Managing Arsenic in the Environment: From Soil to Human Health

Part A

Arsenic around the world

– an overview

1

Arsenic contamination incidents around the world

Mohammad Mahmudur Rahman, Mrinal Kumar Sengupta, Uttam Kumar Chowdhury,

Dilip Lodh, Bhaskar Das, Sad Ahamed, Debapriya Mandal, Md Amir Hossain,

Subhash Chandra Mukherjee, Shymapada Pati, Kshitish Chandra Saha & Dipankar Chakraborti

Introduction

Contamination of groundwater by arsenic (As) has been reported in 20 countries in different parts of the world (Figure 1.1). Of these, four major incidents are in Asia. In order of severity, they are in Bangladesh, West Bengal (India), Inner Mongolia (PR China) and Taiwan. New incidents have been reported from other Asiatic countries including Lao PDR, Cambodia, Myanmar and Pakistan (UNESCAP-UNICEF-WHO Expert Group Meeting 2001). Severe groundwater As contamination has been reported from Vietnam, where several million people consuming untreated groundwater run a considerable risk of chronic As poisoning (Berg et al. 2001). Groundwater As contamination has also been reported from Nepal (Tandukar et al. 2001; Shrestha et al. 2003). It has also been reported that Kurdistan province of western Iran is As-affected, and that people have been drinking contaminated water and suffering from arsenicosis since 1984 (Mosaferi et al. 2003). Arsenic contamination in groundwater has been reported from Bihar in Middle Ganga Plain, India (Chakraborti et al. 2003). The As-affected areas in Asia are illustrated in Figure 1.2.

Figure 1.1 Groundwater As incidents round the world

Figure 1.2 Arsenic-affected areas in Asia

Exposure to As may come from both natural sources and anthropogenic activities, including industrial sources and food and beverages. However, the natural sources of As have led to the largest incidence of poisoning. In this chapter we present an overview of various sources of As and its impact on human health throughout the world.

Contamination from natural sources

Natural groundwater As contamination has been reported from all over the world. Major incidents are presented in Table 1.1 and described below.

Argentina

Arsenic contamination in groundwater was reported in Monte Quemado of Cordoba province, north Argentina (Astolfi et al. 1981). The occurrence of endemic arsenical skin disease and cancer was first recognized in 1955. Total population of the endemic area was about 10 000. From observation in Cordoba, it was concluded (Astolfi et al. 1981; Hopenhayn-Rich et al. 1998) that the regular intake of drinking-water exceeding 100 µgAs/L led to clearly recognizable signs of intoxication and may cause skin cancer. Biagni (1972) followed 116 patients with clear signs of chronic disease; after 15 years 78 had died, 24 (30.7%) from cancer.

Elevated levels of As in surface water, shallow wells and thermal springs was reported from Salta and Jujuy provinces in north-western Argentina (De Sastre et al. 1992). This natural contamination is related to tertiary-quaternary volcanic deposits, together with post-volcanic geysers and thermal springs. The As content of the water abstracted for drinking for the population of 5000 in the town of Antonio de los Cobres was 470–770 µg/L. Arsenic content in thermal springs was 50–9900 µg/L.

Table 1.1 Major groundwater As contamination incidents in the world

Natural groundwater contamination with As and selenium was also reported in the Pampa province of Cordoba, south-eastern Argentina. The As content of nearly half the water samples from this area was 10–316 µg/L, with a maximum concentration of 3810 µg/L (Nicolli et al. 1989; Concha et al. 1998). Groundwater contamination is caused from loess, which differs in composition to loess from Europe, Asia and North America (Nicolli et al. 1989), with As concentration of 5500–37 300 µg/kg, and rhyolitic volcanic glass 6800–10 400 µg/kg.

Bangladesh

The first As groundwater contamination from Padma-Meghna Plain of Bangladesh was reported in 1995 (Post Conference Report 1995; Das 1995). During 1998, 41 of the 64 districts in Bangladesh, from Padma-Meghna to Old Brahmaputra Plain, were identified as having a groundwater concentration of As exceeding 50 µg/L (International Conference on Arsenic 1998). Current data show As levels above 50 µg/L in 2000 villages, recorded at 189 police stations of 50 affected districts in Bangladesh (Chakraborti et al. 2004). The area and population of 50 As-affected districts of Bangladesh are 118 849 km² and 105 million respectively, compared with total area and population of Bangladesh of 148 393 km² and 120 million respectively. This does not mean that all are drinking As-contaminated water and suffering from Asrelated diseases, but they are at risk.

Researchers from the School of Environmental Studies (SOES) at Jadavpur University, India, have so far analyzed 50 515 hand tube-well water samples from Bangladesh by flow injection hydride generation atomic absorption spectrometer (FI-HG-AAS), of which 43% contained As above 10 µg/L and 27.5% contained As above 50 µg/L (Chakraborti et al. 2004). Figure 1.3 shows the status of As in groundwater in all 64 districts of Bangladesh. Table 1.2 shows the physical parameters and As-affected areas of Bangladesh. British Geological Survey (BGS) estimated that 35 million people in Bangladesh are at present drinking As-contaminated water containing As above 50 µg/L (BGS Technical Report 2001). In a preliminary survey, 18 991 people from 244 villages were screened and 3762 (19.8%) were registered with arsenical skin lesions (Chakraborti et al. 2004). The socio-economic status and social problems are similar to those of As-affected villages of West Bengal, India (Chowdhury et al. 2001). The source and mechanism of As leaching to the aquifers is similar to West Bengal (Das et al. 1996; Chowdhury et al. 1999; Nickson et al. 1998,2000; Chakraborti et al. 2001).

Table 1.2 The physical parameters and As-affected areas of Bangladesh

Canada

Ontario

In 1937, Wyllie (1937) reported that water from some deep wells in Rocky Mountain areas of Ontario, Canada, was known to contain large amounts of As: 100–410 µg/L as As2O3. Preliminary experiments showed that As, as ferrous arsenate, was the primary source of As which contaminated the well-water. One person died of As dermatosis and family members of the dead victim are also afflicted.

Nova Scotia

In 1976, several wells in Halifax county of Nova Scotia, Canada, were reported to be contaminated with As (Grantham & Jones 1977) exceeding 3000 µg/L. Some 50 families have been affected by As poisoning (Subramanian et al. 1984). Boyle and Turner (1998) reported occurrences of elevated As content in bedrock groundwater used for individual and municipal water supplies in the mainland coast of southern British Columbia, Canada.

Chile

Antofagasta

Epidemiological and clinical investigations about As-related health problems in the city of Antofagasta, Chile, were reported by the local physician in the early 1960s. The investigations were focused especially on children. In 1970, Feiguenbaun and Hevia (1970) reported that cutaneous lesions, which they had observed in Antofagasta saltpetre workers and which had been described in 1919 and 1945, related to the high amount of As in water in the saltpetre fields of Antofagasta.

Figure 1.3 The status of As contamination in groundwater in all 64 districts of Bangladesh

About 1 300 000 inhabitants of the city had been drinking supplied water with a maximum As content of 800 µg/L for 12 years from 1959 to 1970 (Borgono & Greiber 1971). The source of the high As content in water was the Tocance River, which comes from the Andes mountains at an altitude of 3000 m and flows 300 km to Antofagasta. The first dermatological manifestations were noted at the beginning of the 1960s, especially in children (Borgono & Greiber 1971). Peripheral vascular manifestations in these children included Raynaud’s syndrome, ischemia of the tongue, hemiplegia with partial occlusion of the carotid artery, mesenteric arterial thrombosis and myocardial ischemia. In a survey of 27 088 schoolchildren, 12% were found to have the cutaneous changes of arsenicism; some 30% of these had suggestive systematic symptoms and 11% had acrocyanosis. Of the residents of Antofagasta, 144 had abnormal skin pigmentation, compared with none in the 98 control subjects. Later studies (Smith et al. 1998, 2000) also documented arsenic-induced skin lesions, and increased bladder and lung cancer mortality in northern Chile. Samples taken from 23 locations at Aracamenan settlements near Calama range showed 100–800 µgAs/L. Most of the As was present as arsenate, but some arsenite was also found.

A water treatment plant is now run to remove As from drinking-water before use. The sources of As have been reported as quaternary volcanogenic sediments, minerals and soil (Caceres et al. 1992).

China

Xinjiang Uygur

In 1983, Lianfang and Jianghoung (1994) found a natural lake with a high level of As in the Tianshan mountainous district. The high-As zone is located at the lowest part of the mountain apron of the Tianshan mountain range, ranging from Aibi Lake as far east as the Means River, a distance of about 250 m. The northern part of the area of Kuitun city and Usum county, situated in the middle section of the zone, is an area of endemic severe arsenicism. Human poisonings from As have occurred as a result of drinking high-As water in some villages and towns in this area (Lianfang & Jianghoung 1994). Arsenic found in 41 samples collected from various wells at a depth of 2–30 m had a mean concentration of 18 µg/L, with a range of 0–68 µg/L. Artesian wells deeper than 660 m have been sunk in some areas. It is observed that As concentrations in the water samples collected from the artesian wells at a depth of 70–400 m may increase with depth. In the upper section of the alluvial plain As content was <40 µg/L, whereas in the lower section of the alluvial plain content in the artesian wells was >200 µg/L.

In the period from 1980 to 1984, 31 141 inhabitants were examined for As poisoning in 77 villages and towns situated in the alluvial plain; 523 cases of human poisoning from As were found. Of the 523 cases, 447 (85.5%) had arsenical keratosis and 208 (39.8%) had hyperpigmentation and depigmentation.

Inner Mongolia

The first diagnosis of As poisoning in the Inner Mongolia, Autonomous Region of PR China, occurred in 1990. According to the various research reports compiled by the end of 1995, As contamination in Inner Mongolia had spread to 655 villages of 11 counties and 1774 patients had been identified. The cause of contamination is considered to be geological (Xiau 1997; Gao 1997). Major clinical symptoms observed include keratosis, pigmentation, melanosis or leucoderma in the skin, often accompanied with peripheral neuritis, gastroenteritis, hypertrophy of the liver, bronchitis and cardiac infarction. At later stages skin cancer and gangrene were also found, especially in those people who had been drinking As-contaminated water for more than 10 years.

Since endemic arsenism was first found in the mainland of China in 1983 in Xingjiang province, there have been more cases identified in Inner Mongolia, Shanxi and Guizhou province. It is estimated that the total population exposed to As is over 2 million, with 20 000 diagnosed patients (Sun 2001). The current research in China shows that the epidemic area is still expanding. The cause of arsenism in China is mainly divided into two types: that originating from exposure to drinking-water, and from exposure to As-containing fumes from coalburning. Many people drink water from pump-wells 20–30 m deep which are rich in As, mainly in the range of 200–2000 µg/L, with a maximum of 4400 µg/L. People use coal containing high concentrations of As for cooking, keeping warm and drying grains and peppers in their kitchens; the food and indoor air are seriously contaminated by As in Guizhou province. The average As concentration in coal is 876 300 µg/kg, in polluted kitchen air it is 445 µg/m³ and in corns and peppers it is 4130 and 512 000 µg/kg respectively. This shows significant accumulation of As in these food products. Although some preventive measures have been taken to remove As from drinking-water, arsenism is still a major problem in China (Sun 2001).

Hungary

In Hungary, As ranging from 60–4000 µg/L was observed in well-water between 1941 and 1983 (Egyedi & Pataky 1978; Nagy & Korom 1983). A few thousand people showed symptoms of As poisoning: melanosis, hyperkeratosis, skin cancer, internal cancer, bronchitis, gastroenteritis or hematologic abnormalities (Pataky & Lusztig 1958). Later, As exceeding 50 µg/L was identified in groundwater from alluvial sediments associated with the River Danube in the southern part of the great Hungarian Plain. A maximum As concentration of 150 µg/L, with an average of 32 µg / L (total 85 sample sanalyzed), was reported by Varsanyi (1989) in tube -well waters examined . The plain where As was found, about 110 000 sq km in area, consists of a thick sequence of subsiding quaternary sediments. The highest As concentration in groundwater occurs in the lowest parts of the basin, where the sediment is fine-grained (Varsanyi 1989).

India

Bihar

During June 2002, As in groundwater was first reported in Semria Ojha Patti village of Sahapur police station in Bhojpur district of Bihar state in India (Chakraborti et al. 2003). Bihar state is in the Middle Ganga Plain. The area of Semria Ojha Patti village is about 4 km² and there are 5000 inhabitants. About 20 years ago, the dug wells were abandoned and replaced by hand tube-wells as the source of drinking-water. The villagers were unaware of any As contamination in their drinking-water and its consequent health effects. Analyses of 206 hand tube-well water samples for As from the village, which represents 95% of the total tube-wells, showed that 56.8% of the water samples contained As above 50 µg/L. The highest concentration of As detected in the village was 1654 µg/L. Of the 550 (390 adults and 160 children) subjects examined for arsenical skin lesions, 60 (13% of the adults and 6.3% of the children) were identified with As skin lesions (Chakraborti et al. 2003) (see Figure 1.4). Such a severe case of Asaffected children has not been reported in West Bengal nor in Bangladesh. Analyses of 148 biological samples such as hair, nail and urine (samples were collected from subjects both with and without skin lesions) showed that an average 80% of the samples contained As above the normal levels. The normal level of arsenic in hair ranges from 80–250 µg/kg and 1000 µg/kg is the indication of toxicity (Arnold et al. 1990). The normal level of arsenic in nail ranges from 430–1080 µg/kg (Ioanid et al. 1961). The normal excretion level of arsenic in urine ranges from 5–40 µg/1.5 L per day (Farmer & Johnson 1990). Neuropathy was found in 52.5% of the cases examined, with males less affected (40%) than females (73.3%). The researchers also observed an apparent increase in fetal loss and premature delivery among women where there was 1025 µg/L of As in the drinking-water (Chakraborti et al. 2003).

West Bengal

The first case of arsenicosis in West Bengal was identified in July 1983 (Saha 1983; Chakraborti et al. 2002) with the first publication of contamination in West Bengal in 1984 when 16 As patients in three families from one village of a district were identified (Garai et al. 1984). On the basis of 15 years’ surveying by Chakraborti and his co-researchers, 129 552 hand tube-well water samples were analyzed from As-affected districts of West Bengal. These investigators found that 3200 villages in 90 blocks showed incidences of poisoning. Half the samples contained As above 10 µg/L and 24.7% contained As above 50 µg/L (Chakraborti et al. 2004), with the highest measured in West Bengal at 3880 µg/L (Samanta et al. 1999). The area and population of the nine As-affected districts are 38 865 km² and 50 million respectively. More than 6 million people are at present drinking As-contaminated water exceeding 50 µg/L (Chakraborti et al. 2004). It is estimated that around 0.53 million people may have As-related diseases (Chakraborti et al. 2004). Figure 1.5 shows the present As-affected areas and blocks and Table 1.3 shows the physical parameters and As-affected areas.

Figure 1.4 A group of As-affected children from Semria Ojha Patti village in Bihar

In a preliminary study in West Bengal, 92 000 people (including children) were examined in seven of the nine affected districts; 8900 (9.7% including 1.7% children) had registered with arsenical skin lesions (Chakraborti et al. 2004). At least 100 cancers and several hundred suspected cases of Bowen’s disease were detected. Figure 1.6 (see p. 249) shows one severely affected As patient with gangrene. From some 28 000 biological samples analyzed from Asaffected villages, an average 78% contained As above normal levels (Chakraborti et al. 2004). Thus many people in the affected villages of West Bengal may be subclinically affected.

Children are more susceptible to As toxicity. About 90% of the children younger than 11 years living in As-affected villages show elevated levels of As in hair and nails (Rahman et al. 2001). Infants and children might be at greater risk from As toxicity due to more water consumption on a body-weight basis. Peripheral neuropathy was the predominant neurological complication in patients, affecting 154 (37.3%) of 413 patients in Murshidabad and Nadia districts and 33 (86.8%) of 38 patients in Bardhaman in West Bengal (Rahman et al. 2001; Mukherjee et al. 2003). A study showed that in As-affected areas tons of As are falling on agricultural land irrigated with water from As-contaminated tube-wells (Chowdhury et al. 2001). A preliminary study (Chowdhury et al. 2001) showed the presence of elevated levels of inorganic As in rice and vegetables.

Table 1.3 Physical parameters and As-affected areas of West Bengal, India

A socio-economic study in As-affected villages indicated that villagers are living in very poor conditions. Researchers from SOES at Jadavpur University, India, noticed (Chowdhury et al. 2001) from their last 15 years’ field experience in West Bengal that poor people with poor nutrition are suffering more. Arsenic-affected people also face serious social problems. Sometimes other villagers force an As-affected patient to maintain an isolated life or avoid them socially wherever possible (Chowdhury et al. 2001).

The source of As is geogenic. Arsenic is present in alluvial sediment of the delta. The mechanism and cause of As leaching from the source has not yet been established. Theories of oxidation (Das et al. 1996; Chowdhury et al. 1999; Chakraborti et al. 2001), reduction (Nickson et al. 1998, 2000), and carbon reduction (Harvey et al. 2002) have been suggested.

PN Mitra Lane, Behala, Calcutta

Arsenic contamination in the residential area of Behala, Calcutta, was well known during 1969 to 1989 (Chatterjee et al. 1993; Chatterjee & Mukherjee 1999; Guha Mazumder et al. 1992). Out of a total of 79 people examined (17 families with ages ranging from 1 to 69), 53 were found with chronic arsenicosis (Guha Mazumder et al. 1992). Clinical investigation of 20 affected persons showed typical skin pigmentation as well as palmar and plantar keratoses; gastrointestinal symptoms, anemia and signs of liver disease and peripheral neuropathy were seen in many. The primary suspect for this As episode is the chemical factory located on BL Saha Rd, and PN Mitra Lane is at the back of that factory. The chemical factory was producing several chemical compounds including the insecticide Paris Green (acetocopper arsenite). For about 20 years until 1989 the factory produced about 20 tons of Paris Green per year.

Analysis of soil surrounding the dumping-ground of the waste showed very high concentrations (up to 10 000 µg/g) of As. Soil also showed high concentrations of copper and chromium. The 19 hand tube-wells whose water was used for drinking and cooking showed As concentrations ranging from 100–38 000 µg/L. The concentration of As in all the wells studied decreased with increasing distance from the dumping-ground. A follow-up study in the affected areas eight years later (Chakraborti et al. 1998) showed that total As in these wells had decreased only 10–15%. Eight people who had arsenical skin lesions died, three died from internal cancer. Figure 1.9 shows an As-affected family from PN Mitra Lane.

Figure 1.5 The present As-affected areas and blocks of West Bengal, India.

Hyderabad, Andhra Pradesh

Patancheru in Medak district of Andhra Pradesh in India is an industrial estate and one of the worst places of environmental decay, with many reported cases of As poisoning (Kishan 2001). Arsenic has been reported in high concentrations in these areas (Dhar et al. 1998; Gurunadha et al. 2001; Govil et al. 2001). Many soil, groundwater and surface water samples obtained from the study site contained elevated levels of As (Govil et al. 1998).

The main source of As has been identified as Park Trade Center, Gaddapotharam Bulk Drug Factory, which makes veterinary drugs based on arsonic acid. There are also other sources, such as the pesticide and drug intermediate industries (Anjaneyulu 1999). The solid wastes of these industries are indiscriminately dumped near Kazipally Lake (Anjaneyulu 1999), representing a source of contamination to nearby surface water and soils (Kishan 2001). Recently, Chandra Sekhar et al. (2003) assessed the possible entry of As into human systems near areas with high As concentrations in surface and groundwater. This is one of the major sources of As entry into the human system. It was observed that AsV occurs more than AsIII, with a ratio of 4:1. Vegetables grown in these contaminated soils are rich in As (0.87–12.8 mg/kg), another possible source of As entry into the human food chain (Chandra Sekhar et al. 2003).

North India

A preliminary study on As in dug wells, hand-pumps and spring-water (Datta & Kaul 1976) was reported in 1976 from Chandigarh and different villages of Punjab, Haryana and Himachal Pradesh in northern India. Levels of As as high as 545 µg/L were found in water samples from a hand-pump. Datta (1976) further reported high As content in the liver of five out of nine patients with non-cirrhotic portal hypertension (NCPH) who had been drinking As-contaminated water. It was further stated (Datta 1976) that ‘Cirrhosis (adult and childhood), non-cirrhotic portal fibrosis (NCPF) and extra hepatic portal vein obstruction in adults are very common in India and suggest that consumption of As-contaminated water may have some role in the pathogenesis of these clinical states’. To date no further information on As poisoning from northern India is available.

Rajnandgaon district, Chattisgarh

The state of Chattisgarh was within the state of Madhya Pradesh before 2000. Groundwater As contamination in a few villages in Rajnandgaon district of Chattisgarh was reported in 1999 (Chakraborti et al. 1999). The source of As in groundwater is natural and geologic and from the rocky belt of Dongargarh-Kotri zone of Rajnandgaon district. Total population of the district is 1.5 million. In the 146 groundwater samples collected from 22 villages of Chowki block, As exceeded 10 µg/L in eight villages and 50 µg/L in four villages, with a highest concentration of 880 µg/L. The difference between As contamination in West Bengal and Rajnandgaon district is that dug wells in West Bengal are not As-contaminated but in Rajnandgaon some dug wells and some hand tube-wells are As-contaminated, with the highest concentration of 520 µg/L reported from a dug well.

Arsenical skin lesions were reported in 42 adults out of 150 examined and nine children out of 58. An As-poisoned patient with a non-healing ulcer from Rajnandgaon district is shown in Figure 1.7 (see p. 249). About 75% of people had As in hair above the toxic threshold level (n = 150). Neurological studies performed on 61 persons showed positive signs of poisoning in 34% of the population examined. Another study revealed that the number of people at risk is 10 000 (Pandey et al. 1999).

Iran

In Iran, as in many other countries, naturally occurring As is responsible for As contamination in drinking-water (Mosaferi et al. 2003). Water from springs, dug wells and deep wells are used for drinking purposes. Kurdistan, a western province of Iran, is facing an As contamination problem: As is present in drinking-water of rural areas of this province. As a result, chronic poisoning manifestations such as skin lesions, keratosis, pigmentation and even amputation due to gangrene are reported in these villages. Exposure to As in some villages of this area has occurred for more than 30 years. The first cases of chronic As poisoning due to drinking-water were diagnosed in 1981 (Mosaferi et al. 2003). However, no scientific and systematic study has been conducted in the region. Some villages have As in water supplies exceeding 1000 µg/L, with an average concentration of 290 µg/L. Measurements have shown levels in some water resources as high as 1480 µg/L (Mosaferi et al. 2003).

Japan

Fukuoka prefecture

In March 1994, As above the tolerance level (10 µg/L) was detected in wells in the southern region of Fukuoka prefecture, Japan (Kondo et al. 1999). The highest As concentration detected was 293 µg/L, quite high compared to other As-containing wells reported in Japan.

Mexico

Chronic As exposure via drinking-water was reported in six areas of Lagunera region in the central part of North Mexico, with a population of 200 000, during 1963–83 (Cebrian et al. 1983). The total As concentrations in well-water were 8–624 µg/L and concentrations greater than 50 µg/L were found in half the samples examined. Most of the As was in inorganic form with AsV the predominant species in 93% of the samples (Del Razo et al. 1990) and AsIII predominant in the rest. High concentrations of fluoride in the range 500–3700 µg/L were also reported in the samples (Del Razo et al. 1993).

The symptoms were cutaneous manifestations (skin pigmentation changes, keratosis and skin cancer), peripheral vascular disease (black-foot disease), gastrointestinal disturbances and alteration in the coporphyrin/uroporphyrin excretion ratio (Albores et al. 1979). The proportion of individuals (per age group) affected with cutaneous lesions increased with age until the age of 50. The appearance of skin lesions as calculated was eight years for hypopigmentation, 12 years for hyperpigmentation and palmo planter keratosis, 25 years for papular keratosis and 38 years for ulcerative lesions (Cebrian et al. 1983). The source of As is assumed to be volcanic sediment (Del Razo et al. 1990).

Nepal

About 47% of the total population of Nepal lives in Terai region and 90% of them rely on groundwater as the major source of drinking-water. Recently, As contamination of groundwater has been recognized as a public health problem in Nepal (Tandukar et al. 2001; Shrestha et al. 2003). So far 15 000 hand tube-wells have been analyzed, of which 23% contain As above 10 µg/L and 5% above 50 µg/L. Maximum As concentration of 2620 µg/L was reported from Rupandehi district (Tandukar et al. 2001). It is estimated that around 0.5 million people in Terai are living at risk of As poisoning. Some recent studies have also reported 1.3–5.1% of dermatosis related to arsenicosis (Tandukar et al. 2001; Shrestha et al. 2003).

New Zealand

In 1939, Grimmet and McIntosh described As contamination in groundwater and the related effects on livestock (Grimmet & McIntosh 1939). In 1961, high levels of As were found in water from areas of thermal activity. Thermal water in New Zealand contains As up to 8500 µg/L (Ritchie 1961). Aggett and Aspell (1978) studied the nature of As in water samples in the geothermal bores and reported that more than 90% of the As was present as arsenite (AsIII). For further information on As in New Zealand readers are referred to Chapter 35.

Poland

A small case was observed in Poland in 1898 with skin cancer reported among the affected persons. However, there is no published data on this incident.

Sri Lanka

In a clinical study of 13 cases of polyneuropathy connected with As poisoning in Sri Lanka, Senanayake et al. (1972) found Mee’s line (transverse white bands across fingernails) to be the constant feature at least six weeks after the onset of initial symptoms. In seven of these cases, the source of As was contaminated well-water; four others had a long history of consuming illicit liquor.

Spain

Manzano and Tello summarized their experiences in treating As poisoning caused by well-water in certain areas of Spain (Manzano & Tello 1955).

Taiwan

An As-contamination incident in well-water on the south-west coast of Taiwan (1961–85) with a population of 140 000 is well documented (Tseng et al. 1968; Thornton & Farago 1997; Yeh 1963). In the surveyed villages, the As content of tested well-water ranged from 10–1820 µg/L. Most of the well-water in the endemic area had an As content of 400–600 µg/L. The predominant As species in the well-water was arsenite (AsIII), with an average AsIII to AsV ratio of 2.6. Chronic arsenicism was observed in a population of 40 421 in 37 villages, along with 7418 cases of hyperpigmentation, 2868 of keratosis and 360 of black-foot diseases (Chen et al. 1988). Some cases of cancer (liver, lung, skin, prostate, bladder, kidney) were observed in the endemic areas (Tseng et al. 1968; Yeh 1963; Chen et al. 1988; Tsai et al. 1998; Guo et al. 1997; Bates et al. 1992; Lu et al. 1975).

The source material of the As is likely to be pyretic material or black shale occurring in underlying geological strata (Thornton & Farago 1997). It was originally thought that As alone was responsible for black-foot disease in the area (Wu et al. 1989). But the discovery in 1975 of fluorescent compounds in these well-waters led to the isolation of humic substances which, in combination with As, are now thought to be the probable cause of black-foot disease (Lu 1990). Diseases such as cancer, diabetes mellitus, cardiovascular anomalies, hypertension and cerebral apoplexy occurred at statistically significantly higher levels than in areas free of black-foot.

To minimise human exposure to As in the As-endemic areas of Taiwan, a water treatment plant removes As from groundwater before use.

US

Millard county, Utah

West Millard county is a desert area of Utah with low population density and around 250 people drinking well-water with As concentrations of 180–210 µg/L; the predominant As species is AsV (86%) (Southwick et al. 1983). Participants were examined for specific signs of As toxicity, including dermal signs. Typical signs and symptoms of As intoxication were not found in any of the study participants. Participants from Deseret had the highest average As concentration in urine of 211 µg/L (n = 40) and Hinckley participants had 175 µg/L (n = 95), compared to control from Delta of 48 µg/L (n = 99). The highest average As concentration in hair was 1210 µg/kg (n = 80) from Hinckley residents, and that of Deseret residents was 1090 µg/kg (n = 37) compared to control from Delta of 320 µg/kg (n = 68). Lewis et al. (1999) reported hypertensive heart disease, nephritis, neprosis and prostate cancer among people in the As-affected areas of Utah.

Western Oregon

Water of several wells in central Lane county, located in Western Oregon midway between the Columbia River and the northern boundary of California, were contaminated with As ranging from 50–1700 µg/L from November 1962 to March 1963 (Goldblatt et al. 1963). Wells in Eugene, Creswell and Grove districts in central Lane county known to yield As-rich groundwater occur in an area where there is an underlying group of sedimentary and volcanic rocks that geologists have named the Fisher Formation (Hoover 1963).

Lessen county, California

In Lessen county, California, As poisoning from well-water containing As in the range 50-1400 µg/L was reported during 1970 (Goldsmith et al. 1972). It was found that from drinking-water with As exceeding 50 (±30) µg/L there was an increase of As content in hair, indicating body burden due to As exposure (Goldsmith et al. 1972).

Fallon, Nevada

Viz et al. (1984) were unable to detect any increase in chromosomal aberrations or sister chromatid exchange in residents of Fallon, Nevada, in 1984 where concentrations of As exceeding 100 µg/L were recorded in drinking-water. The literature indicates that the health of these people who were exposed to As was not adversely affected.

New Hampshire

Arsenic concentrations were measured in 992 drinking-water samples collected from randomly selected New Hampshire households. Concentrations up to 180 µg/L were found, with water from domestic wells containing significantly more As than that from municipal sources. Water samples from drilled bedrock wells had the highest As concentrations, while samples from surficial wells had the lowest. These researchers (Peters et al. 1999) suggested that much of the groundwater As in New Hampshire was derived from weathering of bedrock materials and not from anthropogenic contamination. Analysis of rock digests indicates As concentrations up to 60 000 µg/kg in pegmatites, with much lower values in surrounding schists and granites.

Fairbanks, Alaska

In the well-water and springs of Fairbanks, Alaska, As exceeding 50 µg/L was found (Wilson & Hawkins 1978). A study was initiated to evaluate the As content of streams and groundwater of the Pedro Dome summit area, about 30 km north of Fairbanks in the heart of the historic Fairbanks mining district. Arsenic was associated with gold mineralization and is believed to reach the area’s water through weathering of As-containing rocks. The As concentration in 53 water samples from wells and springs ranged from <5-70 µg/L. Eighty per cent of the samples contained <10 µg/L, and 95% contained <50 µg/L (Wilson & Hawkins 1978). The concentration of As in 243 wells was <50->100 µg/L. Well-water As concentrations in the Ester Dome study area was <1000-14 000 µg/L, and for the study population was <1000- 2450 µg/L with a mean As concentration of 224 µg/L. An epidemiological study done in 1976 (Harrington et al. 1978) suggested that there were no clinical or hematological abnormalities among these people.

Vietnam

The first report on As contamination of the Red River alluvial tract in the city of Hanoi and in the surrounding rural districts was published in 2001 (Berg et al. 2001). The contamination levels varied from 1-3050 µg/L in rural groundwater samples from private small-scale tube-wells (n = 196) with an average As concentration of 159 µg/L. In a highly affected rural area, the groundwater used for drinking had an average concentration of 430 µg/L. Analysis of raw groundwater pumped from the lower aquifer for the Hanoi water supply show As levels of 240-320 µg/L in three of eight treatment plants and 37-82 µg/L in another five plants. The high As concentrations found in the tube-wells indicate that several million people consuming untreated groundwater might be at considerable risk of chronic As poisoning (Berg et al. 2001; Chapter 29).

Contamination from industrial sources

Australia

In Australia, old stocks of lead arsenate used as pesticides before 1970 remained in sheds and caused chronic As poisoning among workers (Tallis 1989). Recently, Smith et al. (2003) summarized the behavior of As in the environment, with particular emphasis on the sources, distribution and accumulation of As in the Australian environment. They reported the presence of both anthropogenic and naturally occurring As. Unlike most of the other countries where As poisoning and elevated concentrations of As in water have been reported, groundwater As in Australia was reported to range between 1–5000 µg/L (Hinwood et al. 1998). Arsenic in the Australian environment is further detailed in Chapter 37.

Bulgaria

Srednogorie

Arsenic was found in soils sampled from a copper smelter located near Srednogorie with a population of 32 000 inhabitants and the largest metallurgical center in Bulgaria (Nilsson et al. 1993). The smelter started operation in 1959 and processed sulfide ores containing high As. The ores were mainly from Tjelopetch, which caused contamination of Topolnitza River water. Samples from this river showed As concentration ranging from 750–1500 µg/L from 1987 to 1990. The aerial emission is estimated as 50–100 tons per year. Exposure to the general population is mostly by inhalation and partly by ingestion of locally produced food products such as vegetables. Several health problems were observed around the area of the exposed population, for example high As content in hair, nails and urine.

Canada

Vegetation and soil samples collected in 1974 in the vicinities of two secondary lead smelters located in a large urban area near Toronto, Ontario, showed As over 30 times higher than normal urban background levels of As in unwashed plant foliage, and 200 times higher than normal soil which was found 200 m away from the smelters (Temple et al. 1977).

China

Guizhou province

In Guizhou province some coals containing high As (100–9600 mg/kg) and fluorine caused As poisoning among residents in one city and four prefectures. The local inhabitants used the Asrich coal for cooking, keeping warm and drying grains and peppers in kitchens, so the food and indoor air were seriously contaminated by As. Approximately 3000 patients were found by 1992. According to the research conducted by the Institute of Geo-Chemistry of the Academia Sinica during 1991 and 1994 in Xingren county, of 9202 people investigated 1546 people were affected by arsenicism. The average daily intake of As per person in the affected area was estimated to be 2400 µg, of which 87.92% came from food, 5.53% from air and 6.55% from drinking-water (see Chapter 32 for an overview of As in China). In addition to skin lesions characteristic of As poisoning, many people had cirrhosis, ascites, polyneuritus and skin cancer (Hotta 1989). Zheng and Long (1994) and Sun et al. (2001) reported this incidence. Figure 1.8 (see p. 250) shows an As patient from Guizhou province showing symptoms of fluorosis caused by increases of fluoride in potable water.

Figure 1.9 An As-affected family from PN Mitra Lane, Calcutta

Yunan

Typical As poisoning was found in 1993 in a non-ferrous smelter township with a population of 100 000 in the southern Yunan province. The concentration of As in the air around the smelter always exceeded the national maximum allowable (3 µg/m³) by several-fold. One serious problem was that As-containing air contaminated the food (rice and corn) grown in the area (Sun et al. 2001). A local survey indicated that the main source of As intake of local residents was food, responsible for more than 90% of total As intake; less than 10% is attributable to direct inhalation. By interpolation, the daily As intake is in the range of 300–1100 µg. In 1992, WHO suggested that a daily intake of 2 µg of inorganic As per kg of body-weight should not be exceeded (WHO 1992).

Czechoslovakia

Poisoning among people living near a plant burning coal that contained 900–1500 mg As/kg was attributed to that source (Bencko & Symon 1977).

Germany

Exposure to As-containing pesticides and contaminated wine was claimed to be the causative factor in the large number of cases of liver cirrhosis among German vintners in the 1940s and 1950s (Roth 1957). Of 180 vinedressers and cellarmen with symptoms of chronic As poisoning, about 25% showed vascular disorders of the extremities (Butzengeiger 1940). Of 27 moselle vintners autopsied between 1950 and 1956, 11 had lung cancers and three had hepatic angiosarcomas (Roth 1957). The number of cases diminished in the late 1950s although less severe liver changes are found regularly among vintners (Luchtrath 1972; Wolf 1974). Between 1960 and 1977, 163 post-mortem examinations of German winegrowers were diagnosed (on the basis of cutaneous signs) as having had chronic As poisoning. Luchtrath (1983) found five cases of liver tumors; none were angiosarcomas.

Ghana

Arsenic in drinking-water from streams, shallow wells and bore-holes in the Obuasi goldmining area of Ghana ranges from <2–175 µg/L. The main source of pollution was mining activities and oxidation of naturally occurring sulfide minerals, predominantly arsenopyrite (FeAsS). Some of the water samples had a high AsIII content. This was attributed to the leaching of soils containing kaolinite, muscovite and laterites overlying saprolite (Bowell 1993). It is reported that, in the saprolite, arsenopyrite appears to have been replaced by secondary As- and Fe-bearing minerals, including scorodite (FeAsO4.2H2O), arsenolite and arsenates (Bowell 1992).

Greece

Systematic sampling of soils and dusts in and around the ancient lead-mining and smelting site at Lavrion, Greece, indicated extensive contamination with both As and lead. This instigated studies into possible health implications for the local community (Stavrakis et al. 1994). Arsenic concentrations in garden soil and house dusts ranged up to 14 800 mg/kg and 3800 mg/kg respectively.

Japan

Nakajo

Wastewater from a factory producing As sulfide contaminated nearby well-water in Nakajo, Japan, in 1960 (Tsuda et al. 1989). Melanosis, hyperkeratosis, cardiovascular disease, haepatopathy and hematologic abnormalities were observed among the residents of Nakajo.

Toroku and Matsuo

Toroku is a small mountain village to the north of Miyazaki prefecture, with a population of about 300. Arsenious acid was produced there by roasting arsenopyrite ore from 1920 to 1962 (Hotta 1989). Matsuo is a similar village. It produced white As by calcinating arsenopyrite at very primitive stone furnaces for nearly half a century from 1920. In this system about 10% of As2O3 was lost as fumes through the refining process. The As-rich remains of calcinated ore were dumped into the river. Many mine workers and nearby residents died from acute and sub-acute As poisoning. A six-year follow-up study revealed a high prevalence of malignant neoplasms, especially in the respiratory tract, as the main cause of death (Tsuda et al. 1990). A total of 147 persons were examined during the study, of whom 125 were diagnosed with chronic As poisoning. As of 1995, there were 153 patients in Toroku and 64 in Matsuo who were recognized by the government as suffering from chronic As poisoning (Yokoi 1995).

Other incidents

A severe cutaneous manifestation of chronic As poisoning was detected in seven out of 28 male Japanese workers who were exposed to As in the form of lead arsenate and calcium arsenate used in the manufacture of insecticides (Horiguchi et al. 1977). The lesions were symmetric punctuated palmo-plantar hyperkeratosis and bronze hyperpigmentation.

A retrospecific cohort study of a Japanese population between 1954 and 1959 used well-water contaminated with As from a dye factory. During the follow-up period until 1987, there were 18 deaths from cancer, of which seven were from lung cancer.

Mexico

In the city of Torreon, Mexico, the presence of As ranging from 4000–6000 µg/L in drinking-water from a deep well was reported in 1977 (Williams et al. 1977). In Silesia, spring-water was contaminated by the leaching of As from mining wastes (coal preparation wastes and fly ash from coal-fired power plants) (Williams et al. 1977).

Northern Sweden

At the Ronnskar smelter in northern Sweden, ores with a high As content were handled. Women employed in the plant, as well as those who lived nearby, delivered babies with significantly lower birth weights than those delivered by women not so exposed (Nordstrom et al. 1979). Among women exposed to As, the frequency of spontaneous abortion was generally higher with closer proximity of residence to the smelter (Aschengrau et al. 1989). Although residential proximity to the Ronnskar smelter had no effect on the incidence of congenital malformations, pregnancies during which the mother worked at the smelter were significantly more likely to result in babies with single or multiple malformations, particularly urogenital malformation or hip-joint dislocation (Nordstrom et al. 1979).

Philippines

Mindanao Island

Soon after the construction of a geothermal power plant on Mt Apo in January 1992, people living downstream along the Matingao and Marbol Rivers, which run through the construction site, complained of symptoms such as eruption, headache and stomach-ache. An environmental investigation carried out in August 1993 revealed that river water downstream of the construction site contained 100 µg/L of As and hair samples of some residents showed elevated concentrations of mercury and manganese as well as As (Hironaka 1995). The construction of the geothermal power plant was suspected as the cause of As contamination. In 1995, a medical survey of 39 residents with skin rashes revealed that a few were suspected to be suffering from chronic As poisoning (Hironaka 1995).

Southern Rhodesia

There was excess lung cancer mortality among southern Rhodesian miners of gold-bearing ores containing large amounts of As (Osburn 1957).

Thailand

Ronphibun

In 1987, the skin manifestations of chronic As poisoning were diagnosed among the residents of Ronphibun district, Nakorn Srithammarat province of Thailand (Choprapawon & Rodcline 1997). Some 85% of all reported cases of chronic As poisoning were from Ronphibun subdistrict of Ronphibun district. Most cases were relatively mild, but 21.6% had very significant lesions (Rodklai 1994). Ronphibun district has eight subdistricts and 65 villages, with a total population of 14 085. The main income was from mining and farming. Three out of 14 villages have 20% of the subdistrict population and account for 61% of the cases. The people in those villages used water which drains from the highly contaminated areas of Suan Jun and Ronna Mountains, with 0.1% arsenopyrite. The Department of Geology, Ministry of Industry (1998), investigated the source of As contamination and postulated that contamination was from arsenopyrite probably related to the mining process that had occurred in the area for a hundred years. Oshikawa et al. (2001) reported the long-term changes in arsenical skin lesions among the population. Recently, Pavittranon et al. (2003) carried out a follow-up study of the population of 7785 in the Ronphibul subdistrict, Nakorn Srithammarat province, southern Thailand.

UK

From 1910 to 1943, a British plant manufactured sodium arsenite which was used in dips to combat sheep ticks (Hill & Fanning 1948; Perry et al. 1948). The factory was in a small country town within a specific birth and death registration subdistrict. Here, 75 deaths were reported among factory workers, of which 22 (29%) were due to cancer.

In Armadale, a town in central Scotland (Lloyd 1978; Smith & Lloyd 1986) with a population of 7000, the standardized mortality ratio for respiratory cancer was high from 1969 to 1973 due to exposure to As from a steel foundry located in that area. The soil As concentrations in Armadale were generally higher (52–64 µg/g) than those in the control uncontaminated samples.

US

A serious incident of air pollution by As from copper smelters was recorded in Anaconda, Montana, with the rate of emissions of arsenic trioxide of 16 884 kg/day (Hawkins & Swain 1907; Haywood 1907). Although no atmospheric concentrations were on record, edible plants contained As2O3 up to 482 µg/g, causing a serious health hazard in the surrounding area. Mortality from ischemic heart disease significantly increased among As-exposed workers at the smelter (Welch et al. 1982). The initial 1938–1963 mortality analysis of workers at the Anaconda copper smelter demonstrated a more than three-fold excess respiratory cancer ratio, with excess risk as high as eight-fold among heavily exposed men who had worked there eight years or more (Lee & Fraumeni 1969).

A serious incident of air pollution by As also occurred in a small western town near a gold smelter, manufacturing 36 tons of As2O3 per day (Birmingham et al. 1965). Some studies (Pinto & McGill 1953; Milhan & Strong 1974) involved a copper-smelting plant at Tacoma in the state of Washington that produced As2O3 as a byproduct. The plant had an average employment of 904 during 1944 to 1960 when a total of 229 deaths were reported among active plant employees, 38 of them classified as due to As exposure. Of the 38, six died of cancer, including three cases of cancer of the respiratory tract.

Perham was a town of 1900 situated in the agricultural area of western Minnesota (Feinglass 1973). In May 1979, a contractor for a high-rise building expanded his facilities by building a warehouse and office structure on the outskirts of town; about 13 people worked on the premises. A well was driven and operated for the next 2.5 months. A core sample to a depth of 20 cm revealed 3000 mg/L of arsenic. In early May, a non-febrile illness characterized by nausea, vomiting and sporadic illness occurred with occasional clusters of cases over the next 10 weeks. Of the 12 non-exposed persons, one reported a single episode of vomiting and one reported an episode of cramps of diarrhea. There were 11 positive responses among the 13 employees. The number and severity of symptoms were related to the amount of water consumed. Nine of the 13 workers reported nausea or vomiting, seven abnormal pain and five diarrhea. The symptoms of sub-acute or chronic As intoxication were confirmed for the three persons out of 13 with the highest intake.

Arsenic in food and beverages

England

Beer incident in Manchester

About 500 patients in northern England who consumed 2–16 pints of As-contaminated beer a day (1.14–9.12 L/day) for many months developed cardiac, skin and neurologic symptoms (Royal Medical and Chirurgical Society 1901). Testimony before a Royal Commission from various chemists repeatedly demonstrated the presence of toxic amounts of As in beer from several parts of the country (Royal Commission Meeting 1901).

Japan

Soya sauce incident

Several instances of accidental As poisoning through contaminated foodstuffs have been reported in Japan. Soya sauce which contained As of 5600–71 600 µg/L was implicated in a toxicity outbreak. Arsenic was found in the amino acids (260 000–275 000 µg/L) used during preparation of the sauce. It is likely that hydrochloric acid may have been the source of As in the preparation of amino acid (Nose 1957). Mizuta et al. (1956) examined 220 out of 417 patients who had been poisoned by soya sauce contaminated with inorganic As at a concentration of 100 µg/L. The main findings were facial edema, anorexia and upper respiratory symptoms, followed by skin and neuritic signs after 10–20 days. Though the livers of most patients were enlarged, relatively few abnormalities were found in the liver function tests and liver size gradually decreased after cessation of exposure. Abnormal electrocardiograms were found in 16 out of 20 cases tested (Levander 1977).

Powdered milk incident

Contaminated powdered milk was implicated in a similar outbreak in Japan. It contained As ranging from 13 500–21 000 µg/kg (Kitamura & Kasuyama 1955). Contamination of the milk was from sodium phosphate (7.11% As) used in its manufacture (Kodama et al. 1955). This suggests that the manufacturers of food products must ensure analytical-grade chemicals.

Conclusion

Arsenic contamination in groundwater is a serious threat to humans all over the world. It can also enter the food chain (see Chapters 13 to 15), causing widespread distribution throughout plants and animals. However, fish, fruits and vegetables primarily contain organic rather than inorganic As, although the As content of many foods (milk and dairy products, beef and pork, poultry and cereals) is mainly inorganic, typically 65–75%. A few recent studies report 85– 95% inorganic As in rice and vegetables, which suggest more studies are needed to know the extent of As contamination. Humans are exposed to this toxic As primarily from air, food and water. Hundreds of thousands of people are suffering from the toxic effects of arsenicals worldwide due to groundwater contamination as well as industrial sources. Arsenic causes a variety of adverse health effects to humans after acute and chronic exposures, such as dermal changes (pigmentation, hyperkeratoses and ulceration), respiratory, pulmonary, cardiovascular, gastrointestinal, hematological, hepatic, renal, neurological, developmental, reproductive, immunologic, genotoxic, mutagenetic and carcinogenic effects. More studies are urgently needed to improve As risk assessment at low exposure levels, by all scientists.

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