EPA - 600/R-97-004
March 1997
DEVELOPMENT AND VALIDATION OF A METHOD FOR
MEASURING EXEMPT VOLATILE ORGANIC COMPOUNDS
AND CARBON DIOXIDE IN CONSUMER PRODUCTS
Final Report
Prepared by:
E. E. Rickman, Jr., G.B. Howe, and R. K. M. Jayanty
Center for Environmental Measurements and Quality Assurance
Research Triangle Institute
P.O. Box 12194
Research Triangle Park, NC 27709
EPA Contract Number 68-D3-0045
Work Assignment 2/015
EPA Work Assignment Manager: J. Kaye Whitfield
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Research Triangle Park, NC 27711
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
WASHINGTON, DC 20460
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TECHNICAL REPORT DATA , ...
(Please read Instructions on the reverse before completing; | ||| || |||||| 111|| 111| || 11
1. REPORT NO. 2.
EPA-600/R-97-004
3. RE' 1 111 11 mill lllll 1 1 II llll
PB97-143143
4. TITLE AND SUBTITLE
Development and Validation of a Method for Measuring
Exempt Volatile Organic Compounds and Carbon
Dioxide in Consumer Products
5. REPORT DATE
March 1997
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
E.E.Rickman, Jr., G.B.Howe, and R. K. M. Jayanty
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D3-0045/W. A. 2/015
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 7/95 - 3/96
14. SPONSORING AGENCY CODE
EPA/600/13
is.supplementary notes ^ppc£> project officer is J. Kaye Whitfield, Mail Drop 61, 919/
541-2509.
16. abstract rep0rt describes the development and validation of a method for mea-
suring exempt volatile organic compounds (VOCs) and carbon dioxide in consumer
products. (NOTE: Ground-level ozone can cause a variety of adverse health effects
as well as agricultural and ecological damage. Controlling emissions of VOCs is im-
portant to reducing ground-level ozone; however, not all VOCs are photochemically
reactive, and several have been exempted from control regulations. Currently, there
is no standard method for measuring the exempt VOC content of consumer products.)
The new method involves heating a sample in an oven at 110 C for 1 hour while pur-
ging the sample container with nitrogen gas. The resultant mixture of nitrogen and
volatile compounds from the sample is then collected in a Tedlar bag and analyzed by
gas chromatography with mass selective detection (GC/MSD). An internal standard is
added to the sample container to permit quantitation without measurement of the
purge gas volume. The method was evaluated by analyzing samples that were spiked
with known amounts of the exempt compounds. Recoveries of spiked compounds were
excellent, ranging from 86 to 107% for the compounds and products tested. This me-
thod should be applicable to other volatile compounds that might be present in consu-
mer products and could be useful in evaluating the risk that these products pose.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS ATI Field/Group
Pollution Gas Chromatography
Ozone
Measurement
Organic Compounds
Volatility
Carbon Dioxide
Pollution Control
Stationary Sources
Consumer Products
Volatile Organic Com-
pounds (VOCs)
Mass Selective Dectectio
13 B 07D
07B
14 G
07C
20M
n
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21- NO- <">F PAGES
62
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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NOTICE
This document has been reviewed in accordance with U.S.
Environmental Protection Agency policy and approved for publication.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
PROTECTED UNDER INTERNATIONAL COPYRIGHT
ALL RIGHTS RESERVED.
NATIONAL TECHNICAL INFORMATION SERVICE
U.S. DEPARTMENT OF COMMERCE
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FOREWORD
The U. S. Environmental Protection Agency is charged by Congress with pro-
tecting the Nation's land, air, and water resources. Under a mandate of national
environmental laws, the Agency strives to formulate and implement actions lead-
ing to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental pro-
blems today and building a science knowledge base necessary to manage our eco-
logical resources wisely, understand how pollutants affect our health, and pre-
vent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for
investigation of technological and management approaches for reducing risks
from threats to human health and the environment. The focus of the Laboratory's
research program is on methods for the prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites and groundwater; and prevention and
control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental
technologies; develop scientific and engineering information needed by EPA to
support regulatory and policy decisions; and provide technical support and infor-
mation transfer to ensure effective implementation of environmental regulations
and strategies.
This publication has been produced as part of the Laboratory's strategic long-
term research plan. It is published and made available by EPA's Office of Re-
search and Development to assist the user community and to link researchers
with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
i i i
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ABSTRACT
Ground-level ozone can cause a variety of adverse health effects as well as agricultural
and ecological damage. Controlling emissions of volatile organic compounds (VOCs) is
important to reducing ground-level ozone. However, not all VOCs are photochemically reactive
and several have been exempted from control regulations. Currently, there is no standard method
for measuring the exempt VOC content of consumer products. This report describes the
development of such a method.
The new method involves heating a sample in an oven at 110°C for 1 hour while purging
the sample container with nitrogen gas. The resultant mixture of nitrogen and volatile
compounds from the sample is then collected in a Tedlar bag and analyzed by gas
chromatography with mass selective detection (GC/MSD). An internal standard is added to the
sample container to permit quantitation without measurement of the purge gas volume. The
method was evaluated by analyzing samples that were spiked with known amounts of the exempt
compounds. Recoveries of spiked compounds were excellent, ranging from 86 to 107 percent for
the compounds and products tested. This method should be applicable to other volatile
compounds that might be present in consumer products and could be useful in evaluating the risk
that these products pose to the environment.
i v
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CONTENTS
Section Page
Abstract iv
Figures v
Tables v-j
Abbreviations and Symbols vi i
1 Introduction 1
2 Conclusions 4
3 Recommendations 5
4 Method Development and Testing 6
5 Results and Discussion 19
6 Quality Control and Quality Assurance 32
References 35
Appendix A.
Determination of Exempt Volatile Organic Compounds and Carbon Dioxide in
Consumer Products A-l
FIGURES
Number Page
1 Sample purge and volatiles collection assembly ,.11
2 Schematic diagram of gas-phase standard preparation system 15
3 Calibration check data 34
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TABLES
Number Page
1 Organic Compounds Determined to Have Negligible Photochemical
Reactivity (40 CFR 51.100) 3
2 Exempt VOC Method Target List 7
3 Chromatographic Conditions Evaluated 12
4 Experimental Matrix 18
5 Results of Multiple Injections for Product AB - Aerosol Hairspray 20
6 Results of Multiple Injections for Product AC - Aerosol Deodorant 20
7 Results of Multiple Injections for Product FD - Engine Cleaner 21
8 Results of Multiple Injections for Product FB - Tire Cleaner 21
9 Results of Multiple Injections for Product LC - Pump Hairspray 22
10 Results of Multiple Injections for Product AA- Furniture Polish 22
11 Results of Multiple Injections for Product SA - Stick Deodorant 23
12 Results of Multiple Aliquots for Product AB - Aerosol Hairspray 24
13 Results of Multiple Aliquots for Product AC - Aerosol Deodorant 25
14 Results of Multiple Aliquots for Product FD - Engine Cleaner 25
15 Results of Multiple Aliquots for Product FB - Tire Cleaner 26
16 Results of Multiple Aliquots for Product LC - Pump Hairspray 26
17 Results of Multiple Aliquots for Product AA- Furniture Polish 27
18 Results of Multiple Aliquots for Product SA - Stick Deodorant 27
19 Comparison of Spike Recoveries by Product 28
20 Comparison of Total Volatiles With and Without Purge Gas 30
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ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
ASTM
CAAA
CFC
FID
GC
HCFC
HFC
MSD
NAAQS
PCBTF
perc
TCD
VOC
American Society for Testing and Materials
Amendments to the 1990 Clean Air Act
chlorofluorocarbon
flame ionization detector
gas chromatograph or gas chromatography
hydrochlorofluorocarbon
hydrofluorocarbon
mass selective detector
National Ambient Air Quality Standards
parachlorobenzotrifluoride (a,a,a-trifluoro,4-chlorotoluene)
perchloroethylene (i.e., tetrachloroethylene)
thermal conductivity detector
volatile organic compound
SYMBOLS
C02 carbon dioxide
HCFC-22 chlorodifluoromethane
HCFC-123 l,l,l-trifluoro-2,2-dichloroethane
HCFC-124 -- 2-chloro-l,l,l,2-tetrafluoroethane
HCFC-141b 1,1-dichloro-l-fluoroethane
HCFC 142b -- l-chloro-l,l-difluoroethane
HFC-125 ~ pentafluoroethane
HFC-134 ~ 1,1,2,2-tetrafluoroethane
HFC-134a ~ 1,1,1,2-tetrafluoroethane
HFC-143a ~ 1,1,1-trifluoro ethane
HFC-152a 1,1-difluoroethane
vi i
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SECTION 1
INTRODUCTION
Ground-level ozone can cause a variety of adverse health effects as well as agricultural
and ecological damage (1). To control the levels of ozone in the environment, the U.S.
Environmental Protection Agency (EPA) has established National Ambient Air Quality
Standards (NAAQS) for ozone. In 1990 there were 98 areas in the country that did not meet the
NAAQS for ozone (1), with over 150 million Americans living in these areas. Volatile organic
compounds (VOCs) are important contributors to the formation of ozone in photochemical smog.
Control of VOC emissions is an important strategy for controlling ozone levels. The 1990
Amendments to the Clean Air Act (CAAA) require EPA to conduct a study of VOC emissions
from consumer products. However, there was no standard method for measuring the VOC
content of consumer products. Such measurements are needed to assess the risk posed by VOCs
in consumer products to the environment. Such a method will also be needed if EPA determines
that the risk associated with VOCs in consumer products is sufficient to require control
regulations.
To address the need for measurement of VOCs in consumer products, EPA has established
a research program. This program has already produced results in four previous phases:
Phase I - Preliminary studies were performed on two candidate methods for VOC
measurement (EPA Reference Method 24 and Gravimetric Purge and Trap Gas
Chromatography).
Phase II - A Consumer Products Test Methods Work Group was established with
participation from a number of State and Federal agencies. This Work Group,
after consideration of an initial list of 10 candidate methods, reached a consensus
that further research should be concentrated on two methods: EPA Reference
Method 24 and Gravimetric Purge and Trap Gas Chromatography.
Phase III - A test method was developed to determine the total VOC content of
consumer products. This method was based on EPA Reference Method 24, with
added modifications for sampling and analysis of consumer products.
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Phase IV - The test method developed in Phase III was validated in an
interlaboratory study. (3)
The validated total VOC method (Phase IV) for consumer products gravimetrically
measures the total volatile content and determines the amount of water by gas chromatography
with thermal conductivity detection (GC/TCD). The water content is then subtracted from the
total volatile content to calculate the total VOC content. However, many VOCs have been
exempted from the list of regulated VOCs (40 CFR 51.100, Table 1) due to their low
photochemical reactivity and thus low ozone formation potential. Measurement of these exempt
VOCs in consumer products would allow EPA to correct the total VOC measurements to better
reflect the total ozone formation risk that consumer products pose to the environment. Table 2 in
Section 4 of this report lists the thirteen target compounds selected for this study. The target
compounds consist of 12 from Table 1 plus carbon dioxide. The reasons for selecting these
compounds are given in Section 4. Since it is anticipated that determining these 13 compounds
will be considerably more expensive and time consuming than measurement of total VOC
content, a two-step approach to assessing the ozone formation risk posed by consumer products
is envisioned. The first step would involve measurement of total VOC content for the product.
Consumer products that might pose significant risks for ozone formation based on their total
VOC content would then undergo a second step of having their exempt VOCs measured to
provide a better assessment of their ozone formation risk. This report describes the development
and validation of an exempt VOC measurement method that would be used as the second step of
the VOC risk assessment process.
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Table 1. Organic Compounds Determined to Have
Negligible Photochemical Reactivity
Compound Name
methane
ethane
methylene chloride (dichloromethane)
1.1.1-trichloroethane (methyl chloroform)
1.1.2-trichloro-1,2,2-trifluoroethane (CFC-113)
trichlorofluoromethane (CFC-11)
dichlorodifluoromethane (CFC-12)
chlorodifluoromethane (HCFC-22)
trifluoromethane (HFC-23)
l,2-dichloro-l,l,2,2-tetrafluoroethane (CFC-114)
chloropentafluoroethane (CFC-115)
1,1,1 -trifluoro-2,2-dichloroethane (HCFC-123)
1,1,1,2-tetrafluoroethane (HFC-134a)
1,1 -dichloro-1 -fluoroethane (HCFC- 141b)
1-chloro-l,l-difluoroethane (HCFC 142b)
2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124)
pentafluoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
1,1,1-trifluoroethane (HFC-143a)
1,1-difluoroethane (HFC-152a)
parachlorobenzotrifluoride (PCBTF)
cyclic, branched, or linear completely methylated siloxanes
acetone
perfluorocarbon compounds that fall into these classes
Source: 40 CFR 51.100 (reference 2)
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SECTION 2
CONCLUSIONS
The method for measuring exempt VOC content in consumer products shows good
accuracy as measured by exempt compound spike recoveries. Recoveries for individual
compounds were excellent, ranging from 86 to 107 percent, and are within project goals of 80 to
120 percent. The method is very versatile for the following reasons:
The sampling method developed for this method is suitable for a wide variety of
consumer products, including solid, liquid, and aerosol products.
Detection with a mass selective detector permits identification and quantitation of
exempt compounds, even in the presence of potential interferants.
A small (approximately 2 percent) but statistically significant positive bias was seen in
total volatile measurements made with purge gas. Unless further research can resolve this
problem, total volatile measurements should be made using the validated total VOC method (i.e.,
without purge gas).
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SECTION 3
RECOMMENDATIONS
Although the current method should prove useful for EPA research efforts in assessment
of VOC emissions from consumer products, the ability of other laboratories to use this method
has not been established. An interlaboratory study would be desirable before implementation of
this method in a regulatory context.
Modifications to this method would extend it to a wider range of compounds. Such work
would be useful to evaluate emissions of a wide variety of volatile and semivolatile compounds
from both consumer and industrial products. This information would help EPA to better assess
the risk that these products pose to the environment.
The exempt VOC method (Appendix A), which uses a purge gas to collect volatiles,
should not be used to measure total volatile content (which includes exempt and nonexempt
VOCs as well as water and carbon dioxide). Total volatile content should be measured by the
previously validated total VOC method (3).
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SECTION 4
METHOD DEVELOPMENT AND TESTING
INTRODUCTION
History
A method to measure the volatile content of surface coatings (i.e., paints, varnishes, and
lacquers) was developed by the American Society for Testing and Materials (ASTM), which
issued it under the designation D 2369, "Standard Test Method for Volatile Content of
Coatings" (4). This method determines volatile content based on the weight loss of a sample that
is heated for 1 hour at 110° C. The industrial members of ASTM accepted this method as a
reasonable simulation of volatile compound loss over the coating's lifetime. The method is
easily performed and requires only an analytical balance and a suitable drying oven. Because
this method was widely used and accepted by industry, EPA incorporated it (by reference) into
EPA Method 24 (5) to measure the volatile organic content of surface coatings. ASTM D2369
measures all volatile compounds, including volatile organics and water. To obtain a measure of
the volatile organic content, EPA incorporated (in Method 24) an ASTM water content method
(6) for measurement of the coating's water content. The water content is then subtracted from the
total volatile measurement to obtain the volatile organic content. Further development by RTI
under sponsorship of EPA showed that this method is also suitable for other compounds such as
printing inks.
EPA used its experience with surface coatings to develop a VOC method for consumer
products (3) based on Method 24. Modifications were made to permit sampling of aerosol
products (including aerosol-based foams) and to improve calibration for the water content
analysis. An interlaboratory study (3) was conducted that indicated that the precision of the
VOC consumer products method was comparable to EPA Method 24.
Not all VOCs contribute significantly to ozone formation. Specific VOCs have been
designated as exempt VOCs due to their low photochemical reactivity (Table 1). EPA initiated
the current work to develop a method to quantify these exempt VOCs in consumer products.
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Knowledge of the exempt VOC content permits EPA to correct the total VOC measurements to
better assess the actual ozone formation risk posed by the product.
Selection of Target Compound List
An early step in method development was to select the target compounds to be measured
(Table 2). Several of the compounds on the exempt VOC list (Table 1) are not likely to be found
in consumer products. Inclusion of them would lead to development of a more difficult, and thus
more expensive, method than is actually needed.
Table 2. Exempt VOC Method Target List
Compound Name
carbon dioxidea
methylene chloride (dichloromethane)
1,1,1,2-tetrafluoroethane (HFC-134a)
pentafluoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
1,1,1-trifluoroethane (HFC-143a)
1,1-difluoroethane (HFC-152a)
acetone
tetrachloroethylene (perchloroethylene or perc) b
Class II ozone depleting chemicals c
chlorodifluoromethane (HCFC-22)
1,1,1-trifluoro 2,2-dichloroethane (HCFC-123)
1,1-dichloro 1-fluoroethane (HCFC-141b)
1-chloro 1,1-difluoroethane (HCFC 142b)
a Carbon dioxide is not a VOC, but is measured by the total volatiles
method (3) and has been added to the target list to permit correction of
measured total volatiles.
b Tetrachloroethylene was added to the exempt list during the course of
this work (61 FR 4588, February 7, 1996).
0 Use of class II ozone-depleting chemicals (58 FR 65018, December 10,
1993) is currently restricted. These chemicals may be phased out in the
future.
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Parachlorobenzotrifluoride (PCBTF), siloxanes, and perfluorocarbons are not widely used in
consumer products and were omitted from the method target list. EPA currently restricts use of,
and will phase out most uses of chlorofluorocarbons and 1,1,1-trichloroethane (methyl
chloroform) by January 1, 1996, due to their impact on stratospheric ozone (58 FR 65018,
December 10,1993). Exempt compounds affected include 1,1,1-trichloro-ethane, CFC-11,
CFC-12, CFC-113, CFC-114, and CFC-115. Because these compounds are no longer available
(except to licensed technicians for uses such as air conditioner repair), they were removed from
the method target list. We were not able to obtain 2-chloro-l, 1,1,2-tetrafluoroethane
(HCFC-124) and this compound was also removed from the target list.
Several compounds on the exempt list have too high a vapor pressure to be useful in
consumer products. Methane, ethane, and HFC-23 (trifluoromethane) all have high vapor
pressures at room temperature (methane > 2000 psi, ethane ~ 560 psia at 70° F, HFC-23 ~ 650
psia at 70° F) (7). The high vapor pressures of these compounds make it difficult to incorporate
substantial amounts in consumer products and precludes their use as propellants in aerosol cans.
These compounds were omitted from the method target list.
In addition to the compounds on the exempt list at the start of this project,
tetrachloroethylene (also called perchloroethylene or perc) was added to the method target list.
At the time this project was begun, EPA had proposed adding this compound to the exempt VOC
list (57 FR 48490, October 26, 1992). The final ruling adding tetrachloroethylene as an exempt
compound was announced while the experimental work was being performed (61 FR 4588,
February 7, 1996).
Although carbon dioxide (C02) is not a VOC, it is measured by the total VOC method (3).
Carbon dioxide was added to the target list to permit correction of volatiles measured by the total
VOC current method.
Although methylene chloride is included on the target list, it may be removed from consumer
products in the future because of health concerns.
Overview of Approach
Assessing the ozone formation risk of consumer products is complicated by several issues
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including:
Consumer products consist of a number of different formulations.
Products may be in liquid, solid, or aerosol form.
Any one product may contain hundreds of individual chemical compounds.
The exact chemical composition of many consumer products may not be well known, even
by the manufacturer. For example, essential oils and fragrances contain large numbers of
individual compounds, the identity and amount of which are generally unknown to the
manufacturer.
Based on these considerations, development of a method to separate, identify, and quantify
each individual VOC in a consumer product was considered unnecessarily difficult and
expensive. Instead, a method was developed to separate, identify, and measure only the exempt
VOCs and carbon dioxide present in consumer products. The exempt content can be subtracted
from the total VOC content, as measured by the earlier consumer products VOC method, to
obtain the nonexempt VOC content.
The overall method approach consisted of two parts sampling and analysis. Sampling
consisted of capturing the volatile components from a consumer product in a Tedlar collection
bag (Figure 1). The bag contents were then analyzed using gas chromatography with mass
selective detection (GC/MSD).
SAMPLING
Development of sampling procedures required addressing the wide variety of consumer
products available. These products may be packaged as a liquid, solid, or (propellant-driven)
aerosol, and any single product may contain from one to hundreds of individual chemical
compounds. Dealing with various forms of packaging was addressed in the development of the
total VOC method. In this study a septum sealed vial was used. Liquid and solid samples were
added before crimp sealing the vial. An adapter permitted the injection of aerosol products
through a hypodermic needle into the sealed vial without loss of sample. This approach had been
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verified in the interlaboratory study of the total VOC method.
Because many of the exempt products are condensable gases at room temperature, the
sampling method had to accommodate both liquids and gases. Heating was used to convert all
exempt compounds in the sample to the gaseous phase. Purging the sample with a purge gas
would then sweep out the volatile components and leave behind any solids, tars, and resins that
could complicate the analysis. The volatiles, now mixed with the purge gas, were collected in a
Tedlar collection bag. A new Tedlar sample bag can be used for each sample, if desired, to
prevent problems with contamination between samples and to reduce cleanup costs. Addition of
a sufficient volume of purge gas prevented recondensation of the exempt compounds at room
temperature. The collected gas in the bag was then analyzed by GC/MSD. A known amount of
volatile internal standard (l,2,2-trichloro-l,l-difluoroethane [HCFC 122]) was added to the
sample before purging. The use of an internal standard eliminated the need to make accurate
dilution volume measurements and automatically compensated for differences in sample bag
temperature and atmospheric pressure.
Estimated Minimum Dilution Volume
Previous tests on consumer products (3) indicated that water frequently is a major volatile
component. Sampling of products requires that sufficient dry nitrogen diluent be used to prevent
condensation of water during storage of the sample bag at room temperature. The final partial
pressure of water must be less than the saturation vapor pressure. The minimum dry nitrogen gas
purge volume (V) needed to prevent condensation of a 0.5 g sample composed of 100 percent
water at 20° C would be:
0.5 (g) x 293.15 (K) x Q.Q82 (L-atm/mol/K) x 760 (torr/atm)
18 (molecular weight, g/mol)x 17 (vapor pressure at 20° C, torr) ^
or approximately 30 L. This would require a minimum flow rate of 0.5 L/min for the 1 hour
evaporation time as used in EPA Method 24. Based on this minimum flow, a nominal flow of
1 L/min was selected for the study.
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copper
tubing
as heat
exchanger
flexible Teflon
tubing
1 5 ga hypodermic
needles
sample vial
T edlar
collection bag
Figure 1. Sample purge and volatiles collection assembly
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ANALYSIS
Because exempt VOC compounds are by definition volatile compounds, gas chromatography
was most appropriate for separation. Mass spectral detection was selected due to its ability to
obtain compound-specific information for each peak. Comparison of the measured mass
spectrum with library spectra permitted verification of compound identity. Quantitation on
specific target ions permitted the accurate measurement of exempt compounds, even if perfect
chromatographic separation was not obtainable.
Selection of GC Column and Conditions
The goal for selection of a GC column for this method was to separate as many of the exempt
compounds as possible in a reasonable chromatographic run time. Several capillary columns and
conditions were evaluated. Table 3 summarizes columns and conditions that were evaluated:
Table 3. Chromatographic Conditions Evaluated
Column
Temperature Program
DB-624
-20° C for 1 min, 10° C/min. to 120° C
HP-5
-40° C for 1 min, 10° C/min to 120° C
-60°C for 1 min, 10° C/min to 120° C
VOCOL
40° C for 4 min, 10° C/min to 120° C
40° C for 1 min, 5° C/min to 180° C
GS-Q
-20° C for 1 min, 5° C/min to 180° C
40° C for 1 min, 30° C/min to 220° C
40° C for 1 min, 10° C/min to 220° C
40° C for 1 min, 5° C/min to 150° C, 20° C/min to 220° C, hold for 4.5
min
All columns were 30 m by 0.53 mm ID.
After evaluation of each of these columns and conditions by analyzing a mixture of selected
exempt compounds, the GS-Q column operating under the last set of conditions listed was
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selected. The advantages of using the GS-Q column include:
No subambient column temperatures are necessary.
No cryofocusing of the sample is necessary.
Carbon dioxide is separated from nitrogen, enabling quantitation of the C02 content.
Most of the exempt compounds are separated.
Exempt Compound Detection
Because of the inability to achieve complete chromatographic separation of all the exempt
compounds and the risk of other compounds in consumer products coeluting with the exempt
compounds, a MSD was selected for this method. By careful selection of target ions for
quantitation, it is feasible to measure exempt compounds with no interference from other
compounds. The use of a nonselective detector such as a flame ionization detector (FID) would
require chromatographic resolution of all exempt compounds in all consumer products, which is
not feasible.
The use of an MSD also provides for identification of exempt compounds through the use
of qualifier ion relative abundances.
Calibration
One of the first challenges faced in this project was the development of a suitable
calibration procedure. One approach considered was to prepare calibration standards by loading
a blank sample vial with known amounts of the exempt compounds. A calibration point would
then be obtained by analyzing this vial as a normal sample. This approach was not used for
several reasons. First, because the gas in the Tedlar bag cannot be kept for long periods of time
(i.e., more than a few hours), it is impossible to analyze the same standard on different days to
evaluate instrumental drift. Second, because the sample is effectively consumed, such an
approach does not permit an independent evaluation of the calibration standard. Third, because
many (i.e., five) of the compounds are gases that are easily condensed, it is necessary to spike the
sample vial with each gas individually. This is a time-consuming procedure not generally
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employed by commercial laboratories.
Based on these considerations, the use of a standard mixture of the exempt compounds in a
compressed gas cylinder (with nitrogen as the diluent) for calibration was adopted. The use of
such a mixture permits independent analysis of the calibration standards. Although preparation
of such a standard may not be within the capabilities of many laboratories, a large number of
commercial gas suppliers will produce such mixtures on request. Use of such a preprepared
mixture greatly reduces the time required to perform daily calibration checks, and the fact that
the same mixture can be used on different days permits better tracking of instrument response on
a daily basis.
For this study, RTI prepared three calibration mixtures, each containing different
concentrations of the exempt compounds in nitrogen. The internal standard (HCFC 122) was
added during preparation to obtain approximately the same internal standard concentration in
each mixture. The mixtures were prepared in Summa canisters. A known volume of exempt
compound, either gas or liquid, was injected into an evacuated Summa canister of known
volume. Gases were injected with a gas-tight syringe. Liquids were injected from a fixed
volume sample loop into a vaporization zone which was swept with nitrogen into the canister. A
schematic diagram of the calibration standard preparation system is shown in Figure 2.
The maximum concentration of the high-level standard was limited to that which would be
feasible in a high-pressure (approximately 500 psi) commercial gas cylinder. The limit on
concentration is due to the saturation vapor pressure of the exempt compound.
Tetrachloroethylene had the lowest saturation vapor pressure of 13.9 torr at 20° C. Thus the
maximum concentration that would not condense in a cylinder pressurized to 500 psig would be
given by:
Maximum Concentration (ppm) = 13.9torr * 0.0193 psi/torr ^ jq6
515psia
or approximately 520 ppm. To allow a reasonable safety margin, a practical maximum would be
250 ppm.
14
-------
VALVE KEY
3-Way On/Off Metering
6-Port
Valve
Liquid In
Outlet
Heise
Gauge
(Low
Pressure)
Heise
Gauge
(High
Pressure)
Vent
Fixed-Volume
Loop
Septum Port
N2 Diluent
(or Master
Gas) In
L-Q
Vacuum +
Figure 2. Schematic Diagram of Gas-Phase Standard Preparation System
-------
The equivalent amount of tetrachloroethylene that would correspond to a 250 ppm
concentration in a sample bag with a 1-L/min flow rate for a 1-hour purge time is given by:
. , v 250ppm * lL/min * 60min * latm * 165.8g/mol inS
amount (g) = * 10 .
0.08205 L-atm/molK « 298 K
This corresponds to a weight of approximately 0.1 g or 20 percent by weight of a 0.5-g sample.
SELECTION OF PRODUCTS
It was not considered feasible to find current consumer products with exempt compounds
and obtain information from the manufacturer(s) within the time available for completion of this
project. With the exception of acetone, all of the other exempt compounds are synthetic as such
are not likely to occur in consumer products (at least at percent levels). Most of the compounds
on the target list are considerably more expensive than their nonexempt counterparts and, as
such, are not generally added to consumer products unless they meet some special need (such as
a reduction in flammability). For this reason, few currently available consumer products are
expected to contain exempt compounds, although this could change rapidly if VOC regulations
are imposed on consumer products. In addition, the composition of many consumer products is
considered proprietary and some manufacturers would be unwilling to provide information on
exempt concentrations (especially within the time constraints of this project).
Because products with known levels of exempt compounds were not available for this
study, currently available products were spiked with known amounts of exempt compounds.
This spiking permitted an estimate of the accuracy of the method. The products selected for this
study were those used in previous work involving an interlaboratory study of the total volatile
content of consumer products (3). The same product codes are used to refer to a given product in
both studies.
SPIKING OF SAMPLES
Samples were spiked by adding the exempt compounds to the sample vial after the sample
and internal standard had been added but before the vial had been heated. Five of the compounds
16
-------
(tetrachloroethylene, methylene chloride, HCFC-141b, HCFC-123, and acetone) are liquids at
room temperature. A mixture containing known amounts of four of these compounds (excluding
acetone) was gravimetrically prepared and added to the sealed vial by a gas-tight microliter
syringe. The amount added was gravimetrically determined. To avoid potential problems with
solubility of acetone in the fluorocarbons, a separate solution of acetone (in methanol) was used
to spike products with acetone.
The remaining eight exempt compounds are gases at room temperature. Preparation of a
single spike mixture at the high levels required (approximately 50 to 100 mg loading per
compound) was not considered feasible because many of these gases are easily condensed (all
except C02, HFC-125, and HFC-143a were supplied as condensed gases in low pressure
cylinders). Spiking a mixture with each of these compounds (at approximately 50 mg)
individually involves adding a total of approximately 80 mL of gas to the 100-mL sample vial. It
was not feasible to add this much additional gas to a container that was already pressurized with
an aerosol sample. For these reasons, product samples were spiked with only one or two gases,
although all gases were tested with at least one product.
EXPERIMENTAL MATRIX
Based on the calibration data for the lowest level calibration standard, a bag concentration
of at least 25 mg per compound would be needed to produce bag concentrations greater than the
lowest calibration standard. The samples were prepared and spiked with approximately 30 mg of
each exempt compound (Table 4). As described above, only one or two gases were spiked for
each given product. All liquids were spiked for each product, except for product FD (engine
cleaner) which was only spiked with the liquid HCFC-141b (in hexane).
17
-------
Table 4. Experimental Matrix
AB AC FD FB LC AA SA
aerosol aerosol engine tire pump furniture stick
Compound hairspray deodorant cleaner cleaner hairspray polish deodorant
gases
carbon dioxide X
HFC-125 X
HCFC-22 X
HFC-134a X
HFC-152a X
HFC-134 X X
HCFC-142b X
HFC-134a X
liquids
HCFC-123 X X
HCFC-141b X X
methylene chloride X X
tetrachloroethylene X X
acetone X X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
18
-------
SECTION 5
RESULTS AND DISCUSSION
INTRODUCTION
Consumer product samples spiked with known amounts of exempt compounds were
analyzed by the new method to evaluate the method's accuracy and precision. The percentage of
spike measured (recovered) was used as a measure of the method's accuracy. The method's
precision was evaluated based on the results of multiple aliquots and analyses of aliquots.
Three samples were taken from each product and each sample was spiked and processed to
produce a gas collection bag containing the exempt compounds, internal standard, and any other
volatile compounds from the sample. The variation in results of the analyzes for these three
aliquots provides a measure of the method's precision. In addition, one of these bags was
analyzed (injected) three times to estimate the precision of the GC/MSD system (which is one
component of the total method precision).
RESULTS FOR MULTIPLE INJECTIONS OF ONE SAMPLE
Results for multiple injections of one sample are shown in Tables 5 through 11. Most
analyses had recoveries within 10 percent of the prepared values. Only the analysis of
tetrachloroethylene with product FB (tire cleaner) failed to meet the method accuracy goals of
±20 percent spike recovery. This product is discussed further in the section on "Results for
Multiple Aliquots of One Product". Analysis precision was also good with typical standard
deviations for percent recovery being 2 percent or less.
19
-------
Table 5. Results of Multiple Injections for
Product AB - Aerosol Hairspray
Injection 1,
Injection 2,
Injection 3.
measured
measured
measured
Spike
mg (%
mg (%
mg (%
% Recovery
Compound
mg
recovery)
recovery)
recovery)
Avg
Stdev
tetrachloroethylene
39.6
45.4(114.6%)
44.7(112.8%)
45.2(114.0%)
113.8%
0.9%
methylene chloride
32
31.5 (98.5%)
31.4 (98.1%)
31.6(98.8%)
98.5%
0.3%
HCFC-141b
30.1
30.9 (102.6%)
30.5(101.3%)
30.4 (100.9%)
101.6%
0.9%
HCFC-123
35.2
35.4 (100.7%)
35.6(101.3%)
35.6(101.3%)
101.1%
0.3%
acetone
23.6
24.7 (104.7%)
24.7 (104.7%)
25.1 (106.4%)
105.2%
1.0%
carbon dioxide
18.3
17.4 (94.8%)
17.5 (95.4%)
17.6(95.9%)
95.4%
0.5%
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
27.5
24.4 (88.6%)
24.2 (87.9%)
24.4 (88.6%)
88.4%
0.4%
HFC-134
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
Table 6. Results of Multiple Injections for
Product AC - Aerosol Deodorant
Injection 1,
Injection 2,
Injection 3,
measured
measured
measured
Spike
mg (%
mg (%
mg (%
% Recovery
Compound
mg
recovery)
recovery)
recovery)
Avg
Stdev
tetrachloroethylene
41.1
41.9(101.9%)
41.5(100.9%)
41.4 (100.6%)
101.1%
0.6%
methylene chloride
33.2
34.8 (104.8%)
34.6 (104.2%)
34.6 (104.2%)
104.4%
0.3%
HCFC-14 lb
31.3
31.9(102.0%)
31.0 (99.2%)
31.9(102.0%)
101.1%
1.7%
HCFC-123
36.5
36.7 (100.6%)
36.6 (100.3%)
36.9(101.1%)
100.7%
0.4%
acetone
23.6
26.8(113.6%)
26.1 (110.6%)
26.0(110.2%)
111.5%
1.8%
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
HCFC 142b
41.8
39.9 (95.4%)
39.7 (94.9%)
40 (95.7%)
95.3%
0.4%
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
20
-------
Table 7. Results of Multiple Injections for
Product FD - Engine Cleaner
Injection 1, Injection 2, Injection 3,
measured measured measured
Compound
spike
mg
mg (%
recovery)
mg (%
recovery)
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
NA
NA
NA
NA
NA
NA
methylene chloride
NA
NA
NA
NA
NA
NA
HCFC-141b
11.9
12.7 (106.7%)
12.3 (103.4%)
12.0 (100.8%)
103.6%
2.9%
HCFC-123
NA
NA
NA
NA
NA
NA
acetone
NA
NA
NA
NA
NA
NA
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
49.3
46.6 (94.4%)
48.2 (97.7%)
46.9 (95.1%)
95.8%
1.8%
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was lot added as spike for this sample.
Table 8. Results of Multiple Injections for
Product FB - Tire Cleaner
Injection 1,
Injection 2,
Injection 3,
measured
measured
measured
Spike
mg (%
mg (%
mg (%
% Recovery
Compound
mg
recovery)
recovery)
recovery)
Avg
Stdev
tetrachloroethylene
40.1
48.6(121.3%)
48.4 (120.8%)
48.3 (120.6%)
120.9%
0.4%
methylene chloride
32.3
32.6 (100.8%)
32.9(101.7%)
33.6(103.9%)
102.1%
1.6%
HCFC-141b
30.4
30.2 (99.2%)
28.8 (94.6%)
30.4 (99.8%)
97.9%
2.9%
HCFC-123
35.5
35.4 (99.6%)
35.1 (98.8%)
35.3 (99.3%)
99.2%
0.4%
acetone
23.4
25.4 (108.5%)
25.3 (108.1%)
25.2 (107.6%)
108.1%
0.4%
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
41.4
36.5 (88.1%)
36.5 (88.1%)
37.2 (89.8%)
88.7%
1.0%
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
21
-------
Table 9. Results of Multiple Injections for
Product LC - Pump Hairspray
Injection 1,
Injection 2,
Injection 3,
measured
measured
measured
Spike
mg (%
mg (%
mg (%
% Recovery
Compound
mg
recovery)
recovery)
recovery)
Avg
Stdev
tetrachloroethylene
59.1
60.5 (102.3%)
59.9(101.3%)
59.8 (101.2%)
101.6%
0.6%
methylene chloride
47.7
47.0 (98.5%)
47.3 (99.1%)
47.2 (98.9%)
98.8%
0.3%
HCFC-141b
44.9
47.5 (105.7%)
47.3 (105.3%)
46.4 (103.3%)
104.8%
1.3%
HCFC-123
52.4
51.7 (98.6%)
52.4 (99.9%)
51.6(98.4%)
99.0%
0.8%
acetone
23.3
24.5 (105.3%)
24.6 (105.7%)
24.7 (106.1%)
105.7%
0.4%
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
41.3
34.6 (83.7%)
34.9 (84.5%)
34.8 (84.2%)
84.1%
0.4%
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
Table 10. Results of Multiple Injections for
Product AA - Furniture Polish
Injection 1,
Injection 2,
Injection 3,
measured
measured
measured
Spike
mg (%
mg (%
mg (%
% Recovery
Compound
mg
recovery)
recovery)
recovery)
Avg
Stdev
tetrachloroethylene
39.1
36.2 (92.6%)
36.1 (92.4%)
36.7 (93.9%)
93.0%
0.8%
methylene chloride
31.5
30.3 (96.0%)
30.5 (96.7%)
30.5 (96.7%)
96.5%
0.4%
HCFC-141b
29.7
27.7 (93.3%)
28.2 (94.9%)
28.2 (94.9%)
94.4%
1.0%
HCFC-123
34.7
35.3 (101.8%)
35.6 (102.7%)
35.7 (103.0%)
102.5%
0.6%
acetone
23.3
24.4 (104.6%)
25.0 (107.2%)
24.8 (106.3%)
106.0%
1.3%
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
35.4
32.5 (91.8%)
33.4 (94.3%)
33.5 (94.6%)
93.6%
1.6%
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
41.8
44(105.3%)
45 (107.7%)
44.7 (107.0%)
106.7%
1.2%
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
22
-------
Table 11. Results of Multiple Injections for
Product SA - Stick Deodorant
Compound
Spike
mg
Injection 1,
measured
mg (%
recovery)
Injection 2,
measured
mg (%
recovery)
Injection 3,
measured
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
36.5
34.6 (94.7%)
36.3 (99.4%)
36.7 (100.5%)
98.2%
3.1%
methylene chloride
29.5
29.0 (98.3%)
28.7 (97.3%)
28.6 (97.0%)
97.5%
0.7%
HCFC-141b
27.8
24.2 (87.2%)
24.2 (87.2%)
28.1 (101.2%)
91.8%
8.1%
HCFC-123
32.4
31.2 (96.3%)
30.7 (94.7%)
30.7 (94.7%)
95.2%
0.9%
acetone
23.6
25.3(107.1%)
24.9 (105.4%)
24.7 (104.6%)
105.7%
1.3%
carbon dioxide
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
HFC-143a
34.7
33.2 (95.8%)
32.6 (94.1%)
33 (95.2%)
95.0%
0.9%
NA = Not applicable, compound was not added as spike for this sample.
RESULTS OF MULTIPLE ALIQUOTS OF EACH PRODUCT
Results for multiple aliquots of each spiked product are shown in Tables 12 through 18.
Results for all products are summarized in Table 19. Most analyses had recoveries within 10
percent of the prepared values. Only the analysis of tetrachloroethylene with product FB (tire
cleaner) failed to meet the method accuracy goals of ±20 percent spike recovery. The reason for
the high recoveries seen with this product is not known; however, presence of
tetrachloroethylene in the product is not a likely cause. Although the sample weights for this
product varied between 0.23 and 0.79 g, the percent recoveries for these samples were within
1 percent. Clearly this would not be possible if the high recovery was due to the presence of
tetrachloroethylene in the sample.
Precision was good with standard deviations for percent recovery typically less than
5 percent. Notably poorer precision was seen with a few gaseous exempt compounds, especially
product LC (pump hairspray) with HCFC-134a and product SA (stick deodorant) with
HFC-143a. This reflects good recoveries for two of the three samples, with the third sample
23
-------
showing low recovery (approximately 60 to 70 percent). The poor recovery is believed to be due
to problems with septum material from the apparatus used to fill the syringe with gas for spiking.
This material tended to clog the syringe needle and produce a high backpressure and leakage
around the hypodermic needle used to introduce spike gas into the vial.
Table 12. Results of Multiple Aliquots for Product AB - Aerosol Hairspray
Aliquot 1 a
Aliquot 2
Aliquot 3
Measured
Measured
Measured
Spike
mg (%
Spike
mg (%
Spike
mg (%
%Recovery
Compound
mg
recovery)
mg
recovery)
mg
recovery)
Avg
Stdev
tetrachloroethylene
39.6
45.1 (113.8%)
39
44.9(115.1%)
38.9
40.2 (103.4%)
110.8%
6.4%
methylene chloride
32
31.5 (98.5%)
31.5
31.5(100.1%)
31.4
32.4 (103.2%)
100.6%
2.4%
HCFC-141b
30.1
30.6(101.6%)
29.6
29.9 (100.9%)
29.5
30.1 (101.9%)
101.5%
0.5%
HCFC-123
35.2
35.5(101.1%)
34.6
34.9 (100.9%)
34.5
34.9(101.2%)
101.1%
0.2%
acetone
23.6
24.8(105.2%)
23.4
25.3 (108.2%)
23.3
26.0(111.7%)
108.4%
3.2%
carbon dioxide
18.3
17.5 (95.4%)
18.3
17 (92.7%)
18.3
16.2 (88.5%)
92.2%
3.5%
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
27.5
24.3 (88.4%)
27.5
24.9 (90.4%)
27.5
25.2 (91.7%)
90.2%
1.7%
HFC-134
NA
NA
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
24
-------
Table 13. Results of Multiple Aliquots for Product AC - Aerosol Deodorant
Aliquot 1a
Aliquot 2
Aliquot 3
Measured
Measured
Measured
Spike
mg (%
Spike
mg (%
Spike
mg (%
% Recovery
Compound
mg
recovery)
mg
recovery)
¦mg
recovery)
Avg
Stdev
tetrachloroethylene
41.1
41.6(101.1%)
38.2
39.2 (102.6%)
38.2
39.0(102.1%)
101.9%
0.7%
methylene chloride
33.2
34.7(104.4%)
30.8
32.6 (105.7%)
30.8
31.5 (102.1%)
104.1%
1.8%
HCFC-141b
31.3
31.6(101.1%)
29
31.0(106.7%)
29
29.5 (101.6%)
103.1%
3.1%
HCFC-123
36.5
36.7(100.7%)
33.9
34.7 (102.4%)
33.9
33.2(97.9%)
100.3%
2.2%
acetone
23.6
26.3 (111.5%)
23.7
25.7 (108.6%)
23.7
26.4(111.6%)
110.6%
1.7%
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
NA
NA
HCFC 142b
41.8
39.9 (95.3%)
41.8
41 (98.0%)
41.8
38.8 (92.8%)
95.4%
2.6%
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
Table 14.
Results of Multiple Aliquots for Product FD - Engine Cleaner
Aliquot 1 a
Aliquot 2
Aliquot 3
Measured
Measured
Measured
Spike
mg (%
Spike
mg (%
Spike
mg (%
% Recovery
Compound
mg
recovery)
mg
recovery)
mg
recovery)
Avg
Stdev
tetrachloroethylene
NA
NA
NA
NA
NA
NA
NA
NA
methylene chloride
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-141b
11.9
12.3 (103.6%)
22.8
22.3 (98.0%)
23.3
23.2 (99.8%)
100.5%
2.9%
HCFC-123
NA
NA
NA
NA
NA
NA
NA
NA
acetone
NA
NA
NA
NA
NA
NA
NA
NA
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
49.3
47.2 (95.8%)
49.3
47.3 (95.9%)
49.3
50.5 (102.4%)
98.0%
3.8%
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
25
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Table 15. Results of Multiple Aliquots for Product FB - Tire Cleaner
Aliquot 13 Aliquot 2 Aliquot 3
Compound
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
40.1
48.4(120.9%)
39.6
48.0(121.1%)
39.6
48.2(121.8%)
121.3%
0.5%
methylene chloride
32.3
33.0(102.1%)
32
33.0(103.1%)
31.9
32.5(101.7%)
102.3%
0.7%
HCFC-141b
30.4
29.8 (97.9%)
30.1
29.8 (98.9%)
30.1
30.2(100.4%)
99.1%
1.3%
HCFC-123
35.5
35.3 (99.2%)
35.2
36.2 (103.0%)
35.1
35.7(101.7%)
101.3%
1.9%
acetone
23.4
25.3 (108.1%)
23.8
25.7 (108.1%)
23.4
25.4 (108.4%)
108.2%
0.2%
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
41.4
36.7 (88.7%)
41.4
34.7 (83.8%)
41.4
35.9 (86.7%)
86.4%
2.5%
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
Table 16. Results of Multiple Aliquots for Product LC - Pump Hairspray
Aliquot 1 a Aliquot 2 Aliquot 3
Compound
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
59.1
60.1 (101.6%)
40.2
40.9(101.9%)
40.3
41.7(103.6%)
102.3%
1.1%
methylene chloride
47.7
47.2 (98.8%)
32.4
31.8(98.1%)
32.5
32.3 (99.4%)
98.8%
0.6%
HCFC-141b
44.9
47.1 (104.8%)
30.5
30.7 (100.6%)
30.6
32.0(104.6%)
103.3%
2.3%
HCFC-123
52.4
51.9 (99.0%)
35.6
33.0 (92.6%)
35.7
34.3 (96.0%)
95.9%
3.2%
acetone
23.3
24.6 (105.7%)
23.6
25.2 (106.6%)
23.5
24.7 (105.0%)
105.8%
0.8%
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
41.3
34.8 (84.1%)
41.3
27.3 (66.1%)
41.3
41.6(100.7%)
83.6%
17.3%
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
26
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Table 17. Results of Multiple Aliquots for Product AA - Furniture Polish
Aliquot 1a Aliquot 2 Aliquot 3
Compound
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
39.1
36.3 (93.0%)
38.2
35.0 (91.7%)
37.3
35.3 (94.7%)
93.1%
1.5%
methylene chloride
31.5
30.4 (96.5%)
30.8
29.5 (95.8%)
30.1
27.7 (92.0%)
94.8%
2.4%
HCFC-141b
29.7
28.0 (94.4%)
29
27.6 (95.2%)
28.3
26.1 (92.1%)
93.9%
1.6%
HCFC-123
34.7
35.5 (102.5%)
33.8
34.1 (100.8%)
33.1
32.5 (98.3%)
100.5%
2.1%
acetone
23.3
24.7 (106.0%)
23.3
24.4 (104.7%)
23.4
24.2 (103.6%)
104.8%
1.2%
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
35.4
33.1 (93.6%)
35.4
33.3 (94.0%)
35.4
34.2 (96.6%)
94.7%
1.6%
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
41.8
44.6 (106.7%)
41.8
42.6 (102.0%)
41.8
44.1 (105.6%)
104.7%
2.5%
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
NA
NA
NA
NA
NA
NA
NA
NA
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
Table 18. Results of Multiple Aliquots for Product SA - Stick Deodorant
Aliquot 1 a Aliquot 2 Aliquot 3
Compound
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
Spike
mg
Measured
mg (%
recovery)
% Recovery
Avg Stdev
tetrachloroethylene
36.5
35.9 (98.2%)
37.6
37.1 (98.7%)
40.2
37.6 (93.6%)
96.8%
2.8%
methylene chloride
29.5
28.8 (97.5%)
30.4
29.4 (96.8%)
32.4
30.5 (94.0%)
96.1%
1.9%
HCFC-14 lb
27.8
25.5 (91.8%)
28.6
24.3 (85.0%)
30.5
26.1 (85.5%)
87.4%
3.8%
HCFC-123
32.4
30.9 (95.2%)
33.4
31.1 (93.2%)
35.6
32.6(91.5%)
93.3%
1.9%
acetone
23.6
25.0 (105.7%)
23.4
24.9 (106.5%)
23.3
24.3 (104.4%)
105.6%
1.1%
carbon dioxide
NA
NA
NA
NA
NA
NA
NA
NA
HFC-125
NA
NA
NA
NA
NA
NA
NA
NA
HCFC-22
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-152a
NA
NA
NA
NA
NA
NA
NA
NA
HFC-134
NA
NA
NA
NA
NA
NA
NA
NA
HCFC 142b
NA
NA
NA
NA
NA
NA
NA
NA
HFC-143a
34.7
32.9 (95.0%)
34.7
32.1 (92.6%)
34.7
24.4 (70.4%)
86.0%
13.6%
NA = Not applicable, compound was not added as spike for this sample.
a Average of three injections.
27
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Table 19. Comparison of Spike Recoveries by Product
Compound
AB
aerosol
hairspray
AC
aerosol
deodorant
FD
engine
cleaner
FB
tire
cleaner
LC
Pump
hairspray
AA
furniture
polish
SA
stick
deodorant
Standard
Average deviation
tetrachloroethylene
110.8%
101.9%
NA
121.3%
102.3%
93.1%
96.8%
104.4%
10.2%
methylene chloride
100.6%
104.1%
NA
102.3%
98.8%
94.8%
96.1%
99.4%
3.6%
HCFC-141b
101.5%
103.1%
100.5%
99.1%
103.3%
93.9%
87.4%
98.4%
5.8%
HCFC-123
101.1%
100.3%
NA
101.3%
95.9%
100.5%
93.3%
98.7%
3.3%
acetone
108.4%
110.6%
NA
108.2%
105.8%
104.8%
105.6%
107.2%
2.2%
carbon dioxide
90.8%
NA
NA
NA
NA
NA
NA
90.8%
NA
HFC-125
NA
NA
98.0%
NA
NA
NA
NA
98.0%
NA
HCFC-22
NA
NA
NA
NA
NA
94.7%
NA
94.7%
NA
HFC-134a
NA
NA
NA
86.4%
NA
NA
NA
86.4%
NA
HFC-152a
90.2%
NA
NA
NA
NA
NA
NA
90.2%
NA
HFC-134
NA
NA
NA
NA
83.6%
104.7%
NA
94.2%
14.9%
HCFC 142b
NA
95.4%
NA
NA
NA
NA
NA
95.4%
NA
HFC-143a
NA
NA
NA
NA
NA
NA
86.0%
86.0%
NA
average
maximum
minimum
median
95.7%
107.2%
86.0%
95.4%
NA = Not applicable, compound was not added as spike to this product.
-------
MEASUREMENT OF TOTAL VOLATILES
Similar conditions are used to process consumer product samples in the method for
measuring exempts and in the total VOC method (3) evaluated earlier. The major change is the
use of a purge gas in the exempt VOC method. The change in sample weight due to the heated
purge was used to calculate the total volatile content for the products used in this study. Results
are shown in Table 20. The same product containers had previously been tested in an
interlaboratory study of the total VOC method. The total volatile content as determined by these
laboratories (using the total VOC method) is also included in Table 20. Comparison of the
results using the purge gas to those obtained in the interlaboratory study (without purge gas)
indicates a positive bias, which, although slight (around 2 percent), is statistically significant at
95 percent confidence. The reason for this bias is unknown but may be due to better
volatilization when purge gas is used or to removal of a plug of septum by the large (16 gauge)
needles used in the purge apparatus (this would incorrectly appear to be a loss of volatiles from
the product). Because measurements of total volatiles by the total VOC method (3) are relatively
easy to do and because this method has been validated in an interlaboratory study, it is
recommended that the total volatiles for products be measured as described in the total VOC
method.
ESTIMATED METHOD COST
The cost of analyses by this method will vary widely depending on a number of factors
including:
Number of analyses to be performed at one time
Automation facilities available (e.g., automated multisample gas injection facilities)
Sample handling problems (liquid and solid samples are easier to dispense than
aerosols)
Previous experience with this or similar laboratory methods
Cost of labor
29
-------
Availability of facilities to make multi-component calibration standards (these can be
bought commercially, if the laboratory does not have facilities to prepare their own).
Table 20. Comparison of Total Volatiles With and Without Purge Gas
Expected total
Weight percent total volatiles ("with purged volatile content
Product3
Aliquot 1
Aliquot 2
Aliquot 3
Average
Std Dev
(Without Purge)b
Difference
AB - aerosol hairspray
97.9%
94.0%
97.1%
96.3%
1.7%
95.6%
0.7%
AC - aerosol deodorant
103.8%
100.6%
97.1%
100.5%
2.7%
99.9%
0.6%
FD - engine cleaner
94.4%
95.6%
96.2%
95.4%
0.7%
93.4%
2.0%
FB - tire cleaner
72.0%
74.8%
76.4%
74.4%
1.8%
72.2%
2.3%
LC - Pump hairspray
95.0%
97.1%
95.4%
95.8%
0.9%
94.2%
1.6%
AA -furniture polish
96.1%
97.8%
97.5%
97.1%
0.7%
94.3%
2.9%
SA - stick deodorant
54.8%
55.6%
54.6%
55.0%
0.4%
53.0%
2.0%
Average
1.7%
Standard deviation
0.8%
t (difference = 0)
5.58
t at 95% confidence
2.45
Significant difference exists?
Yes
a Product codes are those used in the interlaboratory study (3).
b Average total volatiles value measured by eight laboratories in an interlaboratory study using the total VOC
method (3).
No overall cost estimate per sample is given, because the actual costs will vary widely among
different laboratories. However, estimates of equipment costs, expendable costs, and labor
hours are provided to assist users in evaluating method costs.
Equipment Costs
Equipment costs for this method should be similar to other methods using GC with MSD.
The largest single item is the GC/MSD itself, with costs for a GC with MSD and data system
ranging between $50,000 and $100,000, depending on model and accessories. Additional
equipment costs will include a drying oven ($3,000 to $5,000 for explosion resistant models, a
standard model could be used if the samples are known in advance to be non-flammable). Most
other reusable items of equipment used for this method are relatively inexpensive, by
comparison, and should be less than $200 in all.
30
-------
Expendable Items
Expendable item costs are fairly small (less than $10 per sample) if the collection bags are
reused. Collection bags cost approximately $20 each.
Labor costs
Total time for sample analysis is approximately 2.5 hours, of which 1.5 hours are used for
sample preparation and 1 hour is used for GC/MSD analysis. This time does not include
calibration and check samples (the number needed will depend on the stability of the system and
the size of sample batches). The actual labor time for analysis is around 1.5 hours per sample,
considerably less than the total sample analysis time, because the sample preparation and purge
for one sample can be performed while the GC/MSD analysis of the previous sample is being
performed.
31
-------
SECTION 6
QUALITY ASSURANCE AND QUALITY CONTROL
INTRODUCTION
The major quality concern in methods development is to provide a method that promotes
quality measurements. A key feature is to reduce the chances for error and minimize the number
and types of measurements required. Discussions among project personnel during the initial
stages of this project resulted in improvements that greatly affected the overall method quality.
The original method approach, contemplated during preparation of the QA plan, was to use
a heated reservoir to collect the volatile components for later analysis by GC using either FID or
MSD. The concentration of exempt compounds in the reservoir would be measured by GC using
calibration based on analyzing standard samples. The measured concentration would then be
converted to a total mass of exempt compounds by using measured reservoir volume,
temperature, and pressure. This approach has several problems, chiefly the potential for
reservoir contamination and the need to have accurate pressure and volume measurements.
Selecting MSD as the detector permits measuring selected target ions for the exempt compounds.
Measuring target ions provides a greater assurance that the correct compound is quantified,
which is especially important with the number and complexity of consumer product samples.
Problems with reservoir contamination were addressed by use of a Tedlar gas collection bag in
place of the reservoir. Problems with volume and pressure measurements were eliminated by use
of an internal standard (HCFC-122). In addition, internal standard methods are more tolerant of
changes in total sensitivity that may occur between runs in GC/MS operation. The use of
prepared cylinders for calibration and daily checks permits comparison of instrument response on
different days and thus provides for better quality control.
CALIBRATION CHECKS
The high-level calibration standard was checked daily. Results are shown in Figure 3. All
compounds were within 20 percent of the original calibration data, except for
tetrachloroethylene. As a result, the reported recoveries for tetrachloroethylene may be biased
32
-------
somewhat high. The limit for calibration drift of ±20 percent was defined in the Quality
Assurance Project Plan. This limit is a reasonable expectation for measurements performed by
GC/MSD. The reason that the check for tetrachloroethylene exeeded the 20 percent criterion is
not known.
33
-------
1 40%
1 20%
<1>
V)
1 00%
in
75 80%
ro
o
o
-------
REFERENCES
1. Study of Volatile Organic Compound Emissions from Consumer and Commercial Products
- Report to Congress, U.S. EPA Office of Air Quality Planning and Standards, Research
Triangle Park, NC, EPA-453/R-94-066-A, March 1995.
2. Code of Federal Regulations, Title 40, Part 51 as cited in 60 FR 31633, June 16, 1995.
3. E. E. Rickman, Jr, G. B. Howe, and R. K. M. Jayanty, Interlaboratory Study of a Test
Method for Measuring Total Volatile Organic Compound Content of Consumer Products,
U.S. EPA Office of Research and Development, Air Pollution Prevention and Control
Division, Research Triangle Park, NC, EPA-600/R-95-163(NTIS PB96-121652),
November 1995.
4. Standard Test Method for Volatile Content of Coatings, ASTM Designation D 2369-87,
American Society for Testing and Materials, Philadelphia, PA, 1987.
5. Determination of Volatile Matter Content, Water Content, Density, Volume Solids, and
Weight Solids of Surface Coatings, Code of Federal Regulations, Title 40, Part 60,
Appendix A, Method 24.
6. Standard Test Method for Water Content of Water-Reducible Paints by Direct Injection into
a Gas Chromatograph, ASTM Designation D 3792-86, American Society for Testing and
Materials, Philadelphia, PA, 1986.
7. Matheson Gas Data Book, fifth edition, Matheson Gas Products, East Rutherford, NJ, 1971.
35
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APPENDIX A
DETERMINATION OF EXEMPT VOLATILE ORGANIC
COMPOUNDS AND CARBON DIOXIDE IN CONSUMER PRODUCTS
A-l
-------
DETERMINATION OF EXEMPT VOLATILE ORGANIC COMPOUNDS
AND CARBON DIOXIDE IN CONSUMER PRODUCTS
Notice
Mention of trade names or commercial products does not
constitute endorsement or recommendation for use.
1.0 APPLICABILITY AND PRINCIPLE
1.1 Applicability
A previously validated method entitled "Determination of Volatile Organic Compounds
in Consumer Products" (1) specifies a gravimetric technique for measuring total volatile content
and a gas chromatographic technique with thermal conductivity detection for measuring water
content. Subtraction of the water content from the total volatile content gives the apparent
volatile organic compound content.
The method described here is for measurement of exempt volatile organic compounds
(VOCs) and carbon dioxide (C02) in consumer products. Exempt VOCs are defined in 40 CFR
51.100. The total nonexempt volatile organic compound content is determined by subtracting the
exempt compound content from the apparent volatile organic compound content.
It is assumed that the personnel employing this method have sufficient experience and
training to properly evaluate any safety and technical issues that might arise from this method's
use. Although some specific hazards have been noted, these do not represent all possible safety
problems that might arise. The user should also be familiar with general laboratory procedures
and the use of gas chromatography (GC) with mass selective detection (MSD).
This method has been validated for several exempt compounds, which are listed below:
Carbon dioxide
1,1,1-Trifluoroethane (HFC-143a)
Pentafluoroethane (HFC-125)
1,1-Difluoroethane (HFC-152a)
A-2
-------
1,1,1,2-T etrafluoroethane (HFC-134a)
Chlorodifluoromethane (HCFC-22)
1,1,2,2-Tetrafluoroethane (HFC-134)
1 -Chloro-1,1 -difluoroethane (HCFC-142b)
Dichloromethane
1,1 -Dichloro-1 -fluoroethane (HCFC- 141b)
Acetone
1,1,1 -Trifluoro-2,2-dichloroethane (HCF C-123)
Tetrachloroethene.
1.2 Principle
The consumer product sample is placed in a sealed septum vial. This vial is attached to a
Tedlar collection bag and dry nitrogen is used to purge the vial while heating at 110°C for 1 hour
(Figure 1). Volatile compounds in the sample are transferred to the collection bag by the purge
gas. After the purge, the bag contents are analyzed by GC with MSD to determine the weight
percent of exempt volatile organic compounds present in the original sample.
1.3 Accuracy and Precision Statement
The accuracy and precision of measuring exempt compounds has been determined by
analyzing consumer product samples that were spiked with known amounts of exempt
compounds. Recoveries for exempt compounds averaged 95.5 percent, with different
compounds ranging from 86 to 107 percent recovery. Precision for spiked samples of the same
product were typically less than 5 percent, expressed as the standard deviation of spike recovery.
Interlaboratory precision and accuracy for this method have not been evaluated.
A-3
-------
2.0 APPARATUS AND MATERIALS
2.1 Analytical Balance
A balance with capacity sufficient to weigh sample vials (approximately 100 g) to a
precision of ±0.0001 g.
2.2 Drying Oven
A forced-draft oven capable of maintaining a temperature of 110 ± 5° C. This oven needs
to be suitable for use with flammable vapors, if flammable samples are to be evaluated.
2.3 Sample Vials
A 100-mL disposable glass serum vial with crimp-type cap and septum.
2.4 Sample Shaker (optional but recommended^
A wrist-action shaker to mix the consumer product containers before sampling.
2.5 Transfer Pipets and Spatulas
Pipets and laboratory spatulas suitable for transferring solids and liquid samples to
sample vials.
2.6 Thermometer
An oven thermometer capable of measuring 110° C with an accuracy of 1 ° C.
2.7 Purge Assembly
The sample is collected in a Tedlar bag for analysis by GC/MSD by using the purge
assembly illustrated in Figure 1. This apparatus is composed of the following parts:
2.7.1 Hypodermic needles
Two 15-gauge hypodermic needles of sufficient length for purging vial (approximately
3.5 in. long).
A-4
-------
One 22-gauge hypodermic needle of sufficient length for relieving vial pressure (into the
bag) before insertion of larger gauge needles.
2.7.2 Rotameter
A rotameter capable of measuring a purge gas flow of approximately 1,000 mL/min.
2.7.3 Needle valve --
A needle valve to control purge gas flow.
2.7.4 Heat exchanger
Ten feet of 0.25-in.-OD copper tubing with connecting fittings.
2.7.5 Flexible tubing --
Several feet of 0.25-in.-OD flexible (accordion pleated) Teflon tubing to connect input
and output lines to the vial assembly.
2.7.6 Sample tubing
Teflon tubing (0.25-in.-OD) to connect output hypodermic needle to sample bag.
2.7.7 Viton tubing ~
A 2-inch length of l/4-in.-OD Viton tubing for connecting the small gauge needle and
Tedlar bag for relieving sample vial pressure.
2.7.8 Connecting adapter
Two adapters to connect hypodermic needles to tubing. A Luer-lok to NPT adapter
(Millipore part No. XX3002567) connected to an NPT to tubing fitting was used in development
of this method; however, other fittings may be used as appropriate.
A-5
-------
2.7.9 Support for sample vial
Although not shown in Figure 1, a support to prevent the vial from turning over in the
oven is recommended. A simple support might consist of a laboratory ring stand and clamp.
2.8 Aerosol Sampling Assembly
Aerosol sampling is accomplished using the apparatus shown in Figure 2. An aerosol can
adapter (e.g., part No. 8048 from Alltech Associates or equivalent) and a double-ended syringe
needle (e.g., part No. 5742 from Becton Dickinson or equivalent) are used to connect the sample
vial to the product container. This adapter is designed to fit over the exit tube of an aerosol
product (i.e., after the spray nozzle has been removed). Obtaining samples from containers with
one-piece exit tube/spray nozzles will require a short length of appropriately sized plastic tubing
to connect the can to the adapter.
2.9 Collection Bags
Tedlar bags capable of containing nominally 80 L of purged gas.
2.10 Vacuum Pumps
Two vacuum pumps are required. One pump should be suitable for evacuation of the
Tedlar bags and the second pump should be suitable for filling the GC gas sample loop with gas
from the collection bag. The sample pump must be installed on the downstream side of the
sample loop.
2.11 Nitrogen Purge Gas
WARNING - EXPLOSION HAZARD: The presence of oxygen in
the nitrogen purge gas may result in explosion. An explosion may
result if air is used as the purge gas.
A-6
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Nitrogen gas free from organic compounds, water, other condensibles, and oxygen. The
nitrogen should be at sufficient pressure to permit a flow of approximately 1 L/min through the
purge apparatus.
2.12 Gas Chromatograph
A gas chromatograph configured with an MSD, a gas sampling valve fitted with a
sampling loop, and a data acquisition system. A 1-mL stainless steel loop was used in method
development.
2.13 GC Column
A column that will provide adequate separation of most of the exempt compounds from
each other and from other consumer product components. A 30-m, and 0.53-mm-ID PLOT
column with GS-Q stationary phase was used successfully in development of this method.
2.14 GC Carrier Gas
Helium, ultra-high-purity grade.
2.15 Internal Standard
1,2,2-trichloro-1,1 -difluoroethane (HCFC-122).
2.16 Microliter Syringe
A 100-/JL syringe with needle for use in adding the internal standard to the sample.
2.17 GC Calibration Standards
Compressed gas mixtures consisting of the exempt compounds of interest and the internal
standard compound (see Section 2.15) in a nitrogen diluent. The concentration of the exempt
compounds should bracket the concentration of exempt compounds expected in the collection
bag from consumer product tests.
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3.0
SAMPLING PROCEDURE
WARNING - EXPLOSION HAZARD: This procedure
uses glass vials under pressure. Wear appropriate eye and
face protection.
3.1 Consumer Product Sample Collection
3.1.1 Solids and liquids (nonpressurized products)
This procedure is to be used for all nonpressurized products including pump aerosol
products. Weigh a 100-mL glass vial with cap and septum and record the weight to the
nearest 0.0001 g as "A" on the data sheet (Table 2).
Mix the consumer product thoroughly immediately before sampling. Using a spatula or
pipet, transfer approximately 0.5 g of sample into the sample vial and weigh along with the
designated cap and septum. (Note: Transfer of extremely volatile liquids may be made with a
hypodermic syringe and needle through the septum of a sealed sample vial). Record the weight
to the nearest 0.0001 g as "B" on the data sheet. Attach the septum (with the Teflon face up) and
cap and securely crimp.
Weigh out approximately 100 mg of the internal standard and add through the septum to
the sample. Reweigh the sample with the internal standard and record the weight as "C" on the
data sheet.
3.1.2 Pressurized aerosol cans
This procedure is to be used for all pressurized samples including aerosol cans,
pressurized foam products, and gaseous products (special adapters may be needed for gaseous
products). The sample vials are filled using an aerosol sampling adapter (Figure 2).
Weigh a 100-mL glass vial with cap and septum and record the weight to the
nearest 0.0001 g as "A" on the data sheet. Affix the cap and septum (with the Teflon face up)
and securely crimp the cap.
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Mix the consumer product thoroughly by shaking the container vigorously for 1 to 2 min.
Shaking should be performed with a wrist-action shaker (preferred method) or by hand. (NOTE:
Aerosol and foam products contain an eductor tube that may be filled with propellant until the
can is first used. Press the sample valve to dispense a short [about 1 second] burst of product to
clear the eductor tube before continuing the sampling procedure. This step should be needed
only upon initial sampling of the product.)
Immediately after shaking the container, insert one end of the double-sided needle into
the aerosol sampling adapter (Figure 2). Remove the spray nozzle from the aerosol or foam
container and connect the sampling adapter to the exit tube of the valve (i.e., in the place of the
spray nozzle). (NOTE: Some containers may have a one-piece spray nozzle and exit tube. These
containers require addition of an exit tube to the sampling adapter before the adapter can be
connected to the container.)
With the product container oriented to dispense product (upright for products whose
instructions specify upright use, inverted for products that specify inverted use), insert the other
end of the needle through the septum on the sample vial. Depress the adapter, opening the
container valve for a sufficient time to allow about approximately 0.5 g of sample into the vial.
While maintaining a firm seal between the adapter and the exit tube, release pressure on the
adapter to close the container's valve. Quickly pull the adapter needle out of the vial septum, so
as to lose as little propellant as possible. (NOTE: A hissing sound will result as some gas
escapes from the adapter assembly.) Reweigh the pressurized vial and sample and record the
weight to the nearest 0.0001 g as "B" on the data sheet.
WARNING: Glass vials under pressure may
explode. Handle the pressurized sample vial
carefully.
Add approximately 100 mg of the internal standard through the septum. Reweigh the vial
and internal standard and record the weight as "C" on the data sheet.
Clean the adapter with a suitable solvent between each set of products. Disassemble and
allow the adapter to dry completely before reuse.
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3.2 Purging Volatiles Into the Collection Bag
Attach one end of a 2-inch length of Viton tubing to the inlet of the empty gas collection
bag. Attach the other end to a 22-gauge hypodermic needle. Pierce the sample vial with the
needle and allow the propellant to transfer to the bag for approximately 5 minutes. Seal the bag
inlet, and then remove the needle from the sample vial. Remove the needle from the Viton
tubing.
Next, preheat the oven to 110° C. Connect the collection bag to the output of the purge
assembly and open the collection bag inlet. Open the oven door and, using a quick motion, insert
the output hypodermic needle through the sample vial's septum. Insert the purge gas (input)
hypodermic needle through the septum. Start the gas flow at approximately 1 L/minute. Record
the time that the purge gas was started as "D" on the data sheet.
Adjust the input needle depth in the vial so that it is about 0.25 inch above the bottom of
the sample vial. Adjust the output needle depth in the vial so that it is at least 1 inch above the
end of the input needle. Place the vial in the oven and close the door. Allow the vial to be
purged at 110° C for 1 hour.
At the end of the purge time, stop the purge gas flow and record the time as "E" on the
data sheet. Seal the collection bag inlet, remove the vial from the oven and remove the needles
from the vial. Allow the vial to cool before discarding.
4.0 ANALYSIS OF BAG CONTENTS TO MEASURE EXEMPT VOC
Details of instrument operation will vary with the individual apparatus and are not
specified in this method.
4.1 Chromatographic Conditions
A column and chromatographic conditions should be selected to adequately separate the
exempt compounds from each other and from other product components. The following
conditions have proven suitable in tests of this method and may be used as a starting point.
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4.1.1 GC column
Thirty-meter, 0.53-mm-ID fused silica PLOT (porous layer open tubular) column with
GS-Q stationary phase.
4.1.2 Column flow rate
Set the flow rate to 4.0 mL/min. An effluent splitter must be used to limit the column
effluent flow which passes into the MSD interface to 1 mL/minute.
4.1.3 Sample loop
Stainless steel loop with nominal volume of 1 mL.
4.1.4 Sampling valve temperature--
Set the sampling valve temperature to 150° C.
4.1.5 Oven temperature program
40° C for 1 minute, 5° C per minute to 150° C, 20° C per minute to 220°C, hold for 4.5
minutes.
4.1.6 Detector temperature
Set the detector temperature at 280° C.
4.2 MSD Operating Conditions
Operating mode: scan
Low mass: 29
High mass: 200
Threshold: 250
A/D samples: 16
A-ll
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4.3 GC Calibration Procedure
Obtain three calibration standards containing the internal standard and exempt
compounds of interest at a range of concentrations that includes the expected bag concentrations.
Analyze each standard in triplicate or until no trend in component response is observed.
Introduction of gas samples from compressed gas calibration standards is performed without the
sample pump operating.
Determine one target ion for each exempt compound for use in quantitation. For closely
eluting compounds, select a unique target ion for each compound. Determine one or more
qualifier ions for each exempt compound for use in compound identification.
Prepare a quantitation database using an internal standard calibration and include
retention times, target ions, qualifier ions, and compound amounts. Instead of entering
compound amounts in parts per million (ppm), enter the product of ppm concentration and gram
molecular weight. This will enable quantitation of the exempt compounds in the samples on a
weight basis.
Using appropriate data analysis software, create a multilevel calibration using the three
analyzed calibration standards.
A summary of exempt compounds, retention times, target ions, and qualifier ions used in
development of this method is presented in Table 1. This information is to be used only as a
guide in method implementation. The specific retention times may vary for other GC columns
and operating conditions.
4.4 Collection Bag Analysis
Before injection of a gas sample from a collection bag for analysis, enter into the data
system the amount (in grams) of internal standard that was loaded into the sample vial. Also
enter the weight of product sample (in grams) being tested. This will enable reporting of the
exempt compound amount directly in weight percent
Connect the sample bag to the gas sampling valve inlet tube and use the sampling pump
to purge the loop at approximately 30 mL/min for 2 minutes. Stop the sample flow through the
loop and inject the sample.
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4.5 Quality Control Procedures
Analyze a calibration standard and blank after every eight sample injections. Before
analysis, enter the product of the ppm concentration and gram molecular weight for the internal
standard. The reported component amounts (ppm x gram molecular weight) should not vary by
more than 10 percent from a previous value on the same day or more than 20 percent between
days. If the response factor is outside of these limits, then recalibrate using all three calibration
standards.
A-13
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TABLE 1. EXEMPT COMPOUND ANALYSIS GUIDELINES
Compound
Retention time,
minutes
Target ion
mass
Qualifier
ion mass
Carbon dioxide
3.26
44
1,1,1 -T rifluoroethane
(HFC-143 a)
7.21
69
65
Pentafluoroethane
(HFC-125)
8.48
51
101
1,1 -Difluoroethane
(HFC-152a)
9.70
51
65
1,1,1,2-T etrafluoroethane
(HFC-134a)
9.84
69
83
Chlorodifluoromethane
(HCFC-22)
10.57
51
67
1,1,2,2-T etrafluoroethane
(HFC-134)
12
51
83
1 -Chloro-1,1 -difluoroethane
(HCFC-142b)
14.82
65
45
Dichloromethane
22.06
49
84
1,1 -Dichloro-1 -fluoroethane
(HCFC-141b)
22.58
81
83
Acetone
22.69
43
58
1,1,1 -Trifluoro-2,2-dichloroethane
(HCFC-123)
23.53
85
69
1,2,2-Trichloro-1,1 -difluoroethane3
(HCFC-122)
27.16
83
133
T etrachloroethene
29.76
85
69
"Internal standard compound.
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5.0 CALCULATIONS
5.1 Sample Weight
The sample weight (SW) is calculated as:
SW = B - A
where
B = weight of vial, cap, septum, and sample
A = weight of vial, cap, and septum.
5.2 Internal Standard Weight
The internal standard weight (ISTDW) is calculated as:
ISTDW = C - B
where
C = weight of vial, cap, septum, sample, and internal standard.
B = weight of vial, cap, septum, and sample.
5.3 Internal Standard Calibration
Because commercial GC-MSD systems include data analysis software that performs the
necessary calculations to establish a multilevel calibration based on an internal standard, the
calculations shown below are given only to describe the approach.
Calculate an amount ratio and response ratio for each level and compound in the
database.
Amount ratio = Amountq/AmountISTD
Response ratio = Respq/RespISTD
Perform a linear regression analysis of Amount ratio versus Response ratio.
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5.4
Exempt VOC Weight Percent
Because all commercial GC-MSD systems include data analysis software that performs
the necessary calculations to determine the exempt VOC weight percent based on an internal
standard, the calculations shown below are given only to describe the approach.
Calculate a response ratio from GC-MSD analysis for each exempt compound.
Response ratio = Respq/RespISTD
Calculate an amount ratio for each compound based on the linear regression
equation determined during calibration.
Multiply the amount ratio by the known amount of internal standard that was
added to the sample to determine the amount of exempt compound.
Calculate the weight percent for each exempt compound by dividing the
component amount (in grams) by the sample amount (in grams) and multiplying
by 100.
Calculate the total exempt VOC weight percent by summing the individual
component weight percents.
6.0 GLOSSARY
C02 Carbon dioxide
GC Gas chromatograph, gas chromatography, or gas chromatographic
NPT National Pipe Thread - used to specify the size and threads associated with a pipe
fitting
OD Outside diameter (of tubing, etc.)
VOC Volatile organic compound
MSD Mass selective detector.
7.0 REFERENCES
1. E.E. Rickman, Jr., G.B. Howe, and R.K.M. Jayanty, "Interlaboratory Study of a Test
Method for Measuring Total Volatile Organic Compound Content of Consumer
Products," U.S. Environmental Protection Agency, National Risk Management Research
Laboratory, Research Triangle Park, NC 27711, EPA-600/R-95-163(NTIS PB96-
121652), November 1995, Appendix A.
A-16
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TABLE 2. DATA SHEET FOR SAMPLE COLLECTION
Weighings
A) Weight of empty sample vial, septum and cap
(g).
B) Weight of vial, septum, cap, and sample (g).
C) Weight of vial, septum, cap, internal standard,
and sample (g).
D) Time purge started
E) Time purge ended
Calculations
G) Sample weight (g) = B - A
H) Weight of internal standard (g) = C - B
A-17
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copper
tubing
as heat
exchanger
flexible Teflon
tubing
15-ga hypodermic
needles
sample vial
Tedlar
collection bag
Figure 1. Sample purge and volatiles collection assembly.
A-18
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Double-Ended Syringe Needle
Aerosol Sampling Adapter
(Alltech part No. 8048)
0
Aerosol
Product
Sample Vial
Figure 2. Aerosol sampling adapter.
A-19
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EPA/600/R-97/027
March 1997
Method Validation for Measurement of
Selected Semivolatile Phenols
in Dust and Soil
by
Jane C. Chuang and Donald V. Kenny
Battelle Memorial Institute
505 King Avenue
Columbus, Ohio 43101-2693
Contract 68-D4-0023
Work Assignment 1-08, Task 1
Project Officer
Nancy K. Wilson
Air Exposure Research Division
National Exposure Research Laboratory
Research Triangle Park, North Carolina 27711
National Exposure Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
TECHNICAL REPORT DATA
1. REPORT NO.
EPA/600/R-97/027
2.
i mini! muni
PB97-14 315 0
4. TITLE AND SUBTITLE
Method Validation for Measurement of Selected
Semivolatile Phenols in Dust and Soil
5.REPORT DATE
March 1997
6. PERFORMING ORGANIZATION CODE
7. AUTHOR (S)
Jane C. Chuang and Donald V. Kenny
8.PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle, Columbus, OH 43201
10.PROGRAM ELEMENT NO.
Projects E0608, E0609 and
E0460
11. CONTRACT/GRANT NO.
Contract 68-D4-0023
12. SPONSORING AGENCY NAME AND ADDRESS
National Exposure Research Laboratory
U. S. Environmental Protection Agency
Research Triangle Park, NC 27711
13.TYPE OF REPORT AND PERIOD COVERED
Symposium proceedings
14. SPONSORING AGENCY CODE
EPA/600/09
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The objectives of this study were to evaluate and validate analytical methods for analysis of persistent organic
pollutants (POP) in dust/soil and to obtain concentration profiles for the target POP in dust/soil samples from the homes of 13
low-income families.
The analytical method for determining p-pentylphenol, p-octylphenol, nonylphenols, and bisphenol-A consisted of
sequential extractions of the dust/soil with 5 % acetic acid in methanol (MeOH), 100 % dichloromethane (DCM), and 5 %
acetic acid in water; liquid-liquid partitioning the resulting extract with water; and analyzing the concentrated DCM extract by
gas chromatography/mass spectrometry (GC/MS). With this method, quantitative recoveries (>80 %) were obtained for the
target phenols from the spiked soil samples. The estimated detection limits for the target phenols are 0.001 ppm.
The analytical method for determining 2-acetylaminofhiorene (2AF) and 3-amino-9-ethylcarbazole (AEC) consisted of
extracting dust/soil with 30 % water in MeOH at pH 10, and analyzing the extract by liquid chromatography with tandem mass
spectrometiy (LC/MS/MS). Recoveries for 2AF and AEC from the spiked soil samples ranged from 98 to 110 % and from 39
to 110 %, respectively. The estimated detection limits were 0.001 ppm for 2AF and 0.005 ppm for AEC.
Sums of the concentrations of target phenols ranged from 1.94 to 14.8 ppm in house dust samples, from 0.047 to 1.51
ppm in entryway dust samples, and from 0.021 to 0.265 ppm in pathway soil samples. The observed concentrations trend was
house dust > entry way dust > pathway soil. There were do detectable amounts of 2AF and AEC in any dust/soil samples.
Other compound classes found in dust/soil samples from one household were alkanes, aliphatic alcohols, fatty acids, fatty acid
esters, and phthalates.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/ OPEN ENDED
TERMS
c.COSATI
18. DISTRIBUTION STATEMENT
Release to public.
19. SECURITY CLASS (This
Report)
Unclassified
21.NO. OF PAGES
34
AU ERVE^RW^L °OPTOIGOT
20. SECURITY CLASS (This
Page)
Unclassified
22. PRICE
-------
NOTICE
The U.S. Environmental Protection Agency, through its Office of Research and
Development, funded and managed the research described here under Contract Number
68-D4-0023 to Battelle Memorial Institute. It has been subjected to the Agency's peer and
administrative review and 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
Battelle does not engage in research for advertising, sales promotion, or endorsement of
our clients' interests including raising investment capital or recommending investment
decisions, or other publicity purposes, or for any use in litigation.
Battelle endeavors at all times to produce work of the highest quality, consistent with
our contract commitments. However, because of the research and/or experimental nature of
this work, the client undertakes the sole responsibility for the consequences of any use,
misuse, or inability to use, any information, apparatus, process or result obtained from
Battelle, and Battelle, its employees, officers, or Trustees have no legal liability for the
accuracy, adequacy, or efficacy thereof.
ii
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FOREWORD
The mission of the National Exposure Research Laboratory (NERL) is to provide
scientific understanding, information and assessment tools that will quantify and reduce the
uncertainty in EPA's exposure and risk assessments for environmental stressors. These
stressors include chemicals, biologicals, radiation, and changes in climate, land use, and water
use. The Laboratory's primary function is to measure, characterize, and predict human and
ecological exposure to pollutants. Exposure assessments are integral elements in the risk
assessment process used to identify populations and ecological resources at risk. The EPA
relies increasingly on the results of quantitative risk assessments to support regulations,
particularly of chemicals in the environment. In addition, decisions on research priorities are
influenced increasingly by comparative risk assessment analysis. The utility of the risk-based
approach, however, depends on accurate exposure information. Thus, the mission of NERL is
to enhance the Agency's capability for evaluating exposure of both humans and ecosystems
from a holistic perspective.
The National Exposure Research Laboratory focuses on four major research areas:
predictive exposure modeling, exposure assessment, monitoring methods, and environmental
characterization. Underlying the entire research and technical support program of the NERL is
its continuing development of state-of-the-art modeling, monitoring, and quality assurance
methods to assure the conduct of defensible exposure assessments with known certainty. The
research program supports its traditional clients ~ Regional Offices, Regulatory Program
Officer, ORD Offices, and Research Committees ~ and ORD's Core Research Program in the
areas of health risk assessment, ecological risk assessment, and risk reduction.
Human exposure to multimedia contaminants, including semivolatile organic
compounds (SVOC) and nonvolatile organic compounds (NVOC) is an area of concern to EPA
because of the possible carcinogenicity of these compounds. These compounds are present in a
variety of microenvironments. The efforts described in this report provide an important
contribution to our capability to measure and evaluate human exposure to toxic pollutants.
Gary J. Foley
Director
National Exposure Research Laboratory
iii
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ABSTRACT
The objectives of this study were to evaluate and validate analytical methods for
analysis of persistent organic pollutants (POP) in dust/soil and to obtain concentration profiles
for the target POP in dust/soil samples from the homes of 13 low-income families.
The analytical method for determining p-pentylphenol, p-octylphenol, nonylphenols,
and bisphenol-A consisted of sequential extractions of the dust/soil with 5 % acetic acid in
methanol (MeOH), 100 % dichloromethane (DCM), and 5 % acetic acid in water; liquid-
liquid partitioning the resulting extract with water; and analyzing the concentrated DCM
extract by gas chromatography/mass spectrometry (GC/MS). With this method, quantitative
recoveries (>80 %) were obtained for the target phenols from the spiked soil samples. The
estimated detection limits for the target phenols are 0.001 ppm.
The analytical method for determining 2-acetylaminofluorene (2AF) and 3-amino-9-
ethylcarbazole (AEC) consisted of extracting dust/soil with 30 % water in MeOH at pH 10,
and analyzing the extract by liquid chromatography with tandem mass spectrometry
(LC/MS/MS). Recoveries for 2AF and AEC from the spiked soil samples ranged from 98 to
110 % and from 39 to 110 %, respectively. The estimated detection limits were 0.001 ppm
for 2AF and 0.005 ppm for AEC.
Concentrations of the sums of target phenols ranged from 1.94 to 14.8 ppm in house
dust samples, from 0.047 to 1.51 ppm in entryway dust samples, and from 0.021 to 0.265
ppm in pathway soil samples. The observed concentrations trend was house dust > entry way
dust > pathway soil. There were no detectable amounts of 2AF and AEC in any dust/soil
samples. Other compound classes found in dust/soil samples from one household were
alkanes, aliphatic alcohols, fatty acids, fatty acid esters, and phthalates.
This report is submitted in fulfillment of Contract Number 68-D4-0023, Work
Assignment No. 1-08, Task 1 by Battelle under the sponsorship of the U.S. Environmental
Protection Agency. This report covers a period from May 1996 to September 1996, and work
was completed as of September 1996.
iv
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Contents
Foreword iii
Abstract iv
Acknowledgment vi
Chapter 1 Introduction 1
Chapter 2 Conclusions 3
Chapter 3 Recommendations 5
Chapter 4 Experimental Procedures 6
Analytical Method for Phenols 6
LC/MS/MS Method Evaluation 7
Analytical Method for 2AF and AEC 8
Chapter 5 Results and Discussion 10
GC/MS Analysis of Dust and Soil Samples 10
LC/MS/MS Analysis of Dust and Soil Samples 15
References 25
Appendices
A Phenol Data in House Dust Entryway Dust and
Pathway Soil Samples 27
B Levels of Target Phenols in the Method Blank 28
v
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ACKNOWLEDGMENT
The authors are grateful to Dr. Nancy K. Wilson, Project Manager, of the U.S.
Environmental Protection Agency, for her invaluable advice during this investigation.
Technical assistance provided by Ms. Mary A. Pollard, Mr. Robert A. Plastridge and Mr.
David B. Davis of Battelle is greatly appreciated.
vi
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Chapter 1
Introduction
Persistent organic pollutants (POP), including polycyclic aromatic hydrocarbons
(PAH), polychlorinated biphenyls (PCB), and other semivolatile organic compounds (SVOC),
nonvolatile organic compounds (NVOC) and some metals (M) are found in air, house dust,
soil, food, and water (1-5). Many of these compounds are putative endocrine disrupters and
are known mutagens or probable human carcinogens. Humans can be exposed to these
pollutants through inhalation, dietary and non-dietary ingestion, and dermal adsorption, and
adverse health effects have been linked to such exposures. The non-dietary pathway resulting
from ingestion of soil and dust may be more important for young children because of their
play activities.
Children of low-income families, or families living in urban environments may have
increased exposure to POP and M. This may arise because of their proximity to areas of high
traffic, industrial activities, or lifestyle aspects. Under Cooperative Agreement CR822073, a
preliminary study to develop and evaluate field methods to estimate children's exposure to
PAH was conducted. The results from the first two years of this study indicated that the
loadings of house dust in several urban low-income households are more than one order of
magnitude higher than those of middle-income families (4,6). Such high dust loadings can
increase children's exposure to POP and M through the non-dietary pathway.
Many POP were not included in the Cooperative Agreement study. It is desirable to
include these pollutants in the evaluation of the field exposure methods targeted at low-income
families. Under Task 1 of this Work Assignment, two analytical techniques, gas
1
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chromatography/mass spectrometry (GC/MS) and liquid chromatography with tandem mass
spectrometry (LC/MS/MS) were evaluated for analysis of target POP that include putative
endocrine disrupters. The GC/MS method was evaluated and validated for analysis of target
phenols. The LC/MS/MS method was evaluated for analysis of all target POP, but only
validated for the analysis of 2-acetylaminofluorene (2AF) and 3-amino-9-ethylcarbazole
(AEC). House dust, entry way dust and pathway soil samples collected from 9 homes under
the Cooperative Agreement study (6) and from 4 homes under Contract Number 68-D4-0023,
Work Assignment 02 (7) were analyzed for target phenols, 2AF, and AEC using the validated
analytical methods.
The objective of this study was to validate analytical methods for analysis of target
POP in dust and soil, and to determine target POP in 39 dust/soil samples collected from the
homes of 13 low-income families using the validated analytical methods.
The following tasks were carried out in this study:
(1) Conduct GC/MS method evaluation/validation for analysis of p-pentylphenol,
p-octylphenol, nonylphenols, and bis-phenol-A.
(2) Conduct LC/MS/MS method evaluation/validation for 2-acetylaminofluorene,
3-amino-9-ethylcarbazole, 2,4-dinitrotoluene, anthraquinone, vinclozolin, and
phenols
(3) Analyze 39 samples and one method blank for target POP using the appropriate
validated methods
(4) Prepare a final report on the results of the study.
2
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Chapter 2
Conclusions
An analytical method for the determination of phenols in dust and soil samples was
validated. This method consisted of (1) sequential sonication of the dust/soil sample with 5%
acetic acid in methanol, 100% dichloromethane (DCM), and 5% acetic acid in water,
(2) liquid-liquid partitioning the resulting extract with water, and (3) GC/MS analysis of the
concentrated DCM extract. With this method, quantitative recoveries (> 80 percent) of the
phenols were obtained from the spiked soil samples and the estimated detection limits are
0.001 ppm of target phenols in dust/soil.
An analytical method consisting of extracting the sample with 30% water in methanol
at pH 10 and analyzing the extract by LC/MS/MS was validated for the determination of
2-acetylaminofluorene (2AF) and 3-amino-9-ethylcarbazole (AEC) in dust/soil. The
recoveries of spiked 2AF ranged from 98 to 110 percent in the soil samples. The recoveries of
spiked AEC ranged from 39 to 110 percent and showed more variations than the recoveries of
2AF. The estimated detection limits for this method were 0.001 ppm for 2AF and 0.005 ppm
for AEC. The LC/MS/MS method was evaluated but not validated for the analysis of other
target POP because appropriate MS/MS conditions could not be established or inadequate
detection limit.
The most abundant target phenols were nonylphenols and the least abundant one was,
in general, p-pentylphenol in the dust/soil samples. The concentrations of target phenols
ranged from 0.043 to 3.56 ppm in house dust, from < 0.001 to 0.974 ppm in entryway dust,
and from < 0.001 to 0.204 ppm in pathway soil. There were no detectible levels of 2AF and
3
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AEC in these dust and soil samples. Other compound classes found in the dust/soil samples
from one household were alkanes, aliphatic alcohols, fatty acids, fatty acid esters, and
phthalates.
The general concentration trend observed for phenols in these samples was:
house dust > entryway dust > pathway soil. Similar relationships among dust/soil samples
were also observed for PAH, alkyl PAH and phthalates from other EPA studies (4,6,7). This
finding suggests that many persistent organic pollutants are enhanced in the house dust
medium. Therefore human exposure to POP, especially that of young children, through non-
dietary ingestion or dermal contact of house dust should not be overlooked.
4
-------
Chapter 3
Recommendations
Levels of many persistent organic pollutants (POP) including nonylphenols, bisphenol-
A, PAH, and phthalates found in house dust were much higher than those found in entryway
dust and pathway soil. House dust is an easily accessible environmental matrix as opposed to
air and food and can provide relevant information on human exposure to POP. Several
important issues remain to be addressed to assess human exposure to POP due to house dust
and soil. In future studies, we recommend:
(1) Conducting a pilot field study to determine concentration profiles of POP that
are potential endocrine disrupters by broad scan analysis, and to
evaluate/validate a cost-effective method that can determine POP of different
compound classes in house dust samples.
(2) Conducting a pilot field study to determine concentration profiles of POP that
are potential endocrine disrupters in multimedia samples; to determine the
effects of geographic location and the social economic status of the households
on POP exposures, and to determine if house dust can be used as a marker
sample matrix for other sample media for human indoor exposure to POP.
5
-------
Chapter 4
Experimental Procedures
Analytical Method for Phenols
Two extraction methods were evaluated for removing phenols from the dust and soil
sample matrices. Initially, the soil samples were spiked with known amounts of target phenols
and extracted with dichloromethane (DCM) in a sonication bath. This approach did not
provide satisfactory recoveries. Another extraction method was then evaluated. For spike
recovery, known amounts of target phenols were spiked into each aliquot of the soil samples.
The spiked sample was extracted sequentially with 10 mL of 5% acetic acid in methanol,
10 mL of DCM, and 10 mL of 5 % acetic acid in distilled water, in a sonication bath for 15
min of each type of solvent. The resulting extracts were combined and transferred to a
separatory funnel. The DCM extract was transferred to another separatory funnel and washed
with 20 mL of distilled water. The DCM extract was dried with sodium sulfate and
concentrated to 2 mL for subsequent GC/MS analysis.
Thirty-nine dust/soil samples collected previously (4,6) from thirteen low-income
households were analyzed for target phenols. The house dust samples were collected using the
High Volume Small Surface Sampler (HVS3, Cascade Stack Sampling Systems, Bend, OR) in
designated areas where the child's greatest play activity occurred. The entryway dust samples
were collected from a doormat at the primary entrance of the house. The walkway soil
samples were collected from a primary walkway into the home. Aliquots of the 39 dust/soil
sample and one method blank were prepared by the above method except that the target
phenols were not spiked into the samples prior to extraction. Known amounts of internal
6
-------
standard, phenanthrene-dj0, were added to each concentrated DCM extract prior to GC/MS
analysis. An aliquot of each DCM extract was also removed for residue weight measurement.
The extracts were analyzed by 70 eV electron impact (EI) gas chromatography/mass
spectrometry (GC/MS). A Finnigan TSQ-45 GC/MS/MS instrument, operated in the GC/MS
mode, was used. Data acquisition and processing were performed with an INCOS 2300 data
system. The GC column was a DB-5 fused silica capillary column (60m x 0.25 mm, 0.25 (im
film thickness, J&W), and the column outlet is located in the MS ion source. Helium was
used as the GC carrier gas. Following injection, the GC column was held at 70 °C for 2 min
and temperature-programmed to 120°C at 20°C/min and then to 300°C at 8°C/min. The MS
was operated in the selected ion monitoring (SIM) mode. Masses monitored were the
molecular ions and their associated characteristic fragment ions. Identification of the target
compounds was based on their GC retention times relative to those of the internal standard
phenanthrene-d10. Quantification of target compounds is based on comparisons of the
respective integrated ion current responses of the target ions to those of the corresponding
internal standards using average response factors of the target compounds generated from
standard calibrations. The dust/soil sample extracts from household A were analyzed by
GC/MS in full mass scan mode to identify major compounds tentatively. The MS was set to
scan from m/e 45 to 450 am/* at 1 sec/scan. Tentative identification of the compounds was
accomplished by manual interpretation of background-corrected spectra together with an on-
line computerized library search. The on-line library was the most currently available
EPA/NIH mass spectral data base, containing 42,197 unique reference spectra.
LC/MS/MS Method Evaluation
The following compounds were evaluated for analysis by LC/MS/MS using the Sciex
TAGA 6000E with an atmospheric pressure chemical ionization (APCI) source: 2-acetylamino-
fluorene (2AF), 3-amino-9-ethylcarbazole (AEC), 2,4-dinitrotoluene (DNT), anthraquinone,
vinclozolin, p-pentylphenol, p-octylphenol, nonylphenols, and bisphenol-A.
7
-------
Each compound was analyzed in the single MS mode to identify the precursor ion
formed by the APCI process. Once the precursor ion was identified, a fragment ion spectrum
(MS/MS) was obtained by introducing energy to the collision cell. Standards of the above
chemicals were introduced into the TAGA ion source as either vapors or liquids. Standards
with sufficient vapor pressure were introduced by placing an open vial of the standard at the
inlet of the TAGA sampling stream. For nonvolatile standards, solutions were prepared at
known concentration levels. Aliquots of the standard solutions were introduced into the ion
source through a Battelle-developed vapor jet system (8). Characteristic fragment ions for each
standard were selected from the MS/MS spectrum, for use in the selected ion monitoring (SIM)
mode. A series of standard solutions was analyzed by LC/MS/MS to establish calibration curves
and to estimate detection limits. The initial evaluation results showed that the LC/MS/MS
technique can provide adequate detection sensitivity for two of the above standards, namely 2AF
and AEC. These two compounds were selected for further analysis in dust/soil samples.
Analytical Method for 2-Acetylaminofluorene and 3-Amino-9-ethyIcarbazole
Extraction recovery experiments were conducted for 2AF and AEC. Two extraction
methods were evaluated for removal of the AEC and 2AF from the dust/soil samples. The first
method, sonication with methanol (MeOH), did not provide satisfactory recoveries for AEC. The
extraction solvent was then changed to 30% water in MeOH at pH 10. A spike recovery study was
conducted, where known amounts of the two target compounds were spiked into aliquots of
selected soil samples. The spiked sample was extracted with 5 mL aliquots of 30% water in
MeOH at pH 10 in a sonication bath for 15 min. This step was repeated four times. The resulting
extracts were combined, filtered, and concentrated to 3 mL for LC/MS/MS analysis.
The LC gradient elution conditions for the analysis of the standards and sample extracts are:
Column: Supelco LC-304 Guard Column
Flow Rate: 1.2 mL/min
Sample Loop: 50 |*L
Gradient Elution Scheme:
0 - 2 min 100% H20
2 - 8 min 100% H2O/0% MeOH ->-25% H20/75% MeOH
8 - 10 min 25% H20/75% MeOH
10 - 15 min 25% H20/75% MeOH -> 100% H20
8
-------
The mass spectrometer was operated in the MS/MS (SIM) mode. Vaporized eluent from
the LC was introduced into the APCI ion source, where the samples were ionized using a
corona discharge. Protonated precursor ions were selected with the first quadrupole mass
analyzer (thus eliminating all other possible interference ions). The precursor ions were then
focused into the collision cell where they were fragmented at a collision energy of 35 volts (E^)
with argon as the collision gas with a target thickness of approximately 350 x 1012
molecules/cm2. Selected fragment ions from the isolated precursor ions were passed through the
second MS and were detected by an electron multiplier. For 2AF, two precursor/fragment ion
transitions were monitored, namely m/z 224/182 and 224/43. For AEC, three
precursor/fragment ion transitions were monitored: m/z 211/182, 211/194, and 211/179.
Identification of the target compounds was based on their correct LC retention times and their
correct relative responses for each of the precursor/fragment ion transitions when compared with
those from the standards calibrations. Quantitation of the target compounds was based on
comparisons of the respective integrated ion current responses of the target compounds in the
sample extract to those in the standard solutions.
9
-------
Chapter 5
Results and Discussion
GC/MS Analysis of Dust and Soil Samples
The analytical method for analyzing target phenols consisted of sequentially extracting
the samples by sonication with 5% acetic acid in methanol, DCM, and 5% acetic acid in water,
followed by liquid-liquid partitioning, and analyzing the concentrated DCM by GC/MS.
Table 5.1 summarizes the recovery data for spiked phenols from the soil samples at three spiked
levels. Quantitative recoveries (>80 percent) of the spiked phenols were obtained. The
recoveries ranged from 90 to 104 percent at 5 ppm spiked levels, from 84 to 101 percent at
0.2 ppm spiked levels and from 84 to 110 percent at 0.1 ppm spiked levels. The precision for
the phenols for the triplicate spiked samples was within 13 percent (relative standard deviation).
Table 5.1. Recoveries of Phenols from Spiked Soil Samples
Recovery, %(a)
Compound
H
M
L
p-Pentylphenol
90
100 ± 8.7
87
p-Octylphenol
91
84 + 2.6
100
Nonylphenols
104
91 + 4.9
110
Bisphenol-A
98
101 ± 13
84
(a) H denotes a single soil sample at 5 ppm spiked level
M denotes triplicate soil samples at 0.2 ppm spiked level
L denotes a single soil sample at 0.1 ppm spiked level.
10
-------
The concentrations of phenols measured in the house dust, entryway dust, and pathway
soil samples are summarized in Table 5.2. The data for individual samples are given in
Appendix A. The reported concentrations were corrected for the background levels from the
method blank and expressed in units of ppm (jig/g). The results of target phenols found in the
method blank are given in Appendix B. Only trace amounts of phenols were found in the
method blank. There are three major nonylphenol isomers present in the nonylphenol standard
solutions, because only technical grade nonylphenols are available. The other target phenol
standards are specific isomers, which are p-pentylphenol, p-octylphenol, and bisphenol-A. Note
that one of the p-pentylphenol isomers was reported and this isomer eluted about 10 scans later
than the p-pentylphenol from the GC column. This compound was estimated using the same
response factor as p-pentylphenol.
Among the measured phenols, the most abundant phenols found were nonylphenols. The
least abundant phenols were in general, p-pentylphenol and its isomer. The concentrations of
phenols ranged from 0.043 ppm of p-pentylphenol to 11.1 ppm of p-octylphenol in house dust
samples. Relative lower concentrations were found in entryway dust samples and ranged from
< 0.001 ppm of p-pentylphenol to 0.974 ppm of nonylphenols. The concentrations of phenols
in pathway soil samples were from < 0.001 ppm of p-octylphenol to 0.204 ppm of
nonylphenols. The relative concentration trend within individual households was
house dust > entryway > pathway soil.
Among the target phenols, nonylphenols and bisphenol-A are potential endocrine
disrupters. Figures 5.1 and 5.2 show the concentration profiles of nonylphenols and bisphenol-
A in the dust/soil samples. Levels of nonylphenols found in house dust samples were greater
than 1 ppm, while those levels found in entryway dust and pathway soil sample are less than 1
ppm. The concentrations of nonylphenols ranged from 1.24 to 3.56 ppm in house dust, from
0.024 to 0.974 ppm in entryway dust, and from 0.015 to 0.204 ppm in pathway soil. The
concentrations of bisphenol-A are lower than those of nonylphenols in the
11
-------
Table 5.2. Summary of Concentrations (ppm) of Phenols in House Dust, Entryway Dust, and Pathway Soil
House Dust Entryway Dust Pathway Soil
Compound
Maximum
Minimum
Average
Maximum
Minimum
Average
Maximum
Minimum
Average
p-Pentylphenol
0.120
0.043
0.088
0.073
<0.001
0.018
0.005
0.001
0.002
Pentylphenol isomer
0.270
0.060
0.129
0.085
0.004
0.019
0.011
0.003
0.004
p-Octylphenol
11.1
0.158
1.49
0.311
<0.001
0.059
0.019
<0.001
0.003
Nonylphenols
3.56
1.24
2.30
0.974
0.024
0.300
0.204
0.015
0.072
Bisphenol-A
3.50
0.322
1.19
0.335
0.019
0.120
0.036
<0.001
0.011
Sum of phenols
14.8
1.94
5.19
1.51
0.047
0.517
0.265
0.021
0.092
-------
Nonylphenols In House Dust, Entryway Dust, And Pathway Soil
u>
E
o.
a
A
b
a
a>
u
a
©
u
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
House Dust
¦ Entryway Dust
~ Pathway Soil
E F G H
House Code
Figure 5.1. Concentrations of nonylphenols in house dust, entryway dust, and pathway soil samples.
-------
Bisphenol-A In House Dust, Entryway Dust, And Pathway Soil
i
o<
C3
U
¦w
fl
-------
dust/soil samples. The levels of bisphenol-A ranged from 0.322 to 3.50 ppm in house dust, from
0.019 to 0.335 ppm in entryway dust, and from <0.001 to 0.036 ppm in pathway soil.
Sample extracts of dust/soil samples from Household A were analyzed by GC/MS in the
full mass scan mode to determine the major components present. The compounds tentatively
identified in these dust and soil samples are summarized in Tables 5.3 through 5.5. Total ion
current chromatograms of the samples are shown in Figures 5.3 through 5.5. The major
compound classes found in house dust were alkanes, fatty acids, fatty acid esters, phthalates, and
aliphatic alcohols. Similar components including alkanes, fatty acid esters and phthalates were
found in entryway dust at lower levels. Pathway soil exhibited the smallest number of
compounds, among them aliphatic alcohols, alkanes, fatty acid esters, and phthalates.
LC/MS/MS Analysis of Dust and Soil Samples
In order for a compound to be ionized by APCI, its gas phase basicity (for positive ion
mode) or gas phase acidity (for negative ion mode) should be greater than the gas phase
basicity/acidity of water. For this reason, the MS/MS spectra of anthraquinone, phenols, and
vinclozoline could not be obtained. Of all the compounds evaluated, MS/MS spectra were
obtained for only three compounds, namely 2-acetylaminofluorene (2AF), 3-amino-9-ethyl
carbazole (AEC), and 2,4-dinitrotoluene (DNT). The 2AF and AEC spectra were obtained
under positive ion APCI conditions and the DNT spectrum was obtained by negative ion APCI.
Standard solutions of 2AF, AEC and DNT were prepared in the range from 1 ng/mL to 1200
ng/mL (1 ppb to 12 ppm) and analyzed using LC/MS/MS. The estimated detection limits for
2AF, AEC and DNT were 1 ng/mL, 5 ng/mL and 500 ng/mL, respectively. Since an adequate
overall method detection limit for DNT could not be obtained, only 2AF and AEC were selected
as target analytes for the spike recovery study.
The analytical method for the analysis of 2AF and AEC consisted of extracting the sample
with 30 % water in MeOH at pH 10, concentrating the extract, and analyzing the concentrated
extract by LC/MS/MS. Table 5.6 summarizes the recovery data for the spiked 2AF and AEC
from the soil samples. As shown in Table 5.6, quantitative recoveries were obtained for 2AF
15
-------
Table 5.3. Compounds Tentatively Identified in House Dust from Household A
Scan Number
Tentative Identification
412
Aliphatic compound
428
Hexanoic acid
438
Aliphatic alkene
459
C5-alkyl furan
470
Aliphatic alcohol
489
Chlorine containing compound
522
Heptanoic acid
569
Aliphatic alcohol
618
Octanoic acid
645
Butoxyethoxy ethanol
657
Alkane (C12H26)
665
Aliphatic alcohol
709
Nonanoic acid
748
Alkane (C13H28)
772
Phthalate
795
Decanoic acid
817
Fatty acid ester
833
Alkane (C14H30)
858
C2-naphthalene
881
Alkane
913
Alkane (C15H32)
919
Aliphatic alcohol
949
Alkane
956
Tridecanoic acid
962
Alkane
968
Alkane
986
Phthalate
990
Alkane (C^H^)
1023
Alkane
1036
Alkane
1062
Alkane (C^H^)
1100
Tetradecanoic acid
1130
Alkane (C18H3g)
1148
Internal standard (phenanthrene-d10)
1175
Phthalate
1195
Alkane (C19H40)
1232
Hexadecanoic acid
1257
Alkane (C20H42)
16
-------
Table 5.3. Continued
Scan Number
Tentative Identification
1310
Aliphatic alcohol
1316
Alkane (C^H^)
1339
Aliphatic alcohol
1351
Octadecanoic acid
1373
Alkane ()
1406
Phthalate
1427
Alkane (C23H4g)
1446
Alkane
1465
Phthalate
1481
Alkane (C^Hjo)
1538
Alkane C25H52)
1562
Phthalate
1597
Alkane (C^H*)
1619
Phthalate
1645
Phthalate
1663
Alkane (C27H56)
1692
Phthalate
1737
Alkane (C28H58)
1756
Phthalate
1782
Phthalate
1823
Alkane (C^Hgo)
1850
Unknown
1885
Unknown
1924
Alkane (C30H62)
2046
Alkane (CjjH^)
2129
Mixture containing chrolestenol isomer
2193
Alkane (CjjHJ
2372
Alkane (C33H6g)
2512
Aliphatic alcohol
2593
Alkane (C^H^)
2831
Alkane
2954
Fatty acid ester
2964
Aliphatic alcohol
17
-------
Table 5.4. Compounds Tentatively Identified in Entryway Dust from Household A
Scan Number
Tentative Identification
395
Hexanoic acid
410
Benzaldehyde
440
C3-alkylbenzene
476
Methylphenol MW 108
547
Aliphatic alcohol
600
Octanoic acid
631
Butoxyethoxyethanol
645
Alkane (C12H26)
700
Nonanoic acid
714
Alkane
742
Alkane (C13H28)
786
Alkane
796
Fatty acid ester
805
Alkane
809
Alkane
814
Fatty acid ester
831
Alkane (C14H30)
871
Alkane
881
Alkane
885
Alkane
890
Alkane
897
Alkane
914
Alkane (C15H32)
919
Alkene
949
Alkane
954
Alkane
963
Alkane
968
Alkane
980
Nitrogen containing compound
986
Phthalate
991
Alkane (C^H^)
1025
Alkane
1032
Alkane
1037
Alkene
1042
Aliphatic alcohol
1150
Internal standard (phenanthrene-d10)
1063
Alkane (C17H36)
1127
Nitrogen containing compound
1132
Alkane (C18H38)
18
-------
Table 5.4. Continued
Scan Number
Tentative Identification
1137
Alkane
1177
Phthalate
1197
Alkane (C19H40)
1238
Phthalate
1259
Alkane (C20H42)
1279
Hydroxy methoxy benzoicacid methyl ester
1312
Aliphatic alcohol
1319
Alkane (C^H^)
1341
Chlorine containing compound
1375
Alkane (C22H46)
1408
Phthalate
1429
Alkane (C23H48)
1467
Phthalate
1477
Fatty acid ester
1483
Alkane (C24H50)
1539
Alkane (C25H52)
1563
Phthalate
1599
Alkane (C^H^)
1665
Alkane (C27H56)
1725
Aliphatic alcohol
1739
Alkane (C28H58)
1825
Alkane (C29H J
1927
Alkane (C30H62)
2049
Alkane (C^H*)
2132
Mixture containing chrolestenol isomer
2197
Alkane (C^H^)
19
-------
Table 5.5. Compounds Tentatively Identified in the Pathway Soil from Household A
Scan Number
Tentative Identification
369
Ethoxyethanol
431
Aliphatic compound
461
C3-alkyl benzene
581
Silicone
612
Silicone
649
Aliphatic alcohol
801
Fatty acid ester
818
Fatty acid ester
828
Alkene
889
Fatty acid ester
915
Alkane (C15H32)
986
Aliphatic alcohol
1063
Alkane (C17H36)
1128
Aliphatic alcohol
1151
Internal standard (phenanthrene-d10)
1238
Phthalate
1466
Phthalate
1477
Fatty acid ester
1539
Alkane (C^t^)
1563
Phthalate
1665
Alkane (C27H56)
1739
Alkane (C2gH5g)
1825
Alkane (C^HJ
2049
Alkane (CjqH^)
20
-------
RIC
03/15/96 13:03:00
OATAi 360916S3 #1
CftLI: 360916ACLQ3 #5
SCANS t TO 3000
100.0-1
SAMPLE: A-HO-X NOHDILUTED FULL SCAN
CONDS.: 70<2>-230/10
RANGE: G 1»3121 LABEL: H 0, 4.0 QUAN: A 0, 1.0 J 0 BASE: U 20 > 3
825344.
RIC
Tl I
i 1 1 1 r
500
8:20
llili
VU
t
wj
Ujjj
¦ mm J**.
i %n n ft,
-JL
l i i i i|iiiiji
1000 1500 2000
16:40 25:00 33:20
Ii 1ii|
2500 3000 SCAN
41:40 50:00 TIME
Figure 5.3. Total ion currents chromatogram of house dust sample from Household A.
-------
to
to
100.0-
ol/tR/qc »o,«5<5.oq 5?TA; 96031554 #* SCANS 1 TO 2800
, CftLI: 960S16ACLQ3 15
SAMPLEJ A-ES-X NONDILUTED FULL SCAN
CONDS.i ?0<2)-2S0/10
RANGEi G 1/3100 LABEL: N 0, 4.0 QUAN: A 0, 1.0 J 0 BASE: U 20# 3
RIC
8:20
I i i i i 1 1 ,i 1 1 , r
1000 1500 2000
16:48 25:80 33:20
134656.
"i 1 1 1 1
2500 SCAN
41:40 TIME
Figure 5.4. Total ion currents chromatogram of entryway dust sample from Household A.
-------
RIC DATA; 960916S5 #i SCANS 1 TO 2800
09/15/36 15:02:09 CALI: S50916ACLQ3 #5
SAMPLE: A-PS-X NOHDILUTED FULL SCAN
CONOS.l 70<2>-290/10
RANGE: G 1,3100 LABEL: N 0, 4.0 QUAN: A 0, 1.0 J 0 BASE: U 20, 3
100.0-1
RIC
99840.
i 1 1 1 [ 1 1 r
500
9:20
I 1 1 1 1 1 1 1 1 1 1 1
1000 1500 2000
IE:40 25:00 33:20
-i r
-t 1 1
2500
41:40
SCAN
TIME
Figure 5.5. Total ion currents chromatogram of pathway soil sample from Household A.
-------
from the spiked soil samples and ranged from 98 to 110 percent. The recoveries for AEC in the
spiked soil samples ranged from 39 to 110 percent. The precision for determining AEC was not
as good as that for 2AF. The estimated detection limits for 2AF and AEC were 0.001 ppm and
0.005 ppm, respectively. The 2AF and AEC were not detected in any of the dust/soil samples or
in the method blank.
Table 5.6. Recoveries of AEC and 2AF from Spiked Soil Samples
Compound Spiked Level, ppm Recovery, %
AEC
2.0
100
2.0
98
1.0
98
1.0
110
2AF
0.2
63
0.2
110
0.1
39
0.1
64
24
-------
References
1. IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans.
International Agency for Research on Cancer (1985) Polynuclear aromatic compounds,
bituminous, coal-tar and derived products, shale oils and soots. International Agency for
Research on Cancer, Lyon, France, Vol. 35, Part 4, 1985.
2. Chuang, J.C., Wise, S.A., Cao, S., and Mumford, J. Chemical characterization of
mutagenic fractions of particles from indoor coal combustion: a study of lung cancer in
Xuan Wei, China. Environ. Sci. Technol. 25(5), 999-1004, 1992.
3. Waldman, J.M. Lioy, P.L., Greenberg, A., and Butler, J.P. Analysis of human exposure
to benzo[a]pyrene via inhalation and food ingestion in the total human environment
exposure study (THEES). Journal of Exposure Analysis of Environ. Epidemiology 1(2),
193-225, 1991.
4. Chuang, J.C., Callahan, P.J., Menton, R.G., Gordon, S.M., Lewis, R.G., Wilson, N.K.
Monitoring methods for polycyclic aromatic hydrocarbons and their distribution in house
dust and track-in soil. Environ. Sci. Technol. 29(2), 494-500, 1995.
5. Takada, H., Onda, T., Harada, M., and Ogura, N. Distribution and sources of
polycyclic aromatic hydrocarbons in street dust from Tokyo Metropolitan area. The Sci
of Total Environ. 107, 45-69, 1991.
6. Chuang, J.C., Callahan, P.J., Lyu, C.W., Pennybacker, M.R. Characterization of
polycyclic aromatic hydrocarbon exposure among children of low income families from
inner city and rural areas. Draft Final Report (Year 2) to U.S. EPA, Cooperative
Agreement CR 822073, October 1995.
7. Chuang, J.C., Callahan, P.J., and Lyu, C.W. Field method evaluation of total exposure
of children from low-income families that include smokers to polycyclic aromatic
hydrocarbon. Final Report to U.S. EPA Contract Number 68-D4-0023, Work
Assignment 1-02 and 1-09, September 1996.
25
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8. Slivon, L.E., Kenny, D.V., and Severance, R.A. A Vaporization Device for Continuous
Introduction of Liquids into a Mass Spectrometer, U.S. Patent 4982097, January 1991.
26
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Appendix A. Phenol Data in House Dust, Entryway Dust, and Pathway Soil Samples
Compound
A-HD-X
B-HD-X
C-HD-X
D-HD-X
E-HD-X
F-HD-X
G-HD-X
H-HD-X
l-HD-X
J-HD-X
K-HD-X
L-HD-X
M-HD-X
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
p-Pentylphenol
0.043
0.099
0.055
0.120
0.090
0.098
0.110
0.102
0.064
0.065
0.106
0.114
0.081
p-Pentylphenol isomer
0.072
0.270
0.113
0.181
0.169
0.101
0.128
0.180
0.087
0.060
0.183
0.061
0.072
p-Octylphenol
0.251
2.142
1.238
0.488
0.271
0.420
11.050
0.584
0.158
0.311
0.741
0.996
0.658
Nonyiphenols
1.249
2.798
3.032
3.563
2.956
1.995
2.720
2.028
1.241
1.307
2.162
2.423
2.463
Bisphenol-A
0.322
2.389
0.899
1.127
0.865
0.769
0.793
0.854
0.505
0.807
1.206
3.505
1.409
sum of phenols
1.937
7.699
5.336
5.479
4.352
3.382
14.802
3.748
2.055
2.550
4.399
7.099
4.682
Compound
A-ES-X
B-ES-X
C-ES-X
D-ES-X
E-ES-X
F-ES-X
G-ES-X
H-ES-X
l-ES-X
J-ES-X
K-ES-X
L-ES-X
M-ES-X
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
p-Pentylphenol
0.073
0.005
0.023
0.005
0.027
0.006
0.006
0.059
0.014
<0.001
0.011
0.006
0.001
p-Pentylphenol isomer
0.028
0.009
0.023
0.008
0.015
0.017
0.016
0.085
0.018
0.004
0.010
0.013
0.007
p-Octylphenol
0.072
0.021
0.311
0.006
0.239
0.009
0.004
0.060
0.005
<0.001
0.009
0.016
0.013
Nonyiphenols
0.488
0.054
0.503
0.103
0.483
0.282
0.317
0.974
0.169
0.024
0.128
0.286
0.094
Bisphenol-A
0.075
0.077
0.164
0.050
0.117
0.038
0.056
0.335
0.294
0.019
0.045
0.025
0.265
sum of phenols
0.735
0.165
1.023
0.173
0.880
0.351
0.399
1.513
0.499
0.047
0.204
0.346
0.381
Compound
A-PS-X
B-PS-X
C-PS-X
D-PS-X
E-PS-X
F-PS-X
G-PS-X
H-PS-X
l-PS-X
J-PS-X
K-PS-X
L-PS-X
M-PS-X
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
p-Pentylphenol
0.002
0.003
0.004
0.003
0.002
0.004
0.003
0.001
0.001
0.005
0.002
0.001
0.002
p-Pentylphenol isomer
0.004
0.004
0.006
0.006
0.004
0.003
0.004
0.011
0.003
0.003
0.004
0.003
0.003
p-Octylphenol
<0.001
0.001
0.019
0.002
<0.001
<0.001
0.002
<0.001
<0.001
0.004
<0.001
0.004
0.002
Nonyiphenols
0.029
0.051
0.204
0.063
0.065
0.027
0.169
0.020
0.018
0.090
0.015
0.139
0.044
Bisphenol-A
0.008
0.003
0.032
0.007
0.004
0.002
0.023
0.009
0.002
0.003
<0.001
0.014
0.036
Sum of phenols
0.043
0.062
0.265
0.079
0.075
0.036
0.201
0.041
0.024
0.105
0.021
0.161
0.086
Sample Code: The first letter indicates the household; the next two letters indicate the sampled medium, HD = house dust, ES = entryway dust!, and PS = pathway soil.
The letter X indicates that the samples were obtained in April 1996 under cooperative agreement CR822073.
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Appendix B. Levels of Target Phenols in the Method Blank
Compound Total ng ppm
p-Pentylphenol 1.263 0.001
p-Pentylphenol isomer 0.727 0.001
p-Octylphenol 7.045 0.007
Nonylphenols 13.489 0.013
Bisphenol-A 1.194 0.001
Sum of phenols 23.718 0.024
28
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