United States
                  Environmental Protection
                  Agency     	
Environmental Monitoring
Systems Laboratory
Research Triangle Park, NC 27711
                  Research and Development
EPA/600/S4-88/028 Sept. 1988
&EPA         Project  Summary
                   Field Evaluation of Sampling
                   and  Analysis  for Organic
                   Pollutants  in  Indoor  Air
                   J. C. Chuang, G. A. Mack, J. W. Stockrahm, S. W. Hannan, C. Bridges, and
                   M. R. Kuhlman
                     The objectives of this study were
                  to determine the feasibility of the use
                  of newly developed indoor  air sam-
                  plers in residential indoor  air sam-
                  pling and to evaluate  methodology
                  for characterization of the  concen-
                  trations of polynuclear aromatic
                  hydrocarbons (PAH), PAH  deriv-
                  atives, and nicotine in residential air.
                     Residential air  sampling was
                  conducted in Columbus, Ohio, during
                  the winter of 1986/87. The residences
                  were selected on the basis  of these
                  characteristics: electric/gas heating
                  system, electric/gas  cooking  appli-
                  ances, and amount  of cigarette
                  smoking in the home. The indoor air
                  sampler was equipped  with  a  quartz
                  fiber  filter to collect particles
                  followed  by XAD-4 resin  to trap
                  vapors. A modified  EPA  medium
                  volume sampler with  an  identical
                  sampling module was used  for
                  outdoor air  sampling.  Eight homes
                  were  sampled; two homes were
                  sampled twice. The  indoor  air was
                  sampled in the kitchen  and the living
                  room over consecutive 8-hr periods.
                  Each outdoor sample  was  a  single
                  16-hr sample taken  simultaneously
                  with the indoor samples.
                     The levels of  PAH detected  in
                  outdoor and  indoor  air  samples
                  ranged   from   4000   ng/m3
                  (naphthalene) to less than 0.1 ng/m3
                  (cyclopenta[c,d]-pyrene). The PAH
                  derivatives were found at much lower
                  levels than their parent PAH. Higher
                  average indoor levels of all but three
                  target compounds  were found
                  compared to outdoor levels. The
 higher outdoor levels of these three
 compounds (naphthalene  dicar-
 boxylic acid  anhydride, pyrene
 dicarboxylic acid  anhydride, and 2-
 nitrofluoranthene) are probably  due
 to atmospheric transformation.  Cig-
 arette smoking was identified  as the
 most significant contributor to indoor
 levels of PAH  and PAH derivatives.
 Homes  with gas heating  systems
 appeared to have higher pollutant
 levels compared to  homes with
 electric  heating systems. However,
 homes with  electric  cooking
 appliances were associated  with
 higher pollutant levels than homes
 with gas appliances, but the true ef-
 fects of  heating and cooking systems
 cannot be accurately known because
 of the small sample  sizes and the
 lack of  statistical significance for
 most pollutant differences.
    This Project Summary  was
 developed by EPA's  Environmental
 Monitoring  Systems Laboratory,
 Research Triangle  Park, NC, to
 announce key findings of the research
 project that is fully documented  in a
 separate report of the same title  (see
 Project Report ordering information at
 back).

 Introduction
    Recently  many  research  and
 monitoring efforts have focused on
 assessing and improving the quality of
 air. Several studies have demonstrated
 that some polynuclear  aromatic
 hydrocarbons  (PAH) and nitrated  PAH
 (NO2-PAH) found in ambient and indoor
 air are potent carcinogens, mutagens, or

-------
both There is an increasing concern over
human exposure to these compounds in
indoor air from the home, workplace, and
school, because we spend more than 80
percent of our time indoors.
    Generally,  the  sampling  method-
ology  used for indoor air sampling has
not been fully established. The existing
sampling devices  used in  outdoor
ambient air sampling are not suitable for
indoor  sampling applications because of
size, lack of portability, and noise.  In a
pilot residential  indoor  air study,  the
sampler pumping  unit  was  located
outside the house in an insulated housing
to minimize the noise level.  Depending
upon  the  structure  of  each house
sampled, there  were  different modifi-
cations  made  to  allow  the  tube
connecting  the sampling  module  to  the
pumping unit to  pass  through  an  open
window.  This  sampling  device
significantly added to the sampling costs
and to the levels  of  inconvenience
experienced by the  residents of  the
sampled house.  Therefore  we  have
developed a prototype  indoor air sampler
that is quiet, transportable, and  relatively
unobtrusive. This  prototype device can
be  operated  at a  flow  rate  (8  cfm)
sufficient to collect  enough particulate-
bound  and  vapor  phase  organic
compounds over a period of eight hours
for chemical analysis and microbioassay
analyses.
    To  determine the feasibility  and
advantages  of  using  this  newly-
developed  prototype  air  sampler  in
residential sampling, a pilot  field study
was conducted  in  eight homes  in
Columbus,  Ohio,  during  the  winter  of
1986/1987.  The  objectives of this study
were to  determine the effectiveness of
the prototype  sampler  in  collecting
residential air samples and to evaluate
methodology for characterization  of  the
concentrations  of nicotine,  polynuclear
aromatic hydrocarbon  (PAH),  and PAH
derivatives in  residential  air.  An
investigation of  the  correlations among
levels of PAH, nicotine, and numbers of
cigarettes smoked was performed. The
correlations between three potential  PAH
markers phenanthrene, pyrene,  and
fluoranthene and  other PAH were  also
investigated. This study consisted of the
following subtasks:
1.  Developing  a study  design for  the
    field study,
2.  Performing  the field study  in  the
    winter of 1986/1987 according to the
    study design,
3.  Conducting  chemical  analyses of the
    collected samples  and preparing
    samples for microbioassay  analyses,
4.   Conducting statistical analyses of the
    collected data.

Procedure
    A newly developed prototype indoor
air sampler was used for the indoor air
sampling, and  a  modified EPA medium
volume sampler was used for the outdoor
air sampling. The sampler was equipped
with a quartz fiber filter followed by an
XAD-2  trap  to collect organic particles
and vapors. The  indoor samples were
collected from  the  kitchen from  approx-
imately  0700 to  1500 eastern  standard
time (EST) and from the living room from
1500 to 2300  (EST).  During the entire
indoor air sampling, a single outdoor air
sample was  collected in the backyard of
each house. The sampler flow rate was
approximately  12.5 m3/hr,   which
collected 100 m of air over 8 hr.
    The sampling design is as follows:


 Smoking Heating  Cooking No. of Homes
 Yes     gas    gas          2
                electric       2
Yes
No
No
electric
gas
electric
electric
gas
electric
electric
2
2
1
1
    The homes selected were chosen to
give the greatest variation in the number
of cigarettes smoked. In addition, homes
were  selected so  that  nearly equal
number of samples could be taken from
each  available  combination of  type  of
heating system and  type of  cooking
appliance. The order in which the homes
were  sampled was  randomized  to
remove potential source  of  bias  that
could result if  some  systematic order
were used. No sampling was done either
during or immediately  following  rain. No
sampling was  performed while the tem-
perature  was  above 60°F.  By  not
sampling during such periods of time we
avoided gross  inconsistencies  due to the
cleaning of the air by  the rain or due to
the shutting off of the heating system'
due to warm weather.  All the homes are
located in Columbus, Ohio,  and the
sampling was  conducted in early March
1987.
    The filter and XAD-4 samples were
combined and  extracted  with dichloro-
methane  for  16  hr.  The  extract  was
further extracted with ethyl acetate for an
additional 8  hr. The dichloromethane
extract and  ethyl acetate extracts were
combined  and  concentrated  by
Kuderna-Danish evaporation.
    The extract was analyzed by positiv
chemical ionization and  negative chen
ical ionization, gas chromatography/mas
spectrometry to determine PAH,  nitroge
heterocyclic  compounds. nitro-PAH ar
oxygenated-PAH. Statistical analysis  i
the data  included  the generation  <
summary  statistics,  the comparison  i
indoor  and  outdoor  pollutant
concentrations, and statistical modelin
to  assess the  separate  influence of tr
individual experimental factors.

Results
    The  extractable  organic mas
concentrations  found in  the XAD-4 ar
filter combined  extracts ranged froi
0.077 mg/m3 to 0.57 mg/m3 indoors ar
0.0091  mg/m3  to 0.047 mg/m3 outdoor
Generally, higher levels of organic rrratti
were found  in the indoor air  sample
compared to that from the correspondir
outdoor air samples.  It appeared th,
cigarette  smoking contributes to th
higher  levels  of extractable  organ
matter  found in the indoor air  sample
The  highest concentrations  of  organ
mass were found in home 5 in the livir
room location where the highest numbei
of  cigarettes were smoked  during th
sampling period.
    Concentrations of the individual PA
measured in homes  ranged from 0.1
ng/m3  to 4200 ng/m3;  naphthalene w<
most  abundant  and cyclopentc
[c,d]pyrene,  in general, was the lea
abundant. The carcinogenic PAH such  i
benzo[a]pyrene and  indeno[1.2.;
c,d]pyrene were  present individually
concentrations  from 0.18 to  3.3 ng/m
The  concentration  of  nicotine range
from 45,000  ng/m3 to 24 ng/m3. Indoi
concentrations  of  quinoline an
isoquinoline  were  8.1  ng/m3  to 11C
ng/m3.  The NO2-PAH  and OXY-PA
concentrations  found  indoors were 0.0(
to  1.3  ng/m3  and  0.021 to 40 ng/rr
respectively.  For  most of  the targi
compounds, higher indoor concentratior
were detected  compared to the outdoi
concentrations.
    The results of the statistical analyst
revealed  that cigarette  smoking  was  tr
most significant contributor to PAH ar
most PAH derivatives in indoor  air. Tf
homes with  gas  heating  systems  a\
peared to have  higher  PAH and othi
pollutant  concentrations in indoor air, b
the effect was not as  important as  tf
effect  of smoking. The use of electr
stoves  appeared to result in higher indo<
pollutant  levels compared to the use
gas stoves. However, the true effect of <
electric cooking system is not well knov
due  to the small sample sizes  and  tl

-------
lack  of statistical significance  of  the
observed differences. In addition, further
.investigation of the data revealed that
most  of  the electric  appliance  mea-
surements were taken using Sampler C,
while  the gas  appliance  measurements
were  primarily taken using Sampler  B.
Sampler  bias could  be responsible for
this difference. Comparisons of the effect
of sampling locations revealed that the
concentrations of the majority of the PAH
and PAH derivatives  were higher in the
living  room than in the kitchen, but the
difference was statistically significant for
only three of the compounds. Sources of
variation  not included  in the  statistical
model constituted the largest  single
source of  random  variation  for most
target compounds.  Home-to-home
variation was second-largest for most of
the  compounds, while day-to-day
variation was the smallest.

Conclusions and
Recommendations
   From this  pilot  field study,  we
concluded  that  the  newly developed
indoor samplers are quiet, transportable,
and acceptable  for residential  indoor air
sampling. The  results of the  current
study were, in  general, consistent with
the results from the previous pilot study
using a different sampling method.
   The  results demonstrated  that
cigarette smoking had the greatest effect
on the levels of  indoor PAH  and  PAH
derivatives. However, the  effect  of
gas/electric heating and cooking systems
were  not well  established due  to  the
small  sample sizes and  the dominance of
the effects of cigarette  smoking on PAH
levels.
   The statistical analyses also showed
that   there  was  strong  evidence a
correlation  among the potential  PAH
markers  (phenanthrene, pyrene and
fluoranthene) and  the  other  PAH and
PAH  derivatives. Phenanthrene and
pyrene appeared to  be  better marker
compounds than fluoranthene.  It was
noted  that  relatively poor correlations
were  found  among PAH  markers and
PAH  derivatives naphthalene dicarboxylic
acid anhydride,  pyrene  dicarboxylic acid
anhydride,  and  2-nitrofluoranthene. The
poor correlation may be  because these
compounds can be  formed through
secondary  emission  sources  (e.g.
atmospheric transformation). The inves-
tigation of correlations among a potential
marker for  cigarette  smoking, nicotine,
and  other pollutants revealed that all
correlations except  one  (naphthalene
Jicarboxylic acid  anhydride)  were
positive and statistically significant. It was
noted  than  quinoline  indoor  concen-
trations correlate very well with nicotine
indoor  concentrations. Therefore, quino-
line can be a marker for the contribution
of cigarette smoke to indoor PAH levels.
    The following recommendations are
based on the results of this study:
1.  A  study  should  be performed to
    improve the acoustic performance of
    the outdoor  ambient samplers, be-
    cause the noise levels produced by
    these units was found to be a source
    of  irritation  to the residents  and
    neighbors in this study  and  would
    probably not be tolerated if sampling
    were performed when windows of
    the houses were open.
2.  A  pilot  field  study  should be
    performed in  the summertime to
    evaluate the sampler performance at
    warmer temperatures and  to collect
    more  data to  assess  the  effect of
    cooking systems on indoor pollutant
    levels.
3.  A  small  scale  study of indoor PAH
    concentrations  should be performed
    during a period of higher furnace use
    so that  the relationship  between
    amount  of furnace use  and  PAH
    levels can be  determined. In  any
    such study it  is important that the
    amount of furnace use be measured.
4.  In  the design of future residential air
    studies,  it should  not be necessary
    to  sample different  locations  within
    the home. Fairly good  air mixing
    occurs  in most homes  so  that
    pollutant  concentrations  should be
    fairly uniform throughout the house.
    The samples are  affected  more by
    the residents'  activities during the
    sampling period. Thus, "living room"
    samples reported  here are likely to
    primarily  reflect the   cooking
    associated with dinner preparation
    while the  "kitchen"  samples reflect
    breakfast and lunch preparation ac-
    tivities.  In  future  studies,  the
    "location" variables should  either be
    replaced  by  a "period  of  day"
    variable  or by  other variables  that
    more specifically  describe the  res-
    idents'  activities conducted  during
    sampling.

-------
  J.C. Chuang, G.A. Mack, J.W. Stockrahm, S.W. Hannan, C.  Bridges, and M.R.
        Kuhlman are  with Battelle Columbus Division,  Columbus,  OH  43201-
        2693.
  Nancy K, Wilson is the EPA Project Officer (see below).
  The complete report, entitled "Field Evaluation of Sampling and Analysis  for
        Organic Pollutants in Indoor Air," (Order No. PB 88-242 565/AS; Cost:
        $19.95, subject to change) will be available only from:
           National Technical Information Service
           5285 Port Royal Road
           Springfield, VA 22161
           Telephone: 703-487-4650
  The EPA Project Officer can be contacted at:
           Environmental Monitoring Systems 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

EPA/600/S4-88/028
        0000329
                                        *6ENCT

-------