descriptive use only and do not constitute endorsements by USDOL-OSHA. Similar products from other sources can be substituted.
OSHA Technical Center Salt Lake City, Utah 1. Introduction This method describes the collection and analysis of airborne nitric oxide (NO). Samples are taken in the breathing zone of workplace personnel and analyses are performed by ion chromatography (IC).
Previous methods involved oxidation of NO to nitrogen dioxide (NO2) using a chromate compound and subsequent conversion of NO2 to nitrite using triethanolamine-impregnated molecular sieve (TEA-IMS) sampling tubes. Common methods used a combination sampling tube and NO was determined colorimetrically (as NO2-) using a modified Griess-Saltzman reaction (8.1.-8.2.). This method, like most colorimetric procedures, can have significant interferences. A differential pulse polarographic (DPP) method (8.3.) was later developed to improve analytical sensitivity and decrease the potential for interferences. The sensitivity of the DPP method was more than adequate for measuring workplace concentrations of NO; however, the nitrite ion is unstable in the pH range (pH 1-2) used during analysis (8.4.). Method no. ID-190 uses the TEA-IMS sampling tube/chromate oxidizer approach. Samples are analyzed by IC. 1.2. Principle A known volume of air is drawn through the sampling device which
captures any nitrogen dioxide (NO2) in the sampled air and
also converts any NO to nitrite ion (NO2-). The
sampling device consists of three glass tubes connected in series. The
front and back tubes contain TEA-IMS, the middle or oxidizer tube
contains an inert carrier impregnated with a chromate salt. The first
TEA-IMS tube does not capture NO; this tube is only used to capture
and convert to The conversion mechanism of NO2 gas to NO2- has been proposed by Gold (8.5.). The following is Gold's proposal for the reaction of equivalent amounts of NO2 and TEA in an aqueous solution:
Nitrogen dioxide disproportionates to NO2- and nitrate (NO3-) in the presence of TEA and water. The NO2- formed from the above reaction can be analyzed via conventional analytical methods (8.1.-8.4., 8.6.-8.7.) including IC. Unfortunately NO3- is found in the commercial TEA-IMS sorbent as a significant contaminant. This contamination ruled out further research to also measure this NO2-TEA disproportionation product by IC. This reaction path requires a stoichiometric factor of 0.5 for the
conversion of 1.3. Advantages and Disadvantages
1.3.2. The sampling device can be used to simultaneously collect NO and NO2; however, results for NO2 may not reflect short-term exposures (see Section 5.2. for more details). 1.3.3. The analysis is simple, rapid, easily automated and is specific for NO2-. 1.3.4. After analytical sample preparation, NO exposures (as nitrite ion) can also be determined by colorimetric or polarographic analytical techniques (8.1.-8.3.). 1.3.5. 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 (DI H2O) to remove any soluble chloride salts. 1.3.6. Another disadvantage is the need for a concentration-dependent conversion factor when calculating results. 1.4. Physical properties (8.10., 8.11.) Nitric oxide (CAS No. 10102-43-9), one of several oxides of nitrogen, is a colorless gas. A deep blue color is usually noted when NO is in the liquid state and a bluish-white color when solid. Other physical characteristics of NO are:
*Nitrogen monoxide has also been used as a synonym for nitrous oxide (N2O). 1.5. Some industrial sources for potential nitric oxide exposures are:
arc or gas welding (esp. confined space operations) electroplating plants food and textile bleaching jewelry manufacturing metal nitrosyl carbonyl production nitric acid production nitrogen fertilizer production nitro-explosive production nitrosyl halide production pickling plants 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 (8.10.):
(K is a temperature dependent constant. At 20 °C, K = 14.8 X 109) An experimental approximation of the NO/NO2 distribution found in various industrial operations is shown (8.10.):
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 (8.11.-8.14.)
Information listed within this section is a synopsis of current knowledge of the physiological effects of nitric oxide and is not intended to be used as a basis for OSHA policy.
1.6.1. Nitric oxide is classified as a respiratory irritant. The main route of exposure is inhalation; however, physiological damage can also occur eyes or skin. The term "silo-fillers' disease" has been used to describe exposure to nitric as well as other nitrogen oxides. The national population-at-risk for exposure to nitrogen oxides has been estimated by NIOSH to be approximately 950,000 employees (National Occupational Hazard Survey, 1972-74). When encountering either NO or NO2 at high concentrations, both species will usually be present. Little scientific data is available regarding exposures to NO only. The majority of collected data concerns exposure to NO2 since NO appears to be only one-fifth as toxic as NO2 at low concentrations. Symptoms immediately following NO exposure are usually mild or not apparent. Severe symptoms may not appear up to 72 hours after exposure. 1.6.2. Mild exposures to NO can result in symptoms such as:
More severe exposures (>100 ppm) are characterized by pulmonary edema , cyanosis, pneumonia, severe methemoglobinemia, respiratory failure, and death. 1.6.3. The IDLH (Immediately Dangerous to Life or Health) concentration is 100 ppm NO. The LCLo (Lethal Concentration - Low) for inhalation by mice is 320 ppm. 1.6.4.Mechanism for toxicity: Nitric oxide is slightly soluble in water and forms nitrous and nitric acid. This reaction occurs with lung tissue and produces respiratory irritation and edema. Alkali present in the lung tissue neutralizes the nitrous and nitric acids to nitrite and nitrate salts which are then absorbed into the bloodstream. The end result is the formation of nitroxy-hemoglobin complexes and methemoglobin in the circulatory system. The formation of hemoglobin complexes is thought to contribute to the toxicity of NO but is not considered to be the sole source of the toxic reaction. The respiratory damage from nitrous and nitric acid appears to be more significant. 2. Range, Detection Limit and Sensitivity The analytical parameters and limits of this method have been previously described (8.8.). Brief descriptions are provided in Section 3 below. 3. Method Performance This method was evaluated in the concentration range of 13.0 to 50.5 ppm. Air volumes of approximately 6 L and flow rates of about 0.025 L/min were used. Samples were collected for 240 min. Sample results were calculated using the concentration-dependent conversion factors mentioned in Section 7. Listed on the cover page (CVT, bias, overall error) and below are evaluation data taken from the backup report (8.9.).
4. Interferences
4.2. Any compound that has 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, column characteristics, and/or pump flow rate. 4.4. If there is an unresolvable interference, alternate polarographic or colorimetric methods may be used (8.1.-8.3.). 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
2) The second (oxidizer) tube converts NO to NO2 and contains approximately 1 g of a chromate compound impregnated on an inert carrier. 3) The last 400 mg TEA-IMS packed tube collects the converted NO2. All molecular sieve used for tube packing must be washed with DI H2O before impregnation with TEA. The dimensions of each TEA-IMS tube are 7-mm o.d., 5-mm i.d., and 70-mm long. A 3-mm portion of silylated glass wool is placed in the front and rear of each tube. The dimensions of the oxidizer tube are 7-mm o.d., 5-mm i.d., and 110-mm long . When the three tubes are connected in series as shown below, NO2 and NO can be collected simultaneously. The first TEA-IMS tube must be in place to prevent the collection of NO2 by the second TEA-IMS tube.
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5.1.3. A stopwatch and bubble tube or meter are used to calibrate pumps. A sampling device is placed in-line during flow rate calibration. 5.1.4. Various lengths of Tygon tubing are used to connect the sampling tubes and pump together. 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 exposure limits [the NO2 PEL is a 1 ppm Short-Term Exposure Limit (8.15.). Nitric oxide is a TWA PEL.] and flow rates dictates a need for a separate assessment of NO2. Nitric oxide is collected at a 0.025 L/min pump flow rate. Nitrogen dioxide can be collected at this flow rate; however, a longer sampling time will be necessary to collect a detectable amount of NO2 than for a short-term measurement. Concentrations of NO2 may vary in the workplace during a longer sampling period.
5.2.2. Connect the sampling device to the pump. The different sampling schemes are listed:
b) Sampling for both NO and NO2: The three-tube device is used. The device must be assembled as shown above. Label the first tube "NO2". Label the tube following the oxidizer section "NO". 5.2.3. Place the sampling tube or device in the breathing zone of the employee. 5.2.4. Collect the sample at the listed flow rates and sampling times:
b) For both NO and NO2: 0.025 L/min for 4 h per sample (Note: The front ube of the three-tube device can be submitted for NO2 analysis; however, analytical results may not represent short-term exposures). 5.2.5. The maximum recommended air volume is 6 L per NO sample. Take enough samples for NO to cover the workshift.
6. Analysis
6.1.2. Observe laboratory safety regulations and practices. 6.1.3. Sulfuric acid (H2SO4) can cause severe burns. Wear protective eyewear, gloves, and labcoat when using concentrated H2SO4. 6.2. Equipment
6.2.2. Automatic sampler (Model AS-1, Dionex) and 0.5 mL sample vials. 6.2.3. Laboratory automation system: Ion chromatograph interfaced to a data reduction and control system (AutoIon 400 or 450, Dionex). 6.2.4. Micromembrane suppressor, anion (Model AMMS-1, Dionex). 6.2.5. Separator and guard columns, anion (Model HPIC-AS4A and AG4A, Dionex). 6.2.6. Disposable syringes (1 mL) and filters.
6.2.8. Miscellaneous volumetric glassware: Micropipettes, volumetric flasks, graduated cylinders, and beakers. 6.2.9. Analytical balance (0.01 mg). 6.3. Reagents - All chemicals should be at least reagent grade.
6.3.2. Triethanolamine
[(HOCH2CH2)3N] 6.3.3. Liquid desorber (1.5% TEA): 6.3.4. Eluent (2.0 mM Na2CO3/1.0 mM
NaHCO3): 6.3.5. Regeneration solution (0.02 N
H2SO4): 6.3.6. Nitrite stock standard (1,000 µg/mL): 6.3.7. Nitrite standard (100 µg/mL): 6.3.8. Nitrite standard (10 µg/mL): 6.3.9. Nitrite standard (1 µg/mL): 6.4. Working Standard Preparation
* Already prepared in Section 6.3. 6.4.2. Pipette appropriate aliquots of standard solutions (prepared in Section 6.3.) into 10-mL volumetric flasks and dilute to volume with liquid desorber. 6.4.3. Pipette a 0.5- to 0.6-mL portion of each standard solution into separate automatic sampler vials. Place a 0.5-mL filter cap into each vial. The large exposed filter portion of the cap should face the standard solution. 6.4.4. Prepare a reagent blank from the liquid desorber solution. 6.5. Sample Preparation
6.5.2. Discard the oxidizer tube appropriately. This tube contains a chromate salt and may be considered a hazardous waste. Local regulations or restrictions should be consulted before disposal. 6.5.3. Clean the 25-mL Erlenmeyer flasks or scintillation vials by rinsing with DI H2O. 6.5.4. Carefully remove the glass wool plugs from the sample tubes, making sure no sorbent is lost in the process. Transfer each TEA-IMS section to individually labeled 25-mL Erlenmeyer flasks or scintillation vials. 6.5.5. Add 10 mL of liquid desorber to each flask containing NO samples, shake vigorously for about 30 s. Allow the solution to stand for at least 1 h. (Note: Add 3 mL to NO2 samples - see reference 8.8. for further details regarding NO2 analysis and result calculations) 6.5.6. If the sample solutions contain suspended particulate, remove the particles using a pre-filter and syringe. Fill the 0.5-mL automatic sampler vials with sample solutions and push a filtercap into each vial. Label the vials. 6.5.7. Load the automatic sampler with labeled samples, standards and blanks. 6.6. Analytical Procedure Set up the ion chromatography and analyze the samples and standards in accordance with the SOP (8.16.). Typical operating conditions for equipment mentioned in Section 6.2. are listed below.
7. Calculations
7.2. Prepare a concentration-response curve by plotting the concentration of the standards in µg/mL (or µg/sample if the same volumes are used for samples and standards) versus peak areas or peak heights. Calculate sample concentrations from the curve and blank correct all samples. 7.3. The concentration of NO in each air sample is expressed in ppm and is calculated as:
Where:
*The conversion of gaseous NO2 to NO2- is concentration dependent. The final concentration of NO should be calculated using whichever example given below is appropriate:
From 0 to 10 ppm, the average ratio has been experimentally determined to be (8.1.-8.3., 8.5.-8.9.):
or conversely:
Simplifying the equation and calculating the ppm NO using a 10-mL sample volume gives:
Above 10 ppm NO, the expected stoichiometric factor of 0.5 mole of
nitrite to 1 mole of nitrogen dioxide gas is seen (8.5., 8.8.-8.9.).
Therefore, the following calculation should be used for sample results
above 10 ppm and a
7.4. Reporting Results Report all results to the industrial hygienist as ppm nitric oxide. 8. References
8.2. Willey, M.A., C.S. McCammon, Jr., and L.J. Doemeny: A
Solid Sorbent Personal Sampling Method for the Simultaneous Collection
of Nitrogen Dioxide and Nitric Oxide in Air. Am. Ind. Hyg. Assoc.
J. 38 8.3. Occupational Safety and Health Administration Analytical
Laboratory: OSHA Analytical Methods Manual
(USDOL/OSHA-SLCAL Method No. ID-109). Cincinnati, OH: American
Conference of Governmental Industrial Hygienists (Pub. No. ISBN:
8.4. Chang, S.K., R. Kozenianskas, and G.W. Harrington:
Determination of Nitrite Ion Using Differential Pulse Polarography.
Anal. Chem. 49: 8.5. Gold, A.: Stoichiometry of Nitrogen Dioxide Determination in Triethanolamine Trapping Solution. Anal. Chem. 49:1448-50 (1977). 8.6. Blacker, J.H.: Triethanolamine for Collecting Nitrogen Dioxide in the TLV Range. Am. Ind. Hyg. Assoc. J. 34:390 (1973). 8.7. Saltzman, B.E.: Colorimetric Microdetermination of Nitrogen Dioxide in the Atmosphere. Anal. Chem. 26:1949 (1954). 8.8. Occupational Safety and Health Administration Technical
Center: Determination of Nitrogen Dioxide in Workplace
Atmospheres (Ion Chromatography) by J.C. Ku
8.9. Occupational Safety and Health Administration Technical Center: Nitric Oxide Backup Data Report (ID-190) by J.C. Ku. Salt Lake City, UT. Revised 1991. 8.10. National Institute for Occupational Safety and Health: Criteria for a Recommended Standard...Occupational Exposure to Oxides of Nitrogen (Nitrogen Dioxide and Nitric Oxide) (DHEW/NIOSH Pub. No. 76-149). Cincinnati, OH: NIOSH, 1976. 8.11. Braker, W. and A.L. Mossman: Matheson Gas Data
Book. 5th ed. East Rutherford, NJ: Matheson Gas Products, 1971.
pp. 8.12. Merchant, J.A. Ed.: Occupational Respiratory
Diseases (DHHS/NIOSH Pub. No. 86-102). Cincinnati, OH: NIOSH,
1986. pp. 8.13. American Conference of Governmental Industrial
Hygienists: Documentation of the Threshold Limit Values and
Biological Exposure Indices. 5th ed. Cincinnati, OH: ACGIH, 1986.
pp. 8.14. Specialty Gas Department: Material Safety Data Sheet for Nitric Oxide. Allentown, PA: Air Products, 1982. 8.15. "Air Contaminants; Final Rule": Federal Register 54:12
(19 Jan. 1989). pp. 8.16. Occupational Safety and Health Administration Technical Center: Standard Operating Procedure - Ion Chromatography. Salt Lake City, UT. In progress (unpublished).
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