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A New Method for Measuring Average 24-Hour

Nitrogen Dioxide Concentrations in the Atmosphere
a

D.A. Levaggi , W. Siu & M. Feldstein

Bay Area Air Pollution Control District

Published online: 15 Mar 2012.

To cite this article: D.A. Levaggi , W. Siu & M. Feldstein (1973) A New Method for Measuring Average 24-Hour Nitrogen
Dioxide Concentrations in the Atmosphere, Journal of the Air Pollution Control Association, 23:1, 30-33
To link to this article: http://dx.doi.org/10.1080/00022470.1973.10469744

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Downloaded by [190.147.198.120] at 13:44 02 December 2014

A New Method for Measuring Average 24-Hour

Nitrogen Dioxide Concentrations
in the Atmosphere

D. A. Levaggi, W. Siu, and M. Feldstein

Bay Area Air Pollution Control District

A long-term manual sampling procedure for nitrogen dioxide is required to

measure compliance with the recently adopted EPA ambient air quality standard
for this substance. The method recommended by EPA has proven to be inadequate. This paper discusses a manual procedure involving absorption of NO2
in a triethanolamine solution or a triethanolamine impregnated molecular sieve
surface. Absorption efficiencies of over 95% are attained, using either the
liquid or solid absorbers. The NO2 (gas) to NO2 (ion) factor was found to be
0.85, evaluated against the Saltzman factor of 0.72.
Field data as well as controlled laboratory trials indicate the method is comparable to continuous air monitoring instrumentation, utilizing the modified Saltzman reagent. Nitric oxide in concentrations as high as 0.6 ppm for 24 hr gave
no interference. The presence of sulfur dioxide causes slightly lower results with
the solid absorber, but has no effect on the liquid absorber at concentrations
normally encountered in ambient air. This new absorbing reagent can be used
for short duration sampling, as well as extended sampling times for up to 4 days.

The need for ambient air analysis of the

oxides of nitrogen, NO and N0 2 , became a reality in the early 1950's following the work of Haagen-Smit.1 N0 2
formation in urban atmospheres is one
of the indicators of photochemical
activity. Nitrogen dioxide is not normally considered a primary pollutant as
is NO, but is rather a secondary contaminant, photochemically "manufactured" in the atmosphere, and with
potential health implications.2 It is
also responsible, in part, for the brown30

ish-hued skies on days of high pollution.

Nitrogen dioxide has for many years
been determined on a continuous basis
in ambient air by the use of Saltzman3
reagent. This modified Griess-Ilosvay
reaction provides an accurate and precise determination on a real time basis.
In the near two decades of continuous
N0 2 measurement, there has not been
developed a comparable long-term manual sampling method. Indeed, until
recently, there has not been a need for
such an analytical technique.

In 1971, the EPA adopted an ambient

air quality standard for N0 2 of 0.05
ppm annual average. Along with the
standard, a recommended method of
analysis for measurement was also proposed. This was a modified version of
the manual method of Jacobs and
Hocheiser,4 which consists of absorption
of NO2 in NaOH, with subsequent
analysis of the nitrite ion formed in
solution. Since its initial use in the
NASN (National Air Sampling Network) it has never been shown to be
comparable with the automated Saltzman method averaged over equivalent
time periods. The results appear to be
on the average, two or three times
greater than the automated procedure
as shown by Tabor and Golden5 in
their comparisons at six CAMP stations
during 1962 and 1963. More recently,
the EPA conducted a National Summer
Implementation Plan, and results at
three of our local monitoring stations
showed the same type of deviations as
reported by Tabor and Golden. The
method has received much criticism,6
and basically suffers from variable absorption efficiency, and a variable undefined stoichiometry.
The following convenient, simple
method was developed in our laboratory
to overcome these difficulties.

Journal of the Air Pollution Control Association

Apparatus

Determination

Spectrophotometer, a B & L Spec.

20, utilizing 10-mm cells. Any comparable instrument may be used.
Fritted bubblers.
Polypropylene
tubes 163 x 32 mm, fitted with polypropylene two-port tube closures. A gas
dispersion tube with a fritted end having
a porosity of 70-100 /xm is used (Ace
Glass Co.).
Observation tube. Becton-Dickenson No. 420 LST, 5.5 cm x %e in. glass,
with a standard luer lock fitting permanently attached to one end.

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Reagents

Liquid absorber. Dissolve 15.0 g of

triethanolamine in approximately 500
ml of distilled water, add 3.0 ml of Nbutanol, and dilute to 1 liter (0.1 N).
Solid absorber. Add 25 g of triethanolamine to a 250-ml beaker, add
4.0 g of glycerol, 50 cc of acetone, and
sufficient distilled water to dissolve.
Dilute to 100 ml total volume with distilled water. To the mixture add about
50 cc of 12-30 mesh molecular sieve
13 X. Stir and let stand in the covered
beaker for about 30 min. Decant the
excess liquid and transfer the molecular
sieve to a porcelain pan. Place under
a heating lamp until the bulk of moisture
has evaporated, and then in an oven at
110C for 1 hr until dry. Store in a
closed glass container.
Hydrogen peroxide. Dilute 0.2 ml
of 30% H2O2 to 250 ml with distilled
water.
Sulfanilamide. Dissolve 10 g of sulfanilamide in 400 ml of distilled water.
Add 25 ml of concentrated phosphoric
acid, mix well, and dilute to 500 ml.
NEDA. Dissolve 0.5 g of N-l-naphthylethylenediamine
dihydrochloride
in 500 ml of distilled water.
Standard solution. Dissolve 0.1500 g
of reagent grade sodium nitrite in distilled water and dilute to 1 liter. This
solution contains 100 /zg of N0 2 /ml.
Procedure
Sampling

Place 50 ml of absorbing solution in a

fritted bubbler, or, if preferred, fill an
observation tube with the solid absorber,
using small glass wool plugs for retainment of the solid. The sampling train
consists of (in tandem) a sampling
probe, bubbler or observation tube, a
critical orifice (27 gauge hypodermic
needle) and a pump having a capacity
of at least 0.5 atmosphere vacuum.
Turn pump on and rapidly check flow
rate entering system and record. This
flow rate should be between 150 and
200 cc/min. Sample for 24 hours. At
the end of the sampling period recheck
How rate and record.
January 1973

Volume 23, No. 1

Liquid absorber. Add distilled water

to 50.0 ml to replace evaporative
losses. Transfer a 10 ml aliquot to a
25-ml graduated tube. To another
tube add 10.0 ml of unexposed absorbing solution. To each, add 1.0 ml of
hydrogen peroxide solution, 10.0 ml of
sulfanilamide solution, and 1.4 ml of
NEDA solution, with thorough mixing
after the addition of each reagent.
Allow 10 min for color development and
measure absorbance at 540 nm against
the prepared blank. From standard
curve determine amount of NO2" in
the aliquot.
Solid absorber. Transfer the molecular sieve and glass wool plugs to a
50-ml test tube. Wash the observation
tube with approximately 10 ml of water
and add washings to the molecular
sieve. The volume occupied by the
molecular sieve and glass wool is so
small (~1%) it may be ignored. Dilute
to 50.0 ml with absorbing solution.
Cap and shake vigorously for about 1
minute. Let stand and shake again
after 10 minutes. Allow the solids to
settle and transfer 10 ml to a 25-ml
graduated tube. Develop color as described under liquid absorber.
Standardization

Dilute stock standard 50:1 with absorbing solution to prepare a solution

containing 2.0 ng N02"/ml. To a series
of tubes add 0, 1, 3, 5, and 7.0 ml of
dilute standard. To each add absorbing solution to the 10.0-ml mark.
Develop color as previously described.
A graph is prepared, plotting absorbance
vs. concentration.
Calculations

The calculation is based on standard

conditions of 25 C and 760 mm of

Table I.

mercury. (Deviation from these conditions introduce such small corrections

they can be ignored.)
pphm NO2 v/v
_ ng NO2~ found in aliquot X 5 X 100
(1.88) (0.85) X R X T
_ fig NO2~ found in aliquot X 313
~
R XT
(1.88 = factor for converting jug NO2~
to/ilN0 2 (g)at25C)
(0.85 = factor for conversion of jug
NO2 (gas) to jug NO2 (ion))
(R sample rate, which is the average of the initial and final
sample rates in liters per
minute)
(T = sample time in minutes)
Field Results

Table I shows a partial listing of data

using this procedure. In all cases,
samples were taken from the same
manifold on which a continuous monitoring NO2 instrument was also sampling. The analyzer used was of the wet
chemical type, utilizing a modified
Saltzman reagent. Results show excellent comparability with the instrumental method averaged for the 24 hr.
Duplicate and triplicate samples also
show excellent agreement. The use of
the method for short and extended
sampling periods is also shown in Table
I.
Experimental

To evaluate the effects of various

parameters on the triethanolamine absorbers, permeation tubes of NO2 were
used to generate NO2 streams. In all
cases, unless noted, the sampling procedure used was the same as described

Field results comparing 24-hour manual samples with the continuous analyzer.

Sampling time, hr

NO2 Manual
Method, pphm

Instrument
average, pphm

22
24
25
25
25
68
68
24
23
24
3a
2.5a

(L)2.5
(L)2.3
(L)1.9 b
(S)2.0 b
(S) 1.9b
(L)5.1b
(L)4.5 b
(L)4.6
(L)4.3
(L)4.1
(L)5.4
(L)9-l

2.4
2.3
2.4
2.4
2.4
5.2
5.2
4.0
3.4
4.2
5.0
9.0

Difference, pphm

+.1
0
.5
-.4
-.5
-.1
-.7

+ .6
+ .9

~.l

+ .1
+ .4

Long Duration Laboratory Tests

96
96
72
72

(S)5.2 b
(S)5.3 b
(S)5.0 b
(S)4.8 b

5.1
5.1
5.0
5.0

+ .1
+ .2
0
-.2

a Using 10.0 ml of absorbing solution in a fine fritted bubbler at 0.4 l/min.

b
Simultaneous samples.
L = liquid absorber, S = solid absorber.

31

Table II. Determination of collection

efficiency of TEA.

Table III. Stability of collected 24-hour

samples using liquid absorbers.

(All Runs are of 24-hr Duration)

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1st imEffect
pinger,
of 1st
imN0 2 ,
Total ngm, 2nd ima
Run pphm
found
pinger pmger
1

(L)
(S)
(S)
(L)
(S)
(S)

(D

20

50

(S)
(S)
(L)
(S)
(L)
(S)

11.0
10.0
13.0
19.5
21.5
22.0
35.0
36.5
37.5
65.0
63.0
210.
233.

Trace

1
4
1

95
95
95
95
95
95
95
98
98
98
98
98
99

Permeation tube used, stream not morii

tored
continuously.
b
Trace indicates an absorbance of 0.0030.010 equivalent to 0.5 fig NO2~.
L = Liquid absorber, S = solid absorber.

earlier. When evaluations were made

for interfering gases, either permeation
tubes were used, or a dilution board in
combination with tanks of gas of known
composition.

Nitrite determination at various

time intervals, Mg/10 ml
Sample Initial
8.2
1.9

32

Nitrite determination at various

time intervals, jug/10, ml

1 wk

2 wk

3 wk

Sample

Initial

1 wk

4 wk

8.2
1.8

8.3
2.0

8.0
1.8

1
2
3

4.4
12.5
36.0

4.5

12.0
32.8

factor of 0.85 obtained with TEA is the

average of 25 tests which ranged from
0.76 to 0.92. This variation seems
quite adequate in that it is calculated
on the basis of the Saltzman factor of
0.72. As Scaringelli has shown, there
are slight variabilities from sample to
sample, even under highly controlled
conditions.
The factor of 0.72 was used for calculation rather than 0.76, since all the continuous instruments used were calibrated with this factor. Using 0.76 as a
basis for comparison, the true factor for
0.1N triethanolamine becomes 0.90.
This is only 10% below the complete
conversion of NO2 (gas) to NO2~ (ion)
in the absorption solution.

Stoichiometry

The nitrite ion equivalence of absorbed NO2 gas in various solutions has
been studied for many years. In NaOH
solutions, the equivalence has been reported to be 0.63 by Morgan et al.,7 and
1.0 by Crecelius and Forweg.8 The
original Saltzman factor of 0.72 appears
to be well established, confirmed by the
excellent work of Scaringelli et al,9 using
calibrated permeation tubes. Their
work suggested a factor of 0.764 0.005.
To establish the stoichiometry of the
0.1N triethanolarhine solution 25 tests
were performed, using NO2 concentrations ranging from 0.03 to 0.40 ppm.
In these tests, 10.0 ml of the absorbing
solution were used in the same type of
fine fritted bubblers prescribed for
NO2, using Saltzman reagent. After
confirming the fact that, the absorbing
solution collects NO2 with 100%
efficiency, parallel samples were then
analyzed using triethanolamine and
Saltzman solutions in each leg. The

Table IV. Stability of collected parallel

samples using solid absorbers.

Collection Efficiency

Use of the recommended impingers

results in excellent collection efficiencies.
The frits used varied from an average
pore size of 90 to 139 /xm, and have
comparable collection properties. This
uniformity of collection efficiency eliminates the need for screening frits, which
is required when using sodium hydroxide
for absorption. The great affinity of
triethanolamine absorption of NO2 was
first noted by Levaggi et al.,10 and
prompted the use of triethanolamine for

quantitive NO2 collection and analysis.

Table II shows the collection efficiencies
found at varying NO2 concentrations.
The excellent collection efficiency,
even at high concentrations, stands Out
clearly. A few tests were run using
triethanolamine without butanol, which
is added as a foamer. These tests indicate an absorption efficiency of 85-90%.
It has been brought to our attention
by personnel evaluating this procedure
that excessive foaming occurred in the
impingers at 200 cc/min flow rate.
This may be due to the use of 175 mm x
31 mm tubes by the individuals who reported excessive foaming which are
slimmer and have a smaller head volume
above the liquid layer than do the
recommended tubes. This can be overcome by reducing the butanol content
of the absorbing solution to 0.5 cc/1,
instead of the specified 3 cc, or using the
recommended tubes.
Sample Storage Prior to Analysis

To ascertain stability of collected

samples, analysis was performed on an
aliquot of liquid absorber sample immediately after a sampling. The impinger was then capped, and stored at
room temperature. An aliquot was

Table V. Effect of sulfur dioxide on absorption of NO2.

Concentration, ppm

NO2 found, ppm

Sample
time, hr

SO2

NO2

Solid absorber

Liquid absorber

24
24
24
24
24
24

0.090
0.150
0.320
0.550
0.700
1.000

0.106
0.150
0.150
0.064
0.060
0.110

0.087
0.109
0.126
0.053
0.049
0.093

0.114
0.157
0.155
0.061
0.058
0.092

Monitored by a Philips Coulometric SO2 analyzer.

Journal of the Air Pollution Control Association

Downloaded by [190.147.198.120] at 13:44 02 December 2014

then taken for analysis at weekly intervals. To evaluate the solid absorber, parallel samples had to be taken.
One sample was analyzed immediately,
the other stored at room temperature
after capping. Samples were then analyzed at varying time intervals.
Tables III and IV summarize the results and show that stability is adequate
for field sampling with the normal delay
in analysis which may be encountered
by shipping samples to a central laboratory for analysis.
Effect of Interfering Gases

Two potentially interfering gases

were checked to obtain information on
interference with the procedure. Nitric
oxide was evaluated at concentrations
as high as 0.6 ppm in the presence of
0.02 and 0.09 ppm NO2. Sampling was
for 24 hr and the streams were monitored with a Beckman Model K-75
oxides of nitrogen analyzer. Neither
the liquid nor solid absorbers showed
any significant effect on the collection
and analysis of NO2.
Potential sulfur dioxide interference
was evaluated at concentrations varying
from 0.09 to 1.0 ppm. Table V shows
the results of the NO2 tests in the presence of SO2. The liquid absorber
shows no significant effect until the
SO2 concentration reaches 1.0 ppm.
The solid absorber shows some effect at
0.09 ppm, but the effect seems to be independent of SO2 concentration. In
areas of high SO2 concentrations it may
be desirable to use liquid absorbers
rather than solid absorbers. It should
be noted that the SO2 concentrations
studied are generally well above most
ambient air 24 hr averages.
January 1973

Volume 23, No. 1

Summary

References

It has been shown that triethanolamine solution or triethanolamine impregnated molecular sieve can be used
for long-time manual sampling of NO2.
Laboratory, and field data indicate that
the method yields results which agree
with automated instruments using Saltzman reagent. The reagent essentially
absorbs NO2 at 100% efficiency at usual
NO2 concentrations, and has a constant
stoichiometric factor of 0.85 for NO2
conversion to nitrite ion. The procedure has been evaluated for snort
(2 hr) and long-term sampling (4 days),
and has application for use in the following areas:

1. A. J. Haagen-Smit, "The chemistry

and physiology of Los Angeles smog,"
Ind. Eng. Chem. 44: 1342 (1952).
2. C. M. Shy, J. P. Creason, K. E.
McClain, F. B. Benson, and M. M.
Young, "The Chattanooga school
children study:
Effects of community exposure to nitrogen dioxide,"
J. Air Poll. Control Assoc. 20: 539
(1970).
3. B. E. Saltzman, "Colorimetric microdetermination of nitrogen dioxide in
the atmosphere," Anal. Chem. 26:
1949 (1954).
4. M. B. Jacobs and S. Hochheiser,
"Continuous sampling and ultramicro
determination of nitrogen dioxide in
air," Anal. Chem. 30: 426 (1958).
5. E. C. Tabor and C. C. Golden, "Results of five years' operation of the
National Gas Sampling Network"
/ . Air Poll. Control Assoc, 15: 7
(1965).
6. J. M. Heuss, G. J. Nebel, and J. M.
Colucci, "National air quality standards for automotive pollutantsA
critical review," J. Air Poll. Control
Assoc. 21: 535 (1971).
7. G. B. Morgan, C. Golden, and E. C.
Tabor, "New and Improved Procedures for Gas Sampling and Analysis
in the National Air Sampling Network." Presented at the 59th Annual Meeting APCA, San Francisco,
Calif., 1966.
8. H. J. Crecelius and W. Forweg,
"Untersuchungen
zum
Saltzman
Factor," Staub, Reinhaltung Luft 30:
294 (1970).
9. F. P. Scaringelli, E. Rosenburg, and
K. A. Rehme, "Comparison of permeation devices and nitrite ion as
standards for the colorimetric determination of nitrogen dioxide," Environ. Sci. Technol, 4 : 924 (1970).
10. D. A. Levaggi, W. Siu, E. Kothny,
and M. Feldstein, "The quantitative
separation of nitric oxide from nitrogen dioxide at atmospheric concentration ranges," Environ. Sci. Technol.

1. Dynamic calibration of NO2 instruments during normal operation.

2. Obtaining trace NO2 backgrounds.
(4 day solid absorber would have sensitivity of ~ 1 ppb)
3. Use in sequential samplers.
4. Establishing sound NO2 concentration distributions in a new geographical
area of interest.
5. Sampling for NO2 in the presence
of high concentrations of NO.

Mr. Leyaggi is Chief of Laboratory Services, Mr. Siu is Chief of

Air Monitoring, and Mr. Feldstein
is Director of Technical Services at
San Francisco Bay Area Air Pollution Control District, 939 Ellis St.,
San Francisco, Calif. 94109. This
paper was presented as Paper No.
72-2 at the 65th Annual Meeting of
APCA at Miami Beach, Fla., in
June 1972.

6:250(1972).
33