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 This information may be superseded by new developments in the field of industrial hygiene.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 DIETHYLAMINE

INTRODUCTION

This guideline summarizes pertinent information about diethylamine 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 Recommendations may be superseded by new developments in these fields; readers are therefore advised to regard these recommendations as general guidelines and to determine whether new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(4)H(11)()N

* Structure

(For Structure, see paper copy)

* Synonyms

2-Aminopentane; N,N-diethylanine; N-ethyl-ethanamine; diethamine; DEN

* Identifiers

1. CAS No.: 109-89-7

2. RTECS No.: HZ8750000

3. DOT UN: 1154 68

4. DOT label: Flammable Liquid

* Appearance and odor

Diethylamine is a colorless liquid with a fishy, ammonia-like odor. The air odor threshold concentration for diethylamine is 0.13 part per million (ppm) parts of air.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 73.14

2. Boiling point (at 760 mm Hg): 55.5 degrees C (132 degrees F)

3. Specific gravity (water = 1): 0.71 at 20 degrees C (68 degrees F)

4. Vapor density: 2.5

5. Melting point: -50 degrees C (-58 degrees F)

6. Vapor pressure at 20 degrees C (68 degrees F): 195 mm Hg

7. Solubility: Completely soluble in water, and soluble in alcohol and chloroform.

8. Evaporation rate (butyl acetate = 1): 16.9

* Reactivity

1. Conditions contributing to instability: Heat or flame.

2. Incompatibilities: Contact between diethylamine and oxidizing materials, sulfuric and other acids, or dicyanofurazan should be avoided. Contact with strong acids will cause spattering. Ignites on contact with cellulose nitrate of sufficiently high surface area.

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

4. Special precautions: None reported.

* Flammability

The National Fire Protection Association has assigned a flammability rating of 3 (severe fire hazard) to diethylamine.

1. Flash point: -23 degrees C (-9 degrees F) (closed cup)

2. Autoignition temperature: 312 degrees C (594 degrees F)

3. Flammable limits in air (percent by volume): Lower, 1.8; upper, 10.1

4. Extinguishant: For small fires use dry chemical, carbon dioxide, water spray, or regular foam. Use water spray, fog, or regular foam to fight large fires involving diethylamine.

Fires involving diethylamine 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. 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 diethylamine 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. 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 diethylamine.

EXPOSURE LIMITS

* OSHA PEL

The current Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) for diethylamine is 25 ppm (75 milligrams per cubic meter (mg/m(3))) as an 8-hour time-weighted average (TWA) concentration [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 diethylamine of 10 ppm (30 mg/m(3)) as a TWA for up to a 10-hour workday and a 40-hour workweek and a short-term exposure limit (STEL) of 25 ppm (75 mg/m(3)) [NIOSH 1992].

* ACGIH TLV

The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned diethylamine a threshold limit value (TLV) of 5 ppm (15 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek and a short-term exposure limit (STEL) of 15 ppm (45 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. The ACGIH assigns a "Skin" notation, which indicates that the cutaneous route of exposure (including mucous membranes and eyes) contributes to overall exposure. The ACGIH lists diethylamine as an A4 substance (not classifiable as a human carcinogen [ACGIH 1994, p. 19].

* Rationale for Limits

The NIOSH limits are based on the risk of eye, skin, and respiratory irritation; myocardial degeneration in animals [NIOSH 1992].

The ACGIH limits are based on the risk of eye and respiratory irritation [ACGIH 1991, p. 460].

HEALTH HAZARD INFORMATION

* Routes of Exposure

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

* Summary of toxicology

1. Effects on Animals: Diethylamine is a severe irritant of the eyes and a moderate irritant of the skin and mucous membranes [Hathaway et al. 1991]. Systemic effects of chronic exposure include damage to the liver and heart [ACGIH 1991]. The acute oral LD(50) in rats is 540 mg/kg. The dermal LD(50) in rabbits is 820 mg/kg. The 4-hour inhalation LC(50) in rats is 4,000 ppm [NIOSH 1995; ACGIH 1991]. Rabbits exposed to 50 ppm diethylamine for 7 hours/day, 5 days/week for 6 weeks, showed signs of corneal erosion (present after 2 weeks), focal degeneration of the liver, and severe lung irritation. In all animals exposed on the same regimen to 100 ppm, striking degenerative changes were noted in the heart and liver [ACGIH 1991; Hathaway et al. 1991; Grant 1986]. A drop of diethylamine into the eye of a rabbit caused an injury graded 10 on a scale of 1 to 10 [Grant 1986]. The most severely injurious substances are rated 10. Topical application of diethylamine to the skin results in serious irritation and can cause blistering and necrosis [ACGIH 1991].

2. Effects on Humans: Diethylamine is corrosive to eyes, mucous membranes, and skin. Liquid splashed in the eye causes intense pain and corneal damage, and permanent visual impairment may occur [Hathaway et al. 1991; NLM 1995]. Prolonged or repeated exposure to vapors at concentrations slightly below the irritant level often results in corneal edema, foggy vision, and the appearance of halos around lights [Hathaway et al. 1991; NLM 1995]. Skin contact with liquid diethylamine causes blistering and necrosis [NLM 1995]. Exposure to high vapor concentrations may cause severe coughing, chest pain, and pulmonary edema [Genium 1986]. Ingestion of diethylamine causes severe gastrointestinal pain, vomiting, and diarrhea, and may result in perforation of the stomach and esophagus [Genium 1986; NLM 1995].

* Signs and symptoms of exposure

1. Acute exposure: Inhalation of diethylamine vapors causes tearing and redness of the eyes, corneal edema, and the appearance of "halos" around lights; irritation of the nose, throat, and lungs, with difficult breathing and coughing; pulmonary edema may also occur. Contact of the skin with the vapors may cause skin irritation and dermatitis. Contact with liquid diethylamine can cause severe eye pain, corneal damage, and skin burns. Inhalation of the vapors may also cause headache, nausea, faintness, and anxiety [Clayton and Clayton 1982; Hathaway et al. 1991].

2. Chronic exposure: By analogy with the effects of other aliphatic amines, dermatitis and chronic pulmonary disease may occur as a result of chronic exposure to diethylamine [Clayton and Clayton 1982].

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 diethylamine and lead to worker exposures to this substance:

* The manufacture and transportation of diethylamine

* Used as a chemical intermediate in synthesis of textile finishing agents surfactants, flotation agents, resins, emulsifiers, rubber processing chemicals, agricultural pesticides, petrochemicals, and pharmaceuticals

* Used as a corrosion inhibitor in the iron, steel, and metal industries and as a solvent

* Used as depilatory of animal skins and in electroplating solutions

* Used as polymerization inhibitor and catalyst in polymer industry, intermediate in dye industry

Methods that are effective in controlling worker exposures to diethylamine, 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 diethylamine 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 diethylamine, 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 skin, 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 diethylamine 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 skin, eyes, or 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 diethylamine exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of diethylamine on the skin, eyes, 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.

* 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. Urinary diethylamine can be detected and quantified using high-performance liquid chromatography; however, urinary levels of diethylamine cannot be correlated with airborne concentrations. Therefore, no biological monitoring test acceptable for routine use has yet been developed for diethylamine.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne diethylamine is made using a coated XAD-7 tube (80/40 mg sections, 20/50 mesh). The coating is 10 percent (w/w) NBD-chloride. Samples are collected at a maximum flow rate of 0.2 liter/minute (STEL or TWA) until a maximum collection volume of 3 liters (STEL) or 10 liters (TWA) is reached. The sample is then treated with tetrahydrofuran. Analysis is conducted by high-performance liquid chromatography; HPLC/FLU/VIS. This method (OSHA 41) is described in the OSHA Computerized Information System [OSHA 1994] and is fully validated. NIOSH has a published method for the determination of a worker's exposure to airborne diethylamine that requires sample collection on a silica gel tube. Analysis for this method (Method No. 2010-amines, aliphatic) is conducted by gas chromatography using a flame ionization detector [NIOSH 1994b].

PERSONAL HYGIENE PROCEDURES

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

Clothing contaminated with diethylamine 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 diethylamine, particularly its potential for causing eye, skin, and respiratory irritation.

A worker who handles diethylamine 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 diethylamine or a solution containing diethylamine is handled, processed, or stored.

STORAGE

Diethylamine 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]. Outdoor or detached storage is preferred; inside storage should be in a standard flammable liquids storage room or cabinet. Containers of diethylamine should be protected from physical damage, heat or other ignition sources, and direct sunlight, and should be stored separately from oxidizing materials, sulfuric and other acids, dicyanofurazan, and cellulose nitrate. Electrical equipment should be suitable for use in atmospheres containing diethylamine vapors. Empty containers of diethylamine should be handled appropriately.

SPILLS AND LEAKS

In the event of a spill or leak involving diethylamine, 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. 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 and to dilute to nonflammable mixture.

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

8. For large liquid spills, build dikes far ahead of the spill to contain the diethylamine 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

diethylamine 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 diethylamine is 1,000 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 diethylamine 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 diethylamine 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 diethylamine 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 diethylamine. 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 diethylamine. The resistance of various materials to permeation by diethylamine is shown below:

(*) Material has been estimated to provide at least four hours of protection (but not tested)
(**) Not recommended, degradation may occur

To evaluate the use of these PPE materials with diethylamine, 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 diethylamine.

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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