H(2)O(2)

* Structure

(For Structure, see paper copy)

* Synonyms

Hydrogen dioxide, perhydrol, albone, hydroperoxide, inhibine, perone, superoxol, t-stuff, hydrogen peroxide 90%, hydrogen peroxide 30%

* Identifiers

1. CAS No.: 7722-84-1

2. RTECS No.: MX0899000 or (MX0900000)

3. DOT UN: 2015 47 (aqueous solutions, > 60% hydrogen peroxide); 2014 45 (aqueous solutions, greater than or equal to 20 percent and less than 60 percent; 2984 45 (aqueous solutions, greater than or equal to 8 percent and less that 20 percent)

4. DOT label: Oxidizer, corrosive (2014 and 2015); oxidizer (2984)

* Appearance and odor

Hydrogen peroxide is a colorless liquid with a bitter taste.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 34.02

2. Boiling point (at 760 mm Hg): 152 degrees C (305.6 degrees F) (90%)

3. Specific gravity: 1.46 (90%) at 0 degrees C (32 degrees F)

4. Vapor density: Data not available.

5. Melting point: -0.43 degrees C (-45.4 degrees F) (90%)

6. Vapor pressure at 30 degrees C (86 degrees F): 5 mm Hg (90%)

7. Solubility: Soluble in alcohol, ether, and water; insoluble in petroleum ether; decomposed by many organic solvents.

8. Evaporation rate: Data not available.

* Reactivity

1. Conditions contributing to instability: Exposure to radiant heat (sunlight), sources of ignition, such as, heat or open flame; and physical or mechanical disturbances can create a potential fire or explosion hazard.

2. Incompatibilities: Contact between hydrogen peroxide and combustible materials such as, wood, paper, oil, etc., may cause immediate spontaneous ignition or combustion. Mixed with organic materials such as alcohols, acetone, and other ketones; aldehydes, and their anhydrides; and glycerol can cause violent explosions. Spontaneous ignition may occur when hydrogen peroxide is added to cotton (cellulose). Contact with metals including iron, copper, chromium, lead, silver, manganese, sodium, potassium, magnesium, nickel, gold, platinum; metal alloys such as, brass or bronze; metal oxides such as lead oxides, mercury oxides, or manganese dioxide; and many metal salts, like potassium permanganate or sodium iodate could result in violent explosions. Tremendous explosions can also be caused by unstable mixtures with concentrated mineral acids.

3. Hazardous decomposition products: None reported.

4. Special precautions: Containers of hydrogen peroxide should be kept shock-free, covered and properly vented.

* Flammability

Hydrogen peroxide is not combustible, but it is a powerful oxidizer [NIOSH 1994].

The National Fire Protection Association has assigned a flammability rating of 0 (minimal fire hazard) to hydrogen peroxide.

1. Flash point: Data not available.

2. Autoignition temperature: Data not available.

3. Flammable limits in air: Data not available.

4. Extinguishant: For small fires use water only; no dry chemical or carbon dioxide. Flood fire area with water from a distance to fight large fires involving hydrogen peroxide.

Fires involving hydrogen peroxide 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 are an explosion and poison hazard indoors, outdoors, or in sewers. This substance may ignite other combustible materials such as wood, paper, oil, etc. Mixed with fuel they may react violently or even explode. Explosions can also be caused by friction, heat or contamination. Containers of hydrogen peroxide 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 hydrogen peroxide.

EXPOSURE LIMITS

* OSHA PEL

The current Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) for hydrogen peroxide is 1 part per million (ppm) parts of air (1.4 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 hydrogen peroxide of 1 ppm (1.4 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 hydrogen peroxide a threshold limit value (TLV) of 1 ppm (1.4 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour workweek [DOT 1993, Guides 45 and 47].

* Rationale for Limits

The NIOSH limit is based on the risk of eye, mucous membrane, and skin irritation [NIOSH 1992].

The ACGIH limit is based on the risk of irritation [ACGIH 1991, p. 782].

HEALTH HAZARD INFORMATION

* Routes of Exposure

Exposure to hydrogen peroxide can occur through inhalation of the vapor or mist, ingestion, and eye or skin contact [Sittig 1991].

* Summary of toxicology

1. Effects on Animals: Hydrogen peroxide is an eye, skin, and mucous membrane irritant. The LC(50) in rats is 2,000 mg/m(3) (1,333 ppm) for 4 hours, and the dermal LD(50) in rats is 4,060 mg/kg [NIOSH 1995]. Dogs exposed to a 7 ppm airborne concentration of 90 percent hydrogen peroxide for 6 hours per day, 5 days per week for 6 months developed external body irritation, sneezing, lacrimation, and bleaching of the hair. At autopsy, their skin was observed to be thickened and their lungs were seen to be irritated [ACGIH 1991]. Rabbits exposed daily to 22 ppm daily for 3 months exhibited irritation around the nose and bleached hair [ACGIH 1991; NLM 1992]. Application to the eyes of rabbits shows that hydrogen peroxide in concentrations of 5 percent or above can cause lasting damage [Grant 1986]. Oral administration of hydrogen peroxide in mice has caused adenomas and carcinomas of the duodenum [IARC 1985]. The International Agency for Research on Cancer has concluded that there is limited evidence of hydrogen peroxide's carcinogenicity in animals [IARC 1985]. Hydrogen peroxide is mutagenic in bacterial test systems and causes DNA damage, sister chromatid exchanges, and chromosomal aberrations in mammalian cells in vitro [IARC 1985].

2. Effects on Humans: Hydrogen peroxide is an irritant of the eyes, mucous membranes, and skin. Inhalation of high concentrations of the vapor or mist may cause extreme irritation of the nose and throat [Hathaway et al. 1991]. The inhalation of 7 ppm causes lung irritation in humans [NLM 1992]. Severe systemic poisoning may cause headache, dizziness, vomiting, diarrhea, tremors, numbness, convulsions, pulmonary edema, unconsciousness, and shock. Exposure for a short period of time to the mist or spray may cause stinging and tearing of the eyes [Hathaway et al. 1991]. Splashes of high concentrations of hydrogen peroxide in the eyes may cause severe corneal damage. At very low concentrations (1 to 3 percent), instillation of hydrogen peroxide into the eye causes severe pain that later subsides [Grant 1986]. Skin contact with liquid hydrogen peroxide causes a temporary whitening or bleaching of the skin; if the skin is not washed promptly, redness and blisters may develop. Ingestion of hydrogen peroxide may cause irritation of the upper gastrointestinal tract and severe damage to the esophagus and stomach [Hathaway et al. 1991]. Hydrogen peroxide has caused DNA damage in in vitro human test systems [NIOSH 1995].

* Signs and symptoms of exposure

1. Acute exposure: The signs and symptoms of acute exposure to hydrogen peroxide include irritation of the eyes, nose, throat, and lungs, ranging from mild bronchitis to pulmonary edema. Corneal ulceration, redness and blisters on the skin, and bleaching of hair may occur after contact of the eyes or skin with the liquid or vapor.

2. Chronic exposure: No signs or symptoms of chronic exposure to hydrogen peroxide 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 hydrogen peroxide and lead to worker exposures to this substance:

* The manufacture and transportation of hydrogen peroxide

* Use in the synthesis of inorganic peroxygen compounds (e.g., sodium perforate and sodium percarbonate)

* Use as an intermediate in the synthesis of plasticizers, organic peroxygen compounds (e.g., methyl ethyl ketone peroxide, benzoyl peroxide), peroxycarbonates, and amine oxides

* Use to bleach textiles, mechanical wood pulps, oils, waxes, fats, discolored silk, straw, ivory, concentrated acids, flour, bone, feathers, fruit, fur, hair, soap, gelatin, glue, and a variety of additional items

* Use to eliminate pollutants in industrial and municipal wastewater treatment systems

* Use to remove hydrogen sulfide from the steam produced by geothermal power plants, and to generate oxygen in respiratory protective equipment

* Use in the manufacture of glycerol acetone, antichlor, benzoyl peroxide, buttons, disinfectants, felt hats, sponge rubber, and pesticides

* Use in various steps during the mining and processing of uranium, pickling of copper and copper alloys, and cleaning of metals and silicon semiconductors used in the electronics industry

* Use in a variety of small-volume applications in photography, cosmetics, antiseptics, painting and engraving restoration, and cleansing agents

* Use as a sterilizing agent in food and wine processing

* Use as a polymerization promoter, a foaming agent, to age wines and liquors, to disinfect water and hides, to refine oils and fats, and for gilding and silvering of metal surfaces [NLM 1995]

* Use as a rocket fuel (the 90-percent solution), an ingredient of explosives, and in military applications

* Use as a component in nonprescription drugs, and as a cleansing and topical antiseptic agent

* Use in medicine to remove ear wax and to treat gingivitis

* Use as a laboratory reagent, a seed disinfectant, and a viscosity control for starch and cellulose derivatives

Methods that are effective in controlling worker exposures to hydrogen peroxide, 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.

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

4. 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 hydrogen peroxide 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 hydrogen peroxide, 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, skin, 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 hydrogen peroxide 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, skin, 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 hydrogen peroxide exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of hydrogen peroxide on the eyes, skin, or respiratory system. Current health status should be compared with the baseline health status of the individual worker or with expected values for a suitable reference population.

* 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 hydrogen peroxide.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne hydrogen peroxide is made using a midget fritted glass bubbler (MFGB) containing 15 mL TiOSO(4). Samples are collected at a recommended flow rate of 0.5 liter/minute until a recommended collection volume of 100 liters is reached. Analysis is conducted by colorimetric methods. This method (OSHA VI-6) is partially validated and is described in the OSHA Computerized Information System [OSHA 1994].

PERSONAL HYGIENE PROCEDURES

If hydrogen peroxide contacts the skin, workers should flush the affected areas immediately with plenty of water, followed by washing with soap and water.

Clothing contaminated with hydrogen peroxide 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 hydrogen peroxide, particularly its potential for causing irritation.

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

STORAGE

Hydrogen peroxide 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 hydrogen peroxide should be protected from physical damage and should be stored separately from combustible materials such as, wood, paper, oil, etc., organic materials such as alcohols, acetone, and other ketones; aldehydes, and their anhydrides; glycerol, cotton (cellulose), metals including iron, copper, chromium, lead, silver, manganese, sodium, potassium, magnesium, nickel, gold, platinum; metal alloys such as, brass or bronze; metal oxides such as lead oxides, mercury oxides, or manganese dioxide; and many metal salts, like potassium permanganate or sodium iodate; and mineral acids .

SPILLS AND LEAKS

In the event of a spill or leak involving hydrogen peroxide, 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 the area of the spill or leak.

4. Keep combustibles (wood, paper, oil, etc.) away from the spilled material.

5. Water spray may be used to reduce vapors, but the spray may not prevent ignition in closed spaces.

6. For small liquid spills, flood the area with large amounts of water.

7. For large liquid spills, flood the area with large amounts of water and dike far ahead of the spill to contain the hydrogen peroxide 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

Employers owning or operating a facility at which there are 1,000 pounds or more of hydrogen peroxide must comply with EPA's emergency planning requirements.

* 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 hydrogen peroxide is 1 pound. 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].

- Notify the emergency response commission of the State likely to be affected by the release [40 CFR 355.40].

- Notify the community emergency coordinator to the local emergency planning committee (or relevant local emergency response personnel) of any area likely to be affected by the release [40 CFR 355.40].

* 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 hydrogen peroxide 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 hydrogen peroxide 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 hydrogen peroxide 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 hydrogen peroxide. 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 hydrogen peroxide. The resistance of various materials to permeation by hydrogen peroxide (30 to 70 percent) is shown below:

 

(*) Not recommended, degradation may occur

To evaluate the use of these PPE materials with hydrogen peroxide, 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 hydrogen peroxide.

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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OHSA website: http://www.osha.gov

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