Metalloid
Arsenic is a chemical element; it has the symbol As and atomic number 33. It is a metalloid and one of the pnictogens, and therefore shares many properties with its group 15 neighbors phosphorus and antimony. Arsenic is notoriously toxic. It occurs naturally in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. It has various allotropes, but only the grey form, which has a metallic appearance, is important to industry.
The primary use of arsenic is in alloys of lead (for example, in car batteries and ammunition). Arsenic is also a common n-type dopant in semiconductor electronic devices, and a component of the III–V compound semiconductor gallium arsenide. Arsenic and its compounds, especially the trioxide, are used in the production of pesticides, treated wood products, herbicides, and insecticides. These applications are declining with the increasing recognition of the persistent toxicity of arsenic and its compounds.
Arsenic containing compounds have been known since ancient times to be poisonous to humans. However, a few species of bacteria are able to use arsenic compounds as respiratory metabolites. Trace quantities of arsenic have been proposed to be an essential dietary element in rats, hamsters, goats, and chickens. Research has not been conducted to determine whether small amounts of arsenic may play a role in human metabolism. …
The word arsenic has its origin in the Syriac word ܙܪܢܝܟܐ zarnika, from Arabic al-zarnīḵ الزرنيخ 'the orpiment', based on Persian zar ("gold") from the word زرنيخ zarnikh, meaning "yellow" (literally "gold-colored") and hence "(yellow) orpiment". It was adopted into Greek (using folk etymology) as arsenikon (ἀρσενικόν) – a neuter form of the Greek adjective arsenikos (ἀρσενικός), meaning "male", "virile".
Latin-speakers adopted the Greek term as arsenicum, which in French ultimately became arsenic, whence the English word "arsenic".
Arsenic sulfides (orpiment, realgar) and oxides have been known and used since ancient times. Zosimos (c. 300 AD) describes roasting sandarach (realgar) to obtain cloud of arsenic (arsenic trioxide), which he then reduces to gray arsenic. As the symptoms of arsenic poisoning are not very specific, the substance was frequently used for murder until the advent in the 1830s of the Marsh test, a sensitive chemical test for its presence. (Another less sensitive but more general test is the Reinsch test.) Owing to its use by the ruling class to murder one another and its potency and discreetness, arsenic has been called the "poison of kings" and the "king of poisons". Arsenic became known as "the inheritance powder" due to its use in killing family members in the Renaissance era for a fortune.
During the Bronze Age, arsenic was melted with copper to make arsenical bronze.
Jabir ibn Hayyan described the isolation of arsenic before 815 AD. …
The three most common arsenic allotropes are grey, yellow, and black arsenic, with grey being the most common. Grey arsenic (α-As, space group R3m No. 166) adopts a double-layered structure consisting of many interlocked, ruffled, six-membered rings. Because of weak bonding between the layers, grey arsenic is brittle and has a relatively low Mohs hardness of 3.5. Nearest and next-nearest neighbors form a distorted octahedral complex, with the three atoms in the same double-layer being slightly closer than the three atoms in the next. This relatively close packing leads to a high density of 5.73 g/cm3. Grey arsenic is a semimetal, but becomes a semiconductor with a bandgap of 1.2–1.4 eV if amorphized. Grey arsenic is also the most stable form. Yellow arsenic is soft and waxy, and somewhat similar to tetraphosphorus (P4). Both have four atoms arranged in a tetrahedral structure in which each atom is bound to each of the other three atoms by a single bond. This unstable allotrope, being molecular, is the most volatile, least dense, and most toxic. Solid yellow arsenic is produced by rapid cooling of arsenic vapor, As4. It is rapidly transformed into grey arsenic by light. The yellow form has a density of 1.97 g/cm3. Black arsenic is similar in structure to black phosphorus.
Black arsenic can also be formed by cooling vapor at around 373–493 K (100–220 °C) and by crystallization of amorphous arsenic in the presence of mercury vapors. It is glassy and brittle. …
Arsenic is the 53rd most abundant element in the Earth's crust, comprising about 1.5 parts per million (0.00015%). Typical background concentrations of arsenic do not exceed 3 ng/m3 in the atmosphere; 100 mg/kg in soil; 400 μg/kg in vegetation; 10 μg/L in freshwater and 1.5 μg/L in seawater. Arsenic is the 22nd most abundant element in seawater and ranks 41st in abundance in the universe.
Minerals with the formula MAsS and MAs2 (M = Fe, Ni, Co) are the dominant commercial sources of arsenic, together with realgar (an arsenic sulfide mineral) and native (elemental) arsenic. An illustrative mineral is arsenopyrite (FeAsS), which is structurally related to iron pyrite. Many minor As-containing minerals are known. Arsenic also occurs in various organic forms in the environment.
In 2015, Peru and China were the top producer of white arsenic with almost 89 % world share, according to the United States Geological Survey. Most arsenic refinement operations in the US and Europe have closed over environmental concerns. Arsenic is found in the smelter dust from copper, gold, and lead smelters, and is recovered primarily from copper refinement dust. Arsenic is the main impurity found in copper concentrates to enter copper smelting facilities. There has been an increase in arsenic in copper concentrates over the years since copper mining has moved into deep high-impurity ores as shallow, low-arsenic copper deposits have been progressively depleted. …
The toxicity of arsenic to insects, bacteria, and fungi led to its use as a wood preservative. In the 1930s, a process of treating wood with chromated copper arsenate (also known as CCA or Tanalith) was invented, and for decades, this treatment was the most extensive industrial use of arsenic. An increased appreciation of the toxicity of arsenic led to a ban of CCA in consumer products in 2004, initiated by the European Union and United States. However, CCA remains in heavy use in other countries (such as on Malaysian rubber plantations).
Arsenic was also used in various agricultural insecticides and poisons. For example, lead hydrogen arsenate was a common insecticide on fruit trees, but contact with the compound sometimes resulted in brain damage among those working the sprayers. In the second half of the 20th century, monosodium methyl arsenate (MSMA) and disodium methyl arsenate (DSMA) – less toxic organic forms of arsenic – replaced lead arsenate in agriculture. These organic arsenicals were in turn phased out in the United States by 2013 in all agricultural activities except cotton farming.
The biogeochemistry of arsenic is complex and includes various adsorption and desorption processes. The toxicity of arsenic is connected to its solubility and is affected by pH. Arsenite (AsO3−3) is more soluble than arsenate (AsO3−4) and is more toxic; however, at a lower pH, arsenate becomes more mobile and toxic. …
Arsenic occurs naturally as a single stable isotope, 75As. Synthetic radioisotopes are known from 64As to 95As, as well as at least 11 isomers.
The most stable of these are 73As with a half-life of 80.30 days and 74As with a half-life of 17.77 days, followed by 71As (65.30 hours), 77As (38.79 hours), 76As (26.24 hours), and 72As (26.0 hours). All others have half-lives under 100 minutes and most under one minute. Isotopes lighter than the stable one generally decay by positron emission or electron capture to germanium isotopes, while those heavier beta decay to selenium isotopes. A notable exception is that 74As decays both ways.
Some species of bacteria obtain their energy in the absence of oxygen by oxidizing various fuels while reducing arsenate to arsenite. Under oxidative environmental conditions some bacteria use arsenite as fuel, which they oxidize to arsenate. The enzymes involved are known as arsenate reductases (Arr).
In 2008, bacteria were discovered that employ a version of photosynthesis in the absence of oxygen with arsenites as electron donors, producing arsenates (just as ordinary photosynthesis uses water as electron donor, producing molecular oxygen). Researchers conjecture that, over the course of history, these photosynthesizing organisms produced the arsenates that allowed the arsenate-reducing bacteria to thrive. One strain, PHS-1, has been isolated and is related to the gammaproteobacterium Ectothiorhodospira shaposhnikovii. The mechanism is unknown, but an encoded Arr enzyme may function in reverse to its known homologues.
In 2010, researchers reported the discovery of a strain of the bacterium Halomonas (designated GFAJ-1) that was allegedly capable of substituting arsenic for phosphorus in its biomolecules, including DNA, when grown in an arsenic-rich, phosphate-limited environment. This claim, published in Science, suggested that arsenic could potentially serve as a building block of life in place of phosphorus, challenging long-standing assumptions about biochemical requirements for life on Earth.
The claim was met with widespread skepticism. …