テトラニトロメタン

Toxic Gases & Vapors -> Oxidizers

Carcinogens

Distinct pungent odor

Pungent odor

1.638 at 68 °F (EPA, 1998) - Denser than water; will sink

1.6229 at 20 °C/4 °C

Density: 1.638 at 25 °C/4 °C /Technical/

Relative density (water = 1): 1.6

1.638

1.6380 @ 20°C

Colorless oily fluid

Colorless to pale-yellow liquid or solid (below 57 degrees F).

less than 1 mg/mL at 68 °F (NTP, 1992)

Soluble in ethanol, ether, and carbon tetrachloride

Freely sol in alcoholic potassium hydroxide

In water, 900 mg/L at 25 °C

Solubility in water, g/100ml at 20 °C: 0.009 (very poor)

Insoluble

greater than 235 °F (NTP, 1992)

Flash point > 235 °F

>235 °F

259 °F at 760 mmHg (EPA, 1998)

126 °C at 760 mm Hg; 40 °C at 25.8 mm Hg; 30 °C at 14.9 mm Hg; 20 °C at 8.4 mm Hg; 13.8 °C at 5.7 mm Hg; 0 °C at 1.9 mm Hg

126 °C

259 °F

126.1 °C @760 [mm Hg]

259 °F

It should not be distilled, as explosive decomposition may occur.

When heated to decomposition it emits highly toxic fumes of /nitrogen oxides/.

57.6 °F (EPA, 1998)

13.8 °C

13 °C

57.6 °F

13.8 °C

57 °F

Danger

H271 (100%): May cause fire or explosion; strong Oxidizer [Danger Oxidizing liquids; Oxidizing solids]

P203, P210, P220, P260, P261, P264, P264+P265, P270, P271, P280, P283, P284, P301+P316, P302+P352, P304+P340, P305+P351+P338, P306+P360, P316, P318, P319, P320, P321, P330, P332+P317, P337+P317, P362+P364, P370+P378, P371+P380+P375, P403+P233, P405, P420, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 39 reports by companies from 2 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Danger

H350: May cause cancer [Danger Carcinogenicity]

Hazard Traits - Carcinogenicity

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

Spontaneous chemical reaction may produce fire. Material is a strong oxidizer. The potential for explosion is severe, especially when exposed to heat or to powerful oxidizing or reducing agents; or when shocked or heated. It is more easily detonated than TNT. Impurities can also cause explosion. The material is highly sensitive; hydrocarbons exposed to it form exceedingly sensitive explosives. When heated to decomposition, it emits highly toxic fumes of oxides of nitrogen. Shock will explode it. Avoid hydrocarbons, aluminum, toluene, cotton, aromatic nitro compounds, alkalis, metals and rubber. Avoid impurities, shock, heat, and reducing agents. (EPA, 1998)

· May explode from friction, heat or contamination.

Gives off irritating or toxic fumes (or gases) in a fire. Explosive.

Acute effects include irritation of the eyes and respiratory passages and mild burns to the skin. After more prolonged inhalation, headache and respiratory distress may occur. After prolonged exposure, central nervous system, heart, liver, and kidney damage can occur as well as pulmonary edema. (EPA, 1998)

· TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death.

Mucous membrane and respiratory irritation, pulmonary edema, and methemoglobinemia have been reported after occupational exposure; similar toxicity plus kidney and liver damage have been observed in animal experiments; Listed in the table Examples of Industrial Chemicals for Which Methemoglobin Formation is NOT the Principal Cause of Toxicity; [ACGIH] Can cause reddening of skin if left on clothes; [CHRIS] A lachrymator; [CHEMINFO] A severe skin, eye, and respiratory tract irritant; Can induce methemoglobinemia; May cause pulmonary edema; [ICSC]

1510 143

1510 143

DHHS/NTP; Toxicology and Carcinogenesis Studies of Tetranitromethane in F344 Rats and B6C3F1 Mice (Inhalation Studies) Report #386 (1990) NIH Pub # 90-2841

National Toxicology Program. Eleventh Report on Carcinogens (2005). The Report on Carcinogens is an informational scientific and public health document that identifies and discusses substances (including agents, mixtures, or exposure circumstances) that may pose a carcinogenic hazard to human health. Tetranitromethane (509-14-8) is listed as reasonably anticipated to be a human carcinogen.[Available from, as of July 31, 2009: http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s171tetr.pdf]

P112; As stipulated in 40 CFR 261.33, when tetranitromethane, 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 container or inner liner used to hold this waste or 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(e)).

Do not move cargo or vehicle if cargo has been exposed to heat. Cool containers that are exposed to flames with water from the side until well after fire is out. For massive fire, use unmanned hose holder or monitor nozzles; if this is impossible, withdraw from area and let fire burn.

Use water in large amounts, water spray. In case of fire: keep drums, etc., cool by spraying with water. Combat fire from a sheltered position.

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.

First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again.

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

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

· 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.

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

Warning: Contact with eyes may result in severe damage to the cornea, conjunctiva, and blood vessels. Caution is advised.

General First Aid:

(General first aid procedures)

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

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

If material on fire or involved in fire: use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Solid streams of water may be ineffective. Use foam, dry chemical, or carbon dioxide.

Tetranitromethane 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. Bulk storage facilities must be of explosion-proof design. Containers of tetranitromethane should be protected from physical damage and should be stored separately from hydrocarbons, strong oxidizing agents, radiant heat, sparks, and open flame. Only nonsparking tools may be used to handle tetranitromethane. To prevent static sparks, containers should be grounded and bonded for transfers. Because containers that formerly contained tetranitromethane may still hold product residues, they should be handled appropriately.

PRECAUTIONS FOR "CARCINOGENS": Storage site should be as close as practical 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 & date it was acquired ... Facilities for dispensing ... should be contiguous to storage area. /Chemical Carcinogens/

Ventilation. Remove all ignition sources. Collect leaking liquid in sealable plastic containers. Absorb remaining liquid in sand or inert absorbent and remove to safe place. Do NOT wash away into sewer. Do NOT absorb in saw-dust or other combustible absorbents.

Remove all ignition sources. Ventilate area of spill or leak. Collect for reclamation or absorb in vermiculite, dry sand, earth, or a similar material. Avoid shock & friction if liquid spills on combustible matter such as wood and paper.

In the event of a spill or leak involving tetranitromethane, 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. Do not touch the spilled material. 2. Notify safety personnel. 3. Remove all sources of heat and ignition. 4. Keep combustibles (wood, paper, oil, etc) away from spilled material. 5. Water spray may be used to reduce vapors. 6. For small liquid spills, flush area with flooding amounts of water. 7. For large liquid spills, build dikes far ahead of the spill to contain the tetranitromethane for later reclamation or disposal.

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 & 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 & labelled. ... Broken glassware ... should be decontaminated by solvent extraction, by chemical destruction, or in specially designed incinerators. /Chemical Carcinogens/

A potential candidate for liquid injection incineration at a temperature range of 650 to 1,600 °C and a residence time of 0.1 to 2 seconds. A potential candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. A potential candidate for fluidized bed incineration at a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases, and longer for solids.

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

PRECAUTIONS FOR "CARCINOGENS": ... Incineration may be only feasible method for disposal of contaminated laboratory waste from biological expt. However, not all incinerators are suitable for this purpose. The most efficient type ... is probably the gas-fired type, in which a first-stage combustion with a less than stoichiometric air:fuel ratio is followed by a second stage with excess air. Some ... are designed to accept ... aqueous & organic-solvent solutions, otherwise it is necessary ... to absorb soln onto suitable combustible material, such as sawdust. Alternatively, chem destruction may be used, esp when small quantities ... are to be destroyed in laboratory. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": HEPA (high-efficiency particulate arrestor) filters ... can be disposed of by incineration. For spent charcoal filters, the adsorbed material can be stripped off at high temp & carcinogenic wastes generated by this treatment conducted to & burned in an incinerator. ... LIQUID WASTE: ... Disposal should be carried out by incineration at temp that ... ensure complete combustion. SOLID WASTE: Carcasses of lab animals, cage litter & misc solid wastes ... should be disposed of by incineration at temp high enough to ensure destruction of chem carcinogens or their metabolites. /Chemical Carcinogens/

For more Disposal Methods (Complete) data for TETRANITROMETHANE (6 total), please visit the HSDB record page.

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 100(SRC), determined from a water solubility of 900 mg/L(2) and a regression-derived equation(3), indicates that tetranitromethane is expected to have high mobility in soil(SRC). Volatilization of tetranitromethane from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 0.0024 atm-cu m/mole(SRC), derived from its vapor pressure, 8.42 mm Hg(4), and water solubility(2). Tetranitromethane is expected to volatilize from dry soil surfaces(SRC) based upon its vapor pressure(4).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 100(SRC), determined from a water solubility of 900 mg/L (2) and a regression-derived equation(3), indicates that tetranitromethane is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected to occur rapidly(3) based upon an estimated Henry's Law constant of 0.0024 atm-cu m/mole(SRC), derived from its vapor pressure, 8.42 mm Hg(4), and water solubility(2). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 2 hours and 6 days, respectively(SRC). According to a classification scheme(5), an estimated BCF of 13(SRC), from its water solubility and a regression-derived equation(3), suggests the potential for bioconcentration in aquatic organisms is low(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), tetranitromethane, which has a vapor pressure of 8.42 mm Hg at 25 °C(2), is expected to exist solely as a vapor. Vapor-phase tetranitromethane 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 31 days(SRC), calculated from its estimated rate constant of 5.2X10-13 cu cm/molecule-sec at 25 °C, that was derived using a structure estimation method(3). Tetranitromethane possesses functional groups that absorb light greater than 290 nm and may be susceptible to direct photolysis(4); however, the rate of this potential reaction is unknown.

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

inhalation, ingestion, skin and/or eye contact

Cough. Blue lips, fingernails and skin. Headache. Laboured breathing. Vomiting. Dizziness. Symptoms may be delayed.

Redness. Pain.

Redness. Pain.

See Inhalation.

irritation eyes, skin, nose, throat; dizziness, headache; chest pain, dyspnea (breathing difficulty); methemoglobinemia, cyanosis; skin burns

The following link will take the user to the National Toxicology Program (NTP) Test Agent Search Results page, which tabulates all of the "Standard Toxicology & Carcinogenesis Studies", "Developmental Studies", and "Genetic Toxicity Studies" performed with this chemical. Clicking on the "Testing Status" link will take the user to the status (i.e., in review, in progress, in preparation, on test, completed, etc.) and results of all the studies that the NTP has done on this chemical. [http://ntp-apps.niehs.nih.gov/ntp_tox/index.cfm?fuseaction=ntpsearch.searchresults&searchterm=509-14-8]

Preplacement medical evaluation: Before a worker is placed in a job with a potential for exposure to tetranitromethane, the examining physician 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 monitoring for respiratory disease should be conducted using the principles and methods recommended by NIOSH and the American Thoracic Society ... Periodic medical examinations and biological monitoring: 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 tetranitromethane exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of tetranitromethane on the eyes, skin, or respiratory system ... No biological monitoring test acceptable for routine use has yet been developed for tetranitromethane ... Medical examinations recommended at the time of job transfer or termination: 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 ...

General medical supervision, including periodic medical exam of workers is also recommended.

PRECAUTIONS FOR "CARCINOGENS": Whenever medical surveillance is indicated, in particular when exposure to a carcinogen has occurred, ad hoc decisions should be taken concerning ... /cytogenetic and/or other/ tests that might become useful or mandatory. /Chemical Carcinogens/

The Koc of tetranitromethane is estimated as 100(SRC), using a water solubility of 900 mg/L(1) and a regression-derived equation(2). According to a classification scheme(3), this estimated Koc value suggests that tetranitromethane is expected to have high mobility in soil(SRC).

/SIGNS AND SYMPTOMS/ Nasal irritation, burning eyes, dyspnea, cough, chest oppression, and dizziness in men who handled crude TNT have been attributed to tetranitromethane exposure. Headache, methemoglobinemia, and a few deaths have also been attributed to similar exposure ... Symptoms experienced in the laboratory production of TNM /are/ ... irritations of eyes, nose, and throat from acute exposures and, after more prolonged inhalation, headache and respiratory distress. Skin irritation is not anticipated when humans or animals are repeatedly exposed to TNM.

/SIGNS AND SYMPTOMS/ EFFECTS OF SHORT-TERM EXPOSURE: ... /Tetranitromethane/ is severely irritating to the eyes, the skin and the respiratory tract. Inhalation of the vapor may cause lung edema ... The substance may cause effects on the blood, resulting in the formation of methemoglobin. The substance may cause effects on the kidneys, liver and lungs. Medical observation is indicated. The effects may be delayed ... The symptoms of lung edema often do not become manifest until a few hours have passed and they are aggravated by physical effort. Rest and medical observation is therefore essential ... EFFECTS OF LONG-TERM OR REPEATED EXPOSURE: ... possibly carcinogenic to humans.

/SIGNS AND SYMPTOMS/ ACUTE ... SYMPTOMS: Inhalation /and Ingestion/--Cough. Blue lips or finger nails. Blue skin. Headache. Labored breathing. Vomiting. Dizziness. Symptoms may be delayed; Skin and Eyes--Redness and Pain.

/SIGNS AND SYMPTOMS/ In contact with the skin, tetranitromethane causes mild skin burns ...

For more Human Toxicity Excerpts (Complete) data for TETRANITROMETHANE (7 total), please visit the HSDB record page.

Tetranitromethane's production and use as a rocket fuel, diesel fuel booster, organic reagent, and as an explosive in admixture with toluene(1), may result in its release to the environment through various waste streams(SRC). It may be released as a result of the production of TNT since it is an impurity in the production of this explosive(2).

No data were located regarding the biodegradation of tetranitromethane(SRC, 2006); however, tetranitromethane possesses antibacterial activity and has been used to kill gram negative, gram positive bacteria, bacterial spores and fungi(1), suggesting biodegradation is unlikely at high concentrations of the chemical(SRC).

P112; As stipulated in 40 CFR 261.33, when tetranitromethane, 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 container or inner liner used to hold this waste or 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(e)).

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 10 lb or 4.54 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).

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Tetranitromethane is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.

Tetranitromethane

1

10000

Flammable chemical that can be released at a facility.

... Chemicals such as tetranitromethane ... generate tumors with mutations consistent with the result of DNA adduct formation ...

Tetranitromethane treatment of 3-ketosteroid-Delta(1)-dehydrogenase of Rhodococcus rhodochrous caused loss of the catalytic activity in a time- and concentration-dependent manner. Peptides (P-81) and (PN-83) were isolated from tryptic digests of the native and tetranitromethane-treated enzyme proteins, respectively. PN-83 was the nitrated form of P-81. The amino acid sequence was GGAPLIDYLESDDDLEFMVYPWPDYFGK (positions 97-124 of the dehydrogenase sequence). PN-83 showed a low yield of PTH-Tyr of position 116, i.e. less than 5% of that of P-81, and instead a high yield of PTH-3-nitrotyrosine. This indicated that tetranitromethane modifies Y-116 under the experimental conditions used. Mutation of Y-104, Y-116, and Y-121 to smaller amino acid residues, Phe, Ser, or Ala, significantly changed the catalytic activity of the dehydrogenase. All of the mutants contained FAD and exhibited the same spectrophotometric properties as those of the wild type enzyme. The K(m) values for 4-androstene-3,17-dione of the Y-104, Y-116, and Y-121 mutants changed to large values. The most drastic change was observed for Y116A. The K(d) values for 1,4-androstadiene-3,17-dione of the Y116 mutants changed to 1.5-2.6-fold larger values than that of the recombinant enzyme. The Y-121 mutant enzymes exhibited catalytic activities like those of the recombinant enzyme, but the catalytic efficiencies of Y121F and Y121A drastically decreased to 0. 014-0.054% of that of the recombinant enzyme. The present results indicate that Y-121 plays an important role in the catalytic function, and that Y-116 and Y-104 act on binding of the substrate steroid.

Chemicals that are used to cause the disturbance, disease, or death of humans during WARFARE.

Substances used for the detection, identification, analysis, etc. of chemical, biological, or pathologic processes or conditions. Indicators are substances that change in physical appearance, e.g., color, at or approaching the endpoint of a chemical titration, e.g., on the passage between acidity and alkalinity. Reagents are substances used for the detection or determination of another substance by chemical or microscopical means, especially analysis. Types of reagents are precipitants, solvents, oxidizers, reducers, fluxes, and colorimetric reagents. (From Grant & Hackh's Chemical Dictionary, 5th ed, p301, p499)

Electron-accepting molecules in chemical reactions in which electrons are transferred from one molecule to another (OXIDATION-REDUCTION).

Substances that are energetically unstable and can produce a sudden expansion of the material, called an explosion, which is accompanied by heat, pressure and noise. Other things which have been described as explosive that are not included here are explosive action of laser heating, human performance, sudden epidemiological outbreaks, or fast cell growth.

Used in rocket fuels, explosives, and diesel fuel; [ACGIH]

Rocket fuel, as an oxidant or monopropellant; qualitative test for unsaturated compounds; diesel fuel booster; organic reagent.

Tetranitromethane has been used as an oxidizing agent in rocket propellants. It has also been used as an explosive, as an additive in diesel fuel to increase octane rating, and as a reagent for nitration of tyrosine in proteins and peptides.

TNM is ... of interest for use as a propellant and as a fuel additive ... TNM-hydrocarbon mixtures are more powerful explosives /than TNT/ and are very sensitive to shock ... TNM has also been used to kill gram-negative and gram-positive bacteria, bacterial endospores, and fungi. This antibacterial activity is attributed to nitrating of critical bacterial membrane proteins by TNM.

Tetranitromethane has been used as ... a reagent for detecting the presence of double bonds in organic compounds ...

Tetranitromethane can be prepared by nitration of acetic anhydride with anhydrous nitric acid ... or by reacting fuming nitric acid with benzene or acetylene ... It has also been prepared by nitration of acetylene with excess nitric acid to form a mixture of trinitromethane and nitric acid, which can be converted to tetranitromethane by sulfuric acid at elevated temperatures

Tetranitromethane is formed by the quantitative reaction between potassium nitroform and nitryl chloride in ether.

Methane, tetranitro-: ACTIVE

Has been proposed as irritant war gas.

Found as a contaminant in trinitrotoluene (TNT)