Development of rapid techniques based on selective dissolution for the determination of the precious metals in geological samples

The development of a rapid analytical technique for the determination of the platinumgroup elements (PGE) and gold in geological samples is described. The technique is based on selective aqua regia acid leach followed by a selective extraction (using diphenylthiourea and 1,2-dichloroethane) to separate the PGE and Au as a group from concomitant matrix elements. Organic extracts and aqueous raffinates were analysed by graphite furnace atomic absorption spectrometry, for which a comprehensive assessment of matrix interference effects was undertaken. Direct analysis of the aqua regia acid leachates by inductively coupled plasma-mass spectrometry (ICP-MS) was also evaluated. A number of other techniques were used to evaluate recoveries following acid attack, including x-ray fluorescence spectrometry and instrumental neutron activation analysis of solid residues and beta-autoradiography of thin sections to characterise PGE mineral solubility. The results of these investigations identified optimum conditions for aqua regia extraction (20 ml of normal (3: 1) aqua regia for a 10 g sample, stirring for two hours at room temperature) and that quantitative recoveries can be expected for Au and semiquantitative for Pd with lower, but variable recoveries for Pt, Rh, Ru and Os and very low recovery of Ir. The solvent extraction procedure was effective in selectively extracting Au and Rh but was not quantitative in the extraction of Pt, Pd and Ru, the extraction of which appeared to be influenced by the sample matrix. Further studies on the solubility in aqua regia of individual PGE minerals indicated that the main control of aqua regia extraction efficiency was sample mineralogy. The aqua regia leach procedure was applied to a range of samples that had been independently analysed by NiS fire assay as well as appropriate reference materials. This extraction procedure, with direct analysis of leachates by ICP-MS, was also used as the primary technique for characterising the homogeneity of two new chromitite reference materials, CHR-Pt+ and CHR-Bkg

Measuring the solid-phase fractionation of lead in urban and rural soils using a combination of geochemical survey data and chemical extractions

The study used 276 urban soils and 447 rural soils collected from in and around the UK town of Northampton and focussed on the fractionation of Pb. The Pb fractionation obtained from total element data was compared to the fractionation of Pb in a subset of 10 urban soils obtained using a sequential extraction method. The fractionation of the Pb from the total element data and from the sequential extractions was estimated using a self-modelling mixture resolution statistical model. The bioaccessibility of Pb in a subset of 50 of the urban soils, as measured using the unified BARGE method, was shown to be quantitatively linked with Pb fractionation from both the total element and the sequential extraction data. Three intrinsic soil components from the regional total element data model and one physico-chemical component from the sequential extraction data model were identified as the sources of bioaccessible Pb. The source of bioaccessible Pb in both rural and urban soils was tentatively identified as a fine-grained pyromorphite mineral

Bioaccessibility performance data for fifty-seven elements in guidance material BGS 102

BGS 102, a guidance material for bioaccessible arsenic (As) and lead (Pb), was produced during validation of the in vitro Unified Bioaccessibility Method (UBM). This paper reports a compilation of reproducible bioaccessible guidance values for fifty-five additional elements in BGS 102, providing guidance for analysts to broaden the scope of UBM analyses for a wider range of elements based on data collected over an average of 60 separate analytical batches per element. Data are presented in categories for both gastric (STOM) and gastrointestinal (STOM + INT) extraction phases, where reproducibility, measured as relative standard deviation (RSD) was; ≤ 10% RSD for 27 elements (Mg, Al, Si, P, Ca, Cr, Mn, Co, Ni, As, Rb, Sr, Y, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb); between 10 and 20% RSD for 10 elements (Li, K, V, Fe, Cu, Zn, Cd, Lu, Pb, U); and ≥ 20% RSD for 19 elements in the gastric phase (Be, B, S, Ti, Ga, Se, Zr, Nb, Mo, Ag, Sn, Sb, Cs, Hf, Ta, W, Tl, Bi, Th). Two elements (Mg, Rb) met the ≤ 10% RSD criteria in the UBM gastrointestinal extraction phase due to the alkaline conditions of this phase precipitating out the majority of determinands. Certain elements, including Na, K, Zn and Se, were found to be a significant component of the extraction fluids with proportionally higher concentrations compared to the guidance material. Bioaccessible fractions (%BAF) were also calculated, but were found to be a less reproducible format for confirming the accuracy of measurements. The low concentration of some elements of interest in BGS 102, such as antimony (Sb), justifies the preparation of an alternative certified reference material (CRM). This paper presents an opportunity to broaden the scope of the UBM method to address food security issues (e.g. Fe and Zn micronutrient deficiencies) and contributions to dietary intake from extraneous dust or soil through evidence of the analytical possibilities and current limitations requiring further investigation

Acid-dissolution of antigorite, chrysotile and lizardite for ex situ carbon capture and storage by mineralisation

Serpentine minerals serve as a Mg donor in carbon capture and storage by mineralisation (CCSM). The acid-treatment of nine comprehensively-examined serpentine polymorphs and polytypes, and the subsequent microanalysis of their post-test residues highlighted several aspects of great importance to the choice of the optimal feed material for CCSM. Compelling evidence for the non-uniformity of serpentine mineral performance was revealed, and the following order of increasing Mg extraction efficiency after three hours of acid-leaching was established: Al-bearing polygonal serpentine (<5%) ≤ Al-bearing lizardite 1T (≈5%) < antigorite (24-29%) < well-ordered lizardite 2H1 (≈65%) ≤ Al-poor lizardite 1T (≈68%) < chrysotile (≈70%) < poorly-ordered lizardite 2H1 (≈80%) < nanotubular chrysotile (≈85%). It was recognised that the Mg extraction efficiency of the minerals depended greatly on the intrinsic properties of crystal structure, chemistry and rock microtexture. On this basis, antigorite and Al-bearing well-ordered lizardite were rejected as potential feedstock material whereas any chrysotile, non-aluminous, widely spaced lizardite and/or disordered serpentine were recommended. The formation of peripheral siliceous layers, tens of microns thick, was not universal and depended greatly upon the intrinsic microtexture of the leached particles. This study provides the first comprehensive investigation of nine, carefully-selected serpentine minerals, covering most varieties and polytypes, under the same experimental conditions. We focused on material characterisation and the identification of the intrinsic properties of the minerals that affect particle’s reactivity. It can therefore serve as a generic basis for any acid-based CCSM pre-treatment

The terrestrial landscapes of tetrapod evolution in earliest Carboniferous seasonal wetlands of SE Scotland

The Lower Mississippian (Tournaisian) Ballagan Formation in SE Scotland yields tetrapod fossils that provide fresh insights into the critical period when these animals first moved onto land. The key to understanding the palaeoenvironments where they lived is a detailed analysis of the sedimentary architecture of this formation, one of the thickest and most completely documented examples of a coastal floodplain and marginal marine succession from this important transitional time anywhere in the world. Palaeosols are abundant, providing a unique insight into the early Carboniferous habitats and climate. More than 200 separate palaeosols are described from three sections through the formation. The palaeosols range in thickness from 0.02 to 1.85 m and are diverse: most are Entisols and Inceptisols (63%), indicating relatively brief periods of soil development. Gleyed Inseptisols and Vertisols are less common (37%). Vertisols are the thickest palaeosols (up to 185 cm) in the Ballagan Formation and have common vertic cracks. Roots are abundant through all the palaeosols, from shallow mats and thin hair-like traces to sporadic thicker root traces typical of arborescent lycopods. Geochemical, isotope and clay mineralogical analyses of the palaeosols indicate a range in soil alkalinity and amount of water logging. Estimates of mean annual rainfall from palaeosol compositions are 1000 –1500 mm per year. The high mean annual rainfall and variable soil alkalinities contrast markedly with dry periods that developed deep penetrating cracks and evaporite deposits. It is concluded that during the early Carboniferous, this region experienced a sharply contrasting seasonal climate and that the floodplain hosted a mosaic of closely juxtaposed but distinct habitats in which the tetrapods lived. The diversification of coastal floodplain environments identified here may link to the evolution and movement of tetrapods into the terrestrial realm

Trends in heavy metals, polychlorinated biphenyls and toxicity from sediment cores of the inner River Thames estuary, London, UK

River islands (Ait or Eyot) within the inner tidal Thames serve as unique recorders of current and historical estuarine chemical pollution. Sediment cores from Chiswick Ait were assessed for contamination using Microtox® solid phase bioassay, stable isotopes (δ13C, δ15N), heavy metals and polychlorinated biphenyls (PCBs). Microtox® classified these sediments as non-toxic to moderately toxic and bulk isotopes identified a change in organic input. Metals Cu, Zn, Cr, Ni, Cd, Hg and Ag showed parallel rise, peak and fall profiles which when allied to a 207/208Pb and 137Cs based chronology supported major changes in trace metal contributions corresponding to approximate input times of 1940 (rise), 1963 (peak) and 1985 (fall). Metals ranged from Cu 15 to 373 mg kg−1 (mean 141 mg kg−1), Zn 137 to 1331 mg kg−1 (mean 576 mg kg−1), Cr 14–351 mg kg−1 (mean 156 mg kg−1), Pb 10 to 1506 mg kg−1 (mean 402 mg kg−1), As 1 to 107 (mean 38 mg kg−1), Ni 11 to 113 mg kg−1 (mean 63 mg kg−1), Cd 0.2 to 53 mg kg−1 (mean 9 mg kg−1), Hg 1 to 8 mg kg−1 (mean 4.6 mg kg−1) and Ag from 0.7 to 50 mg kg−1 (mean 7.5 mg kg−1). Down core total PCBs ranged from 10.5 to 121 μg kg−1 and mean of 39 μg kg−1. The rise, peak and fall of Cu, Zn, Cr, Ni, Cd and Ag pollution matched local sewage works' treatment discharge records. Whereas the Hg, Pb and As profiles were disconnected, reflecting alternative historic sources and or partitioning behaviour. Comparison to marine sediment quality guidelines indicate that Zn, Pb, Ni, Cd and Hg exceed action level 2, whereas sedimentary Cu, Cr and As concentrations were above action level 1 (no action) but below action level 2 (further investigation required). The river islands of the tidal Thames capture a unique contaminant chemistry record due in part to their location in the tidal frame (salinity minimum) and close proximity to west London

Suitability of 210Pbex, 137Cs and 239+240Pu as soil erosion tracers in western Kenya

Land degradation resulting from soil erosion is a global concern, with the greatest risk in developing countries where food and land resources can be limited. The use of fallout radionuclides (FRNs) is a proven method for determining short and medium-term rates of soil erosion, to help improve our understanding of soil erosion processes. There has been limited use of these methods in tropical Africa due to the analytical challenges associated with 137Cs, where inventories are an order of magnitude lower than in the Europe. This research aimed to demonstrate the usability of 239+240Pu as a soil erosion tracer in western Kenya compared to conventional isotopes 210Pbex and 137Cs through the determination of FRN depth profiles at reference sites. Across six reference sites 239+240Pu showed the greatest potential, with the lowest coefficient of variation and the greatest peak-to-detection limit ratio of 640 compared to 5 and 1 for 210Pbex and 137Cs respectively. Additionally, 239+240Pu was the only radionuclide to meet the ‘allowable error’ threshold, demonstrating applicability to large scale studies in Western Kenya where the selection of suitable reference sites presents a significant challenge. The depth profile of 239+240Pu followed a polynomial function, with the maximum areal activities found between depths 3 and 12 cm, where thereafter areal activities decreased exponentially. As a result, 239+240Pu is presented as a robust tracer to evaluate soil erosion patterns and amounts in western Kenya, providing a powerful tool to inform and validate mitigation strategies with improved understanding of land degradation

Tracking Holocene palaeostratification and productivity changes in the Western Irish Sea: a multi-proxy record

The Western Irish Sea preserves an exceptionally thick (ca. 40 m) Holocene succession that is ideally suited to understanding the pattern of palaeostratification and water mass productivity changes in the region, and their relationship with sea level, sedimentation, and biota. Additionally, the presence of shallow-buried methane provides an opportunity to explore its potential impact on the local pattern of Holocene marine environmental change. Multi-proxy investigation of a cored borehole succession through the Holocene interval tracks changes from mixed to seasonally stratified conditions. In the earliest Holocene (11.2–10 ka), high productivity, mixed water conditions prevailed, with abundant and diverse foraminifera and dominant heterotrophic dinoflagellate cysts. Productivity was probably driven by high nutrient fluxes related to high rates of sedimentation (>1600 cm/kyr), in turn influenced by relatively low sea level and restricted sediment accommodation space across shelf areas to the east of the borehole site (eastern Irish Sea Basin). With rising sea level in the later part of the Early Holocene, the region evolved into a relatively lower productivity mixed water mass system, with significant changes in ecology revealed by dinoflagellate cysts and foraminifera. In the latest Early Holocene and earliest Mid Holocene (ca. 8.4–8.2 ka) a return to higher productivity is signalled by dinoflagellate cyst data; a result of seasonal stratification becoming established, evidenced by sharply increased summer sea surface temperature estimates (typically 16–17 °C) that contrast with an opposite (more positive) trend in δ18O values for benthic foraminifera. Reductions in turbulent mixing associated with stratification might have exacerbated the palaeoecological impact of shallow-buried methane associated with the borehole site, potentially evidenced by a significant change in dominant benthic foraminifera and strong, localised excursions in the benthic δ13C/δ18O record

Mining of nickel laterites – towards more environmentally responsible operations

Primary mining of technology metal ores is needed to enable effective decarbonisation. The use of nickel in rechargeable batteries is expected to increase global demand for nickel rapidly over the coming years. Over 60% of annual global nickel production originates from nickel laterites, with Indonesia and the Philippines leading the market. Mining of nickel laterite ore can adversely affect the environment through the release of CO2 and potentially hazardous elements (PHE), such as hexavalent chromium, or asbestiform minerals. Through our better understanding of the social and environmental impacts of mining operations and the availability of technologies that can potentially mitigate adverse impact, it is paramount to aim for more responsible mining and metal recovery operations. This study focuses on the Sta Cruz nickel laterite deposit in the Philippines. Through a multi-scale and multi-technique analytical programme and drawing on existing knowledge1,2, we appraise the deposit holistically, focusing on (i) the geochemistry and mineralogy of major commodities and trace metals, such as the platinum group elements; (ii) carbonate forming metals, e.g. magnesium and (iii) the presence and ecotoxicity of PHE and minerals. We use this understanding to assess the potential for a circular economy in mining, via complete utilisation of the ore to maximise the metal output and minimise the waste produced. This includes the removal of CO2 through the formation of carbonate minerals (mineral carbonation). We also investigate the potential of carbonates to immobilise chromium crystallographically alongside the CO2. This aspect of mineral carbonation is currently poorly understood. We have carried out laboratory synthesis of chromium-doped carbonates at ambient P-T conditions, which indicates that the most common magnesium carbonates do not readily accommodate chromium. However, other carbonate-bearing minerals, including those belonging to layered double hydroxides, present a viable alternative. The combined PHE-CO2 mineral carbonation, when implemented at different stages of metal recovery, from ore extraction to processing, could lead to a reduction of the volume and toxicity of waste, collectively contributing to the mitigation of the adverse environmental impact of nickel laterite mining. [1] Acquino et al (2022) Minerals, 12(3) [2] Bacuta et al (1990) Journal of Geochem.Exploration, 3