Duncan Pirrie

Rapid quantitative mineral and phase analysis using automated scanning electron microscopy (QemSCAN); potential applications in forensic geoscience

Abstract QemSCAN is a scanning electron microscope (SEM) system, initially designed to support the mining industry by providing rapid automated quantitative mineral analyses. The system is based upon Carl Zeiss SEMs fitted with up to four light-element energy dispersive X-ray spectrometers. Representative subsamples are mounted into either resin or wax blocks and polished prior to analysis, or can be mounted onto carbon tape. During analysis, X-ray spectra are collected at a user-defined pixel spacing and are acquired very rapidly (c. 10 ms per pixel). The measured spectra are automatically compared against a database of known spectra and a mineral or phase name is assigned to each measurement point by the QemSCAN computer software programs. In this way the near-surface qualitative elemental composition of each particle is systematically mapped, assigned to a mineral name or chemical compound/species, and digital pixel maps of each particle are created. Depending upon a range of parameters, including the particle size and the user-defined pixel spacing (which can vary between 0.20 μm and 25 μm), approximately 1000 particles, each 1–10 μm in size, can be measured per hour using a 1 μm pixel spacing. In addition to providing a qualitative elemental analysis and mineralogical or phase assignment for each particle, data relating to particle size, shape and calculated specific density are also generated. In this study, the potential application of this automated SEM system in forensic geoscience was evaluated by the analysis of: (1) a series of soil samples, and (2) a series of dust samples from an industrial complex. In both case studies, the mine-ralogy/phase composition of each sample analysed was found to be distinctive. In addition, textural data for the soil samples and particle shape data for the dust samples show that they can be clearly distinguished. Automated SEM using QemSCAN has clear potential application in the analysis of soil or other trace evidence in forensic case work.

Cretaceous-Tertiary high-latitude palaeoenvironments: James Ross Basin, Antarctica

High-latitude settings are sensitive to climatically driven palaeoenvironmental change and the resultant biotic response. Climate change through the peak interval of Cretaceous warmth, Late Cretaceous cooling, onset and expansion of the Antarctic ice sheet, and subsequently the variability of Neogene glaciation, are all recorded within the sedimentary and volcanic successions exposed within the James Ross Basin, Antarctica. This site provides the longest onshore record of Cretaceous–Tertiary sedimentary and volcanic rocks in Antarctica and is a key reference section for Cretaceous–Tertiary global change. The sedimentary succession is richly fossiliferous, yielding diverse invertebrate, vertebrate and plant fossil assemblages, allowing the reconstruction of both terrestrial and marine systems. The papers within this volume provide an overview of recent advances in the understanding of palaeoenvironmental change spanning the mid-Cretaceous to the Neogene of the James Ross Basin and related biotic change, and will be of interest to many working on Cretaceous and Tertiary palaeoenvironmental change.

Controls on the petrographic evolution of an active margin sedimentary sequence: the Larsen Basin, Antarctica

Abstract The sedimentary fill of the Cretaceous-Tertiary Larsen Basin, located at the northern tip of the Antarctic Peninsula, records the evolution of the Antarctic Peninsula source terrain. Uplift, and the possible renewal of arc volcanism within this area, is documented by the wide petrographic spread in the lower Gustav Group (Barremian-Coniacian). The Hidden Lake Formation (Coniacian-Santonian) records a major pulse in proximal calc-alkaline arc volcanism. The overlying Marambio Group shows a change from lithic-volcanic sandstones to quartz-feldspar-rich sandstones, reflecting a change in source terrain. An abrupt change in sandstone composition in the upper Santa Marta Formation (Campanian) may reflect both a switch in volcanism and plutonism from the east to the west coast of the Antarctic Peninsula (i.e. away from the basin margin), and a change to more mafic volcanism. The Lopez de Bertodano Formation (Campanian-Palaeocene) dominantly reflects a change to a quartzo-feldspathic source terrain (the Trinity Peninsula Group). This is also related to both a decrease in the intensity of arc volcanism and an increase in distance from the location of concurrent volcanism in relation to the site of deposition. Controls on petrography other than simple arc-unroofing (e.g. location and nature of arc volcanism and depositional setting) play an important role in sandstone petrography. These controls on sandstone composition should always be considered in interpreting sequences from active plate margin settings.

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.

Reworked late Neogene Austrochlamys anderssoni (Mollusca: Bivalvia) from northern James Ross Island, Antarctica

Abstract We report on the discovery of a new outcrop of fossiliferous Neogene sediments on northern James Ross Island, northern Antarctic Peninsula. Approximately 100 specimens of the pectinid bivalve Austrochlamys anderssoni (Hennig, 1911) were collected from the permafrost active layer. This bivalve species has a late Miocene to late Pliocene range and has previously been reported from both the glaciomarine Hobbs Glacier Formation and the interglacial Cockburn Island Formation in the James Ross Island area. The localized presence of abundant A. anderssoni within the permafrost suggests that the fossils have been frost heaved from an outcrop of either the Cockburn Island or the Hobbs Glacier formations, originally deposited on northern James Ross Island. The overall shell form, general absence of associated Antarctic Peninsula-derived clasts in the host sediment, and the measured 87Sr/86Sr isotope ratio of the shells (0.709050) which is indistinguishable from that for pectinid bivalves from the Cockburn Island Formation on Cockburn Island (0.709047) suggest that the shells were derived from a unit similar in age to the Cockburn Island Formation. This suggests that the Cockburn Island Formation was originally more laterally extensive than was previously known.

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.

Tracing the record of early alluvial tin mining on Dartmoor, UK

Abstract Although there has been considerable speculation, there is as yet no conclusive evidence to confirm Dartmoor as a tin producing region in prehistory. This is in part due to extensive tin mining on the moor during the Medieval period destroying evidence of earlier mining activity. This paper presents the preliminary results of an integrated mineralogical and geochemical geoarchaeological approach to identifying the record of early mining activity. Floodplain sedimentary successions, that have not themselves been mined, and are downstream of known areas of tin streaming, retain a geochemical record of the mining activities because the early tin streaming released large quantities of mine waste tailings. Where these successions can be dated, they provide an indirect means of testing the record of mining activity on Dartmoor. Geochemical and mineralogical analyses of datable fluvial sediments aimed to (a) distinguish between natural and mine contaminated sediments, and (b) to date the onset of sediment aggradation caused by tin mining activity in the headwaters. Results from the Avon Valley show negligible Sn concentrations in basal silts that are dated to pre-2845 ± 45 yrs bp. Overlying silts are enriched in Sn and were deposited after 1560 ± 40 ad, suggesting that the Sn enrichment corresponds with tin streaming in the 16th century. In the Erme Valley, significant Sn enrichment post-dates an organic-rich silt dated at 1280 ± 45 ad. At both sites there is sediment aggradation coupled with an enhancement in Sn concentration consistent with mine waste contamination as a result of Medieval tin streaming.

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.