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 This information may be superseded by new developments in the field of industrial hygiene.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

INTRODUCTION

This guideline summarizes pertinent information about ethyl acetate 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 Recommendations may be superseded by new developments in these fields; readers are therefore advised to regard these recommendations as general guidelines and to determine whether new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(8)O(2)()

* Structure

(For Structure, see paper copy)

* Synonyms

Acetic acid, ethyl ester; acetic ether; acetidin; acetoxyethane; ethyl ethanoate; ethyl acetic ester; vinegar naphtha

* Identifiers

1. CAS No.: 141-78-6

2. RTECS No.: AH5425000

3. DOT UN: 1173 26

4. DOT label: Flammable liquid

* Appearance and odor

Ethyl acetate is a clear, colorless, flammable liquid with a pleasant, fruity odor. The air odor threshold concentration for ethyl acetate is 3.9 parts per million (ppm) parts of air.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 88.10

2. Boiling point (at 760 mm Hg): 77 degrees C (170.6 degrees F)

3. Specific gravity: 0.9 at 20 degrees C (68 degrees F)

4. Vapor density: 3.04

5. Melting point: -83 degrees C (-117.4 degrees F)

6. Vapor pressure at 20 degrees C (68 degrees F): 76 mm Hg

7. Solubility: Slightly soluble in water; miscible with most organic solvents such as alcohol, ether, and chloroform.

8. Evaporation rate: Data not available.

* Reactivity

1. Conditions contributing to instability: Heat, sparks, or open flame.

2. Incompatibilities: Contact between ethyl acetate and nitrates, strong oxidizers, strong alkalies, or strong acids may cause fires and explosions. Ethyl acetate reacts vigorously with chlorosulfonic acid, lithium aluminum hydride, 2-chloromethyl furan, oleum, and potassium t-butoxide.

3. Hazardous decomposition products: Data not available.

4. Special precautions: Ethyl acetate will attack some forms of plastics, rubber, and coatings.

* Flammability

The National Fire Protection Association has assigned a flammability rating of 3 (serious fire hazard) to ethyl acetate.

1. Flash point: -4.44 degrees C (24 degrees F).

2. Autoignition temperature: 426 degrees C (800 degrees F).

3. Flammable limits in air (percent by volume): Lower, 2.0; upper, 11.5.

4. Extinguishant: For small fires use dry chemical, carbon dioxide, water spray, or alcohol- resistant foam. Use water spray, fog, or alcohol- resistant foam to fight large fires involving ethyl acetate.

Fires involving ethyl acetate 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 ethyl acetate 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 ethyl acetate.

EXPOSURE LIMITS

* OSHA PEL

The current Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) for ethyl acetate is 400 ppm (1400 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 ethyl acetate of 400 ppm (1400 mg/m(3)) as a TWA for up to a 10-hour workday and a 40-hour workweek [NIOSH 1992].

* ACGIH TLV

The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned ethyl acetate a threshold limit value (TLV) of 400 ppm (1440 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek [ACGIH 1994, p. 21].

* Rationale for Limits

The NIOSH limit is based on the risk of eye and respiratory irritation [NIOSH 1992].

The ACGIH limit is based on the risk of adverse health effects and irritation [ACGIH 1991, p. 569].

HEALTH HAZARD INFORMATION

* Routes of Exposure

Exposure to ethyl acetate can occur through inhalation, ingestion, and eye or skin contact [Sittig 1991].

* Summary of toxicology

1. Effects on Animals: Ethyl acetate is a respiratory tract irritant and, at high concentrations, it causes narcosis and depression of heart function [Hathaway et al. 1991]. The oral LD(50) for acute exposure to ethyl acetate is 4,935 mg/kg for rabbits and 5,620 mg/kg for rats; and the 8-hour rat inhalation LC(50) is 1600 ppm [Sax and Lewis 1989]. Cats exposed to 9,000 ppm for 8 hours suffered from respiratory irritation and labored breathing. Cats exposed for 45 minutes to 20,000 ppm showed deep narcosis, while exposure to 43,000 ppm for 14 to 16 minutes was lethal; at autopsy, pulmonary edema, hemorrhage, and hyperemia of the lungs were noted [ACGIH 1991]. Repeated 4-hour exposures to 2,000 ppm were well tolerated by experimental animals; no changes in the cellular components of the blood were noted. However, repeated exposure of rabbits to 4,450 ppm caused liver damage and secondary anemia, with elevated white blood cell counts [NLM 1992]. Conjunctival irritation without corneal damage occurred in rabbits exposed chronically to ambient ethyl acetate concentrations that were intolerable to humans. Liquid ethyl acetate instilled into the eyes of rabbits cause orbital irregularities of the cornea that completely resolved within 2 days [Grant 1986].

2. Effects on Humans: Ethyl acetate is an irritant of the eyes and upper respiratory tract at concentrations above 400 ppm [NLM 1992]. Unacclimated human volunteers experienced nose and throat irritation at 400 ppm, but no adverse symptoms were found in acclimated workers exposed to 375 to 1,500 ppm ethyl acetate for several months. Ethyl acetate occasionally causes sensitization, with inflammation of the mucous membranes and eczema of the skin [Hathaway et al. 1991]. Workers exposed chronically to ethyl acetate concentrations ranging from .015 to .05 mg/m(3) and .02 to .08 mg/m(3) amyl acetate in air showed only redness of the conjunctiva [Grant 1986]. One death ascribed to the use of a lacquer solvent containing 80 percent ethyl acetate has been reported in a tank painter, but no details are given [ACGIH 1991].

* Signs and symptoms of exposure

1. Acute exposure: Ethyl acetate causes irritation, redness, and tearing of the eyes and irritation of the nose and throat. It is a defatting agent and may cause skin dryness after acute exposure. Sensitization of the lining of the nose may occur with symptoms of inflammation (swelling, runny nose, redness of lining).

2. Chronic exposure: Chronic exposure of the skin to ethyl acetate may cause dermatitis; no other systemic effects have been reported from chronic exposure to ethyl acetate.

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 ethyl acetate and lead to worker exposures to this substance:

* The manufacture and transportation of ethyl acetate

* Used as a solvent in dry cleaning and for celluloid, shellacs, lacquers, airplane dopes, varnishes, stains, and fats

* Liberated during manufacture of smokeless powder; during manufacture of artificial silk and leather; and during preparation of photographic films and plates

* Liberated and used as a solvent during application of coatings and lacquers containing nitrocellulose, cellulose acetate, and cellulose nitrate, shellac, synthetic rubber, vinyl resins, and inks; used for contact lens mold release

* Liberated during manufacture of linoleum and plastic wood, dyes, pharmaceuticals, drug intermediates, ethyl acetoacetate, acetic acid, n-nitrosodiethanolamine, artificial fruit flavorings and essences, and perfumes and fragrances; and during use of duplicator fluid

Methods that are effective in controlling worker exposures to ethyl acetate, 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 ethyl acetate 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 ethyl acetate, 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 respiratory system, liver, kidneys, blood, and skin. 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 ethyl acetate 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 respiratory system, liver, kidneys, blood, or skin.

* 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 ethyl acetate exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of ethyl acetate on the respiratory system, liver, kidneys, blood, or skin. 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 ethyl acetate.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne ethyl acetate is made using a charcoal tube (100/50 mg sections, 20/40 mesh). Samples are collected at a maximum flow rate of 0.2 liter/minute until a maximum collection volume of 6 liters is reached. The sample is then treated with carbon disulfide to extract the ethyl acetate (a 99:1 carbon disulfide:dimethylformamide or a 95:5 methylene chloride:methanol solvent can also be used). Analysis is conducted by gas chromatography using a flame ionization detector (GC/FID). This method is fully validated and is described in the OSHA Computerized Information System [OSHA 1994]. NIOSH has published a similar method (NIOSH Method No. 1457) that can be used to determine a worker's exposure to airborne ethyl acetate [NIOSH 1994].

PERSONAL HYGIENE PROCEDURES

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

Clothing contaminated with ethyl acetate 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 ethyl acetate, particularly its potential for causing eye, skin, and respiratory tract irritation.

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

STORAGE

Ethyl acetate 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]. The storage area must meet OSHA requirements for Class 1B flammable liquids. Electrical service in storage areas must be explosion proof. Containers of ethyl acetate should be protected from physical damage and ignition sources, and should be stored separately from nitrates, strong oxidizers, strong alkalies, or strong acids, chlorosulfonic acid, lithium aluminum hydride, 2-chloromethyl furan, oleum, and potassium t-butoxide.

SPILLS AND LEAKS

In the event of a spill or leak involving ethyl acetate, 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. Provide maximum explosion-proof ventilation.

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 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 ethyl acetate 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

Ethyl acetate 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 ethyl acetate is 5,000 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 ethyl acetate 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. Ethyl acetate is listed as a hazardous waste under RCRA and has been assigned EPA Hazardous Waste No. U112. It is approved for land disposal after treatment and only if the concentration of ethyl acetate in the waste or treatment residual does not exceed 33 mg/kg.

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 ethyl acetate 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 ethyl acetate. 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 ethyl acetate. The resistance of various materials to permeation by ethyl acetate is shown below:

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

To evaluate the use of these PPE materials with ethyl acetate, 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 ethyl acetate.

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

ACGIH [1991]. Documentation of the threshold limit values and biological exposure indices. 6th ed. Cincinnati, OH: American Conference of Governmental Industrial Hygienists.

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