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OCR for page 133
Ambient Levels of
Anthropogenic Emissions
and Their Atmospheric
Transformation Products
T. E. GRAEDEL
A TAT Bell Laboratories
Concentrations of Atmospheric Trace Constituents / 134
Temporal and Spatial Patterns of Primary Gases / 134 Selected
Particle Constituents / 139 Photochemical Products and
Unregulated Emittants / 143
Indoor Concentrations / 147
Principal Trace Gases / 147 Minor Emittants and Products / 149
Emittants with Potential Global Influence / 151
Carbon Dioxide / 151 Carbon Monoxide / 152 Methane / 152
Summary / 153
Data Adequacy / 153 Trends / 153 Concentrations / 153
Summary of Research Recommendations / 156
Air Pollution, the Automobile, and Public Health. (it) 1988 by the Health Effects
Institute. National Academy Press, Washington, D.C.
133
OCR for page 134
134
Anthropogenic Emissions and Their Atmospheric Transformation Products
Concentrations of Atmospheric
Trace Constituents
Tllc arnounl ana sometimes tne type or
effect produced by an atmospheric constit-
uent on a receptor- a human being, vege-
tation, a building material, for example
depends on its concentration. Relating the
observed effect to its original cause, pre-
dicting effects in new circumstances, and
controlling causes to limit the effects all
require, in one way or another, an under-
standing of concentrations. In a compre-
hensive description, the concentration of a
species reflects its emission flux Johnson,
this volume; Russell, this volume) modi-
fied by transport and turbulent diffusion
(Sampson, this volume), and physical and
chemical transformation and removal (Ar-
kinson, this volume). An observed or statis-
tically or mathematically predicted concen-
tration is the starting point for estimating the
flux delivered to a surface or to a tissue
during respiration (Sexton and Ryan; Schle-
singer; Sun, Bond, and Dahl; Overton and
Miller; Ultman; all in this volume).
This paper reviews what is known about
the measured concentrations of selected at-
mospheric trace constituents emitted or
evolved from human activity, particularly
the operation of motor vehicles. Two cat-
egories of environments, within which
most of the exposure of human beings and
much of the exposure of susceptible mate-
rials takes place, are emphasized: outdoor
air in urban areas and indoor air within
residential and nonindustrial buildings.
Actual concentrations are neither uni-
form over all space nor constant for all
time, although some may be relatively uni-
form and stable for long times over large
regions whereas others, especially concen-
trations of reactive species, those emitted
intermittently, and those emitted at high
concentration from a few widely spaced
points, may be highly variable and/or non-
uniform. Every actual measurement effec-
tively averages the concentration over
some finite volume and finite time interval,
and every set of measurements is a distri-
bution of such individual measurements at
a sample of space/time regions distributed
within the overall region of interest.
-Or
When the effect of an atmospheric species
is approximately proportional to concen-
tration as well as to duration of exposure,
as it is in many cases, average concentration
is a good measure of effective concentra-
tion. If long-term averages are measured,
fewer measurements are required and they
are less likely to be contaminated by occa-
sional extreme conditions. For these rea-
sons, long-term averages often year-long
averages- are considered where possible.
In some cases, however, ambient air qual-
ity standards are established for extreme
values (ozone is an example), so data ap-
propriate to the standard are presented. In
other cases, only a few "spot" measure-
ments rather than an average of any sort are
available. Since these give at least some idea
of typical concentrations, they are pre-
sented with appropriate comments about
their restricted validity. Finally, since the
health effects of an atmospheric species may
be a complex function of time and concen-
tration, a table of extremes, ranges, and
. .. . . .
c ~str~out~ons Is given.
Temporal and Spatial Patterns of
Primary Gases
The primary gases are the principal gases
other than water vapor and carbon dioxide
(CO2) that are directly emitted from com-
bustion sources. Ambient air quality stan-
dards have been established in the United
States and in several other countries for
each primary gas. As a result, extensive mea-
surement programs have been initiated to
monitor concentrations for most of them,
and substantial amounts of data are available.
The quantity reported is usually the one
named in the standard, most often a long-
term average. For some species of gases and
some purposes, however, that form may not
be the best. For toxicologic purposes, for
example, it is often important to know peak
short-term concentrations whereas for other
purposes it may be necessary to know the
variability of concentrations from place to
place and from time to time. These peaks and
variations may go unreported in data sum-
maries from governmental monitoring sta-
tions, yet they may be crucial to assessments
of air quality effects on people and materials.
OCR for page 135
T. E. Gracdel
135
Even so, the data for the primary emitted
gases are more extensive than those for any
other atmospheric constituents. Despite oc-
casional inadequacies, the data base is quite
sufficient to represent atmospheric concen-
trations and predict their consequences. At-
mospheric concentrations of several spe-
cies, their ranges at different monitoring
sites, and their long-term trends have been
illustrated with box plots of data from the
U. S. National Air Monitoring Stations
(NAMS). The technique is shown in figure
1, where the 5th, 10th, and 25th percentiles
of the data depict the concentration at the
"cleaner" monitoring sites, the 75th, 90th,
and 95th percentiles depict it at the
"dirtier" sites, and the median and average
describe the "typical" concentration. Al-
though the average and the median both
characterize typical behavior, the median
has the advantage of not being affected by a
few extremely high or low observations.
The major products of motor vehicle fuel
combustion are, of course, water and CO2,
but their direct impact on human life is not
significant. The totality of man-made CO2
emissions, of which motor vehicle emis-
sions make up only a small part, do have a
measurable global effect, however, which
is discussed in a later section.
~ 95th percentile
in_
L
- - qNth r,rrcentile
75th percentile
Composite average
~Median
.. -.1 ' 25th Percentile
I - 10th percentile
l" 5th percentile
Figure 1. Technique used for box plots in subse-
quent figures in this paper. The 5th, 10th, and 25th
percentiles depict the "cleaner" monitoring sites; the
75th, 90th, and 95th depict the "dirtier" sites; and the
median and average represent typical concentration.
(Adapted from U. S. Environmental Protection
Agency 1985.)
25
1975 1976 1977 1978 1979 1980 1981 ~982 1983
· YEAR
Figure 2. Trends in annual second highest nonover-
lapping 8-fur average CO concentrations at 174 sites
during 197~1983. On this figure and others of its
type, NAAQS indicates the U.S. National Ambient
(outdoor) Air Quality Standard for the gas species.
See figure 1 caption for explanation of plotting tech-
nique. (Adapted from U.S. Environmental Protection
Agency 1985.)
Carbon Monoxide. About two-thirds of
all carbon monoxide (CO) emissions come
from transportation activities, with the
combustion of solid waste and fuel provid-
ing most of the remainder (U.S. Environ-
mental Protection Agency 1985~. As a re-
sult, any reduction in CO emissions from
automobiles is reflected directly in the mea-
sured CO concentrations.
Figure 2 shows the distribution of CO
concentrations at 179 sites in the United
States for nine years. The quantities re-
ported are the second highest 8-fur averages
measured in the over 1,000 non-overlap-
ping 8-fur periods covering the year. Over
the period 1975 to 1983, the median de-
creased from about 12 parts per million by
volume (ppm) to about 7 ppm, well below
the national ambient air quality standard
(NAAQS) of 9 ppm. The concentrations at
a number of sites exceed the standard,
however, with a few at or above 15 ppm.
For the foreseeable future, it appears likely
that reductions in CO emission will be
roughly offset by increases in the total
number of vehicles and in the miles trav-
eled per vehicle, so that little change in the
CO concentration distribution is antici
OCR for page 136
136 Anthropogenic Emissions and Their Atmospheric Transformation Products
70~
60
50
Q
Q
o
~ 40
z
UJ
o 30
8
Cal
0 20
10
1975 1976 1977 1978 1979 1980 1981 1982 1983
YEAR
Figure 3. Trends in annual mean NO2 concentra-
tions at 177 sites during 197~1983. See figure 1 caption
for explanation of plotting technique. (Adapted from
U. S. Environmental Protection Agency 1985.)
pated (U. S. Environmental Protection
Agency 1985~.
Oxides of Nitrogen. The emission flux of
oxides of nitrogen (NOX) is approximately
equally divided between motor vehicles
and stationary combustion activities (U.S.
Environmental Protection Agency 1985~.
The total NOX (NO + NO2) emissions
increased slightly in the late 1970s, de-
creased slightly in the early 1980s, and are
now relatively stable. As a consequence,
major changes in atmospheric concentra-
tions of NOX are not anticipated over the
next few years.
Boxplots of annual mean nitrogen diox-
ide (NO2) concentrations at 174 sites in the
United States for nine years are shown in
figure 3. The quantity reported is the an-
nual mean concentration. The 95th, 90th,
and 75th percentiles increase from 1975 to
1979, followed by a decrease from 1979 to
1983. The trend is less evident in the mean
values of the annual concentrations and
disappears entirely for the lower percentiles
of the data. Most sites have annual mean
concentrations of NO2 in the range of
20-30 parts per billion by volume (ppb).
Nearly all are below the NAAQS of 53
ppb. (Los Angeles is an exception; its NO2
levels are in the upper 5 percent of values
[not shown in the figure].) The detection
technique generally used for NO2 is sensi-
tive to several other nitrogenous com-
pounds as well, so the data are properly
regarded as upper bounds to the true con-
centrat~ons.
Hydrocarbons. The hydrocarbons (HC)
found in the atmosphere comprise an ex-
tremely numerous and chemically diverse
group of atmospheric compounds. They
are of interest not only for their intrinsic
properties but also because, with NOX,
they are precursors to ozone (03) and a
variety of other atmospheric oxidants.
Methane, the most abundant of the HCs, is
of limited reactivity; as a consequence, data
are often given for nonmethane hydrocar-
bons (NMHC) rather than for total HCs
including methane.
Although there is an NAAQS for
NMHC 240 ppb carbon by volume
(ppbC), maximum ~9 a.m. concentration,
to be exceeded no more than once per
year the standard was established to serve
only as a guide in assessing HC emission
reductions needed to achieve O3 standards.
As such it has not been enforced, and only
limited routine monitoring of NMHC has
been performed. Thus the data on HC
concentrations are less extensive than the
data for some of the other species men
. . . . .
tlonec . 1n this section.
Typical concentrations of total NMHC
in urban areas are about 1-2 ppmC
(Graedel and Schwartz 1977; Tilton and
Bruce 1980~. Rather than examining total
concentrations, however, it is often more
instructive to examine concentrations for
individual compounds or groups of com-
pounds that comprise the NMHC. Atmo-
spheric HCs are often grouped into three
classes for convenience of discussion:
alkanes (aliphatic HCs characterized by a
straight or branched carbon chain, generic
formula CnH2n+2), alkenes (aliphatic HCs
having one or more double bonds), and
aromatic compounds (unsaturated cyclic
HCs containing one or more rings). For the
more reactive alkenes and aromatics, dia-
grams of typical concentrations in various
OCR for page 137
T. E. Graedel
137
1 000 r
100
1
Q 1 0
Q 1 00
Q
1 10
4
Alkenes
2
~33
~2
~3
~2
5
~3
MS LS FT D S G F M O U
REGIME
Figure 4. Approximate concentration ranges of alkenes in the following different
atmospheric regimes: U = urban; 0 = oceanic; M = marshland; F = forest; G =
grassland; S = steppes and mountains; D = desert (all of the previous measured
within the boundary layer); FT = free troposphere (~5 km altitude); LS = lower
stratosphere (1~20 km altitude); MS = middle stratosphere (~25 km altitude)
(Graedel et al. 1986). Within the flags, the segments indicate the typical fraction of
total concentration due to alkenes with the number of carbon atoms shown. For
example, oceanic alkenes are typically comprised of about 65 percent ethylene (C =
2) and 35 percent propylene (C = 3).
T 10
con
E
~ ~ 1
_- 100
,[
Q
Q
1 100
10
Aromatics
~6
,777 8
=17
~6
~7
~6
MS LS FT D S G
~7 ~6,7
_ ~6
~7
=16
. i
O U
8
REGIME
F M
Figure 5. Approximate concentration ranges of the aromatic HCs benzene (6),
toluene (7), and xylenes and ethylbenzene (8) in different atmospheric regimes. The
regime code and the segmented division of the flags are explained in the caption of
figure 4.
atmospheric regimes are available; they are
reproduced in figures 4 and 5. In each case,
concentrations in urban areas can be as high
as about a thousand ppbC, and concentra-
tions of several hundred ppbC are com-
mon. In more remote regions the measured
concentrations are sharply lower, reflecting
lack of proximity to the principal sources as
well as diminution of concentrations as a
consequence of atmospheric reactions.
The U. S. Environmental Protection
Agency (EPA) (1985) estimates that 37
OCR for page 138
138
Anthropogenic Emissions and Their Atmospheric Transformation Products
as,
30
~ as
o
20
tar
he
LU
o 15
o
Cat
0 10
CO
5
n
NAAOS
LL
_
r _
1975 1976 1977 1978 1979 1980 1981 1982 1983
YEAR
Figure 6. Trends in annual mean SO2 concentra-
tions at 286 sites during 197~1983. (Adapted from
U.S. Environmental Protection Agency 1985.)
percent of the volatile organic carbon com-
pounds in the atmosphere come from mo-
tor vehicles, 37 percent from industrial
activities, 15 percent from solid waste and
miscellaneous, and 10 percent from volatil-
ization of organic solvents. The total flux of
these emissions decreased slightly over the
period 1975-1983 and is now believed to be
relatively stable.
Sulfur Dioxide. Sulfur dioxide (SO2) is a
trace gas of substantial concern because of
its acid-forming potential in the atmo-
sphere and because of its potential health
effects. Its emission is dominated by fossil
fuel combustion, with industrial activity
being much less important and with motor
vehicles emitting only a few percent of the
total SO2 flux. As increased controls and
cleaner fuels have been used over the past
decade, SO2 concentrations have steadily
decreased. This pattern is illustrated in fig-
ure 6 for annual mean concentrations mea-
sured at NAMS. As of 1983, typical annual
mean concentrations were about 9 ppb.
Spatial and Temporal Variations in Con-
centration. Any effort to assess the effects
of atmospheric trace gases on animate or
inanimate objects must take into account
the very great spatial and temporal variabil-
ity of the trace gas concentrations. If the
effects are cumulative and roughly propor
tional to concentration and duration of
exposure, the problem may not be severe.
If, on the other hand, the effects are strong
functions of peak intensity, some quantita-
tive knowledge of variation from the mean
value is necessary. The present review can
offer no general rules to relate, for example,
peak intensities to annual averages. What
can be done is to illustrate some typical
variations to provide some perspective on
the magnitude of the problem.
Throughout the world, the concentra-
tions of atmospheric trace gases demon-
strate the degree to which sources of emis
. . . . . ~
salons are present In t he vicinity ot t he
monitoring sites, to what degree emissions
from those sources are controlled, and to
what degree the local meteorological situ-
ation influences the measured values. In
figure 7, annual averages of SO2 concentra-
tions at various cities throughout the world
are displayed. The ordinate on figure 7 is
logarithmic, and the figure shows that the
ratio of average SO2 concentration at Milan
(the site with the highest average annual
concentration) and at Aukland (the site
with the lowest) is about 16. The concen-
tration also varies widely within cities be-
cause of local meteorological conditions. In
a typical situation described by Johnson et
al. (1973), circulation patterns in an urban
street canyon concentrate emissions at cer-
tain locations within the canyon. The result
is concentration patterns in which assess-
ments made on one side of a city street can
easily differ by 50 percent or more from
similar assessments made on the other side.
The variation of concentration with
time, as in space, can also be significant. In
figure 8, the seasonal patterns in total HC
(NMHC plus methane) concentration in
Camden, New.lersey, are shown. The dif-
ference between the June value (the lowest)
and the September value (the highest) is
about 0.4 ppmC, or more than 20 percent
of the mean value of about 1.9 ppmC.
Diurnal differences can be important as
well. In figure 9, 10 years of August total
HC data are presented in hour-by-hour
format. The difference between the 7 a.m.
high value and the 4 p.m. low value is
about 1.0 ppmC, that is, half the total
concentration. Seasonal and diurnal fluctu-
ations in concentration vary with location,
OCR for page 139
T. E. Graedel
139
500
300
Q
Q
-
O 100
at
UJ
o
o
~ 10
50
30
3
l
Auckland
Amsterdam
Y
Montreal
London
Figure 7. The range of annual averages of SO2 concentrations measured at
multiple sites within cities throughout the world. Several cities are identified here;
further information is available in Bennett et al. (1985). The asterisk within each bar
is the composite average for the city. (Adapted with permission from Bennett et al.
1985, and the American Chemical Society.)
species, and time of year, but those illus-
trated here are typical.
Because of the degree to which micro-
meteorology or meso- or synoptic-scale
meteorology can influence species concen-
trations at any particular location, many
species concentrations will tend to be in
phase with each other. This situation has
important consequences for studies at-
tempting to link epidemiologic effects to
atmospheric concentrations, for it requires
that all potentially significant atmospheric
variables be monitored simultaneously.
Field measurements of such complexity
have seldom been accomplished by epide
. .
mlo. OglStS.
Recommendation 1. No analytical in-
strument is readily available for routine
monitoring of NMHC concentrations and
concentration trends, although several
techniques are available for potential incor-
poration into such an instrument. It is
extremely important to achieve agreement
on a satisfactory monitoring technique for
NMHC (or some significant fraction
thereof) and to begin to acquire data on a
. ~ .
routine Casts.
Selected Particle Constituents
Elemental Carbon. Carbon comprises 10
to 20 percent by weight of urban aerosols
(Countess et al. 1980; Wolff et al. 1982b).
Of this amount, nearly half is present as
elemental carbon (soot), a consequence of
incomplete combustion of fossil fuels. Die-
sel engines are the most significant of all the
sources of elemental carbon (Wolff and
Klimisch 1982~. Extensive monitoring data
are not available for elemental carbon, but
the limited studies that have been per-
formed suggest concentrations ranging
from 1 to 35 ,ug/m3 and averaging about 7
,ug/m3 (see, for example, Countess et al.
1980; Wolff 1985~. The principal concerns
with regard to soot are its efficient reduc-
tion of atmospheric visibility (Rosen et al.
1978), its potential as a catalytic oxidizer of
SO2 and other compounds in atmospheric
droplets (Brodzinsky et al. 1980), and its
ability to adsorb and concentrate toxic or-
ganic compounds and carry them into the
lung (Sun, Bond, and Dahl, this volume).
Organic Carbon. Organic compounds
are also a significant fraction of the urban
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Representative terms from entire chapter:
motor vehicles
140
Anthropogenic Emissions and Their Atmospheric Transformation Products
atmospheric aerosol. The data of Grosjean
and Friedlander (1975), Countess et al.
(1980), and Wolff (1985) indicate that or-
ganics comprise between 2 and 40 ,ug/m3
annually (mean value of 1 ~15 ,ug/m3)
of the aerosols in urban areas (see also Na-
tional Academy of Sciences 1972~. Motor
vehicle emissions are responsible for perhaps
somewhat less than half this amount.
The diurnal patterns of reactive aerosol
constituents in urban areas have been dem
E
Q
c,' 0.2
en
LL
Or
G
C,
0 0. 1
a:
o
IL
o o
us
J
z
T. E. Graedel
141
0.6
LU
C)
G
by
lo:
ILL
-
~ O
G
I
o
lL
G
~-0.2
C]
-0.4
Monthly midmeans of
hourly TOO (August)
[ill
1
~ ~ ~ ~ ~ ~ I I I I I 1 1 1 1 'I I I I ~ I I I
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
HOUR OF DAY
Figure 9. Diurnal pattern of the seasonal component of total organic carbon
(TOC) data (ppmC) in Camden, New Jersey, for August days from 1968 to 1977.
The overall August midmean is about 2.0 ppmC. The plotting technique is explained
in the caption to figure 1. (Adapted with permission from Graedel and McRae 1982.)
portents measured. (It is not always the
largest component in all cities but is nearly
always one of the major components.) The
second is that the four aerosol constituents,
all of which are produced by smog chem-
istry, comprise very large fractions of the
total particle mass. The remainder of the
mass, which largely consists of soot and
soil dust, is important only during periods
unfavorable for atmospheric chemistry.
Metals. The concentrations of metals in
atmospheric aerosol particles are monitored
routinely in the United States and in other
areas throughout the world. Most of the
metals are primarily by-products of various
industrial processes. Motor vehicles, how-
ever, have historically been major sources
of lead (Pb) because of the use of Pb
compounds as antiknock additives to gas-
oline. Manganese compounds are now be-
coming used for this purpose as well. It is
therefore of interest to examine the atmo-
spheric concentrations and trends of these
two metals.
An NAA`2S exists for Pb, and the result
has been a careful study of its atmospheric
abundance. Figure 11 shows the NAMS Pb
142 Anthropogenic Emissions and Their Atmospheric Transformation Products
r I I , . . . .
100 ~
o
O 8C
UJ
jig 6C
o
he 2C
NH4 ~ @~
so24 ~ _
NO3 ~~
l Organics ~ _
6:30 12:30 16:30
TIME (PDT)
_~___
O
Figure 10. Diurnal patterns of nitrate, sulfate, and
ammonium ions, total aerosol organics (as weight
percent of total dry aerosol), and O3 (-I-, ppm) in
Pasadena, California, on July 25, 1973. The aerosol
constituents were determined from seven 1-fur sam-
ples taken in late morning and throughout the after-
noon. (Adapted with permission from Grosjean and
Friedlander 1975, and the Air Pollution Control
Association. )
data for the past decade. It is easy to see that
the substantial reductions in leaded gasoline
that have occurred during this period have
been reflected in sharply decreasing atmo-
spheric concentrations. As of 1983, the
mean Pb level was about 0.3 ,ug/m3.
Nitrate. The inorganic nitrate component
of atmospheric aerosols is directly related
to emissions of gaseous NOX. Stationary
combustion sources and motor vehicles
may thus be supposed to be about equally
responsible for aerosol nitrate; within ur-
ban areas, that attributable to motor vehi-
cles probably dominates. Typical concen-
trations of nitrate fall within the range 1-10
,ug/m3, with a mean annual value of about
4 ,ug/m3 (Graedel and Schwartz 1977; Har-
rison and Pio 1983~. The diurnal behavior
of urban aerosol nitrate is shown in figure
10. The largest concentrations tend to oc-
cur in the late morning, a circumstance that
Grosjean and Friedlander (1975) attribute to
a combination of rush-hour emissions of
NOX and rapid smog chemistry.
Sulfate. Urban aerosol sulfate concentra-
tions are typically in the range 1-20 ,ug/m3,
with a mean annual value of about 7 ,ug/m3
(Graedel and Schwartz 1977; Harrison and
0.6 Pio 1983~. The sulfate concentration in
o urban areas often increases during the day
°~1, (see figure 10) as a result of the conversion
~of SO2 to sulfate during periods of high
0.2 ~photochemical activity. As with SO2, sta
tionary-source combustion of fossil fuel is
the primary cause of aerosol sulfate in
urban areas.
Ensemble Measurements of Suspended
Particulate Matter. Total suspended par
ticulate matter (TSP) in the atmosphere
(that is, the atmospheric aerosol) is the
most noticeable of the emittants from
sources of atmospheric constituents. As
such, it has been the object of substantial
mitigation and reduction efforts over the
years. As of 1983, emission fluxes from
industrial processes and fuel combustion
comprised about 30 percent each of the
total emission flux. Motor vehicles and
"solid waste and miscellaneous" contrib
uted about 20 percent each (U.S. Environ
mental Protection Agency 1985~.
Concentrations and trends in TSP over
the past decade are illustrated in figure 12.
A very significant reduction in the higher
-
E
~
i,1.~
~ 2.(
6
E
~ 1.(
~ o
.ol
1982 1983
YEAR
Figure 11. Trends in maximum quarterly Pb levels
at 61 sites, 197~1983. See figure 1 caption for expla-
nation of plotting technique. (Adapted from U.S.
Environmental Protection Agency 1985.)
T. E. Graedel
143
percentiles of the data is seen, with the
result that virtually all U. S. sites now meet
the NAAQS for annual concentrations.
The mean and percentiles near the median
have fallen proportionately somewhat less
than the higher percentiles; although, over
the last two years represented in the data,
noticeable reductions in these TSP concen-
trations occurred as well.
A feature that makes TSP data far from
ideal indicators of health effects is that they
are strongly influenced by high concentra-
tions of very large particles (diameters 15
lam), yet such particles are too large to be
readily inhaled. Accordingly, many recent
observations have been made with instru-
ments designed to reject particles larger
than 10 or 15 ,um in aerodynamic diameter.
The remaining particles are designated "in-
halable particles" (IP). During normal
breathing, these particles may travel to the
bronchi and be retained there. Often the IP
are further differentiated experimentally,
the particles with aerodynamic diameter
< 2.5 ,um being known as the "respirable
particles" (RPs). RPs travel as far as the
lung parenchyma during normal breathing
and may be retained there.
Extensive IP and RP data are not avail-
able, but it is clear that the chemical com
~o
Coo
90
me 80
Cal
`3 70
He
,0 60
6
z 50
° 40
o
o So
In
20
10
o
LN0ASA ~ I
1975 1976 1977 1978 1979 1980 1981 1982 1983
YEAR
Figure 12. Trends in annual geometric mean total
suspended particulate (TSP) concentrations at 1,510
sites, 197~1983. See figure 1 caption for explanation
of plotting technique. (Adapted from U. S. Environ-
mental Protection Agency 1985.)
position of larger particles is substantially
different from that of the smaller ones.
Elements residing on larger particles are
emitted mainly by natural processes such as
crustal erosion and sea spray. Those on
smaller particles are commonly generated
by high-temperature anthropogenic pro-
cesses such as welding or soldering, smelt-
ing of metals, and combustion of fossil
fuels (Milford and Davidson 1985~. Thus
sulfate (Wolff et al. 1985a), organic carbon
(Wolff et al. 1982a), and elemental carbon
(Wolff et al. 1982b) are among the species
concentrated on RPs. The potential health
effects of the RPs are much more significant
than those of IPs, because of their chemical
differences as well as the deeper respiratory
system penetration that is characteristic of
the smaller particles.
· Recommendation 2. A difficult but es-
sential job is to monitor the chemistry of
atmospheric aerosol particles in much more
detail than is now being done, concentrat-
ing especially on chemical differences as a
function of particle size. Detailed organic
analyses are particularly important.
Photochemical Products and Unregulated
Emittants
The atmospheric species discussed thus far
include those that are directly emitted from
combustion sources and extensively moni-
tored, either because they are the subject of
a standard or as possible preparatory efforts
in the establishment of a standard. In this
section an attempt is made to discuss other
compounds that may be of concern. One
cannot begin to comment on all possible
atmospheric compounds, however, be-
cause the total number thus far identified
exceeds 2,800 (Graedel et al. 1986) and
many are demonstrably unimportant. To
render the discussion tractable, the follow-
ing criteria have been used to select com-
pounds for attention:
· High chemical reactivity
· Positive toxicologic test results
· Known effects, other than toxicologic,
on humans
· Known effects other than those con-
nected directly with human organisms.
150
Anthropogenic Emissions and Their Atmospheric Transformation Products
(1985a), who injected NO2 into a humid
indoor space and measured the formation
of nitrous acid. The results suggested that
indoor spaces with high concentrations of
NO2, such as can occur near gas stoves,
might also be areas in which a few ppb of
HNO2 can be found. Much more study of
the indoor nitrogen cycle in the presence of
strong sources is needed.
Some data are available on the concen-
trations of major ions on indoor aerosols.
Within fine particles (those with diameters
<2.5 lam), Sinclair and coworkers (1985)
found ammonium, sulfate, and nitrate to be
predominant, whereas within coarse parti-
cles, they found calcium and nitrate con-
centrations to be highest. Typical average
concentrations and peak values in office
buildings were SO42-, 0.1 and 0.3 ,ug/m3;
NO3-, 0.1 and 0.2 ,ug/m3; NH4+, 0.2 and
0.3 ,ug/m3; and Ca2+, 0.05 and 0.2 ,ug/m3.
Aldehydes. Formaldehyde (and to a much
smaller extent, other aldehydes) is one of
the major indoor air quality concerns. The
current understanding of aldehyde sources
is described in a recent report by the Na-
tional Research Council (1981~:
"The primary sources (of formaldehyde
and other organic substances) are in the
indoor environment itself building mate-
rials, combustion appliances, tobacco
smoke, and a large variety of consumer
products. A buildup of formaldehyde may
be exacerbated in buildings that have been
subjected to energy-eff~ciency measures in-
tended to reduce infiltration and, thus, en-
ergy consumption. Emission rates for
formaldehyde and other organic pollutants
emitted in the indoor environment are gen-
erally unknown."
More information on sources of aldehydes
and their effects has been reported by the
National Academy of Sciences (1981~.
The indoor concentrations of formalde-
hydo the only aldehyde for which any
significant amount of data is available
vary greatly. They can be negligibly small
in buildings that contain few or none of its
common indoor sources. Conversely, in
buildings such as new, well-insulated mo
bile homes, concentrations may be as high
as several ppm (National Research Council
1981; Hanrahan et al. 1985), although sev-
eral tenths of a ppm is a more typical value
(Bundesgesundheitsamt 1985; Sexton et al.
1986~. Acetaldehyde concentrations are
typically much lower (Wang 1975; DeBor-
toli et al. 1984~. There is no indication that
formaldehyde from infiltrated outdoor air
plays any significant role in establishing
indoor formaldehyde concentrations unless
there are no indoor sources whatever.
Alcohols. Very limited data exist on the
indoor concentrations of alcohols. Wang
(1975) detected several alcohols in a college
classroom and deduced that the sources
were indoor rather than outdoor. Berglund
and coworkers (1982) measured butanol
concentrations in a school and attributed
the presence of butanol to the vaporization
of solvent from building materials. In both
cases, concentrations of 5-50 ppb were
observed.
Nitro Compounds and Organic Nitrates.
Few studies of indoor nitro compounds
have been conducted. Thompson and co-
workers (1973) examined indoor and out-
door concentrations of gaseous peroxy-
acetyl nitrate (PAN) at several sites in the
Los Angeles Basin. They found PAN levels
of a few ppb, always lower indoors than
outdoors, and attributed them to the infil-
tration of outdoor air. Seifert and co-
workers (1984) detected amines and nitro-
samines, the former at levels as high as a
few hundred ppt, the latter at levels 10 to
100 times smaller. It has been suggested
that the nitrosamines are formed in kitch-
ens when NO and amines are simulta
x
neously trapped in air-cleaning units.
Since condensed-phase nitro compounds
are common outdoor constituents, one
would expect to find them indoors as well,
perhaps at much reduced concentrations.
No studies of such species indoors have
been performed.
Heterocyclic Organic Compounds. The
only study identifying indoor heterocyclic
compounds is that of Jarke et al. (1982~. At
homes in the Chicago area, they found
T. E. Graedel
151
many organic compounds, including furan,
dioxane, and indole. No quantification of
the concentrations was attempted, but the
authors estimated their detection limit for
these compounds was about 0.5 ppb. The
sources of the compounds were not de-
termined but might be supposed to be
either the infiltration of outdoor air or the
by-products of indoor fossil fuel combus-
tion.
Polynuclear Aromatic Hydrocarbons.
PAHs are readily detectable in the indoor
environment, as a consequence of infiltra-
tion of outdoor air as well as from indoor
combustion sources. Their combined con-
centrations indoors total perhaps 5-10
ng/m3 (Butler and Crossley 1979; Sexton et
al. 1985~. Given PAH vapor pressures,
these data imply as well that indoor equi-
librium gaseous PAH concentrations will
be around 1 ppt. Such levels are similar to,
or slightly smaller than, outdoor PAH con-
centrations.
Suspended Particulate Matter. The con-
centration of suspended particulate matter
in buildings without air filtration appears to
be generally higher than it is outdoors. The
National Research Council (1981) states a
range of indoor TSP of 10-500 ,ug/m3.
Typical levels within most buildings are
about 15-50 ,ug/m3 (Sexton et al. 1984,
1985).
The chemical constituents of the indoor
aerosols bear substantial resemblance to
those outdoors. Organic carbon com-
pounds make up perhaps 4-25 ,ug/m3 of the
total (Sexton et al. 1985~; these compounds
include phthalates, alkalies, fatty acids, and
other oxygenated species (Weschler 1980,
1984; Weschler and Fong 1984~. Elemental
carbon accounts for some 10 percent of the
total aerosol mass, or about 2-7 ,ug/m3
(Sexton et al. 1985~. Heavy metals, includ-
ing aluminum, iron, copper, and zinc, are
present at concentrations of a few tens or
hundreds of ng/m3 (Tosteson et al. 1982;
Sexton et al. 1985~. The ions common to
outdoor aerosols are also found indoors
(Sinclair et al. 1985~. The principal sources
of many of the organic and metallic com-
pounds appear to be located within the
buildings. In the case of Pb, however, most
is present on fine particles and exists in-
doors as a result of infiltration of outdoor
air.
Recommendation 7. Air quality re-
searchers have only the most general ideas
of indoor fluxes of trace species, the relative
importance of indoor and outdoor sources
to indoor species concentrations, and total
exposures. A major effort should be made
to acquire such data, without which no
epidemiologic studies can hope to be au-
thoritative. Special effort should be directed
to the passenger compartments of automo-
biles, where total exposure is potentially
quite high.
Emittants with Potential Global
Influence
Carbon Dioxide
CO2 is one of the principal products of the
combustion of fossil fuels. Its emissions
from motor vehicles are substantial but are
small fractions of the global emission flux.
CO2 is not toxic at or near atmospheric
concentrations, but its presence in the at-
mosphere has major effects on biogenic life
cycles on the earth because it is a major
absorber of the infrared radiation emitted
toward space from the earth's surface. As a
result, it is crucial to the establishment and
maintainence of the planetary temperature
structure.
The concentration of CO2 at a remote
atmospheric site is shown in figure 18. The
upward trend is readily evident. It has been
estimated that the atmospheric CO2 con-
centration will double by the year 2030 or
thereabouts, producing a global average
temperature increase of about 1.5 to 4.5°C
(National Research Council 1983~. Despite
considerable study, it appears unlikely that
any global program for the reduction of
CO2 emissions will prove feasible. As a
result, motor vehicle CO2 emissions are
unlikely to be controlled by law. It is
possible that increasing amounts of CO2,
together with other radiation-absorbing
gases, will change the total environment of
152 Anthropogenic Emissions and Their Atmospheric Transformation Products
350
c=` 345
o 340
335
z 330
c, 325
o 320
o 315
() 310
58 60 62 64 66 68 70 72 74 76 78 80 82
YEAR
Figure 18. Concentration of atmospheric CO2 at
Mauna Loa Observatory, Hawaii, expressed as a mole
fraction in parts per million of dry air. The dots depict
monthly averages of visually selected data that
have been adjusted to the center of each month. The
curve represents the fit simultaneously to an expo-
nential function, a spline function, and a linearly
increasing seasonal cycle. (Adapted with permission
from Bacastow et al. 1985, and the American Geophy-
sical Union.)
the planet within two or three generations,
and it may be prudent to keep that change
as small as possible.
Carbon Monoxide
Most of the trace molecules emitted into
the air are ultimately removed from it by
reaction chains initiated by the hydroxyl
(HO ~ radical (Atkinson, this volume). It
appears from the results of photochemical
atmospheric models that the most impor
UJ
120
8 100_
___-
JAN. JAN. JAN. JAN.
1979 19430 19~1 1982
Figure 19. CO concentrations at Cape Meares, Or-
egon. Monthly concentrations are formed from the
440 to 2,200 measurements each month, and these
averages are then combined to form 12-month mov-
ing averages. In this approach, seasonal cycles of a
year or less disappear. The solid line is the trend
calculated by linear least-squares techniques. (Adapted
with permission from Khalil and Rasmussen 1984,
@) 1984 by AAAS.)
tent reactant in controlling the global HO-
concentration is CO, because of its abun-
dance and its rapid reaction with HO.. As
with CO2, the atmospheric concentrations
of CO are steadily increasing (figure 19~. As
was pointed out above, motor vehicles are
responsible for about two-thirds of all CO
emissions and are thus major factors in the
global CO increase. Photochemical model
studies (Levine et al. 1985) suggest that over
the past 35 years the average HO- concentra-
tion has decreased by 25 percent. As a result,
the ability of the atmosphere to cleanse itself
has become increasingly inhibited.
Methane
Methane is an absorber of infrared radiation
as well as a factor in controlling the atmo-
spheric abundance of the HO- radical. As a
consequence, its long-term trend is also of
interest. A summary of atmospheric con-
centration measurements of methane over
the past several years is given in figure 20.
As with CO2 and CO, methane concentra-
tions are increasing, at about 1.2 percent
per year. About a thousandth of the annual
methane emissions are attributable to mo-
tor vehicles (Ehhalt and Schmidt 1978~.
1.65
Q
Q
-
z 1.60
o
z
MU
of
8 1.55
I
;
1.50 I I I I I_
78 79 80 81 82 83 84
YEAR
Figure 20. Average worldwide tropospheric con-
centrations of methane during the period 1978-1983.
The solid line represents a least-squares fit with an
increase of 0.018 ppm per year. (Adapted with per-
mission from Blake and Rowland 1986, and D. Reidel
Publishing Company.)
T. E. Graedel
153
Summary
Data Adequacy
Data adequacy is taken here to mean that
sufficient data are available to permit rea-
sonable assessments of the effects of a given
atmospheric constituent on animate and
inanimate objects, and not that the concen-
trations are known on every street corner.
By this definition, sufficient outdoor data
are available for the "criteria species" CO,
N02' S02, 03, Pb, and TSP. For total or
NMHCs the amount of available data is
marginally adequate, in large part because
. . . . . .
no satlstactory routine monitoring 1nstru
ment is available. Inside buildings a similar
situation exists, with at least the approxi
~ . . .
mate range ot criteria species concentra-
tions having been established. Within the
passenger compartments of automobiles,
very few concentration data have appeared
in the literature.
In the case of atmospheric species for
which ambient standards have not been
established, the available outdoor data are
generally inadequate to do more than infer
order of magnitude concentrations and to
produce some idea of the relative strengths
of the potential sources of the compounds.
For example, the data on formaldehyde and
other small aldehydes are from very few
sites and are not now being enhanced by
any regular monitoring. As with NMHC,
this is partly because no routine, reliable
monitoring instrument is available. For
methanol, ethanol, and manganese, species
that may soon be emitted from motor
vehicles at much higher rates, the data are
extremely sparse. It is important that these
compounds be included soon in routine
monitoring programs in order to establish
baseline concentrations for future refer-
ence. Other species for which more data are
needed are those generally present in aero-
sol form which possess positive bioassay
characteristics. Such compounds include
the nitro derivatives of PAHs and several
heterocyclic species.
Indoors, measurements have been re-
stricted largely to the criteria species and to
formaldehyde. Much greater characteriza
. , . .. . . . .
lion or trace species In the 1nc boor envlron
ment is needed.
Trends
For CO, CO2, and methane, the atmo-
spheric concentrations show an increasing
trend at global background locations, and
stable or slightly decreasing peak levels in
urban areas. For SO2, Pb, and TSP, de-
creasing trends are seen. The concentra-
tions of O3 and NO2 in most U.S. urban
regions appear to be roughly stable on an
annual basis (Los Angeles is the exception,
having shown a 25 percent decrease over
the last eight years); at global background
sites the concentration of 03, at least, ap-
pears to be increasing, thus implying also
an increase in NO2.
Concentrations
As is evident from the information above,
concentrations of airborne species of interest
show wide variations from site to site and
time to time. Notwithstanding this complex-
ity, it is useful to tabulate information from
the literature on typical values of average and
peak concentrations. Such data appear in
table 1 for 21 species. In each case, an attempt
is made to indicate the approximate state of
measurement technology currently required.
The ranges of values for urban areas are
annual averages, if available. Peak values are
given for urban outdoor environments, for
. . .
mc oor nonmanu actunng environments,
and for the passenger compartments of auto-
mobiles. The availability of data generally
decreases from left to right in the table. Many
more data are extant on emitted gases and
TSP than for other species shown.
For gaining a quick perspective on typical
concentrations of trace species, graphical dis-
plays are often convenient. Such displays are
presented here for species for which sufficient
data are available to establish typical ranges of
concentrations. Trace gases are displayed in
figure 21. In most cases, the concentrations in
remote areas are the lowest, those in outdoor
urban air next highest, and those indoors
highest of all. (The exception is 03, which
has roughly the same peak values in all three
regimes.) The ordinate on figure 21 is loga-
rithmic; remote and indoor concentrations
differ by as much as four or five orders of
. .
magmtuc .e In some cases.
154
Anthropogenic Emissions and Their Atmospheric Transformation Products
Table 1. Typical Ranges and Peak Values for Gaseous and Particulate Species
Species
Measure
ment Ca
pability
Concentrations
Urban
Range
Urban Indoor Auto
Peak Peak Peakb References
Emitted gases (ppb)
CO
RM (3-15) x 103
CO2 RM (3-6) x 105
4 x 104 1 X 105 3 x 104 National Research Council
6x 105 3x 106
NOr RM 10 - 50 800 500 1 x 103
- .~
NMHC ET (1-5) x 103
SO2 RM 3-20
Product gases (ppb)
o3
X 104 3 x 104 2 x 103
300 20
RM 90-210 350
HNO2 ES 0.2-4(s)
HNO3
PAN
H202
HCHO
ES
ES
ES
ET
Particle species (,ug/m3)
Pb RM
EC
OC
NOT
so2
PAH
1-5 30
5-10
0.2-2(S)
3-60
25
50 1 x 103
0.1-0.7 1.0 0.1
ET
ET
RM
RM
1-15
5-20
1-10
1-20
ES (5-10) x 10-2(s)
Nitro-PAH ES (1-3) x 1o-4(S) 3 x 10-4
(Table continued next page.)
(1981); U.S. Environmental
Protection Agency (1985);
Mucke et al. (1984)
McRae and Graedel (1979);
Spengler and Sexton (1983)
U.S. Environmental Protec-
tion Agency (1985); Mucke
et al. (1984); Spengler and
Sexton (1983)
DeBertoli et al. (1984);
Mucke et al. (1984); Tilton
and Bruce (1980)
200
35
40
150.7
30 ~_
0.110
National Research Council
(1981); U.S. Environmental
Protection Agency (1985)
National Research Council
(1981); U.S. Environmental
Protection Agency (1985);
Tuazon et al. (1981)
Harris et al. (1982); Pitts et al.
(1985b); Sjodin and Ferm
(1985)
Spicer (1977); Tuazon et al.
(1981)
Tuazon et al. (1981)
Kok et al. (1986)
National Research Council
(1981); National Academy
of Sciences (1981); Tuazon
et al. (1981)
U.S. Environmental Protec-
tion Agency (1985); Toste-
son et al. (1982)
Countess et al. (1980); Wolff
(1985)
Countess et al. (1980); Wolff
(1985)
Graedel and Schwartz (1977);
Graedel et al. (1986)
Graedel and Schwartz (1977);
Graedel et al. (1986)
Lahmann et al. (1984); Mos-
chandreas et al. (1981); Sei-
fert et al. (1983)
Gibson (1982); Pitts et al.
(1985a)
T. E. Graedel
155
Table 1. Continued
S.
penes
Measure
ment Ca
pability
Concentrations
Urban
Range
Urban Indoor Auto
Peak Peak Peakb
References
TSP RM
IP
RP
30-75
RM 5-80 120
RM 10-75 210
400 500
500 150
Bennett et al. (1985); U.S.
Environmental Protection
Agency (1985); Spengler
and Sexton (1983)
Lioy et al. (1983); Wolff et al.
(1985b)
Budiansky (1980); National
Research Council (1981);
DeBortoli et al. (1984)
a Averaging times are annual for urban range except shorter where noted by (s), daily for urban peak, an hour or
two for indoor and automobile interior data.
b Concentrations as measured within the passenger compartment of an automobile.
NOTE: Abbreviations and symbols not elsewhere defined are EC = elemental carbon; 0C = organic carbon; RM
= routine monitoring; ET = event monitoring by technician; ES = event monitoring by scientist.
103
Con
o
z
C)
o
C'
1'°°
10
1 100 _
a,
GO
10
l
1
CO NO2 NMHC SO2 O3 HCHO
TRACE GASES
Figure 21. Typical concentration ranges of selected
atmospheric trace gases in remote areas (R), urban areas
(U), and indoors (I). Data for this display are from
Noxon 1975; Spengler et al. 1979; M0lhave 1982; U.S.
Environmental Protection Agency 1985; Wallace et al.
1985; and Graedel et al. 1986. Because ofthe form ofthe
ambient air quality standards for CO and 03, the urban
data for those compounds represent upper extreme
values (extracted from an annual data set) rather than
mean values.
-
~ 10
of
o
z
10-1
10-2
_ _
$,
1 ~
TSP SO42- NO3- Pb
AIRBORNE PARTICLE CONSTITUENTS
Figure 22. Typical concentration ranges of selected
atmospheric airborne particle constituents in remote
areas (R), urban areas (U), and indoors (I). The data
for this display are from Rhodes et al. 1979; Graedel
1980; Sinclair et al. 1985; and the references given in
table 1.
156
Anthropogenic Emissions and Their Atmospheric Transformation Products
A similar display for particulate matter is
given in figure 22. In general, the data for
the three regimes are much more similar
than was the case for the gases. Two cave-
ats are worth noting, however: adequate
trace metal data, except for Pb, are not
extensive, and few indoor data exist for
other than TSP. Limited studies of trace
metal compositions throughout the world
suggest that urban and remote concentra-
tion differences are substantial.
Summary of Research Recommendations
HIGH PRIORITY
Recommendation 7 The proportion of time spent indoors by most people is high, yet
Indoor Air Quality the available data for indoor air quality is quite sparse. This is
particularly true of nonresidential environments such as automobile
interiors, subway platforms, and the like. Air quality researchers
have only the most general ideas of indoor fluxes of trace species,
the relative importance of indoor and outdoor sources to indoor
species concentrations, and total exposures. A major effort should
be made to acquire such data, without which no epidemiologic
studies can hope to be authoritative. Special effort should be
directed to the passenger compartments of automobiles, where
total exposure is potentially quite high.
.
Recommendation 3 The alkanic aldehydes are unusual atmospheric constituents in
Aldehyde Monitor the sense that they are directly emitted by sources as well as being
produced in the atmosphere by gas-phase chemistry. Their effects
on humans and animals could be significant. The determination of
atmospheric aldehyde levels is a difficult task, but the limited data
available show that much insight into atmospheric processes is
likely to be derived from carefully collected, extended data records.
An effort to develop a monitor for either formaldehyde or the
aldehyde group with appropriate sensitivity (100 ppt or less),
reliability, and an appropriately low cost, is a high priority for
atmospheric chemists, particularly those addressing problems in
urban air.
MODERATE PRIORITY
Recommendation 2Measurements of the total particulate loading of the atmosphere
Unregulatedgive only the crudest possible idea of the condensed-phase aerosol
Species Particlechemistry. A difficult but essential job is to monitor the chemistry
Phaseof atmospheric aerosol particles in much more detail than is now
being done, concentrating especially on chemical differences as a
function of particle size. Detailed organic analyses are particularly
important. It is likely that the most interesting and complex air
quality problems in the next decade will relate to condensed-phase
species; enhancing the level of analysis and depth of study of these
species are thus matters of critical concern.
Recommendation 1Hundreds of NMHCs are present in the atmosphere. They are
NMHC Monitorinvolved in the formation of 03, PAN, formaldehyde, and other
T. E. Graedel
157
lachrymators, some of which are toxic, and some of which serve as
precursors for such potentially hazardous compounds as the nitro-
aromatics. Notwithstanding this central role, no analytical instru-
ment is readily available for routine monitoring of their concentra-
tions and concentration trends, although several techniques are
available for potential incorporation into such an instrument. It is
extremely important to achieve agreement on a satisfactory mon-
itoring technique for NMHCs (or some significant fraction thereof)
and to begin to acquire data on a routine basis.
Recommendation 4 From the bioassay perspective, the complex chemical products of
Unregulated the compounds emitted to the atmosphere are often of the most
Species Gas Phase concern. Perhaps 98 percent of monitoring efforts are directed at
criteria species, however. It is important to recognize that many
~ _ ,
assessments having to do with atmospheric species cannot go
forward unless supporting data for them are available. A few
examples of crucial species listed earlier include PAN, nitric acid,
hydrochloric acid, and others. It is important for atmospheric
chemists to focus their thinking on unmet needs in species diversity
and geographical diversity.
LOW PRIORITY
Recommendation 5 Atmospheric alcohols have not often been studied in the atmo
Alkanic Alcohol sphere, but the limited data suggest that in urban areas, at least,
Monitoring their concentrations rival those of many better known organic
compounds. Once present in the atmosphere, the alcohols will
react to produce aldehydes and organic acids, two groups of
compounds potentially involved in a number of injurious interac
tions with animate and inanimate surfaces. Given the possibility of
sharply increased use of methanol and ethanol in motor vehicle
fuels over the next decade or two, it is important to begin promptly
to establish a satisfactory baseline against which future changes in
atmospheric alcohol concentrations could be assessed. The tech
niques now available, if perhaps not optimum, are satisfactory at
least for a limited screening program.
Recommendation 6 The ultimate concern of the epidemiologist dealing with the
Personal Exposure effects of atmospheric species is not species concentrations at a
Monitors monitoring site, but those encountered by human beings. Personal
exposure monitors thus have important future roles to play in
health effects research. Instrument development is required, how
ever, to improve portability, reliability, and the quantitative detec
tion of many atmospheric species of interest not presently capable
of being monitored in this way.
158
Anthropogenic Emissions and Their Atmospheric Transformation Products
Acknowlecigments
I thank R. S. Freund, l. D. Sinclair, and C.
l. Weschler for useful reviews of this paper,
and K. Sexton and B. Seifert for providing
considerable assistance in locating reference
material dealing with indoor air quality
measurements.
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