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This report contains the collective views of international groups of experts and does not necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the International Labour Organization, or the World Health Organization. The first and second drafts of this monograph were prepared, under the coordination of Dr J.
Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organization, and the World Health Organization, and produced within the framework of the Inter-Organization Programme for the Sound Management of Chemicals. The International Programme on Chemical Safety (IPCS), established in 1980, is a joint venture of the United Nations Environment Programme (UNEP), the International Labour Organization (ILO), and the World Health Organization (WHO). The Inter-Organization Programme for the Sound Management of Chemicals (IOMC) was established in 1995 by UNEP, ILO, the Food and Agriculture Organization of the United Nations, WHO, the United Nations Industrial Development Organization, the United Nations Institute for Training and Research, and the Organisation for Economic Co-operation and Development (Participating Organizations), following recommendations made by the 1992 UN Conference on Environment and Development to strengthen cooperation and increase coordination in the field of chemical safety. The World Health Organization welcomes requests for permission to reproduce or translate its publications, in part or in full. Publications of the World Health Organization enjoy copyright protection in accordance with the provisions of Protocol 2 of the Universal Copyright Convention. The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the World Health Organization concerning the legal status of any country, territory, city or area or of its authorities, or concerning the delimitation of its frontiers or boundaries.
The mention of specific companies or of certain manufacturers’ products does not imply that they are endorsed or recommended by the World Health Organization in preference to others of a similar nature that are not mentioned. Every effort has been made to present information in the criteria monographs as accurately as possible without unduly delaying their publication.
A detailed data profile and a legal file can be obtained from the International Register of Potentially Toxic Chemicals, Case postale 356, 1219 Châtelaine, Geneva, Switzerland (telephone no.
This publication was made possible by grant number 5 U01 ES02617-15 from the National Institute of Environmental Health Sciences, National Institutes of Health, USA, and by financial support from the European Commission. The Commonwealth Department of Health and Aged Care, Australia, contributed financially to the preparation of this Environmental Health Criteria monograph.
The first Environmental Health Criteria (EHC) monograph, on mercury, was published in 1976 and since that time an ever-increasing number of assessments of chemicals and of physical effects have been produced. Since its inauguration the EHC Programme has widened its scope, and the importance of environmental effects, in addition to health effects, has been increasingly emphasized in the total evaluation of chemicals. The original impetus for the Programme came from World Health Assembly resolutions and the recommendations of the 1972 UN Conference on the Human Environment.
The recommendations of the 1992 UN Conference on Environment and Development and the subsequent establishment of the Intergovernmental Forum on Chemical Safety with the priorities for action in the six programme areas of Chapter 19, Agenda 21, all lend further weight to the need for EHC assessments of the risks of chemicals. The criteria monographs are intended to provide critical reviews on the effect on human health and the environment of chemicals and of combinations of chemicals and physical and biological agents.
In the evaluation of human health risks, sound human data, whenever available, are preferred to animal data.
The EHC monographs are intended to assist national and international authorities in making risk assessments and subsequent risk management decisions. Since the inception of the EHC Programme, the IPCS has organized meetings of scientists to establish lists of priority chemicals for subsequent evaluation. If an EHC monograph is proposed for a chemical not on the priority list, the IPCS Secretariat consults with the Cooperating Organizations and all the Participating Institutions before embarking on the preparation of the monograph. The order of procedures that result in the publication of an EHC monograph is shown in the flow chart on p. The draft document, when received by the RO, may require an initial review by a small panel of experts to determine its scientific quality and objectivity. The Task Group members serve as individual scientists, not as representatives of any organization, government or industry. The three cooperating organizations of the IPCS recognize the important role played by nongovernmental organizations.
All individuals who as authors, consultants or advisers participate in the preparation of the EHC monograph must, in addition to serving in their personal capacity as scientists, inform the RO if at any time a conflict of interest, whether actual or potential, could be perceived in their work. When the Task Group has completed its review and the RO is satisfied as to the scientific correctness and completeness of the document, it then goes for language editing, reference checking and preparation of camera-ready copy. All Participating Institutions are informed, through the EHC progress report, of the authors and institutions proposed for the drafting of the documents. A WHO Task Group on Environmental Health Criteria for Arsenic and Arsenic Compounds met at the National Research Centre for Environmental Toxicology, Brisbane, Australia, on 15–19 November 1999. After the meeting, and based on the peer reviewer comments and Task Group advice, Drs Gibb, Hopenhayn-Rich, Järup, Sim, and Aitio revised and updated the section on Effects on Human Health. The document was revised on the basis of the peer review comments received, these revisions were verified, and the document was finalized by a Review Board, consisting of Drs D. The cut-off date for the literature searches for the document was the Task Group meeting, i.e. The efforts of all, especially Queensland Health and the Natinal Research Centre for Environmental Toxicology, Australia, who helped in the preparation and finalization of the monograph are gratefully acknowledged.
Geographic area in south-western Taiwan, where arsenic-contaminated artesian well water has been used as drinking water, and where BFD is endemic; the area has been also called the "arseniasis" area, or "hyperendemic" area. Arsenic is present in more than 200 mineral species, the most common of which is arsenopyrite. It has been estimated that about one-third of the atmospheric flux of arsenic is of natural origin. Inorganic arsenic of geological origin is found in groundwater used as drinking-water in several parts of the world, for example Bangladesh. Organic arsenic compounds such as arsenobetaine, arsenocholine, tetramethylarsonium salts, arsenosugars and arsenic-containing lipids are mainly found in marine organisms although some of these compounds have also been found in terrestrial species.
Mining, smelting of non-ferrous metals and burning of fossil fuels are the major industrial processes that contribute to anthropogenic arsenic contamination of air, water and soil. Arsenic is emitted into the atmosphere by high-temperature processes such as coal-fired power generation plants, burning vegetation and volcanism. Three major modes of arsenic biotransformation have been found to occur in the environment: redox transformation between arsenite and arsenate, the reduction and methylation of arsenic, and the biosynthesis of organoarsenic compounds. Non-occupational human exposure to arsenic in the environment is primarily through the ingestion of food and water.
Absorption of arsenic in inhaled airborne particles is highly dependent on the solubility and the size of particles. Levels of arsenic or its metabolites in blood, hair, nails and urine are used as biomarkers of arsenic exposure. Both inorganic and organic forms of arsenic may cause adverse effects in laboratory animals. Several animal carcinogenicity studies on arsenic have been carried out, but limitations such as high dose levels, limited time of exposure and limited number of animals make these inconclusive. Soluble inorganic arsenic is acutely toxic, and ingestion of large doses leads to gastrointestinal symptoms, disturbances of cardiovascular and nervous system functions, and eventually death. Long-term exposure to arsenic in drinking-water is causally related to increased risks of cancer in the skin, lungs, bladder and kidney, as well as other skin changes such as hyperkeratosis and pigmentation changes. Occupational exposure to arsenic, primarily by inhalation, is causally associated with lung cancer.
Even with some negative findings, the overall weight of evidence indicates that arsenic can cause clastogenic damage in different cell types with different end-points in exposed individuals and in cancer patients. Chronic arsenic exposure in Taiwan has been shown to cause blackfoot disease (BFD), a severe form of peripheral vascular disease (PVD) which leads to gangrenous changes. Conclusions on the causality of the relationship between arsenic exposure and other health effects are less clear-cut. Aquatic and terrestrial biota show a wide range of sensitivities to different arsenic species. Arsenic compounds cause acute and chronic effects in individuals, populations and communities at concentrations ranging from a few micrograms to milligrams per litre, depending on species, time of exposure and end-points measured. Elemental arsenic (As) is a member of Group 15 of the periodic table, with nitrogen, phosphorus, antimony and bismuth. This monograph deals with arsenic and inorganic and organic arsenic compounds, except arsine (AsH3), for which a Concise International Chemical Assessment Document (CICAD) is being prepared.
Arsenical salts exhibit a range of aqueous solubilities depending on the pH and the ionic environment. Under oxidizing and aerated conditions, the predominant form of arsenic in water and soil is arsenate. Historically, colorimetric and gravimetric methods have been used for the determination of arsenic. Hydride generation followed by cryogenic trapping and AAS detection is a relatively inexpensive technique for the speciation of inorganic arsenic and its methylated metabolites (Ng et al., 1998a), although more expensive hyphenated techniques may also be used. Care must be taken to avoid contamination and prevent speciation changes during sample collection and storage. There are very few publications on the use of supercritical fluid extraction (SFE) for the determination of arsenic. Most procedures for the separation and determination of arsenic are based on distillation and hydrogen sulfide precipitation methods.
The overall objectives of the IPCS are to establish the scientific basis for assessment of the risk to human health and the environment from exposure to chemicals, through international peer-review processes, as a prerequisite for the promotion of chemical safety, and to provide technical assistance in strengthening national capacities for the sound management of chemicals. The purpose of the IOMC is to promote coordination of the policies and activities pursued by the Participating Organizations, jointly or separately, to achieve the sound management of chemicals in relation to human health and the environment. Applications and enquiries should be addressed to the Office of Publications, World Health Organization, Geneva, Switzerland, which will be glad to provide the latest information on any changes made to the text, plans for new editions, and reprints and translations already available. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. In the interest of all users of the Environmental Health Criteria monographs, readers are requested to communicate any errors that may have occurred to the Director of the International Programme on Chemical Safety, World Health Organization, Geneva, Switzerland, in order that they may be included in corrigenda.
The Task Group meeting was arranged by the National Research Centre for Environmental Toxicology, Australia. In addition, many EHC monographs have been devoted to evaluating toxicological methodology, e.g. Subsequently the work became an integral part of the International Programme on Chemical Safety (IPCS), a cooperative programme of UNEP, ILO and WHO. Animal and in vitro studies provide support and are used mainly to supply evidence missing from human studies. They represent a thorough evaluation of risks and are not, in any sense, recommendations for regulation or standard setting. Once the RO finds the document acceptable as a first draft, it is distributed, in its unedited form, to well over 150 EHC contact points throughout the world who are asked to comment on its completeness and accuracy and, where necessary, provide additional material. Their function is to evaluate the accuracy, significance and relevance of the information in the document and to assess the health and environmental risks from exposure to the chemical.
Representatives from relevant national and international associations may be invited to join the Task Group as observers.
After approval by the Director, IPCS, the monograph is submitted to the WHO Office of Publications for printing.
A comprehensive file of all comments received on drafts of each EHC monograph is maintained and is available on request. The group reviewed the draft and the peer review comments, revised the draft and made an evaluation of the risks for human health and environment from exposure to arsenic and arsenic compounds. November 1999, with the exception of the section on effects on human health, for which the last literature searches were performed in November 2000. Aitio of the IPCS central unit was responsible for the scientific aspects of the monograph, and Kathleen Lyle for the technical editing.
Volcanic action is the most important natural source of arsenic, followed by low-temperature volatilization.
Historically, use of arsenic-containing pesticides has left large tracts of agricultural land contaminated. Natural low-temperature biomethylation and reduction to arsines also releases arsenic into the atmosphere. Bioaccumulation of organic arsenic compounds, after their biogenesis from inorganic forms, occurs in aquatic organisms.
Of these, food is generally the principal contributor to the daily intake of total arsenic. However, in some places workroom atmospheric arsenic concentrations as high as several milligrams per cubic metre have been reported. Both pentavalent and trivalent soluble arsenic compounds are rapidly and extensively absorbed from the gastrointestinal tract.
Blood arsenic is a useful biomarker only in the case of acute arsenic poisoning or stable chronic high-level exposure.
The effects induced by arsenic range from acute lethality to chronic effects such as cancer. However, a recently reported animal model may be a useful tool for future carcinogenicity studies.
In survivors, bone marrow depression, haemolysis, hepatomegaly, melanosis, polyneuropathy and encephalopathy may be observed. This disease has not been documented in other parts of the world, and the findings in Taiwan may depend upon other contributing factors. The evidence is strongest for hypertension and cardiovascular disease, suggestive for diabetes and reproductive effects and weak for cerebrovascular disease, long-term neurological effects, and cancer at sites other than lung, bladder, kidney and skin. These effects include lethality, inhibition of growth, photosynthesis and reproduction, and behavioural effects. Representative marine arsenic-containing compounds, of which some are found in terrestrial systems, are shown in Table 1; their molecular structures are shown Fig. Under reducing and waterlogged conditions (< 200 mV), arsenites should be the predominant arsenic compounds. Inductively coupled plasma-mass spectrometry (ICP-MS) offers very high sensitivity for the determination of arsenic, and coupled with HPLC enables equally sensitive estimation of a wide variety of arsenic species. Plastic containers should be acid washed and traces of oxidizing and reducing agents avoided to preserve the oxidation state of arsenic compounds.
Wenclawiak & Krah (1995) reported a procedure for the measurement of arsenic species using SFE followed by GC or SFC detection. Beard & Lyerly (1961) reported a gravimetric method for the measurement of arsenic following extraction of arsenic as AsCl3 by benzene in strong hydrochloric acid.
In this manner, with the strong support of the new partners, the importance of occupational health and environmental effects was fully recognized. It is mandatory that research on human subjects is conducted in full accord with ethical principles, including the provisions of the Helsinki Declaration. A designated staff member of IPCS, responsible for the scientific quality of the document, serves as Responsible Officer (RO). The contact points, usually designated by governments, may be Participating Institutions, IPCS Focal Points, or individual scientists known for their particular expertise. A summary and recommendations for further research and improved safety aspects are also required. Although observers may provide a valuable contribution to the process, they can only speak at the invitation of the Chairperson.
At this time a copy of the final draft is sent to the Chairperson and Rapporteur of the Task Group to check for any errors. The Chairpersons of Task Groups are briefed before each meeting on their role and responsibility in ensuring that these rules are followed. It has been estimated that 70% of the world arsenic production is used in timber treatment as copper chrome arsenate (CCA), 22% in agricultural chemicals, and the remainder in glass, pharmaceuticals and non-ferrous alloys.
The use of arsenic in the preservation of timber has also led to contamination of the environment. Arsenic is released into the atmosphere primarily as As2O3 and exists mainly adsorbed on particulate matter. Bioconcentration factors (BCFs) in freshwater invertebrates and fish for arsenic compounds are lower than for marine organisms. In some areas arsenic in drinking-water is a significant source of exposure to inorganic arsenic.
In many species arsenic metabolism is characterized by two main types of reactions: (1) reduction reactions of pentavalent to trivalent arsenic, and (2) oxidative methylation reactions in which trivalent forms of arsenic are sequentially methylated to form mono-, di- and trimethylated products using S-adenosyl methionine (SAM) as the methyl donor and glutathione (GSH) as an essential co-factor.
Arsenic is rapidly cleared from blood, and speciation of its chemical forms in blood is difficult.
Exposure–response relationships and high risks have been observed for each of these end-points.
However, there is good evidence from studies in several countries that arsenic exposure causes other forms of PVD. In general, inorganic arsenicals are more toxic than organoarsenicals and arsenite is more toxic than arsenate.
Arsenic-contaminated environments are characterized by limited species abundance and diversity. The Chemical Abstract Service (CAS), National Institute for Occupational Safety and Health Registry of Toxic Effects of Chemicals (RTECS), Hazardous Substances Data Bank (HSDB), European Commission, and UN transport class numbers are 7440-38-2, HSB 509, CG 05235 000, 033-001-00-X and UN 1558, respectively. However, concentrations may be higher in certain areas as a result of weathering and anthropogenic activities including metal mining and smelting, fossil fuel combustion and pesticide use.
The rate of conversion is dependent on the Eh and pH of the soil as well as on other physical, chemical and biological factors. In recent years, atomic absorption spectrometry (AAS) has become the method of choice, as it offers the possibility of selectivity and sensitivity in the detection of a wide range of metals and non-metals including arsenic. For analysis of biological soft tissues by ICP techniques, a simple partial digestion in a closed vessel at low temperature and pressure is often sufficient for the sample preparation and pretreatment step.
Water has been used for the extraction of soluble arsenic compounds from soil with the aid of ultrasonic treatment (Hansen et al., 1992). The authors described a rapid extraction of organic and inorganic arsenic species from spiked sand and soil samples by SFE with on-line derivatization using thioglycollic acid methylester (TGM) under supercritical conditions.
Other publications have been concerned with epidemiological guidelines, evaluation of short-term tests for carcinogens, biomarkers, effects on the elderly and so forth.
The EHC monographs have become widely established, used and recognized throughout the world. Worldwide data are used and are quoted from original studies, not from abstracts or reviews.
Generally some four months are allowed before the comments are considered by the RO and author(s).
The composition of the Task Group is dictated by the range of expertise required for the subject of the meeting and by the need for a balanced geographical distribution.
Observers do not participate in the final evaluation of the chemical; this is the sole responsibility of the Task Group members. Under reducing conditions, arsenite (As(III)) is the dominant form; arsenate (As(V)) is generally the stable form in oxygenated environments. ICP-MS) can serve as element-specific detectors when coupled to chromatographic separation techniques (e.g. These particles are dispersed by the wind and are returned to the earth by wet or dry deposition. In these cases, arsenic in drinking-water often constitutes the principal contributor to the daily arsenic intake. Methylation of inorganic arsenic facilitates the excretion of inorganic arsenic from the body, as the end-products MMA and DMA are readily excreted in urine.
Arsenic in hair and nails can be indicators of past arsenic exposure, provided care is taken to prevent external arsenic contamination of the samples. The effects have been most thoroughly studied in Taiwan but there is considerable evidence from studies on populations in other countries as well.
If levels of arsenate are high enough, only species which exhibit resistance may be present. Under moderately reducing conditions, arsenite (+3) may be the dominant form, but arsenate (+5) is generally the stable oxidation state in oxygenated environments. In a non-absorbing sandy loam, arsenite is 5–8 times more mobile than arsenate (Gulens et al., 1979). Popular methods for generating atoms for AAS are flame and electrothermally heated graphite furnaces. Concentrated hydrochloric acid (1 ml to 100 ml urine) has been added to urine to prevent bacterial growth (Concha et al., 1998a).
Forms of arsenic compounds can also be separated by sequential extractions based on procedures described by Tessier et al. The TGM derivatives are thermally stable, which makes them amenable to GC–SFC determination.
Both published and unpublished reports are considered and it is incumbent on the authors to assess all the articles cited in the references. The first draft, prepared by consultants or, more usually, staff from an IPCS Participating Institution, is based initially on data provided from the International Register of Potentially Toxic Chemicals, and reference data bases such as Medline and Toxline. A second draft incorporating comments received and approved by the Director, IPCS, is then distributed to Task Group members, who carry out the peer review, at least six weeks before their meeting. Arsines released from microbial sources in soils or sediments undergo oxidation in the air, reconverting the arsenic to non-volatile forms, which settle back to the ground. There are major qualitative and quantitative interspecies differences in methylation, to the extent that some species exhibit minimal or no arsenic methylation (e.g.
Arsenic in hair may also be used to estimate relative length of time since an acute exposure. It is generally considered that inorganic arsenicals are more toxic than organic arsenicals, and within these two classes, the trivalent forms are more toxic than the pentavalent forms, at least at high doses. However, arsenic can produce chromosomal aberrations in vitro, affect methylation and repair of DNA, induce cell proliferation, transform cells and promote tumours. Tobacco smoking has been investigated in two of the three main smelter cohorts and was not found to be the cause of the increased lung cancer risk attributed to arsenic; however, it was found to be interactive with arsenic in increasing the lung cancer risk. This may explain why there are interspecies differences in organism response to arsenate and arsenite. However, a commonly used technique for the measurement of arsenic is the highly sensitive hydride generation atomic absorption spectrometric method (HGAAS). Arsenic salts exhibit a wide range of solubilities depending on pH and the ionic environment. Dissolved forms of arsenic in the water column include arsenate, arsenite, methylarsonic acid (MMA) and dimethylarsinic acid (DMA).
Terrestrial plants may accumulate arsenic by root uptake from the soil or by adsorption of airborne arsenic deposited on the leaves. Speciated metabolites in urine expressed either as inorganic arsenic or as the sum of metabolites (inorganic arsenic + MMA + DMA) provide the best quantitative estimate of recently absorbed dose of arsenic.
Several different organ systems are affected by arsenic, including skin, respiratory, cardiovascular, immune, genitourinary, reproductive, gastrointestinal and nervous systems. One study has indicated that DMA may cause cancer of the urinary bladder in male rats at high doses.
The primary mechanism of arsenite toxicity is considered to result from its binding to protein sulfhydryl groups. However, although it is suitable for total arsenic determination after appropriate digestion the technique is only routinely used to speciate a limited number of compounds – arsenite, arsenate, MMA, DMA, trimethylarsine oxide (TMAO). Unpublished data are used only when relevant published data are absent or when they are pivotal to the risk assessment. Additional sensitivity for a limited range of arsenic compounds can often be achieved by the use of hydride generation techniques.
In well-oxygenated water and sediments, nearly all arsenic is present in the thermodynamically more stable pentavalent state (arsenate). Arsenic levels are higher in biota collected near anthropogenic sources or in areas with geothermal activity. Limited data indicate that approximately 25% of the arsenic present in food is inorganic, but this depends highly on the type of food ingested. However, in humans and most common laboratory animals, inorganic arsenic is extensively methylated and the metabolites are excreted primarily in the urine. However, consumption of certain seafood, mainly seaweed and some bivalves, may confound estimation of inorganic arsenic exposure because of metabolism of arsenosugars to DMA in the body or the presence of DMA in the seafood. In strongly adsorbing soils, transport rate and speciation are influenced by organic carbon content and microbial population. A detailed policy statement is available that describes the procedures used for unpublished proprietary data so that this information can be used in the evaluation without compromising its confidential nature (WHO (1990) Revised Guidelines for the Preparation of Environmental Health Criteria Monographs. Some arsenite and arsenate species can interchange oxidation state depending on redox potential (Eh), pH and biological processes. Naturally elevated levels of arsenic in soils may be associated with geological substrata such as sulfide ores.
Factors such as dose, age, gender and smoking contribute only minimally to the large inter-individual variation in arsenic methylation observed in humans.
Such food should be avoided for 2–3 days before urine sampling for monitoring of exposure to inorganic arsenic.
In environments where phosphate concentrations are high, arsenate toxicity to biota is generally reduced.
Both arsenite and arsenate are transported at a slower rate in strongly adsorbing soils than in sandy soils.
Some arsenic species have an affinity for clay mineral surfaces and organic matter and this can affect their environmental behaviour. Anthropogenically contaminated soils can have concentrations of arsenic up to several grams per 100 ml. Foodstuffs such as meat, poultry, dairy products and cereals have higher levels of inorganic arsenic.
However, lower methylation efficiency in children has been observed in only one study out of three.
As arsenate is a phosphate analogue, organisms living in elevated arsenate environments must acquire the nutrient phosphorous yet avoid arsenic toxicity. There is potential for arsenic release when there is fluctuation in Eh, pH, soluble arsenic concentration and sediment organic content. Studies in humans suggest the existence of a wide difference in the activity of methyltransferases, and the existence of polymorphism has been hypothesized. The concentration of metabolites of inorganic arsenic in urine (inorganic arsenic, MMA and DMA) reflects the absorbed dose of inorganic arsenic on an individual level.
Animal and human studies suggest that arsenic methylation may be inhibited at high acute exposures.
The group of authors met at National Health and Environmental Effects Research Laboratory, US. Many arsenic compounds tend to adsorb to soils, and leaching usually results in transportation over only short distances in soil. The metabolism and disposition of inorganic arsenic may be influenced by its valence state, particularly at high dose levels. Studies in laboratory animals indicate that administration of trivalent inorganic arsenic such as As2O3 and arsenite initially results in higher levels in most tissues than does the administration of pentavalent arsenic.
However, the trivalent form is more extensively methylated, leading to similar long-term excretion. Ingested organoarsenicals such as MMA, DMA and arsenobetaine are much less extensively metabolized and more rapidly eliminated in urine than inorganic arsenic in both laboratory animals and humans.

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