NITROGEN DIOXIDE IN WORKPLACE ATMOSPHERES (ION CHROMATOGRAPHY)
OSHA Technical Center Salt Lake City, Utah 1. Introduction This method describes the collection and analysis of airborne nitrogen dioxide (NO2). Samples are taken in the breathing zone of workplace personnel and analysis is performed by ion chromatography (IC).
Previous methods of analysis for NO2
involved collection of nitrogen dioxide in bubblers of triethanolamine
(TEA) solution or a Method no. 1.2. Principle A known volume of air is drawn through a sampling tube containing
2NO2 < = > N2O4 N2O4 + (HOCH2CH2)3N --> (HOCH2CH2)3NNO+NO3- (HOCH2CH2)3NNO+NO3- + H2O --> (HOCH2CH2)3NH+NO3- + HNO2 HNO2 --> H+ + NO2- Nitrogen dioxide disproportionates to nitrite and nitrate ions in
the presence of TEA. The nitrite ion
(NO2-) formed from the above
reaction can be analyzed via conventional analytical methods This reaction path requires a stoichiometric factor of 0.5 for the
conversion of gaseous NO2 to
NO2-. Experiments indicate the
proposed factor of 0.5 is seen only when NO2
concentrations are greater than 10 ppm (8.6.,
1.3. Advantages and Disadvantages
1.3.2. After sample preparation, nitrogen dioxide (as nitrite
ion) can also be determined by polarographic or colorimetric
analytical techniques 1.3.3. Nitric oxide (NO) can also be sampled when using a
1.3.4. A disadvantage is the potential interference from large
amounts of soluble chloride salts present in commercial molecular
sieve. Prior to TEA impregnation, the molecular sieve should be
washed with deionized water to remove any soluble chloride salts.
1.3.5. Another disadvantage is the need for a
1.4. Physical Properties (8.11.)
Nitrogen dioxide (CAS No.
1.5. Some sources for potential nitrogen dioxide exposures are:
Nitrogen dioxide and nitric oxide usually exist together in
industrial settings. Nitric oxide is reactive in air and produces
NO2 according to the following equations (8.11.):
2NO + O2
---> 2NO2
d(NO2) / dt =
K(O2)(NO)2
(K is a temperature dependent constant. At 20 °C, K =
14.8 × 109)
An experimental approximation of the NO /
NO2 distribution found in various industrial
operations is shown (8.11.).
The potential for exposure to both NO2
and NO should be considered because NO is easily oxidized to
NO2 and both oxides are likely to coexist in
industrial settings.
1.6. Toxicology
Information listed within this section is a synopsis of current
knowledge of the physiological effects of nitrogen dioxide and is not
intended to be used as a basis for OSHA policy.
Unlike the more soluble gases (e.g. chlorine, ammonia) that
produce almost immediate upper respiratory tract irritation,
symptoms of NO2 exposure may be delayed
for up to 12 hours. The lower solubility of
NO2 provides less warning and increases
the potential for physiological damage when exposures occur.
1.6.2. The symptoms from mild exposures (<50 ppm) are
generalized below
Exposures usually result in an increased susceptibility to
respiratory infections. Changes in pulmonary function are evident
when healthy subjects are exposed to 2 to 3 ppm
NO2 and can occur at far lower
concentrations in asthmatic subjects.
More severe exposures (>50 ppm) are characterized by pulmonary
edema, cyanosis, bronchiolitis obliterans, respiratory failure and
death.
1.6.3. The LC50 (Lethal Concentration
50) for a 2. Range, Detection Limit and Sensitivity (8.8.)
1 µg NO2 = 0.63 µg NO2- At NO2 concentrations above 10 ppm, the
conversion factor has been shown to decrease, approaching a value of
0.5 2.2. The qualitative detection limit was 0.08 µg/mL or 0.24 µg (as
NO2-) when using a
2.3. The quantitative detection limit was 0.23 µg/mL or 0.69 µg (as
NO2-) when using a
2.4. The sensitivity of the analytical method was calculated from
the slope of a linear working range curve (1 to 20 µg/mL nitrite). The
sensitivity for this curve was 222,720 area units per 1 µg/mL (a
3. Method Performance (8.8.)
3.2. The collection efficiency at approximately 2 times the PEL was 97.3%. Samples were collected at a generation concentration of 9.45 ppm NO2 for 15 min. Sample generation conditions were 50% RH and 25 °C. 3.3. Breakthrough tests were performed at 30% RH and a concentration of 21 ppm. Samples were collected for 15 min at a flow rate of 0.18 L/min. Breakthrough of NO2 into a second sorbent tube at these parameters was 1.6% NO2. This is within an acceptable limit of <5% breakthrough. 3.4. Samples can be stored at ambient (20 to 25 °C) laboratory conditions for a period of at least 29 days. Storage stability results show the mean of samples analyzed after 29 days was within ±5% of the mean of samples analyzed after one day of storage. Samples were stored on a laboratory bench. 4. Interferences
4.2. Any compound having the same retention time as nitrite, when using the operating conditions described, is an interference. 4.3 Interferences may be minimized by changing the eluent concentration, and/or pump flow rate. 4.4. If there is reason to suspect an unresolvable interference,
alternate polarographic or colorimetric methods can be used 4.5. Contaminant anions normally found in molecular sieve, such as NO3-, SO42-, and PO43-, do not interfere. Large amounts (greater than 4 to 5 µg/mL) of Cl- can interfere. 5. Sampling
5.1.2. Two types of sampling tubes are commercially available (All molecular sieve used for tube packing should be washed with deionized water before impregnation with TEA):
For further information regarding sampling for NO, see reference 8.10. 5.1.3. A stopwatch and bubble tube or meter are used to calibrate
pumps. A sampling tube or device is placed 5.1.4. Various lengths of Tygon tubing are used to connect sampling tubes to pumps. 5.2. Sampling Procedure
Note: If sampling for both NO2 and NO is necessary, two separate pumps and sampling devices should be used. The differences in OSHA Final Rule PELs (NO2 is a STEL and NO is a TWA PEL) and flow rates dictates a need for a singular assessment of NO2. Nitric oxide is collected at a flow rate not to exceed 0.025 L/min
5.2.1. Calibrate the sampling pumps at either recommended flow rate listed in Section 5.2.4. 5.2.2. Connect the sampling tube or device to the pump. The different sampling schemes are listed below:
5.2.3. Place the sampling tube or device in the breathing zone of the employee. 5.2.4. Sample with
5.2.5. The minimum recommended total air volume for collecting NO2 is 3 L. 6. Analysis
6.1.2. Observe laboratory safety regulations and practices. 6.1.3. Sulfuric acid (H2SO4) can cause severe burns. Wear protective gloves and eyewear when using concentrated H2SO4.
6.2.2. Automatic sampler (Model 6.2.3. Data processing system: Ion chromatograph interfaced to a data reduction and control system (AutoIon 400 or 450 System, Dionex). 6.2.4. Printer. 6.2.5. Separator and guard columns, anion (Model
6.2.6. Micromembrane suppressor, anion (Model
6.2.7. Disposable syringes (1 mL) and pre-filters.
Note: Some syringe
6.2.8. Erlenmeyer flasks, 6.2.9. Miscellaneous volumetric glassware: Micropipettes, volumetric flasks, graduated cylinders, and beakers. 6.2.10. Analytical balance (0.01 mg). 6.3. Reagents - All chemicals should be at least reagent grade.
6.3.2. Triethanolamine
[(HOCH2CH2)3N]
sodium bicarbonate (NaHCO3) sulfuric acid (H2SO4, concentrated 95 to 98%) sodium nitrite (NaNO2) 6.3.3. Liquid desorber (1.5% TEA): Dissolve 15 g TEA in a 6.3.4. Eluent (2.0 mM Na2CO3/1.0 mM NaHCO3): Dissolve 0.848 g Na2CO3 and 0.336 g NaHCO3 in 4.0 L of DI H2O. 6.3.5. Regeneration solution (0.02 N H2SO4): Place 1.14 mL concentrated
H2SO4 into a
6.3.6. Nitrite stock standard (1,000 µg/mL): Dissolve 1.5000 g NaNO2 and dilute to
the mark in a 6.3.7. Nitrite standard (100 µg/mL): Dilute 10 mL of the 1,000 µg/mL nitrite stock standard to 100 mL with liquid desorber. Prepare monthly. 6.3.8. Nitrite standard (10 µg/mL): Dilute 10 mL of the 100 µg/mL nitrite stock standard to 100 mL with liquid desorber. Prepare weekly. 6.3.9. Nitrite standard (1 µg/mL): Dilute 10 mL of the 10 µg/mL nitrite stock standard to 100 mL with liquid desorber. Prepare daily. 6.4. Working Standard Preparation
6.4.2. Pipette appropriate aliquots of standard solutions
(prepared in Section 6.3.)
into 6.4.3. Pipette a 0.5- to 0.6-mL portion of each standard solution
into separate automatic sampler vials. Place a 6.4.4. Prepare a reagent blank from the liquid desorber solution. 6.5. Sample Preparation
Note: For NO sample analysis and result calculations, see reference 8.10.
6.5.2. Carefully remove the glass wool plugs from the sample
tubes, making sure that no sorbent is lost in the process. If the
6.5.3. Add 3 mL of liquid desorber to each flask or vial, shake vigorously for about 30 s and allow the solution to settle for at least 1 h. 6.5.4. If the sample solutions contain suspended particulate,
remove the particles using a 6.5.5. Load the automatic sampler with labeled samples, standards and blanks. 6.6. Analytical Procedure Set up the ion chromatograph and analyze the samples in accordance with the SOP (8.15.). Typical operating conditions for equipment mentioned in Section 6.2. are listed below.
7. Calculations
7.2. Prepare a 7.3. Blank correct the samples by subtracting the g/mL NO2- found in the blank from the µg/mL NO2- found in the samples. If a different solution volume was used for blanks and samples, use total micrograms NO2- to blank correct. 7.4. Calculate the concentration of nitrogen dioxide in each air
sample in ppm. A
The conversion of gaseous NO2 to
NO2- is
Below 10 ppm NO2
From 0 to 10 ppm, the average relationship has been
experimentally determined to be 1 µg NO2 (gas) = 0.63 µg NO2- or conversely: 1 µg NO2- = 1.587 µg NO2 (gas) Simplifying the equation and using a
Above 10 ppm NO2
Above 10 ppm NO2, the expected
stoichiometric factor of 0.5 mole of nitrite to 1 mole of nitrogen
dioxide gas is seen (8.6.,
7.5. Reporting Results Report all results to the industrial hygienist as ppm nitrogen dioxide. 8. References
8.2. Saltzman, B.E.: Colorimetric Microdetermination of Nitrogen Dioxide in the Atmosphere. Anal. Chem. 26:1949 (1954). 8.3. Blacker, J.H.: Triethanolamine for Collecting Nitrogen Dioxide in the TLV Range. Am. Ind. Hyg. Assoc. J. 34:390 (1973). 8.4. Occupational Safety and Health
Administration Analytical Laboratory: OSHA Analytical Methods
Manual 8.5. Chang, S.K., R. Kozenianskas and G.W.
Harrington: Determination of Nitrite Ion Using Differential Pulse
Polarography. Anal. Chem. 8.6. Gold, A.: Stoichiometry of Nitrogen
Dioxide Determination in Triethanolamine Trapping Solution. Anal.
Chem. 8.7. Vinjamoori, D.V. and
8.8. Occupational Safety and Health
Administration Technical Center: Nitrogen Dioxide Backup Report
8.9. Occupational Safety and Health
Administration Technical Center: Nitric Oxide Backup Data
Report 8.10. Occupational Safety and Health
Administration Technical Center: Nitric Oxide in Workplace
Atmospheres, by J.C. Ku 8.11. National Institute for Occupational
Safety and Health: Criteria for a Recommended
Standard...Occupational Exposure to Oxides of Nitrogen (Nitrogen
Dioxide and Nitric Oxide) (HEW/NIOSH Pub. No.
8.12. Berkow, R. and JH. Talbott, ed.:
The Merck Manual. 13th ed. Rahway, NJ: Merck, Sharp and Dohme
Research Laboratories, 1977. pp. 8.13. Proctor, N.B. and J.P. Hughes:
Chemical Hazards of the Workplace. Philadelphia, PA: J.B.
Lippincott Company, 1978. pp. 8.14. American Conference of Governmental
Industrial Hygienists: Documentation of the Threshold Limit
Values and Bioloical Exposure Indices. 5th ed. Cincinnati, OH:
ACGIH, 1986. pp. 8.15. Occupational Safety and Health
Administration Technical Center: Standard Operating
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