Christopher J. Oates

Cadmium levels in Europe: implications for human health

In this study we used the Forum of European Geological Surveys geochemical baseline data to examine the distribution of cadmium (Cd) in Europe, with a particular reference to the international soil and water guideline values. The highest cadmium levels were found to occur in topsoil and to follow closely the distribution of P2O5, suggesting that the contamination was from the use of rock phosphate fertilizer in intensive arable agriculture. In terms of human health impacts, food (up to several hundred μg/day) was found as the only major route of exposure to Cd for the non-smoking general population. It appeared that low levels of chronic exposure to Cd resulted in completely different human health impacts than those high levels that had caused the ‘itai–itai’ disease. Some correlations were suggested between cadmium levels and the age-adjusted prostate or breast cancer rates distributed in the European countries under study.

Complexation of platinum, palladium and rhodium with inorganic ligands in the environment

Platinum (Pt), palladium (Pd) and rhodium (Rh) are emitted by vehicle exhaust catalysts (VECs) and their concentrations have increased significantly in various environmental compartments, including airborne particulate matter, soil, roadside dust, vegetation, rivers and oceanic environments, over the last two decades as the use of VECs has increased. However, data on the chemical speciation of the platinum-group elements (PGEs) and their bioavailabilities are limited. In this paper, the thermodynamic computer model, HSC, has been used to predict the interactions of Pt, Pd and Rh with different inorganic ligands and to estimate the thermodynamic stability of these species in the environment. Eh–pH diagrams for the PGEs in aqueous systems under ambient conditions (25°C and 1 bar) in the presence of Cl, N and S species have been prepared. The results indicate that Pt, Pd and Rh can form complexes with all of the inorganic ions studied, suggesting that they are capable of mobilizing the PGEs as aqueous complexes that can be transported easily in environmental and biological systems and that are able to enter the food chain. Hydroxide species can contribute to the transport of PGEs in oxidizing environments such as road-runoff waters, freshwater, seawater and soil solutions, whereas bisulphide complexes could transport Pt and Pd in reducing environments. Ammonia species appear to be significant under near-neutral to basic oxidizing conditions. Chloride species are likely to be important under oxidizing, acidic and saline environments such as seawater and road-runoff waters in snowmelt conditions. Mixed ammonia–chloride species may also contribute to the transport of Pt and Pd in highly saline solutions.

Continuous leach inductively coupled plasma mass spectrometry : applications for exploration and environmental geochemistry

Continuous leach inductively coupled plasma mass spectrometry (CL-ICP-MS) is a new analytical technique developed to address some of the shortcomings of bulk leach techniques while overcoming the uncertainties associated with interpreting selective extraction data. It provides information on the specific geochemical sites and mineral phases from which elements are being released using real-time data generated by continually analysing progressively reactive solutions from water to 30% nitric acid as they are pumped through a sample directly into a high resolution ICP mass spectrometer. Mineral breakdown reactions can be monitored from the major elements released, thereby eliminating uncertainties related to host phase/trace element associations. By comparing major and minor element release patterns, trace elements can be reliably assigned to host phases. Results from single mineral phases, mixtures of mineral phases, and natural ore samples indicate that the release of elements from specific minerals is not obscured in more complex samples and that reprecipitation and back reactions are not a concern with this method. Scanning electron micrograph (SEM) examination of the reaction products has been used to verify which phases react and to support the CL-ICP-MS data interpretation. Results for natural soil samples indicate that ‘false’ mobile element anomalies can be identified using CL-ICP-MS and underscore the importance of understanding where trace elements reside in samples used for environmental studies or mineral exploration.

Till and vegetation geochemistry at the Talbot VMS Cu-Zn prospect, Manitoba, Canada: implications for mineral exploration

The Proterozoic Talbot VMS occurrence in the Flin Flon-Snow Lake terrane is buried under more than 100 m of Palaeozoic dolomites and Quaternary glacial till. Structurally controlled anomalies of Zn, Cu, Ag, Pb, Au, Mn, Hg, Cd, Co, Bi and Se in the clay fraction of till depth-profiles indicate upward element migration from the buried volcanogenic massive sulphide mineralisation and near-surface chemostratigraphic deposition. Principal component analysis and molar element ratios indicate that separation of the <2 µm clay fraction reduces chemical heterogeneity and increases trace-element yield relative to the <250 µm fraction of the till. The greatest anomalies occur at or below 30 cm depth and over faults, suggesting that elements were deposited in the till after upward migration through structures. The ratio Zn/Al in the <250 µm fraction can be used as a proxy for Zn in the clay fraction, producing high-contrast anomalies. Carbon isotopic compositions indicate that these anomalies are related to organic carbon in the clay fraction. Humus, moss and black spruce bark are of limited use for exploration in this environment, because they accumulate atmospheric Pb and Cd, most likely from the Flin Flon smelter at 160 km NW. Black spruce tree rings that formed before smelter operations commenced indicate Zn and Mn anomalies in an uncontaminated sampling material. Much of the initial vertical migration of elements to the surface at the Talbot prospect was driven by upward advection of groundwater through fractures in the dolomite, resulting from a combination of subsurface karst collapse and remnant hydrostatic pressure during glacial retreat.

Lithogeochemistry of the Collahuasi porphyry Cu–Mo and epithermal Cu–Ag (–Au) cluster, northern Chile: Pearce element ratio vectors to ore

Abstract Lithogeochemical vectors to ore-bodies are obscured by the variety of lithological units and the alteration events that have affected them. In the magmatic-hydrothermal context, Pearce element ratio (PER) analysis can be a cost-effective lithogeochemical technique that identifies and eliminates non-hydrothermal sources of variation, thus permitting the definition of material transfer related only to hydrothermal alteration. Dedicated PER diagrams for mafic and felsic lithologies in the world-class porphyry Cu–Mo and epithermal Cu–Ag (–Au) cluster of the Collahuasi district, I Región, northern Chile, effectively model background variability and discriminate between fresh or propylitically altered rocks and those with a hydrolytic alteration overprint. Furthermore, PER diagrams allow for the definition of an alteration index (AI) that quantifies the degree of metasomatic exchange during hydrolytic alteration of a particular rock. Plots of different PER values against the AI show that potassium enrichment during hydrolytic alteration was followed by potassium, calcium and sodium depletion as a result of the destruction of feldspars during sericitic and later argillic alteration. Although PER plots record no mass transfer processes involving major elements during propylitic alteration, the integrated AI for both mafic and felsic units spatially defines the major alteration centres within the district.

From chemical risk assessment to environmental resources management: the challenge for mining

On top of significant improvements and progress made through science and engineering in the last century to increase efficiency and reduce impacts of mining to the environment, risk assessment has an important role to play in further reducing such impacts and preventing and mitigating risks. This paper reflects on how risk assessment can improve planning, monitoring and management in mining and mineral processing operations focusing on the importance of better understanding source–pathway–receptor linkages for all stages of mining. However, in light of the ever-growing consumption and demand for raw materials from mining, the need to manage environmental resources more sustainably is becoming increasingly important. The paper therefore assesses how mining can form an integral part of wider sustainable resources management, with the need for re-assessing the potential of mining in the context of sustainable management of natural capital, and with a renewed focus on its the role from a systems perspective. The need for understanding demand and pressure on resources, followed by appropriate pricing that is inclusive of all environmental costs, with new opportunities for mining in the wastes we generate, is also discussed. Findings demonstrate the need for a life cycle perspective in closing the loop between mining, production, consumption and waste generation as the way forward.

Screening and prioritisation of chemical risks from metal mining operations, identifying exposure media of concern

Metals have been central to the development of human civilisation from the Bronze Age to modern times, although in the past, metal mining and smelting have been the cause of serious environmental pollution with the potential to harm human health. Despite problems from artisanal mining in some developing countries, modern mining to Western standards now uses the best available mining technology combined with environmental monitoring, mitigation and remediation measures to limit emissions to the environment. This paper develops risk screening and prioritisation methods previously used for contaminated land on military and civilian sites and engineering systems for the analysis and prioritisation of chemical risks from modern metal mining operations. It uses hierarchical holographic modelling and multi-criteria decision making to analyse and prioritise the risks from potentially hazardous inorganic chemical substances released by mining operations. A case study of an active platinum group metals mine in South Africa is used to demonstrate the potential of the method. This risk-based methodology for identifying, filtering and ranking mining-related environmental and human health risks can be used to identify exposure media of greatest concern to inform risk management. It also provides a practical decision-making tool for mine acquisition and helps to communicate risk to all members of mining operation teams.

Exploration guidelines for copper-rich iron oxide–copper–gold deposits in the Mantoverde area, northern Chile: the integration of host-rock molar element ratios and oxygen isotope compositions

The Mantoverde area of the III Región of northern Chile hosts numerous copper(–gold) deposits and prospects assigned to the iron oxide–copper–gold (IOCG) clan. These range from sulphide-poor magnetite–apatite–actinolite bodies (e.g. Carmen) to chalcopyrite-rich, hematite-cemented breccias and veins (e.g. Mantoverde, Cerro Negro and Palmira). The most important Cu-rich deposits are associated with the main or, more commonly, subsidiary structures of the plate-boundary-parallel Atacama Fault System, and are hosted by Middle to Upper Jurassic andesites and Lower Cretaceous dioritic to quartz dioritic plutons. The rocks in the wider Mantoverde area exhibit a complex evolution involving early sub-seafloor albitization (stage R1), subsequent, very low-grade diastathermal metamorphism (R2), and more local stage I K and Fe metasomatism and stage II hydrolysis, all preceding the emplacement of sulphide-bearing hematitic breccias and veins (i.e. ore-stage III). We develop a lithogeochemical exploration protocol specifically for Cu-rich IOCG-type deposits hosted by calc-alkaline volcano-plutonic terrains, based on the integration of whole-rock molar element ratios and oxygen isotope chemistry. Zirconium, the most conserved (least mobile) element in the volcanic and plutonic rocks of the area, was used as a common denominator for molar element ratios. The molar ratios Na/Zr, K/Zr and Al/Zr indicate that the host rocks proximal to the major deposits were affected by sodium depletion and potassium enrichment. The molar ratio (14Ca+19Na−14CO2)/(6Si+Al+2Fe+2Mg), recalculated to a percentage scale, constitutes a modified alteration index which can be used to quantify the degree of hydrothermal alteration in the host rocks. However, although this index differentiates barren from potentially prospective sectors (i.e. strongly altered host rocks), it does not identify the hydrolytically altered rocks that are closely associated with economic copper mineralization. The δ18O values of igneous rocks in the Mantoverde area vary widely from +4.2 to +14.1‰. Integrating the modified lithogeochemical alteration index with whole-rock δ18O values differentiates the least altered volcanic and plutonic rocks (i.e. alteration index <30%), with δ18O values close to +7‰, from moderately altered volcanic rocks (alteration index of 30 to 65%) having higher δ18O values of +10 to +13.2‰ due to enrichment in 18O during regional metasomatism hydrothermal alteration sub-seafloor related to albitization and metamorphism. A third group comprises strongly K-feldspathized, Fe-metasomatized and chloritized rocks localized in Cu-mineralized centres which have alteration indexes exceeding 65% and δ18O values of +4.2 to +14.1‰. The δ18O values of paragenetically related minerals indicate that barren, K- and Fe-metasomatized host rocks equilibrated with magmatically derived fluids at temperatures exceeding 420°C. Although no recognizable alteration haloes are associated with the ensuing lower-temperature Cu-(Au) ore stage (III), the genetically related hydrolytic alteration (II) which preceded it generated distinctive alteration indices and Na/Al and K/Al ratios, as well as δ18O values averaging +10‰, with chlorite O and H isotope compositions indicating equilibration with non-magmatic fluids. We propose, in combination, that these parameters can be used to vector onto Cu-rich IOCG-type mineralization in Andean, calc-alkaline terrains.

Solid sampling ETV-ICP-OES to study the distribution of elements in clay and soil samples for mineral exploration

A simple and fast method, using solid sampling electrothermal vapourization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES), was developed to determine the distribution of elements in clay separates and soil samples from across the Talbot Lake VMS Cu-Zn prospect, in the Flin Flon-Snow Lake terrane, Manitoba, Canada in order to locate the undercover ore deposit, which is buried under Palaeozoic dolomites and Quaternary till. In the development of the method, the mass of sample, the mass of carrier agent (polytetrafluoroethylene, PTFE) or flow rate of reactant gas (dichlorodifluoromethane (R12)), the carrier and bypass gas flow rates and the temperature program were optimised. Under optimal conditions and with a four-step ETV temperature program, the distribution of the pathfinder elements (Zn, P, S and I) in clay separates and soils showed clear anomalies at 400 and 650 m. The results for Zn and P are in very good agreement with results obtained, following aqua regia (AR) digestion, by ICP mass spectrometry (ICP-MS) by Anglo American Exploration Division (AA-ED). Moreover, the distributions of S and I could be precisely determined (these elements were not reported in the AA-ED study). Using 0–4 mg of AA-ED S5 standard mixed with 2 mg PTFE or with 4.1 ml/min R12 as reactant gas, and using internal standardisation with an argon emission line, calibration curves were obtained that, when applied to Talbot clay separates and soil samples, yielded Zn, S and P concentrations in agreement with AR-ICP-MS results previously obtained by AA-ED. Hence, ETV-ICP-OES completely eliminates the need for clay separation and for extraction or digestion of samples prior to analysis, which significantly simplifies the analysis of geochemical exploration samples.

Undisclosed chemicals--implications for risk assessment: a case study from the mining industry.

Many of the chemicals used in industry can be hazardous to human health and the environment, and some formulations can have undisclosed ingredients and hazards, increasing the uncertainty of the risks posed by their use. The need for a better understanding of the extent of undisclosed information in chemicals arose from collecting data on the hazards and exposures of chemicals used in typical mining operations (copper, platinum and coal). Four main categories of undisclosed chemicals were defined (incomplete disclosure; chemicals with unspecific identities; relative quantities of ingredients not stated; and trade secret ingredients) by reviewing material safety data sheet (MSDS) omissions in previous studies. A significant number of chemicals (20% of 957 different chemicals) across the three sites had a range of undisclosed information, with majority of the chemicals (39%) having unspecific identities. The majority of undisclosed information was found in commercially available motor oils followed by cleaning products and mechanical maintenance products, as opposed to reagents critical to the main mining processes. All three types of chemicals had trade secrets, unspecific chemical identities and incomplete disclosures. These types of undisclosed information pose a hindrance to a full understanding of the hazards, which is made worse when combined with additional MSDS omissions such as acute toxicity endpoints (LD50) and/or acute aquatic toxicity endpoints (LC50), as well as inadequate hazard classifications of ingredients. The communication of the hazard information in the MSDSs varied according to the chemical type, the manufacturer and the regulations governing the MSDSs. Undisclosed information can undermine occupational health protection, compromise the safety of workers in industry, hinder risk assessment procedures and cause uncertainty about future health. It comes down to the duty of care that industries have towards their employees. With a wide range of chemicals increasingly used, there is a balance that needs to be reached between disclosure requirements, trade secret provisions and definitions of hazardous ingredients for market needs, and the information required to protect the health of their workers.