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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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Download by: [Bangladesh University of Engineering and Technology ] Date: 08 May 2017, At: 23:33
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 aging times for which it was tried. Z,NO. OF STANDARD DEVIATIONS
2 t 0 -I -2
a new mathematical model for the ex- Recent, more extensive computer cal-
pression of air pollutant concentration culations show, however, that the model
as a function of averaging time and is mathematically unstable for averaging STANDARD GEOMETRIC
freqviency and to show how this model times greater than 1 month. As DEVIATION,
16 PERCENTILE
can be used to relate air quality criteria averaging time is increased, the model 50 PERCENTILE
to air quality standards and emission equation changes gradually until the 0106 P P M \ 0.106 PPM = 2 4 e
0.043 PPM
standards. square root of a negative number ap-
Continuous air pollutant concentra- pears and imaginary numbers are pro-
tion data for seven pollutants have duced. A revised model was necessary MEDIAN, m.
been analyzed previously for six cities to overcome this problem.
for 3 years.1 The analyses indicated
A New Mathematical Model 0.01 0.1 1 16 50 80 99 9999
that: FREQUENCY % OF TIME CONC. EXCEEDED STATED VALUE
Air pollutant concentration data can
1. Concentrations are approximately be presented in digital tables (Table Figure 1. Frequency that various 1-hr-averag-
lognormally distributed for all pollu- I) or as analog plots (Figures 1 and 2). ing-time nitrogen oxides concentrations ex-
tants in all cities for all averaging ceeded various values in Washington, D. C.
To determine what mathematical model from 12/1/61 to 12/1/64.
times. might best fit the actual data, a com-
2. Maximum concentration is inversely puter program was written to plot con-
proportional to averaging time to centration data (Figure 2). Data 1 were more than 100) indicates that the data
an exponent. plotted for carbon monoxide, hydro- can be described by a mathematical
carbons, nitric oxide, nitrogen dioxide, model with the following character-
A previous mathematical model2 that nitrogen oxides (NO -f- NO2), oxidant, istics:
gives air pollutant concentration as a and sulfur dioxide for Chicago, Cin-
function of averaging time and fre- 1. Concentrations are approximately
cinnati, Los Angeles, Philadelphia, San lognormally distributed for all pollu-
quency was constructed using these Francisco, and Washington for each
two fundamental characteristics of the tants in all cities for all averaging
of the 3 years and for the 3-year period times (same as previous model).
data. The model worked for all aver- from December 1, 1961 to December 2. The median concentration (50 per-
1, 1964. (A December 1 starting time centile) is proportional to averaging
was selected so that one of the averag- time to an exponent (and thus plots
ing times would be for a 3-month as a straight line on logarithmic
Dr. Larsen is in the Bureau of seasonal value, starting with winter,
Criteria and Standards National Air paper).
Pollution Control Administration, which is defined here as the three cold-
411 West Chapel Hill Street, Dur- est months, December, January, and In the new model maximum concentra-
ham, North Carolina 27701. February.) tion is still approximately inversely
Analysis of these plots (a total of 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 number of samples that could have and thus gives erroneously low values
than 1 month. The plot curves slightly been taken if sampling had been con- for some averaging times of less than
beyond 1 month (Figure 2). tinuous. Although continuous data 1-hr duration.
The plotted percentile lines appear were used here, previous studies indicate Calculating the Standard
to be straight (Figure 2). Actually that fairly accurate approximations can Geometric Deviation
they are parabolas that originate at be obtained with relatively few samples.2 Variability in pollutant concentra-
the "arrowhead" point of the plot. The two points that best depict results tion is indicated by the standard geo-
The model possesses one other basic from continuous air quality data are metric deviation. If two points for
property that results in a very useful the 0.1 and 30 percentile concentrations the same averaging time are available,
equation. This simple property is that for 1-hr-duration samples (x points the standard geometric deviation can
the arithmetic mean for a particular on Figures 1 and 2). A 1-hr-duration be calculated as
set of data is the same value for all sampling time was selected because the
averaging times. This property links response time3 for some air sampling sga = exp{[ln(co/c6)]/(za - zb)} (2)
all averaging times by the equation2: instruments, and especially for the ni-
trogen oxides (Figure 2), is very long where ca and c& are the concentrations
m = mgSg-5lasa (1)
where m is the arithmetic mean, tng is AVERAGING TIME
SECOND MINUTE HOUR DAY MONTH YEAR
the geometric mean and sg is the stan- 1 1 5 15 1 2 4 8 1 2 4 7 14 1 23 6 1 3 10
dard geometric deviation for a particular 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

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

(
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 - 1 1 1 1 1 1 1 11 l i 1 1 1 ll| 1 i 1 1 l 1L

EQUIVALENT STD.
- SLOPE -
RESEARCHER GEO. DEVIATION
OF LINE
_ FOR 1-HR. AVG. TIME -
WIPPERMANN -0.14 1.38
MEADE -0.17 1.49
TNO -0.24 1.77

MEADE'T^o~~;

0.1 1 1 1 1 1 1 1 11 i i i i i i 11 i i i i i i 11
0.1 1 10 100
AVERAGING TIME, HOURS

Figure 3. Maximum concentration at various averaging times as


calculated from meteorologic diffusion equations.

proximately as straight lines on loga- to prevent such plant damage, they theoretically be smelled on the average
rithmic paper (Figure 3). The slopes might set the air quality standard for of once every few minutes. Because
of these lines are associated, in this oxidant at a maximum value of 0.03 of these problems, particular care must
model, with standard geometric devi- ppm for an 8-hr averaging time. be taken in selecting the frequency of
ations ranging from 1.38 to 1.77 (Table How frequently should damaging occurrence values in standards so that
III). These standard geometric devi- levels of oxidant be allowed? On two they are commensurate with the unde-
ations are close to those actually ob- daysJuly 17 and 18, 1959photo- sired effects to be avoided, the pollu-
served1 (Table IV) from samples taken chemical smog caused almost $5 million tant involved, the averaging time, etc.
by the Continuous Air Monitoring damage to tobacco growing in Connecti- Oxidant is irritating to people as well
Program (CAMP) operated by the cut.8 It is important to note that only as damaging to plants. As an ex-
National Air Pollution Control Admin- one such event a year can damage the ample, let us assume that when oxidant
istration. crop. Air Quality standards that spe- concentration exceeds 0.1 ppm, aver-
The least variation in pollutant con- cify that a damaging concentration is aged over 1 hr, it may cause slight eye
centration, as measured by the stan- not to be exceeded for some arbitrary irritation. Thus the air management
dard geometric deviation, occurs for frequency, such as 1 per cent of the board for a particular air quality region
carbon monoxide and hydrocarbons time, would have been inadequate to might specify that the 1-hr-average
(Table IV), two pollutants that are protect the crop. If the standard concentration of oxidant shall not ex-
released fairly continuously at low had specified that the damaging level ceed 0.1 ppm. To prevent plant
levels by motor vehicles. The greatest could be exceeded 1 per cent of the damage, the board might specify that
variation occurs with nitric oxide, a time, then 11 such events per year the plant-damaging concentration shall
pollutant that is changed rapidly to would exceed the limit (Table II). not be exceeded more than once a year.
nitrogen dioxide in sunlight, and thus Incidentally, I will have to take the Since the effects of eye irritation would
shows relatively low concentrations blame for getting air quality standards not be as crucial, the board might decide
during daytime hours and relatively on the wrong track by using the 1 per- that eye irritation could occur 4 times
high values at night. Oxidant concen- centile. The 1 percentile was used in a year. The board might thus have
tration is also influenced by sunlight, 1959 as an arbitrary point on a log- two air quality standards for oxidant:
and shows the next most variation. probability plot, in order to calculate 1. 0.03 ppm for 8-hr-duration samples,
how much reduction in oxidant pre- not to be exceeded more than once
Applications for Air Quality Standards
cursors was necessary to achieve the a year.
The mathematical model allows con- California oxidant standard of 0.15
centration to be expressed as a function ppm for 1-hr-duration samples.9 The 2. 0.1 ppm for 1-hr-duration samples,
of averaging time and frequency. The calculations were based on allowing such not to be exceeded more than 4 times
next step is to relate these results to an event to occur on 1 per cent of the a year.
air quality criteria and air quality days, which would amount to about The standards would apply to nonover-
standards. 3 or 4 days per year. Problems may lapping time periods. All sampling
Simply expressed, air quality criteria arise when the 1 percentile is used for times would begin at midnight. Thus,
enumerate effects5"7 that have been averaging times shorter than 1 day. the 8-hr sampling periods would be
observed at various concentrations If the averaging time were 1 hr, then from midnight to 8 A.M., 8 A.M. to 4
and exposure durations for a particular a 1 percentile standard would be ex- P.M., and 4 P.M. to midnight. Stan-
pollutant or group of pollutants. For ceeded 87 times a year (Table II), or dards would, in effect, be slightly more
instance, studies might indicate that almost twice a week. The problem is restrictive if overlapping time periods
plants grown in a particular area could even worse if odor control is desired. were considered (e.g., 8-hr averages
be visibly damaged if the 8-hr-average Since a pollutant can be smelled if it calculated for sampling periods begin-
concentration of oxidant exceeded 0.03 exceeds the odor threshold for only a ning at 6 A.M., 7 A.M., 8 A.M., etc.).
ppm. Thus, if the air management second, if a 1 percentile standard were Since substantially increased computer
board for this particular area desired used for odor control, the odorant could calculations and data analysis are in-

28 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 Two additional parameters, back- (100%) [(2)(0.13) - 0 . 0 3 ]
done. The nonoverlapping time periods ground concentration and a growth R = (29)
(2) (0.13) - 0.02
should give sufficiently close results, factor, are needed to calculate the re-
and a slight safety factor could be used duction in oxidant needed to prevent R = 96% (30)
to compensate for the slight difference plant damage. Let us assume that the
encountered when nonoverlapping maximum 8-hr-average background con- The additional steps needed to deter-
rather than overlapping sampling pe- centration of oxidant measured in a mine emission standards from air qual-
riods are used. rural area far from and unaffected by ity data, air quality standards, and
In order to see how an air quality oxidant precursors (hydrocarbons and emission data have been described in
standard to prevent plant damage nitrogen oxides) from San Francisco previous articles.7-9"13
might be used, let us assume that it is is 0.02 ppm. Let us also assume that Similar calculations could be made to
to be used by the San Francisco Bay a doubling in oxidant levels due to determine the control needed to achieve
Area Air Pollution Control District. growth will occur (in about 20 years) the eye-irritation standard for the air
The plot of oxidant data from the if no abatement action is taken. The quality control region, allowing 0.1
CAMP station in San Francisco (Figure following equation10 could be used to ppm for 1-hr-duration samples to be
4) indicates that the 8-hr-maximum calculate the reduction in oxidant exceeded no more than 4 times a year.
concentration expected once a year is needed to prevent plant damage: The fourth highest value expected in
0.13 ppm. Maximum values calculated a year would be calculated2 using the
(100%) (gc - q) following steps.
from the model, rather than observed (28)
maxima, are recommended for use. gc - b
rr
Although observed values are about where R is the per cent reduction needed, = 100% (31)
the same as the calculated values, ob- g is the growth factor, q is the air qual-
served maxima vary substantially from ity goal, c is the present concentration, where / is the plotting position for the
year to year, whereas the calculated and b is the background concentration. frequency, r is the rank order (first,
values remain fairly stable. For the example, 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,
SECOND MINUTE DAY MONTH YEAR
5 15 1 2 4 7 14 1 2 3 6 I 3 10..
I I I | I I | I | I I I I | I I I
0.531 0.241 0.126 0.090 0.032 0.018 / - 100% (32)
EXPECTED ANNUAL MAXIMUM CONC IN PPM
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)
O.OOO1 O.OO1 0.01 0.1 1 10 100 1OOO 10,000 c = 0.16 ppm (35)
AVERAGING TIME, HOURS

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 States cities for 3 years. These data 2. Zimmer, C. E., and Larsen, R. I.,
previously described to determine the have been used to develop a mathe- "Calculating air quality and its con-
trol," / . APCA, 15: 565-572 (Dec.
degree of control necessary to achieve matical model to express pollutant con- 1965).
the example standard for controlling centration as a function of averaging 3. Larsen, R. I., Benson, F. B., and
eye irritation. time and frequency. The two essential Jutze, G. A., "Improving the dynamic
The ultimate purpose of emission features of the model are derived from response of continuous air polutant
measurements with a computer,"
standards is to prevent various un- data analyses indicating that: (1) J. APCA, 15: 19-22 (Jan. 1965).
wanted pollutant effects. The chain concentrations are approximately log- 4. Brasser, L. J., Joosting, P. E., and
that joins emission standards to pollu- normally distributed for all pollutants Van Zullen, D., "Sulfur dioxideto
tant effects is composed of many links, in all cities for all averaging times; what level is it acceptable?," Report
G 300 of the Res Inst for Public Health
such as air quality criteria, air quality and (2) median concentration is pro- Eng., p. 10, Delft, The Netherlands
standards, studies of atmospheric reac- portional to averaging time to an ex- (July 1967).
tions, aerometric sampling and data ponent. Applications of this model 5. Jaffe, L. S., "Effects of photochemical
analysis, and emission studies. It is to problems involving pollutant effects, air pollution on vegetation with rela-
air quality criteria, and air quality tion to the air quality requirements,"
important to design every link of this J. APCA, 17: 38-42 (Jan. 1967).
chain to fit its adjacent links. In the standards are shown. Air quality 6. Menser, H. A., and Heggestad, H. E.,
past some links have been proposed standards should be based on the pre- "Ozone and sulfur dioxide synergism:
that look fine by themselves, but just vention of certain combinations of con- injury to tobacco plants," Sci., 153:
don't fit into the total system. For centrations and exposure durations 424^25 (July 22, 1966).
instance, air quality standards can be that may cause various undesirable 7. Larsen, R. I., "Air pollution from
motor vehicles," Anals of the N. Y.
written so that the necessary aerometric effects. It is also recommended that Acad. of Sci., 136 (12): 275-301
data processing related to such stan- air quality standards specify maximum (Aug. 26, 1966).
dards is straightforward and efficient, concentrations that are not to be ex- 8. Heggestad, H. E., "Ozone as a to-
or they can be written so that aero- ceeded more often than a stated fre- bacco toxicant," J. APCA, 11:
691-694 (Dec. 1966).
metric data analysis becomes horren- quency, commensurate with the unde- 9. Larsen, R. I., "A method for deter-
dously complicated and almost im- sirable effects to be avoided, the pollu- mining source reduction required to
possible. Some analyses become so tant involved, and the averaging time. meet air quality standards," / . AP-
complicated that it is almost impossible In comparing air quality in a com- CA, 11: 71-76 (Feb. 1961).
to determine emission standards that munity to the standard, the calculated 10. Larsen, R. I., "Determining reduced-
emission goals needed to achieve air
will achieve the specified air quality expected value based on real air quality quality goalsa hypothetical case,"
standards. The techniques discussed data and the model presented herein, J.APCA, 17: 823-829 (Dec. 1967).
in this and recent companion pa- would be used. 11. Larsen, R. I., "Future air quality
pers1 ' l o ' n fit together into an integrated standards and industrial control re-
Acknowledgments quirements," Proc: The Third Natl.
system that enables emission standards Conf. on Air Poll, 199-204, PHS
to be linked to air pollutant effects. Sincere thanks are expressed to Ray- Publ. No. 1649, U. S. Govt. Printing
Future research will undoubtedly sug- mond Smith, Chief, Air Quality and Office, Washington, D. C. (1967).
gest additional improvements in this Emission Data Division, NAPCA, and 12. Larsen, R. I., "Determining source
air management chain. to his staff for past studies which pro- reduction needed to meet air quality
standards," Internal. Clean Air Cong.
vided the data on which this mathema- Proc, Part 1, pp. 60-64, Natl. Soc.
Summary tical model is based. for Clean Air, London E. C. 4, Eng-
Continuous air pollutant concentra- land (Oct. 1966).
References 13. Larsen, R. I., Stalker, W. W., and
tion data have been analyzed for car-
bon monoxide, hydrocarbons, nitric 1. Larsen, R. I., et al., "Analyzing air Claydon, C. R., "The radial distribu-
pollutant concentration and dosage tion of sulfur dioxide source strength
oxide, nitrogen dioxide, nitrogen oxides, data," / . APCA, 17: 85-93 (Feb. and concentration in Nashville," / .
oxidant, and sulfur dioxide in 6 United 1967). APCA, 11: 529-534 (Nov. 1961).

30 Journal of the Air Pollution Control Association