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Presence of Arsenic in different geological

environment.
In modern parlance, arsenic is viewed as being synonymous
with “toxic”.

By
Dr. Nitish Priyadarshi

As old as recorded history, arsenic has existed through the centuries as a curative, a
pigment, a cosmetic, on mirrors, part of alchemical lore, and most notoriously, the
deadliest of poisons. In its various forms- as tasteless and odorless arsenic trioxide, the
gold-bearing yellow arsenic sulfide, the deadly gas arsine, the practical alloy copper-
arsenic, common pesticide white arsenic, and the electronics staple gallium arsenide-
arsenic has served with fascinating ease human impulses both noble and wicked.

The long history of arsenic in science, medicine and technology has been over shadowed
by its notoriety as a preferred poison in homicides. In modern parlance, arsenic is often
viewed as being synonymous with “toxic”.

Widespread arsenic contamination of groundwater has led to a massive epidemic


of arsenic poisoning in India and Bangladesh and neighbouring countries. Presently 42
major incidents around the world have been reported on groundwater arsenic
contamination. It is estimated that approximately 57 million people are
drinking groundwater with arsenic concentrations elevated above the World Health
Organization's standard of 10 parts per billion.

The notoriety and lingering concern about the potential effects of arsenic on various
fauna and flora has inevitably engendered a lot of research on the many facets of this
element in the environment. This paper represents an attempt to bring together the key
research results from the different geological work.

Arsenic is considered to be a rare but ubiquitous element of the upper lithosphere.


Arsenic is occasionally observed in the native state in nature. However it is more
frequently found combined with sulfur, selenium, tellurium and also as sulfo salts and
arsenides of various heavy metals such as copper, iron, nickel and cobalt. It also forms a
number of pentavalent arsenate minerals that bear a close geochemical relationship with
phosphates and vandates with which it can form some isomorphic compounds.

Arsenopyrite, which is the most abundant and widespread mineral of arsenic, is found in
pegmatites but more frequently in high temperature gold-quartz veins, high temperature
tin-veins, and in contact with metamorphic sulfide deposits.
The numerous oxidic minerals of arsenic observed in nature are a result of the oxidation
of sulfide and arsenide deposits in contact with the free oxygen of the atmosphere. The
arsenate mineral are the most preponderant of the oxide minerals. Some arsenate minerals
have been observed in metamorphic rocks deep in the earth.

It is not surprising to find that there has been increased interest in coals, together with
work on rocks, soils, plants and waste materials, probably because of possible adverse
health effects of high concentrations. Arsenic with some other environmentally sensitive
elements, coal tends to be seen as a major source of arsenic, whereas, where as it only
contributes 1.8 % of the total emissions to the atmosphere, which is about the same as
wood fuel. There is a wide range of values from less than 1 ppm to several hundred ppm,
sometimes enrichment being related to nearly arsenic rich ores. Arsenic has similar
chemical properties to phosphorus (P), the element immediately below arsenic on the
periodic chart. During coal combustion, arsenic oxidizes and forms gaseous As2 O3 and
enters the atmosphere. This volatilization causes concerns for governments of many
countries because of environmental pollution due to extensive use of coal.

Although it has been stated categorically that arsenic is present in coal as arsenopyrite
and that ‘little exists in any other form’, the only good evidence for the nature of the
association of arsenic with pyrite has come from a detailed study of an eastern U.S. coal.
It was found that the arsenic was most likely to be present in solid solution in the pyrite,
and it was noted that the arsenic was predominantely in fractures in the coal and in
microfractures in the pyrite. Arsenic was also detected at isolated points in some pyrite
grains, perhaps because small arsenic and selenium bearing minerals inclusions formed
and were incorporated into the pyrite at the time of crystallization. However, not all high
pyrite coals contain high arsenic, an observations that has also been made in respect of
many Australian bituminous coals. This probably means that some coals contain arsenic
in other forms, for example organically associated, associated with clays, perhaps as
arsenate ions or with phosphate minerals, where (As04)3- could replace some (PO4)3-.
Studies need to be carried out on a variety of coals, in order to clarify the nature of the
mineral association of arsenic in coals. The extent of organically associated of arsenic is
not clear, although organic bonding has been suggested for many Bulgarian coals, for
some low rank Canadian coals and for some low sulfur Siberian coals. For most coals,
arsenic seems to be mainly associated with the mineral matter, with varying smaller
amounts being associated with organic matter.

Many researchers recognize arsenic as a sulphophile element. The occurrence of arsenic


in coal is chiefly associated with sulfide minerals, pyrite in particular , and subordinately
with organic matter. Therefore, there is commonly a positive correlative relationship
between arsenic and total sulfur content in coal.

The distribution of arsenic in a coal - bearing basin appears to have been profoundly
modified by the combined effects of many factors , such as the diagenesis of arsenic
matter derived from vegetal matter , or the surrounding rocks , the geochemistry of peat
formation including pH and Eh conditions of the basin and many other variables. Syn-
depositional tectonic activities also exert an impact on peat accumulation and on the
quality of coal as well.

A high coal bearing index indicates a relative balance between the rate of basin
subsidence and the compensative peat accumulation over a long period of deposition. The
weaker the tectonic disturbance, the higher the coal – bearing index and the lower the
arsenic concentration in the coal. High concentration of arsenic in coals reflects the
relatively vigorous tectonic activities during deposition.

Under the geological and geochemical conditions described above, the secondary arsenic
enrichment occurs in part of coal beds. Because the secondary arsenic enrichment results
from deuterogenic tectonic (mainly faults ) and hydrothermal activities, the enrichment is
local in extent. Thus within the same mining area, the arsenic distribution in coal can be
divided into two major distribution types : synsedimentary and secondary.

Deuterogenic arsenic concentration in coal is controlled to some extent by the original


sulfur content of the coal. This is manifested by the apparent strong positive correlation
of arsenic and total sulfur in the coal.

According to different geo-scientists basalts and diabases contain an average of 2.0ppm


arsenic and gabbros 1.4ppm. At present a value of 1.5ppm arsenic may be assigned to
basaltic rocks. Fifty-six individual samples of granitic rocks analyzed by different
workers gave an average of 1.6ppm arsenic. The average for granitic rocks may be taken
as 1.5ppm. Thus the granitic average does not differ enough from the basaltic and
gabbroic averages (1.5 and 1.4ppm, respectively). Rhyolitic rocks and silicic glasses are
higher in arsenic than other common rock types. The average content of arsenic in
igneous rocks may be taken as 1.5ppm arsenic based on the average for granitic rocks,
basalts and gabbros.

In nonmarine carbonaceous shales and near shore marine shales and claystones , the
arsenic content is not related to the organic carbon content of the samples. However, in
offshore marine samples arsenic is concentrated in high carbon – samples. Arsenic occurs
in some samples in syngenetic pyrite but also is present in relatively large amount in
samples that contain little pyrite. In general, arsenic is present in iron sulfides, clay
minerals ( possibly in adsorbed form), organic matter etc in shales. Because of the wide
variation of arsenic among the shales, it is not easy to obtain a precise average. At present
the average for shales may be taken as 13ppm arsenic. A tentative average for sandstones
may be taken as 1ppm arsenic. Analysis of many sandstone samples from the various
parts of the world are desirable. Cherts usually contain about 1ppm arsenic. An average
of 1ppm arsenic may be given for limestones and dolomites.

Data on the arsenic content of metamorphic rocks are not abundant, and therefore,
behavior of arsenic is metamorphic reactions is not well known. Arsenic is likely to be
lost in the transformation of slates and graywackes into schists and gneiss in regional
metamorphism. In metamorphosed sedimentary iron ores containing coarsely crystalline
hematite the arsenic seemed to have been removed by some leaching process.
Many arsenic compounds are water soluble and hence arsenic contamination of water can
occur readily. Water is the major means of transport of arsenic in the environmental
compartments. Sedimentation of arsenic in association with iron and aluminium may
sometimes be considerable. Rivers and lakes generally contain less than 0.01
mg/1.arsenic. The concentration in ground water depends on the arsenic content of the
bedrock. Where ever arsenic is present in natural waters, it is most often found as the
anion, either as arsenate or arsenite.

The solubility of arsenic oxide in water is 2.05 g. As2 O3 per 100 g. of water at 25 0 C. The
solubility of arsenic sulfide As2 S3 in water in extremely low.

Arsenic as a tendency to become precipitated in the hydralyzates. It is more concentrated


near the surface than deep in the sediments. It is enriched in oxidate sediments, chiefly by
absorption on ferric hydroxide. The manganese – rich oxidates are lower in arsenic than
the iron rich type.

Arsenic is present in air mainly in the particulate form as inorganic arsenic. Though both
tri and pentavalent forms occurs in air, the pentavalent form is more predominant than the
trivalent form. Methylarsenic is also present in small amounts in air of suburban , urban
and industrial areas.

Data on the arsenic content of soils were summarized by different scientists. Their results
showed that about 30% of the soils contained less than 5ppm arsenic, about 50%
contained 5 to 10ppm and about 20% contain more than 10ppm (parts per million). Most
of the recent data on arsenic in various soils give less than 10ppm arsenic. The average
value of arsenic in soils probably lies in the range of 5 to 10ppm arsenic. Thus soils are
enriched in arsenic compared to igneous rocks.

Arsenic, in small quantities, is a universal contaminant of plants and animals and may
sometimes be notably concentrated in organisms, e.g. in land plants growing in soil rich
in arsenic and in marine and fresh – water organisms , such as fishes , mollusks ,
crustaceans , plankton , and some brown algae.

Though organic arsenic compounds are beneficial as a growth stimulant for animals and
arsenic compounds have been used as medicines , there is no firm evidence that arsenic in
any form is essential to man. In fact arsenic compounds are proved to be toxic. The
toxicity of arsenic compounds depends on the chemical and physical form of the
compound, the route by which it enters the body and dose and duration of exposure. In
man, subacute and chronic arsenic poising may be insidious and pernicious. The
symptoms of mild chronic poisoning are fatigue and lot of energy. In more severe
intoxication the following symptoms may be observed: kidney degeneration, tendency to
edema , liver cirrhosis , bone marrow injury , gastrointestinal catarrh , polyneuritis ,
exfoliate dermatitis and altered skin pigmentation.
No true tolerance of arsenic has ever been demonstrated. During chronic exposure,
trivalent arsenic accumulates mainly in bone , muscle , and skin and to a lesser degree in
the liver and kidneys.

A W.H.O task group, applying the linear non-threshold model estimated that a life time
exposure to arsenic in drinking water at a concentration of 0.2 mg/1 gave a 5% risk of
getting cancer of the skin.