Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/uawm16

A New Mathematical Model of Air Pollutant

Concentration Averaging Time and Frequency

R. I. Larsen

To cite this article: R. I. Larsen (1969) A New Mathematical Model of Air Pollutant Concentration
Averaging Time and Frequency, Journal of the Air Pollution Control Association, 19:1, 24-30, DOI:
10.1080/00022470.1969.10466453

To link to this article: http://dx.doi.org/10.1080/00022470.1969.10466453

Published online: 16 Mar 2012.

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 R. I. Larsen
A New Mathematical Model
National Air
Pollution Control Of Air Pollutant Concentration
Administration
Averaging Time and Frequency

A previous mathematical model of air pollutant concentration, averaging time, and frequency gave results
close to actual measurements for the relatively short averaging times for which it was used. However,
recent calculations show that mathematically unsound results are obtained with the model for averaging
times longer than one month. A new mathematical model, described herein, gives mathematically sound
results for all averaging times. The two dominant features of this new model are derived from observa-
tions that indicate: (1) air pollutant concentrations are approximately lognormally distributed for all pollu-
tants in all cities for all averaging times; and (2) median concentration is proportional to averaging time
to an exponent. Applications to problems air pollutant effects and air quality standards are shown.

The purpose of this paper is to present
a new mathematical model for the ex-
pression of air pollutant concentration
as a function of averaging time and
freqviency and to show how this model
can be used to relate air quality criteria
to air quality standards and emission
standards.
Continuous air pollutant concentra-
tion data for seven pollutants have
been analyzed previously for six cities
for 3 years.1 The analyses indicated
that:
1. Concentrations are approximately
lognormally distributed for all pollu-
tants in all cities for all averaging
times.
2. Maximum concentration is inversely
proportional to averaging time to
an exponent.
A previous mathematical model2 that
gives air pollutant concentration as a
function of averaging time and fre-
quency was constructed using these
two fundamental characteristics of the
data. The model worked for all aver-
Dr. Larsen is in the Bureau of
Criteria and Standards National Air
Pollution Control Administration,
411 West Chapel Hill Street, Dur-
ham, North Carolina 27701.
aging times for which it was tried.
Recent, more extensive computer cal-
culations show, however, that the model
is mathematically unstable for averaging
times greater than 1 month. As
averaging time is increased, the model
equation changes gradually until the
square root of a negative number ap-
pears and imaginary numbers are pro-
duced. A revised model was necessary
to overcome this problem.
A New Mathematical Model
Air pollutant concentration data can
be presented in digital tables (Table
I) or as analog plots (Figures 1 and 2).
To determine what mathematical model
might best fit the actual data, a com-
puter program was written to plot con-
centration data (Figure 2). Data 1 were
plotted for carbon monoxide, hydro-
carbons, nitric oxide, nitrogen dioxide,
nitrogen oxides (NO -f- NO2), oxidant,
and sulfur dioxide for Chicago, Cin-
cinnati, Los Angeles, Philadelphia, San
Francisco, and Washington for each
of the 3 years and for the 3-year period
from December 1, 1961 to December
1, 1964. (A December 1 starting time
was selected so that one of the averag-
ing times would be for a 3-month
seasonal value, starting with winter,
which is defined here as the three cold-
est months, December, January, and
February.)
Analysis of these plots (a total of
Z,NO. OF STANDARD DEVIATIONS
2 t 0 -I -2
STANDARD GEOMETRIC
DEVIATION,
16 PERCENTILE
50 PERCENTILE
0106 P P M \ 0.106 PPM = 2 4 e
0.043 PPM
MEDIAN, m.
0.01 0.1 1 16 50 80 99 9999
FREQUENCY % OF TIME CONC. EXCEEDED STATED VALUE
Figure 1. Frequency that various 1-hr-averag-
ing-time nitrogen oxides concentrations ex-
ceeded various values in Washington, D. C.
from 12/1/61 to 12/1/64.
more than 100) indicates that the data
can be described by a mathematical
model with the following character-
istics:
1. Concentrations are approximately
lognormally distributed for all pollu-
tants in all cities for all averaging
times (same as previous model).
2. The median concentration (50 per-
centile) is proportional to averaging
time to an exponent (and thus plots
as a straight line on logarithmic
paper).
In the new model maximum concentra-
tion is still approximately inversely
proportional to averaging time to an

24 Journal of the Air Pollution Control Association

Table I. Concentration vs. averaging time and frequency for nitrogen oxides (ppm) in Washington, D. C , December 1,1961 to December 1,1964.

Averag- Percent Percent of Time Concentratiori Is Exceeded

Arith Data
'Time Mean Max Min Avail. 0.001 0.01 0.1 1 10 20 30 40 50 60 70 80 90 99 9!3.9 99 .99 99.999
5 Min 0.07 1.78 0.00 70. 1.69 1.03 0. 71 0.39 0.14 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.00 0,.00 0 .00 0.00
10 0.07 1.76 0.00 70. 1.03 0. 71 0.39 0.14 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.01 0 .00 0 .00
15 0.07 1.74 0.00 70. 1.03 0. 71 0.39 0.14 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.00 0 .00 0 .00
30 0.07 1.65 0.00 70. 1.00 0. 70 0.39 0.14 0.09 0.07 0.05 0.05 0.04 0.03 0.03 0.02 0.01 0 .00 0 .00
lHour 0.07 1.41 0.00 70. 0. 71 0.39 0.14 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.01 0 .00
2 0.07 1.29 0.00 68. 0. 66 0.37 0.13 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.01 0 .00
4 0.07 0.88 0.00 72. 0. 60 0.36 0.13 0.09 0.07 0.06 0.05 0.04 0.03 0.03 0.02 0.01 0 .00
8 0.07 0.69 0.00 74. 0. 55 0.33 0.13 0.09 0.07 0.06 0.05 0.04 0.04 0.03 0.02 0.01
12 0.07 0.51 0.00 76. 0.29 0.13 0.09 0.07 0.06 0.05 0.05 0.04 0.03 0.03 0.02
1 Day 0.07 0.38 0.01 76. 0.25 0.12 0.09 0.07 0.06 0.06 0.05 0.04 0.04 0.03 0.02
2 0.07 0.35 0.02 69. 0.22 0.12 0.09 0.07 0.07 0.06 0.05 0.04 0.04 0.03 0.02
4 0.07 0.26 0.02 73. 0.12 0.09 0.07 0.07 0.06 0.05 0.05 0.04 0.04
7 0.07 0.20 0.03 74. 0.11 0.09 0.07 0.07 0.06 0.05 0.05 0.04 0.04
14 0.07 0.15 0.03 79. 0.11 0.09 0.08 0.07 0.06 0.05 0.05 0.04 0.04
1 Month 0.07 0.13 0.04 86. 0.10 0.09 0.07 0.06 0.06 0.05 0.05 0.04 0.04
2 0.07 0.11 0.04 89. 0.07 0.06 0.05 0.05 0.05
3 0.07 0.10 0.04 83. 0.08 0.06 0.05 0.05 0.05
6 0.07 0.08 0.06 100. 0.07
lYear 0.07 0.07 0.06 100.

exponent for averaging times of less
than 1 month. The plot curves slightly
beyond 1 month (Figure 2).
The plotted percentile lines appear
to be straight (Figure 2). Actually
they are parabolas that originate at
the "arrowhead" point of the plot.
The model possesses one other basic
property that results in a very useful
equation. This simple property is that
the arithmetic mean for a particular
set of data is the same value for all
averaging times. This property links
all averaging times by the equation2:
m = mgSg-5lasa
where m is the arithmetic mean, tng is
the geometric mean and sg is the stan-
dard geometric deviation for a particular
number of samples that could have and thus gives erroneously low values
been taken if sampling had been con- for some averaging times of less than
tinuous. Although continuous data 1-hr duration.
were used here, previous studies indicate Calculating the Standard
that fairly accurate approximations can Geometric Deviation
be obtained with relatively few samples.2 Variability in pollutant concentra-
The two points that best depict results tion is indicated by the standard geo-
from continuous air quality data are metric deviation. If two points for
the 0.1 and 30 percentile concentrations the same averaging time are available,
for 1-hr-duration samples (x points the standard geometric deviation can
on Figures 1 and 2). A 1-hr-duration be calculated as
sampling time was selected because the
response time3 for some air sampling sga = exp{[ln(co/c6)]/(za - zb)} (2)
instruments, and especially for the ni-
trogen oxides (Figure 2), is very long where ca and c& are the concentrations
(1)
AVERAGING TIME
SECOND MINUTE HOUR DAY MONTH YEAR
1 1 5 15 1 2 4 8 1 2 4 7 14 1 23 6 1 3 10
I I TT I - | - T I | I | I I I I | I I I |
3.412 1.359 0.635 0 . 4 2 8 0.128 0.066
I

averaging time, and In indicates natural EXPECTED ANNUAL MAXIMUM CONC IN PPM
logarithms to the base 2.718.
As will be noted later, the object of the
model is to fit the most polluted one-
half of the air samples, for these are of
most interest for air pollution effects,
criteria, and standards.
The model requires only two items of O.O1 O
information about air quality. These O
items are the concentrations that are
exceeded by a specified percentage of
the air samples. These values may be
for samples of the same or of different 0.0001 O.OO1 O.O1 O.I 1 10 100 1OOO 10,000
averaging time. The accuracy of the AVERAGING TIME, HOURS
model will depend on the number of air Figure 2. Concentration vs. averaging time and frequency for nitrogen
samples taken compared to the total oxides in Washington from 12/1/61 to 12/1/64.

January 1969 Volume 19, No. 1 25

 Table II. Plotting position of extreme concentrations and various percentiles for various
averaging times.
Plotting Position
Z(No. of std.
Averaging time No. of samples Frequency, 60%/N deviations
(hr) in year (% of time) from median)
1 sec 0.000278 31,500,000 0.0000019 5.50
1 min 0.0166 525,000 0.0001142 4.73
5 0.0833 105,000 0.000571 4.39
8.8 0.146 60,000 0.001 4.27
10 0.166 52,500 0.001142 4.24
15 0.25 35,000 0.001715 4.14
30 0.5 17,500 0.00343 3.98
lhr 1 8,760 0.00685 3.81
1.46 1.46 6,000 0.01 3.72
2 2 4,380 0.0137 3.63
4 4 2,190 0.0274 3.46
8 8 1,095 0.0548 3.26
12 12 730 0.0822 3.14
14.6 14.6 600 0.1 3.09
lday 24 365 0.1644 2.94
2 48 183 0.328 2.72
4 96 91 0.657 2.48
5.90 146 60 1 2.33
7 168 52 1.153 2.27
14 346 26 2.31 1.99
1 month 730 12 5 1.64
2 1460 6 10 1.28
3 2190 4 15 1.04
6 4380 2 30 0.52
1 year 8760 1 50 0

at points a and b, In indicates natural
logarithms, za and z& are the number
of deviations the points are from the
median (Table II), sga is the standard
geometric deviation for the averaging
time at which point a is located, and
exp indicates that e, 2.718, is to be
taken to the power that follows in
brackets. The standard geometric devi-
ation for 1-hour averages can be calcu-
f
ing time at point a would then have {w2 - 2(1 -
1
w v) [\n{ca/cb)
been calculated as follows: 1 - v
(10)
v = (4)
When cb is greater than ca, use + radi-
cal. When cb is less than ca, use
where ttot is the total averaging time
radical. For the example
plotted (1 yr, 8760 hr, Table II) and
ta and tb are the averaging times for
soa = exp x
points a and b. For the example

(
cited 2.18 - {2.182 -
lated for Figures 1 and 2 from data in
Tables I and II as ln(8760/96) 2(1 - 0.50) [ln(
=
V (5) 1 - 0.50
saa = exp{[ln(0.71/0.07)]/ ~ ln(8760/l)
(3.09-0.52)} (3) v = 0.50 (6)
soa = 2.46 saa = 2.48 (12)
The next equation is
Figure 2 could have been plotted for which is very close to the 2.46 obtained
averaging times of longer than 1 year. W = Za V^2Zb (7) with Equation (3).
One year was selected for later use in
an example on air quality standards. where za and Zb are the number of devi- Calculating the Geometric Mean
As was mentioned earlier, it is pos- ations the points are from the median The geometric mean for a particular
sible to calculate the standard geometric (Table II). For the example averaging time can be calculated2 as
deviation from any two items of in-
formation about concentration. For w = 3.09 - (0.50)V(1.28) (8) mga == Ca/Sga'a (13)
instance, point b might have been se- w = 2.18 (9) For the example
lected as the 10 percentile concentration
for 4-day-duration samples, a value The next equation is
of 0.12 (Table I). The standard geo- 0.71 ppm
mgrhr = (14)
metric deviation for the 1-hour averag- Sga = exp X 2.463-09

26 Journal of the Air Pollution Control Association

Table III. Slope of maximum concentration line for various 1-hr-average standard geometric deviations.
Std. Geo. Dev. 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
1.00 0.000 -0.004 -0.008 -0.012 -0.017 -0.021 -0.025 -0.029 -0.034 -0.038
1.10 -0.042 -0.046 -0.050 -0.054 -0.057 -0.061 -0.065 -0.069 -0.072 -0.076
1.20 -0.080 -0.083 -0.087 -0.090 -0.094 -0.097 -0.101 -0.104 -0.107 -0.111
1.30 -0.114 -0.117 -0.121 -0.124 -0.127 -0.130 -0.133 -0.136 -0.139 -0.142
1.40 -0.145 -0.148 -0.151 -0.154 -0.157 0.160 -0.163 -0.165 -0.168 -0.171
1.50 -0.174 -0.176 0.179 -0.182 -0.184 -0.187 -0.190 -0.192 -0.195 -0.197
1.60 -0.200 -0.202 -0.205 -0.207 -0.210 -0.212 -0.214 -0.217 -0.219 -0.222
1.70 -0.224 -0.226 -0.229 -0.231 -0.233 -0.235 -0.238 -0.240 -0.242 -0.244
1.80 0.246 -0.248 -0.251 -0.253 -0.255 -0.257 -0.259 -0.261 -0.263 -0.265
1.90 0.267 -0.269 -0.271 -0.273 -0.275 -0.277 -0.279 -0.281 -0.283 -0.285
2.00 -0.287 -0.288 0.290 -0.292 -0.294 -0.296 -0.298 -0.299 -0.301 -0.303
2.10 -0.305 -0.307 0.308 -0.310 -0.312 -0.314 -0.315 -0.317 -0.319 -0.320
2.20 -0.322 -0.324 0.325 -0.327 -0.329 -0.330 -0.332 -0.333 -0.335 -0.337
2.30 -0.338 -0.340 -0.341 -0.343 -0.344 -0.346 -0.347 -0.349 -0.350 -0.352
2.40 -0.353 -0.355 -0.356 -0.358 -0.359 0.361 -0.362 -0.364 -0.365 0.366
2.50 -0.368 -0.369 -0.371 -0.372 -0.373 -0.375 -0.376 0.378 -0.379 -0.380
2.60 -0.382 -0.383 -0.384 -0.386 -0.387 -0.388 -0.390 0.391 -0.392 -0.393
2.70 -0.395 -0.396 -0.397 -0.398 -0.400 -0.401 -0.402 -0.403 -0.405 -0.406
2.80 -0.407 -0.408 -0.410 -0.411 -0.412 -0.413 -0.414 -0.415 -0.417 -0.418
2.90 -0.419 -0.420 -0.421 -0.422 -0.424 0.425 -0.426 -0.427 -0.428 -0.429
3.00 -0.430 -0.431 -0.432 -0.434 -0.435 -0.436 -0.437 -0.438 -0.439 -0.440
3.10 -0.441 -0.442 -0.443 -0.444 -0.445 -0.446 -0.447 -0.448 -0.449 -0.450
3.20 -0.451 -0.452 -0.453 -0.454 -0.455 -0.456 -0.457 -0.458 -0.459 -0.460
3.30 -0.461 -0.462 -0.463 -0.464 -0.465 -0.466 -0.467 -0.468 -0.469 -0.470
3.40 -0.471 -0.472 -0.473 -0.474 0.475 -0.476 -0.477 -0.477 -0.478 -0.479
3.50 -0.480 -0.481 0.482 -0.483 -0.484 0.485 -0.485 -0.486 -0.487 -0.488
3.60 -0.489 -0.490 -0.491 -0.492 -0.492 -0.493 -0.494 -0.495 -0.496 -0.497
3.70 -0.497 -0.498 -0.499 -0.500 -0.501 -0.502 -0.502 -0.503 -0.504 -0.505
3.80 -0.506 0.506 -0.507 -0.508 -0.509 -0.510 -0.510 -0.511 -0.512 -0.513
3.90 -0.514 -0.514 -0.515 0.516 -0.517 0.517 -0.518 -0.519 -0.520 -0.520
4.00 -0.521 -0.522 -0.523 -0.523 -0.524 0.525 -0.526 -0.526 -0.527 -0.528
4.10 -0.529 -0.529 -0.530 -0.531 -0.531 -0.532 -0.533 -0.534 -0.534 -0.535
4.20 -0.536 -0.536 -0.537 -0.538 -0.539 -0.539 -0.540 -0.541 -0.541 -0.542
4.30 -0.543 -0.543 -0.544 -0.545 -0.545 0.546 -0.547 -0.547 -0.548 0.549
4.40 -0.549 -0.550 -0.551 -0.551 -0.552 -0.553 -0.553 -0.554 -0.555 -0.555
4.50 -0.556 -0.556 -0.557 0.558 0.558 0.559 -0.560 -0.560 -0.561 -0.562
4.60 -0.562 -0.563 0.563 -0.564 -0.565 -0.565 -0.566 -0.566 -0.567 -0.568
4.70 -0.568 -0.569 -0.569 -0.570 -0.571 -0.571 -0.572 0.572 -0.573 -0.574
4.80 -0.574 -0.575 -0.575 -0.576 -0.576 -0.577 -0.578 -0.578 -0.579 -0.579
4.90 -0.580 -0.580 -0.581 -0.582 -0.582 -0.583 -0.583 -0.584 0.584 -0.585
Note. The standard geometric deviation for a particular slope is the sum of the left and top margin values.

m
g hr = 0.044 ppm (15) Calculating Frequency and Maximum less than 1 month. The slope of this
Values
line could be determined from any two
The geometric mean for any averaging- Once the geometric mean and stan- points on it. Averaging times of 1
time can be determined from dard geometric deviation have been cal- hour and 1 day were selected for this
culated for an averaging time, the con- purpose, and slope has been calculated
mot = centration expected for any frequency as a function of the standard geometric
moa Sga{{Xn(-t/ia)] -5 l n (16) can be calculated2 as deviation for 1-hr averaging time (Table
For example, the geometric mean for c = masgz (22) III). The equation of the maximum
8-hour averages would be calculated as line can be expressed as:
For instance, the maximum 1-hr-
tngt = (0.044) X average concentration expected once Cmax ~ Cmax hrf v^"/

(2.46) l[ln(8/1)]
- 5In 2
-46)/[ln(8760/l)] a year (z value from Table II) could where t is time, cmax is the maximum
be calculated as concentration for that time, cmax h r is the
(17)
cmaxhr = (0.044 ppm) (2.46)3-81 (23) concentration for the maximum hour
mgt = 0.048 (18) expected once per year, and b is the
ax hr = 1.36 (24) slope of the line on logarithmic paper
Similarly, the standard geometric devi- (Table I I I ) . Thus the maximum 1-
ation can be calculated for any averag- This point is shown as the line plot, day-duration sample expected once a
ing time as appears digitally at the top of the graph year would be calculated as
Sgt = S, o P" I/a (W0]/[lnV*(Wfc)] (19) (Figure 2), and indicates that the ex-
pected annual maximum concentration = (1.36) (24) (26)
axday
For 8-hr averages, this would calculate for 1-hr-duration samples is about 1.36 c raax day = 0.43 p p m (27)
as ppm. Calculated values are also shown
for several other averaging times. Other researchers have calculated
Sgt = As has been noted earlier, the maxi- theoretical maximum concentrations
1/2
2.46 [ln (8760/8)]/[In'/2(8760/D] (2Q) mum concentration line for the mathe- for various averaging times with models
matical model (Figure 2) is essentially that employ meteorologic diffusion
sat = 2.20 (21) a straight line for averaging times of equations. 4 Their data also plot ap-

January 1969 Volume 19, No. 1 27

 10 -
- SLOPE
_ FOR 1-HR. AVG. TIME
0.1
0.1
Figure 3. Maximum concentration at various averaging times as
calculated from meteorologic diffusion equations.
proximately as straight lines on loga-
rithmic paper (Figure 3). The slopes
of these lines are associated, in this
model, with standard geometric devi-
ations ranging from 1.38 to 1.77 (Table
III). These standard geometric devi-
ations are close to those actually ob-
served1 (Table IV) from samples taken
by the Continuous Air Monitoring
Program (CAMP) operated by the
National Air Pollution Control Admin-
istration.
The least variation in pollutant con-
centration, as measured by the stan-
dard geometric deviation, occurs for
carbon monoxide and hydrocarbons
(Table IV), two pollutants that are
released fairly continuously at low
levels by motor vehicles. The greatest
variation occurs with nitric oxide, a
pollutant that is changed rapidly to
nitrogen dioxide in sunlight, and thus
shows relatively low concentrations
during daytime hours and relatively
high values at night. Oxidant concen-
tration is also influenced by sunlight,
and shows the next most variation.
Applications for Air Quality Standards
The mathematical model allows con-
centration to be expressed as a function
of averaging time and frequency. The
next step is to relate these results to
air quality criteria and air quality
standards.
Simply expressed, air quality criteria
enumerate effects5"7 that have been
observed at various concentrations
and exposure durations for a particular
pollutant or group of pollutants. For
instance, studies might indicate that
plants grown in a particular area could
be visibly damaged if the 8-hr-average
concentration of oxidant exceeded 0.03
ppm. Thus, if the air management
board for this particular area desired
28
1 1 1 1 1 1 1 11 l i 1 1 1 ll|
EQUIVALENT STD.
RESEARCHER GEO. DEVIATION
OF LINE
WIPPERMANN -0.14
MEADE -0.17
TNO -0.24
1 1 1 1 1 1 1 11 i i i i i i 11
1 10
AVERAGING TIME, HOURS
to prevent such plant damage, they
might set the air quality standard for
oxidant at a maximum value of 0.03
ppm for an 8-hr averaging time.
How frequently should damaging
levels of oxidant be allowed? On two
daysJuly 17 and 18, 1959photo-
chemical smog caused almost $5 million
damage to tobacco growing in Connecti-
cut.8 It is important to note that only
one such event a year can damage the
crop. Air Quality standards that spe-
cify that a damaging concentration is
not to be exceeded for some arbitrary
frequency, such as 1 per cent of the
time, would have been inadequate to
protect the crop. If the standard
had specified that the damaging level
could be exceeded 1 per cent of the
time, then 11 such events per year
would exceed the limit (Table II).
Incidentally, I will have to take the
blame for getting air quality standards
on the wrong track by using the 1 per-
centile. The 1 percentile was used in
1959 as an arbitrary point on a log-
probability plot, in order to calculate
how much reduction in oxidant pre-
cursors was necessary to achieve the
California oxidant standard of 0.15
ppm for 1-hr-duration samples.9 The
calculations were based on allowing such
an event to occur on 1 per cent of the
days, which would amount to about
3 or 4 days per year. Problems may
arise when the 1 percentile is used for
averaging times shorter than 1 day.
If the averaging time were 1 hr, then
a 1 percentile standard would be ex-
ceeded 87 times a year (Table II), or
almost twice a week. The problem is
even worse if odor control is desired.
Since a pollutant can be smelled if it
exceeds the odor threshold for only a
second, if a 1 percentile standard were
used for odor control, the odorant could
1 i 1 1 l 1L
-
-
1.38
1.49
1.77
MEADE'T^o~~;
i i i i i i 11
100
theoretically be smelled on the average
of once every few minutes. Because
of these problems, particular care must
be taken in selecting the frequency of
occurrence values in standards so that
they are commensurate with the unde-
sired effects to be avoided, the pollu-
tant involved, the averaging time, etc.
Oxidant is irritating to people as well
as damaging to plants. As an ex-
ample, let us assume that when oxidant
concentration exceeds 0.1 ppm, aver-
aged over 1 hr, it may cause slight eye
irritation. Thus the air management
board for a particular air quality region
might specify that the 1-hr-average
concentration of oxidant shall not ex-
ceed 0.1 ppm. To prevent plant
damage, the board might specify that
the plant-damaging concentration shall
not be exceeded more than once a year.
Since the effects of eye irritation would
not be as crucial, the board might decide
that eye irritation could occur 4 times
a year. The board might thus have
two air quality standards for oxidant:
1. 0.03 ppm for 8-hr-duration samples,
not to be exceeded more than once
a year.
2. 0.1 ppm for 1-hr-duration samples,
not to be exceeded more than 4 times
a year.
The standards would apply to nonover-
lapping time periods. All sampling
times would begin at midnight. Thus,
the 8-hr sampling periods would be
from midnight to 8 A.M., 8 A.M. to 4
P.M., and 4 P.M. to midnight. Stan-
dards would, in effect, be slightly more
restrictive if overlapping time periods
were considered (e.g., 8-hr averages
calculated for sampling periods begin-
ning at 6 A.M., 7 A.M., 8 A.M., etc.).
Since substantially increased computer
calculations and data analysis are in-
Journal of the Air Pollution Control Association
 Table IV. Standard geometric deviations for 1-hr-average concentrations of various pollutants
in various cities, 12/1/61-12/1/64.
Pollutant
City CO Hyc NO NO2 NO X Oxi SO2
Chicago 1.49 1.37 1.77 1.65 1.66 2.54 1.98
Cincinnati 1.40 1.77 2.82 1.76 2.13 2.25 2.25
Los Angeles 1.50 1.74 2.45 2.09 2.12 2.30 2.07
Philadelphia 1.70 1.80 3.46 1.83 2.69 2.87 2.31
San Francisco 1.53 1.60 2.09 1.85 1.80 2.13 2.54
Washington 1.76 1.77 3.19 1.67 2.46 2.13 2.03
Median 1 .52 1 .76 2 .64 1 .80 2 .13 2. 28 2 .16
Minimum 1 .40 1 .37 1 .77 1.65 1 .66 2. 13 1 .98
Maximum 1 .76 1 .80 3 .46 2 .09 2 .69 2. 87 2 .54

volved, it is suggested that this not be
done. The nonoverlapping time periods
should give sufficiently close results,
and a slight safety factor could be used
to compensate for the slight difference
encountered when nonoverlapping
rather than overlapping sampling pe-
riods are used.
In order to see how an air quality
standard to prevent plant damage
might be used, let us assume that it is
to be used by the San Francisco Bay
Area Air Pollution Control District.
The plot of oxidant data from the
CAMP station in San Francisco (Figure
4) indicates that the 8-hr-maximum
concentration expected once a year is
0.13 ppm. Maximum values calculated
from the model, rather than observed
maxima, are recommended for use.
Although observed values are about
the same as the calculated values, ob-
served maxima vary substantially from
year to year, whereas the calculated
values remain fairly stable.
SECOND MINUTE
5 15
I I I | I I | I | I I I I | I I I
0.531
EXPECTED ANNUAL
O.OOO1 O.OO1 0.01 0.1
AVERAGING TIME, HOURS
Two additional parameters, back-
ground concentration and a growth
factor, are needed to calculate the re-
duction in oxidant needed to prevent
plant damage. Let us assume that the
maximum 8-hr-average background con-
centration of oxidant measured in a
rural area far from and unaffected by
oxidant precursors (hydrocarbons and
nitrogen oxides) from San Francisco
is 0.02 ppm. Let us also assume that
a doubling in oxidant levels due to
growth will occur (in about 20 years)
if no abatement action is taken. The
following equation10 could be used to
calculate the reduction in oxidant
needed to prevent plant damage:
(100%) (gc - q)
(28)
gc - b
where R is the per cent reduction needed,
g is the growth factor, q is the air qual-
ity goal, c is the present concentration,
and b is the background concentration.
For the example,
DAY MONTH YEAR
1 2 4 7 14 1 2 3 6 I 3 10..
0.241 0.126 0.090 0.032 0.018
MAXIMUM CONC IN PPM
1 10 100 1OOO 10,000
(100%) [(2)(0.13) - 0 . 0 3 ]
R = (29)
(2) (0.13) - 0.02
R = 96% (30)
The additional steps needed to deter-
mine emission standards from air qual-
ity data, air quality standards, and
emission data have been described in
previous articles.7-9"13
Similar calculations could be made to
determine the control needed to achieve
the eye-irritation standard for the air
quality control region, allowing 0.1
ppm for 1-hr-duration samples to be
exceeded no more than 4 times a year.
The fourth highest value expected in
a year would be calculated2 using the
following steps.
rr
= 100% (31)
where / is the plotting position for the
frequency, r is the rank order (first,
second, third, fourth, etc.) that is not
to be exceeded, and N is the total num-
ber of samples in a year. For the
example,
/ - 100% (32)
8760
/ = 0.0411% (33)
Statistical tables similar to Table II
indicate that this frequency is 3.35
deviations from the median. The con-
centration expected would be calculated
with Equation (22), using the values
from Figure 4, as
c = (0.013) (2.13)3-35 (34)
c = 0.16 ppm (35)

Figure 4. Concentration vs. averaging time and frequency for oxidant Thus the fourth highest value expected
in San Francisco from 12/1/61 to 12/1/64. in a year would be 0.16 ppm. This

January 1969 Volume 19, No. 1 29

value could be used with the method
previously described to determine the
degree of control necessary to achieve
the example standard for controlling
eye irritation.
The ultimate purpose of emission
standards is to prevent various un-
wanted pollutant effects. The chain
that joins emission standards to pollu-
tant effects is composed of many links,
such as air quality criteria, air quality
standards, studies of atmospheric reac-
tions, aerometric sampling and data
analysis, and emission studies. It is
important to design every link of this
chain to fit its adjacent links. In the
past some links have been proposed
that look fine by themselves, but just
don't fit into the total system. For
instance, air quality standards can be
written so that the necessary aerometric
data processing related to such stan-
dards is straightforward and efficient,
or they can be written so that aero-
metric data analysis becomes horren-
dously complicated and almost im-
possible. Some analyses become so
complicated that it is almost impossible
to determine emission standards that
will achieve the specified air quality
standards. The techniques discussed
in this and recent companion pa-
pers1 ' l o ' n fit together into an integrated
system that enables emission standards
to be linked to air pollutant effects.
Future research will undoubtedly sug-
gest additional improvements in this
air management chain.
Summary
Continuous air pollutant concentra-
tion data have been analyzed for car-
bon monoxide, hydrocarbons, nitric
oxide, nitrogen dioxide, nitrogen oxides,
oxidant, and sulfur dioxide in 6 United
30
States cities for 3 years. These data
have been used to develop a mathe-
matical model to express pollutant con-
centration as a function of averaging
time and frequency. The two essential
features of the model are derived from
data analyses indicating that: (1)
concentrations are approximately log-
normally distributed for all pollutants
in all cities for all averaging times;
and (2) median concentration is pro-
portional to averaging time to an ex-
ponent. Applications of this model
to problems involving pollutant effects,
air quality criteria, and air quality
standards are shown. Air quality
standards should be based on the pre-
vention of certain combinations of con-
centrations and exposure durations
that may cause various undesirable
effects. It is also recommended that
air quality standards specify maximum
concentrations that are not to be ex-
ceeded more often than a stated fre-
quency, commensurate with the unde-
sirable effects to be avoided, the pollu-
tant involved, and the averaging time.
In comparing air quality in a com-
munity to the standard, the calculated
expected value based on real air quality
data and the model presented herein,
would be used.
Acknowledgments
Sincere thanks are expressed to Ray-
mond Smith, Chief, Air Quality and
Emission Data Division, NAPCA, and
to his staff for past studies which pro-
vided the data on which this mathema-
tical model is based.
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