatility Classes	94
                                     VII

-------
                                 FIGURES


Number                                                                page

 1      Example of a few entries from Table A-l	15

 2      Example of a few entries from Table B-l	17

 3      Example of a few entries from Table C-l	18

 4      Distribution of the 189 HAPs by the most developed type of ambient
        measurement method currently available for each compound	24
                                   vm

-------
                                   TABLES
Number                                                                  page

  1      Summary of HAP categories with corresponding vapor pressure
        ranges and properties reviewed	8
                                            t
  2      Numbers of HAPs in each volatility class	     	    14

  3      Most developed ambient measurement method identified for
        each of the 189 HAPs	20

 4      Type of measurement methods currently available for each of the
        189 HAPs, by volatility class 	26

 5      Identification of the ten HAPs for which ambient methods
        are least developed  	28
                                     IX

-------
                           ACKNOWLEDGMENT

      The involvement and technical insight of Drs. William A. McClenny and
Robert G. Lewis of U.S. EPA in this work are gratefully acknowledged.

-------
                                   SECTION 1
                                INTRODUCTION

       The presence of toxic contaminants in air has been a public health issue for
 many years.  However, the 1990 Clean Air Act Amendments (CAAA) greatly
                                              t
 accelerated the pace of designating and regulating air contaminants by defining a list of
 189 Hazardous Air Pollutants (HAPs).1 The 189 HAPs are remarkably diverse,
 consisting of industrial chemicals and intermediates, pesticides, chlorinated and
 hydrocarbon  solvents, metals, combustion byproducts, chemical groups such as
 polychlorinated biphenyls, and mixed chemicals such as coke oven emissions.  Some of
 the HAPs are common air pollutants, such as volatile organic compounds (VOCs), but
 many other HAPs were assigned to the list based on their recognized toxicity in
 workplace environments,  and had not previously been considered as ambient air
 contaminants. Some of the HAPs are not single compounds,  but rather complex
 mixtures or groups of chemicals spanning broad ranges of chemical and physical
 properties.  A few HAPs, such as titanium tetrachloride, phosphorus, and
 diazomethane, are unlikely to exist in ambient air because of their reactivity.
       Title HI of the CAAA is  aimed at reducing the public health risks from HAPs in
 ambient air, and includes  mandated risk reduction goals. For example, a 75 percent
 reduction in cancer incidence due to area sources of HAPs is  a stated goal of Title in.1
However, determining the current health risks from HAPs, or quantifying reductions in
health risks, requires knowledge of the ambient concentrations of the HAPs.  Partly
because of the diversity of the HAPs, ambient measurements are severely lacking for
many HAPs.  For example, only 70 of the 189 HAPs are included in the U.S. EPA's
National VOC Data Base.2"4 A  recent survey of ambient HAPs data conducted for
U.S. EPA showed no ambient data for 74 of the 189 HAPs,5'7 and furthermore found

                                       1

-------
  less than 100 ambient measurements for 116 of the HAPs.  These findings indicate that
  currently available information may be insufficient to conduct health risk assessments
  for many HAPs.5"7
        The main reason suggested for the absence of ambient data for many HAPs is
  the lack of suitable sampling and analysis methods.5'7  As a result, reviews have been
  conducted of possible measurement methods for the 189 HAPs.8-9  However, those
  reviews have generally considered only long-established standard methods, to the
  exclusion of novel research methods, and have generally taken optimistic views of the
  effectiveness of standard methods for measuring the diverse HAPs.8'9  The chemical
  and physical properties of the individual HAPs have not been carefully considered  in
 previous studies. Instead, the approach generally taken has been to suggest
 measurement methods for HAPs based on the perceived similarity of one HAP to
 another. The diversity of the HAPs makes this approach suspect.  The present study
 was intended to avoid the shortcomings of previous surveys in identifying measurement
 methods for the HAPs.
       This document is the final report on a survey of measurement methods for the
 189 HAPs in ambient air. This work was conducted by Battelle under EPA Contract
 No. 68-DO-0007, Work Assignment 44.  The goal of this project was to identify
 documented measurement methods for the 189 HAPs that could be applied at Superfund
 sites where the presence of such compounds was suspected, or in ambient air in urban
 areas.  This survey differed from previous efforts in four important ways:

 (1)    It includes a detailed review of physical and chemical properties of the HAPs.
       Those properties were  the basis for selection of measurement methods, and  also
       constitute a valuable product of this study in themselves. The HAPs properties
       compiled in this survey are included in this report.
(2)    Grouping of HAPs into classes, and ranking of HAPs within those classes, was
       based on the physical and chemical properties noted above.   Identification of
       measurement methods was based on the properties of individual HAPs and not
       simply on apparent similarities in chemical composition.  As a result, the
                                       2

-------
       identification of methods in this survey is likely to be more realistic than in
       previous surveys.
(3)    The survey was not limited to compilations of standard methods, but included
       extensive literature searches to identify research methods applicable to HAPs in
       ambient air. The research methods identified include (e.g.) several from foreign
       language journals. This detailed search assures that the most recent and novel
       approaches have been identified.
(4)    The measurement methods identified for the HAPs have been categorized by the
       degree of development of the method.  Thus, for example, a method which is
       proven in ambient measurements is distinguished  from one proven  only at higher
       concentration levels, as in workplace air. This approach provides  a wider range
       of information to the user of this survey, and results in methods being identified
       for nearly all the HAPs, albeit at varying levels of development. This approach
       avoids the all-or-nothing results characteristic of previous method surveys.9

       The work detailed in this report was conducted between March 1993 and March
1994.  Subsequent sections describe the Conclusions, Recommendations, Methods, and
Results of this survey.  Appendices to this report present extensive tabulations of the
properties and measurement methods identified for the HAPs, and the associated
literature citations.

-------
                                  SECTION 2
                                CONCLUSIONS

 1.     For 126 of the 189 HAPs, measurement methods designed for use in ambient air
       were identified. Most, but not all, of these methods have actually been used for
       ambient measurements of the pertinent HAPs.

 2.     For 53 other HAPs, measurement methods were identified which are likely to be
       applicable to ambient air after some further development.

 3.     Based on the two conclusions above, ambient measurement methods appear to be
       achievable for the great majority of the 189 HAPs.

4.     For 6 HAPs, existing measurement methods would require extensive further
       development before application to ambient air can be considered.

5.     For 4 HAPs, no measurement methods hi any state of development were
       identified.

6.     The 10 HAPs noted in conclusions 4 and 5 comprise the greatest gap in
       measurement capabilities for the HAPs.

-------
                                   SECTION 3
                             RECOMMENDATIONS

 1.     High priority should be given to further development of measurement methods
       for the 53 HAPs for which such effort is likely to lead to ambient air
       measurement capabilities.

2.     Development of methods should be initiated for the  10 HAPs for which existing
       methods are  most lacking.  However, prioritization of that effort should be
       based on the reactivity, emitted quantities, and potential products of these HAPs.

3.     Method verification efforts should continue for all HAPs, with the ami of
       consolidating or simplifying the wide variety of measurement methods currently
       identified.

-------
                                   SECTION 4
                              SURVEY METHODS

       This section describes the methods used to  obtain and compile information on
 the properties and measurement methods of the  189 HAPs.  It should be noted that hi
 conducting this study we relied on a list of the 189 HAPs that included (in draft form)
 the latest corrections and clarifications from the U.S.  EPA.10

 HAPs PROPERTIES
       The chemical and physical properties of interest hi this survey are those that
 affect the sampling and measurement of HAPs hi the  atmosphere.11  To organize the
 compilation of properties, the HAPs were divided  into groups.  As a starting point, the
 189 HAPs were first divided into organic compounds and inorganic compounds
 (designated OC and INC, respectively). This initial distinction was based largely on
 the designation of chemicals in the CRC Handbook of Chemistry and Physics,12 and on
 the known nature of the HAPs.  The primary  properties then obtained for all the HAPs
 were  vapor pressure (in mm of Hg at 25°C) and boiling point temperature.  The vapor
pressure data were the primary factor used to  categorize the HAPs further, since vapor
pressure indicates the likely physical state of a chemical in the atmosphere.  The 189
HAPs were ranked hi order of vapor pressure, with boiling point a secondary ranking
factor.
       Once ranked according to vapor pressure, the HAPs were grouped according to
ranges hi vapor pressure. Quantitative vapor pressure criteria  were set up defining very
volatile organic and inorganic compounds (i.e., WOC and WTNC), volatile
compounds (VOC and VINC), semivolatile compounds (SVOC and SVINC), and

-------
nonvolatile compounds (NVOC and NVINC).  The vapor pressure criteria corres-
ponding to each of these HAPs volatility classes are shown in Table 1.  The vapor
pressure criteria shown are the same as those used in previous such categorizations,13
except for the very volatile categories (VVOC and VVINC).   This study denoted as
very volatile any compound with a vapor pressure greater than 380 mm Hg (i.e., half
an atmosphere); previous categorizations used a somewhat lower criterion of 10 kPa
(i.e., 0.099 atm). The vapor pressure criteria are somewhat  arbitrary,  and compounds
with vapor pressures near the criterion values generally fall into "gray areas" that
define gradual transitions from one volatility class to the next.  For the volatile and
                                               t
very volatile HAPs, further chemical and physical properties  were compiled, consisting
of electronic polarizability, water solubility, aqueous reactivity, and estimated lifetime
relative to chemical reaction or deposition in the atmosphere.  These properties were
compiled  because they determine the effectiveness with which a HAP may be sampled
in the atmosphere,'' and the extent to which atmospheric processes may obscure
emissions of HAPs to the atmosphere.  Table 1 summarizes the properties reviewed for
the various volatility classes  of HAPs.
       The primary information sources used for the HAPs properties survey were
handbooks and data bases of chemical and physical properties,12"18 including an EPA
computer  data base specifically addressing the 189 HAPs.14  Whenever possible,
inconsistencies and errors were corrected by comparisons of  data from various sources,
and by consultation with EPA staff.
       The chemical and physical property data compiled in this study  are summarized
in Section 5, and presented in detail in Appendix A, for the full list of 189 HAPs.
Additional properties are  shown in Appendix B, for the VVOCs and VOCs on the
HAPs list. Appendix  D provides a separate list identifying the organic and inorganic
HAPs in each of the volatility ranges.

-------
         TABLE 1.  SUMMARY OF HAP CATEGORIES WITH CORRESPONDING VAPOR PRESSURE RANGES
                    AND PROPERTIES REVIEWED
    Volatility
     Class*
                              Range of Vapor Pressures
                                  (mm Hg at 25°)
                                                      Properties Reviewed
00
    VVOC

    VVINC


    VOC

    VINC
    SVOC
    SVINC

    NVOC
    NVINC
                                       >380

                                       >380


                                     0.1 to 380

                                     0.1 to 380
                                   Ix 10-7to0.1
                                   Ix 10-7to0.1

                                     < 1 x lO'7
                                     < 1 x lO'7
                                         Vapor pressure; boiling point; polarizability; water
                                         solubility; aqueous reactivity; atmospheric lifetime
                                         Vapor pressure; boiling point; polarizability; water
                                         solubility; aqueous reactivity; atmospheric lifetime

                                         Vapor pressure; boiling point; polarizability; water
                                         solubility; aqueous reactivity; atmospheric lifetime
                                         Vapor pressure; boiling point; polarizability; water
                                         solubility; aqueous reactivity; atmospheric lifetime

                                         Vapor pressure; boiling point
                                         Vapor pressure; boiling point

                                         Vapor pressure; boiling point
                                         Vapor pressure; boiling point
    a:
VVOC
VVINC
VOC
VINC
SVOC
SVINC
NVOC
NVINC
very volatile organic compounds
very volatile inorganic compounds
volatile organic compounds
volatile inorganic compounds
semivolatile organic compounds
semivolatile inorganic compounds
nonvolatile organic compounds
nonvolatile inorganic compounds.

-------
 HAPs MEASUREMENT METHODS
       The search for measurement methods for the HAPs was intended to be as wide-
 ranging as possible.  Information sources included standard compilations of air
 sampling methods, such as EPA Screening Methods, EPA Contract Laboratory
 Program (CLP) and Compendium (i.e., TO-) methods, as have been used in previous
 surveys.8'9 However, this study also reviewed standard methods designated by the
 Intersociety Committee on Methods of Air Sampling and Analysis, the National
 Institute of Occupational Safety and Health (NIOSH), the Occupational Safety and
 Health Administration (OSHA), and the American Society for Testing and Materials
 (ASTM).  Although not necessarily targeted for ambient air measurements, these
 methods are well documented and might serve as the starting point for an ambient air
 method. EPA solid waste (SW 846) methods were also consulted.  Another resource
 was the EPA database on measurement methods for HAPs,8 which includes primarily
 established EPA methods.  Additional sources of information were the two surveys
 recently conducted by Battelle for EPA on the ambient concentrations5"7 and
 atmospheric transformations7'19*20 of the HAPs. The ambient concentrations survey5"7
 was especially useful as a guide to measurement methods for HAPs, and assured that
 methods were identified for all HAPs that have been measured in ambient air.  In
 addition, reports, journal articles, and meeting proceedings known to contain
 information on HAPs methods were obtained and reviewed.  In general, highly complex
 and expensive spectroscopic research methods were considered unsuitable for
 widespread monitoring and were not included in this survey.
      The aim of the methods survey was to provide information on methods
 immediately applicable to HAPs  measurements, and on those still in development.  As a
result, measurement methods for the 189 HAPs were organized into three categories,
depending on the degree of development of the method.  Those categories are:

      Demonstrated - A Demonstrated method was defined as one which has been
reasonably established and documented for measurement of the target HAP in ambient
air.  In most cases, methods identified as Demonstrated have actually been used for

-------
ambient measurements, i.e., ambient data are available illustrating the effectiveness of
the method. A good example of a Demonstrated method is EPA Compendium Method
TO-14,21 which has been widely used for VOC measurements.  In other cases, a
method was identified as Demonstrated for a specific HAP because of the degree of
documentation and standardization of the method, even though no ambient data were
found. The primary examples of this are a few CLP and TO- methods.  Although such
methods are targeted for a number of HAPs, for a few of those HAPs no ambient
measurements were found, and further development may be needed to achieve ambient
measurement capabilities. It must be stressed that the existence of a Demonstrated
method does not guarantee adequate measurement of the pertinent HAP(s) under all
circumstances.  Further development and evaluation may be needed to assure
sensitivity, freedom from interferences, stability of samples, precision, accuracy, etc.
under the range of conditions found in ambient measurements.

       Likely -  Two types of Likely measurement methods were defined.  The most
common type is a method which has been clearly established and used for the target
HAP in air, but not in ambient air.  The presumption is that further development  (such
as an increase in sensitivity or sampled volume) would allow measurements in ambient
air.  The primary examples of this type of Likely method are  NIOSH or OSHA
methods established for HAPs in workplace air. A specific example is OSHA Method
No. 21, stated to have a detection limit of 1.3 ppbv in workplace air, and designated as
a Likely method for acrylamide.  In a few cases,  such methods have been applied to
ambient air, but in such limited conditions or time periods that demonstration of the
method is judged to be incomplete.  The second type of Likely method consists of
techniques identified as Demonstrated for one HAP, and consequently inferred as
Likely  for another HAP, based on close similarity of chemical and physical properties.
An example of an inferred Likely method is TO-14 for l,2-dibromo-3-chloropropane,
based on the similarity of this compound to other VOCs in terms of volatility, water
solubility, and reactivity.
                                       10

-------
       Potential - A Potential method was defined as one which needs extensive further
 development before application to ambient air measurements will be justified.  Many
 Potential methods have been evaluated under laboratory conditions, or for the target
 HAP in sample matrices other than air (e.g., water, soil).  Potential methods were
 inferred for some HAPs, based on Demonstrated or Likely methods found for other
 HAPs of somewhat similar chemical and physical properties.  The degree of similarity
 of properties between HAPs was used as the guide in designating Potential methods in
 those cases.

       For HAPs for which no Demonstrated or Lik&ly methods were found, further
 searches were conducted beyond the reviews outlined above.  For such HAPs, detailed
 literature searches were conducted using the files of Chemical Abstracts Service (CAS)
 and the National Technical Information Service (NTIS).  Such searches targeted the
 chemical name and CAS number of the HAP of interest, and used  successive sets of
 keywords such as air; trace or ambient or workplace; and detect or measure or monitor.
 Abstracts obtained in such searches were reviewed, and whole papers were obtained for
 review if the abstracts appeared promising.  These additional searches were not
 restricted to English language publications.  Several Likely and Potential methods
 reported in foreign  language publications were identified by these searches.
       In all method searches and reviews,  the chemical and physical properties
 compiled in this study were valuable. The quantitative similarity of properties such as
 vapor pressure, solubility, and reactivity of HAPs was used to suggest Likely and
 Potential methods, and the degree of similarity of properties determined the choice
 between designation as a Likely or Potential method.
       A key characteristic of an ambient air measurement method is  the detection
limit. As part of this methods survey, ambient air detection limits were indicated
whenever they were reported in method documentation. The various units in which
detection limits were reported include parts-per-million by volume  (ppmv), parts-per-
billion by volume (ppbv), parts-per-trillion by volume (pptv), milligrams per cubic
meter (mg/m3), micrograms per cubic meter Otg/m3), nanograms per cubic meter
                                        11

-------
 (ng/m3), and picograms per cubic meter (pg/m3).  Detection limits were reported in this
 review as they were stated in the respective methods.  Detection limits for certain CLP
 methods were reported as a Contract Required Quantitation Limits (CRQL) in mass
 units only (e.g., ng), or as a range of applicable concentrations. In such cases the
 detection limit was reported as stated in the method, along with needed supporting
 information such as the approximate sampled air volume.  An effort was  made to
 indicate the detection limit for at least the most fully developed method(s) for each
 HAP. Estimation  of detection limits, when they were not explicitly stated in the
 material  reviewed, was generally not done.  The detection limits reported should be
 considered primarily a guide to the relative capabilities of the various methods, rather
 than an absolute statement of method performance.
       Citation of  literature in the methods survey was aimed at providing the user of
 the survey enough  information to review at least the basics of the identified  method,
 and to locate further information if needed.  No effort was made to compile all possible
 information  on each method.
       The results  of the HAPs measurement method survey are summarized in
Section 5, and are  presented in detail in Appendix C for the full list of 189 HAPs.
                                       12

-------
                                  SECTION 5
                              SURVEY RESULTS

       This section of the report summarizes the data obtained on properties and
 measurement methods for the 189 HAPs. Complete tables of the information compiled
 in these surveys are presented in Appendices A and B, for the properties, and
 Appendix C, for the measurement methods, respectively.  For convenience, Appendix
 D provides a listing of the HAPs by volatility classes.  Chemical structure and formula
 information is presented for all  the HAPs in the recent HAPs transformation survey,19
 and for selected HAPs in various handbooks and data bases.12>15>16

 HAPs PROPERTIES
       The initial result of the survey of HAPs properties was the assignment of HAPs
 to the various volatility classes. That result is shown in Table 2, which lists the
 number of HAPs in each compound class.  Table 2 shows that the largest classes are
 the volatile and semivolatile compounds.  Organic compounds (166 chemicals)
 predominate over  inorganic compounds (23 chemicals) on the HAPs list as a whole.
 Inorganic elements and compounds comprise the majority of the non-volatile class of
 HAPs, i.e., those  compounds found exclusively in the paniculate phase in the
 atmosphere.
       This report presents the full results of the properties survey, in two different
tabular forms.  Table A-l  in Appendix A lists the 189 HAPs hi the same order as in
the CAAA, along with the CAS number and properties compiled for each HAP.  An
example listing from that table is shown in Figure 1.  The successive columns in the
example in Figure 1 list the  HAP name, CAS number, molecular weight, volatility
                                       13

-------
 TABLE 2.  NUMBERS OF HAPs IN EACH VOLATILITY CLASS
Volatility Class"
                Number of HAPs in Class
woe
WINC
                              15
                               6
voc
VINC
                              82
                               3
SVOC
SVINC
                              64
                               2
NVOC
NVINC
                               5
                              12
                         Total
                              189
a:  VVOC
   VVINC
   VOC
   VINC
   SVOC
   SVINC
   NVOC
   NVINC
very volatile organic compounds
very volatile inorganic compounds
volatile organic compounds
volatile inorganic compounds
semivolatile organic compounds
semivolatile inorganic compounds
nonvolatile organic compounds
nonvolatile inorganic compounds.
                            14

-------
Figure 1. Example of a few entries from Table A-l on physical properties of the 189 HAPs.
Compound
Acetaldehyde; C2H4O
Acetamide; C2H5NO
Acetonitrile; C2H3N
Acetophenone; C8H8O
2-Acetylaminofluorene; C1SH13NO
Acrolein; C3H«O
CAS No.
75-07-0
60-35-5
75-05-8
98-86-2
53-96-3
107-02-8
MW
44.0
59.0
41.0
120.0
223.3
56.0
Compound
Class1
woe
SVOC
VOC
VOC
NVOC
VOC
VP2
(mm Hg/
25eC)
952
7.2E-02
74.0
1.0
1.1E-12(?)
220.0
BP2
<'C)
21
222
82
202
444
53
Water
Solubility3
(g/Lat°C)
33.0 / 25
>100/22
>100/22
6.3/25
<0.1/20.5
>100/21
Comment





Reactive 5

-------
 class, vapor pressure, boiling point, and water solubility. A column for comments is
 also shown.  The second tabular form is Table B-l in Appendix B, which lists
 properties for WOCs and VOCs only.  An example from Table B-l is shown hi
 Figure 2. This example shows  that Table B-l includes some of the information from
 Table A-l, but also includes information on electronic polarizability, aqueous reactivity,
 and lifetime hi ambient air.  The reader is referred to Appendices A and B for the full
 presentation of results on HAP properties.  Appendix B also includes a discussion of
 polarizability and water solubility as defining characteristics of polar VOCs.

 HAPs MEASUREMENT METHODS
       The primary product of this study was the identification of methods for ambient
 measurements of the HAPs.  In this subsection the complete data set as presented hi
 Appendix C is described, followed by summary descriptions and comments.
       The HAPs method survey is presented hi Appendix C hi the form of a
 comprehensive table that presents the 189 HAPs hi the same order as they appear hi the
 CAAA.  An example portion of that table is shown hi Figure 3. For each HAP, the
 name, CAS number, and major volatility class are shown.  The ambient methods
 information is listed hi successive columns for Demonstrated, Likely, and Potential
 methods.  Within each column,  the identified methods are indicated by standard method
 designations (e.g., TO-5, CLP-2, NIOSH 5514), or by citations to the pertinent
 literature (e.g., R-l, R-2, etc.). The final two columns of the Table show the limits of
 detection for selected methods, and provide explanatory comments on the entries,
 respectively.
      The methods and literature  compiled hi conducting the methods survey are cited
 hi a reference  list hi Appendix C,  following the methods table exemplified hi Figure 3.
 Standard methods, such as NIOSH, OSHA, or TO- methods, are listed by title under a
general reference heading. Research methods are listed hi numerical order (R-l, R-2,
etc.). For each research method, the citation includes a brief description of the
method, and one or more literature citations pertinent to the method. In all, this survey
 identified 51 NIOSH methods, 31  OSHA methods; 15 TO- methods, 3 EPA screening

                                       16

-------
Figure 2.  Example of a few entries from Table B-l on physical and chemical properties of VOCs in the HAPs list.
Compound
Acetaldehyde
Acetonitrile
Acetophenone
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Ally! chloride
CAS No.
75-07-0
75-05-8
98-86-2
107-02-8
79-06-1
79-10-7
107-13-1
107-05-1
Sub-
category1
woe
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VP2
(mm Hg at
25°C)
952
74
1
220
0.53
3.2
100
340
Polarizablllty3
(cm3/mole)
11.6
11.0
36.3
16.2
-
17.4
15.6
20.5
Water Solubility4
(gIL at °C)
33.0/25
>100/22
6.3 / 25
>100/21
>100/22
>100/17
716.0/258
19.5 / 208
Reactivity & t% range5
Aqueous6
-
aab
-
aab
*
aab
aab
ah
-
7-28d
-
7-28d
-
1-7d
1-23d
7-14d
Air
-
54-541 d
-
3-34h
-
3-24h
0.6-8d
3-29h
Other7
Polar
Polar
Polar
Polar
Polar
Polar
Polar
Non-Polar

-------
                 Figure 3. Example of a few entries from Table C-l (Ambient Measurement Methods for the 189 HAPs).
00
Compound
Acetaldehyde
Acetamide
Acetonitrile
Acetophenone
2-Acefylaminofluorene
CAS No.
75-07-0
60-35-5
75-05-8
98-86-2
53-96-3
Compd.
Class *
woe
svoc
voc
voc
NVOC
Ambient Measurement Method
Demonstrated
TO-5
TO-11

R-1.CLP-1A,
R-3
CLP-2

Likely
R-4 [14]

TO-15


Potential

OSHA CIM
[A625J; R-37;
R-47

TO-15
OSHA CIM
[0065]
Limit of
Detection1''1''4''
TO-5: 1 ppbv; TO-1 1 : 1
ppbv; [14]: 30 ppmv

R-1:1ppbv
CLP-24: 37 ng/m3 (0.007
ppbv)

Comment

[A625]: not a validated method; R-
47: method developed for analysis of
water


[0065]: not a validated method

-------
 methods, 4 CLP methods, and 64 reference methods pertinent to the HAPs. The reader
 is referred to Appendix C for the full results of the methods survey. However, some
 general comments on the findings of this study are of interest here.
       Table 3 is a summary listing of the methods survey results, indicating whether
 the most fully developed  methods for each HAP fall within the definition of
 Demonstrated, Likely,  or Potential. Table 3 lists the HAPs in the same order as in the
 original Title III list. Table 3 shows the name and volatility class assignment for each
 HAP, and the status of methods identified for  that HAP.  This  table serves as a quick
 reference guide, with details presented in Appendix C.  Table 3 includes brief
 definitions for each of  the types of methods found (Demonstrated, Likely, Potential).
 For the Likely and Potential methods, separate columns are provided for methods
 inferred on the basis of HAP chemical and physical properties, as opposed to those
 established for the HAP in question.  At the end of Table 3, the total number of HAPs
 falling in each method  development column is indicated.
       In considering Table 3, the definition of a Demonstrated method must be
 stressed. A Demonstrated method is one which is targeted for the indicated HAP in
 ambient air, and which has been developed and documented to a reasonable degree.
 This does not mean that all Demonstrated methods have actually been used for ambient
 measurements of the indicated HAPs, or that all sampling and analysis difficulties have
been solved.  An overly optimistic view of the state of HAPs measurement methods
could result if the summary in Table 3 is taken without these reservations.
      Figure 4 is  a graphical overview of the results in Table  3 for the 189 HAPs.
Figure 4 shows that for 126 HAPs (two-thirds of the HAPs list), Demonstrated ambient
measurement methods were found. Note that Table 3 and Figure 4 show only the most
developed state of  methods found; for some of these  126 HAPs, Likely and Potential
methods were also found.  Figure 4 also shows that for 53 HAPs, Likely methods were
found, but no Demonstrated methods.  Most of these Likely methods were specific for
the HAP in question, but for 7 HAPs the identification of Likely methods was inferred
based on HAP properties.  For 6 HAPs only Potential methods could be identified,  and
of those, 3 were inferred  on the basis of chemical and physical properties.  For 4 HAPs

                                       19

-------
Table 3. Most Developed Ambient Measurement Method Identified for Each of the 189 HAPs.

COMPOUND
Acetaldehyde
Acetamide
Acetonitrile
Acetophenone
2-Acetylaminofluorene
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Allyl chloride
4-Aminobiphenyl
Aniline
o-Anisidine
Asbestos
Benzene
Benzidine
Benzotrichloride
Benzyl chloride
Biphenyl
Bis (2-ethylhexyl)phthalate
Bis (chloromethyl) ether
Bromoform
1 ,3-Butadiene
Calcium cyanamide
Caprolactam
Captan
Carbaryl
Carbon disulfide
Carbon tetrachloride
Carbonyl sulfide
Catechol
Chloramben
Chlordane
Chlorine
Chloroacetic acid
2-Chloroacetophenone
Chlorobenzene
Chlorobenzilate
Chloroform
Chloromethyl methyl ether
Chloroprene
Cresol/Cresylic acid (mixed
isomers)
o-Cresol
m-Cresol
p-Cresol
Cumene
2,4-D (2,4-Dichloro
ihenoxyacetic acid) (incl.
salts and esters)
DDE
CLASS
woe
svoc
voc
voc
NVOC
voc
voc
voc
voc
voc
svoc
voc
svoc
NVINC
voc
svoc
svoc
voc
svoc
svoc
voc
voc
woe
NVINC
svoc
svoc
svoc
voc
voc
woe
voc
svoc
svoc
WINC
voc
svoc
voc
svoc
voc
voc
voc
voc
voc
svoc
svoc
voc
svoc
svoc
Most Developed Ambient Method Identified
Demonstrated
Applied in
ambient air
X

X
X

X


X
X
X
X

X
X
X

X
X
X
X
X
X


X
X
X
X
X


X
X


X

X

X
X
X
X
X
X
X
X
Likely
Applied in
non-ambient
air






X





X










X
X









X
X

X

X








Interned






























X

















Potential
Applied for
compound in
other media

X


X











X































Inferred































X
















None
No methods
found







X

































•






                                      20

-------
Table 3. (continued)

COMPOUND
Diazomethane
Dibenzofurans
1 ,2-Dibromo-3-chloropropane
Dibutyl phthalate
1 ,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dichloroethyl ether (Bis[2-
chloroethyl]ether)
1 ,3-Dichloropropene
Dichlorvos
Diethanolamine
Diethyl sulfate
3,3'-Dimethoxybenzidine
4-Dimethylaminoazobenzene
N,N-Dimethylaniline
3,3'-Dimethylbenzidine
Dimethylcarbamoyl chloride
N.N-Dimethylformamide
1 ,1-Dimethylhydrazine
Dimethyl phthalate
Dimethyl sulfate
4,6-Dinitro-o-cresol (including
salts)
2,4-Dinrtrophenol
2,4-Dinrtrotoluene
,4-Dioxane
,2-Diphenylhydrazine
•pichlorohydrin
,2-Epoxybutane
Ethyl acrylate
Ethylbenzene
Ethyl carbamate
Ethyl chloride
Ethylene dibromide
Ethylene dichloride
Ethylene glycol
Ethyleneimine
Ethylene oxide
Ethylene thiourea
Ethylidene dichloride
Formaldehyde
Heptachlor
•lexachlorobenzene
Hexachlorobutadiene
1,2,3,4,5,6-Hexachloro
cyclohexane (all stereo
isomers, including Lindane)
Hexachlorocyclo pentadiene
lexachloroethane
Hexamethylene diisocyanate
Hexamethylphosphoramide
Hexane
CLASS
woe
svoc
voc
svoc
voc
svoc
voc
voc
svoc
svoc
voc
NVOC
NVOC
voc
svoc
voc
voc
voc
svoc
voc
svoc
svoc
svoc
voc
svoc
voc
voc
voc
voc
voc
woe
voc
voc
svoc
voc
woe
svoc
voc
woe
svoc
svoc
voc
svoc
svoc
voc
svoc
svoc
voc
Most Developed Ambient Method Identified
Demonstrated
Applied in
ambient air

X
X
X
X

X
X
X







X

X
X
X
X
X
X

X

X
X

X
X
X


X

X
X
X
X
X
X
X
X


X
Ukely
Applied in
non-ambient
air
X




X



X
X
X
X
X

X

X















X
X

X








X


Inferred










>r



X











X





















Potential
Applied for
compound in
other media
















































Interred
























X























None
No methods
found





























X
















X

       21

-------
Table 3. (continued)

COMPOUND
Hydrazine
Hydrochloric acid (Hydrogen
chloride)
Hydrogen fluoride
(Hydrofluoric acid)
Hydroquinone
Isophorone
Maleic anhydride
Methanol
Methoxychlor
Methyl bromide
Methyl chloride
Methyl chloroform
Methyl ethyl ketone
Methylhydrazine
Methyl iodide
Methyl isobutyl ketone
Methyl isocyanate
Methyl methacrylate
Methyl tert-butyl ether
4,4'-Methylenebis(2-
chloroaniline)
Methylene chloride
4,4'-Methylenediphenyl
diisocyanate
4,4'-Methylenedianiline
Naphthalene
Nitrobenzene
4-Nitrobiphenyl
4-Nitrophenol
2-Nitropropane
N-Nttroso-N-methylurea
vl-Nitrosodimethylamine
vl-Nitrosomorpholine
Parathion
Pentachloronitro benzene
Pentachlorophenol
'henol
p-Phenylenediamine
'hosgene
Phosphine
Phosphorus
'hthalic anhydride
Polychlorinated biphenyl
,3-Propane sultone
beta-Propiolactone
Propionaldehyde
Propoxur (Baygon)
Propylene dichloride
Propylene oxide
1 ,2-Propylenimine
Quinoline
Quinone
CLASS
VINC
VINC
WINC
SVOC
VOC
SVOC
VOC
SVOC
woe
woe
VOC
VOC
VOC
woe
VOC
VOC
VOC
VOC
NVOC
VOC
SVOC
NVOC
SVOC
VOC
SVOC
SVOC
VOC
VOC
VOC
VOC
SVOC
SVOC
SVOC
VOC
SVOC
woe
WINC
SVINC
SVOC
SVOC
VOC
VOC
VOC
SVOC
VOC
woe
VOC
SVOC
SVOC
Most Developed Ambient Method Identified
Demonstrated
Applied in
ambient air

X
X

X

X
X
X
X
X
X




X
X

X


X
X
X
X


X

X

X
X

X
X


X
X

X
X
X


X

Likely
Applied in
non-ambient
air
X


X

X






X
X
X
X


X

X
X




X




X


X


X
X


X



„


X
Infenred





























X















X
X


Potential
Applied for
compound in
other media

















































Inferred



























X





















None
No methods
found

















































        22

-------
                                              Table 3. (continued)

COMPOUND
Styrene
Styrene oxide
2,3,7,8-Tetrachloro dibenzo-p-
dioxin
1 ,1 ,2,2-Tetrachloroethane
Tetrachloroethylene
Titanium tetrachloride
Toluene
Toluene-2,4-diamine
2,4-Toluene diisocyanate
o-Toluidine
Toxaphene (chlorinated
camphene)
1 ,2,4-Trichlorobenzene
1 ,1 ,2-Trichloroethane
Trichloroethylene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Triethylamine
Trifluralin
2,2,4-Trimethylpentane
Vinyl acetate
Vinyl bromide
Vinyl chloride
Vinylidene chloride
Xylene (mixed isomers)
o-Xylene
m-Xylene
>-Xylene
Antimony Compounds
Arsenic Compounds
Inorganic including arsine)
ieryllium Compounds
Cadmium Compounds
Chromium Compounds
Cobalt Compounds
Coke Oven Emissions
Cyanide Compounds
Glycol ethers
.ead Compounds
Manganese Compounds
Mercury Compounds
Fine mineral fibers
Nickel Compounds
Polycyclic Organic Matter
Radionuclides (including
radon)
Selenium Compounds
CLASS
voc
voc
svoc
voc
voc
VINC
voc
svoc
svoc
svoc
svoc
voc
voc
voc
svoc
svoc
voc
svoc
voc
voc
woe
woe
woe
voc
voc
voc
voc
NVINC
WINC/NVINC
NVINC
NVINC
NVINC
NVINC
SVOC/NVOC
WINC/NVINC
SVOC
NVINC
NVINC
SVINC/NVINC
NVINC
NVINC
SVOC/NVOC
WINC/NVINC
NVINC
All HAPs: 1 89 Compounds
Most Developed Ambient Method Identified
Demonstrated
Applied in
ambient air
X

X
X
X

X



X
X
X
X
X
X

X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X


X
X
X

X
X
X '
X
126
Likely
Applied in
non-ambient
air

X





X
X
X






X

















X
X



X




46
Inferred










••









X























7
Potential
Applied for
compound in
other media












































3
Inferred












































3
None
No methods
found





X






































4
Note:  HAPs that can be categorized in more than one compound class, e.g. mercury compounds in vapor and particulate forms
(SVINC and NVINC), have been addressed in this table on the basis of the vapor pressure of the most volatile species present in ambient
air. For example, the methods entry for mercury compounds reflects that for the SVINC category (mercury vapor)
                                                        23

-------
          126

Demonstrated
Methods:
Applied in ambient air
                                                                Likely Methods:
                                                           46  Applied in non-ambient air
                                                                (e.g., workplace, stack)
                                                                      Likely Methods:
                                                                      Inferred based on
                                                                      properties
  Potential Methods:
  Applied for compounds
  in other media
Potential Methods:
Inferred based on
properties
                                                         No Method
  Figure 4. Distribution of the 189 HAPs by the most developed type of ambient measurement
                       method currently available for each compound.
                                                                                   I   i
                                             24

-------
 no measurement methods could be identified at any level of development.  The finding
 of 126 HAPs with Demonstrated methods is consistent with a recent survey5'7 which
 disclosed ambient data for 115 of the HAPs.
        A more detailed look at the study results is shown in Table 4, which presents
 the state of methods found for each of the volatility classes of HAPs.  Each entry in
 Table 4 is the number of HAPs hi the indicated volatility class, for which the most
 developed method falls hi the indicated method category.  For most of the volatility
 classes, Demonstrated methods are identified for the majority of the HAPs.  In total,
 Demonstrated methods were identified for 109 of the 166 organic compounds, and for
 17 of the 23 inorganic compounds.  However,  for the' 5 NVOCs and 2 of the 3 VINCs,
 no Demonstrated methods were found.  Table 4 also shows that hi all volatility classes,
 most compounds with no Demonstrated  methods  could be associated with one or more
 Likely methods.  This result indicates that for the great majority of the HAPs,
 promising methods at least exist from which ambient methods may be developed.
 However, for 6 HAPs (all organic compounds) only Potential methods could be
 identified, and for 4 HAPs (3  organic, 1 inorganic) no methods of any kind were
 identified.
       In terms of method development needs for the HAPs, the most cost-effective
 approach would probably be further development  of the Likely methods that exist for
 the 53 HAPs with no Demonstrated methods.  The definition of a Likely method means
 that a reasonable degree of further development should result in a method applicable to
 ambient air.  Of the 53 HAPs  with only Likely  methods, 44 are WOCs, VOCs, or
 SVOCs (see Table 4).  These three groups are the largest classes of HAPs, so further
 development of methods for such compounds would be particularly beneficial. In
 addition, the large number of Demonstrated methods already available for volatile and
 semi-volatile organics  should enhance development of methods for additional
compounds.  A good example is the current effort to extend canister sampling and
analysis, as embodied  in EPA Compendium Method TO-14,21 to a broader range of
volatile compounds, including HAPs. Activities toward extension of the TO-14 method
include evaluations of the utility of canister sampling for polar HAPs;c-g-
                                       25

-------
   Table 4.  Type of Measurement Methods Currently Available for Each of the 189 HAPs, by
                                             Volatility Class.

VOLATILITY CLASS
woe
VOC
SVOC
NVOC
WINC
VINC
SVINC
NV/INC
Totals
Total in
Class
15
82
64
5
6
3
2
12
189
Most Applicable Ambient Method Identified
Demonstrated
Applied in
ambient air
11
60
38
0
5
1
1
10
126
Ukely
Applied in
non-ambient
air
2
15
20
4
1
1
1
2
46
Inferred
2
4
1
0
0
0
0
0
7
Potential
Applied for
compound in
other media
0
0
2
1
0
0
0
0
3
Inferred
0
1
2
0
0
0
0
0
3
None
No methods
found
0
2
1
0
0
1
0
0
4
Note: HAPs that can be categorized in more than one compound class, e.g. mercury compounds in vapor and parttculate forms
(SVINC and NVINC), have been assigned in this table based on the vapor pressure of the most volatile species present in ambient
air. For example, mercury compounds have been assigned to the SVINC category using this rationale.
                                                     26

-------
modelling of the adsorptive behavior of VOCs in canisters;11'27 and preparation of a
                                                       OQ
more broadly applicable canister method, designated TO-15.
       Continued evaluation of measurement methods for all the HAPs would be
worthwhile. An important goal of that effort should be to consolidate and simplify the
variety of methods available into a smaller number of well-characterized and broadly
applicable methods.  Although some of the standard EPA methods cited in this survey
are intended to be broadly applicable, the diversity of the 189 HAPs calls for further
work in this area.  Development  of a TO-15 canister-based method of broad
applicability to the volatile HAPs is one opportunity for such consolidation.28 Another
area of opportunity for consolidation of methods is the NIOSH and OSHA workplace
methods, many of which are cited hi this survey as Likely methods for various HAPs.
Although generally  targeted for a single chemical or a small group of chemicals, the
workplace methods often share very similar operational and analytical procedures.
Combination or consolidation of  these methods thus would seem feasible. Finally,
further verification  of HAPs methods is needed, even for Demonstrated methods.  The
existence of Demonstrated methods for 126 of the HAPs may present an optimistic
picture of the  state of HAPs measurement capabilities. However, the absence of
ambient data from some Demonstrated methods, the reactivity of some HAPs, the
variability of ambient sampling conditions, and the complexity of air composition that
can be encountered in ambient measurements suggest that for many methods further
testing is needed.  The 64 research methods identified here, which have generally been
applied only to a limited extent by a small number of investigators, are particularly
appropriate candidates for further evaluation.
       The 10 HAPs for which only Potential methods or no methods were found
would seem to indicate  the greatest current need for ambient method development.
Those  10 compounds are identified in Table 5, which also indicates their respective
volatility classes. These 10 HAPs are relatively unusual compounds, not normally
regarded as ambient air contaminants, and some are highly reactive and not likely to be
present for long in the atmosphere.7'19'20 There are no ambient air concentration data
for these 10 HAPs,5"7 and virtually no information on potential atmospheric reaction
                                        27

-------
          TABLE 5. IDENTIFICATION OF THE TEN HAPs FOR WHICH
                     AMBIENT METHODS ARE LEAST DEVELOPED
 Compound                          CAS No.            Volatility Class
Potential Methods Identified
Acetamide
2-Acetylaminofluorene
Benzotrichloride
Chloramben
1 ,2-Diphenylhydrazine
N-nitroso-N-methyl urea
No Methods Identified
Acrylic acid
Ethyl carbamate (urethane)
Hexamethyl phosphoramide
Titanium tetrachloride

60-35-5
53-96-3
98-07-7
133-90-4
122-66-7
684-93-5

79-10-7
51-79-6
680-31-9
7550-45-0

SVOC
NVOC
SVOC
SVOC
SVOC
VOC

VOC
VOC
SVOC
VINC
products,19-20 so it is difficult to determine whether they or their reaction products
cause a significant health risk in ambient ah*.  Method development should be pursued
for these 10 HAPs. However,  because of the very inadequate state of current methods,
such method development should be prioritized based on information on the emissions,
reactivity, and products of these HAPs.  This approach will avoid spending time and
resources on method development for a HAP or HAPs that are, for example, too
reactive (e.g., titanium tetrachloride) or emitted in quantities too small to be present at
measurable levels in the atmosphere. This linkage of method development with other
information should be valuable  for all HAPs, but especially so for the  10 HAPs shown
in Table 5.
                                     28

-------
                                REFERENCES
 (1)   Clean Air Act Amendments of 1990, Conference Report to Accompany S.  1630,
       Report No. 101-952, U.S. Government Printing Office, Washington, D.C
       1990, pp 139-162.

 (2)   Shah, J.J., Heyerdahl, E.K.  National Ambient Volatile Organic Compounds
       (VOCs) Data Base Update, Report EPA-600/3-88/010(a), U.S. Environmental
       Protection Agency, Research Triangle Park, North Carolina, 1988.

 (3)   Shah, J.J., Singh, H.B.  Distribution of Volatile Organic Chemicals in Outdoor
       and Indoor Air: A National VOCs Data Base, Environ. Sci. Techno!.. 1988 22
       1381-1388.

 (4)   Shah, J.J., Joseph, D.W. National Ambient VOC Data Base Update: 3.0,
       report to U.S. Environmental Protection Agency, Contract No. 68-D8-0082, by
       G2 Environmental, Inc., Washington, D.C., under subcontract from Battelle,
       Columbus, Ohio, May 1993.

 (5)   Kelly, T.J., Mukund, R., Pollack, A.J., Spicer, C.W. Ambient Concentration
      Summaries for Clean Air Act Title HI Hazardous Air Pollutants, Final Report to
      U.S. Environmental Protection Agency, Contract No. 68-D8-0082, Battelle,
      Columbus, Ohio, July 1993.

(6)   Kelly, T.J., Mukund, R., Pollack, A.J., Spicer, C.W., Shah, J., Joseph, D.W.,
      Cupitt, L.T.  Surveys of the 189 CAAA Hazardous Air Pollutants: I. Atmos-
      pheric Concentrations in the U.S., in Measurement of Toxic and Related Air
      Pollutants. Proceedings of the 1993 EPA/AWMA International Symposium,
      EPA Report No. EPA/600/A93/024, Publication Vff-34, Air and Waste
      Management Association, Pittsburgh, Pennsylvania, pp 161-166,  1993.

(7)   Kelly, T.J., Mukund, R., Spicer, C.W., Pollack, AJ. The Hazardous Air
      Pollutants:  Their Concentrations, Transformations, and Fate in Urban Air,
      Environ. Sci. Technol.. in press, March 1994.

(8)   Keith, L.H., Walker, M.M. EPA's  Clean Air Act Air Toxics Database.
      Volume I: Sampling and Analysis Methods Summaries. ISBN-0-87371-819-4,
      Lewis Publishers, Boca Raton, Florida, 1992.

                                     29

-------
  (9)   Winberry, W.T., Jr.  Sampling and Analysis Under Title m, Environmental
       Lab.. June/July 1993, pp 46-58.

 (10)   List of Section 112 Hazardous Air Pollutants, update obtained from the U.S.
       Environmental Protection Agency, Office of Air Quality Planning and Standards,
       Technology Transfer Network (TTN) computer bulletin board, National Air
       Toxics Information Clearinghouse (NATICH) subsection, September 15, 1993.

 (11)   Coutant, R.W., McClenny, W.A. Competitive Adsorption Effects and the
       Stability of VOC and PVOC in Canisters, in Proceedings of the 1991
       EPA/AWMA Symposium on Measurement of Toxic and Related Air Pollutants,
       EPA-600/9-91/018, Publication No. VIP-21, Air and Waste Management
       Association,  Pittsburgh, Pennsylvania, pp 382-388,  1991.

 (12)   CRC Handbook of Chemistry and Physics, R.C. Weast, ed., 59th Edition, CRC
       Press, Boca Raton, Florida, 1979.

 (13)   Clements, J.B., Lewis, R.G., Sampling for Organic Compounds, in Principles
       of Environmental Sampling. L.H. Keith, ed., American Chemical Society,
       Washington,  D.C., pp 287-296, 1987.

 (14)   Keith, L.H.,  Walker, M.M.  EPA's Clean Air Act Air Toxics Database.
       Volume II: Air Toxics Chemical and Physical Properties. ISBN-0-87371-820-8,
       Lewis Publishers, Boca Raton, Honda, 1993.

 (15)   Mackay, D.,  Shiu, W.Y., Ma, K.C.  Illustrated Handbook of Physical-Chemical
       Properties and Environmental Fate for Organic Chemicals. Volume HI: Volatile
       Organic Chemicals. ISBN-0-83731-973-5, Lewis Publishers, Chelsea, Michigan,
       1993.

 (16)   Howard, P.H., Boethling, R.S., Jarvis, W.F., Meylan, W.M., Michalenko,
       E.M.  Handbook of Environmental Degradation Rates, ISBN-0-87371-358-3,
       Lewis  Publishers, Chelsea, Michigan, 1991.

 (17)   Jones,  D.L.,  Bursey, J. Simultaneous Control of PM-10 and Hazardous Air
       Pollutants, II: Rationale for Selection of Hazardous Air Pollutants as Potential
       Paniculate Matter,  EPA-452/R-93/013, U.S. Environmental Protection Agency,
       Research Triangle Park, North Carolina, October 1992.

(18)   Weber, R.C., Parker, P.A., Bowser, M.  Vapor Pressure Distribution of
       Selected Organic Chemicals, EPA-600/2-81/021, U.S. Environmental Protection
       Agency, Cincinnati, Ohio, February 1981.
                                      30

-------
 (19)   Spicer, C.W., Pollack, A.J., Kelly, T.J., Mukund, R.  A Literature Review of
       Atmospheric Transformation Products of Clean Air Act Title III Hazardous Air
       Pollutants, Final Report to U.S. Environmental Protection Agency, Contract No.
       68-D80082, Battelle, Columbus, Ohio, July 1993.

 (20)   Kelly, T.J., Pollack, A.J., Mukund, R., Spicer, C.W., Cupitt, L.T. Surveys of
       the 189 CAAA Hazardous Air Pollutants: n. Atmospheric Lifetimes and
       Transformation Products, in Measurement of Toxic and Related Air Pollutants.
       Proceedings of the 1993 EPA/AWMA International Symposium, EPA Report
       No. EPA/600/A93/024, Publication VIP-34, Air and Waste Management
       Association,  Pittsburgh, Pennsylvania, pp 167-172, 1993.

 (21)   McClenny, W.A., Pleil, J.D., Evans, G.F., Oliver, K.D., Holdren, M.W.,
       Winberry, W.T.  Canister-Based Method for Monitoring Toxic VOCs in
       Ambient Air, J. Air Waste Manage. Assoc.. 1991, 41: 1308-1318.

 (22)   McClenny, W.A., Evans, G.F., Oliver, K.D., Daughtery, E.H., Jr., Winberry,
       W.T., Decker, D.L. Status of VOC Methods Development to Meet Monitoring
       Requirements for the Clean Air Act Amendments of 1990, in Measurement of
       Toxic and Related Air Pollutants. Proceedings of the 1991 U.S. EPA/A WMA
       International Symposium, Report No.  EPA-600/9-91/018, Publication VJJP-21,
       Air and Waste Management Assoc., Pittsburgh, Pennsylvania, pp 367-374,
       1991.

 (23)   Kelly, T.J., Holdren, M.W. Applicability of Canister Sampling for Hazardous
       Air Pollutants, Final Report to U.S. Environmental Protection Agency, Contract
       No. 68-DO-0007, Work Assignment 45, Subtask 4, Battelle, Columbus, Ohio,
       March 1994.

 (24)   Kelly, T.J., Callahan, P.J., Pleil, J.D., Evans, G.E. Method Development and
       Field Measurements for Polar Volatile Organic Compounds in Ambient Air,
       Environ. Sci. Technol.. 1993, 27:  1146-1153.

(25)   Oliver, K.D. Sample Integrity of Trace Level Polar VOCs in Ambient Air
       Stored in Summa-Polished Canisters, Technical Note TN-4420-93-03, submitted
       to U.S.  EPA under Contract No. 68-DO-0106, by ManTech Environmental
       Technology, Inc., Research Triangle Park, North Carolina,  November, 1993.

(26)   Pate,  B., Jayanty, R.K.M.,  Peterson,  M.R., Evans, G.F. Temporal Stability of
       Polar Organic Compounds in Stainless Steel Canisters,  J. Air Waste Manage.
       Assoc.. 1992, 42: 460-462.
                                      31

-------
(27)   Coutant, R.W. Theoretical Evaluation of Stability of Volatile Organic
      Chemicals and Polar Volatile Organic Chemicals in Canisters, Final Report to
      U.S. EPA, Contract No. 68-DO-0007, Work Assignment No. 45, Subtask 2,
      Battelle, Columbus, Ohio,  September 1993.

(28)   Holdren, M.W. and Winberry, W.T.  Method TO-15: The Determination of
      Volatile Organic Compounds (VOCs) in Air Collected in Summa Canisters and
      Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS), Final Report to
      U.S. EPA, Contract No. 68-DO-0007, Work Assignment No. 40, Battelle,
      Columbus, Ohio, March 1994.
                                    _32

-------
                      APPENDIX A

RESULTS OF THE SURVEY OF CHEMICAL AND PHYSICAL PROPERTIES
                     OF THE 189 HAPs
                          33

-------
Table A-l. Physical Properties of the 189 Compounds in the HAPs List.
Compound
Acetaldehyde; C2H4O
Acetamide; C2HSNO
Acetonitrile; C2H3N
Acetophenone; CBHeO
2-Acetylaminofluorene; C15H13NO
Acrolein; C3H4O
Acrylamide; C3HSNO
Acrylic acid; C3H4O2
Acrylonitrile; C3H3N
Allyl chloride; C3H5CI
4-Aminobiphenyl; C12HnN
Aniline; CeH7N
o-Anisidine; C7H9NO
Asbestos
Benzene; C8He
Benzidine; C12H12N2
Benzotrichloride; C7H6CI3
Benzyl chloride; C7H7CI
Biphenyl; C12H10
Bis(2-ethylhexyl) phthalate; C2«H3BO«
CAS No.
75-07-0
60-35-5
75-05-8
98-86-2
53-96-3
107-02-8
79-06-1
79-10-7
107-13-1
107-05-1
92-67-1
62-53-3
90-04-0
1332-21-4
71-43-2
92-87-5
98-07-7
100-44-7
92-52-4
117-81-7
MW
44.0
59.0
41.0
120.0
223.3
56.0
71.0
72.0
53.0
76.5
169.0
93.0
123.0
-
78.0
184.2
195.5
126.6
154.0
390.5
Compound
Class1
woe
svoc
voc
voc
NVOC
voc
voc
voc
voc
voc
svoc
voc
svoc
NVINC
voc
svoc
svoc
voc
svoc
svoc
VP2
(mm Hg/ 25°C)
952.0
7.2E-02
74.0
1.0
1.1E-12(?)
220.0
0.53
3.2
100.0
340.0
6.0E-05
0.67
0.1
Very low
76.0
1.0E-05
7.6E-02
1.0
3.9E-04
1.4E-07
BP2
rc)
21
222
82
202
444
53
125/25 mm
141
77
45
302
184
224
Decomposes
at1112°C
80
402
213
179
254
384
Water
Solubility3
(g/Lat'C)
33.0 / 25
>100/22
>1 00/22
6.3 / 25
<0. 1/20.5
>100/21
>100/22
>100/17
716.0 /254
19.5/204
O.1/19
1.0/25*
<0.1/19
Insoluble
1-5/18
<1/22
Reacts
Reacts
Insoluble
0.1/22
Comment





Reactive 5
Reactive 5





Reactive8



Reactive5
Reactive (?)8



-------

Compound
Bis(chloromethyl) ether; C2H4CI2O
Bromofonm; CHBr3
1,3-Butadiene;C4He
Calcium cyanamide; CaCN2
Caprolactam; CgHuNO
Captan; CeHBCI3NO2S
Caibaryl; C12H11NO2
Carbon disulfide; CS2
Carbon tetrachloride; CCI4
Carbonyl sulfide; COS
Catechol; CeH8O2
Chloramben; C7H5CI2NO2
Chlordane; C10HBCle
Chlorine; CI2
Chloroacetic acid; C2H3CIO2
2-Chloroacetophenone; C9H7CIO
Chlorobenzene; CeHsCI
Chlorobenzilate; C18H14CI2O3
Chloroform; CHCI3
Chloromethyl methyl ether; C2HSCIO

CAS No.
542-88-1
75-25-2
106-99-0
156-62-7
105-60-2
133-06-2
63-25-2
75-15-0
56-23-5
463-58-1
120-80-9
133-90-4
57-74-9
7782-50-5
79-11-8
532-27-4
108-90-7
510-15-6
67-66-3
107-30-2
Table A-l. (continued)
MW
115.0
252.8
54.0
80.0
113.0
300.6
201.2
76.0
153.8
60.1
110.0
206.0
409.8
70.9
94.5
154.6
112.6
325.2
119.0
80.5
Compound
Class1
voc
voc
woe
NVINC
SVOC
SVOC
SVOC
voc
voc
woe
voc
SVOC
SVOC
WINC
voc
SVOC
voc
SVOC
voc
voc
VP2
(romHg/25'C)
30.0
5.6
2000.0
«1.0E-10
1.0E-03
9.7E-07
1.4E-06
260.0
90.0
3700.0
0.2
4.7E-06
9.8E-6
4000.0
0.7
1.2E-02
8.8
2.2E-06
160.0
224.0
BP2
(*C)
104
149
-5
1175
139/1 2 mm
479
331
47
77
-50
240
350
175/2 mm
-34
189
245
132
415
61
59
Water
Solubility3
(g/Lat°C)
Reacts
<0.1/22.5
Insoluble
Insoluble
>100/20.5
<1/20
40 /
<1/20
<1/21
>100/20
>100/21.5
<0.1/22
<1/23
>100/0
>100/20
<1/19
<1/20
<0.1/22
0.85 / 20 - 24<
Reacts
Comment
Reactive7

Reactive (?)8
Reactive5

Pesticide
Pesticide




Pesticide
Pesticide - mixture of compds; VP
for a- or y- chlordane




Pesticide

Reactive'

-------

Compound
Chloroprene (2-chloro-1 ,3-butadiene);
C4H5CI
Cresol/Cresylic acid (isomer mixture);
C7H8O
o-Cresol; C7HaO
m-Cresol; C7H9O
p-Cresol; C7H8O
Cumene; C9H,2
2,4-0 (2,4-dichlorophenoxyacetic acid, incl
salts & esters); CaH8CI2O3
DDE (1 ,1-dichloro-2.2-bis(p-chlorophenyl)
ethylene); C14H8CI4
Diazomethane; CH2N2
Dibenzofurans:
Dibenzofuran; C12HBO
Tetrachlorodibenzofuran; C12H4CI4O
1 ,2-Dibromo-3-chloropropane; C3HsBr2CI
Dibutytphthalate; CiaH22O4
1,4-Dichlorobenzene (p-); C6H4CI2
3,3'-Dichlorobenzidine;C12H10CI2N2
Dichloroethyl ether (Bis[2-
Chloroethyljether); C4H8CI2O
1,3-Dichloropropene; C3H4CI2 (cis)
Dichlorvos; C4H7CI2O4P
Diethanolamine; C4H11NO2
Diethyl sulfate; C4H10O4S

CAS No.
126-99-8
1319-77-3
95-48-7
108-39-4
106-44-5
98-82-8
-
72-55-9
334-88-3
132-64-9
5120-31-9
96-12-8
84-74-2
106-46-7
91-94-1
111-44-4
542-75-6
62-73-7
111-42-2
64-67-5

MW
88.5
108.0
108.0
108.0
108.0
120.0
-
318.0
42.1
168.0
306.0
236.4
278.4
147.0
253.0
143.0
111.0
221.0
105.0
154.0
Table A-l. (continued)
Compound
Class1
VOC
VOC
VOC
SVOC
SVOC
VOC
SVOC/NVOC
SVOC
woe
SVOC
SVOC
VOC
SVOC
VOC
SVOC
VOC
VOC
SVOC
SVOC
VOC
VP2
(mm Hg/ 25°C)
226.0
0.3
0.2
4.0E-02
4.0E-02
3.2
1.0E-04 to
1.0E-10
2.4E-05
2800.0
4.4E-03
1.1E-06
0.8
4.2E-05
0.6
2.6E-06
0.7
27.8
5.3E-02
1.0E-02
0.29
BP2
<8C)
59
202
191
202
202
153
135/1 mm
350
-23
287
429
196
340
173
402
178
112
140/20 mm
269
208
Water
Solubility3
(g/Lat'C)
Slightly soluble

25.9/25
10-50/20
<1/21
Insoluble

<0.1/22
Reacts
Slightly
<1/20
<0.1/18
<1/20
<1/23
Insoluble
Reacts
<0.1 / 16.5
0.01 /
>100/14
Reacts
Comment






Pesticide; VP range for acid,
esters, and salts; BP for acid
Pesticide
Highly reactive5
Higher chlorinated species (e.g.,
octa) are SVOCs to NVOCs




Reactive (?)8

Pesticide
Reactive (?)8 ; strong base
Reactive (?)8

-------
Table A-l. (continued)
Compound
3,3'-Dimethoxybenzidine; C14HieN2O2
4-Dimethyl aminoazobenzene; C14H15N3
N.N-Dimethylaniline; CgH^N
3,3'-Dimethylbenzidine; C14H16N2
Dimethylcarbamoylchloride; C3HeCINO
N,N-Dimethylfoimamide; C3H7NO
1,1-Dimethylhydrazine; C2H8N2
Dimethyl phthalate, C10H10O2
Dimethyl sulfate; C2HeO4S
4,6-Dinitro-o-cresol & salts; C7H6N2O5
2,4-Dinitrophenol; C,H4N2OS
2,4-Dinitrotoluene; C7H6N2O4
1 ,4-Dioxane (1 ,4-Diethylene oxide);
C4H802
1 ,2-Diphenylhydrazine; C12H12N2
Epichlorohydrin (1-chloro-2.3-epoxy
propane); C3H5CIO
1,2-Epoxybutane; C4H6O
Ethyl acrylate; C5H8O2
Ethylbenzene; CaH10
Ethyl carbamate (urethane); C3H7NO2
Ethyl chloride; C2H5CI
CAS No.
119-90-4
60-11-7
121-69-7
119-93-7
79-44-7
68-12-2
57-14-7
131-11-3
77-78-1
534-52-1
51-28-5
121-14-2
123-91-1
122-66-7
106-89-8
106-88-7
140-88-5
100-41-4
51-79-6
75-00-3
MW
244.0
225.3
121.0
212.3
107.6
73.0
60.0
194.0
126.1
198.1
184.0
182.0
88.0
184.3
92.5
72.0
100.0
106.0
89.0
64.5
Compound
Class1
NVOC
NVOC
VOC
SVOC
VOC
VOC
VOC
SVOC
VOC
SVOC
SVOC
SVOC
VOC
SVOC
VOC
VOC
VOC
VOC
VOC
woe
Vp2
(mm Hg/ 25"C)
3.2E-13
6.8E-10
0.5
2.9E-07
4.9
2.7
157.0
8.9E-03
1.0
8.3E-05
1.0E-05
3.7E-03
37.0
8.0E-02
12.0
163.0
29.3
7.0
0.54
1000.0
BP2
(°C)
458
407
192
300
166
153
63
282
188
312
Sublimes on
heating
300
101
220
117
63
100
136
183
13
Water
Solubility3
(grt.at8C)
<0.1/20
<1/22
<1/21
<1/19
Reacts
>100/22
Reacts
<1/20
>100/20
slightly soluble
<1/19.5
O.1/17
>100/20
Insoluble
50-100/22
>100/17
4.2 / 204
<1/23
>100/22
>100/20
Comment




Highly reactive7

Reactive (?)8

Reactive (?)8
Pesticide; VP, BP for the cresol;
salts are probably NVOCs



Reactive (?)8
Highly reactive6
Reactive8





-------

Compound
Ethylene dibromide; C2H4Br2
Ethylene dichloride; C2H4CI2
Ethylene gtycol; C2H6O2
Ethyleneimine; C2H5N
Ethylene oxide; C2H4O
Ethylene thiourea; C3H8N2S
Ethylidene dichloride; C2H4CI2
Formaldehyde; CH2O
Heptachlon C10HSCI7
Hexachlorobenzene; CeCI8
Hexachlorobutadiene; C4Cle
1 ,2,3.4,5,6- Hexachlorocyclohexane
(Lindane) (all isomers); C8HeCle
Hexachlorocyclo pentadiene; C5Cle
Hexachloroethane; C2Cle
Hexamethylene-1 ,6-diisocyanate;
CeH12N202
Hexamethylphosphoramide; CeH19N3OP
Hexane; CeH14
Hydrazine; H4N2
Hydrogen chloride; HCI
Hydrogen fluoride; HP
Hydroquinone; CeHeO2

CAS No.
106-93-4
107-06-2
107-21-1
151-56-4
75-21-8
96-45-7
75-34-3
50-00-0
76-44-8
118-74-1
87-68-3
58-89-9
77-47-4
67-72-1
822-06-0
680-31-9
110-54-3
302-01-2
7647-01-0
7664-39-3
123-31-9
Table A-l. (continued)
MW
187.9
99.0
62.0
43.0
44.0
102.0
99.0
30.0
373.3
284.8
260.8
290.8
272.8
236.7
168.2
179.2
86.2
32.1
36.5
20.0
110.0
Compound
Class1
voc
voc
svoc
voc
woe
svoc
voc
woe
svoc
svoc
voc
svoc
svoc
voc
svoc
svoc
voc
VINC
VINC
WINC
svoc
Vp2
(mm Hg/ 25°C)
11.0
61.5
5.0E-02
160.0
1100.0
1.5E-06
230.0
2700.0
2.3E-04
9.5E-04
0.4
5.6E-05
4.0E-02
0.4
1.9E-03
9.0E-02
120.0
16.0
23.5
900.0
7.2E-06
BP2
rc)
132
84
198
56
11
450
57
-20
145/1 .5 mm
324
215
323
234
Sublimes
at 186
255
233
69
113
110
20
218
Water
Solubility3
(g/Lat'C)'
<1/21
5-10/19
>100/17.5
Miscible
Miscible
1-5/18
<1/20
>1 00/20.5
<0.1/18
<1/20
O.1/22
<1/24
<0.1/21.5
<1/21

>100/18
<1/16.5
Miscible
>100/20
Very soluble
10-50/20
Comment
Pesticide
Pesticide

Reactive (?)8
Reactive6



Pesticide
Pesticide

Pesticide
Reactive (?)8

Reactive (?)8







-------

Compound
Isophorone; CeH14O
tfaleic anhydride; C4H2O3
Methanol; CH40
Methoxychlor; CieH1sCl3O2
Methyl bromide; CH3Br
Methyl chloride; CH3CI
Methyl chloroform (1 ,1 ,1-trichloroethane);
C2H3Cl3
Methyl ethyl ketone (2-butanone); C4H8O
Methylhydrazine; CHBN2
Methyl iodide (iodomethane); CH3I
Methyl isobutyl ketone (hexone); C8H12O
Methyl isocyanate; C2H3NO
Methyl methacrylate; C5H8O2
Methyl ter-butyl ether; C5H12O
4,4'-Methylenebis(2-chloroan!line);
C13H12CI2N2
Methylene chloride; CH2CI2
4,4'-Methylenediphenyl diisocyanate (MDI);
Ci$H10N2O2
4,4'-Methylenedianiline; C13H14N2
Naphthalene; C10H8
Nitrobenzene; CeHsNO2
4-Nitrobiphenyl; C12H9NO2

CAS No.
78-59-1
108-31-6
67-56-1
72-43-5
74-83-9
74-87-3
71-55-6
78-93-3
60-34-4
74-88-4
108-10-1
624-83-9
80-62-6
1634-04-4
101-14-4
75-09-2
101-68-8
101-77-9
91-20-3
98-95-3
92-93-3
Table A- 1. (continued)
MW
138.2
98.0
32.0
345.7
94.9
50.5
133.4
72.0
46.1
141.9
100.2
57.1
100.1
86.0
267.2
84.9
250.3
198.3
128.2
123.0
199.2
Compound
Class1
VOC
SVOC
VOC
SVOC
woe
woe
VOC
VOC
VOC
woe
VOC
VOC
VOC
VOC
NVOC
VOC
SVOC
NVOC
SVOC
VOC
SVOC
Vp2
(mm Hg/ 25'C)
0.38
5.0E-05
92.0
1.4E-06
1800.0
3800.0
100.0
77.5
49.6
400.0
6.0
348.0
28.0
249.0
3.9E-16
349.0
1.0E-03
1.7E-10
4.9E-02
0.15
4.0E-07
BP2
(•C)
215
202
65
447
4
-24
74
80
88
42
117
60
101
55
517
40
538
393
218
211
340
Water
Solubility3
(g/Lat'C)
0.1-1/18
Soluble
>100/21
<1/23
Slightly soluble
Slightly soluble
<1/20
>100/19
<1/24
10-50/18
1-5/21
Reacts
*
15.9/20
Soluble
<1/25
10-50 / 21
Insoluble
<1/19
<1/22
1.9/25
Insoluble
Comment

Reactive5

Pesticide
Pesticide



Highly reactive7


Highly reactive7




Reactive (?)8

PAH



-------

Compound
4-Nttrophenol; C6H5NO3
2-Nitropropane; C3H7NO2
N-Nitroso-N-methylurea; C2H5N302
N-Nitrosodimethytamine; C2H8N2O
N-Nitrosomorpholine; C100/19
>100/19
<1/23
<1/22
<1/20
50-100/19
Soluble
Slightly soluble
Slightly soluble
0.0003%
Reacts
Insoluble
Insoluble
0.1
37.0/20
50-100/18
Slightly soluble
Comment


Reactive'
Reactive7

Pesticide

Pesticide


Reactive (?)8
Pesticide
Highly reactive (red and white
forms)
Reactive5
Higher chlorinated species (upto
deca-) are NVOCs
Reactive (?)8


Pesticide

-------

Compound
Propylene dichloride (1,2-dichloropropane);
C3H6CI2
Propylene oxide; C3H8O
1 ,2-Propyleneimine (2-methylaziridine);
C3H7N
Quinoline; CflH7N
Quinone; CeH4O2
Styrene; C8He
Styrene oxide; C«H8O
2,3,7,8-Tetrachlorodibenzo-p-dioxin;
C12H4CI402
1,1,2,2-Tetrachloroethane; C2H2CI4
Tetrachloroethylene; C2CI4
Titanium tetrachloride; TiCI4
Toluene; C7HB
2,4-Toluenediamine; C7H10N2
2,4-Toluene diisocyanate; C9HeN2O2
o-Toluidine; C7H9N
Toxaphene (chlorinated camphene);
C10H10Cla
1,2,4-Trichlorobenzene; CeH3CI3
1.1,2-Trichloroethane; C2H3CI3
Trichloroethytene; C2HCI3
2,4,5-Trichlorophenol; C«H3CI3O
2,4,6-Trichlorophenol; C«H3CI3O

CAS No.
78-87-5
75-56-9
75-55-8
91-25-5
106-51-4
100-42-5
96-09-3
1746-01-6
79-34-5
127-18-4
7550-45-0
108-88-3
95-80-7
584-84-9
95-53-4
8001-35-2
120-82-1
79-00-5
79-01-6
95-95-4
88-06-2

MW
113.0
58.0
57.1
129.2
108.0
104.0
120.2
322.0
167.9
165.8
154.2
92.0
122.2
174.2
107.2
413.8
181.5
133.4
131.4
197.5
197.5
Table A-l. (continued)
Compound
Class1
VOC
woe
VOC
SVOC
SVOC
VOC
VOC
SVOC
VOC
VOC
VINC
VOC
SVOC
SVOC
SVOC
SVOC
VOC
VOC
VOC
SVOC
SVOC
VP2
(mm Hg/ 25'C)
42.0
445.0
112.0
9.5E-02
1.0E-02
6.6
0.3
3.6E-06
5.0
14.0
0.3
22.0
3.2E-05
1.0E-02
0.1
1.1E-05
0.2
19.0
20.0
2.2E-02
1.1E-03
BP2
<°C)
97
34
66
238
201
145
194
495
146
121
136
111
292
251
200
155/0.4 mm
213
114
87
252
245
Water
Solubility3
(g/L at °C)
O.1/21.5
400 / 20
>100/19
<0.1/22.5
Slightly soluble
<1/19
<1/19.5
<1/25
O.1/22
<0.1/17
Soluble
<1 /18
*!
1-5/21
Reacts
5-10/15
<1/19
<1/21
1-5/20
<1 /21
<0.1/18
<1/21
Comment
Pesticide
Reactive8
Highly Reactive (?)8



Highly reactive7



Highly reactive in air, forms TiO2


Reactive5

Pesticide; complex mixture of
somers



'esticide
'esticide

-------
Table A-1. (continued)
Compound
Triethylamine; C6H15N
Trifluralin; C13H18F3N3O4
2,2,4-Trimethyl pentane; C8H18
Vinyl acetate; C«H6O2
Vinyl bromide (bromoethene); C2H3Br
Vinyl chloride (chloroethene); CjH3CI
Vinylidene chloride (1,1-dichloroethylene);
C2H2CI2
Xylene (isomer mixture); CaH10
o-Xylene; C8H10
m-Xylene; C8Hto
p-Xylene; C8H10
Antimony Compounds: participate
Arsenic compounds:
Arsine, AsH3
Particulate
Beryllium compounds: particulate
Cadmium compounds: particulate
Chromium compounds: particulate
Cobalt compounds: particulate
CAS No.
121-44-8
1582-09-8
540-84-1
108-05-4
593-60-2
75-01-4
75-35-4
1330-20-7
95-47-6
108-38-3
106-42-3
-
7784-42-1
-
-
-
-
-
MW
101.2
335.3
114.0
86.0
107.0
62.5
97.0
106.2
106.2
106.2
106.2
-
78.0
-
-
-
-
-
Compound
Class1
VOC
SVOC
VOC
VOC
woe
woe
woe
VOC
VOC
VOC
VOC
NVINC
WINC
NVINC
NVINC
NVINC
NVINC
NVINC
VP2
(mm Hg/ 25'C)
54.0
1.0E-04
40.6
83.0
1100.0
3200.0
500.0
6.7
5.0
6.0
6.5
1 mm / 574°C
>760
1mm/212°C

1mm/1000°C


BP2
(«C)
90
140/4.2 mm
99
72
16
-14
32
142
144
139
138
656 °C (mp)
-63
313(mp)




Water
Solubility3
(g/LafC)
Soluble
<0.1 /22.5
Insoluble
Insoluble
Insoluble
Slightly soluble
5-10/21
<1/22
Insoluble
Insoluble
Insoluble
Insoluble
20 ml/ 100 cc
cold water
Insoluble
Insoluble
Insoluble
Insoluble
Insoluble
Comment
Reactive (?)8 ; strong base
Pesticide









VH and NIK for antimony
trioxide20; Volatile forms exist,
e.g.. stibene, SbH,

VP and MP given for arsenic
trioxide20

VP given for cadmium oxide20
Semi-volatile forms can also exist
in air, e.g., Cr(CO)8
Semi-volatile forms can also exist
in air, e.g., Co(CO)4

-------

Compound
Coke Oven Emissions
Naphthalene; C10H1B
Coronene
Cyanide Compounds
Hydrogen Cyanide; HCN
Particulate
Glycol ethers
Lead compounds: particulate
Manganese compounds: particulate
Mercury Compounds
Mercury Vapor
Particulate
Fine mineral fibers (incl. glass)
Nickel compounds: particulate
Polycyclic Organic Matter (POM):
Naphthalene; C10Hie
Coronene

CAS No.
91-20-3
191-07-1
74-90-8
-
-
-
-
7439-97-6
-
-
-
91-20-3
191-07-1
Table A- 1 . (continued)
MW
128.2
300.4
27.0
-
76.1-
206.3
-
-
200.6
-
-
-
128.2
300.4
Compound
Class1
SVOC
NVOC
WING
NVINC
SVOC/VOC
NVINC
NVINC
SVINC
NVINC
NVINC
NVINC
SVOC
NVOC
VP2
(mm Hg/ 25°C)
8.7E-02
1.5E-12
630.0

0.022 to 10.9
1 mm / 943°C

0.0012 mm/
20°C



8.7E-02
1.5E-12
BP2
(*C)
218
525
26

120-249
890 (mp)

356



218
525
Water
Solubility3
(g/Lat'C)
Insoluble
Insoluble
Soluble
Insoluble
10-100/22'C
Insoluble
Insoluble

Insoluble
*
Insoluble
Insoluble
Insoluble
Insoluble
Comment
Emissions include VOCs, e.g.,
benzene, toluene, xylenes



VP and MP given for lead oxide20




Volatile forms can also exist
briefly in air, e.g., Ni(CO)<
PAH
PAH

-------
                                                 Table A-l. (continued)
Compound
Radionuclides
Various (particulate and gaseous)
Radon; Rn-222
Selenium compounds: particulate
CAS No.
10043-92-2
14859-67-7
-
MW
-
222.0
-
Compound
Class1
NVINC
WING
NVINC
(mm Hg/ 25°C)

-
1mm/157"C
BP2

-62
340 (mp)
Water
Solubility3
(g/Lat'C)

224 cc
Insoluble
Comment
Reactive (?)8
Noble gas
VP and MP given for selenium
dioxide20
Footnotes:
1 Compound Classes:
   WOC = Very Volatile Organic Compounds (Vapor Pressure at 25°C >380 mm Hg)
   WINC or Gases = Very Volatile Inorganic Compounds (Vapor Pressure at 25°C >380 mm Hg)
   VOC  = Volatile Organic Compounds (1 .OE-01 < Vapor Pressure at 25°C <380 mm Hg)
   VINC or Gases = Volatile Inorganic Compounds (1.OE-01 < Vapor Pressure at 25°C <380 mm Hg)
   SVOC = Semi-Volatile Organic Compounds (1.0E-07< Vapor Pressure at 25°C <1.OE-01 mm Hg)
   SVINC = Semi-Volatile Inorganic Compounds (1.0E-07< Vapor Pressure at 25°C <1.OE-01 mm Hg)
   NVOC = Non-Volatile Organic Compounds (Vapor Pressure at 25°C < 1.0E-07 mm Hg)
   NVINC = Non-Volatile Inorganic Compounds (Vapor Pressure at 25°C < 1 .OE-07 mm Hg)
2 Vapor Pressure (VP) and Boiling Point (BP)/Melting Point (MP) data from:
   (a)  D.L. Jones and J. Bursey, "Simultaneous Control of PM-10 and Hazardous Air Pollutants II: Rationale for
        Selection of Hazardous Air Pollutants as Potential Particulate Matter," Report EPA-452/R-93/013,
        U.S. Environmental Protection Agency, Research Triangle Park, NC, October 1992.
   (b)  R.C. Weber, P.A. Parker, and M. Bowser, Vapor Pressure Distribution of Selected Organic Chemicals, Report
        EPA-600/2-81-021, U.S. Environmental Protection Agency, Cincinnati, OH, February 1981.
   (c)  R.C. Weast, ed., "CRC Handbook of Chemistry and Physics," 59th  edition, CRC Press. Boca Raton, 1979.
9 Solubility data from (unless otherwise indicated):
        D. Mackay, W.Y. Shui, and K.C. Ma,  "Illustrated Handbook of Physical-Chemical Properties and Environmental
        Fate for Organic Chemicals:  Volume III Volatile Organic Chemicals," Lewis Publishers, Ann Arbor, Ml, 1993.
4 Obtained from the STN International computer database  (BEILSTEIN file)
5 The Merck Index, 11th Edition, S. Budavari,  ed., Merck & Co., Inc., Rahway, NJ, 1989.
8 R.T. Morrison and R.N. Boyd, "Organic Chemistry," 2nd Edition, Allyn and Bacon, Inc., Boston, MA, 1966.
7 From reactivity data in Table B-1.
8 Reactive (?) or Highly  Reactive (?) indicates judgment based on properties, personal communication from
  Robert G. Lewis, U.S.  EPA, March 1994.

-------
                             APPENDIX B

   PHYSICAL AND CHEMICAL PROPERTIES OF THE VOLATILE ORGANIC
                    COMPOUNDS ON THE HAPs LIST
1.     Table of Physical and Chemical Properties (Table B-l).

2.     Discussion of Polarizability and Water Solubility Characteristics of VOCs.
                                 45

-------
Table B-l. Physical and Chemical Properties of Volatile Organic Compounds in the HAPs List.
Compound
Acetaldehyde
Acetonitrile
Acetophenone
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Ally! chloride
Aniline
Benzene
Benzyl chloride
Bis(chloromethyl) ether
Bromoform
1,3-Butadiene
Carbon disulfide
Carbon tetrachloride
Carbonyl sulfide
Catechol
Chloroacetic acid
Chlorobenzene
Chloroform
Chloromethyl methyl ether
Chloroprene
Cresol/Cresylic acid
o-Cresol
Cumene
Diazomethane
1 ,2-Dibromo-3-chloropropane
1 ,4-Dichlorobenzene
Dichloroethyl ether
CAS No.
75-07-0
75-05-8
98-86-2
107-02-8
79-06-1
79-10-7
107-13-1
107-05-1
62-53-3
71-43-2
100-44-7
542-88-1
75-25-2
106-99-0
75-15-0
56-23-5
463-58-1
120-80-9
79-11-8
108-90-7
67-66-3
107-30-2
126-99-8
1319-77-3
95-48-7
98-82-8
334-88-3
96-12-8
106-46-7
111-44-4
Sub-
category1
woe
VOC
voc
VOC
voc
voc
voc
voc
voc
voc
voc
voc
voc
woe
voc
voc
woe
voc
voc
voc
voc
voc
voc
voc
voc
voc
woe
voc
voc
voc
VP2
(mm Hg at
25°C)
952.0
74.0
1.0
220.0
0.53
3.2
100.0
340.0
0.67
76.0
1.0
30.0
5.6
2000.0
260.0
90.0
3700.0
0.22
0.69
8.80
160.0
224.0
226.0
0.26
0.24
3.20
2800.0
0.80
0.60
0.71
Polarlzablllty3
(cm3/mole)
11.6
11.0
36.3
16.2
-
17.4
15.6
20.5
30.6
26.2
36.0
22.6
29.6
22.4
21.5
26.5
12.6
32.9
17.6
31.1
21.4
18.2
25.2
32.5
32.2
40.5
-
36.3
36.3
32.0
Water Solubility4
(g/L at °C)
33.0/25
>100/22
6.3 / 25
>100/21
>100/22
>100/17
716.0 / 25"
19.5/208
1.0/258
1-5/18
Reacts
Reacts
<0. 1/22.5
Insoluble
<1/20
<1/21
>100/20
>100/21.5
>100/20
<1/20
0.85 / 20-24°
Reacts
Slightly soluble

25.9 / 25
Insoluble
Reacts
<0.1/18
<1/23
Reacts
Reactivity & tVl range5
Aqueous6

aab
_
aab
_
aab
aab
ah
—
aab
ah
ah
aab
aab
-
aab
-
aab
aab
aab
aab
ah
aab
aab
aab
aab
-
aab
aab
aab
	
7-28d

7-28d
_
1-7d
1-23d
7-14d
_
5-16d
12d
0.01-0.1h
28-1 80d
7-28d
—
0.5-1y
—
1-7d
1-7d
68-1 50d
28-168d
0.01-0.03h
28-1 80d
0.04-29d
1-7d
3-22d
-
14-180d
28-1 80d
28-180d
Air

54-541 d
	
3-34h
_
3-24h
0.6-8d
3-29h

2-21 d
1-9d
0.2-2h
54-54 1d
1-8h
_
2-1 8y
~
3-26h
9-86d
3-30d
26-260d
1-10d
3-28h
1-16h
2-1 6h
10-97h
—
6-61 d
8-84d
10-97h
Other7

Polar
Polar
Polar
Polar
Polar
Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Polar
Polar
Polar
Non-Polar
Non-Polar
Polar
Non-Polar
Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Polar

-------
Table B-l. (continued)
Compound
1 ,3-Dichloropropene
Diethyl sulfate
N.N-Dimethylaniline
Dimethylcarbamyl chloride
N,N-Dimethylformamide
1 ,1-Dimethylhydrazine
Dimethyl sulfate
1,4-Dioxane
Epichlorohydrin
1,2-Epoxybutane
Ethyl acrylate
Ethylbenzene
Ethyl carbamate
Ethyl chloride
Ethylene dibromide
Ethylene dichloride
Ethyleneimine
Ethylene oxide
Ethylidene dichloride
Formaldehyde
Hexachlorobutadiene
Hexachloroethane
Hexane
Isophorone
m-Xylene
Methanol
Methyl bromide
Methyl chloride
Methyl chloroform
Methyl ethyl ketone
Methylhydrazine
CAS No.
542-75-6
64-67-5
121-69-7
79-44-7
68-12-2
57-14-7
77-78-1
123-91-1
106-89-8
106-88-7
140-88-5
100-41-4
51-79-6
75-00-3
106-93-4
107-06-2
151-56-4
75-21-8
75-34-3
50-00-0
87-68-3
67-72-1
110-54-3
78-59-1
108-38-3
67-56-1
74-83-9
74-87-3
71-55-6
78-93-3
60-34-4
Sub-
category1
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
VOC
woe
VOC
VOC
VOC
woe
VOC
woe
VOC
VOC
VOC
VOC
VOC
VOC
woe
woe
VOC
VOC
VOC
VP2
(mm Hg at
25"C)
27.8
0.29
0.50
4.9
2.7
157.0
1.0
37.0
12.0
163.0
29.3
7.0
0.54
1000.0
11.0
61.5
160.0
1100.0
230.00
2700.0
0.40
0.40
120.0
0.38
6.0
92.0
1800.0
3800.0
100.0
77.5
49.6
Polarlzability3
(cm3/mole)
25.5
31.6
40.8
-
19.9
18.7
-
21.4
20.5
20.3
26.6
35.7
22.6
16.2
27.0
21.0
-
11.2
21.1
8.4
49.8
-
29.9
42.1
36.0
8.2
15.0
11.5
26.2
20.7
13.7
Water Solubility4
(g/Lat'C)
<0.1 / 16.5
Reacts
<1/21
Reacts
>100/22
Reacts
>100/20
>100/20
50-100/22
>100/17
4.2 / 209
<1/23
>100/22
>100/20
<1/21
5-10/19
Miscible
Miscible
<1/20
> 100/20.5
<0.1 /22
<1/21
<1 / 16.5
0.1-1/18
Insoluble
>100/21
Slightly soluble
Slightly soluble
<1/20
>100/19
<1/24
Reactivity & t./, range5
Aqueous6
ah
ah
aab
ah
-
aab
ah
aab
aab
ah
aab
aab
aab
aab
aab
aab
aab
ah
aab
aab
aab
aab
-
aab
aab
aab
aab
ah
aab
aab
aab
5-1 1d
2-1 2h
17-180d
0.05h
-
8-24d
1-12h
28-1 80d
7-28d
12d
1-7d
3-1 Od
1-7d
7-28d
28-1 80d
100-180d
7-28d
11d
32-1 50d
1-7d
28-1 80d
28-1 80d
-
7-28d
7-28d
1-7d
28-1 80d
292d
0.4-0.5y
1-7d
13-24d
Air
5-80h
4-36h
3-2 1h
1-10h
-
1-8h
2-1 5d
0.3-3d
6-61d
1-13d
2-23h
9-86h
3-30h
7-67d
11-107d
12-122d
11-105h
38-382d
10-1 03d
1-6h
0.3-3y
7-73y
-
0.4-3h
3-26h
3-30d
68-680d
61-613d
0.6-6y
3-27d
0.1-0.4h
Other7
Non-Polar
Polar
Polar
Polar
Polar
Non-Polar
Polar
Polar
Polar
Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Non-Polar
Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Non-Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Non-Polar
Polar
Non-Polar

-------
Table B-l. (continued)
Compound
Methyl iodide
Methyl isobutyl ketone
Methyl isocyanate
Methyl methacrylate
Methyl ter-butyl ether
Methylene chloride
Nitrobenzene
2-Nitropropane
N-Nitroso-N-methylurea
N-Nitrosodimethylamine
N-Nitrosomorpholine
Phenol
Phosgene
1.3-Propanesultone
Beta-Propiolactone
Propionaldehyde
Propylene dichloride
Propylene oxide
1,2-Propyleneimine
Styrene
Styrene oxide
1 , 1 ,2,2-Tetrachloroethane
Tetrachloroethylene
Toluene
1 ,2,4-Trichlorobenzene
1,1,2-Trichloroethane
Trichloroethylene
Triethylamine
2,2,4-Trimethyl pentane
Vinyl acetate
Vinyl bromide
CAS No.
74-88-4
108-10-1
624-83-9
80-62-6
1634-04-4
75-09-2
98-95-3
79-46-9
684-93-5
62-75-9
59-89-2
108-95-2
75-44-5
1120-71-4
57-57-8
123-38-6
78-87-5
75-56-9
75-55-8
100-42-5
96-09-3
79-34-5
127-18-4
108-88-3
120-82-1
79-00-5
79-01-6
121-44-8
540-84-1
108-05-4
593-60-2
Sub-
category1
woe
voc
voc
voc
voc
voc
voc
voc
voc
voc
voc
voc
woe
voc
voc
voc
voc
woe
voc
voc
voc
voc
voc
voc
voc
voc
voc
voc
voc
voc
woe
VP2
(mm Hg at
258C)
400.0
6.0
348.0
28.0
249.0
349.0
0.15
10.0
10.0
3.7
0.32
0.20
1200.0
2.0
3.4
235.0
42.0
445.0
112.0
6.6
0.3
5.0
14.0.
22.0
0.18
19.0
20.0
54.0
40.6
83.0
1100.0
Polarizablllty9
(cm3/mole)
19.3
30.0
14.0
26.5
26.2
16.4
32.7
21.6
-
19.3
-
28.0
-
-
15.7
16.1
25.7
15.7
17.6
36.4
35.5
30.7
30.3
31.0
41.0
25.9
25.4
33.8
39.2
22.2
18.9
Water Solubility4
(g/Lat°C)
10-50/18
1-5/21
Reacts
15.9/20
Soluble
10-50/21
1.9/25
1.7/20
<1/18
>100/19
>100/19
50-100/19
Slightly soluble
100 /
37/20
50-100/18
<0.1/21.5
400 / 20
>100/19
<1/19
<1 / 19.5
O.1/22
<0.1 / 17
<1/18
<1/21
1-5/20
<1/21
Soluble
Insoluble
Insoluble
Insoluble
Reactivity & t,/t range5
Aqueous5
aab
aab
ah
aab
aab
aab
aab
aab
ah
aab
aab
aab
aab
ah
ah
aab
aab
ah
aab
aab
ah
ah
aab
aab
aab
aab
aab
-
-
aab
aab
7-28d
1-7d
0.14-0.33h
7-28d
28-180d
7-28d
13-200d
28-1 80d
0.01-3.5h
21-180d
28-1 80d
6-84h
7-28d
0.4-28d
3-22d
1-7d
0.5-4y
7-1 3d
7-28d
14-28d
0.004-28h
45d
180-3.60d
4-22d
28-1 80d
100-180d
180-360d
-
-
1-7d
28-1 80d
Air
22-223d
5-46h
2-1 9h
1-10h
1-11d
19-1 91 d
0.5-5h
5-49h
0.5-5h
0.5-1 h
0.9-1 8h
2-23h
113-»y
4-40h
8-75d
3-33h
3-27d
-
1-11h
0.9-7h
0.5-5d
9-89d
16-160d
10-104h
5-54d
8-82d
1-11d
-
-
-
9-94h
Other7
Non-Polar
Polar
Polar
Polar
Polar
Non-Polar
Polar
Polar
Polar
Polar
Polar
Polar
Polar
Polar
Polar
Polar
Non-Polar
Polar
Polar
Non-Polar
Polar
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Polar
Non-Polar
Polar
Non-Polar

-------
                                                              Table B-l. (continued)
Compound
Vinyl chloride
Vinylidene chloride
Xylenes (isomer mixture)
o-Xylene
p-Xylene
CAS No.
75-01-4
75-35-4
1330-20-7
95-47-6
106-42-3
Sub-
category1
woe
woe
VOC
VOC
VOC
VP2
(mm Hg at
25°C)
3200.0
500.0
6.7
5.0
6.5
Polarizabillty3
(cm3/mole)
15.5
20.4
36.1
35.8
36.0
Water Solubility4
(g/Lat'C)
Slightly soluble
5-10/21
<1/22
Insoluble
Insoluble
Reactivity & t,/, range5
Aqueous6
aab
aab
aab
aab
aab
28-168d
28-168d
7-28d
7-28d
7-28d
Air
10-97h
10-99h
3-44h
4-44h
4-42h
Other7
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Non-Polar
Footnotes:
1  WOC = Very Volatile Organic Compounds (Vapor Pressure at 25°C >380 mm Hg);
   VOC = Volatile Organic Compounds (0.1< Vapor Pressure at 25°C <380 mm Hg)
2 Vapor Pressure (VP) data from (with some exceptions):
   (a)   D.L. Jones and J. Bursey, "Simultaneous Control of PM-10 and Hazardous Air Pollutants II: Rationale for Selection of Hazardous Air Pollutants
        as Potential Particulate Matter," Report EPA-452/R-93/013, U.S. Environmental Protection Agency, Research Triangle Park, NC, October 1992.
   (b)   R.C. Weber, P.A. Parker, and M. Bowser, Vapor Pressure Distribution of Selected Organic Chemicals, Report EPA-600/2-81-021,
        U.S. Environmental Protection Agency, Cincinnati, OH, February 1981.
3  Electronic Polarizability = (MW/p)[n2 - 1]/f.n2 + 2]
   from: E.B. Sansone, Y.B. Tewari, and L.A. Jonas,  Prediction of Removal of Vapors from Air by Adsorption on Activated Carbon, Environ. Sci.
  Technol.,  13,1511-1513 (1979). Values for molecular weight (MW), density (p), and refractive index (n) are taken from:
   (a)  R.C. Weast, ed., "CRC Handbook of Chemistry and Physics," 59th edition. CRC Press, Boca Raton, 1979.
   (b)  LH. Keith and M.M. Walker, eds.. "EPA's Clean Air Act Air Toxics Database:  Air Toxics Chemical and PhysicaUProperties,"  Vol. II, Lewis
       Publishers, Boca Raton, 1993.
4 Solubility data from (unless otherwise indicated):
    D. Mackay, W.Y. Shiu, and K.C. Ma, "Illustrated Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals:
    Volume III Volatile Organic Chemicals," Lewis Publishers, Ann Arbor, Ml, 1993.
5 Reactivity and Half-Life data from:
    (a) P.H. Howard, R.S. Boethling, W.F. Jarvis, W.M. Meylan. and E.M. Michalenko, "Handbook of Environmental Degradation Rates," Lewis Publishers,
        Boca Raton, 1991.
    (b) C.W. Spicer, A.J. Pollack, T.J. Kelly and R. Mukund, "A Literature Review of Atmospheric Transformation Products of Clean Air Act
        Title III Hazardous Air Pollutants, Final Report to U.S. EPA, Contract No. 68-D80082, Battelle, Columbus, Ohio, July 1993.
8 aab  = aqueous aerobic biodegradation; ah = aqueous hydrolysis
7 Customary classification of VOCs as either  Nonpolar or Polar.
' Obtained from the STN International computer database (BEILSTEIN File)

-------
          Discussion of Polarizability and Water Solubility Characteristics
                       of Polar Volatile Organic Compounds
       Volatile organic compounds (VOCs) in air consist largely of hydrocarbons and
 oxygenated hydrocarbons, as well as some nitrogen- and sulfur-containing compounds.
 The oxygenated hydrocarbons, in turn, consist of several compound classes, including
 alcohols, aldehydes, ketones, ethers,  carboxylic acids, etc.  For analytical purposes,
 airborne organic compounds may be  considered as either nonpolar (i.e., hydrocarbons)
 or polar (i.e., compounds containing oxygen, sulfur, nitrogen, etc.).

       Nonpolar VOCs can be characterized at the part-per-billion by volume (ppbv)
 level using currently available methods.  However, polar VOCs tend to be difficult to
 sample and analyze at trace levels because of their chemical reactivity, affinity for
 metal and other surfaces, and solubility in water.  Because polar VOCs include
 compound classes generally associated with  higher polarizabilities, we have investigated
 the general classification  of the VOCs of interest  as a function of  electronic
 polarizability (molar refractivity). Polarizabilities were calculated from the
 relationship:
                      Molar Refractivity = —
                                                  P
where MW = molecular weight; p = density; and n = refractive index.  Figure B-l
shows the data generated in this way for the VOCs.  This plot ranks the VOCs that are
customarily identified as either nonpolar (N) or polar (P) compounds as a function of
their electronic polarizability. Figure B-l shows that the N and P compounds are well
mixed in the ranking by polarizability.  It is clear from this plot that there is no clear
distinction between the N and P compounds, based on polarizability, as both groups of
compounds are distributed over the entire polarizability range.  *

       Because of the collection and analysis problems known to be associated with the
water solubility of certain VOCs, we also ranked the VOCs on the basis of their
solubility in water at 25 °C.  The most useful literature compilations found were those
of Keith and Walker (1993) and Mackay et al. (1993) (see references 14 and 15 in the
body of this report).  As Coutant has already noted (references 11 and 27), in many
cases values reported for the same compound in the literature differ widely; in many
other cases, only solubility ranges are available. As a result, we have been forced to
group several compounds or make selections based on chemical similarity with other
compounds on the target compound list.  We have also conducted several literature
searches, using the STN computer data base, for solubility data on individual VOCs.
Figure B-2 shows a plot ranking the VOCs as a function of their water solubility.

                                       50

-------
    50
I
5
    30
£
    20
    10
          N Designated Non-Polar VOC

          P Designated Polar VOC
                                                                                         N
20
                                             .-4-

                                             40
                                                           80
                              Compound Electronic Polarizability Rank


          Figure B-1. Lrslributton of electronic polarizabilities for Volatile Organic Compounds (VOCs) on the HAPs list.

-------
      200
      160
      120
I
3
§>


I
00
      40
      N Designated Non-Polar VOC

      P Designated Polar VOC

       * Reacts/decomposes
                                                                                               *•••••*
                                                                                   nnTrTTf*

                           20
     40                60



Compound Solubility Rank
                                                                            00
                                                                                                     100
            Figure B-2.  Distribution of water solubilities Tor Volatile Organic Compounds (VOCs) on the HAPs list.

-------
Here, it is seen that compounds that have conventionally been identified as nonpolar
VOCs are characterized by relatively low water solubilities, whereas compounds that
are generally regarded as polar VOCs are characterized by relatively high water
solubilities.  Classifying VOCs on the basis of their solubility in water therefore
provides a more realistic distinction between polar and nonpolar compounds than does
classification on the basis of polarizability.
                                        53

-------
                             APPENDIX C

  RESULTS OF THE SURVEY OF AMBIENT AIR MEASUREMENT METHODS
                          FOR THE 189 HAPS
1.     Table of Measurement Methods Identified (Table C-l).

2.     List of References Associated with Table C-l.
                                54

-------
Table C-l. Available Ambient Measurement Methods for the 189 HAPs.
Compound

Acetamide
Acetonitrile
Acetophenone
2-Acetylaminofluorene
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Ally! chloride
4-Aminobiphenyl
CAS No.
75-07-0
60-35-5
75-05-8
98-86-2
53-96-3
107-02-8
79-06-1
79-10-7
107-13-1
107-05-1
92-67-1
Compd.
Class*
woe
SVOC
VOC
VOC
NVOC
VOC
VOC
VOC
VOC
VOC
SVOC
Ambient Measurement Method
Ooinonsfrated
TO-5
TO-11

R-1.CLP-1A. R-3
CLP-2

TO-5
TO-11
CLP-1A


TO-2. R-1, CLP-
1A. R-3
TO-14, TO-2, CLP
1A,B, R-3
CLP-2
Likely
R-4 [14]

TO-15


NIOSH III [#2501]
OSHA [#21]

R-4 [141; TO-15

R-36
Potential

OSHA CIM
[A625J; R-37;
R-47

TO-15
OSHA CIM [0065]





R-37
Limit of Detection1'"-4'5
TO-5:1 ppbv; TO-11: 1
ppbv; [14]: 30 ppmv

R-1: 1 ppbv
CLP-24: 37 ng/m3 (0.007
ppbv)

CLP-1A4: 5 ppbv; TO-5: 1
ppbv; TO-1 1 : 1 ppbv
(#21]: 1.3 ppbv

R-1: 1 ppbv
TO-14: a 0.1 ppbv
CLP-24: 183 ng/m3; R-36:
0.1 ng/m3
Comment

[A625]: not a validated method; R-47:
method developed for analysis of water


0065]: not a validated method





R-36: evaluated for particulate phase only

-------
Table C-l. (continued)
Compound

o-Anisidine
Asbestos
Benzene
Benzidine
Benzotrichloride
Benzyl chloride
Biphenyl
Bis (2-ethylhexyl)phthalate
(DEHP)
Bis (chloromethyl) ether
Bromoform
1,3-Butadiene
CAS No.
62-53-3
90-04-0
1332-21-4
71-43-2
92-87-5
98-07-7
100-44-7
92-52-4
117-81-7
542-88-1
75-25-2
106-99-0
Compd.
Class A
VOC
SVOC
NVINC
VOC
SVOC
SVOC
VOC
SVOC
SVOC
VOC
VOC
woe
Ambient Measurement Method
Demonstrated
CLP-2

R-21
TO-14; TO-1;TO-
2;TO-3;R-1;CLP
1A,B; R-3; R-6
CLP-2

TO-14, CLP-1A,
R-3
R-50; R-51
CLP-2; R 28;
R-57
CLP-2
CLP-1B
R-1.CLP-1A. R-3
Likely

NIOSH III [#2514)
NIOSH III [*7400]
& [17402]; OSHA
[101 60); R-63

R-36


NIOSH III
[#2530]


TO-15
NIOSH III
[#1024];
TO-14; TO-15
Potential

OSHA CIM [0225]


R-37
OSHA CIM [B408]






Limit of Detection1'2'3-4'5
CLP-2': 73 ng/m3 (0.02
ppbv)

R-21: <0.1 ng/m3 (I.e., <
0.01 fibers/cc)
TO-14: & 0.1 ppbv;
TO-1: 0.03 ppbv1
CLP-24: 73 ng/m3; R-36: 1
ng/m3

TO-14: 2 0.1 ppbv
R-50: 14-16 ng/m3
CLP-24: 37 ng/m3; R-28:
0.77 - 3.60 ng/m3
CLP-24: 37 ng/m3 (0.006
ppbv)

R-1: 1 ppbv
Comment
Current concern exists that CLP-2
methodology is inadequate for collection
of this compound.
[#2514]: working range = 0.06 - 0.8
mg/m3 (200-L sample volume)
[#7400] & [#7402]: working range= 0.04 -
0.5 fiber/cc (1000-L sample volume)

R-36: Evaluated for particulate phase only
[B408J: not a validated method

[#2530]: working range = 0.13-4 mg/m3
(30-L sample volume); R-50: LOD is
range of ambient data.
R-28: LOD shown Is range of reported
ambient data

CLP-1B minimum quantifiable level of 28
ng
[#1024]: working range = 0.02 - 8.4 ppmv
(25-L sample volume)

-------
Table C-l. (continued)
Compound
Calcium cyanamide
Caprolactam
Captan
Carbaiyl
Carbon disuffide
Carbon tetrachloride
Carbonyl sulfide
Catechol
Chloramben
Chlordane
Chlorine
CAS No.
1 56-62-7
105-60-2
133-06-2
63-25-2
75-15-0
56-23-5
463-58-1
120-80-9
133-90-4
57-74-9
7782-50-5
Compd.
Class *

Participate
SVOC
SVOC
SVOC
VOC
VOC
woe
VOC
SVOC
SVOC
WINC
Ambient Measurement Method
Demonstrated


TO-10; CLP-2;
R-27
R-27
R-11
TO-14;TO-1;CLP
1A,B; R-3; R-6
R-10 '


TO-4; TO-10; CLP
2; R-27 to R-31
R-4 [805]
Likely
R-32
R-43; R-44
TO-4
NIOSH III
[*5006]| OSHA
[63]
NIOSH III
[#1600], EPA-15.
R-4 [14J

EPA-15
R-4 [14]
R-2; TO-8; R-25


OSHA [ID101];
NIOSH III [#6011]
Potential

OSHA CIM [0524]


TO-15



R-27


Limit of Detection1'2-3-4'5
R-32: 0.08 mg/m3
R-43:0.1mg/m3;R-44:5
ug/m3
TO-10: 0.01 - 50 Mg/m3; R-
27: 1.6- 14ng/m5
[63]: 0.028 mg/m3; R-27: 8 -
42 ng/m5
R-11: 0.02 ppbv; EPA-15:
0.5 ppmv MDQ; [14]: 20
ppmv
TO-14: a 0.1 ppbv;
TO-1: 0.03 ppbv1
R-10: 0.03 ppbv; EPA-15:
0.5 ppmv MDQ; [14]: 1
ppmv


TO-4: >1 ng/m3; TO-10:
0.01 -50 ug/m3; R-27: 4 -50
ng/ms; R-29: < 5 pg/m3
(ID101): 14 ppbv
Comment
R-32: recommended range in air = 0.24
mg/m3 (240-L sample volume)
R-43: LOD for GC analysis (100-L sample
volume); R-44: evaluated for particle-
phase samples only

[#5006]: working range = 0.5 - 20 mg/m3
(200-L sample volume); (63): sample
volume = 60 L
LOD of R-1 1 estimated; range of ambient
data 0.025 - 0.34 ppbv; [15]: listed as
target compound for EPA 15

LOD for R-10 estimated based on
calibration data; range of ambient data
0.4 - 0.7 ppbv; [15]: listed as a target
compound for EPA 1 5
R-2 and TO-8 indicated by analogy with
phenol based on similar properties; R-2:
0.02 ppbv (estimated); R-2: 0.02 ppbv
(estimated); R-25: 1 ppbv (estimated)
R-27 indicated based on applicability of
method for other pesticides

[80S]: LOD not established; (6011):
working range = 7 - 500 ppbv ( 90- L
sample volume); [ID101]: sample volume
= 15L

-------
Table C-l. (continued)
Compound

2-Ch!oroacefophenone
Chlorobenzene
Chlorobenzilate
Chloroform
Chloromethyl methyl ether
Chloroprene
Cresol/Cresylic acid (mixed
isomers)
o-Cresol
m-Cresol
p-Cresol
Cumene
CAS No.
79-11-8
532-27-4
108-90-7
510-15-6
67-66-3
107-30-2
126-99-8
1319-77-3
95-48-7
108-39-4
106-44-5
98-82-8
Compd.
Class A
VOC
SVOC
VOC
SVOC
VOC
VOC
VOC
VOC
VOC
SVOC
SVOC
VOC
Ambient Measurement Method
Demonstrated


TO-14. TO-3. CLP
1A,B, R-3

TO-14; TO-1;TO-
2; TO-3: CLP-
1A.B; R-6

R-7
TO-8
TO-8
TO-8
TO-8
TO-14; R-6
Likely
R-42
NIOSHII [*P&
CAM 291]

R-46; CLP-2;
TO-4;TO-10

NIOSH 11(1)
[P&CAM f 220];
R-58
NIOSH III
[*1002]; TO-15
R-60
R-2; R-25; R-60
R-2; R-3; R-60
R-2; R-3; R-59;
R-60
NIOSH III (#1 501]
Potential

OSHACIM[0618)

R-27




R-59
R-59


Limit of Detection1'"'4'*
R-42: 0.2 mg/m3(51 ppbv)
[#291]: 0.18 -0.62 mg/m3
TO-14: 2 0.1 ppbv

TO-14: 20.1 ppbv;TO-1:
0.04 ppbv'
[#220]: 0.5 ppbv; R-56: 1
ppbv
R-7: 0.06 ppbv
TO-8: 1-5 ppbv
TO-8: 1-5 ppbv
TO-8: 4.5 - 22.5 ug/m3; R-
2: 4.5 ug/m3; R-3: 0.09
ug/m3
TO-8: 4.5 - 22.5 Mg/m3; R-
2: 4.5 (jg/ma; R-3: 0.09
ug/m3
TO-14: 2: 0.1 ppbv
Comment

#291]: sample volume = 12 L
(measurement range shown as LOD)

R-46: No LOD's or air concentrations
reported (workplace exposure
measurements)

[#220]: sample volume = 10 L
(measurement range shown as LOD)

Current concern exists that TO-8
sampling technique has not been field
validated.
R-2: 0.02 ppbv (estimated); See also
Cresol/Cresylic acid note above
See also Cresol/Cresylic acid note above
See also Cresol/Cresylic acid note above


-------
Table C-l. (continued)
Compound
2,4-D (2,4-Dichloro
phenoxyacetic acid) (incl. salts
and esters)
DDE (1.1-dichloro-2,2-bis(p-
chlorophenyl) ethylene)
Diazomethane
Dibenzofurans
1 ,2-Dibromo-3-chloropropane
Dibutyl phthalate
1 ,4-Dichtorobenzene
3,3'-Dichlorobenzidine
Dichloroethyl ether (Bis[2-
chloroethyQether)
CAS No.

72-55-9
334-88-3
132-64-9
96-12-8

106-46-7
91-94-1
111-44-4
Compd.
Class A
svoc
svoc
woe
svoc
Dibenzofuran
SVOC
Tetrachloro-
dibenzofuran
VOC
SVOC
VOC
SVOC
VOC
Ambient Measurement Method
Demonstrated
TO-10; R-27
TO-4;TO-10;CLP
2; R-29; R-27;
R-28

R-50
R-5; R-51
R-12
CLP-2; R-28;
R-57
TO-14, TO-1.CLP
1A.B, R-3

CLP-2
Likely
NIOSH III
[#5001];CLP-2;
TCM

NIOSH III (#251 5]
R-4 (836]
TO-9
TO-14; TO-3;
TO-15


NIOSH III
1*5509]; OSHA
[65]; R-36


R-38


EPA 23; OSHA
CIM [D639]




R-37
TO-15
Limit of Detection1'2'3'4'5
TO-10: 0.01 - 50 ug/m3; R-
27: < 0.8 ng/mj
TO-4: >1 ng/m3; TO-10:
0.01-50ng/m';R-29:<5
pg/m3; R-27: 1.4 - 3.6 ng/m3

[836]: 3.3 ng/m3; R-50: 13-
26 ng/m3
R-5: 0.02 pg/m3; R-51 :<
0.01 pg/m3
R-12: < 2 ng/m3 (< 0.2 pptv)
CLP-24: 37 ng/m3; R-28:
0.48 - 3.6 ng/m3; R-57: 5 -
370 ng/m3
TO-14: 20.1ppbv;TO-1:
0.02 ppbv'
65]: 40 ng/m3; R-36: 0.1
ng/m3
CLP-24: 37 ng/m3 (0.006
ppbv)
Comment
T-10 only for esters; 2,4-acid and salts
would require filter for participate; see R-
38; [#5001]: working range = 1 .5 - 20
mg/m3 (100-L sample volume); R-27:
esters only

[#2515]: working range = 0.11 - 0.57
ppmv (10-L sample volume)
836): sample volume = 1500 m3, method
is for total participate aromatic
hydrocarbons; [D639J: not a validated
method: [23]: not a target compound for
EPA 23; R-50: LOD is range of ambient
data
Not a target analyte in TO-9; Higher
chlorinated species (e.g., octa-) are
probably NVOC
TO-14. TO-15 and TO-3 indicated by
analogy with VOC's having similar
properties; R-12: range of ambient data 2
21 ng/m3
R-28: LOD shown is range of reported
ambient data; R-57: LOD shown is range
of ambient data for separate vapor and
>articulate measurements of various
somers.

#5509]: working range = 4 - 200 pg/m3
50-L sample volume); (65): sample
volume = 100 L; R-36: evaluated for
jarticulate phase only
Current concern exists that CLP-2
methodology is inadequate for collection
of this compound.

-------
Table C-l. (continued)
Compound

Dichlorvos
Diethanolamine
Diethyl sulfate
3,3-Dimethoxybenzidine
4-Dimethylaminoazobenzene
N,N-Dimethylaniline
3,3'-Dimethylbenzidine
Dimethylcarfaamoyl chloride
N,N-Dimethylfoimamide
1 , 1 -Dimethylhydrazine
CAS No.
542-75-6
62-73-7
111-42-2
64-67-5
119-90-4
60-11-7
121-69-7
119-93-7
79-44-7
68-12-2
57-14-7
Compd.
Class A
VOC
SVOC
SVOC
VOC
NVOC
NVOC
VOC
SVOC
VOC
VOC
VOC
Ambient Measurement Method
Demonstrated
R-3
TO-10; CLP-2;
R-27







R-9

Likely

TO-4
NIOSH III [43509]
R-40; R-8
R-36
NIOSH II [4P &
CAM 264]
NIOSH III
[#2002]; CLP-2
R-36
R-39
NIOSH III [42004]
R-»[14]
NIOSH ll(3)
|*S143|; R-22
Potential


OSHA CIM [D129]

R-37


R-37



Limit of Detection1-2'3'4'5
TO-14: s 0.1 ppbv
TO-10: 0.01-50ug/m3

R-40: 8 pptv
R-36: 1 ng/m3
[4264]: 4 - 2000 ug/m3

R-36: 1 ng/m3
R-39: 0.05 ppbv
R-9: 0.6 -50 ppbv
R-22: 4 ppbv
Comment


[43509]: working range = 0.4-3 mg/m3
(100-L sample volume)
R-40: not applied to ambient air analysis;
Indication of R-8 based on similarity of
properties with dimethyl sulfate
R-36: Evaluated for particulate phase
only
[4284]: sample volume = 50 L
(measurement range shown as LOD)
[42002]: measurement range = 0.05 - 3.0
mg/sample (unknown sample volume);
CLP-2 indicated by similarity of properties
with aniline
R-36: evaluated for particulate phase only
R-39: sample volume = 48 L
R-9: reports four separate methods
[4S143]: working range = 0.04 - 4 ppmv
(100-L sample volume); R-22: sample
volume = 2 L

-------
Table C-l. (continued)
Compound
Dimethyl phthalate
Dimethyl sulfate
4,6-Dinitro-o-cresol (including
salts)
2,4-Dinitrophenol
2,4-Dinitrotoluene
1,4-Dioxane (1,4-
Diethyleneoxide)
1 ,2-Diphenylhydrazine
Epichlorohydrin (1-Chloro-2,3-
epoxypropane)
1 ,2-Epoxybutane
Ethyl acrylate
Ethylbenzene
Ethyl carbamate (u re thane)
CAS No.
131-11-3
77-78-1
534-52-1
51-28-5
121-14-2
123-91-1
122-66-7
106-89-8
106-88-7
140-88-5
100-41-4
51-79-6
Compd.
Class *
SVOC
VOC
SVOC
SVOC
SVOC
VOC
SVOC
VOC
VOC
VOC
VOC
VOC
Ambient Measurement Method
Demonstrated
CLP-2
R-8
CLP-2
CLP-2
CLP-2
CLP-1B

CLP-1B

R-1
R-3
TO-14;TO-1;CLP
1A.B; R-3; R-6

Likely
R-26; R-2B
NIOSH III (#2524



R-U14J

R-4 [14]
NIOSH III
[#1614]; R-3
TO-15


Potential


R-3


TO-15
R-22





Limit of Detection1'"'"'

CLP-24: 37 ng/m3; R-26: 60
ng/m3
R-B: 0.05 ppbv
CLP-2': 183 ng/m3
CLP-24: 73 ng/m3
CLP-24: 37 ng/m3
14]: 2 ppmv

14]: 20 ppmv

R-1: 0.2 ppbv
O-14: S0.1 ppbv;TO-1.
.005 ppbv' *

Comment
R-28 suggested by analogy with di-n-butyl
phthalate
LOD for R-8 estimated based on ranges
of sampling durations, sampling rates,
and analytical capabilities
R-3 suggested by analogy to other
ihenols


CLP-1B minimum quantifiable level of 13
ng
Suggestion of R-22 based on chemical
imilarity to volatile hydrazines
CLP-1B minimum quantifiable level of 26
g
R-3 and NIOSH methods indicated by
imilarity of properties with ethylene oxide




-------
Table C-l. (continued)
Compound

Ethylene dibromide
Ethylene dichloride
Ethylene glycol
Ethyleneimine
Ethylene oxide
Ethylene thiourea
Ethylidene dichloride
Formaldehyde
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
CAS No.
75-00-3
106-93-4
107-06-2
107-21-1
151-56-4
75-21-8
96-45-7
75-34-3
50-00-0
76-44-8
118-74-1
87-68-3
Compd.
Class *
woe
VOC
VOC
SVOC
VOC
woe
SVOC
VOC
woe
SVOC
SVOC
VOC
Ambient Measurement Method
Demonstrated
TO-14. CLP-1A,
R-3
TO-14
CLP-1A.B
TO-14. TO-2, TO-
3. CLP-1A.B, R-3


R-13

TO-14; CLP-1A.B;
R-3
TO-5
TO-11
TO-10; CLP-2; R-
29; R-30; R-27
TO-10; CLP-2; R-
29; R-28
TO-14, CLP-1A,
R-3
Likely
R-4 [14]


NIOSH III [#5500]
NIOSH 11(5)
[P&CAM*300];
R-4 114]
NIOSH III
[#1614]; R-3
NIOSH III
[*5011]


KM


Potential



OSHACIM[1911]

TO-15






Limit of Detection1'2'3-4-5
TO-14: 20.1 ppbv;[14]: 10
ppmv
TO-14: 2 0.1 ppbv
TO-14: 2 0.1 ppbv

[14]: 15 ppmv
R-13: 0.001 -0.1 ppbv

TO-14: 20.1 ppbv
TO-5: 1 ppbv; TO-11: 1
ppbv
TO-10: 0.01 - 50 ug/m3; R-
29:0.04-0.1 pg/m3; R-30:
1 ng/m3
TO-10: 0.01 - 50 pg/m3; R-
29: 0.04 - 0.1 pg/m3
TO-14: 2 0.1 ppbv
•
Comment



[#5500]: working range = 7 - 330 mg/m3
(3-L sample volume)
[P&CAM #300]: working range = 0.01 -
8.9 ppmv (50-L sample volume)
[#1614]: working range = 0.04 - 4.5 ppmv
(24-L sample volume); R-13 evaluated
five different methods
(#5011): working range = 0.05 - 75
mg/m3 (200-L sample volume)






-------
Table C-l. (continued)
Compound
Hexachlorocydohexane (all stereo
isomers. Including Llndane)
Hexachlorocyclopentadiene
Hexachloroethane
Hexamethylene diisocyanate
Hexamethylphosphoramide
Hexane
Hydrazine
Hydrochloric acid (Hydrogen
chloride)
Hydrogen fluoride (Hydrofluoric
acid)
Hydroquinone
Isophorone
CAS No.

77-47-4
67-72-1
822-06-0
680-31-9
110-54-3
302-01-2
7647-01-0
7664-39-3
123-31-9
78-59-1
Compd.
Class A
SVOC
svoc
voc
svoc
svoc
voc
VINC
VINC
WINC
SVOC
voc
Ambient Measurement Method
Demonstrated
TO-10; CLP-2; R-
28; R-29; R-27
CLP-2
CLP-2


CLP-1A; TO-14;
R-6

R-19
R-20

CLP-2
Likely


TO-14; TO-3;
TO-15
OSHAJ421; R-23


NIOSH III
|#3503]; OSHA
[20]; R-22
NIOSH III
[*7903]; OSHA
[ID174SG]
R-4[609/205];
NIOSH III [#7903]
NIOSH III
[#5004]
NIOSH III
[#2508]; TO-15
Potential



NIOSH III
[#5521]; R-4
[837]; R-62


R-55




Limit of Detection1-"-4-*
TO-10: 0.01 - 50 ug/m3 (g-
BHC); R-30: 1 ng/m3; R-29:
< 5 pg/m3
CLP-24: 37ng/m5
CLP-24: 37 ng/m3 (0.004
ppbv)
[42]: 2.3 ug/m3; R-23: 1
ug/m3

TO-14: Z 0.1 ppbv; R-6:
0.03 ppbv
[20]: 1.2 ppbv; R-22: 4
ppbv
R-19: 0.22 ppbv
R-20: 0.08 ppbv

CLP-24: 37 ng/m3 (0.006
ppbv)
Comment


TO-14 and TO-3 indicated by analogy
with VOC's having similar properties
[42]: sample volume = 15 L

TO-14 by analogy to other VOC's with
similar properties on TO-14 list
[#3503]: working range = 0.07 - 3 ppmv
(100-L sample volume): [20]: sample
volume = 20 L; R-22: sample volume = 2
L
;#7903): working range = 0.0066 - 3.3
ppmv (50-L sample volume)
[#7903]: working range = 0.012 - 6.02
ppmv (50-L sample volume)
#5004]: working range = 2-25 mg/m3
30-L sample volume)
#2508): working range = 0.35 - 70 ppmv
12-L sample volume)

-------
Table C-l. (continued)
Compound
Maleic anhydnde
Methanol
Methoxychlor
Methyl bromide
(Bromomethane)
Methyl chloride
(Chloromethane)
Methyl chloroform
(1,1,1 -Trichloroethane)
Methyl ethyl ketone
[2-Butanone)
Methylhydrazine
Methyl iodide (lodomethane)
Methyl isobutyl ketone
Hexone)
Methyl isocyanate
CAS No.
108-31-6
67-56-1


74-87-3
71-55-6
78-93-3
60-34-4
74-88-4
108-10-1
624-83-9
Compd.
Class *
SVOC
VOC
5VOC
woe
woe
VOC
VOC
VOC
woe
VOC
VOC
Ambient Measurement Method


R-1.CLP-1A. R-3
TO-10; CLP-2; R-
27; R-29
TO-14. CLP-1A,
R-3
TO-14. CLP-1A,
R-3
TO-14; TO-1;TO-
2; TO-3; CLP-
1A.B; R-3; R-6
TO-5. R-1. CLP-
1A. R-3




Likely
NIOSHIII [#P&
CAM 302]; OSHA
[25] & [86]
R-64;TO-15
TO-4



R-58;TO-15
NIOSH ll(3)
[fS149]; R-22
NIOSH III
[*1014], TO-14
NIOSH III
*1300]; R^»[14];
R-1;R-58;TO-15
OSHA [#54]
Potential







R-55
TO-15

R-62
Limit of Detection1'2'3'4'

[86]: 33 ug/m3; [25]: 0.005
mg/m'
R-1: 1 ppbv
rO-10: 0.01 - 50 ug/m3; R-
27: 1 - 8 ng/m3 ; R-29: < 5
pg/m'
TO-14: 5 0.1 ppbv
FO-14: s 0.1 ppbv
FO-14: ;» 0.1 ppbv;
TO-1: 0.03 ppbv1
R-1: 0.2 ppbv; TO-5: 1 ppbv
R-22: 4 ppbv

14): 10ppmv; R-58: <
ppbv
54]: 1.9 ppbv
Comment
[#P & CAM 302J: working range = 0.5 -
2.14mg/m3; [25]: sample volume = 20 L;
[86]: sample volume = 60 L (method not
yet published)






#8149]: working range = 0.018 - 0.55
ppmv (20-L sample volume); R-22:
sample volume = 2 L
#1014]: working range = 1.7 - 16.9 ppmv
50-L sample volume)
#1300]: measurement range = 2.1 - 8.3
mg/sample (1 - 10-L sample volumes); R-
suggested by similarity of properties
with methyl ethyl ketone


-------
Table C-l. (continued)
Compound

Methyl tert-butyl ether
4,4'-Methylenebis-
;2-chloroaniline)
Methylene chloride
(Dichloromethane)
4,4'-Methylenediphenyl
diisocyanate
4.4'-Methylenedianiline
Naphthalene
Nitrobenzene
4-Nitrobiphenyl
4-Nitrophenol
2-Nilropropane
CAS No.
80-62-6
1634-04-4
101-14-4
75-09-2
101-68-8
101-77-9
91-20-3
98-95-3
92-93-3
100-02-7
79-46-9
Compd.
Class *
voc
voc
NVOC
VOC
svoc
NVOC
SVOC
voc
svoc
svoc
voc
Ambient Measurement Method
Demonstrated
CLP-1A
R-1
R-3

TO-14, TO-2. CLP
1A. R-3


TO-13; CLP-2;
R-7
CLP-2
CLP-2; R-53
CLP-2; R-53

Likely
R-4[14]; R-1;
R-3; TO-15
R-64;TO-15
OSHA [71] & [24]

NIOSH III
[#5521]; R-23; R-
4(831]
NIOSH III
[#5029]; OSHA
[57]

NIOSH III
[#2005], R-53
R-52
R-2; R-54
NIOSH III (#2526)
R-4|14];TO-15
Potential


NIOSH III [B302]

R-62


TO-15



Limit of Detection1'2'1-4'5
CLP-1A4: 2 ppbv; [14]: 1
ppmv
R-1: 1 ppbv
[71]: 440 ng/m3; [24]: 3.6
ug/m3
TO-14: 20.1 ppbv
[831]:3-1040|jg/m3;R-
23: 1 Mg/mJ
[57]: 81 ng/m3
TO-13: <100pg/m3

CLP-24: 183 ng/m5; R-53:
0.01 ng/m3
CLP-2*: 183 ng/m3; R-53:
0.04 ng/m3
14]: 10 ppmv
Comment
R-1 and R-3 indicated by similarity of
properties with ethyl acrylate

[24]: sample volume = 100 L; [8320]:
urine matrix

[831]: sample volume = 20 L
[#5029): working range = 0.0002 - 10
mg/m3 (100-L sample volume); [57]:
sample volume = 100 L
R-7: range of measured ambient
concentrations = 5.5 - 182 ng/m3;
Volatility presents collection problems
with PUF/XAD at high sample volume
#2005]: working range = 0.59 - 2.34
jpmv (55-L sample volume); R-53 by
analogy to nitrotoluenes.
R-52 reports ambient data for 3-
nilrobiphenyl
R-2 by analogy with 2- and 3-Nitrophenol;
R-54 by analogy with 2-nitrophenol
#2528]: working range = 1 .4 - 27 ppmv (2
L sample volume)

-------
Table C-l. (continued)
Compound

N-Nitrosodimethylamine
N-Nitrosomorpholine
Parathion
•
Pentachloronitrobenzene
(Quintobenzene)
Pentachlorophenol
*
Phenol
p-Phenylenediamine
Phosgene
Phosphine
Phosphorus
CAS No.
684-93-5
62-75-9
59-89-2
56-38-2
82-68-8
87-86-5
108-95-2
106-50-3
75-44-5
7803-51-2
7723-14-0
Compd.
Class *
voc
voc
voc
svoc
svoc
svoc
voc
svoc
woe
WINC
SVINC
Ambient Measurement Method
Demonstrated

TO-7

CLP-2
i
TO-10; CLP-2
TO-8; R-2; R-54

TO-6
R-33

Likely

NIOSH III (*2522]
TO-7
R-4 [835];
TO-4; TO-10
R-48; R-49
R-50; R-81
R-25; R-60
OSHA|87]

OSHA [ID180]
NIOSH III [I7300J
& [*7905]
Potential
TO-7



CLP-2
R-3
R-53




Limit of Detection1'2'3'4'5

TO-7: < 0.32 ppbv

CLP-24: 146 ng/ms
R-48: 0.1 -10ng/m';R-49:
10.7-1 560 ng/m3
TO-10: 0.01 - 50 pg/m; R-
3: 0.2 ug/m3; R-50: < 1
ng/m3
TO-8: 1-5 ppbv; R-2: 0.02
ppbv; R-54: 56 -110 pptv
|87]: 0.44 pg/m3
TO-6: 0.1 ppbv
R-33: 0.15 ppbv; [ID180]: 9
ppbv

Comment
Based on similarity of properties with N-
nltroso-dimethylamine

Based on similarity of properties with N-
Nitroso-dimethylamine

R-48 and R-49: measurement range
shown as LOD
Use of TO-10 would require filter for
participate material
TO-8: Current concern exists that
sampling technique has not been field
validated; R-54: LOD shown Is range of
ambient data.
[87]: sample volume = 100 L (method not
yet published)

R-33: LOD derived from reference
abstract; [ID180]: sample volume = 36 L
[#7300]: working range= 0.005 - 2 mg/m3
(500-L sample volume); [*7905]: working
range= 0.04 - 0.8 mg/m3 (12-L sample
volume)

-------
Table C-l. (continued)
Compound

Polychlorinated biphenyl
(Aroclors)
1 ,3-Propane sultone
beta-Propiolactone
Propionaldehyde
Propoxur (Baygon)
Propylene dichloride
(1 ,2-Dichloropropane)
Propylene oxide
1 ,2-Propylenimine
(2-Methylaziridine)
Quinoline
CAS No.
85-44-9
1336-36-3
1120-71-4
57-57-8
123-38-6
114-26-1
78-87-5
75-56-9
75-55-8
91-22-5
Compd.
Class *

SVOC
1-Chloro-
biphenyl
SVOC
2.4,6-Trichlo-
robiphenyl
VOC
VOC
VOC
SVOC
VOC
woe
VOC
SVOC
Ambient Measurement Method
Demonstrated

CLP-2; R-29; R-
28
TO-10; CLP-2; R-
29; R-28


TO-5, TO-11
CLP-2; R-27
TO-14; CLP-
1A,B; R-3


R-6
Likely
[#S179J;OSHA
[90]
TO-4
TO-4
R-41
T-40

TO-4; TO-10

R-1. R-3, R-13.
NIOSH III [*1614]
NIOSH ll(5) [#P &
CAM 300]
R-57

R-26; R-28; R-9



TO-15






Limit of Detection1'2'3-4'5
[*S179J: 1 - 36 ng/m3; [90]:
0.048 mg/m3
CLP-24: 146 ng/m3: R-29:
0.04 - 0.1 pg/m3
TO-10: 0.01 -50 pg/m3; R-
29: 0.04 - 0.1 pg/m3

R-40: 1.2pptv
TO-5: 1 ppbv; TO-11: 1
ppbv
CLP-24: 183 ng/m3
TO-14: 50.1 ppbv
R-1: 1 ppbv

R-6: 0.78 -1100 ng/m3
Comment
[#S179]: sample volume = 100 L
(measurement range shown as LOD);
[90]: sample volume = 75 L (method not
yet published)

Note: Higher chlorinated species, up to
decachloro, are probably NVOC

R-40: not applied to ambient air analysis

R-27: LOD shown Is range of reported
ambient data

R-1, R-3, R-13, and NIOSH methods
ndicated by similarity of properties with
ethylene oxide
NIOSH method indicated by similarity of
properties with ethyleneimine
R-6: LOD is range of measured
oncentrations

-------
Table C-l. (continued)
Compound

Styrene
Styrene oxide
2,3,7,8-Tetrachloro dibenzo-p-
dioxin
1 ,1 ,2,2-Tetrachloroethane
Tetrachloroethylene
(Perchloroethylene)
Titanium tetrachloride
Toluene
Toluene-2,4-diamine
2,4-Toluene diisocyanate
o-Toluidine
CAS No.
106-51-4
100-42-5
96-09-3
1746-01-6
79-34-5
127-18-4
7550-45-0
108-88-3
95-80-7
584-84-9
95-53-4
Compd.
Class A

VOC
VOC
SVOC
VOC
VOC
VINC
VOC
SVOC
SVOC
SVOC
Ambient Measurement Method
Domoftsfrvfocf

TO-14;TO-1;CLP
1A.B; R-3; R-8

TO-9; R-5; R-51
TO-14; CLP-
1A.B; R-3
TO-14; TO-1 ;TO-
3; CLP-1A.B; R-3;
.R-6

TO-14; TO-1 ;TO-
2;R-1;CLP-1A,B;
R-3; R-6



Likely


R-40





NIOSH III
[*5516]; OHSA
[65]
NIOSH III
[12535] &
[f5521]; R-4
18371: R-23: R-24
NIOSH III
1*2002); OSHA
173]
Potential
OSHA CIM
[2222]; R-57

R-3; NIOSH III
[#1614)






R-62

Limit of Detection1'"'4-5
[#S181]: 0.17 -0.75 mg/m3
TO-14: sO.1 ppbv;TO-1:
0.02 ppbv1
R-40: 0.41 pptv
TO-9: 1-5pg/ms;R-5:0.02
pg/m3; R-51 :< 0.01 pg/m3
TO-14: i 0.1 ppbv
TO-14: ;> 0.1 ppbv; TO-1:
0.007 ppbv1

TO-14: 50.1 ppbv; R-1: 0.2
ppbv
•
R-23: 1 pg/m3; R-24: 7.24
pg/m3; [837]: 0.05-1.01
mg/m3
[73]: 0.97 ug/m3
Comment
[#S181J: sample volume = 24 L
(measurement range shown as LOD)

R-40: not applied to ambient air analysis;
R-3, [#1614]: Based on comparison of
properties with ethylene oxide and 1,2-
epoxybutane

CLP-1 B minimum quantifiable level of 22
ng

Hydrolyzes extremely rapidly in the
ambient atmosphere

[#5516]: working range = 3-30 Mg/m3
(100-L sample volume)
[#2535]: working range = 0.03 - 2.5
mg/m3 (10-L sample volume); [837]:
sample volume = 20 L
[#2002]: working range = 5-60 mg/m3
[55-L sample volume); [73]: sample
volume = 100L

-------
Table C-l. (continued)
Compound
camphene)
1 ,2,4-Trichlorobenzene
1 , 1 ,2-Trichloroethane
Trichloroethylene
2,4,6-Trichlorophenol
2,4,6-Trichlorophenol
Triethylamine
Trifluralin
2,2,4-Trimethylpentane
Vinyl acetate
Vinyl bromide
CAS No.
8001-35-2
120-82-1
79-00-5
79-01-6
95-95-4
88-06-2
121-44-8
1582-09-8
540-84-1
108-05-4
593-60-2
Compd.
Class *
svoc
voc
s
voc
voc
svoc
svoc
voc
svoc
voc
voc
woe
Ambient Measurement Method
Demonstrated

TO-14. CLP-1A,
R-3
TO-14
R-3
TO-14; TO-1;TO-
3; CLP-1A.B; R-6
TO-10; CLP-2; R-
50
CLP-2; R-50

R-29
R-8
R-1.CLP-1A, R-3

Likely
NIOSHIII [#S67]



R-54
TO-10; R-54
NIOSH ll(3)
l*S152]; R-9
TO-4; CLP-2;
TO-10
TO-14; TO-15
TO-15
TO-14; TO-15
Potential




R-3
R-3

OSHA CIM [T338]



Limit of Detection1'2'3'4'5
R-31:<0.1 ng/m3
TO-14: z 0.1 ppbv
TO-14: 5 0.1 ppbv
TO-14: 20.1 ppbv;TO-1:
0.02 ppbv'
TO-10: 0.01 - 50 ug/m3 ; R-
50: 0.07 ng/m3
CLP-24: 183 ng/m3; R-3:
0.2 pg/m3; R-50: 0.07 ng/m3
[#S152]:2-71 ppbv
R-29: < 100 pg/m3
R-6: 0.025 ppbv
R-1: 1 ppbv

Comment
[#S67]: working range = 0.05 - 1 .5 mg/m3
(15-L sample volume); R-31: LOD
estimated



Use of T-10 would require filter for
particulate-phase material; R-54 reprots
sum of 2,4,5- and 2,4,6- Isomers
TO-10 by analogy with 2,4.5-TCP. Use of
TO-10 would require filter for paniculate
material; R-54 reports sum of 2,4,5- and
2.4.6- isomers
#3152): sample volume = 100 L
measurement range shown as LOD); R-9
ndicated by comparison of properties
with dimethylformamide

TO-14 and TO-15 indicated by analogy
with other VOC's having similar
iroperties, and based on canister stability
data.

TO-14 and TO-15 indicated by analogy to
other WOC's with similar properties

-------
Table C-l. (continued)
Compound

Vtnylidene chloride
(1,1-Dichloroethylene)
Xylene (mixed isomers)
o-Xytene •
m-Xylene
p-Xylene
Antimony Compounds
Arsenic Compounds (Inorganic
including arsine)
Beryllium Compounds
Cadmium Compounds
CAS No.
75-01-4
75-35-4
1330-20-7
95-47-6
108-38-3
106-42-3

•


Compd.
Class A

woe
VOC
VOC
VOC
VOC
NV/INC
WINC
Arsine
NVINC
NVINC
NVINC
Ambient Measurement Method
Demonstrated
TO-14. TO-2, CLP
1A. R-3
TO-14, TO-2, TO-
3.CLP-1A.B. R-3
TO-14; CLP-
1A,B; R-3
TO-14; TO-1; CLP
1A.B; R-3; R-6
TO-14;TO-1;R-6
TO-14; TO-1; R-6
CLP-3; R-4J301J

CLP-3; R-4J302J
CLP-3; R-4 1822]
CLP-3; R-4 1822)
Likely






R-4 [804 & 822B]
NIOSH III
[*8001]; OSHA
[ID105]; R-34
R-4 [804 & 822B]

R-4 [822B]
Potential











Limit of Detection1-2'3-4'5
TO-14: 2 0.1 ppbv
TO-14: 20.1 ppbv
TO-14: 2 0.1 ppbv
TO-14: s 0.1 ppbv; TO-1:
0.02 ppbv1
TO-14: 2 0.1 ppbv; TO-1:
0.014 ppbv1
TO-14: 2 0.1 ppbv; TO-1:
0.014 ppbv1
[3011: 0.05 ug/m'; [804): 4
M9/ms; [822B]2: 17.5 ng/m3
R-34: 1 ppbv
[302]: 0.1 pg/m3; [804): 0.4
ug/m3;J822B]2:10ng/m3
[822]: 0.08 ug/m3
[822): 0.03 pg/m3; [822B]2:
22.5 ng/m3
Comment


CLP-1B minimum quantifiable level of 2
ng



[301]: sample volume= 20 m3; (804):
sample volume= 60 L
[#6001]: working range = 0.3 - 62 ppbv
(10-L sample volume): [ID105]: validated
range = 1.85 - 12.4 ppbv; R-34:
chemiluminescence methods
[302]: sample volume= 10 m3; [804]:
sample volume= 60 L
[822]: sample volume = 0.24 m3
[822): sample volume = 0.24 m3

-------
Table C-l. (continued)
Compound
Chromium Compounds
Cobalt Compounds
Coke Oven Emissions
see also VOCs, e.g., benzene,
toluene, xylene)
Cyanide Compounds
Glycol ethers
Lead Compounds
Manganese Compounds
Mercury Compounds
Fine mineral fibers
CAS No.









Compd.
Class *
NVINC
NVINC
SVOC
Napthalene
NVOC
Coronene
W1NC
Hydrogen
cyanide
NVINC
SVOC
NVINC
NVINC
SVINC
Mercury
vapor
NVINC
NVINC
Ambient Measurement Method
Demonstrated
CLP-3; R-4[822]
CLP-3; R-4[822)
TO-13;CLP-2;
R-7
R-14



CLP-3; R-4I822]
CLP-3; R-4 [822]
R-4[317J;R-18
R-18

Likely
R-4 [822B]
R-4 [822B]

R-4 (836]
NIOSH III
[*6010]; R-35
NIOSH III [#7904]
R-45
R-4 (822B)
R-4 [822B]

R-4 (822B]
NIOSH III
[#7400]; R-21
Potential












Limit of Detection1 "'4'5
[822]: 0.2 pg/m3; [822B]2:
25 ng/m3
[822]: 0.3 ug/m3; [822B]2:
12.5ng/m3
TO-13: <100pg/m3
R-14: 0.09-1. 4 ng/m3


R-45: > 0.74 mg/m3
[822]: 0.8 ug/m3; [822B]J:
10 ng/m3
[822]: 0.1 pg/m3; [822B]2:
20 ng/m3
[317]: 0.002 - 0.06 ppbv; R
18: 0.001 - 0.06 pptv
R-18: 0.01 ng/m3
[#7400]: 7 fibers/mm2 filter
area
Comment
[822]: sample volume = 0.24 m3
[822]: sample volume= 0.24 m3
R-7: range of measured ambient
concentrations = 5.5 - 182 ng/m3
R-14: LOD shown is range of measured
ambient concentrations
[#6010]: working range = 0.893 - 232
ppmv (3-L sample volume); R-35: 1 pg
quantitation limit
[#7994]: working range (as CN") = 05-
15 mg/m3 (sample volume = 90 L)
See also ethylene glycol; R-45:
developed for 9 different glycol ethers.
LOD calculated for ethylene glycol
monobutyl ether
[822]: sample volume = 0.24 m3
822]: sample volume = 0.24 m3


#7400): working range= 0.04 - 0.5
fiber/cc (1000-L sample volume)

-------
                                                             Table C-l. (continued)
Compound
Nickel Compounds
Polycyclic Organic Matter
Radionudides (including radon)
Selenium Compounds
CAS No.




Compd.
Class*
NVINC
SVOC
Napthalene
NVOC
Coronene
WING
Radon
NVINC/ VINC
NVINC
•-
Ambient Measurement Method
Demonstrated

TO-13; CLP-2;
R-7
R-14
R-4 [606, A & B]
R-16; R-17
i
CLP-3
Likely
R-4 [822B]

R-4 [836]

OSHA CIM
[2560); EPA 114
R-4 [804 & 822B]
Potential






Limit of Detection1'2-3*5
[822J: 0.3 (jg/m3; [822B]2:
10 ng/m'
TO-13: <100pg/m3
R-14: 0.09 -1.4 ng/m3
[606B]: 0.1 pCi/L
Varies depending on
radionuclide
[804]: 0.4 pg/m3; [822B]2:
10 ng/m3 ; CLP-33: 83
ng/m3
Comment
[822]: sample volume = 0.24 m3
R-7: range of measured ambient
concentrations = 5.5 - 182 ng/m3
R-14: LOD shown is range of measured
ambient concentrations

Long-lived radionuclides in air Include:
^Rn^Rn,1"! "Kr.'H (gases); 210Po,
210Pb. 7Be, ""Pn, "'Pn, 1MCe, 137Cs. "°Sr
(particles); [1 14]: ^Rn and 210Po listed as
target compounds for EPA 1 14
[804]: sample volume= 60 L
A Compound Classes:
   WOC = Very Volatile Organic Compounds (Vapor Pressure at 25°C >380 mm Hg)
   WINC or Gases = Very Volatile Inorganic Compounds (Vapor Pressure at 25°C >380 mm Hg)
   VOC  = Volatile Organic Compounds (1 .OE-OK Vapor Pressure at 25'C <380 mm Hg)
   VINC or Gases  = Volatile Inorganic Compounds (1.OE-OK Vapor Pressure at 25°C <380 mm Hg)
   SVOC = Semi-Volatile Organic Compounds (1 .OE-07< Vapor Pressure at 25'C <1 .OE-01 mm Hg)
   SVINC = Semi-Volatile Inorganic Compounds (1 .OE-07< Vapor Pressure at 25'C <1 .OE-01 mm Hg)
   NVOC = Non-Volatile Organic Compounds (Vapor Pressure at 25°C < 1.0E-07 mm Hg)
   NVINC or Paniculate = Non-Volatile Inorganic Compounds (Vapor Pressure at 25"C < 1.0E-07 mm Hg)

Limit of Detection:
1   Sampling and analytical procedures similar to TO-1 (Tenax sorbent bed and thermal desorption-injection capillary GC/MS); 18-L sampling volume used;
    method LODs for target compounds reported in ug/m3.
2   R-4 (822B): Concentrations in ng/cm2 of filter converted to ng/m3 of air using the factor 4 m3/cm2 (typical for 24-h Hi-Vol Sample)
3   CLP-3: Contract Required Quantitation Limits (CRQL) assume 2500 m3 air volume per Hi-Vol filter and 40 mL final extraction volume
*   CLP-2: LODs shown are Contract Required Quantitation Limits (CRQL), not absolute detection limits. For VOCs, CRQLs are shown in ppbv,
             converted from reported CRQLs in ng/m3 at 20°C and 1 atm.
5   MDQ = Minimum Detectable Quantity

-------
                                REFERENCES


 Measurement Methods
 TO-1 to 14
 "Compendium of Methods for the Determination of Toxic Organic Compounds in
 Ambient Air", PB90-127374, EPA/600/4-89/017, June 1988, USEPA, Research
 Triangle Park, NC.

 TO-1  Determination of Volatile Organic Compounds in Ambient Air Using Tenax-
        Adsorption and Gas Chromatography (GC/MS) - collection using Tenax and
        analysis using GC/MS

 TO-2  Determination of Volatile Organic Compounds in Ambient Air by Carbon
        Molecular Sieve Adsorption and Gas Chromatography/Mass Spectrometry
        (GC/MS) - collection by molecular sieve adsorption and analysis by GC/MS

 TO-3  Determination of Volatile Organic Compounds in Ambient Air Using Cryogenic
        Preconcentration Techniques and Gas Chromatography with Flame lonization
        and Electron Capture Detection - collection by cryogenic preconcentration and
        analysis by GC/FID and GC/ECD

 TO-4  Determination of Organochlorine Pesticides and Polychlorinated Biphenyls in
        Ambient Air - sampling on glass fiber filter and polyurethane foam, soxhlet
        extraction, and analysis by GC/ECD

 TO-5   Determination of Aldehydes and Ketones in Ambient Air Using High
        Performance Liquid Chromatography (HPLC)  - sampling using midget impinger
        (hydrochloric acid/ 2,4-dinitrophenylhydrazine/ isooctane) and analysis by
        HPLC

 TO-6  Determination of Phosgene in Ambient Air Using High Performance Liquid
       Chromatography (HPLC) - sampling using midget impinger (aniline/ toluene),
       solvent exchange to acetonitrile, and analysis by HPLC

TO-7  Determination of N-Nitrosodimethylamine in Ambient Air Using Gas
       Chromatography - collection on sorbent cartridge (Thermosorb/N), extraction
       by dichloromethane, and analysis by GC/MS

TO-8  Determination of Phenol and Methylphenols (Cresols) in Ambient Air Using
       High Performance Liquid Chromatography (HPLC) - sampling using two
       midget impingers (sodium hydroxide) and analysis by reverse  phase HPLC
                                     73

-------
 TO-9  Determination of Polychlorinated Dibenzo-p-Dioxins (PCDDs) in Ambient Air
       Using High Resolution Gas Chromatography/High Resolution Mass
       Spectrometry - collection on inlet filter and polyurethane foam cartridge,
       extraction with benzene, and analysis by GC/MS

 TO-10 Determination of Organochlorine Pesticides in Ambient Air Using Low Volume
       Polyurethane Foam (PUF) Sampling with Gas Chromatography/Electron
       Capture Detector (GC/ECD) - collection by PUF and analysis by GC/ECD

 TO-11 Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge
       Followed by High Performance Liquid Chromatography (HPLC) - collection by
       silica gel adsorbent and analysis by HPLC

 TO-12 Determination of Nonmethane Organic Compounds (NMOC) in Ambient Air
       Using Cryogenic Preconcentration and Direct Flame lonization Detection
       (PDFID) - collection by cryogenic preconcentration and analysis by FID

 TO-13 Determination of Polynuclear Aromatic Hydrocarbons (PAHs) in Ambient Air
       Using High Volume Sampling with Gas Chromatography/Mass Spectrometry
       (GC/MS) and High Performance Liquid Chromatography Analysis - collection
       on sorbent (XAD-2) and polyurethane foam cartridge, and analysis by GC/FID,
       GC/MS, or HPLC

 TO-14 Determination of Volatile Organic Compounds (VOCs) in Ambient Air Using
       SUMMA Polished Canister Sampling and Gas Chromatographic (GC)
       Analysis - collection by passivated pre-evacuated canister and analysis by
       GC/ECD, NPD, or FID

TO-15
Method TO-15: The Determination of Volatile Organic Compounds (VOCs) in Air
Collected in Summa Canisters and Analyzed by Gas Chromatography/Mass
Spectrometry (GC/MS), EPA Contract No. 68-DO-0007 (WA-40), in progress.
Collection is by canister, with analysis by GC/MS.

CLP-1A.1B. 2. and 3
USEPA Contract Laboratory Program Statement of Work for Analysis of Ambient Air,
Rev. IAIR01.2, US EPA, Research Triangle Park, NC, October 1993.

CLP-1A:   Tenax adsorbent collection and GC/MS/SCAN analysis
CLP-IB:   Summa canister sampling and GC/MS/SCAN analysis
CLP-2:    Collection on filter and XAD-2/polyurethane foam and GC/MS/SCAN
          analysis
CLP-3:    Collection on glass fiber filter and inductively coupled argon plasma
          spectroscopy or graphite furnace atomic adsorption analysis
                                     74

-------
 NIOSH Methods
 NIOSH Manual of Analytical Methods, 2nd edition, Vol.  1-7, Department of Health
 and Human Services, U.S. Government Printing Office, Washington, D.C., 1977-1982
 (available from NTIS).

 S143:  Visible absorption spectrophotometry using midget bubbler (HC1) for 1,1-
        dimethylhydrazine
 S149:  Visible absorption spectrophotometry using midget bubbler (HC1) for
        methylhydrazine
 S152:  Gas Chromatography using bubbler (sulfuric acid), followed by basification for
        triethylamine
 S179:  HPLC-UV using  cellulose membrane filter for collection, followed by
        extraction  and hydrolysis with ammonia for phthalic anhydride
 S181:  HPLC using XAD-2 resin in tube for collection of quinone
 P & CAM 220:   GC-ECD  using glass impingers' (methanolic solution  of the sodium
                  salt of 2,4,6-trichlorophenol) for collection of chloromethyl methyl
                  ether
 P & CAM 284:   Gas Chromatography using glass fiber filter and Gas-Chrom P for
                  collection of 4-dimethyl aminoazobenzene
 P & CAM 291:   GC-FID using Tenax GC in glass tube  for collection of  «-
                  chloroacetophenone
 P & CAM 300:   HPLC-UV using midget bubbler (Folin's  Reagent) for aziridine  and
                  2-methyl aziridine

 NIOSH Manual of Analytical Methods, 3rd edition, Vol. 1-2, U.S. Department of
 Health and Human Services, U.S. Government Printing Office, Washington, D.C.,
 February  1984 (available  from NTIS).

 S67:   GC-ECD using cellulose ester membrane filter for chlorinated camphene
 P & CAM 302:    RPHPLC-UV using glass midget bubbler  (distilled water) for maleic
                  anhydride
 1002:   GC-FID using solid sorbent tube (coconut shell charcoal) for chloroprene
 1014:   GC-FID using solid sorbent tube (coconut shell charcoal) for methyl iodide
 1024:   GC-FID using solid sorbent tube (coconut shell charcoal) for 1,3-butadiene
 1300:   GC-FID using solid sorbent tube (coconut shell charcoal) for methyl isobutyl
        ketone
 1501:   GC-FID using solid sorbent tube (coconut shell charcoal) for cumene
 1600:   GC-Sulfur  FPD using solid sorbent  tube (coconut shell charcoal) 4- drying tube
        (sodium sulfate) for carbon disulfide
 1614:  GC-ECD using solid  sorbent tube (HBr-coated petroleum charcoal) for ethylene
       oxide and propylene oxide
2002:  GC-FID using solid sorbent tube  (silica gel) for o-toluidine and  N,N-dimethyl
       formamide
2004:  GC-FID using solid sorbent tube  (silica gel) for N,N-dimethyl formamide
2005:  GC-FID using solid sorbent tube  (silica gel) for nitrobenzene

                                      75

-------
 2501:  GC-Nitrogen-specific detector using solid sorbent tube (2-
        (hydroxymethyl)piperidine on XAD-2) for acrolein
 2508:  GC-FID using solid sorbent tube (petroleum-based charcoal) for isophorone
 2514:  HPLC-UV using solid sorbent tube (XAD-2) for o-anisidine
 2515:  GC-FID using solid sorbent tube (octanoic acid-coated XAD-2 resin) for
        diazomethane
 2522:  GC-TEA using solid sorbent tube (Thermosorb/N™ air sampler) for N-
        nitrosodimethylamine
 2524:  GC-electrolytic conductivity detector using solid sorbent tube (Porapak P) for
        dimethyl sulfate
 2528:  GC-FID using solid sorbent tube (Chromosorb) for 2-nitropropane
 2530:  GC-FID using solid sorbent tube (Tenax) for biphenyl
 2535:  HPLC-UV using tube with reagent-coated glass wool (N-[(4-
        nitrophenyl)methyl]-propylamine) for 2,4-toluene diisocyanate
 3503:  Visible absorption spectrophotometry using bubbler (HC1) for hydrazine
 3509:  Ion chromatography, ion pairing using impinger (hexanesulfonic acid) for
        diethanolamine
 5001:  HPLC-UV using glass fiber filter for 2,4-D diethylamine
 5004:  HPLC-UV using cellulose ester membrane filter for hydroquinone
 5006:  Visible absorption spectrophotometry using glass fiber filter for carbaryl
 5011:  Visible absorption spectrophotometry using PVC or mixed cellulose ester
        membrane for ethylene thiourea
 5029:  HPLC-UV/Electrochemical detector using acid-treated glass fiber filter for 4,4'-
        methylenedianiline
 5500:  GC-FID using  glass fiber filter + silica gel sorbent for ethylene glycol
 5509:  HPLC-UV using glass fiber filter + silica gel sorbent tube for 3,3'-
        dichlorobenzidine
 5516:  HPLC-UV using impinger (l-(2-methoxyphenyl)-piperazine in toluene) for 2,4-
        toluenediamide
 5521:  HPLC-UV/Electrochemical detector using impinger (l-(2-methoxyphenyl)-
        piperazine in toluene) for 2,4-toluene diisocyanate and 4,4'-methylenediphenyl
        diisocyanate
 6001:  Atomic absorption with graphite furnace using solid sorbent tube (coconut shell
        charcoal) for arsine
 6010:  Visible absorption spectroDhotometry using solid sorbent tube (soda lime) for
        HCN
 6011:  Ion chromatography, conductivity detection using silver membrane filter for
        bromine and chlorine
7300:   Inductively coupled argon plasma, atomic emission spectroscopy using cellulose
        ester membrane filter for phosphorous
7400:   Phase contrast light microscopy using  cellulose ester membrane filter for
        asbestos
7402:   Transmission electron microscopy using cellulose ester membrane filter  for
        asbestos
                                        76

-------
7903:  Ion chromatography using washed silica gel sorbent tube (with glass fiber filter
       plug) for HF and HC1
7904:  Ion-specific electrode using filter (cellulose ester membrane) + bubbler (sodium
       hydroxide) for cyanides, aerosol and gas
7905:  GC-phosphorous FPD using Tenax sorbent tube for phosphorous
8302:  For 4,4'-Methylenebis(2-chloroaniline) in urine matrix
OSHA Methods
"OSHA Analytical Methods Manual", Second Edition, Parts I and II, U.S. Department
of Labor, Occupational Safety and Health Administration, Salt Lake City, Utah,
January 1990.

[10]:   GC-ECD using two bubblers (2,4,6-trichlorophenol and  sodium methoxide in
       methanol) for bis(chloromethyl)ether
[20]:   Spectrophotometry or HPLC-UV using  sulfuric acid-coated Glass Chrom R
       collection tubes for hydrazine
[21]:   GC-nitrogen/phosphorous detector using glass fiber filter and silica gel for
       acrylamide
[24]:   HPLC-UV using bubbler (hydrochloric  acid) for 4,4'-methylenebis(2-
       chloroaniline)
[25]:   HPLC-UV using two adsorption tubes (p-anisidine-coated XAD-2, untreated
       XAD) for maleic anhydride
[42]:   HPLC-UV or fluorescence detection using coated glass fiber filters (l-(2-
       pyridyl)piperazine) for hexamethyl-l,6-diisocyanate
[54]:   HPLC-UV or fluorescence detection using coated XAD-7 tubes (l-(2-
       pyridyl)piperazine) for methyl isocyanate
[57]:   GC-ECD using sulfuric acid-treated glass fiber filters for 4,4'-
       methylenedianiline
[63]:   HPLC-UV using glass fiber filter and XAD-2 adsorbent in OSHA versatile
       sampler tubes for carbaryl
[65]:   GC-ECD using sulfuric acid-treated glass fiber filters for 2,4-toluenediamine
       and 3,3'-dichlorobenzidine
[71]:   GC-ECD using sulfuric acid-treated glass fiber filters for 4,4'-methylenebis(2-
       chloroaniline)
[73]:   GC-ECD using sulfuric acid-treated glass fiber filters for o-toluidine
[86]:   HPLC-UV using coated glass fiber filters (3,4-dimethoxybenzylamine) for
       maleic anhydride
[90]:   HPLC-UV coated glass fiber filters (3,4-dimethoxybenzylamine) for phthalic
       anhydride
[ID101]:   Ion-specific electrode using midget  glass bubbler (sulfamic acid) for chlorine
[ID105]:   Atomic absorption spectroscopy with heated graphite atomizer using mixed-
           cellulose ester filter for arsine
[ID160]:   Phase contrast microscopy using mixed-cellulose ester filter for asbestos
[ID174SG]:       For hydrogen chloride

                                        77

-------
 [ID 180]:  Ion chromatography using potassium hydroxide-impregnated beaded carbon
           for phosphine

 "Chemical Information Manual" (CIM), U.S. Department of Labor, Occupational
 Safety and Health Administration, Washington, D.C., July 1991.

 [0065]:    HPLC-UV using glass fiber filter for 2-acetylaminofluorene
 [P129]:    HPLC-UV using coated XAD-2 tube (1-naphthyl isomiocyanate) for
           diethanolamine
 [0225]:    HPLC-UV using XAD-2 tube for o-anisidine
 [T338]:    HPLC-UV using glass fiber filter with Chromosorb 102 tube for trifluralin
 [B408]:    GC-FID using Tenax GC tube for benzotrichloride
 [0524]:    HPLC-UV using OSHA versatile sampler containing XAD-7 tube with glass
           fiber filter for caprolactam
 [0612]:    GC-ECD using mixed-cellulose ester filter for toxaphene
 [0618]:    HPLC-UV using two Tenax tubes for 2-chloroacetaphenone
 [A625]:    GC-NPD using silica gel tube for acetamide
 [D639]:    HPLC-UV using bulk sample media for dibenzofuran
 [1911]:    GC-FID using glass fiber filter and silica gel tube for ethylene glycol
 [2222]:    HPLC-UV using XAD-2 tube for quinone

 EPA Methods
 "Screening Methods for the Development of Air Toxics Emission Factors", PB92-
 108778, EPA-450/4-91-021, September 1991, USEPA, Research Triangle Park, NC.

 EPA 15:   "Detection of Hydrogen  Sulfide, Carbonyl Sulfide, and  Carbon Disulfide
           from Stationary Sources", Standards of Performance for New Stationary
           Sources.  Compilation U.S. Environmental Protection Agency, EPA-340/1-
           77-015.  Gas sample drawn through heated sample probe followed by a
           paniculate filter. Analysis is by GC/FPD.

EPA 23:    "Determination  of Polychlorinated Dibenzo-p-dioxins (PCDDs) and Poly-
           chlorinated Dibenzofurans (PCDFs) from Stationary Sources" Federal
           Register, February 13, 1991 (56 FR 5758).  To be included in 40 CFR Part
           60, Appendix A. Sample is drawn through a probe, a glass fiber filter, and
          a XAD-2 trap.  Extraction is by toluene and analysis by GC/MS.

EPA 114:  "Test Methods for Monitoring Radionuclide Emissions from Stationary
          Sources"  Standards of Performance for New Stationary Sources.
          Compilation.  U.S. Environmental Protection Agency, EPA-340/1-77-015.
          Paniculate sampling is by a filter that has a high efficiency for
          submicrometer particles.  Gaseous sampling is by various media: silica gel,
          charcoal, caustic solution.  Analysis is by alpha, beta, and gamma analysis.
                                      78

-------
 —
 Collection of whole air in canisters, separation of co-collected water using a two-stage
 sorbent trap, thermal  desorption, and analysis by GC with ion trap MS detection.

 Kelly, T.J., Callahan, P.J., Pleil, J.P., Evans, G.F., Method Development and Field
 Measurements  for Polar Volatile Organic Compounds in Ambient Air, Environ. Sci.
 Technol.,  1993, 27(6), 1146-53.

 R-2
 Sampling at 10 LPM  using a Teflon microfiber matrix (4-in.-dia. filter) impregnated
 with  5 urn particles of AG-1 anion exchange resin; analyzed using BSTFA
 derivatization and EI-GC/MS.

 H. Burkholder, M. Brinkman,  M. Nishioka, J. Hodgeson, and J. Pleil, Anion
 Exchange Resins for Collection of Phenols from Air and Water, in Proceedings of the
 16th  Annual EPA Conference on Analysis of Pollutants in the Environment, Norfolk
 VA,  May  1993.

 Nishioka, M.G.,  Burkholder, H.M., Evaluation of an Anion Exchange Resin for
 Sampling Ambient Level Phenolic Compounds, Final Report for EPA Contract No. 68-
 02-4127/WA-69 and -80, Battelle, Columbus, Ohio, April 1990.
 Collection using three-stage tubes packed with Carbosieve S-m, Carbotrap, and
 Carbotrap C; desorption and refocusing onto an electrically cooled Carbosieve-in and
 Carbotrap sorbent bed; analysis by GC/FID and ECD.

 Pollack, AJ, Gordon, S.M., Moschandreas, D.J., Evaluation of Portable Multisorbent
 Air Samplers for Use with an Automated Multitube Analyzer, Final Report for EPA
 Contract No.. 68-DO-0007/WA-27, September 1992.
Methods of Air Sampling and Analysis, 3rd Ed., Lodge, J.P. Jr., editor, Intersociety
Committee on Methods of Air Sampling and Analysis, Lewis Publishers, Inc., Chelsea,
Michigan, 1989.

[14]     Infrared Absorption Spectroscopy (using Saran or Mylar plastic bag sampler
         or silica gel) for VOCs
[205]:    Determination of Fluoride Content of Plant Tissues (Potentiometric Method)
[301]:    Determination of Paniculate Antimony Content in the Atmosphere (using
         membrane, cellulose or glass fiber filters and visible absorption
         spectrophotometry)
[302]:    Determination of Arsenic Content of Atmospheric Paniculate Matter (using
         membrane or glass fiber filters and visible absorption spectrophotometry)
                                       79

-------
 [317]:    Determination of Elemental Mercury in Ambient and Workroom Air by
          Collection on Silver Wool and Atomic Absorption Spectroscopy
 [606A]:   Estimation of Airborne Radon-222 by Filter Paper Collection and Alpha
          Activity Measurements of Its Daughters (Thomas Method or Modified
          Kusnetz Method)
 [606B]:   Determination of Airborne Radon-222 by Its Absorption from the
          Atmospheric and Gamma Measurement (using charcoal adsorbent)
 [804]:    As, Se, and Sb in Urine and Air by Hydride Generation and Atomic
          Absorption Spectrometry (using cellulose acetate membrane filter)
 [805]:    Determination of Chlorine in Air (using midget impinger with sodium acetate
          and potentiometric analysis)
 [809]:    Determination of Fluorides and Hydrogen Fluoride in Air (using impingers
          with sodium hydroxide)
 [822]:    General Atomic Absorption Procedure  for Trace Metals in Airborne Material
          Collected on Filters (using membrane filters) for paniculate inorganics
 [822B]:   X-Ray Fluorescence Spectrometry for Multielemental Analysis of Airborne
          Paniculate and Biological Material
 [829]:    Determination of Chloromethyl Methyl Ether (CMME) and Bis-Chloromethyl
          Ether (Bis-CME) in Air (using GC-ECD and impingers with a methanolic
          solution of the sodium salt of 2,4,6-trichlorophenol)
 [831]:    Determination of p,p-Diphenylmethane Diisocyanate (MDI) in Air (using
          midget impingers with hydrochloric and acetic acids  and visible absorption
          spectrophotometry)
 [835]:    Determination of EPN, Malathion and Parathion in Air (using glass fiber
          filters and GC-flame photometric detection)
 [836]:    Determination of Total Paniculate Hydrocarbons (TpAH) in Air:  Ultrasonic
          Extraction Method (using glass fiber filters and HPLC-UV)
 [837]:    Determination of 2,4-Toluene Diisocyanate (TDI) in Air (using midget
          impingers with hydrochloric and acetic acids and visible absorption
          spectrophotometry)
High volume air sampling with glass fiber filter and polyurethane foam sorbent; solvent
extraction and chromatographic cleanup; analysis by high resolution gas
chromatography and high resolution mass Spectrometry (HRGC/HRMS), with multiple
isotopically labelled internal surrogate standards. Analysis based on guidelines of EPA
Methods 8280 and 8290.

Hunt, G.T., Maisel, B.E.,  Atmospheric Concentrations of PCDDs/PCDFs in Southern
California, J. Air Waste Mgt. Assoc., 1992, 42:672-680.
Automated gas chromatography with detection by BCD and FID.  Sample collection
performed hourly using a three-stage sorbent trap, with refocusing on a cryogenic
(-186°C) trap for analysis.
                                       80

-------
 Purdue, L.J., Reagan, J.A., Lonneman, W.A., Lawless, T.C., Drago, R.J., Zalaquet,
 G.M., Holdren, M.W., Smith, D.L., Pate, A.D., Buxton, B.E., Spicer, C.W., Atlanta
 Ozone Precursor Monitoring Study Data Report, EPA/600/R-92/157, U.S.
 Environmental Protection Agency, Washington, D.C., September 1992.

 R-7
 Canister collection of whole air samples; analysis by gas chromatography/multiple
 detector (ECD, FID, PID) method.

 McAllister, R., Bowles, E., DeGarmo, J., Rice, J., Jongleux, R.F., Merrill, R.G., Jr.,
 and Bursey, J., 1990 Urban Air Toxics Monitoring Program.  Report No. EPA-450/4-
 91-024, prepared for U.S. Environmental Protection Agency by Radian Corporation,
 Research Triangle park, NC, June 1991.
 Sampling with denuder/filter/XAD resin combinations, extraction, and analysis by ion
 chromatography.

 Eatough,  D.J., White, V.F., Hansen, L.D., Eatough, N.L., Cheney, J.L., Identif-
 ication of Gas-Phase Dimethyl Sulfate and Monomethyl Hydrogen Sulfate in the Los
 Angeles Atmosphere, Environ. Sci. Technol., 1986, 20:867-872.

 Hansen, L.D., White, V.F., Eatough, D.J., Determination of Gas-Phase Dimethyl
 Sulfate and Monomethyl Hydrogen Sulfate, Environ. Sci. Technol., 1986, 20:872-878.
Four distinct methods:  1) collection on Thermosorb A, solvent extraction, and analysis
by GC with nitrogen-selective detector; 2) collection on Tenax, thermal desorption, and
GC/MS analysis; 3) grab sampling with analysis by portable GC/FID; 4) atmospheric
pressure ionization quadrupole MS.

Clay, P.P. (NUS Corp., Bedford, Mass), Spittler, T.M. (U.S. EPA, Region I,
Lexington, Mass), Determination of airborne volatile nitrogen compounds using four
independent techniques. Proceedings of Natl. Conf. Manage. Uncontrolled Hazard
Waste Sites. Hazard. Mater. Control Res. Inst.: Silver Spring, Maryland, 1983, pp
100-104.

R-10
Cryogenic trapping, thermal desorption, and GC analysis with flame photometric
detection

Maroulis, P.J., Torres, A.L., Bandy, A.R., Atmospheric concentrations of carbonyl
sulfide in the southwestern and eastern United States, Geophys. Res. Lett., 1977,
4:510-512.
                                       81

-------
 Torres, A.L., Maroulis, P.J., Goldberg, A.B., Bandy, A.R., Atmospheric OCS
 measurements on Project Gametag, J. Geophys. Res., 1980, C12:7357-7360.

 E-n
 Cryogenic trapping, thermal desorption, and sequential GC analysis of two samples
 collected simultaneously with flame photometric detection.

 Maroulis, P.J., Bandy, A.R., Measurements of atmospheric concentrations of C&2 in
 the eastern United States, Geophys. Res. Lett., 1980, 7:681-684.

 R-12
 Collection on Tenax sorbent, thermal desorption to a cryogenic focussing trap, and
 GC/MS analysis.

 Pellizzari,  E.D., Bunch, I.E., Ambient air carcinogenic vapors:  improved sampling and
 analytical techniques and field studies, EPA-600/2-79-081, NTIS No. PB-297-932, U.S.
 Environmental Protection Agency, Research Triangle Park, NC, May 1979.

 R-13
 Collection  in canisters or cryogenically, with four detection methods.  (1) Ion Trap
 GC/MS - detection limit of 1 pptv. (2) Quadrupole GC/MS with Selective Ion
 Monitoring - detection limit of 10 pptv.  (3) Gas Chromatography with Photoionization
 Detection - detection limit 10 pptv. (4) Quadrupole GC/MS with Full Scan
 Monitoring - detection limit of 0.1 ppbv.  Also Portable Gas Chromatograph with
 Photoionization Detection - detection limit of 0. 1 ppbv.

 Havlicek, S.C., Hilpert, L.R.,  Dai, G., Pierotti, D., Assessment of Ethylene Oxide
 Concentrations and Emissions from Sterilization and Fumigation Processes (PB93-
 216793; available NTIS).  Final report by Coast-to-Coast Analytical Services, Inc., San
 Luis Obispo, CA, to California Air Resources  Board, Sacramento, CA, Contract No.
 ARB-A832-125, 78 pp, May 1992.
Collection on XAD-4 resin Soxhlet extraction in dichloromethane and then in
ethylacetate, analysis by GC/MS with positive chemical ionization.

Chuang, J.C., Mack, G.A., Kuhlman, M.R., Wilson, N.K., Polycyclic Aromatic
Hydrocarbons and Their Derivatives in Indoor and Outdoor Air in an Eight-Home
Study, Atmos. Envir., 1991, 25(3): 369-380.
Collection on XAD-2 or PUF, Soxhlet extraction in 10 percent ether/hexane or
methylene chloride, analysis by GC/MS.
                                       82

-------
 Chuang, J.C., Hannan, S.W., Wilson, N.K., Field Comparison of Polyurethane Foam
 and XAD-2 Resin for Air Sampling for Polynuclear Aromatic Hydrocarbons, Envir.
 Sci. Tech., 1987, 21(8): 798-804.

 R-16
 Air sampling methods discussed with references; minimum detectable levels provided
 for a number of paniculate and gaseous radionuclides in air presented, assuming
 standard gamma-scan-400 to 512 multichannel analyzer - 4 x  4-inch Nal (Te) detector
 or liquid scintillation counting,  with references.

 CRC Handbook of Environmental Radiation, Ed. Alfred W. Clement, Jr., CRC Press,
 Inc., Boca Raton, FL, 1982.

 R-17
 Background information on radioactivity detectors, measurement procedures, quality
 assurance, and statistical analysis of radioactivity measurements.

 Handbook of Radioactivity Measurements Procedures,  NCRP Report No. 58, National
 Council on Radiation Protection and Measurements, Bethesda, MD, 1985.

 R-18
 Collection on Teflon filter and iodated activated carbon, acid  digestion,  and analysis by
 cold vapor atomic absorption.

 Lindbergh,  S.E., Turner, R.R., Meyers, T.P., Taylor, G.E., Jr.,  Schroeder, W.H.,
 Atmospheric concentrations and deposition of Hg to a deciduous forest at Walker
 Branch Watershed, Tennessee, USA, Water, Air, Soil Poll., 1991, 56:577-594.

 Turner, R.R., Bogle, M.A., Heidel, L., McCain, L., Mercury in  ambient air at the
 Oak Ridge Y-12 plant July 1986 through December 1990, Y-12 report Y/TS-574, Oak
 Ridge National Laboratory, Oak Ridge, Tennessee,  1991.

 R-19
 Collection on alkaline-impregnated glass fiber filters, aqueous extraction, and ion
 chromatographic analysis using  "negative" UV photometric detection with a strongly
 UV-absorbing eluent.

 Grosjean, D., Liquid chromatography analysis of chloride and nitrate with "negative"
 ultraviolet detection: ambient levels and relative abundance of gas-phase inorganic and
 organic acids in southern California, Environ. Sci. Technol.,  1990, 24:77-81.

R-20
Revision of ASTM Method D-3266, involving collection of HF on alkaline-impregnated
tape, aqueous extraction, and analysis by ion-selective electrode.
                                       83

-------
 Zankel, K.L., McGirr, R., Romm, M., Campbell, S.A., Miller, R., Measurement of
 ground-level concentrations of hydrogen fluoride, J. Air Poll. Control Assoc.,  1987,
 37:1191-1196.

 R-21
 Collection on Nuclepore (i.e., polycarbonate) filters, carbon coating by vapor
 deposition, and electron microscopic examination.

 Samudra, A.U., Harwood, C.F., Stockhalm, J.D., Electron microscope measurement
 of airborne asbestos concentration. EPA-600/1-77-178, U.S. Environmental Protection
 Agency, Research Triangle Park, NC, 1977.

 See also discussion in:
 Asbestiform Fibers: Nonoccupational  Health Risks, published by National Academy
 Press, National Academy of Sciences, Washington, D.C., pp 82-96, 1984.

 R-22
 Sampling using a chilled acetone collection medium to trap hydrazines and convert to
 stable derivatives; acetone solution analyzed directly for derivatives using a gas
 chromatograph with nitrogen-specific  detectors.

 Holtzclaw, J.R., Rose, S.L., Wyatt, J.R., Ronnbehler, D.P., Fine, D.H., Simultaneous
 Determination of Hydrazine, Methylhydrazine, and 1,1-Dimethyl Hydrazine in Air by
 Derivatization/Gas Chromatography, Anal. Chem., 1984, 56: 2952-2956.
Collection and derivatization in toluene solution containing N-(4-nitrobenzyl)-N-n-
propylamine hydrochloride (NBPA); analysis by HPLC and UV detection.

Holdren, M.W., Spicer, C.W., Riggin, R.M., Gas phase reaction of toluene
diisocyanate with water vapor, Am. Ind. Hygiene Assoc. J., 1984, 45:626-633.

Dunlap, K.L., Sandridge, R. L., Keller, J., Determination of isocyanates in working
atmospheres by high-speed liquid chromatography, Anal. Chem., 1976, 45:497-499.
Continuous real-time monitoring based on color formation in a substrate-impregnated
tape, with electro-optical measurement of color intensity.  The unit has a useful range
up to 200 ppbv of TDI, with a detection limit of 1 ppbv.

The monitor is sold as the TLD-1 by MDA Scientific, Inc., Lincolnshire, Illinois.
                                       84

-------
 Sampling at 0.1 LPM using 200-400 mesh granular AG-1 anion exchange resin;
 analyzed using EI-GC/MS and/or GC/FID; methylation and GC/ECD for chlorinated
 phenols.

 Nishioka, M.G., Burkholder, H.M., Evaluation of an Anion Exchange Resin for
 Sampling Ambient Level Phenolic Compounds, Final Report for EPA Contract No. 68-
 02-4127/WA-69 and -80, Battelle, Columbus, Ohio, April 1990.

 R-26
 Passive sampling using commercial samplers with activated carbon as sorbent; solvent
 extraction and concentration;  analysis by GC/MS.

 Shields, H.C., Weschler, C.J., Analysis of ambient concentrations of organic vapors
 with a passive sampler, J. Air. Poll. Control Assoc., 1987, 37:1039-1045.

 R-27
 Collection on polyurethane foam (sampling for 24 hours at 3.8 L/min), solvent
 extraction and evaporative concentration, analysis by GC/ECD and GC/MS (multiple
 ion mode).

 Immerman, F.W., Schaum, J.L., Final Report of the Nonoccupational Pesticide
 Exposure Study (NOPES), EPA-600/3-90-003, U.S. Environmental Protection Agency,
 Research Triangle Park, NC, 1990.

 Whitmore, R.W., Immerman, F.W., Camann, D.E., Bond, A.E., Lewis, R.G.,
 Schaum, J.L., Nonoccupational Exposures to Pesticides for Residents of Two U.S.
 Cities, Arch. Environ. Contam. Toxicol., 1994, 26:47-59.
Collection on glass fiber filters and polyurethane foam or Florisil sorbents.  Solvent
extraction, cleanup on Florisil, evaporative concentration, and analysis by GC/ECD.

Atlas, E., Giam, C.S., Ambient concentration and precipitation scavenging of
atmospheric organic pollutants, Water Air Soil Poll., 1988, 38:19-36.

Chang, L.W., Atlas, E., Giam, C.S., Chromatographic separation and analysis of
chlorinated hydrocarbons and phthalic acid esters from ambient air samples, Int. J.
Environ.  Anal. Chem.,  1985, 19:145-153.

R-29
Collection with glass fiber filters and polyurethane foam; solvent extraction, cleanup on
Florisil, evaporative concentration; analysis by GC/ECD and GC/MS.
                                      85

-------
  Hoff, R.M., Muir, D.C.G., Grift, N.P., Annual cycle of polychlorinated biphenyls and
  organohalogen pesticides in air in southern Ontario 1. Air concentration data, Environ.
  Sci. Technol., 1992, 26:266-275, and references therein.

  R-30
  High volume or low volume sampling of ambient air.  Collection on glass fiber filters
  and polyurethane foam, solvent extraction,  evaporative concentration, and analysis by
  GC/ECD or GC/MS.

  Lewis, R.G., Bond, A.E., Johnson, D.E.,  Hsu, J.P., Measurement of atmospheric
  concentrations of common household pesticides: a pilot study, Environ. Monitoring and
  Assessment, 1988,  10:59-73.
 Collection on glass fiber filters and on any of three sorbents: polyurethane foam, XAD-
 2 resin, or Tenax GC. Solvent extraction, cleanup, and analysis by GC/ECD.

 Billings, W.N., Bidleman, T.F.,  High volume collection of chlorinated hydrocarbons in
 urban air using three solid sorbents, Atmos. Environ., 1983,  17:383-393.

 R-32
 Filter sampling at 1.5 LPM, total sampling volume of 240-L using PVC filters;
 extraction using buffer solution, pH = 4.5; trisodium pentacyanoaminoferrate reagent;
 colorimetric analysis in 30 min at 475 nm in 1-cm glass cells; paper provides sampling
 conditions, extraction solvents, reagents, analytical conditions, and detection ranges for
 colorimetric determination.

 Freixa, A., Magti, A., Application of colorimetric techniques to the measurement of air
 pesticide content, Pergamon Ser.  Environ. Sci., 1982, 7: 297-298.

 R-33
 Gas chromatography with flame photometric detection (GC-FPD) using a column (0.5
 m x 2.5 mm i.d.) packed with GDX-101.  Phosphene retention time 19 s at 80 C; ratio
 of H to 0 of 10:3.

 Qi, Xiaofei, Quantitative determination of trace phosphine in ambient air by gas
 chromatography with a flame photometric detector, Sepn, 1987,  5(4):  243-5 (in
 Chinese).
Chemiluminescence emission from arsine due to reaction of sampled air with ozone.

Inone, K., Suzuki, M., Kawabayashi, O., Method and Apparatus for
Chemiluminescence Analyses, Ger. Offen., DE 3525700/A1/860206 (German patent),
1986 (reports detection limit of 1 ppb for arsine).


                                      86

-------
 Fraser, M. E., Stedman, D. H., Henderson, M. J., Gas-phase Chemiluminescence of
 Arsine Mixed with Ozone, Anal. Chem., 1982, 54(7): 1200-1.

 R-35
 Analysis using gas chromatography and an alkali flame ionization detector (N-detector);
 acidified aqueous solutions directly injected on the column.

 Donike, M., Gas chromatographic trace analysis of hydrocyanic acid in the nano- and
 picogram range, Mitteilungsbl. GDCh-Fachgrappe Lebensmittelchem. Gerichtl. Chem.,
 1974, 28(1-2): 46-52 (in German).

 R-36
 Collection of paniculate material from air, analysis by HPLC with electrochemical
 detection.

 Riggin, R.M., Howard, C.C., Scott, D.R., Hedgecoke, R.L., Determination of
 benzidine, related  congeners, and pigments in atmospheric paniculate matter, J.
 Chromatogra. Sci., 1983,  21:321-325.

 R-37
 Derivatization of amines to the corresponding amides by reaction with a perfluoro-acid
 anhydride, gas chromatographic separation, and analysis by N-selective thermionic
 detection.

 Skarping, G., Renman,  L., Dalene, M., Trace analysis of amines and isocyanates using
 glass capillary gas chromatography and selective detection, n. Determination of
 aromatic amines as perfluorofatty acid amides using nitrogen-selective detection, J.
 Chromatogr., 1983, 270:207-218.

 R-38
 GC/ECD method for 2,4-D salts and  acid.

 Nishioka, M., Burkholder, H., Brinkman, M., Gordon, S., Lewis, R., "Simulation of
 track-in of lawn-applied herbicide acids from turf to home: Comparison of dislodgeable
 turf residues with carpet dust and carpet surface residues, prepared for submission to
 Environ. Sci. Technol.,  1993.

 R-39
 Collection on Tenax-GK sorbent, thermal desorption, gas chromatography with Hall
electrolytic chlorine-sensitive detection.

Matienzo, L.J., Hensler, C.J., Determination of N,N-dimethylcarbamoyl chloride
(DMCC) in air, Am. Indus. Hygiene  Assoc. J., 1982, 43:838-844.
                                       87

-------
 R-40
 Collection with glass fiber filter and Tenax GC sorbent, thermal desorption, cryogenic
 concentration, and analysis by GC/MS.

 Krost, K.J., Pellizzari, E.D., Wlaburn, S.G., Hubbard, S.A., Collection and analysis
 of hazardous organic emissions, Anal. Chem., 1982, 54:810-817.

 R-41
 Collection in methylisobutyl  ketone, gas chromatography with sulfur-selective detection.
 Alternatively, collection and  derivatization on the pre-coated walls of a diffusion
 denuder tube, and determination by HPLC with UV detection.

 Oldeweme, J., Klockow, D., Chromatographic procedures for the determination of 1,3-
 propanesultone in workplace air, Fresenius Z. Anal. Chem.,  1986, 325:57-63.
 Collection in aqueous KOH solution containing methanol and hydroxyl amine, to form a
 derivative. The iron complex of that derivative is determined quantitatively by
 absorbance of 530 nm.

 Jozwicka, J., Spectrophotometric method for determination of monochloroacetic acid
 vapors in workplace air, Wlokna Chem., 1990,  16:394-401.

•R-43
 Workplace air monitoring of caprolactam; collection on filter and XAD-2 tubes or
 XAD-2 tubes only; desorption with methanol containing 2 percent water, or with
 MeCN; analysis by GC or HPLC.  Sampled air volume of 100 L yields detection limit
 of 0.20 mg/m3 using HPLC analysis, and 0.10 mg/m3 using GC analysis.

 Nau, D.R., Darr, R.W., Gad, S.C., Pai, S.V., Validation study of a method for
 monitoring personnel exposure to caprolactam, Proc Symp. Ind.  Approach Chem. Risk
 Assess.: Caprolactam Relat. Compd. Case Study, 275-91. Ind. Health Found.:
 Pittsburgh, PA, 1984.

 R-44
 Detection of caprolactam in workplace air and toxicol. studies; aerosols sampled on
 filter AFA-KhA-20 at 2 L/min, extracted with di-Et ether or a 1:1  EtOH/ether mixture;
 evaporated, and Chromatographic drying in Cl, analysis by thin-layer chromatography
 with a mobile alcohol solvent system;  and development with o-tolidine solution or fresh
 Kl-starch reagent.  Detection limit is 0.005 mg/m3; cyclohexanone, hydroxylamine, and
 NH3 stated not to interfere with method.

 Ledovskikh, N.G., Sensitive method for the determination of caprolactam in air, Gig.
r. Prof.  Zabol., 1982, 10: 52-3 (in Russian).

-------
 Collection by charcoal adsorbent tube (or silica gel tube under high humidity
 conditions); desorption using distilled water then carbon disulfide; analysis of both
 layers by GC-FID.

 Langhorst, M.L., Glycol Ethers   Validation Procedures for Tube/Pump and Dosimeter
 Monitoring Methods,  Am. Ind. Hyg. Assoc. J., 1984, 45:416-424.

 R-46
 Personal air sampling through polyurethane foam plug; extraction in hexane; solvent
 transfer to toluene; analysis by GLC.

 Nigg, H.N., Stamper, J.H., Exposure of Spray Applicators and Mixer-Loaders to
 Chlorobenzilate Miticide in Florida Citrus Groves,  Arch. Environ.  Contam. Toxicol.,
 1983, 12:477-482.

 R-47
 Headspace gas  chromatography is applied for the analysis of water in liquid and solid
 samples with the preferred quantitation technique being standard addition.

 Kolb, B., Auer, M., Analysis for Water in Liquid and Solid Samples by Headspace
 Gas Chromatography.  Part I:  Liquid and Soluble Solid Samples, Fresenius. Z. Anal.
 Chem., 1990, 336:291-6.

 R-48
 Sampling via an activated carbon fiber felt put between quartz filters and determination
 by gas chromatography-mass spectroscopy.

 Suzuki, S., Simultaneous Determination of Airborne Pesticides by GC/MS, Bunseki
 Kagaku,
 1992, 41:115-24 (in Japanese).

 R-49
 Collection on XAD resins and determination by gas chromatography-mass spectroscopy
 and a nitrogen-phosphorous detector.

 Yeboah, P.O., Kilgore, W.W., Analysis of Airborne Pesticides in a Commercial
 Pesticide Storage Building, Bull. Environ.  Contam. Toxicol., 1984, 32:629-34.

R-50
High volume sampling with collection on a cartridge containing PUF/Tenax/PUF.
Multiple extraction, derivation, and analysis by GC/MS or GC/ECD.

McConnell, L.L., Patton, G.W.,  Zaranski, M.T., Bidleman, T.F., Development of a
collection  method for chlorophenolic compounds in air, in Proceedings of the 1989

                                       89

-------
 EPA/AWMA Symposium on Measurement of Toxic and Related Air Pollutants,
 Publication VIP-13, EPA-600/9-89-060, Air and Waste Mgt. Assoc., Pittsburgh, pp
 623-628, 1989.

 E-51
 Collection with glass fiber filters and polyurethane foam sorbent. Solvent extraction
 after spiking with 13C-labelled isomers, chromatographic cleanup of the extracts, and
 evaporative concentration.  Analysis by GC/MS using electron impact or electron
 capture negative ion modes.

 Eitzer, B.D., Kites, R.A., Polychlorinated dibenzo-p-dioxins and dibenzofurans in the
 ambient  atmosphere of Bloomington, Indiana, Environ. Sci. Technol., 1989, 23:1389-
 1395.

 Edgerton, S.A., Czuczwa, J.M., Rench, J.D., Hodanbosi, R.F., Koval, P.J., Ambient
 air concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans in Ohio:
 Sources  and health risk assessment, Chemosphere,  1989, 18:1713-1730.

 R-52
 High volume sampling with a Teflon-impregnated glass fiber filter and  three PUF
 sorbent plugs in series; addition of deuterated internal  standards; solvent extraction and
 evaporative concentration; analysis by HPLC with UV detection.

 Arey, J., Zielinska, B., Atkinson, R., Winer, A.M., Polycyclic aromatic hydrocarbon
 and nitroarene concentrations in ambient air during a wintertime high-NOx episode in
 the Los Angeles basin, Atmos. Environ., 1987, 21:1437-1444.

 R-53
 Collection on Teflon-impregnated glass fiber filters and XAD-2 resin sorbent; multiple
 solvent extractions with addition of deuterated internal standards, and separation of acid
 and base/neutral fractions by HPLC.  Analysis by negative chemical ionization GC/MS.

 Nishioka, M.G., Lewtas, J., Quantification of nitro- and hydroxylated nitro-
 aromatic/polycyclic aromatic hydrocarbons in selected  ambient air daytime winter
 samples,  Atmos. Environ.,  1992, 26A:2077-2087.

 R-54
 Sampling with glass fiber filters and  Tenax-GC and polyurethane foam  sorbent traps;
 solvent extraction with addition of deuterated internal standards; analysis by GC/MS
 with electron impact ionization.

Leuenberger, C., Ligocki, M.P., Pankow, J.F., Trace organic compounds in rain.  4.
Identities, concentrations, and scavenging mechanisms for phenols in urban air and
rain, Environ. Sci. Technol., 1985, 19:1053-1058.
                                       90

-------
Continuous monitoring in air using ion mobility mass spectrometry.

Leasure, C.S., Eiceman, G.A., Continuous detection of hydrazine and
monomethylhydrazine using ion mobility spectrometry, Anal. Chem., 1985, 57:1890-
1894.

R-56
Derivatization on-column with an alkali metal salt of 2,4,6-trichlorophenol to form a
derivative, which is determined immediately by GC with electron capture detection.

Kallos, G.J., Albe, W.R.,  Solomon, R.A., On-column reaction gas chromatography for
determination of chloromethyl methyl ether at one part-per-billion level in ambient air,
Anal. Chem., 1977, 49:1817-1820.

R-57
Collection with glass fiber  filters and Tenax-GC sorbent; solvent  extraction, evaporative
concentration, and analysis by GC/MS.

Cautreels, W., van Cauwenberghe, K., Experiments on the distribution of organic
pollutants between airborne paniculate matter and the corresponding gas phase, Atmos.
Environ., 1978, 12:1133-1141.
Low volume collection on Tenax-GC, thermal desorption, cryofocusing, and GC/MS
analysis in a mobile field sampling laboratory.

Haggert, B., Havkov, R., Design and implementation of a mobile monitoring unit
(MMU) to measure ambient volatile organic compounds, paper 84-17.2, presented at
the 77th Annual Meeting, Air Pollution Control Association, San Francisco, CA, June
1984.
Method stated to be collection of whole air in sampling bags, with analysis by GC with
photoionization  detection.

Hunt, W.F., Jr., Faoro, R.B., Freas, W., Report on the Interim Data Base for State
and Local Air Toxic Volatile Organic Chemical Measurements, Report No. EPA-450/4-
86-012, U.S. Environmental Protection Agency, Research Triangle Park, NC, 1986.

R-60
Modified version of Compendium Method TO-8, using C,8 Sep-Pak cartridges coated
with NaOH for sampling, with analysis by HPLC.  The resolution of the HPLC
analysis is improved by changing the pH  of the acetate buffer, and by using a
sequential bonding end-capped column.

                                       91

-------
 Bratton, S.A., Sampling and measurement of phenol and methylphenols (cresols) in air
 by HPLC using a modified Method TO-8, in Measurement of Toxic and Related Air
 Pollutants, proceedings of the 1992 EPA/AWMA International Symposium, EPA
 Report No. EPA-600/R-92/131, Publication VIP-25, Air and Waste Mgt. Assoc.,
 Pittsburgh, PA, pp. 719-724 (1992).

 R-61
 Adsorption of pentachlorophenol (PCP) onto OV-17 stationary phase, with collection
 /thermal desorption on a 2-minute cycle.  Analysis of desorbed PCP by atmospheric
 pressure chemical ionization tandem mass spectrometry.  Detection limit 40 ng/m3.

 DeBrou, G.B., Ng, A.C., Karellas, N.S., Near real-time measurements of
 pentachlorophenol in ambient air by mobile mass spectrometry, in Measurement of
 Toxic and Related Air Pollutants, proceedings of the 1992 EPA/AWMA International
 Symposium,  EPA Report No. EPA-600/R-92/131, Publication VIP-25, Air and Waste
 Mgt. Assoc., Pittsburgh, PA, pp. 838-843 (1992).

 R-62
 Collection of 2,4-toluene diisocyanate in a derivatizing solution of l-(2-
 pyridyl)piperazine in toluene, in impingers.  The stable TDI/urea derivative is
 determined by HPLC.  Limit of detection for TDI is 116 ng/m3, limit of quantitation is
 351 ng/m3.

 Wilshire, F.W., Knoll, I.E., Foster, S.C., McGaughey,  J.F., Development and
 validation of a source test method for 2,4-toluene diisocyanate, in Measurement of
 Toxic and Related Air Pollutants, proceedings of the  1993 EPA/AWMA International
 Symposium, EPA Report No. EPA-600/A93/024, Publication VIP-34, Air and Waste
 Mgt. Assoc., Pittsburgh, PA, pp. 399-407 (1993).
Collection of airborne asbestos on a polycarbonate or mixed cellulose ester filter,
deposition of carbon under vacuum, and dissolution of the original filter material.
Analysis and counting is conducted by analytical electron microscopy, with
identification by electron diffraction and energy dispersive x-ray spectroscopy.

Doom, S.S., Bums, S.B., Airborne asbestos analysis by analytical electron
microscopy, in Measurement of Toxic and Related Air Pollutants, proceedings of the
1991 EPA/AWMA International Symposium, EPA Report No. EPA/600/9-91/018,
Publication VIP-21, Air and Waste Mgt. Assoc., Pittsburgh, PA, pp. 226-230 (1991).
                                       92

-------
R-64
Cryogenic concentration of a 100 mL air sample, separation by two dimensional gas
chromatography, with flame ionization detection.

Fung, K., A method for the measurement of alcohols and MTBE in ambent air, in
Measurement of Toxic and Related Air Pollutants, proceedings of the 1991
EPA/AWMA International Symposium, EPA Report No. EPA/600/9-91/018,
Publication VIP-21, Air and Waste Mgt. Assoc., Pittsburgh, PA, pp.770-775 (1991).
                                       93

-------
                     APPENDIX D
LISTINGS OF THE 189 HAPs BY ASSIGNED VOLATILITY CLASSES
                         94

-------
   Table D-l.  HAPs grouped by class of compounds, listed in alphabetical order.
          WOCs
   (VP25oC>380mmI%)
Acetaldehyde
1,3-Butadiene
Carbonyl sulfide
Diazomethane
Ethyl chloride
Ethylene oxide
Fonnaldehyde
Methyl bromide
Methyl chloride
Methyl iodide
Phosgene
Propylene oxide
Vinyl bromide
Vinyl chloride
Vinylidene chloride
(Totd of15 HAPs)
                        VOCs
(0.1 mm
                              < 380 mm
Acetonitrile
Acetophenone
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Allyl chloride
Aniline
Benzene
Benzyl chloride
Bis (chloromethyl) ether
Bromoform
Carbon disulfide
Carbon tetrachloride
Catechol
Chloroacetic acid
Chlorobenzene
Chlorofomi
Chloromethyl methyl ether
Chloroprene
Cresol/Cresylic acid (mixed
isomers)
o-Cresol
Cumene
l^-Dibromo-3-chloropropane
1,4-Dichlorobenzene
Dichloroethyl ether
(Bis[2-chloroethyl]etiier)
1,3-Dichloropropene
Diethyl sulfate
N^-Dimethylaniline
Dimethylcarbamoyl chloride
N^-Dimemylformamide
1,1-Dimethylhydrazine
Dimethyl suliate
1,4-Dioxane
Epichlorohydrin
1,2-Epoxybutane
Ethyl acrylate
Ethylbenzene
Ethyl carbamate
Ethylene dibromide
                  Ethylene dichloride
                  Ethyleneimine
                  Ethylidene dichloride
                  Hexachlorobutadiene
                  Hexachloroethane
                  Hexane
                  Isophorone
                  Methanol
                  Methyl chloroform
                  Methyl ethyl ketone
                  Methylhydrazine
                  Methyl isobutyl ketone
                  Methyl isocyanate
                  Methyl methacrylate
                  Methyl tert-butyl ether
                  Methylene chloride
                  Nitrobenzene
                  2-Nitropropane
                  N-Nhroso-N-methylurea
                  N-Nitrosodimethylamine
                  N-Nitrosomorpholine
                  Phenol
                  1,3-Propane sultone
                  beta-Propiolactone
                  Propionaldehyde
                  Propylene dichloride
                  1,2-Propylenimine
                  Styrene
                  Styrene oxide
                  l,lA2-Tetrachloroemane
                  Tetrachloroethylene
                  Toluene
                  1,2,4-Trichlorobenzene
                  1,1^-Trichloroethane
                  Trichloroethylene
                  Triethylamine
                  2^,4-Trimethylpentane
                  Vinyl acetate
                  Xylene (mixed isomers)
                  o-Xylene
                  m-Xylene
                  p-Xylene
                  (Totd of82 HAPs)
                                           95

-------
Table D-l. (continued)
SVOQ
(HT7 mm Hg < VP^oc < 0.1 mmEfe)
Acetamide
4-Aminobiphenyl
oAnisidine
Benzidine
Benzotrichloride
Biphenyl
Bis (2-ethylhexyl)phthalate
Caprolactam
Captan
*
/"^ _l_ t
Carbaryl
*
Chloramben
Chlordane
2-Chloroacetophenone
Chlorobenzilate
m-Cresol
p-Cresol
2,4-D (2,4-Dichloro
phenoxyacetic acid) (incl.
salts and esters)
DDE
Dibenzofurans
Dibutyl phthalate
3,3'-Dichlorobenzidine
Dichlorvos
Diethanolamine
S^'-Dimemylbenzidine
Dimethyl phthalate
4,6-Dinitro-o-cresol
(including salts)
2,4-Dinitrophenol
2,4-Dinhrotoluene
1 ,2-Dipheny Ihydrazine
Ethylene glycol
Ethylene thiourea
Heptachlor
Hexachlorobenzene
1,2,3,4,5,6-Hexachloro
cyclohexane (all stereo
isomers, including Lindane)
Hexachlorocyclo pentadiene
Hexamethylene diisocyanate
Hexamethylphosphoramide
Hydroquinone
MaJeic anhydride
Methoxychlor
4,4'-Methylenediphenyl
diisocyanate
Naphthalene
4-Nitrabiphenyl
4-Nitrophenol
Parathion

Pentachloronitrobenzene
Pentachlorophenol
p-Phenylenediamine
Phthalic anhydride
Polychlorinated biphenyl
Propoxur (Baygon)
Quinoline
Quinone
2,3,7,8-Tetrachlorodibenzo-p-
dioxin
Toluene-2,4-diamine
2,4-Toluene diisocyanate
o-Toluidine
Toxaphene (chlorinated
campnene)
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
Coke Oven Emissions
Glycol ethers
Polycyclic Organic Matter
(Totdof64HAPs)















































NVOQi
(VP25oC
-------
                                         Table D-l.  (continued)
                           WINCs
                     (VP258C>380inmI%)
            Chlorine
            Hydrogen fluoride (Hydrofluoric acid)
            Phosphine
            Arsenic Compounds (Inorganic including
            arsine)
            Cyanide Compounds
            Radionuclides (including radon)
            (Totd of 6 HAPs)
                                                         VJNCs
                                             (0.1 mm Eg < VP2S=C < 380 mm Hg)
                                          Hydrazine
                                          Hydrochloric acid (Hydrogen chloride)
                                          Titanium tetrachloride
                                          (Totd of 3 HAPs)
CUT7
                           SVINCs
                          < VPo  < 0.1 mmHg)
           Phosphorus
           Mercury Compounds
           (Totd of 2 HAPs)
                                                        NVBVCs
                                          Asbestos
                                          Calcium cyanamide
                                          Antimony Compounds
                                          Beryllium Compounds
                                          Cadmium Compounds
                                          Chromium Compounds
                                          Cobalt Compounds
                                          Lead Compounds
                                          Manganese Compounds
                                          Fine mineral fibers
                                         Nickel Compounds
                                          Selenium Compounds
                                          (Totd of 12 HAPs)
Note: A number of HAPs can be categorized in more than one compound class, e.g. mercury compounds in vapor and
particulate forms (SVINC and NVINC). In such cases, the HAPs have been assigned in mis table based on the vapor
pressure of the most volatile species present in ambient air. Thus, for example, mercury compounds have been assigned
to the SVINC category using this rationale, although they are present in ambient air in both SVINC and NVINC forms.
                                                 97

-------