Arsenic Poisoning
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Arsenic is a
chemical element A chemical element is a species of atoms that have a given number of protons in their nuclei, including the pure substance consisting only of that species. Unlike chemical compounds, chemical elements cannot be broken down into simpler sub ...
with the
symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, object, or relationship. Symbols allow people to go beyond what is known or seen by creating linkages between otherwise very different conc ...
As and
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
33. Arsenic occurs in many minerals, usually in combination with
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
and
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
s, but also as a pure elemental
crystal A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
. Arsenic is a
metalloid A metalloid is a type of chemical element which has a preponderance of material property, properties in between, or that are a mixture of, those of metals and nonmetals. There is no standard definition of a metalloid and no complete agreement on ...
. It has various
allotropes Allotropy or allotropism () is the property of some chemical elements to exist in two or more different forms, in the same physical state, known as allotropes of the elements. Allotropes are different structural modifications of an element: th ...
, but only the gray form, which has a metallic appearance, is important to industry. The primary use of arsenic is in alloys of
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
(for example, in
car batteries An automotive battery or car battery is a rechargeable battery that is used to start a motor vehicle. Its main purpose is to provide an electric current to the electric-powered starting motor, which in turn starts the chemically-powered intern ...
and
ammunition Ammunition (informally ammo) is the material fired, scattered, dropped, or detonated from any weapon or weapon system. Ammunition is both expendable weapons (e.g., bombs, missiles, grenades, land mines) and the component parts of other weap ...
). Arsenic is a common n-type
dopant A dopant, also called a doping agent, is a trace of impurity element that is introduced into a chemical material to alter its original electrical or optical properties. The amount of dopant necessary to cause changes is typically very low. When ...
in
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
electronic devices. It is also a component of the III-V
compound semiconductor Semiconductor materials are nominally small band gap insulators. The defining property of a semiconductor material is that it can be compromised by doping it with impurities that alter its electronic properties in a controllable way. Because of ...
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
. Arsenic and its compounds, especially the trioxide, are used in the production of
pesticide Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and lampri ...
s, treated wood products,
herbicide Herbicides (, ), also commonly known as weedkillers, are substances used to control undesired plants, also known as weeds.EPA. February 201Pesticides Industry. Sales and Usage 2006 and 2007: Market Estimates. Summary in press releasMain page fo ...
s, and
insecticide Insecticides are substances used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers. Insecticides are claimed to b ...
s. These applications are declining with the increasing recognition of the toxicity of arsenic and its compounds. A few species of bacteria are able to use arsenic compounds as respiratory
metabolite In biochemistry, a metabolite is an intermediate or end product of metabolism. The term is usually used for small molecules. Metabolites have various functions, including fuel, structure, signaling, stimulatory and inhibitory effects on enzymes, c ...
s. Trace quantities of arsenic are an essential
dietary element In the context of nutrition, a mineral is a chemical element required as an essential nutrient by organisms to perform functions necessary for life. However, the four major structural elements in the human body by weight (oxygen, hydrogen, carbon, ...
in rats, hamsters, goats, chickens, and presumably other species. A role in human metabolism is not known. However,
arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
occurs in multicellular life if quantities are larger than needed.
Arsenic contamination of groundwater Arsenic contamination of groundwater is a form of groundwater pollution which is often due to naturally occurring high concentrations of arsenic in deeper levels of groundwater. It is a high-profile problem due to the use of deep tube wells for w ...
is a problem that affects millions of people across the world. The
United States The United States of America (U.S.A. or USA), commonly known as the United States (U.S. or US) or America, is a country primarily located in North America. It consists of 50 states, a federal district, five major unincorporated territorie ...
'
Environmental Protection Agency A biophysical environment is a biotic and abiotic surrounding of an organism or population, and consequently includes the factors that have an influence in their survival, development, and evolution. A biophysical environment can vary in scale f ...
states that all forms of arsenic are a serious risk to human health. The United States'
Agency for Toxic Substances and Disease Registry The Agency for Toxic Substances and Disease Registry (ATSDR) is a federal public health agency within the United States Department of Health and Human Services. The agency focuses on minimizing human health risks associated with exposure to haz ...
ranked arsenic as number 1 in its 2001 Priority List of
Hazardous A hazard is a potential source of harm. Substances, events, or circumstances can constitute hazards when their nature would allow them, even just theoretically, to cause damage to health, life, property, or any other interest of value. The probabi ...
Substances at
Superfund Superfund is a United States federal environmental remediation program established by the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA). The program is administered by the United States Environmental Pro ...
sites. Arsenic is classified as a Group-A
carcinogen A carcinogen is any substance, radionuclide, or radiation that promotes carcinogenesis (the formation of cancer). This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes. Several radioactive substan ...
.


Characteristics


Physical characteristics

The three most common arsenic
allotropes Allotropy or allotropism () is the property of some chemical elements to exist in two or more different forms, in the same physical state, known as allotropes of the elements. Allotropes are different structural modifications of an element: th ...
are gray, yellow, and black arsenic, with gray being the most common. Gray arsenic (α-As,
space group In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it unchan ...
Rm No. 166) adopts a double-layered structure consisting of many interlocked, ruffled, six-membered rings. Because of weak bonding between the layers, gray arsenic is brittle and has a relatively low
Mohs hardness The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material. The scale was introduced in 1812 by th ...
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. Gray arsenic is a
semimetal A semimetal is a material with a very small overlap between the bottom of the conduction band and the top of the valence band. According to electronic band theory, solids can be classified as insulators, semiconductors, semimetals, or metals. ...
, but becomes a
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
with a
bandgap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference (in ...
of 1.2–1.4 eV if amorphized. Gray arsenic is also the most stable form. Yellow arsenic is soft and waxy, and somewhat similar to
tetraphosphorus Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus. White phosphorus White ...
(). Both have four atoms arranged in a
tetrahedral In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the o ...
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, . It is rapidly transformed into gray arsenic by light. The yellow form has a density of 1.97 g/cm3. Black arsenic is similar in structure to
black phosphorus Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus. White phosphorus White ...
. Black arsenic can also be formed by cooling vapor at around 100–220 °C and by crystallization of amorphous arsenic in the presence of mercury vapors. It is glassy and brittle. Black arsenic is also a poor electrical conductor. As arsenic's triple point is at 3.628 MPa (35.81 atm), it does not have a melting point at
standard pressure Standard temperature and pressure (STP) are standard sets of conditions for experimental measurements to be established to allow comparisons to be made between different sets of data. The most used standards are those of the International Union o ...
but instead sublimes from solid to vapor at 887 K (615 °C or 1137 °F).


Isotopes

Arsenic occurs in nature as one stable
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
, 75As, a
monoisotopic element A monoisotopic element is an element which has only a single stable isotope (nuclide). There are only 26 elements that have this property. A list is given in a following section. Stability is experimentally defined for chemical elements, as ther ...
. As of 2003, at least 33
radioisotope A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferr ...
s have also been synthesized, ranging in
atomic mass The atomic mass (''m''a or ''m'') is the mass of an atom. Although the SI unit of mass is the kilogram (symbol: kg), atomic mass is often expressed in the non-SI unit dalton (symbol: Da) – equivalently, unified atomic mass unit (u). 1&nbs ...
from 60 to 92. The most stable of these is 73As with a
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ato ...
of 80.30 days. All other isotopes have half-lives of under one day, with the exception of 71As (''t''1/2=65.30 hours), 72As (''t''1/2=26.0 hours), 74As (''t''1/2=17.77 days), 76As (''t''1/2=1.0942 days), and 77As (''t''1/2=38.83 hours). Isotopes that are lighter than the stable 75As tend to decay by β+ decay, and those that are heavier tend to decay by β decay, with some exceptions. At least 10
nuclear isomer A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy excited state, higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited ...
s have been described, ranging in atomic mass from 66 to 84. The most stable of arsenic's isomers is 68mAs with a half-life of 111 seconds.


Chemistry

Arsenic has a similar electronegativity and ionization energies to its lighter congener phosphorus and accordingly readily forms covalent molecules with most of the nonmetals. Though stable in dry air, arsenic forms a golden-bronze tarnish upon exposure to humidity which eventually becomes a black surface layer.Greenwood and Earnshaw, pp. 552–4 When heated in air, arsenic oxidizes to
arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
; the fumes from this reaction have an odor resembling
garlic Garlic (''Allium sativum'') is a species of bulbous flowering plant in the genus ''Allium''. Its close relatives include the onion, shallot, leek, chive, Allium fistulosum, Welsh onion and Allium chinense, Chinese onion. It is native to South A ...
. This odor can be detected on striking
arsenide In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
minerals such as
arsenopyrite Arsenopyrite ( IMA symbol: Apy) is an iron arsenic sulfide (FeAsS). It is a hard ( Mohs 5.5-6) metallic, opaque, steel grey to silver white mineral with a relatively high specific gravity of 6.1. When dissolved in nitric acid, it releases eleme ...
with a hammer. It burns in oxygen to form arsenic trioxide and
arsenic pentoxide Arsenic pentoxide is the inorganic compound with the formula As2O5. This glassy, white, deliquescent solid is relatively unstable, consistent with the rarity of the As(V) oxidation state. More common, and far more important commercially, is arse ...
, which have the same structure as the more well-known phosphorus compounds, and in fluorine to give
arsenic pentafluoride Arsenic pentafluoride is a chemical compound of arsenic and fluorine. It is a toxic, colorless gas. The oxidation state of arsenic is +5. Synthesis Arsenic pentafluoride can be prepared by direct combination of arsenic and fluorine: :2As + 5F2 ...
. Arsenic (and some arsenic compounds) sublimes upon heating at atmospheric pressure, converting directly to a gaseous form without an intervening liquid state at . The
triple point In thermodynamics, the triple point of a substance is the temperature and pressure at which the three phases (gas, liquid, and solid) of that substance coexist in thermodynamic equilibrium.. It is that temperature and pressure at which the subli ...
is 3.63 MPa and . Arsenic makes
arsenic acid Arsenic acid or trihydrogen arsenate is the chemical compound with the formula . More descriptively written as , this colorless acid is the arsenic analogue of phosphoric acid. Arsenate and phosphate salts behave very similarly. Arsenic acid as ...
with concentrated
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
,
arsenous acid Arsenous acid (or arsenious acid) is the inorganic compound with the formula H3AsO3. It is known to occur in aqueous solutions, but it has not been isolated as a pure material, although this fact does not detract from the significance of As(OH)3. ...
with dilute nitric acid, and
arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
with concentrated
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
; however, it does not react with water, alkalis, or non-oxidising acids. Arsenic reacts with metals to form
arsenide In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
s, though these are not ionic compounds containing the As3− ion as the formation of such an anion would be highly endothermic and even the group 1 arsenides have properties of
intermetallic An intermetallic (also called an intermetallic compound, intermetallic alloy, ordered intermetallic alloy, and a long-range-ordered alloy) is a type of metallic alloy that forms an ordered solid-state compound between two or more metallic eleme ...
compounds. Like
germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors s ...
,
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
, and
bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table (halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simila ...
, which like arsenic succeed the 3d transition series, arsenic is much less stable in the group oxidation state of +5 than its vertical neighbors phosphorus and antimony, and hence arsenic pentoxide and arsenic acid are potent oxidizers.


Compounds

Compounds of arsenic resemble in some respects those of
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
which occupies the same
group A group is a number of persons or things that are located, gathered, or classed together. Groups of people * Cultural group, a group whose members share the same cultural identity * Ethnic group, a group whose members share the same ethnic ide ...
(column) of the
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
. The most common
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s for arsenic are: −3 in the
arsenide In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
s, which are alloy-like intermetallic compounds, +3 in the
arsenite In chemistry, an arsenite is a chemical compound containing an arsenic oxyanion where arsenic has oxidation state +3. Note that in fields that commonly deal with groundwater chemistry, arsenite is used generically to identify soluble AsIII anions. ...
s, and +5 in the
arsenates The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate resem ...
and most organoarsenic compounds. Arsenic also bonds readily to itself as seen in the square ions in the mineral
skutterudite Named after Skuterudåsen, a hill in Modum, Norway, skutterudite is a cobalt arsenide mineral containing variable amounts of nickel and iron substituting for cobalt with the ideal formula CoAs3. Some references give the arsenic a variable formula ...
. In the +3
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
, arsenic is typically pyramidal owing to the influence of the
lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC ''Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. Lone ...
of
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...
s.


Inorganic compounds

One of the simplest arsenic compounds is the trihydride, the highly toxic, flammable,
pyrophoric A substance is pyrophoric (from grc-gre, πυροφόρος, , 'fire-bearing') if it ignites spontaneously in air at or below (for gases) or within 5 minutes after coming into contact with air (for liquids and solids). Examples are organolith ...
arsine Arsine (IUPAC name: arsane) is an inorganic compound with the formula As H3. This flammable, pyrophoric, and highly toxic pnictogen hydride gas is one of the simplest compounds of arsenic. Despite its lethality, it finds some applications in ...
(AsH3). This compound is generally regarded as stable, since at room temperature it decomposes only slowly. At temperatures of 250–300 °C decomposition to arsenic and hydrogen is rapid.Greenwood and Earnshaw, pp. 557–558 Several factors, such as
humidity Humidity is the concentration of water vapor present in the air. Water vapor, the gaseous state of water, is generally invisible to the human eye. Humidity indicates the likelihood for precipitation, dew, or fog to be present. Humidity depe ...
, presence of light and certain
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
s (namely
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
) facilitate the rate of decomposition. It oxidises readily in air to form arsenic trioxide and water, and analogous reactions take place with
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
and
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
instead of
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
. Arsenic forms colorless, odorless, crystalline
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
s As2O3 ("
white arsenic Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
") and As2O5 which are
hygroscopic Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption or adsorption from the surrounding environment, which is usually at normal or room temperature. If water molecules become suspended among the substance ...
and readily soluble in water to form acidic solutions. Arsenic(V) acid is a weak acid and the salts are called
arsenate The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate res ...
s, the most common
arsenic contamination of groundwater Arsenic contamination of groundwater is a form of groundwater pollution which is often due to naturally occurring high concentrations of arsenic in deeper levels of groundwater. It is a high-profile problem due to the use of deep tube wells for w ...
, and a problem that affects many people. Synthetic arsenates include
Scheele's Green Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite (also called copper arsenite or acidic copper arsenite), . It is chemically related to Paris Green. Scheele's Green was invented in 1775 by Carl Wilhelm Sch ...
(cupric hydrogen arsenate, acidic copper arsenate),
calcium arsenate Calcium arsenate is the inorganic compound with the formula Ca3(AsO4)2. A colourless salt, it was originally used as a pesticide and as a germicide. It is highly soluble in water, in contrast to lead arsenate, which makes it more toxic. The min ...
, and
lead hydrogen arsenate Lead hydrogen arsenate, also called lead arsenate, acid lead arsenate or LA, chemical formula PbHAsO4, is an inorganic insecticide used primarily against the potato beetle. Lead arsenate was the most extensively used arsenical insecticide.Peryea F ...
. These three have been used as
agricultural Agriculture or farming is the practice of cultivating Plant, plants and livestock. Agriculture was the key development in the rise of Sedentism, sedentary human civilization, whereby farming of Domestication, domesticated species created food ...
insecticide Insecticides are substances used to kill insects. They include ovicides and larvicides used against insect eggs and larvae, respectively. Insecticides are used in agriculture, medicine, industry and by consumers. Insecticides are claimed to b ...
s and
poison Poison is a chemical substance that has a detrimental effect to life. The term is used in a wide range of scientific fields and industries, where it is often specifically defined. It may also be applied colloquially or figuratively, with a broa ...
s. The protonation steps between the arsenate and arsenic acid are similar to those between
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phospho ...
and
phosphoric acid Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, w ...
. Unlike
phosphorous acid Phosphorous acid (or phosphonic acid (singular)) is the compound described by the formula H3PO3. This acid is diprotic (readily ionizes two protons), not triprotic as might be suggested by this formula. Phosphorous acid is an intermediate in th ...
,
arsenous acid Arsenous acid (or arsenious acid) is the inorganic compound with the formula H3AsO3. It is known to occur in aqueous solutions, but it has not been isolated as a pure material, although this fact does not detract from the significance of As(OH)3. ...
is genuinely tribasic, with the formula As(OH)3.Greenwood and Earnshaw, pp. 572–578 A broad variety of sulfur compounds of arsenic are known. Orpiment ( As2S3) and realgar ( As4S4) are somewhat abundant and were formerly used as painting pigments. In As4S10, arsenic has a formal oxidation state of +2 in As4S4 which features As-As bonds so that the total covalency of As is still 3. Both orpiment and realgar, as well as As4S3, have selenium analogs; the analogous As2Te3 is known as the mineral kalgoorlieite, and the anion As2Te is known as a ligand in
cobalt Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
complexes.Greenwood and Earnshaw, pp. 578–583 All trihalides of arsenic(III) are well known except the astatide, which is unknown.
Arsenic pentafluoride Arsenic pentafluoride is a chemical compound of arsenic and fluorine. It is a toxic, colorless gas. The oxidation state of arsenic is +5. Synthesis Arsenic pentafluoride can be prepared by direct combination of arsenic and fluorine: :2As + 5F2 ...
(AsF5) is the only important pentahalide, reflecting the lower stability of the +5 oxidation state; even so, it is a very strong fluorinating and oxidizing agent. (The pentachloride is stable only below −50 °C, at which temperature it decomposes to the trichloride, releasing chlorine gas.)


Alloys

Arsenic is used as the group 5 element in the
III-V semiconductor Semiconductor materials are nominally small band gap insulators. The defining property of a semiconductor material is that it can be compromised by doping it with impurities that alter its electronic properties in a controllable way. Because of t ...
s
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
,
indium arsenide Indium arsenide, InAs, or indium monoarsenide, is a narrow-bandgap semiconductor composed of indium and arsenic. It has the appearance of grey cubic crystals with a melting point of 942 °C. Indium arsenide is similar in properties to galli ...
, and aluminium arsenide. The valence electron count of GaAs is the same as a pair of Si atoms, but the
band structure In solid-state physics, the electronic band structure (or simply band structure) of a solid describes the range of energy levels that electrons may have within it, as well as the ranges of energy that they may not have (called ''band gaps'' or '' ...
is completely different which results in distinct bulk properties. Other arsenic alloys include the II-V semiconductor
cadmium arsenide Cadmium arsenide (cadmium, Cd3arsenic, As2) is an inorganic semimetal in the List of semiconductor materials#Types of semiconductor materials, II-V family. It exhibits the Nernst effect. Properties Thermal Cd3As2 dissociates between 220 and ...
.


Organoarsenic compounds

A large variety of organoarsenic compounds are known. Several were developed as chemical warfare agents during World War I, including vesicants such as
lewisite Lewisite (L) (A-243) is an organoarsenic compound. It was once manufactured in the U.S., Japan, Germany and the Soviet Union for use as a Chemical warfare, chemical weapon, acting as a vesicant (blister agent) and lung irritant. Although the substa ...
and vomiting agents such as
adamsite Adamsite or DM is an organic compound; technically, an arsenical diphenylaminechlorarsine, that can be used as a riot control agent. DM belongs to the group of chemical warfare agents known as vomiting agents or sneeze gases. First synthesized in ...
.
Cacodylic acid Cacodylic acid is an organoarsenic compound with the formula (CH3)2 AsO2H. With the formula R2As(O)OH, it is the simplest of the arsinic acids. It is a colorless solid that is soluble in water. Neutralization of cacodylic acid with base gives ca ...
, which is of historic and practical interest, arises from the
methylation In the chemical sciences, methylation denotes the addition of a methyl group on a substrate, or the substitution of an atom (or group) by a methyl group. Methylation is a form of alkylation, with a methyl group replacing a hydrogen atom. These t ...
of arsenic trioxide, a reaction that has no analogy in phosphorus chemistry.
Cacodyl Cacodyl, also known as dicacodyl or tetramethyldiarsine, (CH3)2As–As(CH3)2, is an organoarsenic compound that constitutes a major part of " Cadet's fuming liquid" (named after the French chemist Louis Claude Cadet de Gassicourt). It is a poisono ...
was the first organometallic compound known (even though arsenic is not a true metal) and was named from the Greek ''κακωδία'' "stink" for its offensive odor; it is very poisonous.Greenwood, p. 584


Occurrence and production

Arsenic comprises about 1.5  ppm (0.00015%) of the
Earth's crust Earth's crust is Earth's thin outer shell of rock, referring to less than 1% of Earth's radius and volume. It is the top component of the lithosphere, a division of Earth's layers that includes the crust and the upper part of the mantle. The ...
, and is the 53rd most abundant element. 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.
Mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. ( ...
s with the formula MAsS and MAs2 (M = Fe, Ni, Co) are the dominant commercial sources of arsenic, together with
realgar Realgar ( ), also known as "ruby sulphur" or "ruby of arsenic", is an arsenic sulfide mineral with the chemical formula α-. It is a soft, sectile mineral occurring in monoclinic crystals, or in granular, compact, or powdery form, often in asso ...
(an arsenic sulfide mineral) and native (elemental) arsenic. An illustrative mineral is
arsenopyrite Arsenopyrite ( IMA symbol: Apy) is an iron arsenic sulfide (FeAsS). It is a hard ( Mohs 5.5-6) metallic, opaque, steel grey to silver white mineral with a relatively high specific gravity of 6.1. When dissolved in nitric acid, it releases eleme ...
( FeAs S), which is structurally related to
iron pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Fe S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic luster and pale brass-yellow hue giv ...
. Many minor As-containing minerals are known. Arsenic also occurs in various organic forms in the environment. In 2014, China was the top producer of white arsenic with almost 70% world share, followed by Morocco, Russia, and Belgium, according to the
British Geological Survey The British Geological Survey (BGS) is a partly publicly funded body which aims to advance geoscientific knowledge of the United Kingdom landmass and its continental shelf by means of systematic surveying, monitoring and research. The BGS h ...
and the
United States Geological Survey The United States Geological Survey (USGS), formerly simply known as the Geological Survey, is a scientific agency of the United States government. The scientists of the USGS study the landscape of the United States, its natural resources, ...
. Most arsenic refinement operations in the US and Europe have closed over environmental concerns. Arsenic is found in the smelter dust from
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
,
gold Gold is a chemical element with the symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a bright, slightly orange-yellow, dense, soft, malleable, and ductile met ...
, and
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
smelters, and is recovered primarily from copper refinement dust. On
roasting Roasting is a cooking method that uses dry heat where hot air covers the food, cooking it evenly on all sides with temperatures of at least from an open flame, oven, or other heat source. Roasting can enhance the flavor through caramelization ...
arsenopyrite in air, arsenic sublimes as arsenic(III) oxide leaving iron oxides, while roasting without air results in the production of gray arsenic. Further purification from sulfur and other chalcogens is achieved by sublimation in vacuum, in a hydrogen atmosphere, or by distillation from molten lead-arsenic mixture.


History

The word ''arsenic'' has its origin in the
Syriac Syriac may refer to: *Syriac language, an ancient dialect of Middle Aramaic *Sureth, one of the modern dialects of Syriac spoken in the Nineveh Plains region * Syriac alphabet ** Syriac (Unicode block) ** Syriac Supplement * Neo-Aramaic languages a ...
word ''(al) zarniqa'', from Arabic al-zarnīḵ 'the
orpiment Orpiment is a deep-colored, orange-yellow arsenic sulfide mineral with formula . It is found in volcanic fumaroles, low-temperature hydrothermal veins, and hot springs and is formed both by sublimation and as a byproduct of the decay of another a ...
', based on
Persian Persian may refer to: * People and things from Iran, historically called ''Persia'' in the English language ** Persians, the majority ethnic group in Iran, not to be conflated with the Iranic peoples ** Persian language, an Iranian language of the ...
zar 'gold' from the word ''zarnikh'', meaning "yellow" (literally "gold-colored") and hence "(yellow) orpiment". It was adopted into
Greek Greek may refer to: Greece Anything of, from, or related to Greece, a country in Southern Europe: *Greeks, an ethnic group. *Greek language, a branch of the Indo-European language family. **Proto-Greek language, the assumed last common ancestor ...
as ''arsenikon'' (), a form that is
folk etymology Folk etymology (also known as popular etymology, analogical reformation, reanalysis, morphological reanalysis or etymological reinterpretation) is a change in a word or phrase resulting from the replacement of an unfamiliar form by a more famili ...
, being the neuter form of the Greek word ''arsenikos'' (), meaning "male", "virile". The Greek word was adopted in Latin as ''arsenicum'', which in French became ''arsenic'', from which the English word arsenic is taken. Arsenic sulfides (orpiment,
realgar Realgar ( ), also known as "ruby sulphur" or "ruby of arsenic", is an arsenic sulfide mineral with the chemical formula α-. It is a soft, sectile mineral occurring in monoclinic crystals, or in granular, compact, or powdery form, often in asso ...
) and oxides have been known and used since ancient times. Zosimos (circa 300 AD) describes roasting ''sandarach'' (realgar) to obtain ''cloud of arsenic'' (
arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
), which he then reduces to gray arsenic. As the symptoms of
arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
are not very specific, it was frequently used for
murder Murder is the unlawful killing of another human without justification (jurisprudence), justification or valid excuse (legal), excuse, especially the unlawful killing of another human with malice aforethought. ("The killing of another person wit ...
until the advent of the
Marsh test The Marsh test is a highly sensitive method in the detection of arsenic, especially useful in the field of forensic toxicology when arsenic was used as a poison. It was developed by the chemist James Marsh and first published in 1836. The metho ...
, a sensitive chemical test for its presence. (Another less sensitive but more general test is the
Reinsch test Reinsch is a Germanic surname. It may refer to: * Diether Roderich Reinsch (born 1940), a German Byzantinist * Gabriele Reinsch (born 1963), a German track and field athlete * Hugo Reinsch Hugo or HUGO may refer to: Arts and entertainment * ''H ...
.) 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". In the Renaissance era, arsenic was known as “inheritance powder” due to use in killing family members. During the
Bronze Age The Bronze Age is a historic period, lasting approximately from 3300 BC to 1200 BC, characterized by the use of bronze, the presence of writing in some areas, and other early features of urban civilization. The Bronze Age is the second pri ...
, arsenic was often included in
bronze Bronze is an alloy consisting primarily of copper, commonly with about 12–12.5% tin and often with the addition of other metals (including aluminium, manganese, nickel, or zinc) and sometimes non-metals, such as phosphorus, or metalloids such ...
, which made the alloy harder (so-called "
arsenical bronze Arsenical bronze is an alloy in which arsenic, as opposed to or in addition to tin or other constituent metals, is combined with copper to make bronze. The use of arsenic with copper, either as the secondary constituent or with another component ...
"). The isolation of arsenic was described by
Jabir ibn Hayyan Abū Mūsā Jābir ibn Ḥayyān (Arabic: , variously called al-Ṣūfī, al-Azdī, al-Kūfī, or al-Ṭūsī), died 806−816, is the purported author of an enormous number and variety of works in Arabic, often called the Jabirian corpus. The ...
before 815 AD.
George Sarton George Alfred Leon Sarton (; 31 August 1884 – 22 March 1956) was a Belgian-born American chemist and historian. He is considered the founder of the discipline of the history of science as an independent field of study. His most influential works ...
, ''Introduction to the History of Science''. "We find in his writings ..preparation of various substances (e.g., basic lead carbonatic, arsenic and antimony from their sulphides)."
Albertus Magnus Albertus Magnus (c. 1200 – 15 November 1280), also known as Saint Albert the Great or Albert of Cologne, was a German Dominican friar, philosopher, scientist, and bishop. Later canonised as a Catholic saint, he was known during his life ...
(Albert the Great, 1193–1280) later isolated the element from a compound in 1250, by heating soap together with
arsenic trisulfide Arsenic trisulfide is the inorganic compound with the formula . It is a dark yellow solid that is insoluble in water. It also occurs as the mineral orpiment (Latin: auripigmentum), which has been used as a pigment called King's yellow. It is produ ...
. In 1649, Johann Schröder published two ways of preparing arsenic. Crystals of elemental (native) arsenic are found in nature, although rare.
Cadet's fuming liquid Cadet's fuming liquid was a red-brown oily liquid prepared in 1760 by the French chemist Louis Claude Cadet de Gassicourt (1731-1799) by the reaction of potassium acetate with arsenic trioxide. It consisted mostly of dicacodyl (((CH3)2As)2) an ...
(impure
cacodyl Cacodyl, also known as dicacodyl or tetramethyldiarsine, (CH3)2As–As(CH3)2, is an organoarsenic compound that constitutes a major part of " Cadet's fuming liquid" (named after the French chemist Louis Claude Cadet de Gassicourt). It is a poisono ...
), often claimed as the first synthetic
organometallic compound Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and s ...
, was synthesized in 1760 by
Louis Claude Cadet de Gassicourt Louis Claude Cadet de Gassicourt (24 July 1731 – 17 October 1799) was a French chemist who synthesised the first organometalic compound. He obtained a red liquid by the reaction of potassium acetate with arsenic trioxide. This liquid is ...
by the reaction of
potassium acetate Potassium acetate (CH3COOK) is the potassium salt of acetic acid. It is a hygroscopic solid at room temperature. Preparation It can be prepared by treating a potassium-containing base such as potassium hydroxide or potassium carbonate with acetic ...
with
arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
. In the
Victorian era In the history of the United Kingdom and the British Empire, the Victorian era was the period of Queen Victoria's reign, from 20 June 1837 until her death on 22 January 1901. The era followed the Georgian period and preceded the Edwardia ...
, "arsenic" ("white arsenic" or arsenic trioxide) was mixed with
vinegar Vinegar is an aqueous solution of acetic acid and trace compounds that may include flavorings. Vinegar typically contains 5–8% acetic acid by volume. Usually, the acetic acid is produced by a double fermentation, converting simple sugars to et ...
and
chalk Chalk is a soft, white, porous, sedimentary carbonate rock. It is a form of limestone composed of the mineral calcite and originally formed deep under the sea by the compression of microscopic plankton that had settled to the sea floor. Chalk ...
and eaten by women to improve the
complexion Complexion in humans is the natural color, texture, and appearance of the skin, especially on the face. History The word "complexion" is derived from the Late Latin ''complexi'', which initially referred in general terms to a combination of thi ...
of their faces, making their skin paler to show they did not work in the fields. The accidental use of arsenic in the adulteration of foodstuffs led to the Bradford sweet poisoning in 1858, which resulted in 21 deaths. Wallpaper production also began to use dyes made from arsenic, which was thought to increase the pigment's brightness. Two arsenic pigments have been widely used since their discovery – Paris Green and
Scheele's Green Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite (also called copper arsenite or acidic copper arsenite), . It is chemically related to Paris Green. Scheele's Green was invented in 1775 by Carl Wilhelm Sch ...
. After the toxicity of arsenic became widely known, these chemicals were used less often as pigments and more often as insecticides. In the 1860s, an arsenic byproduct of dye production, London Purple, was widely used. This was a solid mixture of arsenic trioxide, aniline, lime, and ferrous oxide, insoluble in water and very toxic by inhalation or ingestion But it was later replaced with Paris Green, another arsenic-based dye. With better understanding of the toxicology mechanism, two other compounds were used starting in the 1890s. Arsenite of lime and
arsenate of lead Lead hydrogen arsenate, also called lead arsenate, acid lead arsenate or LA, chemical formula PbHAsO4, is an inorganic insecticide used primarily against the potato beetle. Lead arsenate was the most extensively used arsenical insecticide.Peryea ...
were used widely as insecticides until the discovery of
DDT Dichlorodiphenyltrichloroethane, commonly known as DDT, is a colorless, tasteless, and almost odorless crystalline chemical compound, an organochloride. Originally developed as an insecticide, it became infamous for its environmental impacts. ...
in 1942.


Applications


Agricultural

The toxicity of arsenic to
insect Insects (from Latin ') are pancrustacean hexapod invertebrates of the class Insecta. They are the largest group within the arthropod phylum. Insects have a chitinous exoskeleton, a three-part body ( head, thorax and abdomen), three pairs ...
s,
bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...
, and
fungi A fungus ( : fungi or funguses) is any member of the group of eukaryotic organisms that includes microorganisms such as yeasts and molds, as well as the more familiar mushrooms. These organisms are classified as a kingdom, separately from ...
led to its use as a wood preservative. In the 1930s, a process of treating wood with
chromated copper arsenate Chromated copper arsenate (CCA) is a wood preservative containing compounds of chromium, copper, and arsenic, in various proportions. It is used to impregnate timber and other wood products, especially those intended for outdoor use, in order to pr ...
(also known as CCA or
Tanalith Chromated copper arsenate (CCA) is a wood preservative containing compounds of chromium, copper, and arsenic, in various proportions. It is used to impregnate timber and other wood products, especially those intended for outdoor use, in order to pr ...
) 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 The European Union (EU) is a supranational political and economic union of member states that are located primarily in Europe. The union has a total area of and an estimated total population of about 447million. The EU has often been des ...
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 Lead hydrogen arsenate, also called lead arsenate, acid lead arsenate or LA, chemical formula PbHAsO4, is an inorganic insecticide used primarily against the potato beetle. Lead arsenate was the most extensively used arsenical insecticide.Peryea F ...
was a common insecticide on
fruit tree A fruit tree is a tree which bears fruit that is consumed or used by animals and humans — all trees that are flowering plants produce fruit, which are the ripened ovaries of flowers containing one or more seeds. In horticultural usage, ...
s, but contact with the compound sometimes resulted in
brain damage Neurotrauma, brain damage or brain injury (BI) is the destruction or degeneration of brain cells. Brain injuries occur due to a wide range of internal and external factors. In general, brain damage refers to significant, undiscriminating t ...
among those working the sprayers. In the second half of the 20th century,
monosodium methyl arsenate Monosodium methyl arsenate (MSMA) is an arsenic-based herbicide. It is an organo-arsenate; less toxic than the inorganic form of arsenates. However, the EPA states that all forms of arsenic are a serious risk to human health and the United Stat ...
(MSMA) and
disodium methyl arsenate Disodium methyl arsonate (DSMA) is the organoarsenic compound with the formula CH3AsO3Na2. It is a colorless, water-soluble solid derived from methanearsonic acid. It is used as a herbicide. Tradenames include Metharsinat, Arrhenal, Disomear, ...
(DSMA) – less toxic organic forms of arsenic – replaced lead arsenate in agriculture. These organic arsenicals were in turn phased out 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 () is more soluble than arsenate () and is more toxic; however, at a lower pH, arsenate becomes more mobile and toxic. It was found that addition of sulfur, phosphorus, and iron oxides to high-arsenite soils greatly reduces arsenic phytotoxicity. Arsenic is used as a feed additive in
poultry Poultry () are domesticated birds kept by humans for their eggs, their meat or their feathers. These birds are most typically members of the superorder Galloanserae (fowl), especially the order Galliformes (which includes chickens, quails, a ...
and
swine production The pig (''Sus domesticus''), often called swine, hog, or domestic pig when distinguishing from other members of the genus '' Sus'', is an omnivorous, domesticated, even-toed, hoofed mammal. It is variously considered a subspecies of ''Sus ...
, in particular in the U.S. to increase weight gain, improve feed efficiency, and prevent disease. An example is roxarsone, which had been used as a
broiler A broiler is any chicken (''Gallus gallus domesticus'') that is bred and raised specifically for meat production. Most commercial broilers reach slaughter weight between four and six weeks of age, although slower growing breeds reach slaught ...
starter by about 70% of U.S. broiler growers. Alpharma, a subsidiary of Pfizer Inc., which produces roxarsone, voluntarily suspended sales of the drug in response to studies showing elevated levels of inorganic arsenic, a carcinogen, in treated chickens. A successor to Alpharma,
Zoetis Zoetis Inc. (/zō-EH-tis/) is an American drug company, the world's largest producer of medicine and vaccinations for pets and livestock. The company was a subsidiary of Pfizer, the world's largest drug maker, but with Pfizer's spinoff of its ...
, continues to sell
nitarsone Nitarsone is an organoarsenic compound that is used in poultry production as a feed additive to increase weight gain, improve feed efficiency, and prevent histomoniasis (blackhead disease). It is marketed as Histostat by Zoetis. Nitarsone once ...
, primarily for use in turkeys. Arsenic is intentionally added to the feed of chickens raised for human consumption. Organic arsenic compounds are less toxic than pure arsenic, and promote the growth of chickens. Under some conditions, the arsenic in
chicken feed Poultry feed is food for farm poultry, including chickens, ducks, geese and other domestic birds. Before the twentieth century, poultry were mostly kept on general farms, and foraged for much of their feed, eating insects, grain spilled by cattl ...
is converted to the toxic inorganic form. A 2006 study of the remains of the
Australia Australia, officially the Commonwealth of Australia, is a Sovereign state, sovereign country comprising the mainland of the Australia (continent), Australian continent, the island of Tasmania, and numerous List of islands of Australia, sma ...
n racehorse,
Phar Lap Phar Lap (4 October 1926 – 5 April 1932) was a champion New Zealand–bred Thoroughbred racehorse who is widely regarded as New Zealand's greatest racehorse ever. Achieving incredible success during his distinguished career, his initial ...
, determined that the 1932 death of the famous champion was caused by a massive overdose of arsenic. Sydney veterinarian Percy Sykes stated, "In those days, arsenic was quite a common tonic, usually given in the form of a solution (
Fowler's Solution Fowler's solution is a solution containing 1% potassium arsenite (KAsO2), and was once prescribed as a remedy or a tonic. Thomas Fowler (1736–1801) of Stafford, England, proposed the solution in 1786 as a substitute for a patent medicine, "ta ...
) ... It was so common that I'd reckon 90 per cent of the horses had arsenic in their system."


Medical use

During the 17th, 18th, and 19th centuries, a number of arsenic compounds were used as medicines, including
arsphenamine Arsphenamine, also known as Salvarsan or compound 606, is a drug that was introduced at the beginning of the 1910s as the first effective treatment for syphilis, relapsing fever, and African trypanosomiasis. This organoarsenic compound was the f ...
(by
Paul Ehrlich Paul Ehrlich (; 14 March 1854 – 20 August 1915) was a Nobel Prize-winning German physician and scientist who worked in the fields of hematology, immunology, and antimicrobial chemotherapy. Among his foremost achievements were finding a cure ...
) and
arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
(by Thomas Fowler). Arsphenamine, as well as
neosalvarsan Neosalvarsan is a synthetic chemotherapeutic that is an organoarsenic compound. It became available in 1912 and superseded the more toxic and less water-soluble salvarsan as an effective treatment for syphilis. Because both of these arsenica ...
, was indicated for
syphilis Syphilis () is a sexually transmitted infection caused by the bacterium ''Treponema pallidum'' subspecies ''pallidum''. The signs and symptoms of syphilis vary depending in which of the four stages it presents (primary, secondary, latent, an ...
, but has been superseded by modern
antibiotics An antibiotic is a type of antimicrobial substance active against bacteria. It is the most important type of antibacterial agent for fighting bacterial infections, and antibiotic medications are widely used in the treatment and prevention o ...
. However, arsenicals such as
melarsoprol Melarsoprol is an arsenic-containing medication used for the treatment of sleeping sickness (African trypanosomiasis). It is specifically used for second-stage disease caused by ''Trypanosoma brucei rhodesiense'' when the central nervous system i ...
are still used for the treatment of
trypanosomiasis Trypanosomiasis or trypanosomosis is the name of several diseases in vertebrates caused by parasitic protozoan trypanosomes of the genus ''Trypanosoma''. In humans this includes African trypanosomiasis and Chagas disease. A number of other diseas ...
, since although these drugs have the disadvantage of severe toxicity, the disease is almost uniformly fatal if untreated. Arsenic trioxide has been used in a variety of ways since the 15th century, most commonly in the treatment of
cancer Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
, but also in medications as diverse as
Fowler's solution Fowler's solution is a solution containing 1% potassium arsenite (KAsO2), and was once prescribed as a remedy or a tonic. Thomas Fowler (1736–1801) of Stafford, England, proposed the solution in 1786 as a substitute for a patent medicine, "ta ...
in
psoriasis Psoriasis is a long-lasting, noncontagious autoimmune disease characterized by raised areas of abnormal skin. These areas are red, pink, or purple, dry, itchy, and scaly. Psoriasis varies in severity from small, localized patches to complete ...
. The US
Food and Drug Administration The United States Food and Drug Administration (FDA or US FDA) is a List of United States federal agencies, federal agency of the United States Department of Health and Human Services, Department of Health and Human Services. The FDA is respon ...
in the year 2000 approved this compound for the treatment of patients with acute promyelocytic leukemia that is resistant to
all-trans retinoic acid Tretinoin, also known as all-''trans'' retinoic acid (ATRA), is a medication used for the treatment of acne and acute promyelocytic leukemia. For acne, it is applied to the skin as a cream, gel or ointment. For leukemia, it is taken by mouth f ...
. A 2008 paper reports success in locating tumors using arsenic-74 (a positron emitter). This isotope produces clearer
PET scan Positron emission tomography (PET) is a functional imaging technique that uses radioactive substances known as radiotracers to visualize and measure changes in metabolic processes, and in other physiological activities including blood flow, r ...
images than the previous radioactive agent,
iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...
-124, because the body tends to transport iodine to the thyroid gland producing signal noise.
Nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...
s of arsenic have shown ability to kill cancer cells with lesser
cytotoxicity Cytotoxicity is the quality of being toxic to cells. Examples of toxic agents are an immune cell or some types of venom, e.g. from the puff adder (''Bitis arietans'') or brown recluse spider (''Loxosceles reclusa''). Cell physiology Treating cells ...
than other arsenic formulations. In subtoxic doses, soluble arsenic compounds act as
stimulant Stimulants (also often referred to as psychostimulants or colloquially as uppers) is an overarching term that covers many drugs including those that increase activity of the central nervous system and the body, drugs that are pleasurable and inv ...
s, and were once popular in small doses as medicine by people in the mid-18th to 19th centuries; its use as a stimulant was especially prevalent as sport animals such as
race horses Race Horses were a Welsh band based in Cardiff, Wales and originally from Aberystwyth. Formed in 2005 as Radio Luxembourg, they changed their name in 2009 due to possible legal problems with the radio station of the same name. Initially the m ...
or with
work dog A working dog is a dog used to perform practical tasks, as opposed to pet or companion dogs. Definitions vary on what a working dog is, they are sometimes described as any dog trained for and employed in meaningful work; other times as any dog ...
s.


Alloys

The main use of arsenic is in alloying with lead. Lead components in
car batteries An automotive battery or car battery is a rechargeable battery that is used to start a motor vehicle. Its main purpose is to provide an electric current to the electric-powered starting motor, which in turn starts the chemically-powered intern ...
are strengthened by the presence of a very small percentage of arsenic. Dezincification of brass (a copper-zinc alloy) is greatly reduced by the addition of arsenic. "Phosphorus Deoxidized Arsenical Copper" with an arsenic content of 0.3% has an increased corrosion stability in certain environments.
Gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
is an important
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
material, used in
integrated circuit An integrated circuit or monolithic integrated circuit (also referred to as an IC, a chip, or a microchip) is a set of electronic circuits on one small flat piece (or "chip") of semiconductor material, usually silicon. Large numbers of tiny ...
s. Circuits made from GaAs are much faster (but also much more expensive) than those made from
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic tab ...
. Unlike silicon, GaAs has a
direct bandgap In semiconductor physics, the band gap of a semiconductor can be of two basic types, a direct band gap or an indirect band gap. The minimal-energy state in the conduction band and the maximal-energy state in the valence band are each characteriz ...
, and can be used in
laser diode file:Laser diode chip.jpg, The laser diode chip removed and placed on the eye of a needle for scale A laser diode (LD, also injection laser diode or ILD, or diode laser) is a semiconductor device similar to a light-emitting diode in which a di ...
s and
LED A light-emitting diode (LED) is a semiconductor Electronics, device that Light#Light sources, emits light when Electric current, current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy i ...
s to convert
electrical Electricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by ...
energy directly into
light Light or visible light is electromagnetic radiation that can be perceived by the human eye. Visible light is usually defined as having wavelengths in the range of 400–700 nanometres (nm), corresponding to frequencies of 750–420 tera ...
.


Military

After
World War I World War I (28 July 1914 11 November 1918), often abbreviated as WWI, was one of the deadliest global conflicts in history. Belligerents included much of Europe, the Russian Empire, the United States, and the Ottoman Empire, with fightin ...
, the United States built a stockpile of 20,000 tons of weaponized
lewisite Lewisite (L) (A-243) is an organoarsenic compound. It was once manufactured in the U.S., Japan, Germany and the Soviet Union for use as a Chemical warfare, chemical weapon, acting as a vesicant (blister agent) and lung irritant. Although the substa ...
(ClCH=CHAsCl2), an
organoarsenic Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fu ...
vesicant A blister agent (or vesicant), is a chemical compound that causes severe skin, eye and mucosal pain and irritation. They are named for their ability to cause severe chemical burns, resulting in painful water blisters on the bodies of those affe ...
(blister agent) and
lung The lungs are the primary organs of the respiratory system in humans and most other animals, including some snails and a small number of fish. In mammals and most other vertebrates, two lungs are located near the backbone on either side of t ...
irritant. The stockpile was neutralized with bleach and dumped into the
Gulf of Mexico The Gulf of Mexico ( es, Golfo de México) is an oceanic basin, ocean basin and a marginal sea of the Atlantic Ocean, largely surrounded by the North American continent. It is bounded on the northeast, north and northwest by the Gulf Coast of ...
in the 1950s. During the
Vietnam War The Vietnam War (also known by #Names, other names) was a conflict in Vietnam, Laos, and Cambodia from 1 November 1955 to the fall of Saigon on 30 April 1975. It was the second of the Indochina Wars and was officially fought between North Vie ...
, the United States used
Agent Blue Agent Blue is one of the " rainbow herbicides" that is known for its use by the United States during the Vietnam War. It contained a mixture of dimethylarsinic acid (also known as cacodylic acid) and its related salt, sodium cacodylate, and w ...
, a mixture of
sodium cacodylate Cacodylic acid is an organoarsenic compound with the formula (CH3)2 AsO2H. With the formula R2As(O)OH, it is the simplest of the arsinic acids. It is a colorless solid that is soluble in water. Neutralization of cacodylic acid with base gives cac ...
and its acid form, as one of the
rainbow herbicides The Rainbow Herbicides are a group of tactical-use chemicals used by the United States military in Southeast Asia during the Vietnam War. Success with Project AGILE field tests with herbicides in South Vietnam in 1961 and inspiration by the Briti ...
to deprive North Vietnamese soldiers of foliage cover and rice.


Other uses

* Copper acetoarsenite was used as a green
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compo ...
known under many names, including Paris Green and Emerald Green. It caused numerous
arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
s.
Scheele's Green Scheele's Green, also called Schloss Green, is chemically a cupric hydrogen arsenite (also called copper arsenite or acidic copper arsenite), . It is chemically related to Paris Green. Scheele's Green was invented in 1775 by Carl Wilhelm Sch ...
, a copper arsenate, was used in the 19th century as a coloring agent in
sweets Candy, also called sweets (British English) or lollies (Australian English, New Zealand English), is a confection that features sugar as a principal ingredient. The category, called '' sugar confectionery'', encompasses any sweet confection, i ...
. * Arsenic is used in bronzing and
pyrotechnics Pyrotechnics is the science and craft of creating such things as fireworks, safety matches, oxygen candles, explosive bolts and other fasteners, parts of automotive airbags, as well as gas-pressure blasting in mining, quarrying, and demolition. ...
. * As much as 2% of produced arsenic is used in lead alloys for
lead shot Shot is a collective term for small spheres or pellets, often made of lead. These were the original projectiles for shotguns and are still fired primarily from shotguns and less commonly from riot guns and grenade launchers, although shot shells ...
and
bullet A bullet is a kinetic projectile, a component of firearm ammunition that is shot from a gun barrel. Bullets are made of a variety of materials, such as copper, lead, steel, polymer, rubber and even wax. Bullets are made in various shapes and co ...
s. * Arsenic is added in small quantities to alpha-brass to make it dezincification-resistant. This grade of brass is used in plumbing fittings and other wet environments. * Arsenic is also used for taxonomic sample preservation. It was also used in embalming fluids historically. * Arsenic was used as an opacifier in ceramics, creating white glazes. * Until recently, arsenic was used in optical glass. Modern glass manufacturers, under pressure from environmentalists, have ceased using both arsenic and
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
. * In
computer A computer is a machine that can be programmed to Execution (computing), carry out sequences of arithmetic or logical operations (computation) automatically. Modern digital electronic computers can perform generic sets of operations known as C ...
s; arsenic is used in the
chips ''CHiPs'' is an American crime drama television series created by Rick Rosner and originally aired on NBC from September 15, 1977, to May 1, 1983. It follows the lives of two motorcycle officers of the California Highway Patrol (CHP). The serie ...
as the n-type doping


Biological role


Bacteria

Some species of
bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...
obtain their energy in the absence of oxygen by
oxidizing Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
various fuels while reducing arsenate to arsenite. Under oxidative environmental conditions some bacteria use arsenite as fuel, which they oxidize to arsenate. The
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products. A ...
s involved are known as arsenate reductases (Arr). In 2008, bacteria were discovered that employ a version of
photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored i ...
in the absence of oxygen with arsenites as
electron donor In chemistry, an electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. Typical reducing agents undergo permanent chem ...
s, 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 Strain may refer to: Science and technology * Strain (biology), variants of plants, viruses or bacteria; or an inbred animal used for experimental purposes * Strain (chemistry), a chemical stress of a molecule * Strain (injury), an injury to a mu ...
PHS-1 has been isolated and is related to the
gammaproteobacterium Gammaproteobacteria is a class of bacteria in the phylum Pseudomonadota (synonym Proteobacteria). It contains about 250 genera, which makes it the most genera-rich taxon of the Prokaryotes. Several medically, ecologically, and scientifically im ...
''
Ectothiorhodospira shaposhnikovii The Ectothiorhodospiraceae are a family of purple sulfur bacteria, distinguished by producing sulfur globules outside of their cells.George M. Garrity: ''Bergey's Manual of Systematic Bacteriology''. 2. Auflage. Springer, New York, 2005, Volume 2 ...
''. The mechanism is unknown, but an encoded Arr enzyme may function in reverse to its known homologues. In 2011, it was postulated that a strain of ''
Halomonadaceae Halomonadaceae is a family of halophilic Pseudomonadota. History The family was originally described in 1988 to contain the genera ''Halomonas'' and ''Deleya''. In 1989, ''Chromobacterium marismortui'' was reclassified as ''Chromohalobacter m ...
'' could be grown in the absence of phosphorus if that element were substituted with arsenic, exploiting the fact that the
arsenate The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate res ...
and
phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phospho ...
anions are similar structurally. The study was widely criticised and subsequently refuted by independent researcher groups.


Essential trace element in higher animals

Some evidence indicates that arsenic is an essential trace mineral in birds (chickens), and in mammals (rats, hamsters, and goats). However, the
biological function In evolutionary biology, function is the reason some object or process occurred in a system that evolved through natural selection. That reason is typically that it achieves some result, such as that chlorophyll helps to capture the energy of sunl ...
is not known.


Heredity

Arsenic has been linked to epigenetic changes, heritable changes in gene expression that occur without changes in
DNA sequence DNA sequencing is the process of determining the nucleic acid sequence – the order of nucleotides in DNA. It includes any method or technology that is used to determine the order of the four bases: adenine, guanine, cytosine, and thymine. Th ...
. These include DNA methylation, histone modification, and
RNA Ribonucleic acid (RNA) is a polymeric molecule essential in various biological roles in coding, decoding, regulation and expression of genes. RNA and deoxyribonucleic acid ( DNA) are nucleic acids. Along with lipids, proteins, and carbohydra ...
interference. Toxic levels of arsenic cause significant DNA hypermethylation of tumor suppressor genes
p16 p16 (also known as p16INK4a, cyclin-dependent kinase inhibitor 2A, CDKN2A, multiple tumor suppressor 1 and numerous other synonyms), is a protein that slows cell division by slowing the progression of the cell cycle from the G1 phase to the S p ...
and
p53 p53, also known as Tumor protein P53, cellular tumor antigen p53 (UniProt name), or transformation-related protein 53 (TRP53) is a regulatory protein that is often mutated in human cancers. The p53 proteins (originally thought to be, and often s ...
, thus increasing risk of
carcinogenesis Carcinogenesis, also called oncogenesis or tumorigenesis, is the formation of a cancer, whereby normal cells are transformed into cancer cells. The process is characterized by changes at the cellular, genetic, and epigenetic levels and abnor ...
. These epigenetic events have been studied ''in vitro'' using human
kidney The kidneys are two reddish-brown bean-shaped organs found in vertebrates. They are located on the left and right in the retroperitoneal space, and in adult humans are about in length. They receive blood from the paired renal arteries; blood ...
cells and ''in vivo'' using rat
liver The liver is a major Organ (anatomy), organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the Protein biosynthesis, synthesis of proteins and biochemicals necessary for ...
cells and peripheral blood
leukocytes White blood cells, also called leukocytes or leucocytes, are the cells of the immune system that are involved in protecting the body against both infectious disease and foreign invaders. All white blood cells are produced and derived from mult ...
in humans.
Inductively coupled plasma mass spectrometry Inductively coupled plasma mass spectrometry (ICP-MS) is a type of mass spectrometry that uses an inductively coupled plasma to ionize the sample. It atomizes the sample and creates atomic and small polyatomic ions, which are then detected. It is ...
(ICP-MS) is used to detect precise levels of intracellular arsenic and other arsenic bases involved in epigenetic modification of DNA. Studies investigating arsenic as an epigenetic factor can be used to develop precise biomarkers of exposure and susceptibility. The Chinese brake fern (''
Pteris vittata ''Pteris vittata'', commonly known variously as the Chinese brake, Chinese ladder brake, or simply ladder brake, is a fern species in the Pteridoideae subfamily of the Pteridaceae. It is indigenous to Asia, southern Europe, tropical Africa and Au ...
'') hyperaccumulates arsenic from the soil into its leaves and has a proposed use in
phytoremediation Phytoremediation technologies use living plants to clean up soil, air and water contaminated with hazardous contaminants. It is defined as "the use of green plants and the associated microorganisms, along with proper soil amendments and agronom ...
.


Biomethylation

Inorganic arsenic and its compounds, upon entering the
food chain A food chain is a linear network of links in a food web starting from producer organisms (such as grass or algae which produce their own food via photosynthesis) and ending at an apex predator species (like grizzly bears or killer whales), det ...
, are progressively metabolized through a process of
methylation In the chemical sciences, methylation denotes the addition of a methyl group on a substrate, or the substitution of an atom (or group) by a methyl group. Methylation is a form of alkylation, with a methyl group replacing a hydrogen atom. These t ...
. For example, the mold ''
Scopulariopsis brevicaulis ''Microascus brevicaulis'' is a microfungus in the Ascomycota. It is the teleomorph form of ''Scopulariopsis brevicaulis.'' ''Microascus brevicaulis'' occurs world-wide as a saprotroph in soil, a common agent of biodeterioration, an irregular pl ...
'' produces
trimethylarsine Trimethylarsine (abbreviated TMA or TMAs) is the chemical compound with the formula (CH3)3As, commonly abbreviated As Me3 or TMAs. This organic derivative of arsine has been used as a source of arsenic in microelectronics industry, a building bloc ...
if inorganic arsenic is present. The organic compound arsenobetaine is found in some marine foods such as fish and algae, and also in mushrooms in larger concentrations. The average person's intake is about 10–50 µg/day. Values about 1000 µg are not unusual following consumption of fish or mushrooms, but there is little danger in eating fish because this arsenic compound is nearly non-toxic.


Environmental issues


Exposure

Naturally occurring sources of human exposure include
volcanic ash Volcanic ash consists of fragments of rock, mineral crystals, and volcanic glass, created during volcano, volcanic eruptions and measuring less than 2 mm (0.079 inches) in diameter. The term volcanic ash is also often loosely used t ...
, weathering of minerals and ores, and mineralized groundwater. Arsenic is also found in food, water, soil, and air. Arsenic is absorbed by all plants, but is more concentrated in leafy vegetables, rice, apple and grape juice, and seafood. An additional route of exposure is inhalation of atmospheric gases and dusts.Arsenic
The Agency for Toxic Substances and Disease Registry (2009).
During the
Victorian era In the history of the United Kingdom and the British Empire, the Victorian era was the period of Queen Victoria's reign, from 20 June 1837 until her death on 22 January 1901. The era followed the Georgian period and preceded the Edwardia ...
, arsenic was widely used in home decor, especially wallpapers.


Occurrence in drinking water

Extensive arsenic contamination of groundwater has led to widespread
arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
in
Bangladesh Bangladesh (}, ), officially the People's Republic of Bangladesh, is a country in South Asia. It is the eighth-most populous country in the world, with a population exceeding 165 million people in an area of . Bangladesh is among the mos ...
and neighboring countries. It is estimated that approximately 57 million people in the Bengal basin are drinking
groundwater Groundwater is the water present beneath Earth's surface in rock and soil pore spaces and in the fractures of rock formations. About 30 percent of all readily available freshwater in the world is groundwater. A unit of rock or an unconsolidate ...
with arsenic concentrations elevated above the
World Health Organization The World Health Organization (WHO) is a specialized agency of the United Nations responsible for international public health. The WHO Constitution states its main objective as "the attainment by all peoples of the highest possible level of h ...
's standard of 10
parts per billion In science and engineering, the parts-per notation is a set of pseudo-units to describe small values of miscellaneous dimensionless quantities, e.g. mole fraction or mass fraction. Since these fractions are quantity-per-quantity measures, they ...
(ppb). However, a study of cancer rates in
Taiwan Taiwan, officially the Republic of China (ROC), is a country in East Asia, at the junction of the East and South China Seas in the northwestern Pacific Ocean, with the People's Republic of China (PRC) to the northwest, Japan to the nort ...
suggested that significant increases in cancer mortality appear only at levels above 150 ppb. The arsenic in the groundwater is of natural origin, and is released from the sediment into the groundwater, caused by the anoxic conditions of the subsurface. This groundwater was used after local and western
NGOs A non-governmental organization (NGO) or non-governmental organisation (see spelling differences) is an organization that generally is formed independent from government. They are typically nonprofit entities, and many of them are active in h ...
and the Bangladeshi government undertook a massive shallow tube
well A well is an excavation or structure created in the ground by digging, driving, or drilling to access liquid resources, usually water. The oldest and most common kind of well is a water well, to access groundwater in underground aquifers. The ...
drinking-water program in the late twentieth century. This program was designed to prevent drinking of bacteria-contaminated surface waters, but failed to test for arsenic in the groundwater. Many other countries and districts in
Southeast Asia Southeast Asia, also spelled South East Asia and South-East Asia, and also known as Southeastern Asia, South-eastern Asia or SEA, is the geographical United Nations geoscheme for Asia#South-eastern Asia, south-eastern region of Asia, consistin ...
, such as
Vietnam Vietnam or Viet Nam ( vi, Việt Nam, ), officially the Socialist Republic of Vietnam,., group="n" is a country in Southeast Asia, at the eastern edge of mainland Southeast Asia, with an area of and population of 96 million, making i ...
and
Cambodia Cambodia (; also Kampuchea ; km, កម្ពុជា, UNGEGN: ), officially the Kingdom of Cambodia, is a country located in the southern portion of the Indochinese Peninsula in Southeast Asia, spanning an area of , bordered by Thailand t ...
, have geological environments that produce groundwater with a high arsenic content. Arsenicosis was reported in
Nakhon Si Thammarat Nakhon Si Thammarat Municipality ( th, เทศบาลนครนครศรีธรรมราช, ; from Pali ''Nagara Sri Dhammaraja'') is a municipality (''thesaban nakhon'') in Southern Thailand, capital of Nakhon Si Thammarat pro ...
,
Thailand Thailand ( ), historically known as Siam () and officially the Kingdom of Thailand, is a country in Southeast Asia, located at the centre of the Indochinese Peninsula, spanning , with a population of almost 70 million. The country is bo ...
in 1987, and the
Chao Phraya River The Chao Phraya ( or ; th, แม่น้ำเจ้าพระยา, , or ) is the major river in Thailand, with its low alluvial plain forming the centre of the country. It flows through Bangkok and then into the Gulf of Thailand. Et ...
probably contains high levels of naturally occurring dissolved arsenic without being a public health problem because much of the public uses
bottled water Bottled water is drinking water (e.g., well water, distilled water, mineral water, or spring water) packaged in plastic or glass water bottles. Bottled water may be carbonated or not. Sizes range from small single serving bottles to large car ...
. In Pakistan, more than 60 million people are exposed to arsenic polluted drinking water indicated by a recent report of
Science Science is a systematic endeavor that builds and organizes knowledge in the form of testable explanations and predictions about the universe. Science may be as old as the human species, and some of the earliest archeological evidence for ...
. Podgorski's team investigated more than 1200 samples and more than 66% exceeded the WHO minimum contamination level. Since the 1980s, residents of the Ba Men region of Inner Mongolia, China have been chronically exposed to arsenic through drinking water from contaminated wells. A 2009 research study observed an elevated presence of skin lesions among residents with well water arsenic concentrations between 5 and 10 µg/L, suggesting that arsenic induced toxicity may occur at relatively low concentrations with chronic exposure. Overall, 20 of China's 34 provinces have high arsenic concentrations in the groundwater supply, potentially exposing 19 million people to hazardous drinking water. In the United States, arsenic is most commonly found in the ground waters of the southwest. Parts of
New England New England is a region comprising six states in the Northeastern United States: Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont. It is bordered by the state of New York to the west and by the Canadian provinces ...
,
Michigan Michigan () is a state in the Great Lakes region of the upper Midwestern United States. With a population of nearly 10.12 million and an area of nearly , Michigan is the 10th-largest state by population, the 11th-largest by area, and the ...
,
Wisconsin Wisconsin () is a state in the upper Midwestern United States. Wisconsin is the 25th-largest state by total area and the 20th-most populous. It is bordered by Minnesota to the west, Iowa to the southwest, Illinois to the south, Lake M ...
,
Minnesota Minnesota () is a state in the upper midwestern region of the United States. It is the 12th largest U.S. state in area and the 22nd most populous, with over 5.75 million residents. Minnesota is home to western prairies, now given over to ...
and the Dakotas are also known to have significant concentrations of arsenic in ground water. Increased levels of skin cancer have been associated with arsenic exposure in Wisconsin, even at levels below the 10 part per billion drinking water standard. According to a recent film funded by the US
Superfund Superfund is a United States federal environmental remediation program established by the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA). The program is administered by the United States Environmental Pro ...
, millions of private wells have unknown arsenic levels, and in some areas of the US, more than 20% of the wells may contain levels that exceed established limits. Low-level exposure to arsenic at concentrations of 100 parts per billion (i.e., above the 10 parts per billion drinking water standard) compromises the initial immune response to H1N1 or swine flu infection according to NIEHS-supported scientists. The study, conducted in laboratory mice, suggests that people exposed to arsenic in their drinking water may be at increased risk for more serious illness or death from the virus. Some Canadians are drinking water that contains inorganic arsenic. Private-dug–well waters are most at risk for containing inorganic arsenic. Preliminary well water analysis typically does not test for arsenic. Researchers at the Geological Survey of Canada have modeled relative variation in natural arsenic hazard potential for the province of New Brunswick. This study has important implications for potable water and health concerns relating to inorganic arsenic. Epidemiological evidence from
Chile Chile, officially the Republic of Chile, is a country in the western part of South America. It is the southernmost country in the world, and the closest to Antarctica, occupying a long and narrow strip of land between the Andes to the east a ...
shows a dose-dependent connection between chronic arsenic exposure and various forms of cancer, in particular when other risk factors, such as cigarette smoking, are present. These effects have been demonstrated at contaminations less than 50 ppb. Arsenic is itself a constituent of
tobacco smoke Tobacco smoke is a sooty aerosol produced by the incomplete combustion of tobacco during the tobacco smoking, smoking of cigarettes and other tobacco products. Temperatures in burning cigarettes range from about 400 °C between puffs to abo ...
. Analyzing multiple epidemiological studies on inorganic arsenic exposure suggests a small but measurable increase in risk for bladder cancer at 10 ppb. According to Peter Ravenscroft of the Department of Geography at the University of Cambridge, roughly 80 million people worldwide consume between 10 and 50 ppb arsenic in their drinking water. If they all consumed exactly 10 ppb arsenic in their drinking water, the previously cited multiple epidemiological study analysis would predict an additional 2,000 cases of bladder cancer alone. This represents a clear underestimate of the overall impact, since it does not include lung or skin cancer, and explicitly underestimates the exposure. Those exposed to levels of arsenic above the current WHO standard should weigh the costs and benefits of arsenic remediation. Early (1973) evaluations of the processes for removing dissolved arsenic from drinking water demonstrated the efficacy of co-precipitation with either iron or aluminum oxides. In particular, iron as a coagulant was found to remove arsenic with an efficacy exceeding 90%. Several adsorptive media systems have been approved for use at point-of-service in a study funded by the
United States Environmental Protection Agency The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it be ...
(US EPA) and the
National Science Foundation The National Science Foundation (NSF) is an independent agency of the United States government that supports fundamental research and education in all the non-medical fields of science and engineering. Its medical counterpart is the National I ...
(NSF). A team of European and Indian scientists and engineers have set up six arsenic treatment plants in
West Bengal West Bengal (, Bengali: ''Poshchim Bongo'', , abbr. WB) is a state in the eastern portion of India. It is situated along the Bay of Bengal, along with a population of over 91 million inhabitants within an area of . West Bengal is the fourt ...
based on in-situ remediation method (SAR Technology). This technology does not use any chemicals and arsenic is left in an insoluble form (+5 state) in the subterranean zone by recharging aerated water into the aquifer and developing an oxidation zone that supports arsenic oxidizing micro-organisms. This process does not produce any waste stream or sludge and is relatively cheap. Another effective and inexpensive method to avoid arsenic contamination is to sink wells 500 feet or deeper to reach purer waters. A recent 2011 study funded by the US National Institute of Environmental Health Sciences' Superfund Research Program shows that deep sediments can remove arsenic and take it out of circulation. In this process, called ''adsorption'', arsenic sticks to the surfaces of deep sediment particles and is naturally removed from the ground water. Magnetic separations of arsenic at very low magnetic field
gradient In vector calculus, the gradient of a scalar-valued differentiable function of several variables is the vector field (or vector-valued function) \nabla f whose value at a point p is the "direction and rate of fastest increase". If the gradi ...
s with high-surface-area and monodisperse
magnetite Magnetite is a mineral and one of the main iron ores, with the chemical formula Fe2+Fe3+2O4. It is one of the oxides of iron, and is ferrimagnetic; it is attracted to a magnet and can be magnetized to become a permanent magnet itself. With the ...
(Fe3O4)
nanocrystal A ''nanocrystal'' is a material particle having at least one dimension smaller than 100 nanometres, based on quantum dots (a nanoparticle) and composed of atoms in either a single- or poly-crystalline arrangement. The size of nanocrystals dist ...
s have been demonstrated in point-of-use water purification. Using the high specific surface area of Fe3O4 nanocrystals, the mass of waste associated with arsenic removal from water has been dramatically reduced. Epidemiological studies have suggested a correlation between chronic consumption of drinking water contaminated with arsenic and the incidence of all leading causes of mortality. The literature indicates that arsenic exposure is causative in the pathogenesis of diabetes. Chaff-based filters have recently been shown to reduce the arsenic content of water to 3 µg/L. This may find applications in areas where the potable water is extracted from underground
aquifer An aquifer is an underground layer of water-bearing, permeable rock, rock fractures, or unconsolidated materials (gravel, sand, or silt). Groundwater from aquifers can be extracted using a water well. Aquifers vary greatly in their characterist ...
s.


San Pedro de Atacama

For several centuries, the people of
San Pedro de Atacama San Pedro de Atacama is a Chilean town and commune in El Loa Province, Antofagasta Region. It is located east of Antofagasta, some 106 km (60 mi) southeast of Calama and the Chuquicamata copper mine, overlooking the Licancabur volcano. ...
in
Chile Chile, officially the Republic of Chile, is a country in the western part of South America. It is the southernmost country in the world, and the closest to Antarctica, occupying a long and narrow strip of land between the Andes to the east a ...
have been drinking water that is contaminated with arsenic, and some evidence suggests they have developed some immunity.


Hazard maps for contaminated groundwater

Around one-third of the world's population drinks water from groundwater resources. Of this, about 10 percent, approximately 300 million people, obtains water from groundwater resources that are contaminated with unhealthy levels of arsenic or fluoride. These trace elements derive mainly from minerals and ions in the ground.


Redox transformation of arsenic in natural waters

Arsenic is unique among the trace
metalloids A metalloid is a type of chemical element which has a preponderance of properties in between, or that are a mixture of, those of metals and nonmetals. There is no standard definition of a metalloid and no complete agreement on which elements are ...
and oxyanion-forming trace metals (e.g. As, Se, Sb, Mo, V, Cr, U, Re). It is sensitive to mobilization at pH values typical of natural waters (pH 6.5–8.5) under both oxidizing and reducing conditions. Arsenic can occur in the environment in several oxidation states (−3, 0, +3 and +5), but in natural waters it is mostly found in inorganic forms as oxyanions of trivalent arsenite s(III)or pentavalent arsenate
s(V) S, or s, is the nineteenth letter in the Latin alphabet, used in the modern English alphabet, the alphabets of other western European languages and others worldwide. Its name in English is ''ess'' (pronounced ), plural ''esses''. History ...
Organic forms of arsenic are produced by biological activity, mostly in surface waters, but are rarely quantitatively important. Organic arsenic compounds may, however, occur where waters are significantly impacted by industrial pollution. Arsenic may be solubilized by various processes. When pH is high, arsenic may be released from surface binding sites that lose their positive charge. When water level drops and
sulfide Sulfide (British English also sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to chemical compounds lar ...
minerals are exposed to air, arsenic trapped in sulfide minerals can be released into water. When organic carbon is present in water, bacteria are fed by directly reducing As(V) to As(III) or by reducing the element at the binding site, releasing inorganic arsenic. The aquatic transformations of arsenic are affected by pH, reduction-oxidation potential, organic matter concentration and the concentrations and forms of other elements, especially iron and manganese. The main factors are pH and the redox potential. Generally, the main forms of arsenic under oxic conditions are H3AsO4, H2AsO4, HAsO42−, and AsO43− at pH 2, 2–7, 7–11 and 11, respectively. Under reducing conditions, H3AsO4 is predominant at pH 2–9. Oxidation and reduction affects the migration of arsenic in subsurface environments. Arsenite is the most stable soluble form of arsenic in reducing environments and arsenate, which is less mobile than arsenite, is dominant in oxidizing environments at neutral pH. Therefore, arsenic may be more mobile under reducing conditions. The reducing environment is also rich in organic matter which may enhance the solubility of arsenic compounds. As a result, the
adsorption Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a f ...
of arsenic is reduced and dissolved arsenic accumulates in groundwater. That is why the arsenic content is higher in reducing environments than in oxidizing environments. The presence of sulfur is another factor that affects the transformation of arsenic in natural water. Arsenic can
precipitate In an aqueous solution, precipitation is the process of transforming a dissolved substance into an insoluble solid from a super-saturated solution. The solid formed is called the precipitate. In case of an inorganic chemical reaction leading ...
when metal sulfides form. In this way, arsenic is removed from the water and its mobility decreases. When oxygen is present, bacteria oxidize reduced sulfur to generate energy, potentially releasing bound arsenic. Redox reactions involving Fe also appear to be essential factors in the fate of arsenic in aquatic systems. The reduction of iron oxyhydroxides plays a key role in the release of arsenic to water. So arsenic can be enriched in water with elevated Fe concentrations. Under oxidizing conditions, arsenic can be mobilized from
pyrite The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral. Pyrite's metallic Luster (mineralogy), lust ...
or iron oxides especially at elevated pH. Under reducing conditions, arsenic can be mobilized by reductive desorption or dissolution when associated with iron oxides. The reductive desorption occurs under two circumstances. One is when arsenate is reduced to arsenite which adsorbs to iron oxides less strongly. The other results from a change in the charge on the mineral surface which leads to the desorption of bound arsenic. Some species of bacteria catalyze redox transformations of arsenic. Dissimilatory arsenate-respiring prokaryotes (DARP) speed up the reduction of As(V) to As(III). DARP use As(V) as the electron acceptor of anaerobic respiration and obtain energy to survive. Other organic and inorganic substances can be oxidized in this process.
Chemoautotrophic A Chemotroph is an organism that obtains energy by the oxidation of electron donors in their environments. These molecules can be organic ( chemoorganotrophs) or inorganic (chemolithotrophs). The chemotroph designation is in contrast to phototro ...
arsenite oxidizers (CAO) and
heterotrophic A heterotroph (; ) is an organism that cannot produce its own food, instead taking nutrition from other sources of organic carbon, mainly plant or animal matter. In the food chain, heterotrophs are primary, secondary and tertiary consumers, but ...
arsenite oxidizers (HAO) convert As(III) into As(V). CAO combine the oxidation of As(III) with the reduction of oxygen or nitrate. They use obtained energy to fix produce organic carbon from CO2. HAO cannot obtain energy from As(III) oxidation. This process may be an arsenic
detoxification Detoxification or detoxication (detox for short) is the physiological or medicinal removal of toxic substances from a living organism, including the human body, which is mainly carried out by the liver. Additionally, it can refer to the period of ...
mechanism for the bacteria. Equilibrium thermodynamic calculations predict that As(V) concentrations should be greater than As(III) concentrations in all but strongly reducing conditions, i.e. where SO42− reduction is occurring. However, abiotic redox reactions of arsenic are slow. Oxidation of As(III) by dissolved O2 is a particularly slow reaction. For example, Johnson and Pilson (1975) gave
half-lives Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable at ...
for the oxygenation of As(III) in seawater ranging from several months to a year. In other studies, As(V)/As(III) ratios were stable over periods of days or weeks during water sampling when no particular care was taken to prevent oxidation, again suggesting relatively slow oxidation rates. Cherry found from experimental studies that the As(V)/As(III) ratios were stable in anoxic solutions for up to 3 weeks but that gradual changes occurred over longer timescales. Sterile water samples have been observed to be less susceptible to speciation changes than non-sterile samples. Oremland found that the reduction of As(V) to As(III) in Mono Lake was rapidly catalyzed by bacteria with rate constants ranging from 0.02 to 0.3-day−1.


Wood preservation in the US

As of 2002, US-based industries consumed 19,600 metric tons of arsenic. Ninety percent of this was used for treatment of wood with
chromated copper arsenate Chromated copper arsenate (CCA) is a wood preservative containing compounds of chromium, copper, and arsenic, in various proportions. It is used to impregnate timber and other wood products, especially those intended for outdoor use, in order to pr ...
(CCA). In 2007, 50% of the 5,280 metric tons of consumption was still used for this purpose. In the United States, the voluntary phasing-out of arsenic in production of consumer products and residential and general consumer construction products began on 31 December 2003, and alternative chemicals are now used, such as
Alkaline Copper Quaternary Alkaline copper quaternary, usually abbreviated ACQ, is a type of water-based wood preservative product containing a soluble copper(II) complex and quaternary ammonium alkyl- or aryl-substituted compounds ("quats"). Thus the product was originall ...
,
borate A borate is any of several boron oxyanions, negative ions consisting of boron and oxygen, such as orthoborate , metaborate , or tetraborate ; or any salt with such anions, such as sodium metaborate, and disodium tetraborate . The name also refe ...
s, copper azole,
cyproconazole Cyproconazole is an agricultural fungicide of the class of azoles, used on cereal crops, coffee, sugar beet, fruit trees and grapes, on sod farms and golf courses and on wood as a preservative. It was introduced to the market by then Sandoz in 19 ...
, and
propiconazole Propiconazole is a triazole fungicide, also known as a DMI, or demethylation inhibiting fungicide due to its binding with and inhibiting the 14-alpha demethylase enzyme from demethylating a precursor to ergosterol. Without this demethylation st ...
. Although discontinued, this application is also one of the most concerning to the general public. The vast majority of older pressure-treated wood was treated with CCA. CCA lumber is still in widespread use in many countries, and was heavily used during the latter half of the 20th century as a structural and outdoor
building material Building material is material used for construction. Many naturally occurring substances, such as clay, rock (geology), rocks, sand, wood, and even twigs and leaves, have been used to construct buildings. Apart from naturally occurring materia ...
. Although the use of CCA lumber was banned in many areas after studies showed that arsenic could leach out of the wood into the surrounding
soil Soil, also commonly referred to as earth or dirt, is a mixture of organic matter, minerals, gases, liquids, and organisms that together support life. Some scientific definitions distinguish ''dirt'' from ''soil'' by restricting the former te ...
(from playground equipment, for instance), a risk is also presented by the burning of older CCA timber. The direct or indirect ingestion of wood ash from burnt CCA lumber has caused fatalities in animals and serious poisonings in humans; the lethal human dose is approximately 20 grams of ash. Scrap CCA lumber from construction and demolition sites may be inadvertently used in commercial and domestic fires. Protocols for safe disposal of CCA lumber are not consistent throughout the world. Widespread
landfill A landfill site, also known as a tip, dump, rubbish dump, garbage dump, or dumping ground, is a site for the disposal of waste materials. Landfill is the oldest and most common form of waste disposal, although the systematic burial of the waste ...
disposal of such timber raises some concern, but other studies have shown no arsenic contamination in the groundwater.


Mapping of industrial releases in the US

One tool that maps the location (and other information) of arsenic releases in the United States is
TOXMAP TOXMAP was a geographic information system (GIS) from the United States National Library of Medicine (NLM) that was deprecated on December 16, 2019. The application used maps of the United States to help users explore data from the United States ...
. TOXMAP is a Geographic Information System (GIS) from the Division of Specialized Information Services of the
United States National Library of Medicine The United States National Library of Medicine (NLM), operated by the United States federal government, is the world's largest medical library. Located in Bethesda, Maryland, the NLM is an institute within the National Institutes of Health. Its ...
(NLM) funded by the US Federal Government. With marked-up maps of the United States, TOXMAP enables users to visually explore data from the
United States Environmental Protection Agency The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it be ...
's (EPA)
Toxics Release Inventory The Toxics Release Inventory (TRI) is a publicly available database containing information on toxic chemical releases and other waste management activities in the United States. Summary of requirements The database is available from the United St ...
and
Superfund Basic Research Program The Superfund Research Program (SRP) was created within the National Institute of Environmental Health Sciences in 1986 under the Superfund Amendments and Reauthorization Act (SARA). The SRP is a university-based research program that supports the ...
s. TOXMAP's chemical and environmental health information is taken from NLM's Toxicology Data Network (TOXNET),
PubMed PubMed is a free search engine accessing primarily the MEDLINE database of references and abstracts on life sciences and biomedical topics. The United States National Library of Medicine (NLM) at the National Institutes of Health maintain the ...
, and from other authoritative sources.


Bioremediation

Physical, chemical, and biological methods have been used to remediate arsenic contaminated water. Bioremediation is said to be cost-effective and environmentally friendly. Bioremediation of ground water contaminated with arsenic aims to convert arsenite, the toxic form of arsenic to humans, to arsenate. Arsenate (+5 oxidation state) is the dominant form of arsenic in surface water, while arsenite (+3 oxidation state) is the dominant form in hypoxic to anoxic environments. Arsenite is more soluble and mobile than arsenate. Many species of bacteria can transform arsenite to arsenate in anoxic conditions by using arsenite as an electron donor. This is a useful method in ground water remediation. Another bioremediation strategy is to use plants that accumulate arsenic in their tissues via
phytoremediation Phytoremediation technologies use living plants to clean up soil, air and water contaminated with hazardous contaminants. It is defined as "the use of green plants and the associated microorganisms, along with proper soil amendments and agronom ...
but the disposal of contaminated plant material needs to be considered. Bioremediation requires careful evaluation and design in accordance with existing conditions. Some sites may require the addition of an electron acceptor while others require microbe supplementation ( bioaugmentation). Regardless of the method used, only constant monitoring can prevent future contamination.


Toxicity and precautions

Arsenic and many of its compounds are especially potent poisons. Small amount of arsenic can be detected by pharmacopoial methods which includes reduction of arsenic to arsenious with help of zinc and can be confirmed with mercuric chloride paper.


Classification

Elemental arsenic and arsenic sulfate and trioxide compounds are classified as "
toxic Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a subst ...
" and "dangerous for the environment" in the
European Union The European Union (EU) is a supranational political and economic union of member states that are located primarily in Europe. The union has a total area of and an estimated total population of about 447million. The EU has often been des ...
under
directive 67/548/EEC The Dangerous Substances Directive (as amended) was one of the main European Union laws concerning chemical safety, until its full replacement by the new regulation CLP Regulation (2008), starting in 2016. It was made under Article 100 (Art. 94 ...
. The
International Agency for Research on Cancer The International Agency for Research on Cancer (IARC; french: Centre International de Recherche sur le Cancer, CIRC) is an intergovernmental agency forming part of the World Health Organization of the United Nations. Its role is to conduct and ...
(IARC) recognizes arsenic and inorganic arsenic compounds as group 1 carcinogens, and the EU lists arsenic trioxide,
arsenic pentoxide Arsenic pentoxide is the inorganic compound with the formula As2O5. This glassy, white, deliquescent solid is relatively unstable, consistent with the rarity of the As(V) oxidation state. More common, and far more important commercially, is arse ...
, and
arsenate The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate res ...
salts as category 1
carcinogen A carcinogen is any substance, radionuclide, or radiation that promotes carcinogenesis (the formation of cancer). This may be due to the ability to damage the genome or to the disruption of cellular metabolic processes. Several radioactive substan ...
s. Arsenic is known to cause arsenicosis when present in drinking water, "the most common species being arsenate As(V)and arsenite As(III).


Legal limits, food, and drink

In the United States since 2006, the maximum concentration in drinking water allowed by the
Environmental Protection Agency A biophysical environment is a biotic and abiotic surrounding of an organism or population, and consequently includes the factors that have an influence in their survival, development, and evolution. A biophysical environment can vary in scale f ...
(EPA) is 10 ppb and the FDA set the same standard in 2005 for bottled water. The Department of Environmental Protection for New Jersey set a drinking water limit of 5 ppb in 2006. The
IDLH The term immediately dangerous to life or health (IDLH) is defined by the US National Institute for Occupational Safety and Health (NIOSH) as exposure to airborne contaminants that is "likely to cause death or immediate or delayed permanent advers ...
(immediately dangerous to life and health) value for arsenic metal and inorganic arsenic compounds is 5 mg/m3 (5 ppb). The
Occupational Safety and Health Administration The Occupational Safety and Health Administration'' (OSHA ) is a large regulatory agency of the United States Department of Labor that originally had federal visitorial powers to inspect and examine workplaces. Congress established the agenc ...
has set the
permissible exposure limit The permissible exposure limit (PEL or OSHA PEL) is a legal limit in the United States for exposure of an employee to a chemical substance or physical agent such as high level noise. Permissible exposure limits are established by the Occupational ...
(PEL) to a time-weighted average (TWA) of 0.01 mg/m3 (0.01 ppb), and the
National Institute for Occupational Safety and Health The National Institute for Occupational Safety and Health (NIOSH, ) is the United States federal agency responsible for conducting research and making recommendations for the prevention of work-related injury and illness. NIOSH is part of the C ...
(NIOSH) has set the
recommended exposure limit A recommended exposure limit (REL) is an occupational exposure limit that has been recommended by the United States National Institute for Occupational Safety and Health. The REL is a level that NIOSH believes would be protective of worker safet ...
(REL) to a 15-minute constant exposure of 0.002 mg/m3 (0.002 ppb). The PEL for organic arsenic compounds is a TWA of 0.5 mg/m3. (0.5 ppb). In 2008, based on its ongoing testing of a wide variety of American foods for toxic chemicals, the U.S.
Food and Drug Administration The United States Food and Drug Administration (FDA or US FDA) is a List of United States federal agencies, federal agency of the United States Department of Health and Human Services, Department of Health and Human Services. The FDA is respon ...
set the "level of concern" for inorganic arsenic in apple and pear juices at 23 ppb, based on non-carcinogenic effects, and began blocking importation of products in excess of this level; it also required recalls for non-conforming domestic products. In 2011, the national '' Dr. Oz'' television show broadcast a program highlighting tests performed by an independent lab hired by the producers. Though the methodology was disputed (it did not distinguish between organic and inorganic arsenic) the tests showed levels of arsenic up to 36 ppb. In response, FDA tested the worst brand from the ''Dr.'' ''Oz'' show and found much lower levels. Ongoing testing found 95% of the apple juice samples were below the level of concern. Later testing by
Consumer Reports Consumer Reports (CR), formerly Consumers Union (CU), is an American nonprofit consumer organization dedicated to independent product testing, investigative journalism, consumer-oriented research, public education, and consumer advocacy. Founded ...
showed inorganic arsenic at levels slightly above 10 ppb, and the organization urged parents to reduce consumption. In July 2013, on consideration of consumption by children, chronic exposure, and carcinogenic effect, the FDA established an "action level" of 10 ppb for apple juice, the same as the drinking water standard. Concern about arsenic in rice in Bangladesh was raised in 2002, but at the time only Australia had a legal limit for food (one milligram per kilogram). Concern was raised about people who were eating U.S. rice exceeding WHO standards for personal arsenic intake in 2005. In 2011, the People's Republic of China set a food standard of 150 ppb for arsenic. In the United States in 2012, testing by separate groups of researchers at the Children's Environmental Health and Disease Prevention Research Center at
Dartmouth College Dartmouth College (; ) is a private research university in Hanover, New Hampshire. Established in 1769 by Eleazar Wheelock, it is one of the nine colonial colleges chartered before the American Revolution. Although founded to educate Native A ...
(early in the year, focusing on urinary levels in children) and
Consumer Reports Consumer Reports (CR), formerly Consumers Union (CU), is an American nonprofit consumer organization dedicated to independent product testing, investigative journalism, consumer-oriented research, public education, and consumer advocacy. Founded ...
(in November) found levels of arsenic in rice that resulted in calls for the FDA to set limits.Lawmakers Urge FDA to Act on Arsenic Standards
Foodsafetynews.com (24 February 2012). Retrieved 2012-05-23.
The FDA released some testing results in September 2012, and as of July 2013, is still collecting data in support of a new potential regulation. It has not recommended any changes in consumer behavior. Consumer Reports recommended: # That the EPA and FDA eliminate arsenic-containing fertilizer, drugs, and pesticides in food production; # That the FDA establish a legal limit for food; # That industry change production practices to lower arsenic levels, especially in food for children; and # That consumers test home water supplies, eat a varied diet, and cook rice with excess water, then draining it off (reducing inorganic arsenic by about one third along with a slight reduction in vitamin content). # Evidence-based public health advocates also recommend that, given the lack of regulation or labeling for arsenic in the U.S., children should eat no more than 1.5 servings per week of rice and should not drink rice milk as part of their daily diet before age 5. They also offer recommendations for adults and infants on how to limit arsenic exposure from rice, drinking water, and fruit juice. A 2014
World Health Organization The World Health Organization (WHO) is a specialized agency of the United Nations responsible for international public health. The WHO Constitution states its main objective as "the attainment by all peoples of the highest possible level of h ...
advisory conference was scheduled to consider limits of 200–300 ppb for rice.


Reducing arsenic content in rice

In 2020, scientists assessed multiple preparation procedures of
rice Rice is the seed of the grass species ''Oryza sativa'' (Asian rice) or less commonly ''Oryza glaberrima ''Oryza glaberrima'', commonly known as African rice, is one of the two domesticated rice species. It was first domesticated and grown i ...
for their capacity to reduce arsenic content and preserve nutrients, recommending a procedure involving
parboiling Parboiling (or leaching) is the partial or semi boiling of food as the first step in cooking. The word is from the Old French 'parboillir' (to boil thoroughly) but by mistaken association with 'part' it has acquired its current meaning. The wo ...
and water-absorption.


Occupational exposure limits


Ecotoxicity

Arsenic is
bioaccumulative Bioaccumulation is the gradual accumulation of substances, such as pesticides or other chemicals, in an organism. Bioaccumulation occurs when an organism absorbs a substance at a rate faster than that at which the substance is lost or eliminated ...
in many organisms, marine species in particular, but it does not appear to biomagnify significantly in food webs. In polluted areas, plant growth may be affected by root uptake of arsenate, which is a phosphate analog and therefore readily transported in plant tissues and cells. In polluted areas, uptake of the more toxic arsenite ion (found more particularly in reducing conditions) is likely in poorly-drained soils.


Toxicity in animals


Biological mechanism

Arsenic's toxicity comes from the affinity of arsenic(III) oxides for
thiol In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl gro ...
s. Thiols, in the form of
cysteine Cysteine (symbol Cys or C; ) is a semiessential proteinogenic amino acid with the formula . The thiol side chain in cysteine often participates in enzymatic reactions as a nucleophile. When present as a deprotonated catalytic residue, sometime ...
residues and
cofactors Cofactor may also refer to: * Cofactor (biochemistry), a substance that needs to be present in addition to an enzyme for a certain reaction to be catalysed * A domain parameter in elliptic curve cryptography, defined as the ratio between the order ...
such as
lipoic acid Lipoic acid (LA), also known as α-lipoic acid, alpha-lipoic acid (ALA) and thioctic acid, is an organosulfur compound derived from caprylic acid (octanoic acid). ALA is made in animals normally, and is essential for aerobic metabolism. It is a ...
and
coenzyme A Coenzyme A (CoA, SHCoA, CoASH) is a coenzyme, notable for its role in the synthesis and oxidation of fatty acids, and the oxidation of pyruvate in the citric acid cycle. All genomes sequenced to date encode enzymes that use coenzyme A as a subs ...
, are situated at the active sites of many important
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products. A ...
s. Arsenic disrupts ATP production through several mechanisms. At the level of the
citric acid cycle The citric acid cycle (CAC)—also known as the Krebs cycle or the TCA cycle (tricarboxylic acid cycle)—is a series of chemical reactions to release stored energy through the oxidation of acetyl-CoA derived from carbohydrates, fats, and proteins ...
, arsenic inhibits
lipoic acid Lipoic acid (LA), also known as α-lipoic acid, alpha-lipoic acid (ALA) and thioctic acid, is an organosulfur compound derived from caprylic acid (octanoic acid). ALA is made in animals normally, and is essential for aerobic metabolism. It is a ...
, which is a cofactor for
pyruvate dehydrogenase Pyruvate dehydrogenase is an enzyme that catalyzes the reaction of pyruvate and a lipoamide to give the acetylated dihydrolipoamide and carbon dioxide. The conversion requires the coenzyme thiamine pyrophosphate. Pyruvate dehydrogenase is us ...
. By competing with phosphate, arsenate uncouples
oxidative phosphorylation Oxidative phosphorylation (UK , US ) or electron transport-linked phosphorylation or terminal oxidation is the metabolic pathway in which cells use enzymes to oxidize nutrients, thereby releasing chemical energy in order to produce adenosine tri ...
, thus inhibiting energy-linked reduction of
NAD+ Nicotinamide adenine dinucleotide (NAD) is a coenzyme central to metabolism. Found in all living cells, NAD is called a dinucleotide because it consists of two nucleotides joined through their phosphate groups. One nucleotide contains an aden ...
, mitochondrial respiration and ATP synthesis. Hydrogen peroxide production is also increased, which, it is speculated, has potential to form reactive oxygen species and oxidative stress. These metabolic interferences lead to death from multi-system
organ failure Organ dysfunction is a condition where an organ does not perform its expected function. Organ failure is organ dysfunction to such a degree that normal homeostasis cannot be maintained without external clinical intervention. It is not a diagnosi ...
. The organ failure is presumed to be from
necrotic Necrosis () is a form of cell injury which results in the premature death of cells in living tissue by autolysis. Necrosis is caused by factors external to the cell or tissue, such as infection, or trauma which result in the unregulated dige ...
cell death, not
apoptosis Apoptosis (from grc, ἀπόπτωσις, apóptōsis, 'falling off') is a form of programmed cell death that occurs in multicellular organisms. Biochemical events lead to characteristic cell changes (morphology) and death. These changes incl ...
, since energy reserves have been too depleted for apoptosis to occur.


Exposure risks and remediation

Occupational exposure and
arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
may occur in persons working in industries involving the use of inorganic arsenic and its compounds, such as wood preservation, glass production, nonferrous metal alloys, and electronic semiconductor manufacturing. Inorganic arsenic is also found in coke oven emissions associated with the smelter industry. The conversion between As(III) and As(V) is a large factor in arsenic environmental contamination. According to Croal, Gralnick, Malasarn and Newman, " heunderstanding fwhat stimulates As(III) oxidation and/or limits As(V) reduction is relevant for
bioremediation Bioremediation broadly refers to any process wherein a biological system (typically bacteria, microalgae, fungi, and plants), living or dead, is employed for removing environmental pollutants from air, water, soil, flue gasses, industrial effluent ...
of contaminated sites (Croal). The study of chemolithoautotrophic As(III) oxidizers and the heterotrophic As(V) reducers can help the understanding of the oxidation and/or reduction of arsenic.


Treatment

Treatment of chronic arsenic poisoning is possible. British anti-lewisite (
dimercaprol Dimercaprol, also called British anti-Lewisite (BAL), is a medication used to treat acute poisoning by arsenic, mercury, gold, and lead. It may also be used for antimony, thallium, or bismuth poisoning, although the evidence for those uses is not ...
) is prescribed in doses of 5 mg/kg up to 300 mg every 4 hours for the first day, then every 6 hours for the second day, and finally every 8 hours for 8 additional days. However the USA's
Agency for Toxic Substances and Disease Registry The Agency for Toxic Substances and Disease Registry (ATSDR) is a federal public health agency within the United States Department of Health and Human Services. The agency focuses on minimizing human health risks associated with exposure to haz ...
(ATSDR) states that the long-term effects of arsenic exposure cannot be predicted. Blood, urine, hair, and nails may be tested for arsenic; however, these tests cannot foresee possible health outcomes from the exposure. Long-term exposure and consequent excretion through urine has been linked to
bladder The urinary bladder, or simply bladder, is a hollow organ in humans and other vertebrates that stores urine from the kidneys before disposal by urination. In humans the bladder is a distensible organ that sits on the pelvic floor. Urine enters ...
and
kidney cancer Kidney cancer, also known as renal cancer, is a group of cancers that starts in the kidney. Symptoms may include blood in the urine, lump in the abdomen, or back pain. Fever, weight loss, and tiredness may also occur. Complications can include sp ...
in addition to cancer of the liver, prostate, skin, lungs, and
nasal cavity The nasal cavity is a large, air-filled space above and behind the nose in the middle of the face. The nasal septum divides the cavity into two cavities, also known as fossae. Each cavity is the continuation of one of the two nostrils. The nasal c ...
.The Tox Guide for Arsenic
(2007). The US Agency for Toxic Substances and Disease Registry.


See also

*
Aqua Tofana Aqua Tofana (also known as Acqua Toffana and Aqua Tufania and Manna di San Nicola) was a strong poison created in Sicily around 1630 that was reputedly widely used in Palermo, Naples, Perugia, and Rome, Italy. It has been associated with Giulia ...
* '' Arsenic and Old Lace'' *
Arsenic biochemistry Arsenic biochemistry refers to biochemical processes that can use arsenic or its compounds, such as arsenate. Arsenic is a moderately abundant element in Earth's crust, and although many arsenic compounds are often considered highly toxic to most ...
*
Arsenic compounds Compounds of arsenic resemble in some respects those of phosphorus which occupies the same group (column) of the periodic table. The most common oxidation states for arsenic are: −3 in the arsenides, which are alloy-like intermetallic compound ...
*
Arsenic poisoning Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, bu ...
* Arsenic toxicity *
Arsenic trioxide Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...
*
Fowler's solution Fowler's solution is a solution containing 1% potassium arsenite (KAsO2), and was once prescribed as a remedy or a tonic. Thomas Fowler (1736–1801) of Stafford, England, proposed the solution in 1786 as a substitute for a patent medicine, "ta ...
*
GFAJ-1 GFAJ-1 is a strain of rod-shaped bacteria in the family Halomonadaceae. It is an extremophile that was isolated from the hypersaline and alkaline Mono Lake in eastern California by geobiologist Felisa Wolfe-Simon, a NASA research fellow in resi ...
*
Grainger challenge The Grainger challenge is a scientific competition to find an economical way to remove arsenic from arsenic-contaminated groundwater. This competition is being funded by the United States National Academy of Engineering and the Grainger Foundation ...
*
Hypothetical types of biochemistry Hypothetical types of biochemistry are forms of biochemistry agreed to be scientifically viable but not proven to exist at this time. The kinds of living organisms currently known on Earth all use carbon compounds for basic structural and metabo ...
*
Organoarsenic chemistry Organoarsenic chemistry is the chemistry of compounds containing a chemical bond between arsenic and carbon. A few organoarsenic compounds, also called "organoarsenicals," are produced industrially with uses as insecticides, herbicides, and fungic ...
*
Toxic heavy metal A toxic heavy metal is any relatively dense metal or metalloid that is noted for its potential toxicity, especially in environmental contexts. The term has particular application to cadmium, mercury and lead, all of which appear in the World He ...
*
White arsenic Arsenic trioxide, sold under the brand name Trisenox among others, is an inorganic compound and medication. As an industrial chemical, whose major uses include in the manufacture of wood preservatives, pesticides, and glass. As a medication, i ...


References


Bibliography

* * *


Further reading

*


External links


Arsenic
Cancer Causing Substances, U.S. National Cancer Institute.
CTD's Arsenic page
an
CTD's Arsenicals page
from the
Comparative Toxicogenomics Database The Comparative Toxicogenomics Database (CTD) is a public website and research tool launched in November 2004 that curates scientific data describing relationships between chemicals/drugs, genes/proteins, diseases, taxa, phenotypes, GO annotations ...

Arsenic intoxication: general aspects and chelating agents
b
Geir BjørklundMassimiliano Peana
et al. Archives of Toxicology (2020) 94:1879–1897.
A Small Dose of Toxicology


Book on arsenic in groundwater by IAH's Netherlands Chapter and the Netherlands Hydrological Society
Contaminant Focus: Arsenic
by the
EPA The Environmental Protection Agency (EPA) is an independent executive agency of the United States federal government tasked with environmental protection matters. President Richard Nixon proposed the establishment of EPA on July 9, 1970; it be ...
.
Environmental Health Criteria for Arsenic and Arsenic Compounds, 2001
by the
WHO Who or WHO may refer to: * Who (pronoun), an interrogative or relative pronoun * Who?, one of the Five Ws in journalism * World Health Organization Arts and entertainment Fictional characters * Who, a creature in the Dr. Seuss book '' Horton He ...
. *
National Institute for Occupational Safety and Health – Arsenic Page


at ''
The Periodic Table of Videos ''Periodic Videos'' (also known as ''The Periodic Table of Videos'') is a video project and YouTube channel on chemistry. It consists of a series of videos about chemical elements and the periodic table, with additional videos on other topics i ...
'' (University of Nottingham) {{Authority control Chemical elements Metalloids Hepatotoxins Pnictogens Endocrine disruptors IARC Group 1 carcinogens Trigonal minerals Minerals in space group 166 Teratogens Fetotoxicants Suspected testicular toxicants Native element minerals Chemical elements with rhombohedral structure