Cadmium

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Cadmium, 48Cd
Cadmium
Pronunciation/ˈkædmiəm/ ​(KAD-mee-əm)
Appearancesilvery bluish-gray metallic
Standard atomic weight Ar°(Cd)
Cadmium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Zn
↑
Cd
↓
Hg
silver ← cadmium → indium
kJ/mol
Heat of vaporization99.87 kJ/mol
Molar heat capacity26.020 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 530 583 654 745 867 1040
Atomic properties
Discovery and first isolation
Karl Samuel Leberecht Hermann and Friedrich Stromeyer (1817)
Named byFriedrich Stromeyer (1817)
Isotopes of cadmium
Main isotopes[6] Decay
abun­dance half-life (t1/2) mode pro­duct
106Cd 1.25%
stable
107Cd synth 6.5 h ε
107Ag
108Cd 0.89% stable
109Cd synth 462.6 d ε
109Ag
110Cd 12.5% stable
111Cd 12.8% stable
112Cd 24.1% stable
113Cd 12.2% 7.7×1015 y
β−
113In
113mCd synth 14.1 y β− 113In
IT
113Cd
114Cd 28.8% stable
115Cd synth 53.46 h β−
115In
116Cd 7.51% 3.1×1019 y β−β−
116Sn
 Category: Cadmium
| references

Cadmium is a

symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it demonstrates oxidation state +2 in most of its compounds, and like mercury, it has a lower melting point than the transition metals in groups 3 through 11. Cadmium and its congeners in group 12 are often not considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states. The average concentration of cadmium in Earth's crust is between 0.1 and 0.5 parts per million (ppm). It was discovered in 1817 simultaneously by Stromeyer and Hermann, both in Germany, as an impurity in zinc carbonate
.

Cadmium occurs as a minor component in most zinc ores and is a byproduct of zinc production. Cadmium was used for a long time[

glass, and to stabilize plastic. Cadmium use is generally decreasing because it is toxic (it is specifically listed in the European Restriction of Hazardous Substances Directive[7]) and nickel–cadmium batteries have been replaced with nickel–metal hydride and lithium-ion batteries. One of its few new uses is in cadmium telluride solar panels
.

Although cadmium has no known biological function in higher organisms, a cadmium-dependent carbonic anhydrase has been found in marine diatoms.

Characteristics

Physical properties

Cadmium is a soft,

flammable; however, in its powdered form it may burn and release toxic fumes.[10]

Chemical properties

See also: Category:Cadmium compounds

Although cadmium usually has an oxidation state of +2, it also exists in the +1 state. Cadmium and its congeners are not always considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states.[11] Cadmium burns in air to form brown amorphous cadmium oxide (CdO); the crystalline form of this compound is a dark red which changes color when heated, similar to zinc oxide. Hydrochloric acid, sulfuric acid, and nitric acid dissolve cadmium by forming cadmium chloride (CdCl2), cadmium sulfate (CdSO4), or cadmium nitrate (Cd(NO3)2). The oxidation state +1 can be produced by dissolving cadmium in a mixture of cadmium chloride and aluminium chloride, forming the Cd22+ cation, which is similar to the Hg22+ cation in mercury(I) chloride.[8]

Cd + CdCl2 + 2 AlCl3 → Cd2(AlCl4)2

The structures of many cadmium complexes with nucleobases, amino acids, and vitamins have been determined.[12]

Isotopes

The cadmium-113 total cross section clearly showing the cadmium cut-off
Main article: Isotopes of cadmium

Naturally occurring cadmium is composed of eight

meta states, with the most stable being 113mCd (t1⁄2 = 14.1 years), 115mCd (t1⁄2 = 44.6 days), and 117mCd (t1⁄2 = 3.36 hours).[13]

The known isotopes of cadmium range in

beta emission producing element 49 (indium).[13]

One isotope of cadmium, 113Cd,

fast neutrons.[14]

Cadmium is created via the s-process in low- to medium-mass stars with masses of 0.6 to 10 solar masses, over thousands of years. In that process, a silver atom captures a neutron and then undergoes beta decay.[15]

History

Friedrich Stromeyer

Cadmium (

discovered in contaminated zinc compounds sold in pharmacies in Germany[16] in 1817 by Friedrich Stromeyer.[17] Karl Samuel Leberecht Hermann simultaneously investigated the discoloration in zinc oxide and found an impurity, first suspected to be arsenic, because of the yellow precipitate with hydrogen sulfide. Additionally Stromeyer discovered that one supplier sold zinc carbonate instead of zinc oxide.[7] Stromeyer found the new element as an impurity in zinc carbonate (calamine), and, for 100 years, Germany remained the only important producer of the metal. The metal was named after the Latin word for calamine, because it was found in this zinc ore. Stromeyer noted that some impure samples of calamine changed color when heated but pure calamine did not. He was persistent in studying these results and eventually isolated cadmium metal by roasting and reducing the sulfide. The potential for cadmium yellow as pigment was recognized in the 1840s, but the lack of cadmium limited this application.[18][19][20]

Even though cadmium and its compounds are toxic in certain forms and concentrations, the British Pharmaceutical Codex from 1907 states that cadmium iodide was used as a medication to treat "enlarged joints, scrofulous glands, and chilblains".[21]

In 1907, the

ångström in terms of a red cadmium spectral line (1 wavelength = 6438.46963 Å).[22][23] This was adopted by the 7th General Conference on Weights and Measures in 1927. In 1960, the definitions of both the metre and ångström were changed to use krypton.[24]

After the industrial scale production of cadmium started in the 1930s and 1940s, the major application of cadmium was the coating of iron and steel to prevent corrosion; in 1944, 62% and in 1956, 59% of the cadmium in the United States was used for plating.[7][25] In 1956, 24% of the cadmium in the United States was used for a second application in red, orange and yellow pigments from sulfides and selenides of cadmium.[25]

The stabilizing effect of cadmium chemicals like the carboxylates cadmium laurate and cadmium stearate on PVC led to an increased use of those compounds in the 1970s and 1980s. The demand for cadmium in pigments, coatings, stabilizers, and alloys declined as a result of environmental and health regulations in the 1980s and 1990s; in 2006, only 7% of total cadmium consumption was used for plating, and only 10% was used for pigments.[7] At the same time, these decreases in consumption were compensated by a growing demand for cadmium for nickel–cadmium batteries, which accounted for 81% of the cadmium consumption in the United States in 2006.[26]

Occurrence

Cadmium metal
See also: Category:Cadmium minerals

Cadmium makes up about 0.1 

ppm of Earth's crust. It is much rarer than zinc, which makes up about 65 ppm.[27] No significant deposits of cadmium-containing ores are known. The only cadmium mineral of importance, greenockite (CdS), is nearly always associated with sphalerite (ZnS). This association is caused by geochemical similarity between zinc and cadmium, with no geological process likely to separate them. Thus, cadmium is produced mainly as a byproduct of mining, smelting, and refining sulfidic ores of zinc, and, to a lesser degree, lead and copper. Small amounts of cadmium, about 10% of consumption, are produced from secondary sources, mainly from dust generated by recycling iron and steel scrap. Production in the United States began in 1907,[20] but wide use began after World War I.[28][29]

Metallic cadmium can be found in the

Vilyuy River basin in Siberia.[30]

Rocks mined for phosphate fertilizers contain varying amounts of cadmium, resulting in a cadmium concentration of as much as 300 mg/kg in the fertilizers and a high cadmium content in agricultural soils.

coal fly ash.[33]

Cadmium in soil can be absorbed by crops such as rice and cocoa. In 2002, the

Chinese ministry of agriculture measured that 28% of rice it sampled had excess lead and 10% had excess cadmium above limits defined by law. Consumer Reports tested 28 brands of dark chocolate sold in the United States in 2022, and found cadmium in all of them, with 13 exceeding the California Maximum Allowable Dose level.[34]

Some plants such as willow trees and poplars have been found to clean both lead and cadmium from soil.[35]

Typical background concentrations of cadmium do not exceed 5 ng/m3 in the atmosphere; 2 mg/kg in soil; 1 μg/L in freshwater and 50 ng/L in seawater.[36] Concentrations of cadmium above 10 μg/L may be stable in water having low total solute concentrations and p H and can be difficult to remove by conventional water treatment processes.[37]

Production

Cadmium is a common impurity in

precipitated from the electrolysis solution.[29][39]

The British Geological Survey reports that in 2001, China was the top producer of cadmium with almost one-sixth of the world's production, closely followed by South Korea and Japan.[40]

  • History of the world production of cadmium
    History of the world production of cadmium
  • Cadmium production in 2010.
    Cadmium production in 2010.

Applications

Cadmium is a common component of electric batteries, pigments,[41] coatings,[42] and electroplating.[43]

Batteries

Ni–Cd batteries

In 2009, 86% of cadmium was used in

alkaline electrolyte (potassium hydroxide).[44] The European Union put a limit on cadmium in electronics in 2004 of 0.01%,[45] with some exceptions, and in 2006 reduced the limit on cadmium content to 0.002%.[46] Another type of battery based on cadmium is the silver–cadmium battery
.

Electroplating

A photograph and representative spectrum of photoluminescence from colloidal CdSe quantum dots

Cadmium electroplating, consuming 6% of the global production, is used in the aircraft industry to reduce corrosion of steel components.[43] This coating is passivated by chromate salts.[42] A limitation of cadmium plating is hydrogen embrittlement of high-strength steels from the electroplating process. Therefore, steel parts heat-treated to tensile strength above 1300 MPa (200 ksi) should be coated by an alternative method (such as special low-embrittlement cadmium electroplating processes or physical vapor deposition).

Titanium embrittlement from cadmium-plated tool residues resulted in banishment of those tools (and the implementation of routine tool testing to detect cadmium contamination) in the A-12/SR-71, U-2, and subsequent aircraft programs that use titanium.[47]

Nuclear fission

Cadmium is used in the control rods of nuclear reactors, acting as a very effective neutron poison to control neutron flux in nuclear fission.[43] When cadmium rods are inserted in the core of a nuclear reactor, cadmium absorbs neutrons, preventing them from creating additional fission events, thus controlling the amount of reactivity. The pressurized water reactor designed by Westinghouse Electric Company uses an alloy consisting of 80% silver, 15% indium, and 5% cadmium.[43]

Televisions

QLED TVs have been starting to include cadmium in construction. Some companies have been looking to reduce the environmental impact of human exposure and pollution of the material in televisions during production.[48]

Anticancer drugs

Complexes based on cadmium and other heavy metals have potential for the treatment of cancer, but their use is often limited due to toxic side effects.[49]

Compounds

Train painted with cadmium orange

Cadmium oxide was used in black and white television phosphors and in the blue and green phosphors of color television cathode ray tubes.[50] Cadmium sulfide (CdS) is used as a photoconductive surface coating for photocopier drums.[51]

Cadmium sulfide

Various cadmium salts are used in paint pigments, with CdS as a

watercolors, gouaches, acrylics, and other paint and pigment formulations. Because these pigments are potentially toxic, users should use a barrier cream on the hands to prevent absorption through the skin[41] even though the amount of cadmium absorbed into the body through the skin is reported to be less than 1%.[10]

In

coefficient of friction and fatigue resistance.[43] It is also found in some of the lowest-melting alloys, such as Wood's metal.[53]

Semiconductors

Cadmium is an element in some

HgCdTe detectors are sensitive to mid-infrared light[43]
and used in some motion detectors.

Laboratory uses

monochromatic color arises from the 441.563 nm transition line
of cadmium.

Helium–cadmium lasers are a common source of blue or ultraviolet laser light. Lasers at wavelengths of 325, 354 and 442 nm are made using this

fluorescence microscopy as well as various laboratory uses requiring laser light at these wavelengths.[54][55]

Cadmium selenide quantum dots emit bright luminescence under UV excitation (He–Cd laser, for example). The color of this luminescence can be green, yellow or red depending on the particle size. Colloidal solutions of those particles are used for imaging of biological tissues and solutions with a fluorescence microscope.[56]

In molecular biology, cadmium is used to block

Hif-1α.[57]

Cadmium-selective sensors based on the fluorophore BODIPY have been developed for imaging and sensing of cadmium in cells.[58] One powerful method for monitoring cadmium in aqueous environments involves electrochemistry. By employing a self-assembled monolayer one can obtain a cadmium selective electrode with a ppt-level sensitivity.[59]

Biological role

Cadmium has no known function in higher organisms and is considered toxic.[60] Cadmium is considered an environmental pollutant hazardous to living organisms.[61] A cadmium-dependent carbonic anhydrase has been found in some marine diatoms,[62] which live in environments with low zinc concentrations.[63]

Cadmium is preferentially absorbed in the kidneys of humans. Up to about 30 mg of cadmium is commonly inhaled throughout human childhood and adolescence.[64]

Cadmium is under research for its potential toxicity to increase the risk of cancer, cardiovascular disease, and osteoporosis.[65][66][67][68]

Environmental impact

The biogeochemistry of cadmium and its release to the environment is under research.[69][70]

Safety

Main article: Cadmium poisoning
Cadmium
Hazards
GHS labelling:[71]
GHS06: Toxic GHS08: Health hazard GHS09: Environmental hazard
Danger
H301, H330, H341, H350, H361fd, H372, H410
P201, P202, P260, P264, P273, P304+P340+P310
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
0
0

Individuals and organizations have been reviewing cadmium's bioinorganic aspects for its toxicity.[72] The most dangerous form of occupational exposure to cadmium is inhalation of fine dust and fumes, or ingestion of highly soluble cadmium compounds.[7] Inhalation of cadmium fumes can result initially in metal fume fever, but may progress to chemical pneumonitis, pulmonary edema, and death.[73]

Cadmium is also an environmental hazard. Human exposure is primarily from fossil fuel combustion, phosphate fertilizers, natural sources, iron and steel production, cement production and related activities, nonferrous metals production, and municipal solid waste incineration.[7] Other sources of cadmium include bread, root crops, and vegetables.[74]

Jinzū River area, which was contaminated with cadmium

There have been a few instances of general population poisoning as the result of long-term exposure to cadmium in contaminated food and water. Research into an estrogen mimicry that may induce breast cancer is ongoing, as of 2012.

glucosuria.[75] The victims of this poisoning were almost exclusively post-menopausal women with low iron and low body stores of other minerals. Similar general population cadmium exposures in other parts of the world have not resulted in the same health problems because the populations maintained sufficient iron and other mineral levels. Thus, although cadmium is a major factor in the itai-itai disease in Japan, most researchers have concluded that it was one of several factors.[7]

Cadmium is one of six substances banned by the European Union's

Restriction of Hazardous Substances (RoHS) directive, which regulates hazardous substances in electrical and electronic equipment, but allows for certain exemptions and exclusions from the scope of the law.[76]

The International Agency for Research on Cancer has classified cadmium and cadmium compounds as carcinogenic to humans.[77] Although occupational exposure to cadmium is linked to lung and prostate cancer, there is still uncertainty about the carcinogenicity of cadmium in low environmental exposure. Recent data from epidemiological studies suggest that intake of cadmium through diet is associated with a higher risk of endometrial, breast, and prostate cancer as well as with osteoporosis in humans.[78][79][80][81] A recent study has demonstrated that endometrial tissue is characterized by higher levels of cadmium in current and former smoking females.[82]

Cadmium exposure is associated with a large number of illnesses including kidney disease,

MAPK signaling pathways at low doses.[87][88][89]

The

tobacco plant absorbs and accumulates heavy metals such as cadmium from the surrounding soil into its leaves. Following tobacco smoke inhalation, these are readily absorbed into the body of users.[90] Tobacco smoking is the most important single source of cadmium exposure in the general population. An estimated 10% of the cadmium content of a cigarette is inhaled through smoking. Absorption of cadmium through the lungs is more effective than through the gut. As much as 50% of the cadmium inhaled in cigarette smoke may be absorbed.[91]
On average, cadmium concentrations in the blood of smokers is 4 to 5 times greater than non-smokers and in the kidney, 2–3 times greater than in non-smokers. Despite the high cadmium content in cigarette smoke, there seems to be little exposure to cadmium from passive smoking.[92]

In a non-smoking population, food is the greatest source of exposure. High quantities of cadmium can be found in

fungi and algae products. However, grains, vegetables, and starchy roots and tubers are consumed in much greater quantity in the U.S., and are the source of the greatest dietary exposure there.[93] Most plants bio-accumulate metal toxins such as cadmium and when composted to form organic fertilizers, yield a product that often can contain high amounts (e.g., over 0.5 mg) of metal toxins for every kilogram of fertilizer. Fertilizers made from animal dung (e.g., cow dung) or urban waste can contain similar amounts of cadmium. The cadmium added to the soil from fertilizers (rock phosphates or organic fertilizers) become bio-available and toxic only if the soil pH is low (i.e., acidic soils). In the European Union, an analysis of almost 22,000 topsoil samples with LUCAS survey concluded that 5.5% of samples have concentrations higher than 1 mg kg-1.[94]

Zinc, copper, calcium, and iron ions, and selenium with vitamin C are used to treat cadmium intoxication, though it is not easily reversed.[83]

Regulations

Because of the adverse effects of cadmium on the environment and human health, the supply and use of cadmium is restricted in Europe under the

REACH Regulation.[95]

The EFSA Panel on Contaminants in the Food Chain specifies that 2.5 μg/kg body weight is a tolerable weekly intake for humans.[93] The Joint FAO/WHO Expert Committee on Food Additives has declared 7 μg/kg body weight to be the provisional tolerable weekly intake level.[96] The state of California requires a food label to carry a warning about potential exposure to cadmium on products such as cocoa powder.[97] The European Commission has put in place the EU regulation (2019/1009) on fertilizing products (EU, 2019), adopted in June 2019 and fully applicable as of July 2022, sets a Cd limit value in phosphate fertilizers to 60 mg kg-1 of P2O5.

The U.S.

IDLH (immediately dangerous to life and health) level for cadmium is 9 mg/m3.[98]

Lethal dose[99] Organism Route Time
LD50: 225 mg/kg rat oral n/a
LD50: 890 mg/kg mouse oral n/a
LC50: 25 mg/m3 rat airborne 30 min

In addition to mercury, the presence of cadmium in some batteries has led to the requirement of proper disposal (or recycling) of batteries.

Product recalls

In May 2006, a sale of the seats from

Wal-Mart[103]
stores.

In June 2010,

Arc International, of Millville, New Jersey, USA.[105]

See also

Notes

  1. ^ The thermal expansion is anisotropic: the parameters (at 20 °C) for each crystal axis are αa = 18.91×10−6/K, αc = 55.03×10−6/K, and αaverage = αV/3 = 30.95×10−6/K.[3]

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Further reading

  • Hartwig, Andrea (2013). "Cadmium and Cancer". In Astrid Sigel; Helmut Sigel; Roland K. O. Sigel (eds.). Cadmium: From Toxicity to Essentiality. Metal Ions in Life Sciences. Vol. 11. Springer. pp. 491–507.
    PMID 23430782
    .

External links

Look up cadmium in Wiktionary, the free dictionary.
Wikimedia Commons has media related to Cadmium.
Wikisource has the text of the 1911 Encyclopædia Britannica article "Cadmium".

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