In classical toxicology, speciation of carbon is taken for granted and the carbon compounds responsible for toxicity are always described with the appropriate chemical nomenclature. By contrast, speciation of other elements is largely ignored and elements other than carbon are often condemned as toxic because of evidence relating toxicity to only a few of the chemical species in which they occur. In some cases, such as chromium, the distinction between oxidation states (chromium III and chromium VI) may be recognized as important. The fact that chromium VI may only be a toxicological problem in certain well defined forms, such as specific chromate salts that may cause nasal and lung cancer, and then only by the respiratory route of exposure, is largely ignored. Failure to consider properly chemical speciation of elements other than carbon can lead to poor use of our resources. Laws and regulations based on simple elemental analysis may wrongly condemn environmental media or products as toxic and prevent the use of important resources.

Changes in the lability and local environment of Cd sorbed onto calcite, hydroxylapatite and humic acid have been investigated as a function of time (30 min–9 months) using a combination of X-ray adsorption spectroscopy (XAS) and isotopic dilution techniques with Cd concentrations between 1 and 1000 mmol kg –1. Enhanced X-ray absorption fine structure (EXAFS) shows that precipitation of Cd carbonate was initially observed on calcite. Ageing of a 10 mmol kg–1 sample showed replacement of Cd in the fourth shell with Ca, indicating diffusion between the two phases had occurred. This diffusion appeared to be ongoing for a 10 mmol kg–1 sample even after 9 months of reaction. Only 20% of the Cd in a sample with 10 mmol kg–1 Cd remained labile after 6 months of reaction, suggesting a high degree of incorporation into the solid phase, in agreement with the XAS results. The XAS results for hydroxylapatite indicated that Cd is not fixed in the mineral lattice and Cd lability in a sample loaded with 10 mmol kg–1 Cd was ∼55% after 6 months of reaction. This indicates that a relatively high proportion of the Cd sorbed to hydroxylapatite remained as kinetically active surface species. Little change was observed in the local environment of Cd adsorbed on flocculated Ca-humate samples as a function of time and ∼75% of the Cd remained radio-labile after 6 months of reaction regardless of initial Cd loading. High lability is expected because incorporation into a solid matrix or surface precipitation of a Cd phase is less likely than with the mineral phases.

Cornwall (UK) has suffered extensive arsenic contamination due to the historic mining and processing of mineral ores. Standard procedures for contaminated land risk assessment (DEFRA and Environment Agency, 2002a) are probably unworkable in Cornwall, with a very large number of sites classified as contaminated by arsenic. Methods of measuring the speciation and mobility of arsenic are essential for effective and rapid risk assessments of arsenic contamination.

Three clusters of lysimeters were installed in three different areas of an arsenic-contaminated Cornish site. A novel phosphoric acid microwave extraction technique was applied to the soils removed from the lysimeter holes; HPLC-HG-AFS analysis showed the majority of solid-phase arsenic to be arsenate (AsV). Pore waters obtained from the lysimeters showed variable, relatively low levels of arsenite (AsIII) and arsenate (AsV) to be present (<1–129 μg l–1). Less toxic arsenate predominated in most pore waters, with the presence of minor amounts of arsenite suggesting heterogeneous redox conditions. Pore-water arsenic concentrations were strongly positively related to solid-phase arsenate concentrations.

The use of techniques that assess the speciation of arsenic both in the solid and aqueous phases of a soil provides important information about the mobility of arsenic. The methodology presented in this paper may offer a novel basis for risk assessments of other contaminated sites.

The distribution of sorbed arsenic(V) among different geochemical fractions for arsenic(V)-loaded red mud, an oxide-rich residue from bauxite refining that has been proposed as an adsorbent for arsenic, was studied as a function of sorbed arsenic(V) concentration using a sequential extraction procedure. The release of previously sorbed arsenic(V) was also studied as a function of pH and arsenic(V) concentration. Most sorbed arsenic(V) (0.39–7.86 mmol kg–1) was associated with amorphous and crystalline Al and Fe oxides (24.1–43.8% and 24.7–59.0% of total sorbed arsenic, respectively). Exchangeable arsenic was the smallest fraction (0.4–5.2% of total sorbed arsenic). The distribution of sorbed arsenic(V) was related to the arsenic surface coverage. For arsenic surface coverages >∼30% the percentage of arsenic(V) associated with the amorphous Al oxide fraction increased and that associated with the crystalline oxide fraction decreased. The arsenic(V) exchangeable fraction increased from 1.4 to 756 μmol kg–1 as surface coverage increased from 388 to 7855 μmol kg–1. The release of sorbed arsenic(V) from red mud was greater at alkaline pH values (maximum release of ∼33% of previously sorbed arsenic at pH = 12), but for high arsenic(V) initial concentration (0.2 mM arsenic) considerable amounts of arsenic (6.5% of previously sorbed arsenic) were released at pH 4, in accordance with the dissolution of amorphous Al oxides in the red mud. The results obtained suggest a greater mobility of sorbed arsenic(V) as its surface concentration approaches saturation.

The basis for an ecological risk assessment based on meeting the needs of recent UK and EU legislation is described. The background to the framework and the legislative driver and relevant definitions of harm are provided, prior to an overview of the proposed ecological risk assessment process, which has been broken down into a Tiered approach. Tier 0 requires the establishment of a conceptual site model, where potential contaminant-pathway-receptor linkages are sought and, assuming they are identified, lead on to higher Tier assessments. Tier 1 relies largely on chemical analysis of soil contaminant levels and comparison with soil quality guideline values to assess the likelihood of harm. In some cases biological screening assays may also be undertaken within this Tier. Based on a weight of evidence approach, should data from Tier 1 indicate harm or leave uncertainty, then Tier 2 biological testing is undertaken using assays relevant to the site of interest. In situations where harm is identified under Tier 2 then Tier 3 is reserved for establishing the extent of harm within the ecosystem. Finally the use of the 'weight-of-evidence' approach to generate scientifically robust conclusions regarding the harm (or potential for harm) within the ecosystem is briefly outlined. The framework discussed is currently being adopted by the UK Environment Agency, with implementation expected in 2005. The UK scheme compares favourably with comparative schemes operating in other countries possessing the merits of being iterative, tiered, flexible with agreed exit points subject to satisfying defined criteria and so speeding the decision-making process.

This issue of Mineralogical Magazine is the 5th in a loosely defined series of special thematic issues (or part issues), deriving from conferences organized by the Mineralogical Society. The associated conference was entitled ‘Environmental Mineralogy, Geochemistry and Human Health’ and took place in January 2005, in Bath. A common thread to all these Mineralogical Society conferences has been the role of mineralogy in applied science and technology and particularly in environmental science, focussing on the multidisciplinarity of modern mineralogy; the conferences (and special issues) have been particularly successful in bringing along scientists from outside traditional Mineralogy/Earth Sciences. Notably, the series comes at a time when the popularity of Mineralogy/Geology, but also science in general, is low, and many, particularly young, scientists are seeking to place themselves in a better position in the eye of the public and the media, and often also to find new focus for their research. A primary ambition for the series is thus to demonstrate Mineralogy's extensive outreach and has so far succeeded in giving the scientific community a sense of the wider role mineralogists can play.

Biominerals are a subset of the mineral kingdom, those created by living creatures. In spite of usually fine grain size and intimate association with organic materials, biominerals are readily identified as common mineral species. Iron hydroxides and oxyhydroxides, calcium carbonates and calcium phosphates from uni- and multi-cellular species are presented as examples of biominerals, and biomineralization processes. Their special morphological, and crystal chemical, characteristics provide unique structural contributions to the life forms that create them. Investigations of novel habitats should present opportunities to expand the number of biominerals and their potential for industrial applications.

The mineral in bones and teeth is an impure form of hydroxylapatite (HAP), the principal impurity being 2—5 wt.% carbonate. This mineral dissolves during remodelling of bone and also in dental caries as a result of the action of acids produced by osteoclasts and by bacteria, respectively. In enamel, demineralization proceeds with preferential loss of carbonate relative to phosphate. Surprisingly, in the early stages, the demineralization is subsurface. In order to facilitate the understanding of physical chemical aspects of these processes, we have undertaken studies of demineralization in model systems. We give three examples here. The first two used scanning microradiography in which the specimen is stepped across a 10—30 μm diameter X-ray beam. Intensity measurements allow calculation of the mineral mass per unit area in the X-ray path through the specimen. In the first experiment, porous HAP sections were separated from a reservoir of acidic buffer by a column initially filled with water (the diffusion length) and scanned with the X-ray beam perpendicular to the axis of the diffusion length. The rate of total loss of mineral along each profile was calculated from the scans. The rate of demineralization fell as the diffusion length increased. We believe the explanation is that the rate-controlling step is the diffusion of dissolved HAP away from the solid to the buffer reservoir. In the second experiment, demineralizing solution and water were pumped alternately, for equal lengths of time, past blocks of porous HAP or enamel. The X-ray beam was perpendicular to the exposed surface. As the rate of switching between solutions decreased, the mean rate of demineralization also fell. We propose that this effect is due to retention of acid in the pores of the HAP during the time when water flows, allowing further demineralization to take place during this time. The third study used X-ray microtomography, a form of 3D microscopy, to study the loss of mineral in compacted carbonate apatite powders. The powders were packed in six 10 mm internal diameter acrylic cylinders to a depth of 4 mm (after pressing). One end was covered with a porous polyethylene disc and each tube placed in acidic buffer for 70 days. Periodic examination by microtomography showed the development of subsurface demineralization. Infrared spectroscopy of the dissected-out surface layers showed preferential loss of carbonate over phosphate by comparison with deeper layers. Rietveld analysis of X-ray powder diffraction data showed changes in the crystallographic structures of the apatites between the initial and dissected-out apatite.

In this reconnaissance study, skeletal materials from people, dating from ∼1500 B.P., who lived by or worked at the ancient copper mines and furnaces of the Wadi Faynan in southern Jordan, were analysed using atomic absorption spectrophotometry (AAS) to determine the intensities of accumulation of copper and lead in their bones. Many of the bones analysed contained concentrations of these metals which are comparable to those of modern individuals who are heavily exposed to metals through contemporary industrial processes.

Patterns of partitioning throughout the skeleton of a number of individuals were also studied. These AAS data suggest that within the human organism there may be some ability to influence the patterns of accumulation of copper within the skeleton. The humerus was frequently found to contain more copper than other bones studied. Within the humerus itself, the medial epicondyle frequently contained the highest concentrations, which may indicate a significant degree of organization or control of the process. These metal concentration data together with their toxicological consequences suggest that the health of the ancient human populations must have been adversely affected by exposure during life to copper in the environment. They also point to the need for further detailed studies of metal partitioning within the bones of the human skeleton.

Ferrihydrite and goethite are amongst the most important substrates for the sorption of contaminants in soil and other environmental media. Isotopic studies of the transition elements, particularly those that exhibit more than one oxidation state and show pH- and/or redox-sensitive behaviour at low temperatures, have been shown to be potentially useful present-day and past proxies for redox (or palaeoredox) conditions. We have made preliminary investigations of Fe isotope fractionation that take place during the formation of FeIII (oxy)hydroxides (FeIIIox) from an aqueous FeIII(NO3)3 solution (FeIIIaq) under laboratory conditions. We have attempted to keep the chemical system simple by excluding 'vital effects' and major changes in redox through the maintenance of abiotic conditions and use of FeIIIaq. Isotopic measurements (56Fe/54Fe, 57Fe/54Fe) of the FeIII(NO3)3 stock solution, the original ferrihydrite and the mixed ferrihydrite/goethite-supernatant FeIIIaq 'pairs' were carried out using a double focusing multicollector inductively coupled plasma mass spectrometer. The results reveal an apparent systematic variation indicating larger ΔFeIIIaq—FeIIIox with decrease in the ferrihydrite:goethite ratio, which reflects the time allowed for isotopic exchange. These values range from virtually zero (0.03%) after 24 h to 0.30% after 70 h. In each FeIIIox-FeIIIaq 'pair' the lighter Fe isotope is partitioned into the FeIIIox, leaving the FeIIIaq isotopically heavier. The observed fractionation reflects isotopic exchange of Fe between the FeIIIox and FeIIIaq upon at least a two step transition of ferrihydrite to goethite.

Fuel-oil contamination of groundwater and waterways is common throughout the world. The fuel components methyl-tert-butyl ether (MTBE) and benzene, toluene, ethylbenzene and o-, p- and m-xylenes (BTEX) compounds are most likely to reach a borehole after a contamination event, and also those that pose the greatest risk.

Various gas chromatography-mass spectrometry (GCMS) methods are available for the analysis of volatile organic compounds (VOCs) but many of these are not suitable for rapid and combined analysis of MTBE and BTEX. Here we describe and validate a simple and reliable method that fulfils these requirements. The method is quick: 48 samples can be analysed in a 24 hour period using the Precept II® autosampler and therefore is suitable for high throughput work. Validation of our experiments is presented in the form of linearity, precision and intra-day repeatability of standards as well as limits of detection and limits of quantification for the range 1—20 μg/l.

This MTBE/BTEX analytical method developed was used to study the optimization of a modular post-abstraction remediation system incorporating air-stripping and granular activated carbon (GAC) technologies (Hall, 2004), from which a selection of sample data is presented.

Studies of the weathering of platinum-group minerals in natural deposits have indicated that the platinum-group elements (PGE) can be mobilized under appropriate conditions and have sufficient solubility to move into solution. Although inorganic chemistry provides feasible mechanisms under the extreme conditions encountered in laterites it appears likely that PGE-organic complexes offer a more convincing explanation of the apparent solubility. Experimental work undertaken to illustrate the organic processes and the reaction timescale examined various reactions including those between Pt and Pd foils and humic and fulvic acid solutions. These reactions appear pertinent to those that may occur between the PGE particles ejected by vehicle exhaust catalysts and the natural environment.

The experimental work produced up to 195 μ/l Pt and 102 μ/l Pd in humic acid solutions exposed to the metal foils for about a year at room temperature. The experimental conditions can be compared to those encountered in roadside drainage supplied with PGE particles and decaying vegetation.

Consideration of the possible health effects of the PGE from the particles ejected by vehicle exhaust catalysts has centred on inhalation of the particles or absorption through the skin. Intake from drinking water or from food produced using PGE-bearing water should now also be investigated. Due to the variety of organic compounds produced by decaying vegetation the identity of the PGE-organic products is not yet known so their toxicity cannot be estimated.

The Mathiatis massive sulphide deposit in Cyprus was a low-grade (0.3% Cu), three million ton ore body of pyrite and minor chalcopyrite occurring within basaltic lavas of the Troodos ophiolite. Cessation of mining in 1987 left a deep open pit surrounded by large heaps of spoil, which are undergoing oxidation and leaching. The aim of this study was to determine the mineralogical controls on the storage and potential remobilization of As, Cu, Pb and Zn within, and from, mine spoil heaps. Most of the spoil samples collected, and related materials (stream sediment, reaction zone between a boulder of massive pyrite and calcareous chert, salt crusts on stream beds), are enriched in As (27—220 ppm), Cu (110—400 ppm), Pb (10—140 ppm) and Zn (290—12,000 ppm) relative to both the basalt and calcareous chert (As 4—10 ppm, Cu 20—76 ppm, Pb 3—6 ppm, Zn 39—200 ppm).

Arsenic, Cu, Pb and Zn in the spoil and related materials are associated with Fe(-Al-S)-O, Fe(-Al-Mg)-S-O, Al(-Mg-Fe)-S-O and Mg(-Al-Fe)-S-O phases (the brackets represent minor components of less than 20 wt.% within the phases). Chemical extraction work using CaCl2 suggests that Cu, Zn and to some extent, As, are potentially more soluble than Pb. This is corroborated by the very high total concentrations of Cu and Zn in both the secondary salt crusts and the reaction zone material, high CaCl2-extractable As, Cu and Zn in the salt crusts, and aqueous data for the Mathiatis mine area collected for a European Union LIFE report. This may have implications for ecosystem health and water quality in the Mathiatis area and areas of similar mineralogy and climate world wide.

This paper hypothesizes that arsenic in drinking water indirectly contributes to Buruli ulcer (BU), a skin disease caused by Mycobacterium ulcerans (MU) infection. Samples of groundwater and surface water used as drinking water by the population in Ghana's Amansie West district (part of which has a high prevalence of BU), were collected near rural settlements and analysed for arsenic. Arsenic concentration levels per settlement were compared with BU prevalence. A positive exposure-response relationship was obtained between arsenic in surface water and BU (r2 = 0.82). However, there is no significant exposure-response relation between groundwater and BU.

The headwaters of the Río Pilcomayo drain the Cerro Rico de Potosí precious metal-polymetallic tin deposits of southern Bolivia. Mining of these deposits has taken place for around 500 years, leading to severe contamination of the Pilcomayo's waters and sediments for at least 200 km downstream. Communities living downstream of the mines and processing mills rely on the river water for irrigation, washing and occasionally, cooking and drinking, although most communities take their drinking water from springs located in the mountains above their village. This investigation focuses on arsenic exposure in people living in riverside communities up to 150 km downstream of the source. Sampling took place in April–May 2003 (dry season) and was repeated in January–March 2004 (wet season) in five communities: El Molino, Tasapampa, Tuero Chico, Sotomayor and Cota. Cota was the control in 2003 and again in 2004; a nearby city, Sucre, and several locations in the UK were also used as controls in 2004. Drinking, irrigation and river waters, hair and urine samples were collected in each community, digested where appropriate and analysed for As using ICP-MS. Arsenic concentrations in drinking waters ranged 0.2–112 μg 1–1, irrigation water 0.6–329 μg 1–1, river waters 0.9–12,800 μg 1–1, hair 37–2110 μg kg–1 and urine 11–891 μg 1–1. All but one drinking water sample was found to contain As below the World Health Organization recommended guideline of 10 μg 1–1, although a number of irrigation and river water concentrations were above Canadian and Bolivian guidelines. Many As concentrations in the hair and urine samples from this study exceeded published values for non-occupationally exposed subjects. Analysis of mean concentration values for all media types showed that there were no statistically significant differences between the control locations and the communities exposed to known As contamination, suggesting that the source of As may not be mining-related. Arsenic concentration appears to increase as a function of age in hair samples from males and females older than 30 years. Male volunteers over the age of 35 showed increasing urine-As concentrations as a function of age, whereas the opposite was true for the females.

The reactivity of primary Pb metallurgical slags in high-molecular-weight (HMW) organic solutions has been studied in order to determine the processes of release and attenuation of metal and metalloid contaminants (Pb, Zn, Cu, As) in 'soil-like' environments. Slag was submitted to a 112-day batch leaching experiment in Suwannee River fulvic acid solution and peat water (∼50 mg DOC l–1). The leaching was coupled with investigation of the secondary phases (SEM/EDS, Raman microspectrometry) and thermodynamic speciation-solubility modelling using MINTEQA2. Metals and As are released in large amounts during the early stage of the experiment, followed by a decrease in the concentrations in the leachate as a result of adsorption on secondary (hydrous) ferric oxides (HFO/FO), predicted by MINTEQA2 calculations and confirmed on the leached slag surface by SEM and Raman spectrometry. Compared to other contaminants, Zn exhibits more pronounced mobility and is adsorbed on HFO/FO only at pH >7. Such a scavenging process may be predominant during the long-term interaction of slag with an HMW organic solution of real soil. As a result, the soil cover and subsequent re-vegetation of slag dumps may be considered as a possible scenario for slag management.

Here we describe preliminary research into the in situ electrokinetic generation of continuous iron-rich precipitates to act as sub-surface barriers for the containment of contaminated sites. This is achieved using sacrificial iron electrodes emplaced either side of a soil/sediment mass to introduce iron into the system, and their dissolution and re-precipitation under the influence of an applied (DC) electric field. Continuous vertical and horizontal iron-rich bands (up to 2 cm thick) have been generated over a timescale of 300—500 h, at voltages of <5 V with an electrode separation of between 15 and 30 cm. The thickness of the iron-rich band increases as the applied voltage is increased. Geotechnical tests in sand indicate that the iron-rich band produced is practically impervious (coefficient of permeability of 10—9 ms—1 or less), and has significant mechanical strength (unconfined compressive strength of 10.8 N mm—2). By monitoring the current, the integrity of the iron-rich band may be assessed, and by continued application of current, the barrier may 'self heal'. The iron-rich barrier is composed of amorphous iron, goethite, lepidocrocite, maghemite and native iron.

Gully pot sediments and pavement and road gutter dusts have been collected from the city of Coventry in the West Midlands, UK. These samples have been subjected to metallic element analysis and the activity of a number of gamma-emitting radionuclides have been measured in order to assess whether they exceed published trigger or action levels, and whether their disposal or dispersal may have implications for receiving landfills and/or water courses. Results indicate above-background levels of metallic elements in dusts and sediments with Cu and Zn exceeding ICRCL action levels in some cases. The highest activities of some radionuclides are found in road gutter and street dusts and the lowest activities are found in gully pot sediments. Road dusts are more likely to be recirculated into the ambient air by passing traffic and could potentially pose a risk to pedestrians. The effective dose rates calculated for these dusts and sediments indicate that some samples approach and even exceed the 1 mSv y—1 limit to members of the public recommended by ICRP (1991). Some individual nuclides exceed their clearance levels laid down in the revised basic safety standards of the 1993b Radioactive Substances Act, 1993 (DoETR, 1999), by as much as 2.5 times. This is especially true of 210Pbun and 7Be, two fallout nuclides, and also of 40K.

Arsenic(V) removal from aqueous solution following addition of either a mixture of synthetic hydroxylapatite and baryte or bone-char is discussed. Arsenic concentrations of 4, 10 and 100 mg/l were investigated and additions of 0.2—10 g/l of solid (hydroxylapatite, baryte or bone-char) were tested, at an initial pH of either 5 or 7. Although the mixture of hydroxylapatite and baryte had a small influence on arsenic concentrations, bone-char was found to be a very effective sorbing agent for arsenic(V). Packed-column studies to investigate the bone-char capacity, followed by leaching tests were carried out. The capacity of bone-char was found to be superior to that of granular activated carbon. The experiments presented here indicate that the mechanism involved is adsorption rather than co-precipitation.