1,4-Dioxane

Excerpt from ERG Guide 127 [Flammable Liquids (Water-Miscible)]:

Use powder, alcohol-resistant foam, water spray, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water.

Fresh air, rest. Refer immediately for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower.

Rinse with plenty of water for several minutes (remove contact lenses if easily possible).

Rinse mouth. Do NOT induce vomiting. Seek medical attention if you feel unwell.

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area.

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.

General First Aid:

(General first aid procedures)

· Wear positive pressure self-contained breathing apparatus (SCBA).

10.0 [ppm]

Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. Use water spray, dry chemical. "alcohol resistant" foam, or carbon dioxide. Use water spray to keep fire-exposed containers cool.

Fire fighting: Self contained breathing apparatus with a full facepiece operated in pressure demand or other positive pressure mode.

Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Wear self-contained breathing apparatus for firefighting if necessary. ...Use water spray to cool unopened containers.

Store in a cool, dry, well-ventilated location. Store away from heat, oxidizing materials, and sunlight. Outside or detached storage is preferred. Inside storage should be in a standard flammable liquids storage warehouse, room, or cabinet.

PRECAUTIONS FOR "CARCINOGENS": Storage site should be as close as practicable to lab in which carcinogens are to be used, so that only small quantities required for ... expt need to be carried. Carcinogens should be kept in only one section of cupboard, an explosion-proof refrigerator or freezer (depending on chemicophysical properties ...) that bears appropriate label. An inventory ... should be kept, showing quantity of carcinogen and date it was acquired ... Facilities for dispensing ... should be contiguous to storage area. /Chemical Carcinogens/

Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage. Storage class (TRGS 510): Flammable liquids

1) Remove all ignition sources. 2) ventilate area of spill or leak. 3) for small quantities, absorb on paper towels. Evaporate in safe place (such as flame hood). Allow ... to completely clear hood ductwork. Burn in suitable location away from combustible materials. Large quantities can be collected and atomized in suitable combustion chamber equipped with appropriate effluent gas cleaning device. Dioxane should not be allowed to enter confined space, such as sewer. ...

PRECAUTIONS FOR "CARCINOGENS": A high-efficiency particulate arrestor (HEPA) or charcoal filters can be used to minimize amt of carcinogen in exhausted air ventilated safety cabinets, lab hoods, glove boxes or animal rooms ... Filter housing that is designed so that used filters can be transferred into plastic bag without contaminating maintenance staff is avail commercially. Filters should be placed in plastic bags immediately after removal ... the plastic bag should be sealed immediately ... the sealed bag should be labelled properly ... Waste liquids ... should be placed or collected in proper containers for disposal. The lid should be secured and the bottles properly labelled. Once filled, bottles should be placed in plastic bag, so that outer surface ... is not contaminated ... The plastic bag should also be sealed and labelled. ... Broken glassware ... should be decontaminated by solvent extraction, by chemical destruction, or in specially designed incinerators. /Chemical Carcinogens/

ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Evacuate personnel to safe areas. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Methods and materials for containment and cleaning up Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and place in container for disposal according to local regulations.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U108, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Good candidate for rotary kiln incineration with a temperature range of 820-1,600 °C with residence times for liquids and gases: seconds; solids: hours. Also, a good candidate for liquid injection incineration with a temperature range of 650-1,600 °C with residence times of 0.1-2.0 seconds. Also, a good candidate for fluidized bed incineration with a temperature range of 450-980 °C with residence times for liquids and gases: seconds; solids: longer.

This compound should be susceptible to removal from waste water by air stripping.

PRECAUTIONS FOR "CARCINOGENS": There is no universal method of disposal that has been proved satisfactory for all carcinogenic compounds and specific methods of chem destruction ... published have not been tested on all kinds of carcinogen-containing waste. ... summary of avail methods and recommendations ... /given/ must be treated as guide only. /Chemical Carcinogens/

For more Disposal Methods (Complete) data for 1,4-DIOXANE (11 total), please visit the HSDB record page.

1,4-Dioxane was detected at mean levels of 0.2 ug/cu m (N = 110) and 0.05 ug/cu m (N = 24) in the exhaled breath of human subjects at two different locations in Los Angeles, CA. 1,4-Dioxane was also detected at a mean level of 0.2 ug/cu m (N = 67) in the exhaled breath of persons in Contra Costa, CA(1).

Gastrointestinal

[in animals: lung, liver & nasal cavity tumors]

... /In Swiss Webster mice/ skin paintings /with 0.2 mL of unspecified concn of 1,4-dioxane/ were preceded 1 wk earlier by application of 50 ug 7,12-dimethylbenzanthracene (DMBA); 4 males and 5 females survived 59 wk of treatment. Among 15 mice examined, 8 skin tumors were observed (2 papillomas, 2 squamous-cell carcinomas and 4 sarcomas); in addition 24 other tumors (mainly malignant lymphomas and lung tumors) occurred. 8 skin papillomas and 1 malignant lymphoma occurred in 55 animals receiving 50 ug DMBA followed by thrice weekly paintings with acetone alone.

Dioxane ... was investigated as a rat liver altered foci promoter in an initiation/promotion protocol. Animals were initiated with diethylnitrosamine, 30 mg/kg, injected ip 24 hr after 2/3 partial hepatectomy. The chemical under study was administered by gavage once a day, 5 times a week for 7 weeks. Ten days after the last administration the animals were killed. Liver sections were stained for gamma-glutamyl-transpeptidase (GGT) and the number and total volume of gamma-glutamyl-transpeptidase-positive foci was studied. Dioxane (1000 mg/kg) significantly increased the number and total volume of foci ... .

Cancer, Developmental (effects while organs are developing), Hepatic (Liver), Ocular (Eyes), Renal (Urinary System or Kidneys), Respiratory (From the Nose to the Lungs)

Hepatic

Eyes, skin, respiratory system, liver, kidneys

1,4-Dioxane for short period of time cause eye and nose irritation at low levels, and severe kidney and liver effects and possibly death at very high levels. For long-term exposure, studies in animals have shown that breathing vapors of 1,4-dioxane, swallowing liquid 1,4-dioxane or contaminated drinking water, or having skin contact with liquid 1,4-dioxane affects mainly the liver and kidneys. Studies in workers did not indicate whether 1,4-dioxane causes cancer, but animal studies suggest that it is a probable human carcinogen. (L1189)

LC50; Species: Lepomis macrochirus (Bluegill sunfish); Conditions: freshwater, static bioassay, 23 °C, mild aeration applied after 24 hr; Concentration: 10,000 ppm for 96 hr

LC50; Species: Menidia beryllina (Inland silverside); Conditions: static bioassay in synthetic seawater, 23 °C, mild aeration applied after 24 hr; Concentration: 6,700 ppm for 96 hr

LC50; Species: Pimephales promelas (Fathead minnow); Conditions: /static/; Concentration: 13,000 mg/L for 96 hr (nominal concentration) (95% confidence interval: 10,000-17,000 mg/L) /from table/

LC50; Species: Pimephales promelas (Fathead minnow); Conditions: flow through; Concentration: 9,850 mg/L for 96 hr /from table/

For more Ecotoxicity Values (Complete) data for 1,4-DIOXANE (12 total), please visit the HSDB record page.

TERRESTRIAL FATE: Based on a classification scheme(1), measured Koc values of 29(2) and 17(3) indicate that 1,4-dioxane is expected to have very high mobility in soil(SRC). Volatilization of 1,4-dioxane from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 4.8X10-6 atm-cu m/mole(4). 1,4-Dioxane is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 38.1 mm Hg at 25 °C(5). A 0% of theoretical BOD using activated sludge in the Japanese MITI test(6) suggests that 1,4-dioxane is not readily biodegradable(SRC). Other screening study results indicate that 1,4-dioxane is resistant to biodegradation and slow to biodegrade(7). Using soil microcosms 1,4-dioxane was not biodegraded within 120 days and, therefore, considered recalcitrant(8). 1,4-Dioxane did not biodegrade in most of 20 environmental samples (rivers waters, soils, activated sludge), but it was degradable in soils collected from drainage areas of a chemical factory within 33 days, presumably due to acclimation(9).

AQUATIC FATE: Based on a classification scheme(1), measured Koc values of 29(2) and 17(3) indicate that 1,4-dioxane is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(4) based upon a Henry's Law constant of 4.8X10-6 atm-cu m/mole(5). Using this Henry's Law constant and an estimation method(4), volatilization half-lives for a model river and model lake are 7.3 and 56 days, respectively(SRC). According to a classification scheme(6), a BCF range of 0.2-0.7 measured in carp (Cyprinus carpio)(7) suggests the potential for bioconcentration in aquatic organisms is low(SRC). A 0% of theoretical BOD using activated sludge in the Japanese MITI test(7) suggests that 1,4-dioxane is not readily biodegradable(SRC). Other screening studies have found 1,4-dioxane to be resistant to biodegradation and slow to biodegrade(8) and to be recalcitrant(9). 1,4-Dioxane is considered non-biodegradable under conventional bio-treatment technologies based on results of wastewater treatment monitoring data(10). 1,4-Dioxane is a very weak absorber of UV light(11)and results of aqueous photolysis studies(12) suggest that direct photolyis is not an important environmental fate process(SRC). 1,4-Dioxane is not expected to undergo hydrolysis in the environment due to the lack of functional groups that hydrolyze under environmental conditions(4).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 1,4-dioxane, which has a vapor pressure of 38.1 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase 1,4-dioxane is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 33 hours(SRC), calculated from its rate constant of 1.18X10-11 cu cm/molecule-sec at 25 °C(3). 1,4-Dioxane is a very weak absorber of UV light(4). Results of aqueous photolysis studies(5) suggest that direct photolysis is not an important environmental fate process(SRC).

The level of 1,4-dioxane in various cooked food samples ranged from not detected to 11 ug/kg according to a result of analysis by GC-MS with a detection limit of 2 ug/kg(1). 1,4-Dioxane was qualitatively detected in the volatile compounds of fried chicken(2).

The substance can be absorbed into the body by inhalation of its vapour and through the skin.

inhalation, skin absorption, ingestion, skin and/or eye contact

Oral (L1189) ; inhalation (L1189) ; dermal (L1189)

IDENTIFICATION AND USE: 1,4-Dioxane is a colorless liquid or solid. It is used as a stabilizer for chlorinated solvents, particularly, 1,1,1-trichloroethane. 1,4-Dioxane is used as a solvent for cellulose acetate, ethyl cellulose, benzyl cellulose, resins, oils, waxes, and fats; in spectroscopic and photometric measurements; and in the pulping of wood. Other uses of 1,4-dioxane include the manufacture of adhesives, cements, deodorant fumigants, cosmetics, drugs, cleaning preparations, magnetic tape, plastic, rubber, insecticides, and herbicides, and as a chemical intermediate, as a polymerization catalyst, in the purification of drugs, and in the extraction of animal and vegetable oils. In the laboratory, it is used in the preparation of histological sections for microscopic examination and as a liquid scintillation counting medium. HUMAN EXPOSURE AND TOXICITY: Short-term inhalation exposure to 1,4-dioxane may cause irritation of the eyes, nose, throat, and lungs. Symptoms of acute exposure include coughing, drowsiness, vertigo, headache, nausea, vomiting, stomach pains, coma, and death. There is a report of a fatal case of acute poisoning by inhalation that led to hepatic and renal lesions, and demyelination and edema of the brain. Workplace exposures to high concentrations of 1,4-dioxane have resulted in death. The deaths occurred 5-8 days after the initial symptoms of illness. Postmortem evaluation revealed extensive liver and kidney damage and in three out of five cases described in one study, kidney disease was considered to be the direct cause of death. A small prospective study of 165 U.S. workers exposed intermittently to low levels of 1,4-dioxane found no excess of death from cancer; however, the study was limited by the small number of cancer deaths (3) among the exposed workers. ANIMAL STUDIES: Oral exposure to 1,4-dioxane caused tumors in several species of experimental animals and at several different tissue sites. Inhalation exposure of male rats to 1,4-dioxane caused benign liver tumors (hepatocellular adenoma), nasal cancer (squamous-cell carcinoma), and mesothelioma of the peritoneum. 1,4-Dioxane was not mutagenic to Salmonella typhimurium with and without metabolic activation. 1,4-Dioxane has a non-genotoxic, yet unknown, mode of action. 1,4-Dioxane induced meiotic non-disjunction in mature oocytes from 3- and 6-day-old Drosophila melanogaster females. ECOTOXICITY STUDIES: A long-term static renewal test (7 days) with Ceriodaphnia dubia has been carried out. A NOEC of 625 mg/L(nominal) was found in this test.

Though the mechanism of toxicity of 1,4-dioxane has not yet been elucidated, it is known that its carcinogenic effects are caused by a non-genotoxic mechanism that is most likely cytotoxic in nature. (L1189, L1881)

U108; As stipulated in 40 CFR 261.33, when 1,4-diethylene oxide, as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to Federal and/or State hazardous waste regulations. Also defined as a hazardous waste is any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5).

This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements. 1,4-Dioxane is produced, as an intermediate or a final product, by process units covered under this subpart.

Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. 1,4-Dioxane is included on this list.

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 100 lb or 45.4 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV.D.3.b).

(CA) CALIFORNIA 3 ug/L

(FL) FLORIDA 5 ug/L

(MA) MASSACHUSETTS 0.3 ug/L

(ME) MAINE 32 ug/L

(NH) NEW HAMPSHIRE 3 ug/L

1,4-Dioxane is used as a solvent for cellulose acetate, ethyl cellulose, benzyl cellulose, resins, oils, waxes, some dyes, and other organic and inorganic compounds.

Used as a solvent for cellulose esters, ethers, and other organic chemicals; [ACGIH] Used as a solvent in resins, polymers, oils, waxes, dyes, wood pulping, adhesives, varnishes lacquers, paints, and cosmetics; [HSDB]

Metal Degreasing [Category: Clean]

Stabilizer in chlorinated solvents. Organic solvent for cellulose acetate, ethyl cellulose, benzyl cellulose, resins, oils, waxes, oil and spirit-soluble dyes, and many other organic as well as some inorganic compounds.

The largest single use of 1,4-dioxane is the stabilization of 1,1,1-trichloroethane against chemical attack by aluminum.

Historically, 1,4-dioxane has been used as a stabilizer for the solvent 1,1,1-trichloroethane. However, this use is no longer expected to be important due to the 1990 Amendments to the Clean Air Act and the Montreal Protocol, which mandate the eventual phase-out of 1,1,1-trichloroethane production in the U.S.

1,4-Dioxane may contain bis(2-chloroethyl) ether ... as an impurity.

The tendency of 1,4-dioxane to form peroxides may be lessened by the addition of a reducing agent, such as stannous chloride or ferrous sulfate.

Peroxides: 0.003% max (certified reagent), 50 mg/kg max (technical); acetic acid: 0.01% max (certified reagent), 0.1% max (technical); Water : 0.02% max (certified), 0. 1% max (technical); Non-volatile matter : 0.004% max (certified), 0.0025% max (technical) ; 2-methyl-1,3-dioxolane: not reported (certified), 0.05%. /From table/

Certified reagent grade: carbonyl : 0.05% max; heavy metals (Pb) : 0.25 ppm max; iron: 0.25 ppm max. /From table/

(1978) No Data

(1982) No Data

(1987) No Data

(1977) AT LEAST 9.08X10+7 G

(1982) No Data

(1987) No Data

2023: 75,000 - <100,000 lb

(1982) 6.80X10+9 G

(1973) 7.357X10+9 G

(1974) 8.003X10+9 G

(1975) 5.712X10+9 G

For more U.S. Production (Complete) data for 1,4-DIOXANE (15 total), please visit the HSDB record page.

1,4-Dioxane is manufactured commercially by dehydration and ring closure of diethylene glycol. Concentrated sulfuric acid (ca. 5%) is used as a catalyst, although phosphoric acid, p-toluenesulfonic acid, and strongly acidic ion-exchange resins are recognized alternatives. The process is continuous, with dioxane vaporized from the reaction vessel. The vapors are passed through an acid trap and two distillation columns to remove water and to purify the product. Yields of ca. 90% are possible.

Dioxane can ... be prepared by dehydrohalogenation of 2-chloro-2'-hydroxydiethyl ether, by reacting ethylene glycol with 1,2-dibromoethane, and by dimerizing ethylene oxide either over NaHSO4, SiF4, or BF3, or at elevated temperature with an acidic cation-exchange resin.

From beta,beta-dichloroethyl ether by treatment with alkali.

Cosmetics product ingredient: 1,4-Dioxane (1,4-Diethyleneoxide)

Information on 92 consumer products that contain 1,4-Dioxane in the following categories is provided:

Fabricated Metal Product Manufacturing

1,4-Dioxane: ACTIVE

Commercial production of 1,4-dioxane in the United States was first reported in 1951, but semi-commercial quantities were available in 1939.

1,4-Dioxane is a toxic by-product formed during the synthesis of surfactants used in finished cosmetic products.