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This guideline summarizes pertinent information about tetranitromethane for workers and employers as well as for physicians, industrial hygienists, and other occupational safety and health professionals who may need such information to conduct effective occupational safety and health programs. Recommendations may be superseded by new developments; readers are therefore advised to regard these recommendations as general guidelines and to determine periodically whether new information is available.
SUBSTANCE IDENTIFICATION * Formula C(NO(2))(4) * Structure (For Structure, see paper copy) * Synonyms TNM; Tetan. * Identifiers
Tetranitromethane is a colorless to pale yellow liquid; its vapor has an acrid, pungent odor. Tetranitromethane is a weak but highly sensitive explosive. CHEMICAL AND PHYSICAL PROPERTIES * Physical data
The National Fire Protection Association has not assigned a flammability rating to tetranitromethane. Other sources (such as the Hazardous Materials Identification System (HMIS) developed by the National Paint and Coatings Association (NPCA)) assign a flammability rating of 3 (serious hazard) to tetranitromethane.
No quantitative data are available on the odor threshold for tetranitromethane. For the purpose of respirator selection, this substance is therefore considered to have inadequate odor warning properties. * Eye irritation properties The eye irritation threshold for tetranitromethane is below 1 ppm. EXPOSURE LIMITS The current Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) for tetranitromethane is 1 part per million (ppm) parts of air (8 milligrams per cubic meter (mg/m3)) as an 8-hour timeweighted average (TWA) concentration [29 CFR 1910.1000, Table Z-1-A]. The National Institute for Occupational Safety and Health (NIOSH) has not issued a recommended exposure limit (REL) for tetranitromethane; however, NIOSH concurs with the PEL established for this substance by OSHA [NIOSH 1988]. The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned tetranitromethane a threshold limit value (TLV) of 1 ppm (8 mg/m3) as a TWA for a normal 8-hour workday and a 40-hour workweek [ACGIH 1991, p. 35]. The OSHA and ACGIH limits are based on the risk of respiratory and other irritant effects associated with exposure to tetranitromethane. HEALTH HAZARD INFORMATION * Routes of exposure Exposure to tetranitromethane can occur via inhalation, ingestion, and eye or skin contact. * Summary of toxicology
In the event of an emergency, remove the victim from further exposure, send for medical assistance, and initiate the following emergency procedures:
EXPOSURE SOURCES AND CONTROL METHODS The following operations may involve tetranitromethane and lead to worker exposures to this substance:
Workers who may be exposed to chemical hazards should be monitored in a systematic program of medical surveillance that is intended to prevent occupational injury and disease. The program should include education of employers and workers about work-related hazards, placement of workers in jobs that do not jeopardize their safety or health, early detection of adverse health effects, and referral of workers for diagnosis and treatment. The occurrence of disease or other work-related adverse health effects should prompt immediate evaluation of primary preventive measures (e.g., industrial hygiene monitoring, engineering controls, and personal protective equipment). A medical monitoring program is intended to supplement, not replace, such measures. To place workers effectively and to detect and control work-related health effects, medical evaluations should be performed (1) before job placement, (2) periodically during the period of employment, and (3) at the time of job transfer or termination. * Preplacement medical evaluation Before a worker is placed in a job with a potential for exposure to tetranitromethane, the examining physician should evaluate and document the worker's baseline health status with thorough medical, environmental, and occupational histories, a physical examination, and physiologic and laboratory tests appropriate for the anticipated occupational risks. These should concentrate on the function and integrity of the eyes, skin, and respiratory system. Medical monitoring for respiratory disease should be conducted using the principles and methods recommended by NIOSH and the American Thoracic Society. A preplacement medical evaluation is recommended to assess an individual's suitability for employment at a specific job and to detect and assess medical conditions that may be aggravated or may result in increased risk when a worker is exposed to tetranitromethane at or below the prescribed exposure limit. The examining physician should consider the probable frequency, intensity, and duration of exposure as well as the nature and degree of any applicable medical condition. Such conditions (which should not be regarded as absolute contraindications to job placement) include a history and other findings consistent with diseases of the eyes, skin, or respiratory system. * Periodic medical examinations and biological monitoring Occupational health interviews and physical examinations should be performed at regular intervals during the employment period, as mandated by any applicable Federal, State, or local standard. Where no standard exists and the hazard is minimal, evaluations should be conducted every 3 to 5 years or as frequently as recommended by an experienced occupational health physician. Additional examinations may be necessary if a worker develops symptoms attributable to tetranitromethane exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of tetranitromethane on the eyes, skin, or respiratory system. Current health status should be compared with the baseline health status of the individual worker or with expected values for a suitable reference population. Biological monitoring involves sampling and analyzing body tissues or fluids to provide an index of exposure to a toxic substance or metabolite. No biological monitoring test acceptable for routine use has yet been developed for tetranitromethane. * Medical examinations recommended at the time of job transfer or termination The medical, environmental, and occupational history interviews, the physical examination, and selected physiologic or laboratory tests that were conducted at the time of placement should be repeated at the time of job transfer or termination to determine the worker's medical status at the end of his or her employment. Any changes in the worker's health status should be compared with those expected for a suitable reference population. WORKPLACE MONITORING AND MEASUREMENT PROCEDURES Determination of a worker's exposure to airborne tetranitromethane is made using a midget impinger containing 15 milliliters of ethyl acetate. Samples are collected at a maximum flow rate of 1.0 liter per minute until a maximum air volume of 250 liters is collected. Analysis is conducted by gas chromatography using a nitrogen phosphorus detector. This method has a sampling and analytical error of 0.13 and is described in NIOSH Method No. 5224 [NIOSH 1977]. PERSONAL HYGIENE PROCEDURES If tetranitromethane contacts the skin, workers should flush the affected areas immediately with plenty of water for 15 minutes, followed by washing with soap and water. Clothing contaminated with tetranitromethane should be removed immediately, and provisions should be made for the safe removal of the chemical from the clothing. Persons laundering the clothes should be informed of the hazardous properties of tetranitromethane, particularly its potential to cause burns of the skin. A worker who handles tetranitromethane should thoroughly wash hands, forearms, and face with soap and water before eating, using tobacco products, or using toilet facilities. Workers should not eat, drink, or use tobacco products in areas where tetranitromethane or a solution containing tetranitromethane is handled, processed, or stored. STORAGE Tetranitromethane should be stored in a cool, dry, well-ventilated area in tightly sealed containers that are labeled in accordance with OSHA's Hazard Communication Standard. Bulk storage facilities must be of explosion-proof design. Containers of tetranitromethane should be protected from physical damage and should be stored separately from hydrocarbons, strong oxidizing agents, radiant heat, sparks, and open flame. Only nonsparking tools may be used to handle tetranitromethane. To prevent static sparks, containers should be grounded and bonded for transfers. Because containers that formerly contained tetranitromethane may still hold product residues, they should be handled appropriately. SPILLS AND LEAKS In the event of a spill or leak involving tetranitromethane, persons not wearing protective equipment and clothing should be restricted from contaminated areas until cleanup has been completed. The following steps should be undertaken following a spill or leak:
The Environmental Protection Agency's (EPA's) regulatory requirements for emergency planning, community right-to-know, and hazardous waste management may vary over time. Users are therefore advised to determine periodically whether new information is available. * Emergency planning requirements Employers owning or operating a facility at which there are 500 pounds or more of tetranitromethane must comply with EPA's emergency planning requirements. * Reportable quantity requirements (releases of hazardous substances) A hazardous substance release is defined by EPA as any spilling, pumping, pouring, emitting, emptying, discharging, injecting, escaping, leaching, dumping, or disposing into the environment (including the abandonment or discarding of containers) of hazardous substances. In the event of a release that is above the reportable quantity for that chemical, employers are required by the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) to notify the proper Federal, State, and local authorities. The reportable quantity for tetranitromethane is 10 pounds. If an amount equal to or greater than this quantity is released within a 24-hour period, CERCLA requires employers to notify the National Response Center IMMEDIATELY at (800) 424-8802 (in Washington, D.C. at (202) 426-2675), and 40 CFR Part 355.40 requires employers to notify (1) the State emergency response commission of any State likely to be affected by the release, and (2) the community emergency coordinator of the local emergency planning committee (or relevant local emergency response personnel) and to identify any area likely to be affected by the release. * Community right-to-know requirements Employers are not required by Section 313 of the Superfund Amendments and Reauthorization Act (SARA) to submit a Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of tetranitromethane emitted or released from their facility annually. * Hazardous waste management requirements EPA considers a waste to be hazardous if it exhibits any of the following characteristics: ignitability, corrosivity, reactivity, or toxicity, as defined in 40 CFR 261.21-261.24. Under the Resource Conservation and Recovery Act (RCRA), EPA has specifically listed many chemical wastes as hazardous. Tetranitromethane is listed as a hazardous waste under RCRA and has been assigned EPA Hazardous Waste No. P112. This substance has been banned from land disposal and may be treated by fuel substitution, chemical oxidation, chemical reduction, or incineration. Tetranitromethane also may be disposed of in an organometallic or organic lab pack that meets the requirements of 40 CFR 264.316 or 265.316. Providing more information about the removal and disposal of specific chemicals is beyond the scope of this guideline. EPA, U.S. Department of Transportation, and State and local regulations should be followed to ensure that removal, transport, and disposal of this substance are conducted in accordance with existing regulations. To be certain that chemical waste disposal meets EPA regulatory requirements, employers should address any questions to the RCRA hotline at (202) 382-3000 (in Washington, D.C.) or toll-free at (800) 424-9346 (outside Washington, D.C.). In addition, relevant State and local authorities should be contacted for information on any requirements they may have for the waste removal and disposal of this substance. RESPIRATORY PROTECTION * Conditions for respirator use Good industrial hygiene practice requires that engineering controls be used where feasible to reduce workplace concentrations of hazardous materials to the prescribed exposure limit. However, some situations may require the use of respirators to control exposure. Respirators must be worn if the ambient concentration of tetranitromethane exceeds prescribed exposure limits. Respirators may be used (1) before engineering controls have been installed, (2) during work operations such as maintenance or repair activities that involve unknown exposures, (3) during operations that require entry into tanks or closed vessels, and (4) during emergency situations. If the use of respirators is necessary, the only respirators permitted are those that have been approved by NIOSH and the Mine Safety and Health Administration (MSHA). * Respiratory protection program Employers should institute a complete respiratory protection program that, at a minimum, complies with the requirements of OSHA's Respiratory Protection Standard. Such a program must include respirator selection (see Table 1), an evaluation of the worker's ability to perform the work while wearing a respirator, the regular training of personnel, fit testing, periodic workplace monitoring, and regular respirator maintenance, inspection, and cleaning. The implementation of an adequate respiratory protection program (including selection of the correct respirator) requires that a knowledgeable person be in charge of the program and that the program be evaluated regularly. For additional information on the selection and use of respirators and on the medical screening of respirator users, consult the NIOSH Respirator Decision Logic and the NIOSH Guide to Industrial Respiratory Protection. Table 1 lists the respiratory protection that NIOSH recommends for workers exposed to tetranitromethane. The recommended protection may vary over time because of changes in the exposure limit for tetranitromethane or in respirator certification requirements. Users are therefore advised to determine periodically whether new information is available. PERSONAL PROTECTIVE EQUIPMENT Protective clothing (gloves, boots, aprons, and gauntlets, as necessary) should be worn to prevent any possibility of skin contact with tetranitromethane. Chemical protective clothing should be selected on the basis of available performance data, manufacturers' recommendations, and evaluation of the clothing under actual conditions of use. No reports have been published on the resistance of various protective clothing materials to tetranitromethane permeation. If permeability data are not readily available, protective clothing manufacturers should be requested to provide information on the best chemical protective clothing for workers to wear when they are exposed to tetranitromethane. If tetranitromethane is dissolved in an organic solvent, the permeation properties of both the solvent and the mixture must be considered when selecting personal protective equipment and clothing. Safety glasses, goggles, or face shields should be worn during operations in which tetranitromethane might contact the eyes (e.g., through splashes of solution). Eyewash fountains and emergency showers should be available within the immediate work area whenever the potential exists for eye or skin contact with tetranitromethane. Contact lenses should not be worn if the potential exists for tetranitromethane exposure.
ACGIH [1991]. TLVs. Threshold limit values and biological exposure indices for 1991-1992. Cincinnati, OH: American Conference of Governmental Industrial Hygienists. AIHA [1964]. Hygienic guide series. Akron, OH: American Industrial Hygiene Association. Clayton G, Clayton F [1982]. Patty's industrial hygiene and toxicology. 3rd revised edition. New York, NY: John Wiley & Sons. [CFR]. Code of Federal regulations. Title 29 (Department of Labor), Parts 1910.1000 and 1910.1200. Washington, DC: U.S. Government Printing Office, Office of the Federal Register. [CFR]. Code of Federal regulations. Title 40 (Protection of Environment). Washington, DC: U.S. Government Printing Office, Office of the Federal Register. Hathaway GJ, Proctor NH, Hughes JP, and Fischman, ML [1991]. Proctor and Hughes' chemical hazards of the workplace. 3rd edition. New York, NY: Van Nostrand Reinhold. Horn HJ [1954]. Inhalation toxicology of tetranitromethane. AMA Archives of Industrial Hygiene and Occupational Medicine 10:213-222. NIOSH [1977]. NIOSH manual of analytical methods. 2nd edition. Volume 3. Cincinnati, OH: U.S. Department of Health, Education, and Welfare, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. NIOSH [1987a]. NIOSH guide to industrial respiratory protection. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. DHHS (NIOSH) Publication No. 87-116. NIOSH [1987c]. Respirator decision logic. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. DHHS (NIOSH) Publication No. 87-108. NIOSH [1988]. Testimony of the National Institute for Occupational Safety and Health on the Occupational Safety and Health Administration's proposed rule: 29 CFR 1910, Docket No. H-020, August 2, 1988. NIOSH policy statements. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. RTECS [1992]. Tetranitromethane. Bethesda, MD: Registry of Toxic Effects of Chemical Substances, National Library of Medicine.
ACGIH [1986]. Documentation of the threshold limit values and biological exposure indices. 5th edition. Cincinnati, OH: American Conference of Governmental Industrial Hygienists. Clayton G, Clayton F [1982]. Patty's industrial hygiene and toxicology. 3rd revised edition. New York, NY: John Wiley & Sons. [CFR]. Code of Federal regulations. Title 49 (Department of Transportation). Washington, D.C.: U.S. Government Printing Office, Office of the Federal Register. DOT [1987]. 1987 Emergency response guidebook, guide 47. Washington, DC: U.S. Department of Transportation, Office of Hazardous Materials Transportation, Research and Special Programs Administration. Hathaway GJ, Proctor NH, Hughes JP, and Fischman, ML [1991]. Proctor and Hughes' chemical hazards of the workplace. 3rd edition. New York, NY: Van Nostrand Reinhold. Hawley's condensed chemical dictionary [1987]. Sax NI, Lewis RJ. 11th edition. New York, NY: Van Nostrand Reinhold Company. HSDB [1992]. Tetranitromethane. Bethesda, MD: The Hazardous Substances Data Bank, National Library of Medicine. Material Safety Data Sheet No. 667 [1988]. Schenectady, NY: Genium Publishing Corporation. Merck Index [1983]. Windholz M. 10th edition. Rahway, NJ: Merck & Company. NFPA [1986]. Fire protection guide on hazardous materials. 9th edition. Quincy, MA: National Fire Protection Association. NIOSH [January 1981]. NIOSH/OSHA occupational health guidelines. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health. DHHS (NIOSH) Publication No. 81-123. RTECS [1992]. Tetranitromethane. Bethesda, MD: Registry of Toxic Effects of Chemical Substances, National Library of Medicine. Sax NI, Lewis RJ [1989]. Dangerous properties of industrial materials. 7th edition. New York, NY: Van Nostrand Reinhold Company. Sittig M [1985]. Handbook of toxic and hazardous chemicals. 2nd edition. Park Ridge, NJ: Noyes Publications.
Table 1. NIOSH recommended respiratory protection for workers exposed to tetranitromethane*
* The OSHA PEL is 1 ppm (8 mg/m3) as an 8-hour TWA. No NIOSH REL has been issued. ** Only NIOSH/MSHA-approved equipment should be used. Also note the following:
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