Arsenic is a chemical element with symbol As and atomic
Arsenic occurs in many minerals, usually in
combination with sulfur and metals, but also as a pure elemental
Arsenic is a metalloid. It has various allotropes, but only
the gray form is important to industry.
The primary use of metallic arsenic is in alloys of lead (for example,
in car batteries and ammunition).
Arsenic is a common n-type dopant in
semiconductor electronic devices, and the optoelectronic compound
gallium arsenide is the second most commonly used semiconductor after
Arsenic and its compounds, especially the trioxide, are
used in the production of pesticides, treated wood products,
herbicides, and insecticides. These applications are declining,
A few species of bacteria are able to use arsenic compounds as
respiratory metabolites. Trace quantities of arsenic are an essential
dietary element in rats, hamsters, goats, chickens, and presumably
many other species, including humans. However, arsenic poisoning
occurs in multicellular life if quantities are larger than needed.
Arsenic contamination of groundwater
Arsenic contamination of groundwater is a problem that affects
millions of people across the world.
The United States'
Environmental Protection Agency
Environmental Protection Agency states that all
forms of arsenic are a serious risk to human health. The United
Agency for Toxic Substances and Disease Registry
Agency for Toxic Substances and Disease Registry ranked
arsenic as number 1 in its 2001 Priority List of
Arsenic is classified as a Group-A
1.1 Physical characteristics
2.1 Inorganic compounds
3 Occurrence and production
5.2 Medical use
5.5 Other uses
6 Biological role
7 Essential trace element in higher animals
8 Environmental issues
8.2 Occurrence in drinking water
8.2.1 San Pedro de Atacama
8.2.2 Hazard maps for contaminated groundwater
Redox transformation of arsenic in natural waters
8.4 Wood preservation in the US
8.5 Mapping of industrial releases in the US
Toxicity and precautions
9.2 Legal limits, food, and drink
9.3 Occupational exposure limits
Toxicity in Animals
9.6 Biological mechanism
9.7 Exposure risks and remediation
10 See also
13 Further reading
14 External links
Crystal structure common to Sb, AsSb and gray As
The three most common arsenic allotropes are metallic gray, yellow,
and black arsenic, with gray being the most common. Gray arsenic
(α-As, space group R3m No. 166) adopts a double-layered structure
consisting of many interlocked, ruffled, six-membered rings. Because
of weak bonding between the layers, gray arsenic is brittle and has a
Mohs hardness of 3.5. Nearest and next-nearest
neighbors form a distorted octahedral complex, with the three atoms in
the same double-layer being slightly closer than the three atoms in
the next. This relatively close packing leads to a high density of
5.73 g/cm3. Gray arsenic is a semimetal, but becomes a
semiconductor with a bandgap 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 (P
4). Both have four atoms arranged in a tetrahedral structure in which
each atom is bound to each of the other three atoms by a single bond.
This unstable allotrope, being molecular, is the most volatile, least
dense, and most toxic.
Solid yellow arsenic is produced by rapid
cooling of arsenic vapor, As
4. 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. Black arsenic can also be formed by
cooling vapor at around 100–220 °C. It is glassy and brittle.
It is also a poor electrical conductor.
Main article: Isotopes of arsenic
Arsenic occurs in nature as a monoisotopic element, composed of one
stable isotope, 75As. As of 2003, at least 33 radioisotopes have
also been synthesized, ranging in atomic mass from 60 to 92. The most
stable of these is 73As with a half-life of 80.30 days. All other
isotopes have half-lives of under one day, with the exception of 71As
(t1/2=65.30 hours), 72As (t1/2=26.0 hours), 74As (t1/2=17.77 days),
76As (t1/2=1.0942 days), and 77As (t1/2=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 isomers 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.
Arsenic has a similar electronegativity and ionization energies to its
lighter congener phosphorus and as such 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. When heated in air,
arsenic oxidizes to arsenic trioxide; the fumes from this reaction
have an odor resembling garlic. This odor can be detected on striking
arsenide minerals such as arsenopyrite with a hammer. It burns in
oxygen to form arsenic trioxide and arsenic pentoxide, which have the
same structure as the more well-known phosphorus compounds, and in
fluorine to give arsenic pentafluoride.
Arsenic (and some arsenic
compounds) sublimes upon heating at atmospheric pressure, converting
directly to a gaseous form without an intervening liquid state at
887 K (614 °C). The triple point is 3.63 MPa and
1,090 K (820 °C).
Arsenic makes arsenic acid with
concentrated nitric acid, arsenous acid with dilute nitric acid, and
arsenic trioxide with concentrated sulfuric acid; however, it does not
react with water, alkalis, or non-oxidising acids.
with metals to form arsenides, 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 compounds. Like germanium, selenium, and bromine,
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.
See also: Category:
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 compounds, +3 in the arsenites, and +5 in
the arsenates and most organoarsenic compounds.
Arsenic also bonds
readily to itself as seen in the square As3−
4 ions in the mineral skutterudite. In the +3 oxidation state,
arsenic is typically pyramidal owing to the influence of the lone pair
One of the simplest arsenic compound is the trihydride, the highly
toxic, flammable, pyrophoric arsine (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. Several factors, such as humidity, presence
of light and certain catalysts (namely aluminium) facilitate the rate
of decomposition. It oxidises readily in air to form arsenic
trioxide and water, and analogous reactions take place with sulfur and
selenium instead of oxygen.
Arsenic forms colorless, odorless, crystalline oxides As2O3 ("white
arsenic") and As2O5 which are hygroscopic and readily soluble in water
to form acidic solutions. Arsenic(V) acid is a weak acid and the salts
are called arsenates, the most common arsenic contamination of
groundwater, and a problem that affects many people. Synthetic
Scheele's Green (cupric hydrogen arsenate, acidic
copper arsenate), calcium arsenate, and lead hydrogen arsenate. These
three have been used as agricultural insecticides and poisons.
The protonation steps between the arsenate and arsenic acid are
similar to those between phosphate and phosphoric acid. Unlike
phosphorous acid, arsenous acid is genuinely tribasic, with the
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 complexes.
All trihalides of arsenic(III) are well known except the astatide,
which is unknown.
Arsenic pentafluoride (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
Arsenic is used as the group 5 element in the III-V semiconductors
gallium arsenide, indium arsenide, and aluminium arsenide. The
valence electron count of GaAs is the same as a pair of Si atoms, but
the band structure is completely different which results distinct bulk
properties. Other arsenic alloys include the II-V semiconductor
A large variety of organoarsenic compounds are known. Several were
developed as chemical warfare agents during World War I, including
vesicants such as lewisite and vomiting agents such as
adamsite. Cacodylic acid, which is of historic and
practical interest, arises from the methylation of arsenic trioxide, a
reaction that has no analogy in phosphorus chemistry. Indeed, cacodyl
was the first organometallic compound known, and was named from the
Greek κακωδἰα "stink" for its offensive odor; like all arsenic
compounds, it is very poisonous.
Occurrence and production
Arsenide minerals and
A large sample of native arsenic
Arsenic comprises about 1.5 ppm (0.00015%) of the Earth's
crust, 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; and 10 μg/L in freshwater.
Minerals with the formula MAsS and MAs2 (M = Fe, Ni, Co) are the
dominant commercial sources of arsenic, together with realgar (an
arsenic sulfide mineral) and native arsenic. An illustrative mineral
is arsenopyrite (FeAsS), which is structurally related to iron pyrite.
Many minor As-containing minerals are known.
Arsenic also occurs in
various organic forms in the environment.
Arsenic output in 2006
China was the top producer of white arsenic with almost 70%
world share, followed by Morocco, Russia, and Belgium, according to
British Geological Survey
British Geological Survey and the
United States Geological
Survey. Most arsenic refinement operations in the US and Europe
have closed over environmental concerns.
Arsenic is found of the
smelter dust from copper, gold, and lead smelters, and is recovered
primarily from copper refinement dust.
On roasting arsenopyrite in air, arsenic sublimes as arsenic(III)
oxide leaving iron oxides, while roasting without air results in
the production of metallic 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
2014 As2O3 Production
World Total (rounded)
Alchemical symbol for arsenic
The word arsenic has its origin in the Syriac word ܠܐ ܙܐܦܢܝܐ
(al) zarniqa, from the Persian word زرنيخ zarnikh, meaning
"yellow" (literally "gold-colored") and hence "(yellow) orpiment". It
was adopted into Greek as arsenikon (ἀρσενικόν), a form that
is folk etymology, being the neuter form of the Greek word arsenikos
(ἀρσενικός), 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.
(orpiment, realgar) 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), which he then
reduces to metallic arsenic. As the symptoms of arsenic poisoning
were somewhat ill-defined, it was frequently used for murder until the
advent of the Marsh test, a sensitive chemical test for its presence.
(Another less sensitive but more general test is the Reinsch test.)
Owing to its use by the ruling class to murder one another and its
potency and discreetness, arsenic has been called the "poison of
kings" and the "king of poisons".
The arsenic labyrinth, part of Botallack Mine, Cornwall.
Bronze Age, arsenic was often included in bronze, which
made the alloy harder (so-called "arsenical bronze"). Albertus
Magnus (Albert the Great, 1193–1280) is believed to have been the
first to isolate the element from a compound in 1250, by heating soap
together with arsenic trisulfide. 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 (impure cacodyl), often claimed as the first
synthetic organometallic compound, was synthesized in 1760 by Louis
Claude Cadet de Gassicourt by the reaction of potassium acetate with
Satirical cartoon by
Honoré Daumier of a chemist giving a public
demonstration of arsenic, 1841
In the Victorian era, "arsenic" ("white arsenic" or arsenic trioxide)
was mixed with vinegar and chalk and eaten by women to improve the
complexion of their faces, making their skin paler to show they did
not work in the fields.
Arsenic was also rubbed into the faces and
arms of women to "improve their complexion". The accidental use of
arsenic in the adulteration of foodstuffs led to the Bradford sweet
poisoning in 1858, which resulted in around 20 deaths.
Two arsenic pigments have been widely used since their discovery –
Paris Green and Scheele's Green. 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
were used widely as insecticides until the discovery of
Roxarsone is a controversial arsenic compound used as a feed
ingredient for chickens.
The toxicity of arsenic to insects, bacteria, and fungi led to its use
as a wood preservative. In the 1930s, a process of treating wood
with chromated copper arsenate (also known as CCA or Tanalith) was
invented, and for decades, this treatment was the most extensive
industrial use of arsenic. An increased appreciation of the toxicity
of arsenic led to a ban of CCA in consumer products in 2004, initiated
European Union and United States. However, CCA remains
in heavy use in other countries (such as on Malaysian rubber
Arsenic was also used in various agricultural insecticides and
poisons. For example, lead hydrogen arsenate was a common insecticide
on fruit trees, but contact with the compound sometimes resulted
in brain damage among those working the sprayers. In the second half
of the 20th century, monosodium methyl arsenate (MSMA) and disodium
methyl arsenate (DSMA) – less toxic organic forms of arsenic –
replaced lead arsenate in agriculture. These organic arsenicals were
in turn phased out by 2013 in all agricultural activities except
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.
3) is more soluble than arsenate (AsO3−
4) 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
Arsenic is used as a feed additive in poultry and swine production, in
particular in the U.S. to increase weight gain, improve feed
efficiency, and to prevent disease. An example is roxarsone,
which had been used as a broiler starter by about 70% of U.S. broiler
growers. The Poison-Free Poultry Act of 2009 proposed to ban the
use of roxarsone in industrial swine and poultry production.
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, continues to sell
nitarsone, 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 is converted to the toxic inorganic
A 2006 study of the remains of the Australian racehorse, Phar Lap,
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) ... It was so common that I'd
reckon 90 per cent of the horses had arsenic in their system."
During the 18th, 19th, and 20th centuries, a number of arsenic
compounds were used as medicines, including arsphenamine (by Paul
Ehrlich) and arsenic trioxide (by Thomas Fowler). Arsphenamine, as
well as neosalvarsan, was indicated for syphilis and trypanosomiasis,
but has been superseded by modern antibiotics.
Arsenic trioxide has been used in a variety of ways over the past 500
years, most commonly in the treatment of cancer, but in medications as
Fowler's solution in psoriasis. The US Food and Drug
Administration in the year 2000 approved this compound for the
treatment of patients with acute promyelocytic leukemia that is
resistant to all-trans retinoic acid.
Recently, researchers have been locating tumors using arsenic-74 (a
positron emitter). This isotope produces clearer PET scan images than
the previous radioactive agent, iodine-124, because the body tends to
transport iodine to the thyroid gland producing signal noise.
In subtoxic doses, soluble arsenic compounds act as stimulants, and
were once popular in small doses as medicine by people in the mid-18th
to 19th centuries.
The main use of metallic arsenic is in alloying with lead. Lead
components in car batteries 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 is an important semiconductor material, used in
integrated circuits. Circuits made from GaAs are much faster (but also
much more expensive) than those made from silicon. Unlike silicon,
GaAs has a direct bandgap, and can be used in laser diodes and LEDs to
convert electrical energy directly into light.
After World War I, the
United States built a stockpile of 20,000
tonnes of weaponized lewisite (ClCH=CHAsCl2), an organoarsenic
vesicant (blister agent) and lung irritant. The stockpile was
neutralized with bleach and dumped into the
Gulf of Mexico
Gulf of Mexico in the
1950s. During the
Vietnam War, the
United States used Agent Blue,
a mixture of sodium cacodylate and its acid form, as one of the
rainbow herbicides to deprive North Vietnamese soldiers of foliage
cover and rice.
Copper acetoarsenite was used as a green pigment known under many
Paris Green and Emerald Green. It caused numerous
arsenic poisonings. Scheele's Green, a copper arsenate, was used in
the 19th century as a coloring agent in sweets.
Arsenic is used in bronzing and pyrotechnics.
As much as 2% of produced arsenic is used in lead alloys for lead shot
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.
Until recently, arsenic was used in optical glass. Modern glass
manufacturers, under pressure from environmentalists, have ceased
using both arsenic and lead.
Some species of bacteria obtain their energy by oxidizing various
fuels while reducing arsenate to arsenite. Under oxidative
environmental conditions some bacteria oxidize arsenite to arsenate as
fuel for their metabolism. The enzymes involved are known as
arsenate reductases (Arr).
In 2000, bacteria were discovered that employ a version of
photosynthesis in the absence of oxygen with arsenites as electron
donors, producing arsenates (just as ordinary photosynthesis uses
water as electron donor, producing molecular oxygen). This may be
classified as chemolithoautotrophic arsenite oxidation, for which
oxygen is used as the terminal electron acceptor, arsenite is the
electron donor, and carbon dioxide is the carbon source.
Researchers conjecture that, over the course of history, these
photosynthesizing organisms produced the arsenates that allowed the
arsenate-reducing bacteria to thrive. One strain PHS-1 has been
isolated and is related to the gammaproteobacterium Ectothiorhodospira
shaposhnikovii. The mechanism is unknown, but an encoded Arr enzyme
may function in reverse to its known homologues.
Although the arsenate and phosphate anions are similar structurally,
no evidence exists for the replacement of phosphate in ATP or nucleic
acids by arsenic.
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 is not known.
Arsenic has been linked to epigenetic changes, heritable changes in
gene expression that occur without changes in DNA sequence. These
include DNA methylation, histone modification, and
Toxic levels of arsenic cause significant DNA hypermethylation of
tumor suppressor genes p16 and p53, thus increasing risk of
carcinogenesis. These epigenetic events have been studied in vitro
using human kidney cells and in vivo using rat liver cells and
peripheral blood leukocytes in humans. Inductively coupled plasma
mass spectrometry (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 be used to develop precise biomarkers of exposure
The Chinese brake fern (Pteris vittata) hyperaccumulates arsenic from
the soil into its leaves and has a proposed use in
Inorganic arsenic and its compounds, upon entering the food chain, are
progressively metabolized through a process of methylation.
For example, the mold
Scopulariopsis brevicaulis produces significant
amounts of trimethylarsine 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.
Naturally occurring sources of human exposure include volcanic ash,
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.
Occurrence in drinking water
Arsenic contamination of groundwater
Extensive arsenic contamination of groundwater has led to widespread
arsenic poisoning in Bangladesh and neighboring countries. It is
estimated that approximately 57 million people in the Bengal
basin are drinking groundwater with arsenic concentrations elevated
above the World Health Organization's standard of 10 parts per billion
(ppb). However, a study of cancer rates in Taiwan 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 and the Bangladeshi government undertook a
massive shallow tube well 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, such as
Vietnam and Cambodia, have geological environments that
produce groundwater with a high arsenic content. Arsenicosis was
reported in Nakhon Si Thammarat,
Thailand in 1987, and the Chao Phraya
River probably contains high levels of naturally occurring dissolved
arsenic without being a public health problem because much of the
public uses bottled water. In Pakistan, more than 60 million
people are exposed to arsenic polluted drinking water indicated by a
recent report of Science. Podgorski’s team investigated more than
1200 samples and more than 66% samples exceeded the WHO minimum
In the United States, arsenic is most commonly found in the ground
waters of the southwest. Parts of New England, Michigan,
Minnesota 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,
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
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 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
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
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
Environmental Protection Agency
Environmental Protection Agency (US EPA) and the National
Science Foundation (NSF). A team of European and Indian scientists and
engineers have set up six arsenic treatment plants in West Bengal
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
Magnetic separations of arsenic at very low magnetic field gradients
with high-surface-area and monodisperse magnetite (Fe3O4) nanocrystals
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
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
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 aquifers.
San Pedro de Atacama
For several centuries, the people of
San Pedro de Atacama
San Pedro de Atacama in Chile
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.
Redox transformation of arsenic in natural waters
Arsenic is unique among the trace metalloids 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 [As(III)] or pentavalent arsenate [As(V)]. 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 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
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 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
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
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 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
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 arsenite oxidizers (CAO) and heterotrophic 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 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 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 (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, borates, copper azole,
cyproconazole, and propiconazole.
Although discontinued, this application is also one of the most
concern 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. 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 (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 disposal of such timber raises some concern, but other
studies have shown no arsenic contamination in the
Mapping of industrial releases in the US
One tool that maps the location (and other information) of arsenic
releases in the United State is TOXMAP.
TOXMAP is a Geographic
Information System (GIS) from the Division of Specialized Information
Services of the
United States National Library of Medicine (NLM)
funded by the US Federal Government. With marked-up maps of the United
TOXMAP enables users to visually explore data from the United
States Environmental Protection Agency's (EPA) Toxics Release
Superfund Basic Research Programs. TOXMAP's chemical and
environmental health information is taken from NLM's Toxicology Data
Network (TOXNET), PubMed, and from other authoritative sources.
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
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 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.
Elemental arsenic and arsenic compounds are classified as "toxic" and
"dangerous for the environment" in the
European Union under directive
67/548/EEC. The International Agency for Research on
recognizes arsenic and inorganic arsenic compounds as group 1
carcinogens, and the EU lists arsenic trioxide, arsenic pentoxide, and
arsenate salts as category 1 carcinogens.
Arsenic is known to cause arsenicosis when present in drinking water,
"the most common species being arsenate [HAsO2−
4; As(V)] and arsenite [H3AsO3; As(III)]".
Legal limits, food, and drink
United States since 2006, the maximum concentration in drinking
water allowed by the
Environmental Protection Agency
Environmental Protection Agency (EPA) is 10
ppb and the FDA set the same standard in 2005 for bottled
water.[unreliable source?] The Department of Environmental
Protection for New Jersey set a drinking water limit of 5 ppb in
IDLH (immediately dangerous to life and health) value
for arsenic metal and inorganic arsenic compounds is 5 mg/m3 (5
Occupational Safety and Health Administration
Occupational Safety and Health Administration has set the
permissible exposure limit (PEL) to a time-weighted average (TWA) of
0.01 mg/m3 (0.01 ppb), and the National Institute for
Occupational Safety and Health (NIOSH) has set the recommended
exposure limit (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
set the "level of concern" for inorganic arsenic 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
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 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
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.
United States in 2012, testing by separate groups of
researchers at the Children's Environmental Health and Disease
Prevention Research Center at
Dartmouth College (early in the year,
focusing on urinary levels in children) and
Consumer Reports (in
November) found levels of arsenic in rice that resulted in
calls for the FDA to set limits. 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
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.
World Health Organization
World Health Organization advisory conference was scheduled to
consider limits of 200–300 ppb for rice.
Occupational exposure limits
Confirmed human carcinogen
TWA 0.05 mg/m3 - Carcinogen
TWA 0.1 mg/m3 - Carcinogen
Confirmed human carcinogen
Confirmed human carcinogen
TWA 0.01 mg/m3
TWA 0.2 mg/m3
Ceiling concentration 0.01 mg/m3 - Skin, carcinogen
TWA 0.2 mg/m3
Group 1 carcinogen
Confirmed human carcinogen
TWA 0.2 mg/m3
TWA 0.05 mg/m3 - Carcinogen
TWA 0.02 mg/m3
TWA 0.5 mg/m3
TWA 0.01 mg/m3
Confirmed human carcinogen
TWA 0.01 mg/m3
TWA 0.01 mg/m3
TWA 0.5 mg/m3
TWA 0.5 mg/m3
TWA 0.1 mg/m3
TWA 0.01 mg/m3
Confirmed human carcinogen
Arsenic is bioaccumulative 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
Arsenic trioxide (As(III))
im = injected intramuscularly
ip = administered intraperitoneally
Arsenic's toxicity comes from the affinity of arsenic(III) oxides for
thiols. Thiols, in the form of cysteine residues and cofactors such as
lipoic acid and coenzyme A, are situated at the active sites of many
Arsenic disrupts ATP production through several mechanisms. At the
level of the citric acid cycle, arsenic inhibits lipoic acid, which is
a cofactor for pyruvate dehydrogenase. By competing with phosphate,
arsenate uncouples oxidative phosphorylation, thus inhibiting
energy-linked reduction of NAD+, mitochondrial respiration and ATP
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. The organ failure is presumed to be from
necrotic cell death, not apoptosis, since energy reserves have been
too depleted for apoptosis to occur.
Although arsenic causes toxicity it can also play a protective
Exposure risks and remediation
Occupational exposure and arsenic poisoning 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
The conversion between As(III) and As(V) is a large factor in arsenic
environmental contamination. According to Croal, Gralnick, Malasarn
and Newman, "[the] understanding [of] what stimulates As(III)
oxidation and/or limits As(V) reduction is relevant for bioremediation
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 of chronic arsenic poisoning is possible. British
anti-lewisite (dimercaprol) 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 (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 and
kidney cancer in addition to cancer of the liver, prostate, skin,
lungs, and nasal cavity.
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Wikimedia Commons has media related to Arsenic.
Look up arsenic in Wiktionary, the free dictionary.
Arsenic page and CTD's Arsenicals page from the Comparative
A Small Dose of Toxicology
Arsenic in groundwater
Book on arsenic in groundwater by IAH's
Netherlands Chapter and the Netherlands Hydrological Society
Arsenic by the EPA.
Environmental Health Criteria for
Arsenic Compounds, 2001
by the WHO.
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National Institute for Occupational Safety and Health
National Institute for Occupational Safety and Health –
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