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ABSTRACT
Arsenic is a metalloid of great environmental concern because of its highly toxic nature and
wide abundance. Arsenic contamination in groundwater has been reported in Bangladesh, India,
China, Taiwan, Vietnam, USA, Argentina, Chile and Mexico. The clinical symptoms of arsenic
toxicity in human body include skin itching to sun rays, burning and watering of the eyes, weight loss,
loss of appetite, weakness, fatigue, limited physical activities and working capacities, chronic
respiratory problems, moderate to severe anemia etc. The Bengal basin is regarded to be the most
acutely arsenic infested geological province in the world. Heavy withdrawal of groundwater for
fulfilling the needs of the increasing population in Bengal Basin resulted in increased arsenic level in
the groundwater. Mobilization of arsenic in Bengal delta is further interfered by microbial activities
and interactions. Different microbial strains have been isolated from Bengal Delta which can tolerate,
transform and resist arsenic. The use of arsenic contaminated groundwater for irrigation purpose in
crop fields elevates arsenic concentration in surface soil and in the plants grown in these areas. Several
plant species have been studied for their ability to accumulate arsenic in the Bengal Delta. Rice is
generally grown in submerged flooded condition, where arsenic bioavailability is high in soil. As
arsenic species are very much toxic to plants and can execute oxidative stresses, they can also affect
the overall production of rice and other vegetables, and can affect the agricultural and economic
development of Bengal Basin. Cattle population also consume arsenic infested water in those areas
and usually eat edible plants contaminated with arsenic, which, in turn, can further increase the
toxicity level in their bodies and also can increase the arsenic bioaccumulation in meat and milk. In the
rural areas of the Bengal Delta, arsenic contamination raised a number of social problems which are
continuously weakening the structural integrity of rural society. Uses of phytoremediation and
microbial remediation technologies, rainwater harvesting, use of arsenic resistant plant varieties for
cultivation are some sustainable methods which can be applied for arsenic remediation. Besides, nanoagglomerates of mixed oxides have been synthesized and successfully employed for arsenic removal
from aqueous solutions. Intensive investigation on a complete food chain is urgently needed in the
arsenic contaminated zones, which should be our priority in future researches.
Keywords: Arsenic; Bengal Delta; Toxicity; Bioaccumulation Groundwater; Phytoremediation
1. INTRODUCTION
Arsenic (As) is a metalloid (atomic no. 33) of great environmental concern because of
its highly toxic nature and colossal abundance. Since hundreds of years, people have worked
and lived with this dangerous element, many people have died of its toxicity and even more
have been sickened by it. Today, arsenic still remains a part of our daily lives and millions of
people are being chronically exposed to elevated doses of arsenic through their food, air,
water, and soils with unknown long-term health consequences (Mondal and Suzuki, 2002).
Since its isolation in 1250 A.D. by Albertus Magnus, this element has been a center of
controversy in human history. Its therapeutic use started from about 400 B.C. and many
reports on arsenic are documented by Hippocrates, Aristotle, Dioscorides and Pliny the Elder
(Gontijo and Bittencourt, 2005). Since then, arsenic has been the object of many studies and
imaginary legends and traditions.
Arsenic ranks 20th in abundance in the earths crust, 14th in the seawater and 12th in the
human body (Mondal and Suzuki, 2002). Arsenic naturally occurs in over 200 different
mineral forms, of which around 60% are arsenates, 20% are sulfides and sulfosalts and the
rest 20% are arsenides, arsenites, oxides, silicates and elemental arsenic (Bissen and Frimmel,
2003). Major arsenic containing primary minerals are arsenopyrite (FeAsS), realgar (As4S4),
and orpiment (As2S3). Realgar (As4S4) and orpiment (As2S3) are the two common reduced
forms of arsenic whereas the oxidized form is the mineral arsenolite (As2O3). Other naturally
occurring arsenic bearing minerals include loellingite (FeAs2), safforlite (CoAs), niccolite
(NiAs), rammelsbergite (NiAs2), arsenopyrite (FeAsS), cobaltite (CoAsS), enargite
(Cu3AsS4), gerdsorfite (NiAsS), glaucodot ((Co,Fe)AsS), and elemental arsenic (Greenwood
and Earnshaw, 1989).
Exposure to sufficiently high concentrations of inorganic arsenic in natural environment
has proved to be harmful to the organisms. The main pathways of arsenic exposure to the
human beings include ingestion of drinking water and consumption of foods and, to a lesser
extent, inhalation of air. In addition to the natural occurrence, herbicides, insecticides,
desiccants, feed additives, wood preservatives, chemical warfare agent, constituents of
organic and inorganic pigments and drugs are significant sources of arsenic (Bissen and
Frimmel, 2003). The geological contamination is till date the most alarming source of arsenic
in many countries. Arsenic contamination in groundwater has been reported in Bangladesh,
India, China, Taiwan, Vietnam, USA, Argentina, Chile and Mexico (Figure 1). In many of
these places the concentration has exceeded the permissible limit of 50 ppb recommended by
WHO (WHO, 2001).
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2. Chronic respiratory complains are also common. Chronic cough with or without
expectoration was evident in more than 50% affected populations.
3. Gastrointestinal symptoms of anorexia, nausea, dyspepsia, altered taste, pain in abdomen,
enlarged liver and spleen, and ascites (collection of fluid in abdomen).
4. Moderate to severe anemia was evident in some cases,
5. Conjunctival congestion, Leg edema was less common (Ghosh and Singh, 2010).
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Soil arsenic levels are very much related with local well water arsenic concentration,
which suggests that the source of soil contamination is the irrigation water (Bhattacharya et
al., 2012a). The absorption of arsenic by plants is influenced by the concentration of arsenic in
the soil. In Bangladesh, where irrigation is carried out with arsenic contaminated
groundwater, soil arsenic level can reach up to 83 mg/kg (Roychowdhury et al., 2005a).
Except in the rainy season, the agricultural land has been exposed to irrigated groundwater
round the year. Sometimes the farmers used to run the shallow tube wells in the rainy season
due to insufficient rain. Most of the vegetables and other crops, used by the villagers were
cultivated in this area and entered the local market.
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ecological behavior and interactions in the natural environment is very much important and
relevant for using these organisms in arsenic bioremediation.
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If arsenate has lower concentration than phosphate level in soil, phosphate is a much
better competitor for uptake than arsenate (Meharg et al., 1994). In contrast, arsenite is the
predominant species of arsenic in soil under anaerobic conditions (Masscheleyn et al., 1991).
Recent studies have shown that in rice plants, arsenite is taken up at high rates of influx which
follows the Michaelis-Menten kinetics (Abedin et al., 2002). In rice, arsenic uptake shares the
same pathway as silicon uptake. Rice is a strong accumulator of silicon which may allow
efficient uptake and translocation of arsenite in the shoots (Hodson et al., 2005). The
aquaporin Lsi1 (protein) which is responsible for the influx of silicon (as silicic acid) into the
root cells, is permeable to arsenite (Ma et al., 2008). The reason behind it is the similarity
between the size and coordination chemistry of silicic acid and arsenite. Inside plant tissues,
arsenic is reduced from pentavalent to trivalent state or is biotransformed to less toxic organic
compounds such as DMA, MMA (Ma et al., 2008). Trivalent arsenic can form complex with
thiol groups inside the plant tissues (Zhao et al., 2010). Many plants can synthesize arsenic
reductase, which can convert the pentavalant arsenic into trivalent form (Zhao et al., 2010).
Interestingly, trivalent arsenic is the predominant species in the plant tissues and 50-65 % of
the total arsenic accumulated in stem or leaf parts is trivalent (Peralta-Videa et al., 2009). The
arsenic detoxification in plants involves arsenic mobilization from roots to aerial parts of the
plant (translocation). This movement is controlled by the external arsenic concentration (Zhao
et al., 2010). Plants generally have a low efficiency of arsenic translocation from roots to
shoots, may be due to the formation of complexes of arsenite and thiol compounds and
subsequent sequestration in the root vacuoles, or because of the strong efflux of arsenite to the
external medium (Zhao et al., 2009).
Toxicity limit and mobility of arsenic in soil depend on the properties of soil like
particle size, texture, mineral nutrient content, pH, presence of other ions, moisture regimes,
transformations by microbes and the chemical form of arsenic (Bhattacharya et al., 2007).
Arsenic is more mobile and bio-available in sandy soil than in clayey soil. The effect of
arsenic toxicity in plants increase in low pH, but the uptake mechanism can enhance in higher
pH soil. These properties of soil are very much relevant to evaluate the influence of arsenic on
its accumulation and distribution in plants. Arsenic accumulation in soil irrigated by arsenic
contaminated water and its transfer into rice may vary depending on the soil types, cropping
pattern, arsenic concentration in irrigation water, distance from the water source, depth of
water source and duration of the monsoon flood (Hossain et al., 2008). The typical transfer
factor for arsenic varied from 0.01 to 0.1 (Kloke et al., 1984). The volume of water used for
the irrigation of a specific crop varies considerably depending not only on climatic factors, but
also on the permeability of soil. The water demand of rice is particularly high; the volume of
water used for irrigation of Boro rice in the Indo-Gangetic Plain are in the range between
1000 and 1800 mm/a (Gupta et al., 2002; Huq et al., 2003).
In seasonally flooded soil, soil change between the oxidized state in the dry season and
the reduced state in the wet season when the soil is submerged (Bhattacharya et al., 2012). So
arsenic may present in the soil in different form and in different concentration in different
times of the year. However, flooding leads to fundamental changes in the soil. The overlying
floodwater inhibits oxygen movement into the soil and the remaining oxygen is depleted
within a short time (Bhattacharya et al., 2007). Rice plants are generally grown in submerged
soil condition, where arsenic bioavailability is generally high (Bhattacharya et al., 2007). Rice
roots can constitutively form aerenchyma and waterlogging or O2-deficient conditions can
enhance the process (Colmer, 2003a; Colmer, 2003b; Colmer et al., 2006).
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Figure 3. Simplified scheme summarizing the effects of metals and metalloids on seeds; the
images of Oryza sativa (rice) are used to represent seeds and plants generally.
Kranner and Colville, 2011).
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high as 25 mg/kg (Xiong et al., 1987). It has been shown that in T-Aman rice (Oryza sativa
L.), the grain and straw yields were significantly reduced by the artificial introduction of
arsenic in soil (Azad et al., 2009). Experiments proved that arsenic in the growth medium of
rice seedlings caused quantitative changes in the level of RNA, soluble proteins, free amino
acids and proline and inhibits the activities of RNase and protease. Further, arsenite toxicity
can lead to change in isoform pattern of RNase in growing rice seedlings. The impact of such
responses could be visible in the form of decreased growth and vigour of rice seedlings in
arsenic-polluted environments (Mishra and Dubey, 2006). Figure 3 shows the adverse effects
of arsenic and other heavy metal toxicity on rice plants.
The major portion of the population at risk of arsenic poisoning also suffer from
malnutrition in the Bengal delta of India and Bangladesh, and there is a direct link between
malnutrition and the risk of arsenic poisoning in human body (Milton et al., 2010). The long
term effects are slowly executed by more cancers, stillbirths, defective childbirths,
hypertension and lots of other diseases (Milton et al., 2010). Several studies showed that
arsenic accumulation significantly affects body weight, biological and intellectual
development in children (Majumder et al., 2000). This, in turn, can affect the social and
economic structure of a family as a whole. Rural populations generally eat locally-grown rice
in arsenic affected areas and the chances of arsenic toxicity are much more than the urban
populations. In urban areas, middle class and rich people usually eat wheat, vegetables and
potatoes from mixed or diverse sources, which contain lesser amount of arsenic in general.
Difference in locations and economic classes should be examined properly in dietary studies
to identify the problem in details.
The accumulation of arsenic in plants occurs primarily through the root systems and the
highest arsenic concentrations have been reported in plant roots and tubers. The edible parts
of the tuber crops are exposed continuously to soil and irrigation water contaminated with
arsenic, which, in turn, can increase arsenic level in the tuber part (Bhattacharya et al.,
2012a).
Rice straw is often used as a cattle feed in South Asia. This represents another entry
route of arsenic into the food chain, as rice straw typically contains much higher amount of
arsenic than grains .Cattle population also used to drink water contaminated with arsenic in
those areas, which, in turn, can further increase the toxicity level. But the toxicity mechanism
is highly dependent on the nature of arsenic species in the straw and on the metabolism of the
cattle (Abedin et al., 2002). Cattle manure is often used as fuel in household purposes, which
can also increase the contamination risk (Pal et al., 2007). Besides, the dry straw often been
used by people as fuel, which can release arsenic in air as oxides, and can cause pollution and
health hazards.
8. 4. Mitigation policies for arsenic contamination in rice
When arsenic is accumulated in the rice grains, it is very difficult to remove it properly.
Cooking with high volume of arsenic free water can help to some extent, but, it can also
remove beneficial vitamins and thus can decrease the food value. Levels of toxicity also
depend on the cooking methods which vary in different regions. For example, in Hungary,
rice is generally cooked with an excessive amount of water and the water remaining is
discarded; on the other hand, in China, rice is generally cooked with aliquots of water in order
to absorb it all (Mihucz et al., 2007).
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decrease trivalent arsenic in grains. Production of rice grains that possess a high
organic/inorganic arsenic ratio could help to reduce inorganic arsenic contamination level.
Development of a toxicity database is very much essential for different rice cultivars
and other crops for setting standards for arsenic in flooded and non-flooded soils. The low
levels of inorganic arsenic detected in Chinese rice could be important in rice cultivation to
reduce the dietary exposure (Williams et al., 2006). Phytoexcluder crops for arsenic can also
be developed through laboratory techniques or through proper identification of existing plant
species for growing crops in arsenic contaminated soils without absorbing arsenic (Hossain et
al., 2008). A search should be made for locally-adapted wetland plants that could extract
arsenic from soils during the monsoon season when deeply flooded.
9. Use of nanotechnology in arsenic mitigation
Nanomaterials are fast emerging as potent candidates for water treatment in place of
conventional technologies which, notwithstanding their efficacy, are often very expensive and
time consuming. This would be in particular, immensely beneficial for developing nations
like India and Bangladesh where cost of implementation of any new removal process could
become an important criterion in determining its success. Qualitatively speaking
nanomaterials can be substituted for conventional materials that require more raw materials,
are more energy intensive to produce or are known to be environmentally harmful. Employing
green chemistry principles for the production of nanoparticles can lead to a great reduction in
waste generation, less hazardous chemical syntheses, and an inherently safer chemistry in
general (Shah and Ahmed, 2011). However, to substantiate these claims more quantitative
data is required and whether replacing traditional materials with nanoparticles does indeed
result in lower energy and material consumption and prevention of unwanted or unanticipated
side effects is still open to debate. There is also a wide debate about the safety of
nanoparticles and their potential impact on the environment. There is fervent hope that
nanotechnology can play a significant role in providing clean water to the developing
countries in an efficient, cheap and sustainable way. On the other hand, the potential adverse
effects of nanoparticles cannot be overlooked either. For instance the catalytic activity of a
nanoparticle can be advantageous when used for the degradation of pollutants, but can trigger
a toxic response when taken up by a cell. So this Janus face of nanotechnology can prove to
be a hurdle in its widespread adoption. However as mentioned before nanotechnology can
step in a big way in lowering the cost and hence become more effective than current
techniques for the removal of contaminants from water in the long run (Shah and Ahmed,
2011). In this perspective nanoparticles can be used as potent sorbents as separation media, as
catalysts for photochemical destruction of contaminants; nanosized zerovalent iron used for
the removal of metals and organic compounds from water and nanofiltration membranes
(Savage and Diallo, 2005).
Two vital properties make nanoparticles highly lucrative as sorbents. On a mass basis,
they have much larger surface areas compared to macro particles. They can also be enhanced
with various reactor groups to increase their chemical affinity towards target compounds.
These properties are increasingly being exploited by workers to develop highly selective and
efficient sorbents for removal of organic and inorganic pollutants from contaminated water.
Many materials have properties dependent on size. Hematite particles with a diameter of 7
nm, for example, adsorbed Cu ions at lower pH values than particles of 25 or 88 nm diameter,
indicating the enhanced surface reactivity for iron oxides particles with decreasing diameter.
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10. CONCLUSIONS
In the rural areas of the Bengal Delta, arsenic contamination raised a number of social
problems which are continuously weakening the structural integrity of rural society. Married
women affected by arsenic are sent back to their parents with their children. Affected children
are prevented from attending school, and many young men are deprived of jobs when
employers find black spots on their body and hands. Affected young unmarried women and
men are advised to stay unmarried. They are not allowed even to go to their neighbors to fetch
water. (Biswas et al., 1998; Samanta et al., 1999).
The overall scenario can reflect that the contamination of arsenic in water, soil as well
as in the food chain in Bengal Delta must be addressed properly to understand the importance
of arsenic exposure from food sources. The importance of rice in food security in India and
Bangladesh and the high dietary intake of rice indicate that the impact of arsenic in
groundwater on rice productivity and quality should continue to be carefully monitored
(Roychowdhury et al., 2005a). Arsenic may serve as essential role in growth and nutrition in
minute concentration, but excess intake can be lethal for a population. Arsenic is an element,
not a compound, so it is not possible to break or metabolize it chemically or biologically. The
only thing we can do is to remove it or to prevent it from accumulation and contamination.
Intensive investigation on a complete food chain is urgently needed in the arsenic
contaminated zones, which should be our priority in future researches (Bhattacharya et al.,
2012). Differences in environmental and socio-economic conditions within the contaminated
regions and within countries need to be considered in a sustainable manner.
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