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The Arsenic Foundation
"It is an uncanny
thought that this lurking poison (arsenic) is everywhere about
ready to gain unsuspected entrance to our bodies from the food we eat,
the water we drink and the air we breathe" Karl Vogel, 1928.
Arsenic has been used since 3000 BC. In the United Kingdom, for example, it was used to extract iron from iron ore. It has long been known that arsenic is acutely toxic. Anyone who drinks arsenic in water at 60 parts per million (ppm) will soon die. There are several toxicological summary references for acute effects available on the web such as SCORECARD, ASTDR, USEPA and LSUMC.
Arsenic has been used for many years for medicinal purposes. It used to be used as a cure for diseases such as syphilis and has been shown to assist in curing some leukemias. It was taken as a medicine in Fowler's Solution for well over a century. That arsenic at low levels is safe seemed to be reinforced by animal studies that seemed to show that arsenic is beneficial (to animals) at low doses. Indeed, the fact that laboratory animals could not be persuaded to develop cancer misled toxicologists throughout the world and greatly contributed to the present catastrophe. Others have written about other possible beneficial effects at very low levels. It is important to note that the beneficial effects are for different medical outcomes (end points) than either the acute or chronic adverse effects and that both beneficial and adverse effects can be observed simultaneously (as is well known for alcohol ingestion). Another detailed article about beneficial uses of arsenic can be found here. Mineral hot springs in the USA still advertise arsenic pools and their users, including this webmaster, are convinced that the effects are beneficial! (But arsenic penetrates the skin only slowly).
Chronic effects of prolonged low level exposure have recently showed up. Among various summaries we link to an information site run by ASTDR. Skin pigmentation, keratosis and skin cancers were found by Tseng in Taiwan in 1966 among people who drank from arsenic contaminated wells (but no effect was seen below about 150 parts per billion (ppb), which might therefore be a biological threshold) and a very high incidence of lung, bladder and other cancers was found in Taiwan by Dr. Chien-Jen Chen in 1986 and by Dr. Allan Smith and collaborators in Chile in 1993. These convinced WHO to recommend lowering the regulatory level from 50 ppb to 10 ppb for arsenic in water. It appears that there are no data on humans to contest the idea that prolonged exposure to low doses is dangerous. Although arsenic was used medicinally in "Fowler's Solution" (1% arsenite), prolonged use had led to these chronic skin effects. This was observed as early as 1888 by Hutchinson. A follow up of a number of English patients treated with Fowler's Solution has been reported by Dr. Susan Evans in published literature, in a report at the February 1998 conference in Dhaka and in a presidential address by Susan Evans to the Liverpool Medical Institute, which is available for download in PDF format. This shows that the use of "Fowler's solution" (which is primarily medicinal arsenic) in the UK is probably responsible for 5 bladder cancer cases among the patients among whom only 1.6 were expected from natural causes. The arsenic dose was equivalent to an average lifetime dose that would come from drinking water with about 25 ppb of arsenic therein.
After several years of low level arsenic exposure, various skin lesions appear. These are manifested by hyperpigmentation (dark spots), hypopigmentation (white spots) and keratoses of the hands and feet. After a dozen or so years skin cancers are expected. Twenty or thirty years after exposure to 500 ppb of arsenic, internal cancers (lung, kidney, liver and bladder) appear among 10% of all exposed. Moreover, the dose-response relationship for these internal cancers is consistent with being linear with no threshold. Photographs of a number of victims of this poisoning are available both from Bangladesh and from Inner Mongolia.
Although the most dramatic effect was the observation of internal cancers in Taiwan, the most extensive epidemiological studies have come from the work in Chile, in which Dr. Allan Smith of UC Berkeley has been heavily involved. They find the extraordinarily surprizing result that ingested arsenic in Chile has produced lung cancer at a rate greater than that of a heavy cigarette smoker! Recently, the group identified an effect of arsenic exposure to children - who have developing lungs -. Children exposed to arsenic have ten times the normal lung cancer incidence.
An important issue for coping with arsenic exposure is the effect of diet. A general issue can be stated: there is frequently more than one cause of a cancer or a lesion. For example lung cancer can be caused by cigarette smoking or asbestos or both together, in a synergistic way such that the risks multiply (rather than add) when both are present. In the USA it has been found that people who have a good diet of fresh fruit and vegetables (5 servings per day) have half the risk of many cancers, including lung cancers caused by cigarettes, as those without a good diet. By analogy, one might expect that the lung cancer risk from arsenic will be less among those with a good diet. Anecdotal indications from Bangladesh suggests that a good diet reduces skin lesions, and the effect is seen in West Bengal, but the effect is small and the authors recommend that effort is better spent on obtaining pure water. Nonetheless epidemiological studies to confirm this are highly desirable. Khaliquzzaman and Khan have calculated the "Arsenic Exposure of Bangladesh Population through Food Chain" using known amounts in food, in an unpublished World Bank report. The amount is less than from drinking water but not much less.
There are several specific chemicals that have been suggested that would either (I) help to prevent arsenic lesions by rapid removal of arsenic from the body or (ii) help to cure arsenic lesions. Encouragement of methylation of the arsenic probably accelerates methylation, but the methylation has been suggested as a cause of internal cancers. The specific chemical that has come to the mind of many health experts is selenium. It was noted in the 1930s that effects of excess selenium can be counteracted by adding arsenic to the diet because As and Se combine. Does the inverse take place? It is reported that areas with high incidence of arsenical lesions have low selenium in the water. Some victims have low selenium levels. Does adding selenium to the diet really help, either to prevent the lesions from forming (likely), or to treat them afterwards (less likely)? We have, with help from others, compiled a list of references and a recent paper on the subject. Professor Zuberi of Rajshashi University has suggested methionine to reduce the arsenic lesions. Dr. OGB Nambiar has suggested that ferrous sulphate, after conversion to sulfide by bacteria in the colon, absorbs arsenic and assists safe excretion. The evidence for these remains indirect, and there may be (as suggested above) competing adverse effects. Only good epidemiology can tell and this is under way in several places.
The regulatory limits on arsenic exposure were set primarily to be sure that these acute toxic effects were avoided. The first regulatory limit of which the webmasters are aware was set as a result of a public inquiry (subsequent to arsenic being found in beer) of six members chaired by the physicist William Thompson, first Lord Kelvin, in 1903. They recommended that sake of liquids with more than 100 grains of arsenious oxide per gallon (which works out at about 90 ppb of arsenic or 0.09 ug/l) This was reduced two fold over the next century and until recently the limit set by Bangladesh, the United Kingdom, and the United States was 50 parts per billion (ppb). But the discovery that there are adverse effects of continuous chronic exposure led WHO to lower their recommendation to 10 parts per billion (10 ppb). The European Union (EU) plans to enforce a standard of 10 ppb by 2003. After a long travail, on October 31st 2001, the administrator of US EPA confirmed a new standard for drinking water of 10 ppb to be enforced by 2006. In Australia there does not seem to be a specific regulatory level but there are work rules for those working around mine tailings sites.
The US EPA has recently come out with an extensive review of mechanisms of action of Dimethyl Arsenic (DMA) and its possible mechanisms of action. They cannot rule out a linear dose response at the lowest doses. It is effectively impossible to reduce the content of arsenic in drinking water to a risk level of one in a million lifetime risk calculated with a linear dose-response relationship, a risk level and a calculational procedure frequently used by the U.S. EPA. The present 10 ppb standard is perhaps the first in which the U.S EPA explicitly compared costs and benefits and used a value of $6.1 million per calculated life saved. References to the extensive US national discussion are available on the "countries" page and in particular the section on travail.
Arsenic contamination has become a problem in many parts of the world. At first as a result of leaching from mine tailings in Australia, Canada, Japan, Mexico, Thailand, United Kingdom, and the United States, but now also from the arsenic in natural aquifers now or recently used for water supply in Argentina, Bangladesh, Cambodia, Chile , China, Ghana, Hungary, Inner Mongolia, Mexico, Nepal, New Zealand, Philippines, Taiwan, the United States and Vietnam. Arsenic was also widely used as a pesticide. 20,000 tons a year was imported into the USA, and perhaps double that amount was used, to spray on crops in the USA alone. No attention was paid to the ultimate fate of the chemical, and in consequence arsenic now appears in foodstuffs . (Papers describing data in some of these countries are listed by country in the list of useful references. ) It is important to distinguish the problems in Bangladesh, West Bengal and, to a lesser extent, Inner Mongolia, Chile, Nepal and Vietnam, from the problems that have been found so far in the rest of the world. These situations have in common that they are an alluvial plain where arsenic has been brought down from the surrounding hills for millennia. It seems that no one has looked carefully at similar geological situations such as the Mekong delta or the Irrawaddy delta. In most of the world exposures above 50 parts per billion (50 ppb) are rare, and once observed, can easily be avoided. But the sheer scale of the problems in Bangladesh dwarfs the imagination. The catastrophe is much worse than the well-known catastrophe of the Chernobyl nuclear power plant accident, the Bhopal isothiocyanate leak or the Kuwait oil fires. For 90% of the Bangladeshi communities, pure water is still a long time away.The World Bank made a study for SE Asia in the beginning of the 21st century which is available on the web:
"Arsenic Contamination of Groundwater in South and East Asian Countries"
Volume I: Policy Report Full Report (1,038kb pdf)
Volume II: Technical Report Full Report (2,879kb pdf)
Paper 1: Arsenic Occurrence in Groundwater in South and East Asia -- Scale, Causes, and Mitigation (715kb) Paper 2: An Overview of Current Operational Responses to the Arsenic Issue in South and East Asia (413kb) Paper 3: Arsenic Mitigation Technologies in South and East Asia (345kb)
The situation in Bangladesh has received a lot of attention because it is the most important. The new Bangladeshi government has made the solution of the problem a priority as stated clearly by Prime Minister Begum Khaleda Zia as she opened the special WHO workshop in Dhaka on January 14th -16th 2002. Feroze Ahmed presented an excellent review of the situation at that time. Participants made recommendations to the government of Bangladesh (GoB). Another (2002) review from the NGO forum is copied here from the NAISU website in pdf. Professor Chakriborti of Kolkata (Calcutta), a tireless and enthusiastic worker in the field regularly issues his reports on the Bangladesh situation, has a year 2001 report on Bangladesh which we have also captured in a local file.
This is the subject of a whole issue of the journal Applied Geochemistry: Bhattacharya, P., A. H. Welch, K. M. Ahmed, G. Jacks and R. Naidu (Eds.)
Arsenic is plentiful in the ground. Yet it does not always appear in the water supply. Scholars at the Cambridge University Department of Geography have identified the following mechanisms for arsenic entering the water which vary between locations. Alkali-desorption, Geothermal, Reductive dissolution and Sulphide oxidation. Although the worst arsenic catastrophe is in Bangladesh, where 35 million people are exposed to levels above the US EPA standard, the amount of arsenic in the soil is less than in many other areas, including areas such as Massachusetts, USA, where it does not, nonetheless, appear in unsafe quantities in ground water. In most of these areas, such as the delta of the Ganges and Irrawaddy, and the bend of the Yellow river, arsenic has come down from the mountains over millennia, attached itself to iron, forming iron pyrites, and been deposited. Professor McArthur of UC London argues: "It becomes increasingly clear that severe arsenic pollution of ground water in most alluvial aquifers worldwide is driven by the microbially-mediated metabolism of organic matter, with FeOOH acting as the source of oxygen: the oxide is reduced during the process and its sorbed arsenic is released to ground water. Despite the widespread acceptance of this mechanism, much about it remains obscure." One issue is whether the reduction takes place at the surface before the water filters down to the aquifer in the monsoon (as suggested by group (a) below) or whether it is reduced in the aquifer itself.
Papers describing this mechanism include:
An older idea was that water was being drained from the aquifer, allowing oxidation. A recent paper describing arsenic contamination in Perth, Australia - shows that there is one location, in Perth where pyrite oxidation clearly WAS the source of the As (although there is evidence that anaerobic release from Fe oxyhydroxides is also taking place deeper in the aquifer). But the ideas that pyrite oxidation is the problem in Bangladesh whether caused by recent rapid pumping that allowed for oxidation and release of arsenic, or by the man-made change in river flow, such as the barrage across the Ganges are now considered to be untenable.
In the Americas, from Alaska in the north, through Crater Lake in Oregon, Mono Lake and Searles Lake in California, volcanic lakes in Nicaragua and Costa Rica, and on to the Andes, lie a chain of volcanic activity that brings arsenic to the surface. This mechanism of sulfate reduction in the arsenic-rich soda lakes (Mono Lake and Searles Lake) of is being studied in detail by Dr. Oremland and his group at the US Geological Survey in Menlo Park. They attribute the mechanism to bacteria, but of course different bacteria from those responsible for the reduction of iron pyrites in SE Asia and Bangladesh. Presumably this is the same mechanism as is responsible for the arsenic pollution in the mountains of Argentine and Chile where so much epidemiological studies have been made.
Western experts from developed countries often regard the arsenic pollution problem as a technical problem to be solved by purely technical means. But that is naive. There are tremendous social issues which control the ability of anyone to help. One set of papers discussing was prepared by the Arsenic Policy Support Unit in Bangladesh, (APSU) which is now defunct, but these papers are copied on this site.
The first and most obvious necessity is to measure the arsenic levels in any ground water that is intended for human use. The next step is to purify the water or, better still, provide an alternate supply of pure water. The way in which this is done varies from country to country. In SE ASIA, and Bangladesh in particular, two facets of a solution seem to be agreed.
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