Vanadium tetrachloride

· 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.

· Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

General First Aid:

Suitable extinguishing media: Dry powder

Advice for firefighters: Wear self-contained breathing apparatus for firefighting if necessary.

If material involved in fire: Use dry chemical, dry sand, or carbon dioxide. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

Use appropriate extinguishing agents on nearby combustible fires. Dry chemical or carbon dioxide preferred. DO NOT use water. Violent reaction may result.

From a secure, explosion-proof location, use water spray to cool exposed containers. Use water spray to keep fire-exposed containers cool and to reduce vapors but do not get water inside containers of vanadium tetrachloride or on spilled material. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming) withdraw immediately to a secure position. ... The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand of other positive-pressure mode.

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. Never allow product to get in contact with water during storage.

Store in a cool, dry, well-ventilated location. Keep cylinders restrained.

Store separately in a corrosion-resistant location. ... Vanadium tetrachloride must be stored to avoid contact with water, heat, and poisonous gases since violent reactions occur. Store in tightly closed containers in a cool, well-ventilated area away from radiant heat and flammable and combustible materials, lithium, chlorine, and trifluoride. ... Open containers in dry oxygen-free atmosphere or in inert gas, wearing appropriate personal protective equipment. Chill to below 20 °C before opening.

Containers of vanadium shall be kept tightly closed at all times when not in use. Containers shall be stored in a safe manner to minimize accidental breakage, spillage, or contact with moisture. Combustible materials, such as finely ground vanadium carbide, vanadium aluminum alloys, vanadium metal, or ferrovanadium should be kept away from heat, sparks, or flames. /Vanadium compounds/

Divalent and trivalent vanadium compounds are reducing agents and require storage under an inert atmosphere to avoid oxidation. /Divalent and trivalent vanadium compounds/

ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Wear respiratory protection. Avoid breathing vapors, mist, or gas. Ensure adequate ventilation. Evacuate personnel to safe 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: Soak up with inert absorbent material and dispose of as hazardous waste. Do not flush with water. Keep in suitable, closed containers for disposal.

Keep water away from release. Use water spray to cool and disperse vapors and protect personnel. Use appropriate foam to blanket release and suppress vapors.

Evacuate and restrict persons not wearing protective equipment from area of spill or leak until cleanup is complete. Remove all ignition sources. Ventilate area of spill or leak. Do not use water or wet method. Absorb liquids in vermiculite, dry sand, earth, peat, carbon, or a similar material and deposit in sealed containers. Keep out of sewers because of the possibility of fire and explosion. It may be necessary to contain and dispose of this chemical as a hazardous waste. If material or contaminated runoff enters waterways, notify downstream users of potentially contaminated waters.

Environmental considerations: Water spill: Use natural deep water pockets, excavated lagoons, or sand bag barriers to trap material at bottom. Use mechanical dredges or lifts to remove immobilized masses of pollutants and precipitates. /Vanadium compound, N.O.S./

Environmental considerations: 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./ Cover solids with plastic sheet to prevent dissolving in rain or fire fighting water. Dike surface flow using soil, sand bags, foamed polyurethane, or foamed concrete. /Vanadium compound, N.O.S./

SRP: 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 air, soil or water; effects on animal, aquatic and plant life; and conformance with environmental and public health regulations. If it is possible or reasonable use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination.

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 permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. 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 be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

Product: Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber; Contaminated packaging: Dispose of as unused product.

Waste material contaminated with vanadium shall be disposed of in a manner not hazardous to employees. The disposal method must conform with applicable local, state, and federal regulations and must not constitute a hazard to the surrounding population or environment. /Vanadium/

The following wastewater treatment technologies have been investigated for vanadium: Concentration process: chemical precipitation. /Vanadium/

ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Wear respiratory protection. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains.

Precautions for safe handling: Avoid contact with skin and eyes. Avoid inhalation of vapor or mist.

Appropriate engineering controls: Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling the product.

Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands.

For more Preventive Measures (Complete) data for VANADIUM TETRACHLORIDE (14 total), please visit the HSDB record page.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

Immediate precautionary measure

EYES: irrigate opened eyes for several minutes under running water. INGESTION: do not induce vomiting. Rinse mouth with water (never give anything by mouth to an unconscious person). Seek immediate medical advice. SKIN: should be treated immediately by rinsing the affected parts in cold running water for at least 15 minutes, followed by thorough washing with soap and water. If necessary, the person should shower and change contaminated clothing and shoes, and then must seek medical attention. INHALATION: supply fresh air. If required provide artificial respiration.

IDENTIFICATION AND USE: Vanadium tetrachloride is a red-brown, oily liquid. It is used in preparation of vanadium trichloride, vanadium dichloride, and organovanadium compounds. HUMAN EXPOSURE AND TOXICITY: Breathing vanadium tetrachloride can irritate the lungs causing coughing and/or shortness of breath. Higher exposures can cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency, with severe shortness of breath. Exposure may cause a green coating on the tongue. ANIMAL STUDIES: Accidental poisoning in a herd of cattle which had been grazing on pastures contaminated by vanadium tetrachloride has been reported.

Vanadium damages alveolar macrophages by decreasing the macrophage membrane integrity, thus impairing the cells' phagocytotic ability and viability. The pentavalent form of vanadium, vanadate, is a potent inhibitor of the Ca+-ATPase and Na+,K+-ATPase of plasma membranes, which decreases intracellular ATP concentration. Vanadium is also believed to induce the production of reactive oxygen species. This may damage DNA and also cause oxidative stress, which can damage the reproductive system. Vanadium also inhibits protein tyrosine phosphatases, producing insulin-like effects. (L837, A247, A248, A249, A250, A251)

Biological monitoring of vanadium in serum, blood, and urine has been used to monitor vanadium levels in the general population or in occupationally exposed workers. Vanadium levels in these matrices have not, however, been shown to correlate with vanadium levels in the air and as such are of limited usefulness as quantitative biomarkers of exposure. /Vanadium compounds/

Because of cases of bronchial asthma and bronchitis in worker population exposed to vanadium compounds, periodic testing of pulmonary function is recommended. /Vanadium compounds/

The assessment of vanadium exposure can be accomplished through measurement of vanadium. This test may be useful for assessing /exposure/ to larger than normal amounts of vanadium, but there was no information found in the literature showing a correlation of these levels with environmental levels or onset of clinical effects. Blood Reference Ranges: Normal - less than 1 ug/L; Exposed - not established; Toxic - not established. Serum or Plasma Reference Ranges: Normal - less than 0.24 ug/L; Exposed - not established; Toxic - not established. Urine Reference Ranges: Normal - 0.06 to 0.87 ug/L; Exposed - Workers exposed to average 8 hr air concentrations of 6.0 to 6.4 mg/cu m had urine vanadium levels between 2.6 to 4.6 ug/L in specimens that were collected at the start of the next work day. BAT for vanadium pentoxide (sampling time for long term exposures: after several shifts, measured as vanadium): 70 ug/g creatinine; Toxic - In a study involving controlled human exposure to vanadium pentoxide, where levels caused development of mild respiratory effects, the peak urine vanadium level was 130 ug/L at 3 days after exposure. /Vanadium/

Pulmonary Function Tests: The tests that have been found to be practical for population monitoring include: spirometry and expiratory flow-volume curves; determination of lung volumes; diffusing capacity for carbon monoxide; single-breath nitrogen washout; inhalation challenge tests; serial measurements of peak expiratory flow; exercise testing. /Vanadium/

Differentiating vanadium pulmonary toxicity from infection or allergy of the respiratory tract is difficult in that presenting signs and symptoms are similar. A specific vanadium exposure history must be elicited from affected individuals. Examination may reveal a patient with clear watery discharge from the eyes and nose. Mucosal surfaces may be erythematous. Auscultation of lung fields will reveal rhonchi or wheezing. /Vanadium compounds/

/SIGNS AND SYMPTOMS/ A corrosive irritant to skin, eyes, and mucous membranes.

/SIGNS AND SYMPTOMS/ Breathing vanadium tetrachloride can irritate the lungs causing coughing and/or shortness of breath. Higher exposures can cause a build-up of fluid in the lungs (pulmonary edema), a medical emergency, with severe shortness of breath.

/SIGNS AND SYMPTOMS/ Exposure may cause a green coating on the tongue.

Vanadium tetrachloride is readily hydrolyzed(1). Vanadium tetrachloride forms acid mists in moist air; reacts with water to form corrosive fumes of HCl; can react violently or explosively with water(2). Vanadium tetrachloride decomposes by the action of light with the formation of chlorine gas(2).

According to the 2012 TSCA Inventory Update Reporting data, 1 reporting facility estimates the number of persons reasonably likely to be exposed during the manufacturing, processing, or use of vanadium tetrachloride in the United States may be as low as <10 workers per plant; the data may be greatly underestimated due to confidential business information (CBI) or unknown values(1).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1,445 workers (230 of these are female) were potentially exposed to vanadium chloride in the US(1). Occupational exposure to vanadium tetrachloride may occur through inhalation and dermal contact with this compound at workplaces where vanadium tetrachloride is produced or used.

D002; A solid waste containing vanadium tetrachloride may become characterized as a hazardous waste when subjected to testing for corrosivity as stipulated in 40 CFR 261.22, and if so characterized, must be managed as a hazardous waste.

D003; A solid waste containing vanadium tetrachloride may become characterized as a hazardous waste when subjected to testing for reactivity as stipulated in 40 CFR 261.23, and if so characterized, must be managed as a hazardous waste.

Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, exposure, and use to EPA as cited in the preamble in 51 FR 41329. Effective date: 7/11/03; Reporting date: 9/9/03.

(AZ) ARIZONA 7 ug/L /Vanadium/

(FL) FLORIDA 49 ug/L /Vanadium/

(MN) MINNESOTA 50 ug/L /Vanadium/

(WI) WISCONSIN 30 ug/L /Vanadium/

(CA) CALIFORNIA 50 ug/L /Vanadium/