Arsenic Contamination in Groundwater

Abstract

Arsenic is a worldwide problem due to its high toxicity and widespread prevalence in

drinking water and groundwater. Even at very low amounts, continued and prolonged

digestion can result in significant arsenic-related diseases. The major sources of arsenic

pollution are geochemical process (e.g., dissolution of arsenic-containing minerals) and

anthropogenic activities (e.g., percolation of water from mines, etc.) This report examines

arsenic contamination in groundwater, including its occurrence, sources, consequences, and

remedial techniques.

Keyword: arsenic, groundwater, arsenic removal, treatment technology.

Introduction

Arsenic (As) is a necessary trace element for the body, although it is extremely

hazardous in high concentrations. Arsenic has a deadly acute toxicity; and its long-term

toxicity produces hemoglobin alterations in the skin, as well as skin cancer. People who

consume more arsenic than is permitted in their food or drinks are more likely to develop

lung, kidney, and bladder cancer (Wu et al., 1998; WHO, 2001).

Arsenic-contaminated water is defined as water with an arsenic content that exceeds

the permitted level for its intended usage. In other words, the water quality deteriorated as a

result of the high arsenic concentration, and it no longer met the standard for usage. High

concentrations of arsenic-rich ores released into ground and surface waters can harm human

health if consumed in substantial quantities over time (Guo et al., 2006).

Arsenic in groundwater poses a major health concern for millions of people in many

countries. Due to its ubiquity, toxicity and exposure to humans, arsenic ranks the most toxic
chemicals on the list of hazardous substances in the US Comprehensive Environmental

Response, Compensation, and Liability Act (CERCLA). Arsenic exposure has been

associated to cardiovascular and peripheral vascular illness, neurological disorders, diabetes,

and a varied form of cancer.

The widespread contamination of the inorganic form of arsenic, as well as its toxicity,

is a critical concern as it does not degrade nor decompose in the environment; instead, it

circulates around the globe. Arsenic cycling and mobility depend on the availability of

arsenic in the geological source, in addition to the oxidation state, speciation and other

environmental factors (Langdon et al., 2003). Arsenic can transport long distances before

settling out or being carried to the earth's surface by rain or snow. It can be converted to a

variety of forms once it reaches water from the atmosphere, runoff, discharges, or other

sources, with arsenate being the most common. Aquatic microorganisms can also methylate

arsenic and convert arsenate to arsenite. In addition, arsenic can enter the body through

inhalation, direct ingestion, or dermal contact. Even at low concentrations (2 μg/L), arsenic

can harm human health (Casarett et al., 2008). Unacceptably high amounts of arsenic in

groundwater have been detected in Bangladesh, India, Pakistan, Thailand, the United States,

and Vietnam, etc. India is the country most at risk of groundwater arsenic contamination,

followed by Bangladesh with average arsenic levels in the groundwater of these two

countries far exceed the WHO standard guideline.

The demand for clean water rises in tandem with the development of the economy and

society. Understanding the mechanism of arsenic contamination in groundwater allows

management authorities to take appropriate steps to safeguard groundwater sources and

minimize further pollution of water sources due to exploitation. This report summarizes

knowledge of the occurrence and mobility of arsenic, as well as its consequences, in order to

provide a more thorough assessment of the interaction between the arsenic contamination
problem, groundwater exploitation, and its use. Furthermore, a thorough understanding of the

sources and behaviors of arsenic is the foundation for developing treatment technology and

proposing appropriate techniques to provide clean water to consumers and minimize the risk

of arsenic’s influence on public health.

Occurrence and speciation of arsenic

In Mendeleev's periodic table, arsenic is a chemical element with atomic number 33,

of group VA, atomic weight 74.9216u. It possesses chemical and physical properties

intermediate between a metal and a non-metal, and is frequently referred to as a metalloid or

semimetal with a density of 5.73 g/cm 3 at 25°C. This transition element is comparable to

phosphorus, however it has more metallic qualities than non-metallic properties. Arsenic has

two isotopes: As (stable isotope) and

75 78
As (radioactive isotope); and is found in two

crystalline forms: yellow arsenic and metallic arsenic. Yellow arsenic has a low density, is

metastable, highly volatile, and degrades quickly to its metallic form. The metallic form is a

tin-white mineral that tarnishes to a dark gray color very quickly. Metallic arsenic crystals are

extremely brittle, good heat conductors but poor electrical conductors.

The form of arsenic determines its toxicity (Vahter, 1983). In nature, arsenic exists in

the form of compounds and rarely found in the form of elemental arsenic. With valence

numbers ranging from +3 to +5, arsenic can be found in both organic and inorganic forms.

The inorganic form (As3+ and As5+) is far more toxic and mobile in the environment than the

organic form (As3- and As5-) (Rosen et al., 2009). Arsenite (As3+) has been reported to be 10

times more toxic than arsenate (As5+) (Srivastava et al., 2011). Many arsenic compounds,

according to the Environmental Protect of America (EPA), can agglomerate in the air, soil,

and water for long periods of time.

Arsenic is typically found in groundwater as +3 and +5 valence ions, such as HAsO 4-2

and HAsO3-2 ions. The concentration of those ions is determined by the type of ore,
thermodynamic conditions, and landscape geochemical conditions (oxidation-reduction

potential, pH). Redox potential (Eh) and pH are the most important factors controlling arsenic

speciation. In a reducing condition, arsenic is often found as arsenite, while in an oxidizing

condition, arsenic is mostly found as arsenate (Brookins, 1988). Due to redox conditions,

microbial activity, and oxygen transport and convection from the environment, the ratio of

As3+ and As5+ differ (Smedley and Kinniburgh, 2002).

Figure 1. Redox potential (Eh)-pH diagram for aqueous arsenic speciation (Smedley and

Kinniburgh, 2002).

Sources and mobility of arsenic in groundwater

It is generally recognized that properly addressing the problem of arsenic pollution

sources helps improve the implementation of preventative measures, treatment, and

prediction of the impacts of arsenic pollution. However, determining the sources of arsenic in

groundwater is challenging and complex.

Arsenic in groundwater can be characterized by two sources: geochemical and

anthropogenic (Smedley et al., 2002). Geochemical sources include those resulting from

geological and sedimentary processes influenced by oxidation, reduction, and

biochemical processes. Anthropogenic sources include coal combustion, emissions, arsenic-

containing wastewater, pesticide use, irrigation water, industrial wastes, etc. (Nhan et al.,

2007; Postma et al., 2007); which account for 82.000 metric tons/year worldwide.

(Bhattacharya et al., 2002).

There are thousands of arsenic-containing minerals exist in the soil, and these

minerals form in tandem with ore formation geological processes. Arsenic can be found in

various forms in over 200 minerals, including elemental arsenic, arsenide, sulphide, oxide,

arsenite, and arsenate (World Bank, 2004). The highest levels of arsenic, on the other hand,

are found in sulphide minerals and metal oxides, particularly iron oxides. Arsenic

contamination can occur in areas where these minerals are abundant, however, only if the

geochemical conditions favor the release of arsenic from these minerals. In many parts of the

world, such as Bangladesh, Australia, India, and Vietnam, arsenic associated with arsenide of

copper, lead, gold, iron hydroxides, and sulfides is stored in sedimentary rocks or arsenic-rich

aquifer matrices (Mandal et al., 2002). Arsenic and arsenic-containing minerals are

transported by water currents to low-lying places and accumulated, deposited with

sedimentation processes over time, under the impact of tectonic and geodynamic processes,

as well as weathering and erosion processes.

According to Luu T. (2008), arsenic in rocks is eroded by weathering processes and

transported to low-lying areas with water and other sedimentary materials in the Northern

Delta, the South, West Bengal, and Bangladesh. Arsenic in rocks is eroded by weathering

processes and transported to low-lying areas with water and other sedimentary materials.

However, due to varying hydrodynamic, sedimentary, climatic, and weathering conditions,

the practice of transporting materials over long distances across different topographical

regions has resulted in areas with significantly diverse amounts of arsenic in the sediments.
Thus, the oxidation of minerals, ores, and rocks is the primary cause of arsenic release from

soil.

Upstream, arsenic-containing parent rocks or ores are subjected to weathering, which

releases Arsenic in the form of ions or complex ions, which leave the parent rock and are

promptly absorbed by iron complexes and fine-grained sediments. These sedimentary

materials are carried downstream by water currents and deposited in low-lying areas. As a

result, their contents gradually accumulate over time and distance. For example, in Vietnam,

when the dry season arrives, the water level in rivers and streams decreases, and groundwater

from the two banks along streams and tributaries flows into the main river, where it is

entirely oxidized. In calm waters, oxidizing materials deposit as bottom sludge.

Heath consequences of arsenic exposure

Arsenic exposure has serious health consequences and has been identified as a major

public health concern worldwide in the last two to three decades. Many people have been

unknowingly exposed to arsenic for years because it has no effect on the taste or smell of

water or food. The carcinogenic influence of arsenic on humans is one of the most dangerous

consequences of chronic arsenic exposure, as it is classed as a Group 1 carcinogenic chemical

based on epidemiological evidence (IARC, 1987). As a result, prolonged arsenic exposure

has resulted in widespread poisoning among local communities, manifesting as dermal

lesions, cardiovascular diseases, and various types of cancer (Karagas et al., 2015).

According to Vietnamese standards dating back to 2002, water containing more than

50 μg/L of arsenic was classified as contaminated. Vietnam did not lower the national

standard of arsenic concentration in drinking water to 10 μg/L until mid-2002, in conformity

with World Health Organization (WHO) and certain European countries' regulations. The

current recommended limit for arsenic in drinking water is 10 μg/L, although this value is
considered provisional due to practical difficulties in eliminating arsenic from drinking water.

When resources are available, every effort should be taken to keep concentrations as low as

reasonably practical and below the guideline value (WHO, 1996).

Arsenic enters water through the dissolution of minerals, from industrial wastewater

streams, and byproducts of accumulation from the atmosphere. In oxygen-rich surface water,

arsenic is mostly found as As5+, whereas in low-oxygen environments like deep lake

sediments or underground water, it's primarily As3+. The amount of arsenic dissolved in water

can also increase when pH rises. Arsenic levels in the air range from 0.4 to 30 ng/m 3. Arsenic

levels in natural water range from 1 to 2 μg/L. However, arsenic levels can be greater in

mineral-rich areas, up to 12 mg/L in some regions.

The most common pathway for arsenic to enter the human body is through ingestion,

with water being the most prevalent route. When arsenic-containing water enters the body, it

accumulates over time and, if the dose is significant enough, causes illnesses. Arsenic

poisoning can be lethal at doses ranging from 100 to 300 mg/L (Schoolmeester et al., 1980).

The acute fatal dosage of inorganic arsenic to humans has been estimated to be approximately

0.6 mg/kg/day, according to the Risk Assessment Information System database (Opresko,

1992). If a small amount of arsenic is consumed and accumulates over time, it will reach a

toxic level and cause disease with common symptoms such as vomiting and aches, etc. When

consumed, elemental arsenic is difficult to absorb and is generally removed in its natural state

or by the body. Water-soluble arsenic compounds are quickly absorbed by the digestive

system. When inorganic arsenic enters the body, it can accumulate in the skin, bones, and

muscles. It takes 20 to 40 days for it to decompose in the human body.

High-concentration arsenic exposure has been linked to both carcinogenic and non-

carcinogenic consequences in numerous studies (WHO, 2001). Chronic disorders such as

cardiovascular, pulmonary, immunological, neurological and diabetes are non-carcinogenic

consequences. High concentration of arsenic exposure can adverse pregnancy outcomes and

impair child development. The most evident non-carcinogenic impact is skin breakdown

(Ravencroft et al., 2001). Skin darkening (diffuse or spotted melanosis) over the chest, back,

or other parts of the body is one of the most common early indications of chronic arsenic

exposure. Skin lesion incidence has been associated to drinking water concentrations of less

than 10 μg/L, and these lesions persist even after the patient has reduced their arsenic

exposure in recent years (Argos M. et al., 2011). In terms of carcinogenic consequences,

excessive arsenic exposure increases the risk of cancer, a risk that persists for decades after

initial arsenic exposure and its withdrawal (Ahsan et al., 2006). Arsenic-infected people are

more likely to develop skin cancer, lung cancer, sinusitis, arthritis, and other diseases.

(Nickson et al., 1998; Dowling et al., 2002). Arsenic has also been demonstrated to be

genotoxic, in addition to its tumorigenic potential (Ning, 2002). Arsenic has been recognized

for inhibiting the functioning of numerous transcriptional co-regulators, proteins, and

enzymes, particularly transcription activity in body cells, and can induce a variety of non-

carcinogenic effects in systems (Chen et al., 2014; Pournara et al., 2014; Khairul et al., 2017).

Treatment

Arsenic removal from contaminated water is critical since arsenic is a hazardous

substance that poses severe health problems. A variety of treatment approaches for

eliminating arsenic from groundwater have been investigated. There are two oxidation states

of inorganic arsenic at normal pH: As3+ and As5+. The remediation of these two oxidation

states from a particular source entails converting arsenic from As3+ to As5+ in a less toxic

form. Arsenic removal from water can involve a variety of simple to sophisticated

technologies, each with its own set of pros and cons. The appropriate technology depends on

the source and levels, the route and distribution, and the chemical form of arsenic (Ng K. et
al., 2004). These technologies are primarily based on oxidation, co-precipitation, sorption,

filtration, and ion exchange.

The most prevalent and practical technologies for removing arsenic in developing

countries are oxidation, co-precipitation, and adsorption onto coagulated flocs, as well as

adsorption onto sorptive media (Ahmed M., 2001), which may be the most cost-effective for

removing arsenic in developing countries (Jiang J., 2001).

Recommendation

As geological disturbances caused by excessive groundwater withdrawal have largely

been held responsible arsenic contamination of groundwater, remedial measures aimed at

reducing the pressure of such withdrawal are likely to be effective.

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