drinking water standards and often the water is not suitable even for irrigation and

1 GROUNDWATER CONTAMINATION BY ARSENIC AND

FLUORIDE industrial activities. Among the various groundwater pollutants reported, arsenic and

fluoride are of major concern owing to their widespread occurrence and highly detrimental
2 Dr. S.M Maliyekkal, VITCC
effects on human health. They are now considered as the top priority drinking water
GENERAL pollutants (WHO, 2006).
Water is one of the essential natural resources for sustaining all forms of life on Earth.
Many cases of groundwater contamination with arsenic have been reported from all over
Though more than two-thirds
the world. Major incidences of arsenic were experienced in the Ganges Delta of
fresh water available is limited. Moreover, many of the resources are located far from
Bangladesh and West Bengal, India (Chowdhury et al., 1999), where arsenic is said to be
human habitations. Groundwater often provides a water supply that is more reliable in
associated with iron and manganese oxides in the alluvial sediments. In West Bengal,
terms of quantity and quality as compared to surface water. Groundwater drawn from deep
approximately 7 million persons, including 2 million children are routinely exposed to
aquifers is usually free from microbial contamination and has economic and operational
arsenic poisoning through arsenic contaminated drinking water. The extent of
advantages due to reduced treatment requirements (Robins, 1990). Thus, it accounts for a
contamination in Bangladesh is much higher, where 28 to 77 million persons are thought to
significant portion of drinking water supply in many countries around the world (World
be at risk from drinking arsenic contaminated groundwater (Nickson et al., 1998;
Bank, 1998). In India, more than 80% of the rural water supplies are obtained from
Nordstrom, 2002; WHO, 2002). This scale of disastrous effects is greater than the accidents
groundwater (Census of India, 2001).
in Bhopal (India) in 1984 and Chernobyl (Ukraine) in 1986 (Smith et al., 2000). The
Over the years, number of quantitative and qualitative changes has occurred in groundwater reported health effects of chronic arsenic exposure include lung, kidney and skin cancers;
systems due to natural causes and human intervention. Large depletions in groundwater hyperpigmentation; keratosis; and peripheral disorders (Tseng et al., 1968; Borgono et al.,
levels and decline in water quality have become a common problem in many countries 1977, NRC, 1999).
across the world. Various contaminants like fluoride, nitrate, sulphate, phosphate,
Although fluoride is thought to be less harmful than arsenic, long term consumption of
pesticides and other heavy metals such as arsenic, lead, chromium etc. have been found in
fluoride can cause various health problems such as skeletal and dental fluorosis, and can
many ground water sources (Mulligan et al., 2001; Muhammad et al., 2004; Rukah and
increase the risk of bone fracture, bone cancer (osteosarcoma cancer), and DNA damage.
Alsokhny, 2004; Charles et al., 2005; Ahamed et al., 2006; Mathava and Philip, 2006;
Fluoride also has adverse effects on thyroid, immune system, brain and kidney (Sorg, 1978;
Uchino et al., 2006). In many places, concentrations of these pollutants are much above the
Tsutsui et al., 1984; Mahramanlioglu et al., 2002; Wang et al., 2004). According to the

1 2

latest information, fluorosis is endemic in at least 20 countries around the world, including Origin of Arsenic in Groundwater Sources

countries from Africa and Asia, and USA (Lee et al., 1995; Naoki et al., 1996; Mameri et It is widely reported that a large number of groundwater sources from various parts of the

al., 1998). India is the most affected nation where more than 25 million persons in 150 world have been contaminated with arsenic. Arsenic is usually mobilized by natural

districts (17 states) are affected by fluorosis and approximately 66 million persons are at weathering reactions, biological activities, and geochemical reactions. Anthropogenic

the risk of fluorosis (Susheela, 1999). In Indian states like West Bengal, Madhya Pradesh, activities like mining and waste disposal from various industries can also mobilize arsenic

Uttar Pradesh, Punjab, Hariyana, and Assam, the occurrence of arsenic and fluoride are in the environment. However, most environmental arsenic problems are primarily due to

reported in ground water (Table 1), but the data on the combined occurrence of these natural reasons rather than anthropogenic or geothermal activities (Lackovic et al., 2000).

pollutants is scarce. Unfortunately, there is no authentic study, which provides evidence for the origin of

dissolved arsenic in groundwater. Thus, the best approach for the long-term mitigation of

this hazard has not been found yet.

In West Bengal and Bangladesh regions, it is widely agreed that arsenic occurs naturally in

the alluvial sediments of the region (BGS and DPHE, 2000). However, there is debate on

how arsenic is released into the groundwater and whether the problem is man-made or not.

At present, there are a few hypotheses stating the existence of arsenic in groundwater

systems of West Bengal and Bangladesh (Fazal et al., 2001b; Zheng et al., 2004; Horneman

et al., 2004). According to one of the hypotheses (Pyrite-oxidation Hypothesis), arsenic is

assumed to be present in certain sulphide minerals (pyrite) that are deposited within the

aquifer sediments. The increased extraction of groundwater has exposed the previously

submerged sediment to air that resulted in the oxidation of arseno-pyrite in the vadose zone

and releases of arsenic. This arsenic can be re-adsorbed on iron hydroxide during the

subsequent recharge period; the reduction of iron hydroxide releases arsenic into

groundwater. According to this hypothesis, the origin of arsenic-rich groundwater is man-

made, and would be a recent phenomenon (Karim et al., 1997). Another group of

3 4
researchers has suggested that phosphate from chemical fertilizers is displacing arsenic The decreasing order of toxicity of different organic and inorganic arsenic species are:

from the sediments. However, there is no observable correlation between most arsenic arsine > arsenite > arsenate > alkyl arsenic acids > arsonium compounds and metallic

contaminated areas and the distribution of groundwater extraction, and none of the arsenic (WHO, 1981). Among these chemical forms, As(III) and As(V) are commonly

anthropogenic explanation can account for the regional extent of the groundwater found in ground water. As(III) is generally considered to be more toxic compared to As(V);

contamination in West Bengal and Bangladesh (DPHE /BGS/ MMIL, 1999). at least in some aspects (Lamble and Hill, 1996; NRC, 1999) . In human acute toxicity

studies, As(III) has been shown to be more potent than As(V) (EPA, 1988). With regard to
Apart from the above two hypotheses, there is one more contradictory hypothesis, called
human chromosome breakage, As(III) is about an order of magnitude more potent than
Oxyhydroxide Reduction Hypothesis (ORH), describing the occurrence of dissolved
As(V) (EPA, 1988). Squibb and Fowler (1983) found that As(III) was 10 times more toxic
arsenic in groundwater. This hypothesis was proposed by Nickson et al (1998) and was
than As(V) and 70 times more toxic than monomethylarsonic acid [MMA(V)] and
later supported by a few other researchers (Acharyya et al., 1999; Nickson et al, 2000).
dimethylarsinic [DMA(V)]. However, monomethylarsonous acid [MMA(III)] and
Groundwaters of West Bengal and Bangladesh region are generally in a reducing state
dimethylarsinous acid [DMA(III)] have been found to be more toxic than inorganic arsenic
(because of the presence of relatively high sedimentary organic matter), and arsenic is
because they are more efficient in causing DNA breakdown (Styblo et al., 2000; Dopp et
released when arsenic iron complexes in the sediments are reduced by the oxygen deficit
al., 2004). Toxicity of arsenic in humans is principally due to the inhibition of sulfhydryl
groundwater. According to this hypothesis, the process is a natural one, and the ground
enzymes by reaction with arsenoxide and arsenite, which is probably the first step in cell
water extraction does not cause or worsen the arsenic contamination.
damage. Although the arsenite ion is capable of uncoupling phosphorylation through the
Health Effects
formation of arsenite esters, the significance of this substitution in human metabolism is
Arsenic is a potent toxicant that may exist in the natural system in a variety of chemical
unknown.
forms. It includes inorganic As(III) and As(V), and several mono, di, and tri methylated
The major human exposure to arsenic is through oral route, primarily through food and
arsenic compounds (Goswami and Das, 2000). The toxicity and mobility of these
drinking water. Consumption of drinking water obtained from arsenic rich ground strata is
compounds differs from one another depending on their chemical forms and valence state
the major exposure mechanism for public population in West Bengal and Bangladesh
(NRC, 1999; Thomas et al., 2001). Although the data on the effect of arsenic on human
(Mondal, et al., 2006). Arsenic [both As(III) and As(V)] in drinking water can affect the
health is scarce, organic arsenicals are generally considered less toxic as compared to its
health of human beings in variety of ways. Short-term exposure (ingestion of large amount
inorganic forms.
of arsenic in a very short time) can cause severe abdominal cramps, internal bleeding and

5 6

may even lead to death. Small doses of inorganic arsenic cause vasodilatation, splanchnic major affected districts include Burdwan, Naira, Malda, Murshidabad, North-24 Paraganas,

hyperemia resulting in nausea, diarrhoea, vomiting, skin pigmentation, headaches, and South-24 Paraganas, Nawadwip and Hoogly. Approximately 3.93 million persons were

anorexia. Additionally, chronic exposure frequently causes the condition of garlic breath affected by this toxic contaminant. The total affected area covers, approximately, 37,493

with excessive salivation and sweating, stomatitis, oedema, hyperkeratosis, liver square kilometers. In most of the cases, arsenic concentration values ranged from 0.3 to 0.7

enlargement, jaundice and renal damage. Chronic exposure may also lead to peripheral mg/L. Occasionally the values were as high as 1.86 and 5.0 mg/L, reported from two places

arteriosclerosis (Black Foot disease), peripheral neuritis and encephalopathy. Apart from in West Bengal (Mandal et al., 1996, Balakameswari et al., 1999). Arsenic contamination

these non-cancerous effects, long-term consumption of these compounds can also cause was also reported from various other states of India, including Chattisgarh, Bihar,

cancerous diseases such as bladder, lung, and skin cancers (NRC, 1999). Though, reported Jharkhand, Uttar Pradesh, Assam, Punjab and Haryana (Table 1).

toxicity effects of As(III) are more compared to As(V), it is worth mentioning that at low
Arsenic contamination of groundwater is much more severe in the neighboring country,
concentration, (less than 0.5 mg/L of water) As(V) compounds are readily reduced to
Bangladesh, where the groundwater of 59 out of 64 districts is contaminated with high
As(III) in human body (Vahter and Envall, 1983). Hence, the chronic health effects caused
levels of arsenic (DPHE and BGS, 1999; BGS and DPHE, 2000). It is estimated that out of
by the injection of arsenic contaminated water is least affected by its speciation and a mere
the 125 million inhabitants of Bangladesh, 35 to 77 million are at the risk of drinking
conversion of As(III) to As(V) does not lower the toxicity of contaminated groundwater
contaminated water (Khan et al., 1997; Lepkowski 1999). Besides, West Bengal (India)
(DeMarco et al., 2003).
and Bangladesh, other countries, where occurrence of arsenic poisoning were reported, are

Arsenic Problem Across the World Chile, Mexico, Japan, Taiwan, Argentina, Vietnam, Northern China, Hungary, Romania

In recent years, occurrence of high concentrations of inorganic arsenic in groundwater has and South-Western part of U.S.A (Mondal, et al., 2006). According to a study conducted

become an epidemiological problem. Groundwater rich in arsenic is found in many regions by the Taiwan Provincial Institute of Environmental Sanitation, it has been established that

around the globe (Smedley and Kinniburgh, 2002). The most significant occurrence was 119 townships in the affected area had arsenic concentrations in groundwater greater than

identified in West Bengal (India) and Bangladesh (Bagla and Kaiser, 1996; Nickson, et al., 50 µg/L and 58 townships had arsenic concentration greater than 350 µg/L (Lo et al.,

1998; BGS and DPHE, 2000). The first case of arsenic contamination in groundwater from 1977). The first case of arsenic poisoning in China was recognized in Xinjiang province in

the Bengal Basin was recorded in 1978 in West Bengal (Acharyya et al., 2000). Reports early 1980s. High concentrations of arsenic (> 50 µg/L) were detected in groundwater from

have shown that groundwater in more than 8 districts of West Bengal (out of 18 districts) is Inner Mongolia, Xinjiang and Provinces of Shanxi, in deep artesian aquifers of Dzungaria

contaminated with high levels of arsenic (Mandal et al., 1977; Chatterjee et al., 1995). The

7 8
Basin, aquifers in the Huhhot Basin, Bameng region and Tument Plain (Wang and Huang Table 1 Arsenic contamination in various states of India
1994; Niu et al., 1997; Luo et al., 1997; Ma et al., 1999). Districts /Villages/Sampling Concentartion
State Reference
stations range ( mg/L)
Bardaman, Nadia, Malda,
The Lagunera Region of North Central Mexico estimated with a population of 400,000 has Das et al 1996;
Murshidabad, North-24 Paraganas,
West Bengal 0.003 3.7 Mandal and
South-24 Paraganas, Nawadwip,
been exposed to arsenic concentration greater than 50 µg/L (Del Razo et al., 1990). A study Suzuki, 2002
Hooghly, Kolkata and Howrah
conducted by Berg and co-workers (2001) found that a large number of groundwaters in Chhatisgarh, Rajnandgaon, Durg, Ropar, Mondal et al.,
Punjab, Manimajra, Chandigarh, N. Garh, <0.01 0.545 2006; Datta and
Hanoi and surrounding rural districts are contaminated with arsenic with an average arsenic Hariyana Patiala and Ambala Kaul, 1976
Bhojpur, Harail Chapar of
concentration of 159 µg/L, the contamination levels varied from 1 to 3050 µg/L. High Samastipur district, Paschimi
Champaran, Purba Champaran,
Chakraborti et
concentration of arsenic has been detected in Northern Chile and Argentina. (Nicolli et al., Bihar Sitamarhi Supaul, Aroria, <0.01 1.654
al., 2003
Kishanganj, Purnia, Katihar, Patna,
1989; Caceres et al., 1992). Arsenic associated with geothermal waters has been reported in Bhojpur, Buxar, Saran (Chapra)
Vaishali,
several areas, including hot springs from parts of USA, Japan, Chile, New Zealand and Sahebgunj (B), Rajmahal and
Bhattacharjee et
Jharkhand Udhawa blocks of Sahebgunj <0.01 - 0.1
al., 2005
France (Welch et al., 1988; Criaud and Fouillac, 1989). Localised arsenic problems in districts
Ahamed et al.,
Uttar Pradesh Ballia, Gazipur and Varanasi <0.01 3.192
groundwater have been reported from an increasing number of countries and many new 2006
Madhya Koudikasa village, Rajnandgaon Chakraborti et
<0.01 - 0.99
cases are likely to be discovered in future (Smedley and Kinniburgh, 2002). Pradesh. district al., 1999

Assam Dhimaji, Karimganj ---

Bawana, Mehrauli, Moti Bagh, Tilak

Lalwani et al.,
Delhi Nagar, Raney Well 7, K M Pur, 0.017 - 0.1
2004
Raghubir Nagar, RK Puram-6

FLUORIDE

Properties, Occurrence and Source

Fluorine (F2) is a non-metallic gaseous element having an atomic weight of 18.999. In its

pure form, fluorine is a toxic, pale yellow-green gas. It is the most reactive halogen and

reacts readily with all other elements except inert gases. It is the 13 th most abundant

element in the earth crust. In nature, it occurs in various minerals such as fluorospar (CaF2),

cryolite (Na3AlF6) and fluorapatite (Ca5(PO4)3F) and many others. In aqueous environment,

9 10

it generally occurs as fluoride ion (F-). The undissociated hydrofluoric acid (HF) and its typical symptoms of skeletal fluorosis. Severe exposure may even lead to complete

complexes with aluminium, iron and boron are the other most likely soluble forms of physical disability.

fluoride in natural water (Pitter, 1985).

There are many other reported health problems, including cancerous and non-cancerous

Groundwater is the major exposure source of fluoride. Other sources of fluoride poisoning diseases associated with chronic ingestion of fluoride (Dean and Elvove, 1937; Singh et al.,

are food, industrial exposure, drugs and cosmetics (Meenakshi and Maheshwari, 2006). 1961; WHO, 1984). Acute ingestion of fluoride can also cause various health problems

Both natural and anthropogenic sources can contribute fluoride into the environment. such as vomiting, nausea, abdominal pain, diarrhoea, drowsiness, coma, fatigue, cardiac

However, most groundwater contaminations with fluoride are primarily due to natural arrest and even death (Robins, 1990; Whitford; 1990; Hiscock, 1994). The severity of acute

reasons. In groundwater, the natural concentration of fluoride varies with physical and effects varies with exposure, concentration, and the type of salts exposed to. More the

chemical characteristics of the aquifer, which includes porosity, acidity of the soil and solubility of the salt, more will be the toxic effect.

rocks, temperature, action of other chemicals and depth of wells.

Fluoride Problem Across the World

Health Effects of Fluoride Excess fluoride in groundwater is reported in many countries around the world, notably in

Low concentrations of fluoride in drinking water are considered as beneficial to prevent the United States of America, Africa, and Asia (Lee et al., 1995; Naoki et al., 1996;

dental caries. However, scientists are now debating on the health benefits of fluoride even Mameri et al., 1998). According to a recent report, more than 20 countries across the world

at low concentrations. Chronic intake of excessive fluoride (> 1 mg/L) can lead to severe have reported cases of endemic fluorosis (Meenakshi and Maheswari, 2006). India is

dental and skeletal fluorosis. It not only affects teeth and skeleton, but accumulation over a among the most affected nations, where fluoride in drinking water is prevalent in 150

long period can lead to change in the DNA structure (Tsutsui et al., 1984, Wang, et al., districts of 17 states of the country (Table 2). In India, it was first detected in Nellore

2004). Typical symptoms of dental fluorosis consist of loss of normal teeth colour (creamy district of Andhra Pradesh in 1937 (Shortt, 1937). In China, cases of endemic fluorosis

white translucent) and the formation of discoloured, blackened, and mottled or chalky were reported as early as in 1930's (Lian-Fang and Jian-Zhong, 1995). According to a

white teeth. This teeth characterisation is an indication of over exposure to fluoride during recent report, endemic fluorosis is prevalent in 29 provinces, municipalities or autonomous

the teeth development stage. Skeletal fluorosis is caused due to excessive accumulation of regions in China (Zhu et al., 2006). In South Korea, excessive fluoride concentrations are

fluoride in bones that results in increased bone density and outgrowth (ATSDR, 1993). The frequently encountered in deep groundwater (Kim and Jeong, 2005; Jeong et al., 2003). In

early signs of skeletal fluorosis are tingling sensation in legs and feet, sporadic pains, Korea, many incidence of dental fluorosis have been reported in children who drink water

stiffness of joints, headache and muscle weakness. The bowlegs and knock-knees are two with elevated fluoride concentrations over a long period of time (Yi et al., 2001, Choi et al.,

11 12
 2004). Carrillo-Rivera et al. (2002) reported that significant amount of fluoride is found in
Table 2. Fluoride contamination in various states of India
the abstracted groundwater of San Luis Potosí, Mexico. Studies have shown that the (Adapted from Susheela, 1999)
Concentrati
problem of high fluoride content in groundwater is very acute in mainland Tanzania
on
States Districts
range
(Mjengera and Mkongo, 2002). Agrawal (1997) reported that in Sri Lanka, fluoride has a
(mg/L)
strong geographical control linked to climatic conditions, with high fluoride waters being Assam Karbianglong, Nagaon 0.2 18.1
All districts except Adilabad, Nizamabad, West
restricted to the dry zone on the eastern side of the island. In some parts, wells have
Andhra Pradesh Godhavari, Visakhapattnam, Vijzianagaram, 0.11 20.0
Srikakulam
fluoride concentrations more than 10 mg/L. Analysis of many groundwater samples
Palamu, Daltonganj, Gridh, Gaya, Rohtas,
Bihar 0.6 8.0
collected from different parts of Ethiopia have shown excess fluoride than the guideline Gopalganj, Paschim, Champaran

concentration recommended by World Health Organisation (Tekle-Haimanot et al., 2006). Delhi Kanjhwala, Najafgarh, Alipur 0.4 10.0
Gujarat All districts except Dang 1.58 31
Mgalela (1997) reported high fluoride concentrations in groundwater in some parts of
Bhiwani, Sirsa, Hisar, Rewari, Faridabad, Karnal,
Haryana Sonipat, Jind, Gurgaon, Mohindergarh, Rohtak, 0.17 24.7
Gokwe district in Zimbabwe. Many other cases of endemic fluorosis have been reported
Kurukshetra, Kaithal,
from various parts of the world and many new cases are likely to be discovered in future. Jammu and 0.05 4.210
Doda
Kashmir

Though literature regarding the occurrence of both arsenic and fluoride together is less, it is Dharwad, Gadag, Bellary, Belgam, Raichur, Bijapur,
2 18.0
Karnataka Gulbarga, Chitradurga, Tumkur, Chikmagalur,
clear from the literature that both arsenic and fluoride are present in states like West Mandya, Bangalore, Mysore,
Kerala Palghat, Vamanapuram, Alappuzha 0.2 2.5
Bengal, Madhya Pradesh, Uttar Pradesh, Punjab, Hariyana, Assam, etc. However the
Chandrapur, Bhandara, Nagpur, Jalgaon, Bulduna,
possibility of simultaneous occurrence of these pollutants in the same drinking water Maharashtra 0.11 10.2
Amravati, Akola, Yavatmal, Nanded, Sholapur

cannot be riled out. Most of the current investigations have concentrated only on the Shivpuri, Jabua, Mandla, Dindori, Chhindwara, Dhar,
Madhya Pradesh 0.08 4.2
Vidhisha, Seoni, Sehore, Raisen and Bhopal
monitoring of either of these pollutants. A more detailed investigation may be required in
Orissa Phulbani, Koraput, Dhenkanal 0.6 5.7
future to test the combined occurrence of these pollutants in affected states of India. Mansa, Faridcot, Bhatinda, Muktsar, Moga, Sangrur,
0.44 6.0
Punjab Ferozepur, Ludhiana, Amritsar, Patila, Ropar,
Jallandhar, Fatehgarh sahib
Rajasthan All the 32 districts 0.2 37.0
Salem, Periyar, Dharampuri, Coimbatore,
Tamilnadu 1.5 5.0
Tiruchirapalli, Vellore, Madurai, Virudunagar
Unnao, Agra, Meerut, Mathura, Aligarh, Raibareli,
Uttar Pradesh 0.12 8.9
Allahabad

13 14

(SOES, 1999). Considering these facts the arsenic standards in India and Bangladesh should be
West Bengal Birbhum, Bhardaman, Bankura 1.5 13.0
lower than the international standards.

Fluoride
WATER QUALITY CRITERIA AND STANDARDS
The safe drinking water limit of fluoride is < 1mg/L (WHO, 2006). However, this guideline
Arsenic
value of fluoride is not universal. The limit varies among countries and the age of persons
Presence of dissolved arsenic in drinking water has been a public health concern for the last few
exposed to it. In India, maximum contaminant level is restricted to 1.5 mg/L. The US standard
decades. Arsenic was one of the first chemicals to be considered as a carcinogen (Smith et al.,
for fluoride is between 0.6 and 0.9 mg/L. As the amount of water consumed and consequently
2002). In order to protect the public from its toxicity, arsenic in water was first regulated by
the amount of fluoride ingested is influenced primarily by air temperature, USPHS (1962) has set
United States Public Health Service (USPHS), which set a maximum permissible concentration
a range of concentrations for maximum allowable fluoride in drinking water for communities

based on the climatic conditions (Meenakshi and Maheshwari, 2006).

/L. Based on lung and bladder cancer risk, the United

States Environmental Protection Agency (USEPA) promulgated a Maximum Contaminant Level

January 22, 2001 (USEPA, 2001). This new standard became effective on January 23, 2006.

is going on regarding lowering

the permissible arsenic level to

person drinking an average of 2L of water per day over his/her life span. However, persons from

Bangladesh and West Bengal tend to drink more amount of water than Europeans or US

residents because of hot climatic conditions. Another important issue to be addressed is the poor

dietary levels of the persons living in affected areas of West Bengal and Bangladesh. It is evident

that persons with less nutritional levels are more affected by arsenic compared to healthy persons

15 16