United States
             Environmental Protection
             Agency
National Risk Management
Research Laboratory
Research Triangle Park, NC 27711
             Research and Development
EPA/600/SR-97/004
March 1997
4>EPA   Project  Summary

             Development and Validation  of a
             Method for  Measuring Exempt
             Volatile Organic Compounds  and
             Carbon Dioxide  in  Consumer
             Products
             E. E. Rickman, Jr., G. B. Howe, and R. K. M. Jayanty
               Ground-level ozone can cause a va-
             riety of adverse health effects as well
             as agricultural and ecological damage.
             Controlling  emissions of volatile or-
             ganic compounds (VOCs) is important
             to reducing ground-level ozone; how-
             ever, not all VOCs are photochemically
             reactive and several have been ex-
             empted from control regulations. Cur-
             rently, there is no standard method for
             measuring the exempt VOC content of
             consumer products. This report de-
             scribes the development of such  a
             method. The new method involves heat-
             ing a sample in  an oven at 110°C for 1
             hour while  purging  the  sample  con-
             tainer with nitrogen gas.  The resultant
             mixture of nitrogen and  volatile com-
             pounds from the sample is then col-
             lected  in a Tedlar™ bag  and analyzed
             by gas chromatography with mass se-
             lective detection (GC/MSD). An internal
             standard is added to the sample con-
             tainer  to  permit quantitation without
             measurement of the purge gas volume.
             The method was evaluated by analyz-
             ing samples that were spiked  with
             known amounts of the exempt com-
             pounds. Recoveries of  spiked  com-
             pounds were excellent,  ranging from
             86% to 107% for the compounds and
             products  tested. This method should
             be applicable to other volatile com-
             pounds that might be present in con-
             sumer products and could be useful in
             evaluating the risk that these products
             pose to the environment.
               This Project Summary was developed
             by EPA's National Risk Management
 Research Laboratory's Air Pollution
 Prevention and Control Division, Re-
 search Triangle Park, NC, to announce
 key findings of the research project
 that is fully documented in a separate
 report of the same title (see Project
 Report ordering information at back).
  Ground-level ozone can cause a variety
 of adverse health effects as well as agri-
 cultural and ecological damage. To con-
 trol the levels of ozone in the environ-
 ment,  the U.S. Environmental Protection
 Agency (EPA) has established National
 Ambient Air Quality Standards (NAAQS)
 for ozone. In 1990, 98 areas in the coun-
 try did not meet the NAAQS for ozone,
 with over 150 million Americans living in
 these areas. VOCs are important contribu-
 tors to the formation of  ozone in photo-
 chemical 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 to the environment posed by VOCs in
 consumer products. Such a method will
 also be needed if EPA  determines that
 the  risk associated with VOCs in  con-
 sumer products is sufficient to require con-
 trol regulations.
  To address the need for measurement
 of VOCs in consumer products, EPA has
 established a research program. This pro-
 gram has already produced results in four
 previous phases:

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   Phase I  -  Preliminary studies were
   performed on two candidate methods
   for VOC measurement (EPA Refer-
   ence Method 24 and  Gravimetric
   Purge and Trap  Gas Chromatogra-
   phy).
   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 meth-
   ods: EPA Reference Method 24 and
   Gravimetric Purge  and  Trap  Gas
   Chromatography.
   Phase III - A test method was devel-
   oped to determine the total VOC con-
   tent of consumer  products.  This
   method was  based  on  EPA Refer-
   ence Method 24,  with added  modifi-
   cations for sampling  and  analysis of
   consumer products.
   Phase IV - The test method devel-
   oped in Phase III was validated in an
   interlaboratory study.
  The validated  total  VOC  method
(Phase IV) for consumer  products gravi-
metrically measures the total volatile con-
tent and determines the amount of water
by gas Chromatography with thermal con-
ductivity 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) due to their low photo-
chemical  reactivity and thus  low ozone
formation potential.  Measurement of these
exempt VOCs in consumer products would
allow  EPA to correct the total  VOC mea-
surements to better reflect the  total ozone
formation risk that consumer products pose
to the environment.
  Upon examination  of the  exempt VOC
compounds,  only 12  compounds are  rel-
evant to consumer products. Carbon diox-
ide, which is measured by the total VOC
method, is also  exempt and therefore is
added to the target list shown  in Table 1.
  Since it is anticipated that determining
the exempt compound content  will be con-
siderably more expensive and time con-
suming than measurement  of total VOC
content, a two-step approach  to  assess-
ing  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 sec-
ond  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. The
measurement 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 ni-
trogen  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. Re-
coveries of spiked compounds were ex-
cellent, ranging from 86% to 107% for the
compounds and products tested.
Table 1. Exempt VOC Method Target List

Compound Name
                    Class II Ozone Depleting Chemicals0
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 orperc)b
                    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)
'Carbon dioxide is not a VOC, but ismeasured by the total volatilesmethod and hasbeen added to the target list to permit correction of measured total volatiles.
bTetrachloroethylene was added to the exempt list during the course of this work (61 FR 4588, February 7, 1996).
c 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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 £. E. Rickman, Jr., G. B. Howe, and R. K. M. Jayanty are with Research Triangle
   Institute, Research Triangle Park, NC 27709.
 J. Kaye Whitfield is the EPA Project Officer (see below).
 The complete report, entitled "Development and Validation of a Method for Measur-
   ing Exempt Volatile  Organic Compounds and Carbon Dioxide in  Consumer
   Products," (Order No. PB97-143143; Cost: $21.50, subject to change) will be
   available only from:
         National Technical Information Service
         5285 Port Royal Road
         Springfield, VA22161
         Telephone: 703-487-4650
 The EPA Project Officer can be contacted at:
         Air Pollution Prevention and Control Division
         National Risk Management Research Laboratory
         U.S. Environmental Protection Agency
 	Research Triangle Park, NC 27711	
United States
Environmental Protection Agency
Center for Environmental Research Information
Cincinnati, OH 45268
Official Business
Penalty for Private Use $300
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         EPA
   PERMIT NO. G-35
EPA/600/SR-97/004

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