1,2,4-Trichlorbenzol

Fire Extinguishing Agents: Small fires: dry chemical, CO2, water spray or foam; large fires: water spray, fog or foam. (USCG, 1999)

Use water spray, powder, foam, carbon dioxide.

Fresh air, rest. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Give one or two glasses of water to drink. Refer for medical attention .

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 procedures)

Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may spread fire. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use foam, dry chemical, or carbon dioxide.

1,2,4-Trichlorobenzenes are liquids at room temperature and are shipped in bulk in aluminum tank trucks and steel or stainless steel tank cars.

1,2,4-Trichlorobenzene must be stored to avoid contact with oxidizers (such as perchlorates, peroxides, permanganates, chlorates and nitrates) since violent reactions occur. Sources of ignition, such as smoking and open flames, are prohibited where 1,2,4-trichlorobenzene is used, handled, or stored in a manner that could create a potential fire or explosion hazard.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a POTW is acceptable only after review by the governing authority. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must meet Hazardous Material Criteria for disposal.

If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters. Notify local health and fire officials and pollution control agencies.

Absorb the spills with paper towels or like materials. Place in a hood to evaporate. Dispose by burning the towel.

SMALL SPILLS AND LEAKAGE: If you spill this chemical, FIRST REMOVE ALL SOURCES OF IGNITION. Then, use absorbent paper to pick up all liquid spill material. Your contaminated clothing and absorbent paper should be sealed in a vapor-tight plastic bag for eventual disposal. Solvent wash all contaminated surfaces with 60-70% ethanol followed by washing with a soap and water solution. Do not reenter the contaminated area until the Safety Officer (or other responsible person) has verified that the area has been properly cleaned.

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal, aquatic, and plant life; and conformance with environmental and public health regulations.

Land spill. Dig a pit, pond, lagoon, holding area to contain liquid or solid material. /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./Dike surface flow using soil, sand bags, foamed polyurethane, or foamed concrete. Absorb bulk liquid with fly ash, cement powder, or commercial sorbents. Apply universal gelling agent to immobilize spill. Apply appropriate foam to diminish vapor and fire hazard. Water spill. Use natural deep water pockets, excavated lagoons, or sand bag barriers to trap material at bottom. If dissolved, in region of 10 ppm or greater concentration, apply activated carbon at ten times the spilled amount. Remove trapped material with suction hoses. Use mechanical dredges or lifts to remove immobilized masses of pollutants and precipitates. Air spill. Apply water spray or mist to knock down vapors. Combustion products include corrosive or toxic vapors.

Incineration, preferably after mixing with another combustible fuel. Care must be exercised to assure complete combustion to prevent the formation of phosgene. An alkali scrubber is necessary to remove the halo acids produced. Recommendable method: Incineration.

In the powdered activated carbon treatment (PACT) process, powdered activated carbon is used with the activated sludge method for wastewater treatment. Primary treatment consists of neutralization with lime and settling followed by combined powdered activated carbon-activated sludge for secondary/tertiary treatment. Primary sludge consisting of metal salts and unreacted lime is dewatered before disposal in a lined landfill. Powdered activated carbon and return powdered activated carbon treatment sludge are added to the primary effluent as it is fed to aeration tanks. Treated effluent is discharged after first passing through a settling lagoon. Consistency and efficiency of removal varies greatly among cmpd reported and ranges from 44% for 1,2-dichlorobenzene to 99% for a number of volatile organic compounds. For 1,2,4-trichlorobenzene, 66% was removed giving an average powdered activated carbon treatment effluent of 169 ppb.

The following wastewater treatment technologies have been investigated for 1,2,4-trichlorobenzene: biological treatment, stripping, solvent extraction, activated carbon, and resin adsorption.

Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Collect leaking liquid in sealable containers. Absorb remaining liquid in sand or inert absorbent. If solid: sweep spilled substance into sealable containers. Then store and dispose of according to local regulations.

SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.

SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.

Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Build dikes to contain flow as necessary. Attempt to stop leak if without undue personnel hazard. Use water spray to knock-down vapors. ... Avoid breathing vapors. Keep upwind. ... Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water.

The worker should immediately wash the skin when it becomes contaminated.

Work clothing that becomes wet or significantly contaminated should be removed and replaced.

1,2,4-Trichlorobenzene has been detected in 26% of Canadian human adipose tissue at a mean concn of 103 ng/g(1). Combined trichlorobenzene and tetrachlorobenzene isomers were detected in human adipose tissue in Slovenia at a concn of 60 ng/g and in human hair samples at 40 ng/g(2). A 1992 epidemiologic study of 497 Canadian samples resulted in 49.1% positive detection of 1,2,4-trichlorobenzene at a median concn of 3.4 ng/g lipid with a 118 ng/g lipid maximum concn(3). 1,2,4-Trichlorobenzene was detected in 21 samples of follicular fluid, taken at the time of oocyte retrieval for in vitro fertilization at a concn of 212 pg/mL(4). 1,2,4-Trichlorobenzene was detected in human milk in Yugoslavia at a concn of 25 ppb(5) and human milk in Canada at 0.11 ng/g (whole milk) and 3.81 ng/g (milk fat)(6).

The halogenated benzenes, inducers of xenobiotic metabolism, were studied for their effects on the metabolism of malathion, malaoxon (lindane), and paraoxon and on the toxicity and lethality of these organophosphorus insecticides and parathion. One mmol/kg of 1,4-dichlorobenzene (p-dichlorobenzene), 1,2,4-trichlorobenzene, 1,4-dibromobenzene, 1,2,4-tribromobenzene, or hexabromobenzene or 0.1 mmol/kg hexachlorobenzene was administered po to male mice daily for 7 days. In general, the trihalogenated benzenes increased the LD50 of all 4 insecticides 2- to 6-fold. These increases were larger than those observed with the di- or hexahalogenated isomers. The bromide-substituted benzenes were usually more active than the chlorinated ones with the exception being hexabromobenzene. There was a good correlation between their effects on lethality and increases in in vitro carboxylesterase activity with either malathion or malaoxon as the substrate. The trihalogenated benzenes decreased the inhibitory effect of malathion on cholinesterase activity in the brain and to a lesser degree in the red blood cells, but not in liver or plasma. There was also a good correlation between protection against parathion and paraoxon lethality, protection against inhibition of cholinesterase in the brain and liver by paraoxon, and increases in the dealkylation of paraoxon by microsomal mixed-function oxidases but not by hepatic or plasma esterases. It appears that the halogenated benzenes are able to protect against organophosphorus insecticide toxicity. With malathion, increases in carboxylesterase activity may be important, and with paraoxon, increases in microsomal mixed-function oxidase dealkylation and tissue binding cannot be excluded from contributing to the protection seen.

Endocrine

Eyes, skin, respiratory system, liver, reproductive system

LC50; Species: Allolobophora tuberculata (Earthworm, adult) multiple environmental routes (using filter paper) 23 ug/sq cm for 48 hr (95% confidence interval: 16-32 ug/sq cm)

LC50; Species: Allolobophora tuberculata (Earthworm, adult) direct application (artificial soil, 69% sand, 20% clay, pH 6.0, and 10% organic matter, 35% moisture) 251 mg/kg for 48 hr (95% confidence interval: 167-378 mg/kg)

LC50; Species: Eisenia fetida (Earthworm, adult) multiple environmental routes (using filter paper) 27 ug/sq cm for 48 hr (95% confidence interval: 24-32 ug/sq cm)

LC50; Species: Eisenia fetida (Earthworm, adult) direct application (artificial soil, 69% sand, 20% clay, pH 6.0, and 10% organic matter, 35% moisture) 197 mg/kg for 48 hr (95% confidence interval: 137-282 mg/kg)

For more Ecotoxicity Values (Complete) data for 1,2,4-TRICHLOROBENZENE (41 total), please visit the HSDB record page.

TERRESTRIAL FATE: Based on a classification scheme(1), Koc values of 440(2) to 10,715(3), indicate that 1,2,4-trichlorobenzene is expected to have moderate to no mobility in soil(SRC). Volatilization of 1,2,4-trichlorobenzene from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 1.42X10-3 atm-cu m/mole(4). However, adsorption to soil is expected to attenuate volatilization(SRC). 1,2,4-Trichlorobenzene is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 0.46 mm Hg(5). 1,2,4-Trichlorobenzene is expected to biodegrade slowly in soils with biodegradation half-lives ranging from several weeks to a few months(6,7).

AQUATIC FATE: Based on a classification scheme(1), Koc values of 440(2) 10,715(3), indicate that 1,2,4-trichlorobenzene is expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(4) based upon a Henry's Law constant of 1.42X10-3 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 4.8 hours and 5.6 days, respectively(SRC). However, volatilization from water surfaces is expected to be attenuated by adsorption to suspended solids and sediment in the water column. The volatilization half-life from a model pond is up to 86 days when adsorption is considered(6). According to a classification scheme(7), BCF values of 120 in carp(8) to 57,544 in Atlantic croaker(2), suggest bioconcentration in aquatic organisms is high to very high(SRC). A hydrolysis half-life was given as 3.4 years for 1,2,4-trichlorobenzene(2). The aerobic and anaerobic biodegradation half-lives of 1,2,4-trichlorobenzene in natural waters was reported as 28 and 110 days, respectively(9).

AQUATIC FATE: 1,2,4-Trichlorobenzene has estimated half-lives of 0.3-3, 3-30, and 30-300 days in rivers, lakes and groundwater, respectively(1).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 1,2,4-trichlorobenzene, which has a vapor pressure of 0.46 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase 1,2,4-trichlorobenzene 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 30 days(SRC), calculated from its rate constant of 5.3X10-13 cu cm/molecule-sec at 25 °C(3). The half-life of 1,2,4-trichlorobenzene in surface waters, when exposed to summer sunlight at 40 deg latitude, was calculated as 450 years(4), suggesting that the compound is not expected to be susceptible to direct photolysis by sunlight(SRC).

1,2,4-Trichlorobenzene was detected in corn oil at 0.01 ppm and sunflower oil at 0.003 ppm(1). 1,2,4-Trichlorobenzene was identified, not quantified, in rape seed, walnuts and poppies, soybeans, sesame, and hazelnut(1). 1,2,4-Trichlorobenzene was detected in potatoes at 0.032 ug/kg (peel), cabbage at 0.0159 ug/kg (outer), cauliflower at 0.0104 ug/kg (stem), lettuce at 0.007 ug/kg (outer), and peas at 0.0159 (pod) and 0.0676 ug/kg (seeds)(2).

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.

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

Oral (T38) ; inhalation (T38) ; dermal (T38)

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 1,2,4-Trichlorobenzene is included on this list. Effective date 10/4/82; Sunset date: 10/4/92.

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. Trichlorobenzenes are produced, as an intermediate or final product, by process units covered under this subpart. /The standards apply to all of the isomers and mixtures./

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. 1,2,4-Trichlorobenzene 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 5 ug/L

(NJ) NEW JERSEY 9 ug/L

(AZ) ARIZONA 140 ug/L

(ME) MAINE 70 ug/L

1,2,4-Trichlorobenzene is used as a dye carrier, a herbicide intermediate, a heat-transfer medium, a dielectric fluid in transformers, a degreaser, a lubricant, in synthetic transformer oils, and as a solvent in chemical manufacturing. 1,2,4-Trichlorobenzene was formerly used as an insecticide against termites.

Used as a dielectric and heat transfer fluid and as an intermediate for other organic chemicals; [ACGIH] Used as a degreaser, wood preservative, and dye solvent; [HSDB]

Metal Degreasing [Category: Clean]

For 1,2,4-trichlorobenzene (USEPA/OPP Pesticide Code: 081101) there are 0 labels match. /SRP: Not registered for current use in the U.S., but approved pesticide uses may change periodically and so federal, state and local authorities must be consulted for currently approved uses./

Solvent in chemical manufacturing, dyes and intermediates, dielectric fluid, synthetic transformer oils, lubricants, heat-transfer medium, insecticides.

Trichlorobenzene ... has been used as a soil treatment to repel or poison termites around the foundation of buildings. The technical product is a mixture of the 1,2,3- and 1,2,4- isomers. /SRP: Former use/

(1975) 8.78X10+8 g (Principle Customs Distributors)

(1983) 1.39X10+9 g /1,2,3- and 1,2,4-Trichlorobenzene/

2023: 1,000,000 - <5,000,000 lb

(1972) 7.10X10+9 g

(1973) 1.28X10+10 g

(1982) 2,750,000 to 8,070,000 lb/yr

Benzene, 1,2,4-trichloro- is listed as a High Production Volume (HPV) chemical (65FR81686). Chemicals listed as HPV were produced in or imported into the U.S. in >1 million pounds in 1990 and/or 1994. The HPV list is based on the 1990 Inventory Update Rule. (IUR) (40 CFR part 710 subpart B; 51FR21438).

For more U.S. Production (Complete) data for 1,2,4-TRICHLOROBENZENE (6 total), please visit the HSDB record page.

The batch reaction of benzene with a 2.8-fold molar quantity of chlorine in the presence of ferric chloride at temperatures increasing to 100 °C gives a chlorination mixture consisting of 26% 1,4-dichlorobenzene, 4.5% 1,2-dichlorobenzene, 48% 1,2,4-trichlorobenzene, 8% 1,2,3-trichlorobenzene, 8% 1,2,3,4-tetrachlorobenzene, 5.5% 1,2,4,5-tetrachlorobenzene, and less than 1% pentachlorobenzene. The proportion of 1,4-dichlorobenzene, and thus also of 1,2,4-trichlorobenzene, can be raised by adding sulfur compounds as cocatalysts. After the chlorination mixture has been neutralized it can be separated by fractional distillation provided a column with more than 60 practical plates is used.

... Production method applicable to 1,2,4- and 1,2,3-trichlorobenzenes is based on the dehydrohalogenation of 1,2,3,4,5,6-hexachlorocyclohexane (stereoisomeric mixture), a byproduct of gamma-hexachlorocyclohexane production. In the presence of aqueous alkali or alkaline earth solutions or of ammonia, or directly through use of catalysts, hexachlorocyclohexane is converted at a temperature of 90 - 250 °C mainly to trichlorobenzene. The yield lies between 80 and 99%, with the product mixture consisting of 70 - 85% 1,2,4-trichlorobenzene and 13 - 30% 1,2,3-trichlorobenzene.

Chlorination of monochlorobenzene

... From 2,4-dichloroaniline or 2,5-dichloroaniline or 3,4-dichloroaniline by diazotization and treatment with Cu2Cl2. ... From 1,3-diaminobenzene by tetrazotization & treatment with Cu2Cl2.

Dehydrochlorination at 60 °C of the alpha, delta, and gamma isomers of benzene hexachloride.

Paint and Coating Manufacturing

Benzene, 1,2,4-trichloro-: ACTIVE

1,2,4-Trichlorobenzene is formed in minor quantities during the production of monochlorobenzene.