This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: D1607 − 91 (Reapproved 2018)´1

Standard Test Method for

Nitrogen Dioxide Content of the Atmosphere (Griess-
Saltzman Reaction)1
This standard is issued under the fixed designation D1607; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the U.S. Department of Defense.

ε1 NOTE—Warning notes were editorially updated throughout in July 2018.

1. Scope 2. Referenced Documents

2
1.1 This test method covers the manual determination of 2.1 ASTM Standards:3
nitrogen dioxide (NO2) in the atmosphere in the range from 4 D1071 Test Methods for Volumetric Measurement of Gas-
to 10 000 µg/m3 (0.002 to 5 ppm(v)) when sampling is eous Fuel Samples
conducted in fritted-tip bubblers. D1193 Specification for Reagent Water
D1356 Terminology Relating to Sampling and Analysis of
1.2 For concentrations of NO2 in excess of 10 mg/m3 (5
Atmospheres
ppm(v)), as occur in industrial atmospheres, gas burner stacks,
D1357 Practice for Planning the Sampling of the Ambient
or automotive exhaust, or for samples relatively high in sulfur
Atmosphere
dioxide content, other methods should be applied. See for
D1608 Test Method for Oxides of Nitrogen in Gaseous
example Test Method D1608.
Combustion Products (Phenol-Disulfonic Acid Proce-
1.3 The maximum sampling period is 60 min at a flow rate dures)
of 0.4 L/min. D3195 Practice for Rotameter Calibration
1.4 The values stated in SI units are to be regarded as D3609 Practice for Calibration Techniques Using Perme-
standard. The values given in parentheses are mathematical ation Tubes
conversions to inch-pound units that are provided for informa- D3631 Test Methods for Measuring Surface Atmospheric
tion only and are not considered standard. Pressure
E1 Specification for ASTM Liquid-in-Glass Thermometers
1.5 This standard does not purport to address all of the E128 Test Method for Maximum Pore Diameter and Perme-
safety concerns, if any, associated with its use. It is the ability of Rigid Porous Filters for Laboratory Use
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter- 3. Terminology
mine the applicability of regulatory limitations prior to use. 3.1 For definitions of terms used in this test method, refer to
See also 7.2.2 for other precautions. Terminology D1356.
1.6 This international standard was developed in accor-
4. Summary of Test Method
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the 4.1 The NO2 is absorbed in an azo-dye-forming reagent
Development of International Standards, Guides and Recom- (1).4 A red-violet color is produced within 15 min, the intensity
mendations issued by the World Trade Organization Technical of which is measured spectrophotometrically at 550 nm.
Barriers to Trade (TBT) Committee. 5. Significance and Use
5.1 Nitrogen dioxide plays an important role in photochemi-
1
cal smog-forming reactions and, in sufficient concentrations, is
This test method is under the jurisdiction of ASTM Committee D22 on Air
deleterious to health, agriculture, materials, and visibility.
Quality and is the direct responsibility of Subcommittee D22.03 on Ambient
Atmospheres and Source Emissions.
3
Current edition approved July 1, 2018. Published July 2018. Originally approved For referenced ASTM standards, visit the ASTM website, www.astm.org, or
in 1958. Last previous edition approved in 2011 as D1607 – 91 (2011). DOI: contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
10.1520/D1607-91R18E01. Standards volume information, refer to the standard’s Document Summary page on
2
Adapted from “Selected Methods for the Measurement of Air Pollutants,” PHS the ASTM website.
4
Publication No 999-AP-11, May 1965. A similar version has been submitted to the The boldface numbers in parentheses refer to a list of references at the end of
Intersociety Committee. this standard.

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 D1607 − 91 (2018)´1
5.2 In combustion processes, significant amounts of nitric 7.2.1 The porosity of the fritted bubbler, as well as the
oxide (NO) may be produced by combination of atmospheric sampling flow rate, affect absorption efficiency. An efficiency
nitrogen and oxygen; at ambient temperatures NO can be of over 95 % may be expected with a flow rate of 0.4 L/min or
converted to NO2 by oxygen and other atmospheric oxidants. less and a maximum pore diameter of 60 µm. Frits having a
Nitrogen dioxide may also be generated from processes involv- maximum pore diameter less than 60 µm will have a higher
ing nitric acid, nitrates, the use of explosives, and welding. efficiency but will require an inconvenient pressure drop for
sampling. Considerably lower efficiencies are obtained with
6. Interferences coarser frits.
6.1 A ten-fold ratio of sulfur dioxide (SO2) to NO2 produces 7.2.2 Measure the porosity of an absorber in accordance
no effect. A thirty-fold ratio slowly bleaches the color to a with Test Method E128. If the frit is clogged or visibly
slight extent. The addition of acetone to the reagent retards the discolored, carefully clean with concentrated chromic-sulfuric
fading by forming a temporary addition product with SO2. This acid mixture, and rinse well with water and redetermine the
permits reading the color intensity within 4 to 5 h (instead of maximum pore diameter. (Warning—Do not dispose of this
the 45 min required without the acetone) without appreciable reagent in the drain system.)
losses. 7.2.3 Rinse the bubbler thoroughly with water and allow to
dry before using.
6.2 A five-fold ratio of ozone to NO2 will cause a small
interference, the maximal effect occurring in 3 h. The reagent 7.3 Mist Eliminator or Gas Drying Tube, filled with acti-
assumes a slightly orange tint. vated charcoal or soda lime is used to prevent damage to the
flowmeter and pump.
6.3 Peroxyacetyl nitrate (PAN) can produce a color change
in the absorbing reagent. However, in ordinary ambient air, the 7.4 Air-Metering Device—A calibrated, glass, variable-area
concentration of PAN is too low to cause any significant error flowmeter, or dry gas meter coupled with a flow indicator
in the measurement of NO2. capable of accurately measuring a flow of 0.4 L/min.
6.4 Interferences may exist from other nitrogen oxides and 7.5 Thermometer—ASTM Thermometer 33C, meeting the
other gases that might be found in polluted air. requirements of Specification E1, will be suitable for most
applications of this test method.
7. Apparatus 7.6 Manometer, accurate to 670 Pa (0.20 in. Hg). See Test
7.1 Sampling Probe—A glass or TFE-fluorocarbon (pre- Methods D3631.
ferred) tube, 6 to 10 mm in diameter provided with a 7.7 Air Pump—A suction pump capable of drawing the
downwind facing intake (funnel or tip). The dead volume of the required sample flow for intervals of up to 60 min is suitable.
system should be kept minimal to avoid losses of NO2 on the 7.8 Spectrophotometer or Colorimeter—An instrument suit-
surfaces of the apparatus. able for measuring the intensity of absorption at 550 nm, with
7.2 Absorber—An all-glass bubbler with a 60-µm maximum stoppered tubes or cuvettes. The wavelength band-width is not
pore diameter frit, similar to that illustrated in Fig. 1. critical for this determination.
7.9 Stopwatch or Timer.

8. Reagents and Materials

8.1 Reagent grade chemicals shall be used in all tests. All
reagents shall conform to the specifications of the Committee
on Analytical Reagents of the American Chemical Society,
where such specifications are available.5 Other grades may be
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, water shall
be deionized water in accordance with Specification D1193 for
Type I or II reagent water. Water shall be free of nitrite.
8.3 Absorbing Reagent—Dissolve 5 g of anhydrous sulfa-
nilic acid (or 5.5 g of sulfanilic acid monohydrate) in almost a
L of water containing 140 mL of glacial acetic acid. Gentle

5
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
FIG. 1 Fritted Bubbler for Sampling Nitrogen Dioxide MD.

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 D1607 − 91 (2018)´1
heating is permissible to speed up the process. To the cooled 10.2.2 Alternate Procedure:
mixture, add 20 mL of the 0.1 % stock solution of N-(1- 10.2.2.1 Standardization is based upon the empirical obser-
naphthyl)-ethylenediamine dihydrochloride, and 10 mL of vation (1, 3)6 that 0.82 mol of NaNO2 produces the same color
acetone. Dilute to 1 L. The solution will be stable for several as 1 mol of NO2. One mL of the working standard solution
months if kept well-stoppered in a brown bottle in the contains 24.6 µg of NaNO2. Since the molecular weight of
refrigerator. The absorbing reagent shall be at room tempera- NaNO2 is 69.1, this is equivalent to (24.6/
ture before use. Avoid lengthy contact with air during prepa- 69.1) × (46.0 ⁄0.82) = 20 µg NO2.
ration and use since discoloration of reagent will result because 10.2.2.2 For convenience, standard conditions are taken as
of absorption of NO2. 101 kPa (29.92 in. Hg) and 25°C, at which the molar gas
8.4 N-(1-Naphthyl)-Ethylenediamine Dihydrochloride, volume is 24.47 L. This is very close to the standard conditions
Stock Solution (0.1 %)—Dissolve 0.1 g of the reagent in 100 used for air-handling equipment–101 kPa (29.92 in. Hg), 70°F
mL of water. Solution will be stable for several months if kept (21.1°C), and 50 % relative humidity, at which the molar gas
well-stoppered in a brown bottle in the refrigerator. volume is 24.76 L, or 1.2 % greater. Ordinarily, the correction
(Alternatively, preweighed amounts of the solid reagent may of the sample volume to these standard conditions is slight and
be stored.) may be omitted, however, for greatest bias, it may be made by
means of the perfect gas equation.
8.5 Sodium Nitrite, Standard Solution (0.0246 g/L)—One
mL of this working solution of sodium nitrite (NaNO2) 10.2.2.3 Add graduated amounts of NaNO2 solution up to 1
produces a color equivalent to that of 20 µg of NO2 in 1 L of mL (measured accurately in a graduated pipet or small buret) to
air at 101 kPa (29.92 in. Hg) and 25°C (see 10.1). Prepare fresh a series of 25-mL volumetric flasks, and dilute to the marks
just before use by dilution from a stock solution containing with absorbing reagent. Mix, allow 15 min for complete color
2.46 g of the reagent grade granular solid per litre. Assay the development, and read the absorbance (see 11.2).
solid reagent. The stock solution is stable for 90 days at room 10.2.2.4 Good results can be obtained with these small
temperature, and for 1 year in a brown bottle under refrigera- volumes of standard solution if they are carefully measured.
tion. Making the calibration solutions up to 25-mL total volume,
rather than the 10-mL volume used for samples, increases
8.6 NO2 Permeation Device—With a permeation rate of 0.1 accuracy.
to 0.2 µg/min.
10.2.2.5 Plot absorbances of the standards against micro-
9. Sampling grams of NO2 per mL of absorbing reagent. The plot follows
Beer’s law. Find the standardization factor, K, as described in
9.1 Sampling procedures are described in Section 11. Dif- 10.2.1.1.
ferent combinations of sampling rates and time may be chosen
to meet specific needs, but sample volumes and air flow rates
11. Procedure
shall be adjusted so that linearity is maintained between
absorbance and concentration over the dynamic range. 11.1 Assemble in order as shown in Fig. 2, a sampling probe
(optional), fritted-tip absorber, mist eliminator or trap,
9.2 See Practice D1357 for sampling guidelines.
flowmeter, and pump. Measure temperature and pressure
10. Calibration and Standardization difference from atmospheric so that corrections for gas volume
may be applied. Keep the flowmeter free from spray or dust.
10.1 Sampling Equipment:
Use ground-glass connections. Butt-to-butt glass connections
10.1.1 Flowmeter—Calibrate flowmeter prior to use, using
with vinyl tubing also may be used for connections without
Practice D3195.
losses if lengths are kept minimal.
10.1.2 Gas Meter—Calibrate gas meter prior to use, using
Test Methods D1071. 11.2 Pipet 10.0 mL of absorbing reagent into a dry fritted
10.2 Analysis: bubbler. Draw an air sample through it at the rate of 0.4 L/min,
10.2.1 Recommended Procedure: long enough to develop sufficient final color (about 10 to 60
10.2.1.1 The recommended procedure for preparation of min). Note the total air volume sampled. Measure and record
calibration standards is by the use of permeation devices (2). air temperature and pressure. After using the bubbler, rinse
Analysis of known concentrations gives calibration curves that well with water and dry. If fritted tip is visibly discolored, clean
simulate all of the operational conditions performed during in accordance with the procedure in 7.2.2.
sampling and analytical procedures. 11.3 After sampling, development of the red-violet color is
10.2.1.2 Using the apparatus described in Practice D3609, complete within 15 min at room temperatures. Transfer to a
generate a gas stream of known concentration. Sample it as stoppered cuvette and read in a spectrophotometer at 550 nm,
described in 11.1, five times, adjusting the sample times so that using distilled water as a reference. Deduct the absorbance of
the amount of NO2 in each collected sample solution covers the the reagent blank from that of the sample.
dynamic range of this test method. Analyze each as described
in 11.2, and prepare a calibration curve using regression
analysis by this test method of least squares. Determine the 6
Supporting data have been filed at ASTM International Headquarters and may
reciprocal of the slope of the line, and denote it as K, the be obtained by requesting Research Report RR:D22-1019. Contact ASTM Customer
volume of NO2, in µL, intercepted at an absorbance of 1.0. Service at [email protected].

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 D1607 − 91 (2018)´1

FIG. 2 Sampling Train

11.4 Colors too dark to read may be quantitatively diluted where:

with unexposed absorbing reagent. Then multiply the mea- K = standardization factor (micrograms of NO2 per mL of
sured absorbance by the dilution factor. absorbing solution/absorbance),
Vr = volume of air sample, L (see 12.1),
12. Calculation 103 = L/m3, and
12.1 Air Volume—Convert the volume of air sampled to the v = volume of absorbing reagent, mL.
volume at standard conditions of 25°C and 101.3 kPA (1 atm), 13. Precision and Bias
as follows:
13.1 The information in this section is derived from the data
V R 5 @ V 3 P/101.3# 3 @ 298.15/T # (1)
collected and analyzed as part of ASTM “Project Threshold”
where: (4).
VR = volume of air sampled at standard conditions, L 13.2 Repeatability (Single-Analyst)—The standard devia-
V = volume of air sampled at ambient conditions, L tion of results obtained by a single analyst on separate samples
P = average ambient atmospheric pressure, kPa from the same flowing air stream is also shown in Fig. 3 as a
T = average ambient atmospheric temperature, K function of the mean value of NO2 determined. The range of
101.3 = pressure of standard atmosphere, kPa, and data used is 10 to 400 µg/m3. Duplicate analyses should be
290.15 = temperature of standard atmosphere, K. considered suspect (95 % confidence level) if they differ by
12.2 Compute the concentrations of NO2 in the sample as more than 2.89 times the standard deviation of repeatability.
follows: 13.3 Reproducibility (Multilaboratory)—The standard de-
NO2 , µg/m 3 5 ~ absorbance 3 K 3 10 3 3 v ! /V (2) viation of single analyses, obtained by analysts from different

FIG. 3 Repeatability and Reproducibility (4)

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 D1607 − 91 (2018)´1
laboratories taking separate samples from the flowing air of NO2 gas to a sample stream and determining the percent
stream, is plotted in Fig. 3 against the mean value of NO2 recovery on the basis of simultaneous analyses of spiked and
determined. The range of data used is 16 to 400 µg/m3. “unspiked” samples. Bias is the difference between the deter-
Duplicate values should be considered suspect (95 % confi- mined recovery and 100 %.
dence level) if they differ by more than 2.81 times the standard 13.5 The method for determining the bias detects only those
deviation of reproducibility. errors that are proportional to the NO2 level; fixed errors are
13.4 Bias—Although the measurement of bias was designed cancelled in the subtraction process. Fixed errors shall refer to
to produce data that described the bias of this test method, no interferences. For this reason, bias is expressed in percentage
generally applicable statements regarding bias can be made. terms rather than in absolute units.
Table 1 gives the average bias found at each of the three 13.6 Based on the data in Table 1, it is clear that the bias
locations used during the interlaboratory test program. The found in Manhattan, NY, is significantly higher than that found
method of evaluating bias consisted of adding a known amount in Los Angeles, CA, or Bloomington, IL. This difference in
bias is not due to the fact that the average NO2 levels found in
TABLE 1 Bias Found in NO2 Measurement Found During Project Manhattan were higher than those found at the other two sites
Threshold (4) (4). The difference in bias may be caused by other interfering
Uncertainty of substances, such as NO or other nitrogen oxides, but these data
Mean Degrees of Mean NO2
Location
Bias Freedom Measured
mean (95 % alone are not conclusive.
Confidence)
Los Angeles, CA +11 % 86 150 µg/m3 ±10 % 14. Keywords
Bloomington, IN −11 % 82 50 µg/m3 ±10 %
New York, NY +35 % 70 210 µg/m3 ±10 % 14.1 ambient atmospheres; analysis; colorimetric analysis;
Griess-Saltzman Reaction; nitrogen dioxide; sampling

REFERENCES

(1) Saltzman, B. E., “Colorimetric Microdetermination of Nitrogen Di- Determination of Nitrogen Dioxide,” Environmental Science and
oxide in the Atmosphere,” Analytical Chemistry, Vol 26, 1954, pp. Technology, Vol 4, 1970, pp. 924–929.
1949–1955. (4) Foster, J. F., and Beatty, G. H., “Final Report on Interlaboratory
(2) O’Keefe, A. E., and Ortman, G. C., “Primary Standards for Trace Gas Cooperation, Study of the Precision and Accuracy of the Measure-
Analysis,” Analytical Chemistry, ANCHA, Vol 38, 1966, pp. ment of Nitrogen Dioxide Content in the Atmosphere Using ASTM
760–763. Method D1607,” Battelle, Columbus Laboratories, Columbus, Ohio,
(3) Scaringelli, F. P., Rosenberg, E., and Rehme, K. A., “Comparison of 1973.
Permeation Devices and Nitrite Ion as Standards for the Colorimetric

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