Pauline Smedley

A review of the source, behaviour and distribution of arsenic in natural waters

The range of As concentrations found in natural waters is large, ranging from less than 0.5 μg l−1 to more than 5000 μg l−1. Typical concentrations in freshwater are less than 10 μg l−1 and frequently less than 1 μg l−1. Rarely, much higher concentrations are found, particularly in groundwater. In such areas, more than 10% of wells may be ‘affected’ (defined as those exceeding 50 μg l−1) and in the worst cases, this figure may exceed 90%. Well-known high-As groundwater areas have been found in Argentina, Chile, Mexico, China and Hungary, and more recently in West Bengal (India), Bangladesh and Vietnam. The scale of the problem in terms of population exposed to high As concentrations is greatest in the Bengal Basin with more than 40 million people drinking water containing ‘excessive’ As. These large-scale ‘natural’ As groundwater problem areas tend to be found in two types of environment: firstly, inland or closed basins in arid or semi-arid areas, and secondly, strongly reducing aquifers often derived from alluvium. Both environments tend to contain geologically young sediments and to be in flat, low-lying areas where groundwater flow is sluggish. Historically, these are poorly flushed aquifers and any As released from the sediments following burial has been able to accumulate in the groundwater. Arsenic-rich groundwaters are also found in geothermal areas and, on a more localised scale, in areas of mining activity and where oxidation of sulphide minerals has occurred. The As content of the aquifer materials in major problem aquifers does not appear to be exceptionally high, being normally in the range 1–20 mg kg−1. There appear to be two distinct ‘triggers’ that can lead to the release of As on a large scale. The first is the development of high pH (>8.5) conditions in semi-arid or arid environments usually as a result of the combined effects of mineral weathering and high evaporation rates. This pH change leads either to the desorption of adsorbed As (especially As(V) species) and a range of other anion-forming elements (V, B, F, Mo, Se and U) from mineral oxides, especially Fe oxides, or it prevents them from being adsorbed. The second trigger is the development of strongly reducing conditions at near-neutral pH values, leading to the desorption of As from mineral oxides and to the reductive dissolution of Fe and Mn oxides, also leading to As release. Iron (II) and As(III) are relatively abundant in these groundwaters and SO4 concentrations are small (typically 1 mg l−1 or less). Large concentrations of phosphate, bicarbonate, silicate and possibly organic matter can enhance the desorption of As because of competition for adsorption sites. A characteristic feature of high groundwater As areas is the large degree of spatial variability in As concentrations in the groundwaters. This means that it may be difficult, or impossible, to predict reliably the likely concentration of As in a particular well from the results of neighbouring wells and means that there is little alternative but to analyse each well. Arsenic-affected aquifers are restricted to certain environments and appear to be the exception rather than the rule. In most aquifers, the majority of wells are likely to be unaffected, even when, for example, they contain high concentrations of dissolved Fe.

Hydrogeochemistry of arsenic and other inorganic constituents in groundwaters from La Pampa, Argentina

Groundwaters from Quaternary loess aquifers in northern La Pampa Province of central Argentina have significant quality problems due to high concentrations of potentially harmful elements such as As, F, NO3-N, B, Mo, Se and U and high salinity. The extent of the problems is not well-defined, but is believed to cover large parts of the Argentine Chaco-Pampean Plain, over an area of perhaps 106 km2. Groundwaters from La Pampa have a very large range of chemical compositions and spatial variability is considerable over distances of a few km. Dissolved As spans over 4 orders of magnitude (<4–5300 μg l−1) and concentrations of F have a range of 0.03–29 mg l−1, B of 0.5–14 mg l−l, V of 0.02–5.4 mg l−1, NO3–N of <0.2–140 mg l−1, Mo of 2.7–990 μg l−1 and U of 6.2–250 μg l−1. Of the groundwaters investigated, 95% exceed 10 μg As l−1 (the WHO guideline value) and 73% exceed 50 μg As l−1 (the Argentine national standard). In addition, 83% exceed the WHO guideline value for F (1.5 mg l−1), 99% for B (0.5 mg l−1), 47% for NO3-N (11.3 mg l−1), 39% for Mo (70 μg l−1), 32% for Se (10 μg l−1) and 100% for U (2 μg l−1). Total dissolved solids range between 730 and 11400 mg l−1, the high values resulting mainly from evaporation under ambient semi-arid climatic conditions. The groundwaters are universally oxidising with high dissolved-O2 concentrations. Groundwater pHs are neutral to alkaline (7.0–8.7). Arsenic is present in solution predominantly as As(V). Groundwater As correlates positively with pH, alkalinity (HCO3), F and V. Weaker correlations are also observed with B, Mo, U and Be. Desorption of these elements from metal oxides, especially Fe and Mn oxides under the high-pH conditions is considered an important control on their mobilisation. Mutual competition between these elements for sorption sites on oxide minerals may also have enhanced their mobility. Weathering of primary silicate minerals and accessory minerals such as apatite in the loess and incorporated volcanic ash may also have contributed a proportion of the dissolved As and other trace elements. Concentrations of As and other anions and oxyanions appear to be particularly high in groundwaters close to low-lying depressions which act as localised groundwater-discharge zones. Concentrations up to 7500 μg l−1 were found in saturated-zone porewaters extracted from a cored borehole adjacent to one such depression. Concentrations are also relatively high where groundwater is abstracted from close to the water table, presumably because this zone is a location of more active weathering reactions. The development of groundwaters with high pH and alkalinity results from silicate and carbonate reactions, facilitated by the arid climatic conditions. These factors, together with the young age of the loess sediments and slow groundwater flow have enabled the accumulation of the high concentrations of As and other elements in solution without significant opportunity for flushing of the aquifer to enable their removal.

The geochemistry of rare earth elements in groundwater from the Carnmenellis area, southwest England

Shallow groundwater samples from the Carnmenellis area of southwest England collected from wells, boreholes, springs, adits and stream baseflow represent recently recharged waters of low salinity. Their major ion concentrations closely reflect the lithology of their host rocks which comprise the Carnmenellis granite and Devonian metasediments (and metabasite) of greenschist grade. Groundwaters from the granite are predominantly Na-Cl or Na-Ca-Cl type whilst those from the metasediment are Na-Ca-Mg-Cl-HCO3 waters with a larger range of compositions. The major ion compositions are predominantly a function of water-rock interaction processes and the larger range of metasediment-water compositions probably reflects the greater lithological variation. The pH of groundwater samples circulating through granite is typically lower than that of groundwater in the metasediments, the range being 4.3 to 7.2 (median 5.7) and 4.7 to 8.0 (median 6.6) respectively. Rare earth element (REE) concentrations of 0.45 μm-filtered groundwater samples have been determined by inductively coupled plasma mass spectrometry (ICP-MS). A large range of concentrations exists and many are below detection limits but levels reach up to 229 μg/1 (1.6 μm) total REEs. The REEs are strongly controlled by pH with higher levels in groundwaters of pH < 6. Chondrite-normalised profiles are light rare earth element (LREE) enriched compared to heavy rare earths (HREEs), with a common slight negative Eu anomaly: both features reflecting the compositions of their host rocks. REE profiles therefore appear to be controlled by water-rock interactions involving predominantly REE-enriched minerals. In the granite, the REEs are probably derived mainly from the accessory minerals monazite and apatite as well as the high-REE framework minerals biotite and muscovite. The source of REEs in groundwater from the metasediments is more uncertain but probably includes clay minerals, chlorite, and carbonate. REE compositions normalised to shale have flatter profiles, although many are slightly convex with higher normalised Sm, Eu, and Gd values. A few metasediment-derived waters with high total REE concentrations have LREE-enriched shale-normalised patterns. It is suggested that the bulk of the REEs in these few samples is colloidal rather than totally dissolved. Groundwaters from the metasediments have a notable depletion in Ce which is distinct from waters in the granite. This depletion is problematic in that it is difficult to see how redox processes could be the dominant control, since groundwaters from the metasediments are unlikely to be more oxidising than those from the granite. Likewise, variations in pH fail to totally explain the distinctions in Ce concentration and La/Ce ratios between the two water types. It is therefore suggested that the Ce contents are largely source-related rather than process-related. The observed REE compositions of granite- and metasedimentderived groundwaters from the Carnmenellis area are so distinctive that the REEs in general and Ce in particular might be useful as future tracers in studies of water-rock interaction and groundwater provenance.

Fluoride in Natural Waters

The element fluorine has long been recognised to have benefits for dental health: low-fluoride intake has been linked to development of dental caries and the use of fluoride toothpastes and mouthwashes is widely advocated in mitigating dental health problems. Fluoridation of water supplies to augment naturally low fluoride concentrations is also undertaken in some countries. However, despite the benefits , optimal doses of fluoride appear to fall within a narrow range. The detrimental effects of ingestion of excessive doses of fluoride are also well documented. Chronic ingestion of high doses has been linked to the development of dental fluorosis, and in extreme cases, skeletal fluorosis. High doses have also been linked to cancer (Marshall 1990), although the association is not well-established (Hamilton 1992).

Residence time indicators in groundwater : the East Midlands Triassic sandstone aquifer

The East Midlands Triassic (Sherwood Sandstone) aquifer which has been the subject of detailed radiometric age studies, is used to investigate both inert and reactive constituents of groundwater as indicators of residence time. Detailed resampling of the aquifer in 1992 has provided a considerable body of new inorganic geochemistry data, though without radiocarbon. Several inert indicators are defined including the isotopic ratios δ18O, δ2H, 36Cl, noble gas ratios, as well as the halogen elements (Cl, Br, F, I) and their element ratios. These form a group of essentially unreactive tracers primarily reflecting changing rainfall inputs and palaeoclimatic conditions, except at outcrop where human impacts are also seen clearly. The concentrations of Cl, mainly from atmospheric sources, remain below 25 mg l−1 Cl over a distance of some 30 km from outcrop. Reactive indicators, the result of time-dependent water–rock interactions, include δ13C, Mg/Ca, Sr/Ca, Na/Cl and show diagnostic trends along the flow lines. However the concentrations of certain trace elements — Li, Rb, Cs, Mn and Mo — which are not limited by solubility constraints show linear trends along the present day flow gradient. This water–rock interaction is taking place in groundwaters with low total mineralisation and it can be demonstrated that reactions involving these elements and isotopes are occurring entirely within the aquifer since high salinity groundwaters are found below the Sherwood Sandstone. There is good correlation between some of the elements and 14C activities in the 1977 data set and this has been used to derive a concentration–age relationship for the 1992 set of data. A chemical timescale for the aquifer is then established using (a) Li and (b) a combination of five trace elements. The age of the fresh groundwater is thus shown to be up to 100 ka BP, indicating the likelihood of semi-continuous recharge during the Devensian glacial period preceding the glacial maximum, when no recharge occurred (10–20 ka BP). This approach may be of value in extending groundwater dating beyond the radiocarbon timescale as well as interpreting sites where no radiocarbon data are available. The scatter from the mean age line indicates those groundwaters which are derived from either rapid or slower than average flow zones within the aquifer, as well as age stratification. This stratification is borne out by a depth profile of groundwater from a new borehole near to outcrop which is shown, by a combination of chemical and isotopic tracers, to contain Holocene overlying late Pleistocene water.

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin, Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l−1 and 1480 μg l−1. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH4, dissolved organic C (DOC), HCO3 and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l−1) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO4 concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO4 reduction has been an active process. High concentrations of Fe, Mn, NH4, HCO3 and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg−1 (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO3, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l−1) and F− (up to 6.8 mg l−1). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO3 as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.

Arsenic and selenium

This chapter outlines the main effects of arsenic and selenium on human and animal health, their abundance and distribution in the environment, sampling and analysis, and the main factors controlling their speciation and cycling. Such information should help identify aquifers, water resources and soils at risk from high concentrations of arsenic and selenium, and areas of selenium deficiency. Human activity has had, and is likely to continue to have, a major role in releasing arsenic and selenium from the geosphere and in perturbing the natural distribution of these and other elements over the Earths surface.

Mobility of arsenic in groundwater in the Obuasi gold-mining area of Ghana: some implications for human health

Abstract Arsenic in drinking water from streams, shallow wells and boreholes in the Obuasi gold-mining area of Ghana range between < 2 and 175 μgl−1. The main sources are mine pollution and natural oxidation of sulphide minerals, predominantly arsenopyrite (FeAsS). Streamwaters have been most affected by mining activity and contain some of the highest As concentrations observed. They are also of poor bacteriological quality. Some of the streams have a high As(III) content (As(III)/Astotal > 0.5), probably as a result of methylation and reduction reactions mediated by bacteria and algae. Concentrations of As in groundwaters reach up to 64 μgl−1, being highest in deeper (40–70 m) and more reducing (220–250 mV) waters. The As is thought to build up as a result of the longer residence times undergone by groundwaters in the deeper parts of the aquifer. The proportion of As present as As(III) is also higher in the deeper groundwaters. Deep mine exploration boreholes (70–100 m) have relatively low As contents of 5–17 μgl−1, possibly due to As sorption onto precipitating ferric oxyhydroxides or to localized low As concentrations of sulphide minerals. Median concentrations of inorganic urinary As from sample populations in two villages, one a rural streamwater-drinking community and the other a suburb of Obuasi using groundwater for potable supply, were 42 μgl−1 and 18 μgl−1 respectively. The value for the community drinking groundwater is typical of background concentrations of urinary As. The slightly higher value for the streamwater-drinking community probably reflects different provenance of foodstuffs and higher As concentrations of water sources local to the village. The low value obtained for the inhabitants of the Obuasi suburb, living close to and abstracting groundwater from the area of major mining activity, suggests that groundwater can form a useful potable supply of good inorganic quality provided that deep, long residence time sources are avoided.

Arsenic in rural groundwater in Ghana

Arsenic concentrations in groundwaters from two areas in Ghana, the Obuasi area in the Ashanti region and the Bolgatanga area of the Upper East region vary from 40 m) of weathered regolith and lateritic soil. Arsenic concentrations are low in the shallowest groundwaters, but increase at greater depths (40–70 m below ground level in Obuasi and 20–40 m in Bolgatanga). At depths greater than this, total As concentrations are relatively low. The lateral and vertical variations in dissolved As concentrations are controlled by ambient pH and redox conditions and by the relative influences of sulphide oxidation and sorption. In the weathered regolith and lateritic soils, oxidation has been extensive. Shallow groundwaters are oxidizing and acidic. Under these conditions, As is readily oxidized to As(V) and may precipitate as ferric arsenate or be sorbed onto ferric hydroxide surfaces. At greater depth, groundwaters have longer contact times with the aquifer minerals and pH values are therefore higher (>6.0 in Obuasi and >6.5 in Bolgatanga). The oxidation of sulphide minerals may proceed, but dissolved O is consumed during the process and mildly reducing conditions (Eh 200–300 mV) result. Sorption of As onto ferric hydroxide minerals is less favoured under such pH and redox conditions and the element is relatively mobile. At the greatest abstraction depths, groundwaters are more reducing (Eh ≤200 mV; dissolved O <0.1 mg 1−1) and few electron acceptors are available in the system to drive sulphide oxidation. Dissolved As concentrations therefore remain relatively low. The mildly reducing groundwaters in the sulphide-bearing basement aquifer are therefore of the poorest potable quality with respect to dissolved As concentrations.

Arsenic in groundwater and the environment

Awareness of the problems associated with arsenic in drinking water and the environment has grown significantly over the last two decades or so and today an enormous literature exists documenting its occurrence, behaviour and impacts in many places across the globe. The mobilisation of arsenic in the environment occurs through a complex combination of natural biogeochemical reactions and human interactions. Most recognised problems are generated by mobilisation and transport under natural conditions, but mobilisation has also been caused, or exacerbated, by mining, fossil-fuel combustion and use of synthetic arsenical compounds (pesticides, herbicides, crop desiccants and arsenic-based additives in livestock feed). Arsenical pesticides and herbicides have been used much less over the last few decades, and more recent restrictions have been imposed on the use of arsenic in wood preservation (e.g. European Communities’ Directive 2003/2/EC), but the legacy of such sources may still pose a localised threat to the environment.