Calcium cyanide

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

Use powder, dry sand. NO hydrous agents. NO water. NO carbon dioxide.

Administration of oxygen may be needed. Fresh air, rest. Artificial respiration may be needed. No mouth-to-mouth artificial respiration. Refer immediately for medical attention.

Wear protective gloves when administering first aid. Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer immediately for medical attention .

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

Rinse mouth. Administration of oxygen may be needed. NO mouth-to-mouth artificial respiration. Do NOT induce vomiting. Refer immediately 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.

· 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:

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

2.0 [mg/m3], inhalable fraction, as CN[German Research Foundation (DFG)]

Use powder, dry sand. NO hydrous agents. NO water. NO carbon dioxide.

Extinguish fire using agent suitable for surrounding fire. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. Use water spray to keep fire-exposed containers cool.

Carbon dioxide fire extinguishers must not be used where cyanide salts are present. /Cyanide salts/

If material involved in fire: Extinguish fire using agent suitable for type of surrounding fire. (Material ifself does not burn or burns with difficulty.) Use foam, dry chemical, or carbon dioxide. Do not use water on meterial itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors. /Calcium cyanide, solid/

Store in cool, dry, well-ventilated location. Separate from acids, oxidizing materials.

Cyanide salts as solids must be stored in sealed or tightly closed containers. No hooks should be used in handling cyanide containers. ... Storage areas must be adequately ventilated to ensure that cyanide concentrations do not exceed the recommended workplace environmental limits. ... /Cyanide salts/

All containers of cyanide salts should be kept covered or in exhaust hood when not in use. /Cyanides/

Cyanide salts as solids or solutions must be ... protected from corrosion or damage. They should be stored so there is no contact with nitrate-nitrite mixtures or peroxides. /Cyanide salts/

... Should be stored in cool, well-ventilated place, out of direct rays of sun, away from ... fire hazard, & should be periodically inspected & monitored. Incompatible materials should be isolated ... /Cyanides and Copper compounds/

Environmental considerations - Water spill: Add dilute caustic soda. Add calcium hypochlorite. Adjust pH to neutral (pH= 7). /Calcium cyanide, solid/

Environmental considerations - Land spill: Dig a pit, pond, lagoon, or 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 a plastic sheet to prevent dissolving in rain or fire fighting water. /Calcium cyanide, solid/

Spills of cyanide salts should be immediately and carefully cleaned up by shoveling the material into a proper container. Care must be exercised to minimize any dispersal of cyanide dust into the air. /Cyanide salts/

Waste cyanide salts from case hardening of steel are destroyed by reacting the salts at 650-700 °C with waste ferric hydroxide sludges from various sources. /Cyanide salts/

For more Cleanup Methods (Complete) data for CALCIUM CYANIDE (6 total), please visit the HSDB record page.

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.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P021; D003, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Cyanide salts should not be flushed into any drain which may contain or subsequently receive acid waste. ... Cyanide process waste solutions and flushings from spills should be passed through a cyanide waste disposal system. /Cyanide salts/

Calcium cyanide is a poor candidate for incineration.

The cyanides are well known to be extremely toxic. Hydrogen cyanide /HCN/ is a gas, and calcium cyanide /CaCN2/ is a solid which releases HCN slowly in moist air or rapidly in acid: CaCN(2) should never be treated with acid in disposal. The cyanides are rapidly converted to the much less toxic cyanates by treatment with alkaline hypochlorite: CN- + ClO- --- pH 10-11.5 --- H2O ---> CNO- Cl-. This reaction forms the basis of the Manufacturing Chemists Association (USA) for the treatment of "package lots" of cyanide wastes: "Add with stirring to strong alkaline soln of calcium hypochlorite. Let stand 24 hr. Flush the cyanate down the drain with large excess of water." In fact, however, the cyanate is also oxidized in mild alkaline hypochlorite to carbon dioxide and nitrogen as shown by the equation: 2CNO- + 3ClO- + H2O --- pH 7.0-9.5 --- H20 ---> 2CO2 + N2 + 3Cl- + 2OH-. Thus the overall reaction for disposal of calcium cyanide with sodium hypochlorite would be: Ca(CN)2 + 6NaClO + H2O --- pH 9.5 ---> Ca(OH)2 + 6NaCl + 2CO2 + N2. Hydrogen cyanide is not persistent in the environment and very small amt of it could be disposed of alternatively by slow release to the atmosphere in a well ventilated outdoor location. Similarly very small amt of Ca(CN)2 could be disposed of by exposure to moist air followed by water dilution. Recommendable methods: Oxidation, landfill, & discharge to sewer. Peer-review: Cyanides can be incinerated either directly or after liberation of HCN by acid but unless extensive equipment is available this cannot be recommended. Acid treatment of cyanides liberates HCN. If this gas cannot be handled safely in properly designed equipment, acidification cannot be recommended. Alkaline oxidation of cyanide can be achieved with sodium hypochlorite, hydrogen peroxide. Depending on the cyanides present the product will be a sludge or soln which if sufficient reaction time has been allowed, will be largely free from free cyanide. Soluble cyanides can be reacted with alkaline ferrous sulfate (excess) and allowed to stand (stirred) several hr. The resulting sludge containing insoluble complex iron cyanides, will still contain small amt of free cyanide, but can be deposited in a landfill. Cyanide is efficiently destroyed in soln, by reaction with formaldehyde. (Peer-review conclusions of an IRPTC expert consultation (May 1985))

Evacuate danger area! Consult an expert! Personal protection: chemical protection suit including self-contained breathing apparatus. Do NOT let this chemical enter the environment. Do NOT wash away into sewer. Sweep spilled substance into covered containers. Carefully collect remainder. Then store and dispose of according to local regulations. Prevent contact with water or moist substances.

Antidotes to cyanide poisoning include hydroxocobalamin and sodium nitrite, which release the cyanide from the cytochrome system, and rhodanase, which is an enzyme occurring naturally in mammals that combines serum cyanide with thiosulfate, producing comparatively harmless thiocyanate. Oxygen therapy can also be administered. (L97)

Exposure to high levels of cyanide for a short time harms the brain and heart and can even cause coma, seizures, apnea, cardiac arrest and death. Chronic inhalation of cyanide causes breathing difficulties, chest pain, vomiting, blood changes, headaches, and enlargement of the thyroid gland. Skin contact with cyanide salts can irritate and produce sores. (L96, L97)

AQUATIC FATE: The alkali metal salts are very soluble in water, and as a result, they readily dissociate into their respective anions and cations upon release to water. The resulting cyanide ion may then form hydrogen cyanide or react with various metals present in natural water. If the cyanide ion is present in excess, complex metallocyanides may form; however, if metals are prevalent, simple metal cyanides may form. /Alkali metal cyanides/

Calcium cyanide was detected in one of 13,085 samples of foods collected in 10 state laboratories (CA, FL, IN, MA, MI, NC, NY, OR, VA, WI) over 1988 (0.007% samples positive); the concentration was below the tolerance limit. The compound was not detected in samples collected in 1989(1). Fumigation of greenhouses with 0.5 and 1.0 oz calcium cyanide followed by airing as recommended did not result in HCN residues on tomatoes. Amount of residues present on first day after fumigation was insignificant(2).

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

Inhalation (L96) ; oral (L96) ; dermal (L96)

Organic nitriles decompose into cyanide ions both in vivo and in vitro. Consequently the primary mechanism of toxicity for organic nitriles is their production of toxic cyanide ions or hydrogen cyanide. Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L97)

/AQUATIC SPECIES/ Except for the more sensitive invertebrate species, such as Daphnia pulex and Gammarus pseudolimnaeus (scud), invertebrate species are usually more tolerant of cyanide than are freshwater fish species, which have most acute values clustered between 50 to 200 ug/L. A long-term survival and two life cycle test with fish gave chronic values of 7.9, 14, and 16 ug/L, respectively, with Gammarus pseudolimnaeus being comparable to fish in sensitivity and isopods being considerably more tolerant. /Free cyanide: HCN and CN-/

Headache. Weakness. Dizziness. Cough. Chest tightness. Laboured breathing. Shortness of breath. Irregular heartbeat. Confusion. Convulsions. Unconsciousness.

MAY BE ABSORBED! Redness. Further see Inhalation.

Redness. Pain.

Nausea. Vomiting. Further see Inhalation.

Cyanide poisoning is identified by rapid, deep breathing and shortness of breath, general weakness, giddiness, headaches, vertigo, confusion, convulsions/seizures and eventually loss of consciousness. (L96, L97)

Calcium cyanide

Reproductive

1 x 10 ^-3 mg/kg-day

P021; As stipulated in 40 CFR 261.33, when calcium cyanide, 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)).

/SRP:/ D003; A solid waste containing calcium cyanide 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.

As the federal pesticide law FIFRA directs, EPA is conducting a comprehensive review of older pesticides to consider their health and environmental effects and make decisions about their continued use. Under this pesticide reregistration program, EPA examines newer health and safety data for pesticide active ingredients initially registered before November 1, 1984, and determines whether the use of the pesticide does not pose unreasonable risk in accordance to newer saftey standards, such as those described in the Food Quality Protection Act of 1996. Pesticides for which EPA had not issued Registration Standards prior to the effective date of FIFRA '88 were divided into three lists based upon their potential for human exposure and other factors, with List B containing pesticides of greater concern than those on List C, and with List C containing pesticides of greater concern than those on List D. Calcium cyanide is found on List C. Case No: 3086; Pesticide type: rodenticide; Case Status: RED Approved 09/94; OPP has made a decision that some/all uses of the pesticide are eligible for reregistration, as reflected in a Reregistration Eligibility Decision (RED) document.; Active ingredient (AI): calcium cyanide; AI Status: The active ingredient is no longer contained in any registered pesticide products ... "cancelled."

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).

Calcium cyanide is designated as a hazardous substance under section 311(b)(2)(A) of the Federal Water Pollution Control Act and further regulated by the Clean Water Act Amendments of 1977 and 1978. These regulations apply to discharges of this substance. This designation includes any isomers and hydrates, as well as any solutions and mixtures containing this substance.

Toxic pollutant designated pursuant to section 307(a)(1) of the Federal Water Pollution Control Act and is subject to effluent limitations. /Cyanides/

Used to make stainless-steel and other cyanides; Also used to leach ores for precious metals and to stabilize cement; No longer registered as a pesticide product (rodenticide, fumigant, insecticide, and miticide); [HSDB] Produced only in South Africa and used there to leach precious metals from ores; [Ullmann]

Steel Producing [Category: Industry]

For calcium cyanide (USEPA/OPP Pesticide Code: 074001) 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./

The active ingredient is no longer contained in any registered pesticide products ... "cancelled."

Calcium cyanide is used as a cement stabilizer...

Calcium cyanide was introduced by American Cyanamid Co (who no longer manufacture or market it) and by Degesch AG (now Detia Degesch GmbH).

(1984) 2.19X10+7 g

(1986) 468,246 Lb

The alkaline earth metal cyanides can be obtained by reaction of the corresponding metal hydroxides with hydrogen cyanide. However, only liquid calcium cyanide is produced by this method. The resulting product has a brownish color due to polymerization of HCN, liberated by hydrolysis.

Black cyanide is produced by treating calcium carbide with nitrogen gas to give calcium cyanamide. The crude cyanamide is then mixed with sodium chloride and heated in electric furnaces above 1000 °C. The cyanamide is converted into calcium cyanide, which is quenched to produce amorphous flakes. The reaction product is gray-black because of the presence of 1-2% carbon. The cyanide content of the amorphous black cyanide is ca. 45-50% NaCN equivalent. Other constituents are 32% NaCN, 12% CaO, 2-3% CaCl2, and 2-3% CaNCN.

Calcium cyanide is manufactured by heating calcium cyanamide with a source of carbon in electric furnaces at temperatures >1,000 °C. It may also be produced by neutralization of lime with hydrogen cyanide.

Calcium cyanide may be prepd by fusing calcium cyanamide ... With sodium chloride to give crude mixt of calcium cyanide and sodium cyanide.

For more Methods of Manufacturing (Complete) data for CALCIUM CYANIDE (6 total), please visit the HSDB record page.

Commercial preparations contain 40-50% Ca(CN)2 /calcium cyanide/.

GRADES or PURITY: 42% with 58% inert ingredients. May contain up to 3% calcium carbide, which releases flammable acetylene gas when wet.

Crude calcium cyanide containing about 48-50% NaCN, is ... commonly called black cyanide and is marketed in flake form, as a powder, or as cast blocks under the trademarks Aero and Cyanogas of the American Cyanamid Company.

Calcium cyanide (Ca(CN)2): ACTIVE

The WHO Recommended Classification of Pesticides by Hazard identifies calcium cyanide (technical grade) as Class IA: extremely hazardous; Main Use: fumigant.

... Pure solid calcium cyanide is unstable, and the commercial product can only be manufactured in amorphous form with a content of about 45 - 50% NaCN equivalent, known as black cyanide. As a solution, calcium cyanide is only sufficiently stable for commercial use at concentrations below 17%.

Liquid and solid calcium cyanide are only produced in South Africa, where they are used for the leaching of precious metals from ores.

Calcium cyanide solutions of about 15% concentration have been prepared for use in gold extraction in South Africa from hydrogen cyanide and lime.