Gavyn Rollinson

Geochemistry and mineralogy of arsenic in mine wastes and stream sediments in a historic metal mining area in the UK

Mining generates large amounts of waste which may contain potentially toxic elements (PTE), which, if released into the wider environment, can cause air, water and soil pollution long after mining operations have ceased. The fate and toxicological impact of PTEs are determined by their partitioning and speciation and in this study, the concentrations and mineralogy of arsenic in mine wastes and stream sediments in a former metal mining area of the UK are investigated. Pseudo-total (aqua-regia extractable) arsenic concentrations in all samples from the mining area exceeded background and guideline values by 1-5 orders of magnitude, with a maximum concentration in mine wastes of 1.8×10(5)mgkg(-1) As and concentrations in stream sediments of up to 2.5×10(4)mgkg(-1) As, raising concerns over potential environmental impacts. Mineralogical analysis of the wastes and sediments was undertaken by scanning electron microscopy (SEM) and automated SEM-EDS based quantitative evaluation (QEMSCAN®). The main arsenic mineral in the mine waste was scorodite and this was significantly correlated with pseudo-total As concentrations and significantly inversely correlated with potentially mobile arsenic, as estimated from the sum of exchangeable, reducible and oxidisable arsenic fractions obtained from a sequential extraction procedure; these findings correspond with the low solubility of scorodite in acidic mine wastes. The work presented shows that the study area remains grossly polluted by historical mining and processing and illustrates the value of combining mineralogical data with acid and sequential extractions to increase our understanding of potential environmental threats.

Automated SEM-EDS (QEMSCAN®) Mineral Analysis in Forensic Soil Investigations: Testing Instrumental Reproducibility

The complex mix of organic and inorganic components present in urban and rural soils and sediments potentially enable them to provide highly distinctive trace evidence in both criminal and environmental forensic investigations. Organic components might include macroscopic or microscopic plants and animals, pollen, spores, marker molecules, etc. Inorganic components comprise naturally derived minerals, mineralloids and man-made materials which may also have been manu- factured from mineral components. Ideally, in any forensic investigation there is a need to gather as much data as possible from a sample but this will be constrained by a range of factors, commonly the most significant of which is sample size. Indeed, there are a very wide range of analytical approaches possible, and a range of parameters that can be measured in the examination of the inorganic components present in a soil or sediment. These may include bulk colour, particle size distribution, pH, bulk chemistry, mineralogy, mineral chemistry, isotope geochemistry, micropalaeontology

Trinitite redux: Mineralogy and petrology

Abstract Trinitite is the glass formed during the first atomic bomb test near Socorro, New Mexico, on July 16, 1945. The protolith for the glass is arkosic sand. The majority of the glass is bottle green in color, but a red variety is found in the northern quadrant of the test site. Glass beads and dumbbells, similar in morphology to micro-tektites, are also found at the Trinity site. The original description of this material, which appeared in American Mineralogist in 1948, noted the presence of two glasses with distinctly different indices of refraction (n = 1.46 and 1.51-1.54). Scanning electron microscopy (SEM) and Quantitative Evaluation of Minerals by SCANning electron microscopy (QEMSCAN) analysis is used to investigate the chemical composition and fine-scale structure of the glass. The glass is heterogeneous at the tens of micrometer scale with discrete layers of glass showing flow-like structures. The low index of refraction glass is essentially SiO2 (high-Si glass), but the higher index of refraction glass (low-Si glass) shows a range of chemical compositions. Embedded in the glass are partially melted quartz (α-quartz as determined by X-ray diffraction) and feldspar grains. The red trinitite consists of the same two glass components along with additional Cu-rich, Fe-rich, and Pb-rich silicate glasses. Metallic globules are common in the red trinitite. In terms of viscosity, the high-Si and low-Si glasses differ by several orders of magnitude, and there is minimal mixing between the two glasses. QEMSCAN analysis reveals that there are several chemical subgroups (that can be characterized as simple mixtures of melted mineral components) within the low-Si glasses, and there is limited mixing between these glass subgroups. The red trinitite contains regions of Fe-rich glass, which show sharp contact with surrounding Fe-poor glass. Both the textural and chemical data suggest that these two glasses existed as immiscible liquids. The metallic droplets in the red trinitite, which consist of variable amounts of Cu, Pb, and Fe, show textural evidence of unmixing. These metals are largely derived from anthropogenic sources-Cu wire, Pb bricks, and the steel tower and bomb casing. The combination of mineralogical and chemical data indicate that temperatures on the order of 1600 °C and pressures of at least 8 GPa were reached during the atomic detonation and that there was a reducing environment during cooling, as evidenced by the presence of native metals, metal sulfides, and a low-Fe3+/Fe2+ ratio. Independent estimates of maximum temperature during the detonation are on the order of 8000 K, far higher than suggested by the mineral data. This discrepancy is probably due to the very short duration of the event. In all respects, the trinitite glasses are similar to tektites and fulgurites, and by analogy one conclusion is that temperature estimates based on mineralogical observations for these materials also underestimate the maximum temperatures.

Automated Mineralogical Analysis of PM10: New Parameters for Assessing PM Toxicity

This work provides the first automated mineralogical/phase assessment of urban airborne PM10 and a new method for determining particle surface mineralogy (PSM), which is a major control on PM toxicity in the lung. PM10 was analyzed on a TEOM filter (Aug.-Sept. 2006 collection) from the London Air Quality Network Bexley, East London, U.K. A cross-section of the filter was analyzed using a QEMSCAN automated mineralogical analysis system which provided 381,981 points of analysis for 14,525 particles over a period of 9 h 54 min. The method had a detection limit for individual mineral components of 0.05 ppm (by area). Particle shape and mineralogical characteristics were determined for particles in the size ranges PM(10-4), PM(4-2.5), and PM(2.5-0.8). The PM(2.5-0.8) fraction contained 2 orders of magnitude more mineral particles than the PM(10-4) and PM(4-2.5) fractions, however the PM(10-4) fraction forms 94% and 79% of the mineral mass and surface area, respectively. PSM of the PM10 was dominated by gypsum (36%), plagioclase (16%), Na sulphates (8%), and Fe-S-O phases (8%) in the PM(10-2.5), which may be important in explaining the toxicity of the coarse fraction. The wider implications of the study are discussed.

Automated forensic soil mineral analysis; testing the potential of lithotyping

Abstract In the investigation of serious crimes, soil can be, in some cases, a very valuable class of trace evidence. The complexity of soil is part of the reason why it is useful as trace evidence but is also an inherent problem, as there are many different parameters in a soil sample that could potentially be characterized. The inorganic components of soils are dominated by minerals, along with anthropogenic particulate grains; thus, the analysis of soil mineralogy as the main technique for inorganic forensic soil characterization is recommended. Typical methods that allow the bulk mineralogy to be determined, such as X-ray diffraction (XRD), do not allow the texture of the particles to be characterized. However, automated scanning electron microscopy (SEM) provides both modal mineralogy and also allows particle textures to be characterized. A recent advance in this technique has been the ability to report the modal mineralogy of a sample as ‘lithotypes’, which are defined on the basis of a combination of mineralogy and other parameters, such as grain size and mineral associations. Defined lithotype groups may include monominerallic grains but also, importantly, allow the automated quantification of rock types and other anthropogenic materials. Based on a simulated forensic scenario, the use of lithotyping is evaluated as an aid in the analysis of soil samples. This technique provides additional discrimination when comparing different soil samples.

Geotechnical and mineralogical characterisations of marine-dredged sediments before and after stabilisation to optimise their use as a road material

ABSTRACT Dredging activities to extend, deepen and maintain access to harbours generate significant volumes of waste dredged material. Some ways are investigated to add value to these sediments. One solution described here is their use in road construction following treatment with hydraulic binders. This paper presents the characterisation of four sediments, in their raw state and after 90 days of curing following stabilisation treatment with lime and cement, using a combination of novel and established analytical techniques to investigate subsequent changes in mineralogy. These sediments are classified as fine, moderately to highly organic and highly plastic and their behaviour is linked to the presence of smectite clays. The main minerals found in the sediments using X-ray diffraction (XRD) and automated mineralogy are quartz, calcite, feldspars, aluminium silicates, pyrite and halite. Stabilisation was found to improve the mechanical performances of all the sediments. The formation of cementitious hydrates was not specifically detected using automated mineralogy or XRD. However, a decrease in the percentage volume of aluminium silicates and aluminium-iron silicates and an increase of the percentage volume of feldspars and carbonates was observed.

Mapping arsenopyrite alteration in a quartz vein-hosted gold deposit using microbeam analytical techniques

Abstract An unworked quartz vein-hosted gold deposit occurs in the Clew bay area of County Mayo, western Ireland. The veins are late-Caledonian in age and transect greenschist-facies poly-deformed Silurian quartzites. The veins contain disseminated arsenopyrite thatmay be a primary mineral source for elevated levels of arsenic (As) found in groundwater samples recovered from wells related spatially to the gold deposit. Levels from 5 to 188 μg/L (significantly above the 7.5 μg/L threshold for safe drinking water) have been detected. A series of element distribution maps using a scanning electronmicroscope (Hitachimodel S-4700) linked to an energydispersive spectrometer (INCA® Oxford Instruments) and mineral distribution maps generated by QEMSCAN® (Quantitative Evaluation of Minerals by Scanning electron microscopy) were used to map the distribution of the primary arsenopyrite and related secondary As-bearing phases. Laser Raman microspectroscopy was used to identify the secondary As-bearing phases. ‘Island weathering’ of primary arsenopyrite together with hydrated pseudomorphs of arseniosiderite, pharmacosiderite and scorodite after arsenopyrite are recorded. Circulating groundwater hydrates the primary arsenopyrite, providing the release mechanism that forms the secondary As-bearing phases that occur as microfracture infills together with muscovite and biotite. The textural relationships between the primary and secondary As minerals indicate their potential as mineral sources of As that could enter transport pathways leading to its release into groundwater.