Disclaimer: These guidelines were developed under contract using generally accepted secondary sources. The protocol used by the contractor for surveying these data sources was developed by the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA), and the Department of Energy (DOE). The information contained in these guidelines is intended for reference purposes only. None of the agencies have conducted a comprehensive check of the information and data contained in these sources. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The secondary sources used for supplements 111 and 1V were published before 1992 and 1993, respectively, and for the remainder of the guidelines the secondary sources used were published before September 1996. This information may be superseded by new developments in the field of industrial hygiene. Therefore readers are advised to determine whether new information is available.

OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR DINITROBENZENE (ALL ISOMERS)

INTRODUCTION

This guideline summarizes pertinent information about dinitrobenzene 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 Recommendations may be superseded by new developments in these fields; readers are therefore advised to regard these recommendations as general guidelines and to determine whether new information is available.

SUBSTANCE IDENTIFICATION

* Formula

C(6)H(4)N(2)O(4) (all isomers)

* Structure

(For Structure, see paper copy)

* Synonyms

Binitrobenzene; o-dinitrobenzene; 1,2-dinitrobenzene;

m-dinitrobenzene; 1,3-dinitrobenzene; p-dinitrobenzene;

1,4-dinitrobenzene; DNB; binitrobenzol; dinitrobenzol;

1,2-dinitro benzol

* Identifiers

1. CAS No.: 25154-54-5 (dinitrobenzene); 528-29-0 (ortho); 99-65-0 (meta); 100-25-4 (para)

2. RTECS No.: CZ7450000 (ortho); CZ7350000 (meta); CZ7525000 (para)

3. DOT UN: 1597 56

4. DOT label: Poison

* Appearance and odor

The ortho-, and para-isomers of dinitrobenzene occur as white crystals; the meta-isomer consists of yellowish crystals.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 168.12

2. Boiling point (at 760 mm Hg): Ortho- 319 degrees C (606.2 degrees F); meta- 300-303 degrees C (572-577.4 degrees F); para- 299 degrees C (570.2 degrees F)

3. Specific gravity at 20 degrees C (68 degrees F): Ortho 1.57; meta 1.57; para 1.63

4. Vapor density: 5.79 (ortho)

5. Melting point: Ortho- 118 degrees C (244.4 degrees F); meta- 89 degrees C (192.2 degrees F); para- 173-174 degrees C (343.4-345.2 degrees F)

6. Vapor pressure at 20 degrees C (68 degrees F): Less than 1 mm Hg

7. Solubility: Slightly soluble in water; soluble in chloroform, alcohol, ethyl acetate; and sparingly soluble in benzene.

8. Evaporation rate: Data not available.

* Reactivity

1. Conditions contributing to instability: Heat, shock, or flames. Ortho-dinitrobenzene may detonate when subjected to shock or exposed to heat or flame. Meta-dinitrobenzene may be detonated by shock or heat when it is confined. All isomers are volatile in contact with steam.

2. Incompatibilities: Contact between dinitrobenzene and strong oxidizers should be avoided, and contact with caustics and metals (such as tin or zinc), may cause evolution of heat and increase in pressure. Mixed with nitric acid, all isomers are highly explosive.

3. Hazardous decomposition products: Toxic gases and vapors (such as oxides of nitrogen and carbon monoxide) may be released in a fire involving dinitrobenzene.

4. Special precautions: None reported.

* Flammability

The National Fire Protection Association has assigned a flammability rating of 1 (slight fire hazard) to ortho-dinitrobenzene. The National Fire Protection Association (NFPA) has not assigned a flammability rating to meta- or para-dinitrobenzene.

1. Flash point: meta- and ortho- 150 degrees C (302 degrees F) (closed cup); para- Data not available

2. Autoignition temperature: Data not available.

3. Flammable limits in air: Data not available

4. Extinguishant: Dry chemical, carbon dioxide, water spray, or standard foam for small fires. Use water spray, fog, or standard foam for large fires involving dinitrobenzenes.

Fires involving dinitrobenzene should be fought upwind from the maximum distance possible. Keep unnecessary people away; isolate the hazard area and deny entry. For a massive fire in a cargo area, use unmanned hose holders or monitor nozzles; if this is impossible, withdraw from the area and let the fire burn. Emergency personnel should stay out of low areas and ventilate closed spaces before entering. Containers of dinitrobenzene may explode in the heat of the fire and should be moved from the fire area if it is possible to do so safely. If this is not possible, cool fire exposed containers from the sides with water until well after the fire is out. Stay away from the ends of containers. Firefighters should wear a full set of protective clothing and self-contained breathing apparatus when fighting fires involving dinitrobenzene.

EXPOSURE LIMITS

* OSHA PEL

The current Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) for dinitrobenzene (all isomers) is 1 milligram per cubic meter (mg/m(3)) of air as an 8-hour time-weighted average (TWA) concentration. The OSHA PEL also bears a "Skin" notation, which indicates that the cutaneous route of exposure (including mucous membranes and eyes) contributes to overall exposure [29 CFR 1910.1000, Table Z-1].

* NIOSH REL

The National Institute for Occupational Safety and Health (NIOSH) has established a recommended exposure limit (REL) for dinitrobenzene 1 mg/m(3) as a TWA for up to a 10-hour workday and a 40-hour workweek. NIOSH also assigns a "Skin" notation to dinitrobenzene [NIOSH 1992].

* ACGIH TLV

The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned dinitrobenzene a threshold limit value (TLV) of 0.15 ppm (1 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek. The ACGIH also assigns a "Skin" notation to dinitrobenzene [ACGIH 1994, p. 20].

* Rationale for Limits

The NIOSH limit is based on the risk of anoxia from formation of methemoglobin; liver damage [NIOSH 1992].

The ACGIH limit is based on analogy to the toxicity of aniline [ACGIH 1991, p. 502].

HEALTH HAZARD INFORMATION

* Routes of Exposure

Exposure to dinitrobenzene can occur through inhalation, ingestion, and eye or skin contact, and absorption through the skin [Sittig 1991, p. 663].

* Summary of toxicology

1. Effects on Animals: Dinitrobenzene causes respiratory tract irritation, methemoglobinemia, and anemia. The oral LD(50) in rats is 83 mg/kg [Genium 1992]. Rats injected intravenously with 0.45 umol o-dinitrobenzene/kg developed a methemoglobin concentration of 49 percent and an increase in urinary catecholamine excretion [NLM 1992]. A 1-percent suspension of dinitrobenzene in corn oil fed to rats was toxic in both sexes, causing incoordination, weakness, difficult breathing, rapid heart rate, coma, and respiratory failure. Rats given drinking water with concentrations of dinitrobenzene of 200 mg/L were growth-retarded, and 4 of 6 males died after 5 weeks. Surviving rats had reduced hematocrits, enlarged spleens, and testicular atrophy. Although there was no acute toxicity in rats exposed to concentrations of 3, 8, or 20 mg/L in their drinking water, female rats appeared growth-retarded and behavioral abnormalities were observed in male rats 8 weeks later [NLM 1992]. m-Dinitrobenzene is mutagenic in bacterial test systems [NIOSH 1991]. Reproductive toxicology studies have shown that m-dinitrobenzene is a testicular toxicant in experimental animals. Rats fed 20 mg/liter in drinking water experienced testicular atrophy. Ingestion of 200 mg/liter caused more than 50% of the seminiferous tubules to collapse, with neither germinal cells nor Sertoli cells present. In another study, male rats receiving daily dose of 3.0 mg/kg for 5 days/week did not sire litters when bred with females during treatment week 10. The effects reported include diminished sperm production, decreased caudaepididymal sperm reserves, nonmotile spermatozoa, atypical sperm motility, decreased weights of the testes and epididymis, and seminiferous tubular atrophy [ACGIH 1991].

2. Effects on Humans: Dinitrobenzene causes the formation of methemoglobin. This substance is an irritant of the eyes and respiratory tract. The signs and symptoms of exposure, which range from thirst to staggering gait and coma, are all related to the loss of the blood's oxygen-carrying ability [Hathaway et al. 1991]. The onset of symptoms may be delayed for as long as 4 hours; headache is often the first symptom. At a methemoglobin concentration of 15 percent, cyanosis occurs, but weakness does not occur until this concentration reaches 40 percent or more [Hathaway et al. 1991]. The toxic effects of dinitrobenzene are aggravated by the ingestion of alcohol [Hathaway et al. 1991]. Industrial experience has shown that approximately 5 percent of workers are susceptible to cyanosis [Parmeggiani 1983]. Workers exposed to dinitrobenzene have complained of a burning sensation in the mouth, dry throat, and thirst. Severe industrial exposures have resulted in coma [Hathaway et al. 1991]. A large number of toxic industrial exposures occurred in munitions factories as late as World War I [Grant 1986]. Chronic poisoning has been documented in workers exposed for 9 to 18 months [Grant 1986]. Prolonged exposure may cause liver damage [Genium 1992]. Poisoned workers complained of headache, as well as of burning pain and numbness in their hands, forearms, feet, and ankles [Grant 1986]. They have found to have decreased peripheral vision and central scotomas, especially to red and green wavelengths [Grant 1986]. Skin contact with dinitrobenzene may cause yellowing of the skin, conjunctiva, and cornea [Grant 1986]. Rapid absorption of dinitrobenzene through the skin is a well-emphasized factor in the toxicity and hazard of this substance [ACGIH 1991].

* Signs and symptoms of exposure

1. Acute exposure: Acute exposure to dinitrobenzene results in the symptoms of methemoglobinemia. These include headache, difficult breathing, shortness of breath, rapid and irregular heartbeat, irritability, dizziness, weakness, and coma.

2. Chronic exposure: Chronic exposure to dinitrobenzenes may result in irritability, weakness, headache, anorexia, weight loss, nausea, vomiting, cyanosis, shortness of breath, yellowish discoloration of the skin, decreased vision, anemia, and liver damage.

EMERGENCY MEDICAL PROCEDURES

* Emergency medical procedures: [NIOSH to supply]

5. Rescue: Remove an incapacitated worker from further exposure and implement appropriate emergency procedures (e.g., those listed on the Material Safety Data Sheet required by OSHA's Hazard Communication Standard [29 CFR 1910.1200]). All workers should be familiar with emergency procedures, the location and proper use of emergency equipment, and methods of protecting themselves during rescue operations.

EXPOSURE SOURCES AND CONTROL METHODS

The following operations may involve dinitrobenzene and lead to worker exposures to this substance:

* The manufacture and transportation of dinitrobenzene

* Use in preparation of dyes and dye intermediates; in organic synthesis; as photographic developers; and as explosives

* Use in plastics as a substitute for camphor in production of celluloid, and as a polymerization inhibitor

* Use as an explosive substitute for TNT and in explosive shells

Methods that are effective in controlling worker exposures to dinitrobenzene, depending on the feasibility of implementation, are as follows:

* Process enclosure

* Local exhaust ventilation

* General dilution ventilation

* Personal protective equipment

Workers responding to a release or potential release of a hazardous substance must be protected as required by paragraph (q) of OSHA's Hazardous Waste Operations and Emergency Response Standard [29 CFR 1910.120].

Good sources of information about control methods are as follows:

1. ACGIH [1992]. Industrial ventilation--a manual of recommended practice. 21st ed. Cincinnati, OH: American Conference of Governmental Industrial Hygienists.

2. Burton DJ [1986]. Industrial ventilation--a self study companion. Cincinnati, OH: American Conference of Governmental Industrial Hygienists.

3. Alden JL, Kane JM [1982]. Design of industrial ventilation systems. New York, NY: Industrial Press, Inc.

4. Wadden RA, Scheff PA [1987]. Engineering design for control of workplace hazards. New York, NY: McGraw-Hill.

5. Plog BA [1988]. Fundamentals of industrial hygiene. Chicago, IL: National Safety Council.

MEDICAL SURVEILLANCE

OSHA is currently developing requirements for medical surveillance. When these requirements are promulgated, readers should refer to them for additional information and to determine whether employers whose employees are exposed to dinitrobenzene are required to implement medical surveillance procedures.

* Medical Screening

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, 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 surveillance program is intended to supplement, not replace, such measures. To detect and control work-related health effects, medical evaluations should be performed (1) before job placement, (2) periodically during the term 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 dinitrobenzene, a licensed health care professional 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 blood, liver, cardiovascular system, eyes, and central nervous system.

A preplacement medical evaluation is recommended to assess medical conditions that may be aggravated or may result in increased risk when a worker is exposed to dinitrobenzene at or below the prescribed exposure limit. The health care professional 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 blood, liver, cardiovascular system, eyes, and central nervous system.

* Periodic medical evaluations

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 dinitrobenzene exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of dinitrobenzene on the blood, liver, cardiovascular system, eyes, or central nervous 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.

* Termination medical evaluations

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. Because occupational exposure to dinitrobenzene may cause diseases with prolonged latent periods, the need for medical surveillance may extend well beyond the termination of employment.

* Biological monitoring

Biological monitoring involves sampling and analyzing body tissues or fluids to provide an index of exposure to a toxic substance or metabolite. However, no biological monitoring test acceptable for routine use has yet been developed for dinitrobenzene.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne dinitrobenzene is made using an OSHA versatile sampler (OVS-2) 13 mm XAD-2 tube (270/140 mg sections, 20/60 mesh) with a glass fiber filter enclosed. Samples are collected at a maximum flow rate of 1 liter/minute until a maximum collection volume of 60 liters is reached. The sample is then treated with ethyl acetate. Analysis is conducted by gas chromatography using a flame ionization detector (GC/FID). This method is partially validated and is described in the OSHA Computerized Information System [OSHA 1994].

PERSONAL HYGIENE PROCEDURES

If dinitrobenzene contacts the skin, workers should immediately wash the affected areas with soap and water.

Clothing contaminated with dinitrobenzene 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 dinitrobenzene, particularly its potential for causing toxic effects through dermal absorption.

A worker who handles dinitrobenzene should thoroughly wash hands, forearms, and face with soap and water before eating, using tobacco products, using toilet facilities, applying cosmetics, or taking medication.

Workers should not eat, drink, use tobacco products, apply cosmetics, or take medication in areas where dinitrobenzene or a solution containing dinitrobenzene is handled, processed, or stored.

STORAGE

Dinitrobenzene 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 [29 CFR 1910.1200]. Containers of dinitrobenzene should be protected from physical damage and should be stored separately from strong oxidizers, caustics and metals (such as tin or zinc).

SPILLS AND LEAKS

In the event of a spill or leak involving dinitrobenzene, persons not wearing protective equipment and fully-encapsulating, vapor-protective clothing should be restricted from contaminated areas until cleanup has been completed. The following steps should be undertaken following a spill or leak:

1. Notify safety personnel.

2. Remove all sources of heat and ignition.

3. Ventilate potentially explosive atmospheres.

4. Do not touch the spilled material; stop the leak if it is possible to do so without risk.

5. Use non-sparking tools.

6. Water spray may be used to reduce vapors.

7. For small dry spills, use a clean shovel and place the material into a clean, dry container; cover and remove the container from the spill area.

8. For small liquid spills, take up with sand or other noncombustible absorbent material and place into closed containers for later disposal.

9. For large liquid spills, build dikes far ahead of the spill to contain the dinitrobenzene for later reclamation or disposal.

SPECIAL REQUIREMENTS

U.S. Environmental Protection Agency (EPA) requirements for emergency planning, reportable quantities of hazardous releases, community right-to-know, and hazardous waste management may change over time. Users are therefore advised to determine periodically whether new information is available.

* Emergency planning requirements

Dinitrobenzene is not subject to EPA emergency planning requirements under the Superfund Amendments and Reauthorization Act (SARA) (Title III) in 42 USC 11022.

* Reportable quantity requirements for hazardous releases

A hazardous substance release is defined by EPA as any spilling, leaking, pumping, pouring, emitting, emptying, discharging, injecting, escaping, leaching, dumping, or disposing into the environment (including the abandonment or discarding of contaminated containers) of hazardous substances. In the event of a release that is above the reportable quantity for that chemical, employers are required to notify the proper Federal, State, and local authorities [40 CFR 355.40].

The reportable quantity of dinitrobenzene is 100 pounds. If an amount equal to or greater than this quantity is released within a 24-hour period in a manner that will expose persons outside the facility, employers are required to do the following: - Notify the National Response Center immediately at (800) 424-8802 or at (202) 426-2675 in Washington, D.C. [40 CFR 302.6].

* Community right-to-know requirements

Employers who own or operate facilities in SIC codes 20 to 39 that employ 10 or more workers and that manufacture 25,000 pounds or more of dinitrobenzene per calendar year or otherwise use 10,000 pounds or more of dinitrobenzene per calendar year are required by EPA [40 CFR Part 372.30] to submit a Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of dinitrobenzene 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) [40 USC 6901 et seq.], EPA has specifically listed many chemical wastes as hazardous. Although dinitrobenzene is not specifically listed as a hazardous waste under RCRA, EPA requires employers to treat waste as hazardous if it exhibits any of the characteristics discussed above.

Providing detailed information about the removal and disposal of specific chemicals is beyond the scope of this guideline. The U.S. Department of Transportation, EPA, 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 (703) 412-9810 (in the Washington, D.C. area) 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 dinitrobenzene 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 emergencies. Workers should only use respirators 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 [29 CFR 1910.134]. Such a program must include respirator selection, an evaluation of the worker's ability to perform the work while wearing a respirator, the regular training of personnel, respirator 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 latest edition of the NIOSH Respirator Decision Logic [NIOSH 1987b] and the NIOSH Guide to Industrial Respiratory Protection [NIOSH 1987a].

PERSONAL PROTECTIVE EQUIPMENT

Workers should use appropriate personal protective clothing and equipment that must be carefully selected, used, and maintained to be effective in preventing skin contact with dinitrobenzene. The selection of the appropriate personal protective equipment (PPE) (e.g., gloves, sleeves, encapsulating suits) should be based on the extent of the worker's potential exposure to dinitrobenzene. There are no published reports on the resistance of various materials to permeation by dinitrobenzene.

To evaluate the use of PPE materials with dinitrobenzene, users should consult the best available performance data and manufacturers' recommendations. Significant differences have been demonstrated in the chemical resistance of generically similar PPE materials (e.g., butyl) produced by different manufacturers. In addition, the chemical resistance of a mixture may be significantly different from that of any of its neat components.

Any chemical-resistant clothing that is used should be periodically evaluated to determine its effectiveness in preventing dermal contact. Safety showers and eye wash stations should be located close to operations that involve dinitrobenzene.

Splash-proof chemical safety goggles or face shields (20 to 30 cm long, minimum) should be worn during any operation in which a solvent, caustic, or other toxic substance may be splashed into the eyes.

In addition to the possible need for wearing protective outer apparel (e.g., aprons, encapsulating suits), workers should wear work uniforms, coveralls, or similar full-body coverings that are laundered each day. Employers should provide lockers or other closed areas to store work and street clothing separately. Employers should collect work clothing at the end of each work shift and provide for its laundering. Laundry personnel should be informed about the potential hazards of handling contaminated clothing and instructed about measures to minimize their health risk.

Protective clothing should be kept free of oil and grease and should be inspected and maintained regularly to preserve its effectiveness.

Protective clothing may interfere with the body's heat dissipation, especially during hot weather or during work in hot or poorly ventilated work environments.

REFERENCES

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NIOSH [1991, 1995]. Registry of toxic effects of chemical substances: Dinitrobenzene. Cincinnati, OH: U.S. Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health, Division of Standards Development and Technology Transfer, Technical Information Branch.

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