United States National Exposure

Environmental Protection Research Laboratory

Agency Research Triangle Park, NC 27711

E AP Project Summary

Research and Development EPA/600/SR-96/091 August 1996

Abstract

A literature search-based study was

performed to evaluate a selected subset of the 189 analytes listed in Title III

of the Clean Air Act Amendments of

1990 for certain criteria. The overall

objective of this program was to acquire sufficient information about physical properties and chemical characteristics of the compounds to suggest a

technical approach for the sampling

and analysis of these compounds from

stationary sources. A database of the selected Clean Air Act Amendments compounds was prepared in spreadsheet format with detailed physical properties,

chemical characteristics, and a summary categorizing the compounds in

terms of potential sampling and analytical approaches. Recommendations

for the sampling and analytical methodology for selected compounds or

compound classes are also included

where no methods have been documented or evaluated.

This Project Summary was developed

by the National Exposure Research

Laboratory’s Air Methods Research Division, Research Triangle Park, NC, to

announce key findings of the research

project that is fully documented in a

separate report of the same title (see

Project Report ordering information at

back).

Introduction

Title III of the Clean Air Act Amendments (CAAA) of 1990 contains 189 entries as substances to be regulated. Far

more than 189 individual chemicals are to

be regulated, for some of the entries enEvaluation of CAAA Compounds:

Approaches for Stationary

Source Method Development

Denny E. Wagoner, Raymond G. Merrill, Jr., James F. McGaughey and Joan T.

Bursey

compass hundreds of individual compounds: e.g., dibenzofurans as a category

include 135 individual compounds, and

polychlorinated biphenyls include more

than two hundred individual compounds.

The EPA has developed or is evaluating

methods for many of the major chemical

classes of these 189 compounds. Stationary source sampling and analytical methods for these compounds are under various stages of development or evaluation.

In this program, compounds requiring further investigation have been identified and

searches of the literature have been performed to gather information and evaluate

a selected subset of the 189 CAAA entries for certain criteria. Physical properties and chemical characteristics of the

compounds have been evaluated in order

to propose a technical approach for the

sampling and analysis of these compounds

form stationary sources.

The CAAA analytes fall into several categories:

• Compounds which should perform

reasonably well with existing methodologies because they meet the suggested method criteria such as boiling point. However, minimal method

evaluation data are available for the

CAAA analytes, so the performance

of the methodology for the analytes

must be evaluated.

• Compounds which should perform

reasonably well when existing methodology is modified (i.e., compounds

which must be derivatized before gas

chromatographic analysis, compounds

which require a specialized gas chromatographic column, or compounds

which will require use of high perfor-
2

mance liquid chromatography rather

than gas chromatography for analysis).

• Compounds for which a completely

new sampling and analytical approach

must be developed and evaluated.

The study of the literature and evaluation of existing data clearly indicate that

the general sampling and analytical techniques that are commonly utilized (i.e.,

VOST, Method 18, Method 0010/Method

8270, Method 0011) provide adequate

monitoring capability for many of the volatile and semivolatile organic compounds

listed in the CAAA. However, the complexity of the chemical behavior of CAAA

compounds will require the development

of many new and/or modified sampling

and analytical techniques for successful

monitoring.

The mandate of this study was restricted

to selected compounds from the total of

189 entries from the Clean Air Act Amendments. The families of metallic compounds

were excluded from consideration, as were

the families of compounds such as polycyclic organic matter (POM). Also excluded

from consideration were compounds for

which development of specific methods is

presently in progress under EPA Contract

68-D1-0010, including the application of

VOST to volatile halogenated organic compounds and Method 0010/8270 for

semivolatile halogenated organic compounds.

Procedure

The information used to develop the

spreadsheet of chemical information was

derived from a variety of sources, including:

• Internal sources such as various investigators who have been involved

in the development and evaluation of

sampling and analytical methodology

for a wide variety of organic and inorganic compounds;

• “Screening Methods for the Development of Air Toxics Emission Factors,”

an EPA report prepared under EPA

Contract number 68-D9-0054 (EPA450/ 4-91-021);

• “Handbook of GC/MS Data and Information for Selected Clean Air Act

Amendments Compounds,” an EPA report prepared under Contract number

68-D1-0010;

• CRC Handbook;

• NIOSH;

• HON Database;

• Merck Index;

• The Environmental Monitoring Methods Index System (EMMI), which includes information on more than 2,600

analytes from over 80 regulatory and

nonregulatory lists and more than 900

analytes from the Clean Water Act

(CWA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA), Superfund

Amendments and Reauthorization Act

(SARA), Resource Conservation and

Recovery Act (RCRA), Safe Drinking

Water Act (SDWA), the Clean Air Act

(CAA), and analytes from other EPA

and State lists;

• Material Safety Data Sheets for individual compounds;

• Agrochemical Handbook;

• Environmental Science and Technology; and

• Handbook of Toxic and Hazardous

Chemicals.

An Appendix to the report includes a

summary of physical and chemical properties for the compounds of interest, including structures for the compounds.

When sampling or analytical methodology is required for a compound, there are

usually several choices:

• On the basis of physical parameters

such as boiling point, an analyte is

assigned to a methodology, and the

performance of this methodology for

this analyte has been demonstrated

to be effective in previous evaluation

of the methodology;

• An analyte is conditionally assigned

to a methodology on the basis of

physical parameters, chemical judgment, and experience, but no data

are available to define the performance of the assigned methodology;

• An existing methodology does not

work or does not work well for a given

analyte, but a modification of the

methodology (i.e., substitution of

HPLC/MS for GC/MS, substitution of

basic impingers for sorbent in a sampling train) can produce acceptable

performance for a given analyte when

the modified methodology is evaluated; or

• No known sampling/analytical methodology has a reasonable expectation of successful performance; a completely new sampling/analytical

method must be developed to obtain

test data for the analyte.

Existing methodology must be evaluated for a wide variety of Clean Air Act

Amendments analytes, to determine the

range and limitations of existing methodology. To evaluate existing methodology

the following steps are required:

• Establish a successful analysis. The

applicability of the sampling methodology and the sample recovery cannot be evaluated until a given compound can be analyzed accurately and

reproducibly.

• Evaluate the recovery of the compound of interest from the proposed

collection media. Once the compound

analysis is established, the ability to

recovery the compound from the collection media can be evaluated and

new recovery procedures developed,

if required.

• Establish the collection ability of the

proposed collection media. For example, if a sorbent is proposed as

the collection medium and successful

recovery from the sorbent and successful analysis of the analyte have

been established, the ability of the

sorbent to quantitatively collect the

compound of interest must be evaluated. The collection ability of the medium can be established by dynamic

spiking of the sampling train, incorporating as many of the characteristic

source variables as possible. For example, if hot, wet, acidic sources are

expected, this source environment can

be created in the laboratory or located in the field, and dynamic spiking into replicate sampling trains with

recovery and analysis will demonstrate

that the sampling train does indeed

collect the compound of interest quantitatively.

Results and Discussion

Compounds expected to be amenable

to existing methods are shown in Table 1.

Compounds expected to require development of specialized methodology or major

modification of existing methodology are

shown in Table 2, with the expected problem areas. Other analytes are discussed

on an individual basis, to formulate suggestions for sampling and analytical approaches which may provide effective sampling/analysis for the analyte, e.g.,

diethanolamine.

Diethanolamine

Diethanolamine is a water-soluble compound used as an emulsifier and dispersing agent. Diethanolamine should be collected in a Method 0010 XAD-2®/water

collection system. Because of the water

solubility of diethanolamine, aqueous

impingers may constitute a better collection system. Extraction of diethanolamine
3

Table 1. Compounds Expected to be Amenable to Existing Methods without Modification Currently Being Tested in the Methodology Indicated

SemiVOST VOST

(Method 0010/82701) (Method 0030/5041) Method 0011

acetophenone acetonitrile acetaldehyde

2-acetylaminofluorene acrylonitrile acetophenone

benzidine benzene acrolein

biphenyl carbon disulfide 2-chloroacetophenone

b9s(2-ethylhexyl) phthalate 1,1-dimethylhydrazine formaldehyde

catechol 1,4-dioxane hydroquinone

chlordane 1,2-epoxybutane isophorone

2-chloracetophenone ethyl acrylate methyl ethyl ketone

cresols ethyl imine methyl isobutyl ketone

o-cresol hexane propionaldehyde

m-cresol methyl ethyl ketone quinone

p-cresol methyl isobutyl ketone

cumene methyl methacrylate

DDE methyl tert-butyl ether

dibenzofuran propylene oxide

di-n-butyl phthalate 1,2-propyleneimine

dichlorvos triethylamine

N,N-dimethylaniline 2,2,4-trimethylpentane

N,N-diethylaniline vinyl acetate

3,3’-dimethoxybenzidine

dimethylaminoazobenzene

3,3’-dimethylbenzidine

dimethyl phthalate

4,6-dinitro-o-cresol

2,4-dinitrophenol

2,4-dinitrotoluene

1,4-dioxane

ethylbenzene

ethyl carbamate

ethylene thiourea

heptachlor

hexamethylene-1,6-diisocyanate

hexamethylphosphoramide

hydroquinone
4

Table 1. Compounds Expected to be Amenable to Existing Methods without Modification Currently Being Tested in the Methodology Indicated (continued)

SemiVOST VOST

(Method 0010/82701) (Method 0030/5041) Method 0011

isophorone

lindane

maleic anhydride

methoxychlor

4,4’-methylene bis(2-chloroaniline)

4,4’-methylenedianiline

naphthalene

nitrobenzene

4-nitrobiphenyl

4-nitrophenol

N-nitrosodimethylamine

N-nitrosomorpholine

parathion

phenol

p-phenylenediamine

phthalic anhydride

1,3-propane sultone

propoxur

quinoline

quinone

styrene

styrene oxide

2,4-toluenediamine

o-toluidine

trifluralin

xylenes

m-xylene

o-xylene

p-xylene

1 Use of Method 8270 for an analytical method does not imply that all of the analytes listed in Method 8270 can be sampled successfully by Method 0010 or

quantitatively extracted from XAD®. Method 8270 analytical conditions are applicable to a far wider range of analytes than the analytes amenable to the

SemiVOST method.
5

Table 2. Compounds Expected to Perform Poorly in Existing Methodology

Compound Problem

acetamide Very polar; chromatographs poorly

2-acetylaminofluorene Polar; high molecular weight; solubility problems

acrylamide Very polar

acrylic acid Polar and reactive; does not chromatograph well on most GC columns

acrylonitrile Very polar

4-aminobiphenyl Polar; high molecular weight; solubility problems

benzidine Polar and reactive; does not chromatograph well on most GC columns

bis(chloromethyl)ether Polar, reactive; reacts with water

1,3-butadiene Very volatile, very reactive

caprolactam Very polar; chromatographs poorlyy using GC techniques

captan Polar; chromatographs poorly by GC

carbaryl Polar; reactive; chromatographs poorly ; poor GC/MS response

carbon disulfide Volatile; polar; water-soluble

carbonyl sulfide Reactive gas

catechol Very polar and water-soluble; chromatographs very poorly on most GC columns

chloroacetic acid Polar; reactive; reacts with water; chromatographs very poorly on most GC columns

2,4-D, salts and esters Not all amenable to GC techniques; polar and reactive

DDE Very reactive

diazomethane Very reactive; polar; cannot be chromatographed as diazomethane

3,3’-dichlorobenzidine Very polar; chromatographs poorly on most GC columns

dichlorvos Polar; chromatographs poorly on most GC columns

diethanolamine Very polar; chromatographs poorly on most GC columns

diethyl sulfate Very reactive; chromatographs poorly on most GC columns

3,3’-dimethoxybenzidine Very polar: high molecular weight; chromatographs poorly on most GC columns

dimethylaminoazobenzene Very polar; chromatographs poorly on most GC columns

3,3’-dimethylbenzene Very polar; chromatographs poorly on most GC columns

dimethyl carbamoyl chloride Very polar; not amenable to GC techniques

N,N-dimeylformamide Very polar; chromatographs very poorly on most GC columns

1,1-dimethylhydrazine Very polar; reactive; chromatographs very poorly on most GC columns

dimethyl sulfate Very polar; reactive; chromatographs poorly

4,6-dinitro-o-cresol and salts Very polar; not all amenable to GC techniques

2,4-dinitrophenol Very polar; reactive; chromatographs poorly on most GC columns

1,2-diphenylhydrazine Very polar; reactive; decomposes to azobenzene in the injector port of the GC

epichlorohydrin Very polar; water-soluble; reacts with water; chromatographs poorly on most GC columns
6

Table 2. Compounds Expected to Perform Poorly in Existing Methodology (continued)

Compound Problem

1,2-epoxybutane Polar; water-soluble

ethyl acrylate Polar; water-soluble

ethyl carbamate Polar; chromatographs poorly; poor MS response

ethylene glycol Polar; water-soluble; chromatographs poorly on most GC columns

ethyleneimine Polar; water soluble; reactive

ethylene oxide Polar; water-soluble; reacive; mass 44 difficult to analyze by GC/MS

ethylene thiourea Polar; water-soluble; chromatographs poorly on most GC columns

hexamethylphosphoramide Polar; chromatographs poorly on most GC columns; poor MS response

maleic anhydride Polar; water-soluble; chromatographs poorly on most GC columns

methanol Polar; water-soluble; volatile; mass 32 is difficult to analyze by GC/MS; requires a special column for good chromatography

methoxychlor Polar; chromatographs poorly on most GC columns

methyl hydrazine Polar; water-soluble; reactive

methyl methacrylate Polar; water-soluble; volatile

4,4’-methylene bis (2-chloroaniline) Polar; chromatographs very poorly on most GC columns

4,4’-methylenedianiline Polar; chromatographs very poorly on most GC columns

4-nitrobiphenyl Polar; chromatographs very poorly on most GC columns

4-nitrophenol Polar; chromatographs very poorly on most GC columns

2-nitropropane Polar; not amenable to GC analysis

N-nitrosodimethylurea Very polar; chromatographs poorly on most GC columns

N-nitrosodimethylamine Very polar

N-nitrosomorpholine Very polar; chromatographs poorly on most GC columns

p-phenylenediamine Polar; chromatographs poorly on most GC columns

phthalic anhydride Very polar; reacts with water; chromatographs poorly on most GC columns; poor MS response

1,3-propane sultone Very polar; chromatographs poorly on most GC columns

ß-propiolactone Polar; reactive

propoxur Polar; chromatographs poorly on most GC columns

propylene oxide Polar; water-soluble; volatile

1,2-propyleneimine Polar; water-soluble; volatile

styrene Semivolatile, but styrene is a component of the XAD-2® polymer. Sampling styrene with Method 0010 may require

a special polymer.

2,4-toluenediamine Polar; water-soluble; chromatographs poorly on most GC columns

o-toluidine Polar; water-soluble; chromatographs poorly on most GC columns

toxaphene Multicomponent pesticide (at least 50-60 components); will require very sensitive and specific analysis, with pattern recognition

triethylamine Polar; water-soluble; volatile; chromatographs poorly on most GC columns

trifluralin Polar; chromatographs poorly on most GC columns; poor MS response

vinyl acetate Polar; water-soluble; volatile
7

from water by either an organic solvent or

solid phase extraction techniques should

be explored as an alternative to analysis

by direct aqueous injection, because direct aqueous injection has high detection

limits. The inability to perform GC/MS

analysis of diethanolamine under Method

8270 analytical conditions has been demonstrated. Use of a polar gas chromatographic column may improve the analysis,

or HPLC or HPLC/MS may be required

for analysis of this analyte.

Individual evaluations of more than 90

Clean Air Act Amendments analytes are

provided.

Conclusions and

Recommendations

The following conclusions can be drawn

from the literature studied for this program

and from available method evaluation data:

• Performance of a given sampling/analytical methodology for a given analyte

is strongly matrix-dependent. Availability of excellent method evaluation

data at one particular source category

does not establish that the methodology will always perform successfully

for the analyte at any source. The

only way to establish with complete

certainty that a given methodology

will perform successfully for a given

analyte at a particular source is to

demonstrate the efficacy of the methodology for the analyte, using some

kind of field spiking technique.

• Because of the chemical properties

of many of the Clean Air Act Amendments analytes (such as polarity or

water solubility), standard analytical

conditions such as those used in

Method 8270 or Method 5041 will not

provide an adequate analysis. New

analytical approaches must be considered and evaluated.

• Multistep analytical procedures will be

required for the broadest possible extension of the applicability of a given

sampling methodology. For example,

analytes collected on XAD-2® may

be extracted by use of a sequence of

solvents, extracts may be divided so

an aliquot can undergo a derivatization

procedure, sequential analysis on different chromatographic columns may

be required, analysis by both GC/MS

and HPLC/MS may be required. The

alternative to multistep analytical procedures is the collection of multiple

samples for individual analytical procedures.

• Alternative extraction techniques such

as supercritical fluid extraction should

be considered for Tenax® and XAD2®, the most commonly used collection sorbents.

• Creative new sampling and analytical

approaches are required to resolve

the sampling and analytical problems

posed by polar water-soluble compounds.

• The ultimate demonstration of a successful overall sampling/analytical

method is the application of dynamic

spiking procedures in a field test. The

analyte(s) must be introduced as close

to the tip of the probe of the sampling

train as possible throughout the duration of the sampling process. In many

cases for the compounds of interest,

dynamic spiking procedures need to

be developed and/or evaluated before they can be applied in the field.

• The applicability of broad-based methods such as VOST and Method 0010/

8270 should be evaluated for the widest possible range of analytes to determine the range and limitations of

these methods prior to the development of multiple methods for individual

analytes.
8

Denny E. Wagoner, Raymond G. Merrill, Jr., James F. McGaughey, and Joan T.

Bursey are with Radian Corporation, Research Triangle Park, NC 27709.

Merrill D. Jackson is the EPA Project Officer (see below).

The complete report, entitled “Evaluation of CAAA Compounds Approaches for

Stationary Source Method Development,” (Order No. PB96-193206; Cost:

$41.00, subject to change) will be available only from:

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22161

Telephone: 703-487-4650

The EPA Project Officer can be contacted at:

Air Methods Research Division

National Risk Management Research Laboratory

U.S. Environmental Protection Agency

Research Triangle Park, NC 27711

• •

United States

Environmental Protection Agency

National Risk Management Research Laboratory (G-72)

Cincinnati, OH 45268

EPA/600/SR-96/091

Official Business

Penalty for Private Use $300

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