Disclaimer: The information contained in these guidelines is intended for reference purposes only. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The information contained in these guidelines is current as of date of publication (September, 1996); recommendations may be superseded by new developments in the field of industrial hygiene. Readers are therefore advised to regard these recomendations as general guidelines and to determine whether new information is available.

OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR TRIMETHYLAMINE

INTRODUCTION

This guideline summarizes pertinent information about trimethylamine 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 Recommendations may be superseded by new developments in these fields; readers are therefore advised to regard these recommendations as general guidelines and to determine whether new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(3)H(9)N

* Structure

(For Structure, see paper copy)

* Synonyms

Dimethylmethaneamine; N,N-dimethylmethaneamine; TMA

* Identifiers

1. CAS No.: 75-50-3

2. RTECS No.: PA0350000

3. DOT UN: 1083 19 (anhydrous), 1297 29 (aqueous solutions, not more than 50 percent trimethylamine by mass)

4. DOT label: Flammable gas (anhydrous); Flammable liquid (aqueous solutions)

* Appearance and odor

Trimethylamine is a colorless gas at ambient temperature and pressure. It has a pungent, fishy, ammonia-like odor and a saline taste. Odor threshold ranges of 0.0004 to 0.8 part per million (ppm) parts of air have been reported.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 59.11

2. Boiling point (at 760 mm Hg): 2.9 degrees C (37.22 degrees F)

3. Specific gravity: 0.662 at -5 degrees C (23 degrees F)

4. Vapor density: 2.00

5. Melting point: -117.1 degrees C (-178.8 degrees F)

6. Vapor pressure at 2.9 degrees C (37.22 degrees F): 760 mm Hg

7. Solubility: Very soluble in water; soluble in ether, alcohol, benzene, toluene, xylene, ethylbenzene, and chloroform.

8. Evaporation rate: Data not available.

* Reactivity

1. Conditions contributing to instability: Heat, shock, open flames, oxidizing agents, and combustible materials.

2. Incompatibilities: Contact between trimethylamine and mercury, strong oxidizing materials (such as chlorine, bromine, and fluorine) ethylene oxide, nitrosating agents (e.g., sodium nitrite), strong acids, and metals (such as zinc, brass, aluminum, and copper) should be avoided.

3. Hazardous decomposition products: Toxic gases (such as oxides of nitrogen) may be released in a fire involving trimethylamine.

4. Special precautions: Use only non-sparking tools and equipment when handling trimethylamine. Trimethylamine is corrosive to some metals including zinc, brass, aluminum, and copper.

* Flammability

The National Fire Protection Association has assigned a flammability rating of 4 (severe fire hazard) to trimethylamine.

1. Flash point (at 25% solution): 3.3 degrees C (38 degrees F) (open cup)

2. Autoignition temperature: 190 degrees C (374 degrees F)

3. Flammable limits in air (percent by volume): Lower, 2.0 ; upper, 11.6

4. Extinguishant: For small fires that involve anhydrous trimethylamine, use dry chemical or carbon dioxide. For small fires that involve aqueous solutions of trimethylamine, use dry chemical, carbon dioxide, water spray or regular foam. Use water spray, fog, or regular foam to fight large fires that involve trimethylamine.

Fires involving trimethylamine should be fought upwind from the maximum distance possible. Keep unnecessary people away; isolate the hazard area and deny entry. Isolate the area for 1/2 mile in all directions if a tank, rail car, or tank truck is involved in the fire. 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. Vapors may travel to a source of ignition and flash back. Vapors are an explosion and poison hazard indoors, outdoors, or in sewers. Containers of trimethylamine 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. Do not get water inside containers of trimethylamine in the form of aqueous solution. Stay away from the ends of containers. Personnel should withdraw immediately if a rising sound from a venting safety device is heard or if there is discoloration of a container due to fire. Firefighters should wear a full set of protective clothing and self-contained breathing apparatus when fighting fires involving trimethylamine.

EXPOSURE LIMITS

* OSHA PEL

The Occupational Safety and Health Administration (OSHA) does not currently regulate trimethylamine.

* NIOSH REL

The National Institute for Occupational Safety and Health (NIOSH) has established a recommended exposure limit (REL) for trimethylamine of 10 ppm (24 milligrams per cubic meter (mg/m(3))) as a TWA for up to a 10-hour workday and a 40-hour workweek and 15 ppm (36 mg/m(3)) as a 15-minute TWA short-term exposure limit (STEL). A STEL is the maximum 15-minute concentration to which workers may be exposed during any 15-minute period of the working day [NIOSH 1992].

* ACGIH TLV

The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned trimethylamine a threshold limit value (TLV) of 5 ppm (12 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek and a STEL of 15 ppm (36 mg/m(3)) for periods not to exceed 15 minutes. Exposures at the STEL concentration should not be repeated more than four times a day and should be separated by intervals of at least 60 minutes() [ACGIH 1994, p. 35].

* Rationale for Limits

The NIOSH limits are based on the risk of eye, skin, and respiratory system irritation [NIOSH 1992].

The ACGIH limits are based on the risk of irritation and by analogy to the toxicity of dimethylamine [ACGIH 1991, p. 1646].

HEALTH HAZARD INFORMATION

* Routes of Exposure

Exposure to trimethylamine can occur through inhalation, and eye contact [Hathaway et al. 1991].

* Summary of toxicology

1. Effects on Animals: Trimethylamine causes irritation and affects the lungs, cardiovascular system, spleen and thymus in experimental animals. Aqueous solutions of trimethylamine can be irritating to the eye [Grant 1986]. A 1 percent solution caused severe irritation, a 5 percent solution caused hemorrhagic conjunctivitis, and a 16.5 percent solution caused severe reactions with conjunctival hemorrhages, corneal edema, and opacities [Grant 1986]. Trimethylamine is also a sensory irritant causing a 50 percent reduction in the respiratory rate of mice at a concentration of 61 ppm [ACGIH 1991]. The oral LD(50) in rats is 500 mg/kg [ACGIH 1991]. A four hour exposure of rats to 3,500 ppm reportedly was "an approximate lethal concentration" [ACGIH 1991]. In one study, rats were exposed to 0, 75, 250, or 750 ppm trimethylamine for 6 hours/day, 5 days/week, for 2 weeks [ACGIH 1991]. After 10 exposures, a dose dependent degeneration in nasal and respiratory mucosa was observed. In addition, the 750 ppm group had depressed growth, dehydration, increased pulmonary and cardiac weights, and decreased spleen and thymus weights. All pathological effects except the degeneration of the nasal mucosa had resolved by the end of the 2 week recovery period [ACGIH 1991]. Trimethylamine was not mutagenic in the Ames assay in the presence or absence of metabolic activation [ACGIH 1991].

2. Effects on Humans: Trimethylamine is corrosive to the eye and skin in humans [ACGIH 1991]. A blast of trimethylamine vapor has caused epithelial sloughing in the eye, which healed promptly [Grant 1986]. A concentrated aqueous solution of trimethylamine applied to intact human skin caused severe burning and hyperemia [ACGIH 1991]. Petechial hemorrhages were observed after 1 to 2 hours and slight desquamation was observed 2 to 3 hours later [ACGIH 1991].

* Signs and symptoms of exposure

1. Acute exposure: Acute exposure to trimethylamine has caused eye and skin irritation and may cause corrosion upon contact.

2. Chronic exposure: No signs or symptoms of chronic exposure to trimethylamine have been reported in humans.

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 trimethylamine and lead to worker exposures to this substance:

* The manufacture and transportation of trimethylamine
* Use as an insect attractant, a flotation agent, a warning agent in natural gas, and an intermediate in chemical synthesis

Methods that are effective in controlling worker exposures to trimethylamine, 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 trimethylamine 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 trimethylamine, 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 eyes and respiratory system. Medical surveillance for respiratory disease should be conducted using the principles and methods recommended by the American Thoracic Society.

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 trimethylamine 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 eyes and respiratory 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 trimethylamine exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of trimethylamine on the eyes and 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.

* 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.

* Biological monitoring

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 trimethylamine.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne trimethylamine is made using a coated XAD-7 tube (80/40 mg sections). The coating is 10 percent phosphoric acid. Samples are collected at a maximum flow rate of 0.2 liter/minute until a maximum collection volume of 20 liters is reached. The sample is then treated with 50:50 methanol:deionized water. Analysis is conducted by gas chromatography using a flame ionization detector (GC/FID). This method is described in the OSHA Computerized Information System [OSHA 1994] and is partially validated.

PERSONAL HYGIENE PROCEDURES

If aqueous solution of trimethylamine contacts the skin, workers should immediately wash the affected areas with large amounts of soap and water.

Clothing contaminated with aqueous solution of trimethylamine 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 trimethylamine, particularly its potential for being corrosive to the skin and eyes.

A worker who handles aqueous solutions of trimethylamine 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 trimethylamine or a solution containing trimethylamine is handled, processed, or stored.

STORAGE

Trimethylamine 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 trimethylamine should be protected from physical damage and should be stored separately from mercury, strong oxidizing materials (such as chlorine, bromine, and fluorine) ethylene oxide, nitrosating agents (e.g., sodium nitrite), strong acids, and metals (such as zinc, brass, aluminum, and copper).

SPILLS AND LEAKS

In the event of a spill or leak involving trimethylamine, 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:

1. In the event of a trimethylamine gas leak, stop the leak if it is possible to do so without risk, and use water spray to reduce vapors.

2. Remove all ignition sources and ventilate area of leak.

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

Trimethylamine 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 trimethylamine 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 are not required by EPA in 40 CFR Part 372.30 to submit a Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of trimethylamine 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 trimethylamine 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 trimethylamine 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 trimethylamine. 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 trimethylamine. The resistance of butyl rubber to permeation by trimethylamine is shown below:

To evaluate the use of this or other PPE materials with trimethylamine, 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 trimethylamine.

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.

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