Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

Laboratory study of calcite–gypsum sludge–water interactions in a flooded tailings impoundment at the Kristineberg Zn–Cu mine,northern Sweden

Due to liming of acid mine drainage, a calcite–gypsum sludge with high concentrations of Zn (24,400 ± 6900 μg g⁻¹), Cu (2840 ± 680 μg g⁻¹) and Cd (59 ± 20 μg g⁻¹) has formed in a flooded tailings impoundment at the Kristineberg mine site. The potential metal release from the sludge during resuspension events and in a long-term perspective was investigated by performing a shake flask test and sequential extraction of the sludge. The sequentially extracted carbonate and oxide fractions together contained ⩾97% of the total amount of Cd, Co, Cu, Ni, Pb and Zn in the sludge. The association of these metals with carbonates and oxides appears to result from sorption and/or coprecipitation reactions at the surfaces of calcite and Fe, Al and Mn oxyhydroxides forming in the impoundment. If stream water is diverted into the flooded impoundment, dissolution of calcite, gypsum and presumably also Al oxyhydroxides can be expected during resuspension events. In the shake flask test (performed at a pH of 7–9), remobilisation of Zn, Cu, Cd and Co from the sludge resulted in dissolved concentrations of these metals that were significantly lower than those predicted to result from dissolution of the carbonate fraction of the sludge. This may suggest that cationic Zn, Cu, Cd and Co remobilised from dissolving calcite, gypsum and Al oxyhydroxides were readsorbed onto Fe oxyhydroxides remaining stable under oxic conditions. In a long-term perspective (≳10² a), ⩾97% of the Cd, Co, Cu, Ni, Pb and Zn content of the sludge potentially is available for release by dissolution of calcite and reductive dissolution of Fe oxyhydroxides if the sludge is subject to a soil environment with lower dissolved Ca concentrations, pH and redox than in the impoundment.     

Chemical and physical properties of iron hydroxide precipitates associated with passively treated coal mine drainage in the Bituminous Region of Pennsylvania and Maryland

Changes in precipitate mineralogy, morphology, and major and trace element concentrations and associations throughout 5 coal mine drainage (CMD) remediation systems treating discharges of varying chemistries were investigated in order to determine the factors that influence the characteristics of precipitates formed in passive systems. The 5 passive treatment systems sampled in this study are located in the bituminous coal fields of western Pennsylvania and northern Maryland, and treat discharges from Pennsylvanian age coals. The precipitates are dominantly (>70%) goethite. Crystallinity varies throughout an individual system, and lower crystallinity is associated with enhanced sorption of trace metals. Degree of crystallinity (and subsequently morphology and trace metal associations) is a function of the treatment system and how rapidly Fe(II) is oxidized, forms precipitates, aggregates and settles. Precipitates formed earlier in the passive treatment systems tend to have the highest crystallinity and the lowest concentrations of trace metal cations. High surface area and cation vacancies within the goethite structure enable sorption and incorporation of metals from coal mine drainage-polluted waters. Sorption affinities follow the order of Zn > Co ≈ Ni > Mn. Cobalt and Ni are preferentially sorbed to Mn oxide phases when these phases are present. As pH increases in the individual CMD treatment systems toward the pH_pzc of goethite, As sorption decreases and transition metal (Co, Mn, Ni and Zn) sorption increases. Sulfate, Na and Fe(II) concentrations may all influence the sorption of trace metals to the Fe hydroxide surface. Results of this study have implications not only for solids disposal and resource recovery but also for the optimization of passive CMD treatment systems.     

Concentration of metals in surface water and sediment of Luilu and Musonoie Rivers,Kolwezi-Katanga,Democratic Republic of Congo

The pollution and deterioration of most important vital rivers in the Katanga region, Democratic Republic of Congo (DRC) are mainly due to the discharge of untreated industrial effluents as well as to the mining and artisanal mineral exploitation activities. In this study, the concentrations of metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, and Pb) and major elements (Na, Mg, and K) in mining effluents, water and sediment samples of two main rivers of the district of Kolwezi (Katanga, DRC) were subjected to analysis by Inductive Coupled Plasma-Mass Spectroscopy (ICP-MS). The results showed that, in general, the metal concentrations in the sampling sites from the mining effluent and river waters exceed largely the World Health Organization and the Aquatic Quality Guidelines for the Protection of Aquatic Life recommendation limits. The highest metal concentrations in water and sediment samples were detected surrounding the mining effluents discharge. In the surface sediments of Luilu River, the values of 47,468 and 13,199 mg kg⁻¹ were observed for Cu and Co, respectively. For the sediment samples from Musonoie River, the maximum values of 370.8 and 240.6 mg kg⁻¹ for Cu and Co, respectively were observed. The results of this study suggest that the mining effluents being discharged into the rivers and the accumulation of pollutants in sediments might represent a source of toxicity for aquatic living organisms and could pose significant human health risks. The measures to establish a monitoring program and the application of wastewater treatment techniques to the mining effluents prior to discharge are recommended to reduce the load of contaminants into the receiving systems.     

Assessment of trace metal and rare earth elements contamination in rivers around abandoned and active mine areas. The case of Lubumbashi River and Tshamilemba Canal,Katanga, Democratic Republic of the Congo

Active and abandoned mine activities constitute the sources of deterioration of water and soil quality in many parts of the world, particularly in the African Copperbelt regions. The accumulation in soils and the release of toxic substances into the aquatic ecosystem can lead to water resources pollution and may place aquatic organisms and human health at risk. In this study, the impact of past mining activity (i.e., abandoned mine) on aquatic ecosystems has been studied using ICP-MS analysis for trace metals and Rare Earth Elements (REE) in sediment samples from Lubumbashi River (RL) and Tshamilemba Canal (CT), Katanga, Democratic Republic of the Congo (DRC). Soil samples from surrounding CT were collected to evaluate trace metal and REE concentrations and their spatial distribution. The extent of trace metal contamination compared to the background area was assessed by Enrichment Factor (EF) and Geoaccumulation Index (I_geo). Additionally, the trace metal concentrations probable effect levels (PELs) for their potential environmental impact was achieved by comparing the trace metal concentrations in the sediment/soil samples with the Sediment Quality Guidelines (SQGs). Spearman's Rank-order correlation was used to identify the source and origin of contaminants. The results highlighted high concentrations of trace metals in surface sediments of CT reaching the values of 40152, 15586, 610, 10322, 60704 and 15152 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. In the RL, the concentrations reached the values of 24093, 2046, 5463, 3340, 68290 and 769 mg kg⁻¹ for Cu, Co, Zn, Pb, Fe and Mn, respectively. The ΣREE varied from 66 to 218 and 142–331 mg kg⁻¹ for CT and RL, respectively. The soil samples are characterized by variable levels of trace metals. The EF analysis showed “extremely severe enrichment” for Cu and Co. However, no enrichment was observed for REE. Except for Mo, Th, U, Eu, Mo, Ho and Tm for which Igeo is classified as “moderately polluted and/or unpolluted”, all elements in different sites are classified in the class 6, “extremely polluted”. The trace metal concentrations in all sampling sites largely exceeded the SQGs and the PELs for the Protection of Aquatic Life recommendation. Cu and Co had positive correlation coefficient values (r = 0.741, P < 0.05, n = 14). This research presents useful tools for the evaluation of water contamination in abandoned and active mining areas.     

Geochemical associations for evaluating the availability of potentially harmful elements in urban soils: Lessons learnt from Athens,Greece

The estimation of potentially harmful element (PHE) availability in urban soil is essential for evaluating impending risks for human and ecosystem health. In the present study five single extraction procedures were evaluated based on the analysis of 45 urban top-soil samples from Athens, Greece. The pseudototal (aqua regia), potentially phytoavailable (0.05 M EDTA), mobilizable (0.43 M HAc), bioaccessible (0.4 M glycine) and reactive pools (0.43 M HNO₃) of PHEs were determined. In general, geogenic elements in Athens soil (Ni, Cr, Co, As) are relatively less available than typical tracers of anthropogenic contamination (Pb, Zn, Cu, Cd). Results of principal component analysis (PCA) indicate an association between available fractions of Pb, Cu, Zn, Cd and amorphous Fe oxides, whereas amorphous Mn oxides account for the available concentrations of Mn, Ni and Co. Empirical multiple linear regression models demonstrate that pseudototal concentration is the predominant explanatory factor of variability for the available pools of the anthropogenic elements. Major elemental composition and total organic carbon (TOC) improve the predictions for the geogenic group of elements, although the explained variability remains low. Dilute HNO₃ is a better predictor of Zn, Ni, As and Mn availability, whereas Pb and Cu available fractions are predicted more accurately by the classical aqua regia protocol. This study contributes to the international database on the environmental behavior of PHEs and provides additional knowledge that can be used toward the harmonization of chemical extraction methodology in urban soil.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.     

Scenario of particulate trace metal and metalloid transport during a major flood event inferred from transient geochemical signals

High-resolution sampling (every 3 h) of SPM was performed during a major flood event in a heterogeneous, medium scale watershed of the Garonne-Gironde fluvial-estuarine system (the Lot River; A = 10,700 km²; Q = 151 m³/s). Particulate metal and metalloid (Cd, Zn, Pb, Co, Cr, Ni, Mo, V, U, As, Sb, Th) concentrations were compared with monthly data of the same site (Temple site) obtained during 1999–2002. During the flood event, suspended particulate matter (SPM) concentrations closely followed river discharge with a maximum value (1530 mg/L) coinciding with the discharge peak (2970 m³/s). Trace metal/metalloid concentrations showed significant temporal variations and very contrasted responses. Particulate concentrations were similar to baseline values at the beginning of the flood and mostly increased during the event, showing anticlockwise and complex shape hystereses. Comparison of SPM yield (440,000 t) and particulate metal/metalloid fluxes during the flood with annual fluxes (1999–2002) highlights the great importance of major flood events in fluvial transport. Adequate sampling frequency during floods is necessary for reliable annual flux estimates and provides geochemical signals that may greatly improve our understanding of fluvial transport processes. The scenario of SPM and metal and metalloid transport during the flood are reconstructed by combining variations of Zn, Cd and Sb concentrations, concentration ratios (e.g. Zn/Cd, As/Th, Cd/Th) and hysteresis loops. Changes in SPM and metal/metalloid transport during distinct key stages of the flood were attributed to successive dominance of different water masses transporting material from different sources (e.g. industrial point source, bed sediment from reservoirs, plain erosion). Flood management (dam flushing) clearly enhanced the remobilization of up to 30-a old polluted sediment from reservoir lakes. Sediment remobilization accounted for ∼185,000 t of SPM (i.e. 42% of the total SPM fluxes during the flood) and strongly contributed to particulate metal/metalloid transport for Cd (90%), Zn (83%) and Pb (61%). Therefore, flood management needs to be taken into consideration in future models for erosion and pollutant transport.     

Metal species in a Boreal river system affected by acid sulfate soils

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations but on their chemical form. Consequently, knowledge of aqueous metal speciation is essential in investigating potential metal toxicity and mobility. Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic C (OC) and 18 metals/metalloids were investigated in the extremely acidic Vörå River system in Western Finland, which is strongly affected by acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these acidic waters. The most important finding of this study is that the very large amounts of elements known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si and U) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and particularly dissolved Al can be expected to have acute effects on fish and other organisms. In the study area, only the relatively forested upstream area (higher pH and contents of OC) had significant amounts of a few bioavailable elements (including Al, Cu, Ni and U) due to complexation with the more abundantly occurring colloidal OC in the upstream area. It is, however, notable that some of the colloidal/particulate metals were most likely associated with metal bearing phyllosilicates eroded from clay soils. Moreover, the mobilisation of Fe and As was small and As was predicted to be associated with Fe oxides, indicating a considerable influence of Fe oxides on the mobilisation/immobilisation processes of As. Elements will ultimately be precipitated in the recipient estuary, where the acidic metal-rich river water will gradually be diluted/neutralised with brackish seawater in the Gulf of Bothnia. According to speciation modelling, such a pH rise may first cause precipitation of Al, Cu and U together with organic matters closest to the river mouth, in line with previous sediment studies from the estuary.     

Geochemical exploration for gold in the Nile Valley Block (A) area,Wadi Allaqi,South Egypt

The present work aims to estimate Au-anomalous distribution patterns, the optimum grain size fraction and pathfinder elements for gold placer. The obtained data of analyzed elements (Au, Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hg, Li, Mn. Mo, Ni, Pb, Rb, Sb, Se, Sr, Te, Ti, V, Y and Zn) in both the fine (?0.25 mm) and coarse (?1 mm+0.25 mm) grain size fractions of 32 dry stream sediment samples, which have been derived from metamorphosed Island Arc volcanic rocks of Late Proterozoic age, revealed that most of the analyzed elements in both grain size fractions are asymmetrically distributed and did not pass the tests of normality. The coarse grain size fraction appears to be the better size fraction for Au detection and can be considered as the optimum grain size fraction for future application in regional stream sediment surveys. The presence of Au anomalies in the upper part of the stream and beside the mine is either sourced by the main Au-mineralization or new potential extension of the mineralization in the study area. Silver, Cd, Se, Zn and Te can be considered as useful pathfinder elements for Au in the coarse grain size fraction, and they may be used for future geochemical exploration for Au in the area. Recommendation of the authors is pointing to perform lithogeochemical survey in the eastern and western parts of the mine.     

Contaminant removal from acidic mine pit water via in situ hydrotalcite formation

Remediation of 56 ML of acidic, contaminant-laden Baal Gammon mine pit water was undertaken using in situ hydrotalcite formation. The pit water composition was modified via the addition of MgCl₂·6H₂O to form a 2.5:1 M²⁺:M³⁺ metal ion ratio followed by the addition of NaOH to increase the pH 10 to induce spontaneous hydrotalcite precipitation. As a result of the in situ hydrotalcite precipitation a broad spectrum of elements of environmental concern including Al, Cd, Co, Cr, Cu, Fe, In, Mn, Mo, Ni, V and Zn were removed from solution. Significantly, an ore grade hydrotalcite precipitate containing Cu (8.0 ± 1.0%) and Zn (3.9 ± 0.5%) was produced directly from the mine pit water column allowing for potential recovery of valuable metals to offset remediation costs. The final water quality produced after in situ remediation was of a simple Na–Cl–SO₄ type.     

Measurement of labile metals in acid rock drainage springs,New Zealand: Field application of anodic stripping voltammetry

Spring waters were analysed in the field by anodic stripping voltammetry, using equipment which is sufficiently portable to be useful in a remote heavily forested area accessible by foot only. The equipment and techniques are capable of producing analyses on site to the μg/L level for labile metals. Field analysis avoids issues of sample storage and transport protocols that limit confidence in laboratory measurements of labile elements. Samples were taken as a feedback to immediate analysis resulting in a fine grid map of the geological site. Acid rock drainage emanates from a New Zealand historic mine site, with elevated concentrations of metals. However, ground water and surface water discharging naturally from mineralised rocks in the same area also have elevated levels of metals. This study quantifies natural metalliferous discharges from a single site, and compares this to the overall metal flux from the mine area. Acid (pH 3) metalliferous springs emanate from colluvium and bedrock in a young (months-old) landslide. Labile Cu, Pb, Zn and Cd are the environmentally most significant metals in the studied area. Labile metal concentrations observed in the natural springs are up to 24 μg/L Cu, up to 50 μg/L Pb, up to 5 μg/L Cd and up to 9 mg/L Zn. Labile Cu and Zn concentrations are similar to laboratory-determined total concentrations, whereas labile Pb and Cd concentrations are generally distinctly lower than total Pb and Cd concentrations. Four different spring water compositions occur within metres of each other: acid metalliferous water with high Pb, acid metalliferous water with low Pb, high Cu, Pb, Zn acid water and high pH water with elevated Cu. High metal concentrations in these waters are readily attenuated by adsorption to Fe oxyhydroxides (HFO), especially when rain raises spring water pH at the surface. Copper, Pb and Cd are >99% adsorbed, and Zn >95% adsorbed, during this rainfall dilution. Natural spring waters have potential to contribute up to 10% of the total Zn flux from the catchment, but negligible proportions of Cu, Pb and Cd.     

Seasonal variations of arsenic at the sediment–water interface of Poyang Lake,China

Arsenic species including arsenite, arsenate, and organic arsenic were measured in the porewaters collected from Poyang Lake, the largest freshwater lake of China. The vertical distributions of dissolved arsenic species and some diagenetic constituents [Fe(II), Mn(II), S(−II)] were also obtained in the same porewater samples in summer and winter. In sediments the concentration profiles of total As and As species bound to Fe–Mn oxyhydroxides and to organic matter were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicate that, in the summer season, the concentrations of total dissolved As varying from 3.9 to 55.8 μg/L in sediments were higher than those (5.3–15.7 μg/L) measured in the winter season, while the concentrations of total As species in the solid phase varied between 10.97 and 25.32 mg/kg and between 7.84 and 30.52 mg/kg on a dry weight basis in summer and winter, respectively. Seasonal profiles of dissolved As suggest downward and upward diffusion, and the flux of dissolved As across the sediment–water interface (SWI) in summer and winter were estimated at 3.88 mg/m² a and 0.79 mg/m² a, respectively. Based on porewater profiles and sediment phase data, the main geochemical behavior of As was controlled by adsorption/desorption, precipitation and molecular diffusion. The solubility and migration of inorganic As are controlled by Fe–Mn oxyhydroxides in summer whereas they appear to be more likely controlled by both amorphous Fe–Mn oxyhydroxides and sulfides in winter. A better knowledge of the cycle of As in Poyang Lake is essential to a better management of its hydrology and for the environmental protection of biota in the lake.     

Environmental assessment of abandoned mine tailings in Adak,Västerbotten district (northern Sweden)

Sulfide-rich mine tailings in Adak that are exposed to weathering cause acid mine drainage characterized by low pH (2–4) and high SO₄ (up to 800 mg L⁻¹). Surface water, sediment and soil samples collected in this study contain higher concentrations of As, Cu, Fe and Zn, compared to the target and/or intervention limits set by international regulatory agencies. In particular, high As concentrations in water (up to 2900 μg L⁻¹) and sediment (up to 900 mg kg⁻¹) are of concern. There is large variability in trace element concentrations, implying that both physical (grain size) and chemical factors (pH, secondary phases as sulfides, Al-oxides or clay minerals) play an important role in their distribution. The low pH keeps the trace elements dissolved, and they are transported farther downstream. Trace element partition coefficients are low (log K_d = 0.3–4.3), and saturation indices calculated with PHREEQC are <0 for common oxide and sulfidic minerals. The sediment and soil samples indicate an enhanced pollution index (up to 17), and high enrichment factors for trace elements (As up to 38,300; Zn up to 800). Finally, leaves collected from different plant types indicate bioaccumulation of several elements (As, Al, Cu, Fe and Zn). However, some of the plants growing in this area (e.g., Salix, Equisétum) are generally resistant to metal toxicity, and hence, liming and phytoremediation could be considered as potential on-site remediation methods.     

Tailings dam seepage at the rehabilitated Mary Kathleen uranium mine,Australia

This study reports on the seepage of metals, metalloids and radionuclides from the Mary Kathleen uranium mill tailings repository. Since rehabilitation in the 1980s, the capped tailings have developed a stratified hydrochemistry, with acid (pH 3.7), saline, metal-rich (Fe, Mn, Ni, U ± As, Pb, Zn), oxygenated (1.05 mg L⁻¹ DO), radioactive waters in the upper tailings pile and near-neutral pH (pH 7.57), metal-poor, reduced (0.08 mg L⁻¹ DO) waters at depth. Seepage (∼0.5 L s⁻¹) of acid (pH 5.5), metal-rich (Fe, Mn ± Ni, U, Zn), radioactive (U-235, U-238, Ra-226, Ra-228, Ac-227) waters occurs from the base of the tailings dam retaining wall into the former evaporation pond and local drainage system. Oxygenation of the seepage waters causes the precipitation of Fe and coprecipitation and adsorption of other metals (U, Y), metalloids (As), rare earth elements (Ce, La) and radionuclides (U-235, U-238). By contrast, alkalis and alkaline–earth elements (Ca, K, Mg, Na, Sr), Mn, sulfate and to some degree metals (U, Zn, Ni), rare earth elements (Ce, La) and radionuclides (U-235, U-238, Ra-226, Ra-228) remain in solution until pH neutralisation and evaporation lead to their precipitation in efflorescences and sulfate-rich evaporative sediments. While the release of contaminant loads from the waste repository through seepage is insignificant (e.g. ∼5 kg of U per year), surface waters downstream of the tailings impoundment possess TDS, U and SO₄ concentrations that exceed Australian water quality guideline values in livestock drinking water. Thus, in areas with a semi-arid climate, even insignificant load releases of contaminants from capped tailings repositories can still cause the deterioration of water quality in ephemeral creek systems.     

Partitioning and mobility of trace metals in the Blesbokspruit: Impact assessment of dewatering of mine waters in the East Rand,South Africa

A suite of trace metals was analyzed in water and sediment samples from the Blesbokspruit, a Ramsar certified riparian wetland, to assess the impact of mining on the sediment quality and the fate of trace metals in the environment. Limited mobility of trace metals was observed primarily because of their high partition coefficient in alkaline waters. Nickel was most mobile with a mean K_d of 10^3.28 L kg⁻¹ whereas Zr was least mobile with a mean K_d of 10^5.47 L kg⁻¹. The overall trace metal mobility sequence, derived for the Blesbokspruit, in increasing order, is: Zr < Cr < Pb < Ba < V < Cu < Zn < Sr < Mn < U < Mo < Co < Ni. Once removed from the solution, most trace metals were preferentially associated with the carbonate and Fe–Mn oxide fraction followed by the exchangeable fraction of the sediments. Organic C played a limited role in trace metal uptake. Only Cu was primarily associated with the organic fraction whereas Ti and Zr were mostly found in the residual fraction. Compared to their regional background, Au and Ag were most enriched, at times by a factor of 20–400, in the sediments. Significant enrichment of U, Hg, V, Cr, Co, Cu and Zn was also observed in the sediments.The calculated geoaccumulation indices suggest that the sediments are very lightly to lightly polluted with respect to most trace metals and highly polluted with respect to Au and Ag. The metal pollution index (MPI) for the 20 sampled sites varied between 2.9 and 45.7. The highest MPI values were found at sites that were close to tailings dams. Sediment eco-toxicity was quantified by calculating the sediment quality guideline index (SQG-I). The calculated SQG-I values (0.09–0.69) suggest that the sediments at the study area have low to moderate potential for eco-toxicity.     

Metal and arsenic distribution in soil particle sizes relevant to soil ingestion by children

Ingestion of soil is a common behaviour in young children as a means of exploring their surroundings. Much attention has been given to remediation of point-source polluted sites with regard to potential health risks for children. However, because of diffuse pollution and long-range atmospheric deposition, soil contaminant levels are generally increased in urban areas compared to their rural counterparts, even in areas located away from any point sources of pollution. Intake of urban soil can thereby result in significant amounts of the child’s daily metal intake. In the present study, soil samples were collected from 25 playgrounds around urban Uppsala, Sweden and analysed for contents of Al, As, Fe, Cr, Cu, Cd, Hg, Mn, Ni, Pb, W and Zn. Prior to aqua regia digestion, the samples were wet-sieved in order to separate soil particle fractions representing deliberate (<4 mm) and involuntary (<50 μm) soil ingestion by children, as well as a third size fraction of 50–100 μm representing soil that is easily transported by suspension. While the metal and As contents in the 50–100 μm fraction were similar to those of the <4 mm fraction, the <50 μm fraction had metal and As contents on average one and a half times higher than those of the <4 mm fraction. The metal and As contents correlated negatively with the sand content in both particle size fractions <4 mm and 50–100 μm, suggesting a general decrease in metal and As content with increasing sand content. However, a positive correlation was found between sand content and the metal and As contents of the finest fraction (<50 μm), suggesting that when the sand content is high, the bulk of the sorbed elements are on the finest particles. The difference between metal and As contents in the different size fractions was greater in the soil sample with the highest sand content than in the sample with the lowest sand content. This implies that texture is a significant factor in metal and As distribution in soils with moderate metal and As contents, when the number of binding sites associated with small particles is low. Tolerable daily intake (TDI) values for Pb and As were exceeded at all sites, and at two sites for Cd, for children with pica behaviour. A high ingestion rate of mainly small particles could also result in the TDI value for Pb being exceeded at 10 sites and that for As at one site. This study also found that soil analysis by the procedure recommended by Swedish authorities accurately represents the metal intake from deliberate soil ingestion, whereas involuntary soil ingestion of mainly small particles could result in metal intakes which are up to twice as high.     

Total concentration,speciation and mobility of potentially toxic elements in soils around a mining area in central Iran

The current study was designed to investigate the extent and severity of contamination as well as the fractionation of potentially toxic elements (As, Cd, Cr, Cu, Pb, Zn, Ni) in minesoils and agricultural soils around a Pb–Zn mine in central Iran. For this purpose, 20 agricultural soils and eight minesoils were geochemically characterized. Results showed that minesoils contained elevated concentrations of As (12.9–254 mg kg⁻¹), Cd (1.2–55.1 mg kg⁻¹), Pb (137–6239 mg kg⁻¹) and Zn (516–48,889 mg kg⁻¹). The agricultural soils were also polluted by As (5.5–57.1 mg kg⁻¹), Cd (0.2–8.5 mg kg⁻¹), Pb (22–3451 mg kg⁻¹) and Zn (94–9907 mg kg⁻¹). The highest recorded concentrations for these elements were in soils influenced directly by tailing ponds. Chromium, Cu and Ni content in agricultural soils (with average value of 74.1, 34.6 and 50.7 mg kg⁻¹, respectively) were slightly higher than the minesoils (with average value of 54.5, 33.1 and 43.4 mg kg⁻¹, respectively). Sequential extraction data indicated that there were some differences between the speciation of PTEs in soil samples. In the agricultural soils, Zn and Cd were mainly associated with carbonate bound fraction, As and Pb with reducible fraction, Cu with oxidisable fraction and Cr and Ni with residual phase. With respect to mobility factor values, Zn and Cd in the agricultural soils have been found to be the most mobile while As mobility is negligible. Also, the mobility factor of As, Cd and Pb in agricultural soils adjoining tailing ponds was high. In minesoil sample Cd was most abundant in the carbonate form, whereas other studied elements were mainly present in the reducible and residual fractions; therefore, despite the high total concentrations of As, Pb and Zn in the minesoils, the environmental risk of these elements was low. Based on the obtained data, a portion of Cu, Cr and Ni input was from agricultural activities.     

Measuring reactive pools of Cd,Pb and Zn in coal fly ash from the UK using isotopic dilution assays

Large volumes of coal fly ash are continually being produced and stockpiled around the world and can be a source of environmentally sensitive trace elements. Whilst leaching tests are used for regulatory purposes, these provide little information about the true geochemical behaviour and ‘reactivity’ of trace elements in coal ash because they are poorly selective. Isotope dilution (ID) assays are frequently used in soil geochemistry as a means of measuring the reactive pools of trace metals that are in equilibrium with soil pore waters. This paper examines the applicability of multi-element ID assays in measuring the labile or reactive pool of Cd, Pb and Zn in a range of fresh and weathered fly ash, where pH is generally much more alkaline than in soils. The method generally worked well using 0.0005 M EDTA as a background electrolyte as it provided robust analytical ICP-MS measurements as well as fulfilling the important principle of ID that non-labile metal should not be solubilised. Reactive pools were equivalent to 0.5–3% of the total Pb pool and 4–13% of the total Cd pool. For Zn, where samples had pH < 11.5, the reactive Zn pool varied between 0.3% and 2%; when fresh ash samples with pH > 11.5 were tested, the method failed as the spiked isotope appeared to be sorbed or precipitated. Ash weathering was found to exert little impact on the lability of Cd, Pb and Zn. Isotope dilution results were compared with 0.43 M HNO₃ and 0.05 M EDTA extractions, these commonly being used as analogues of the ID assay, and concluded that these can be used as fast, cost-effective and simple proxies for the ID assays. Results suggest that ID methods can be used to enhance knowledge of trace element behaviour in fresh and weathered fly ash.     

Rare greenockite (CdS) within the chromite–PGE association in the Bangur Gabbro,Baula-Nuasahi Complex,Eastern India

We report the presence of greenockite from the chromite–PGE–base metal sulfide association in the Bangur Gabbro, Baula-Nuasahi mafic–ultramafic complex. The CdS phase occurs, sans any precursor Cd-bearing phase, as minute grains within siderite micro-veins in close proximity to chlorite in the chalcopyrite + pyrrhotite + pentlandite + violarite assemblage. Using various calibrations, chlorite compositions yielded temperature ranges of 245 to 325 °C. The associated siderite might have formed at or little below the above temperature. Electron probe micro-analyses (EPMA) of greenockite reveal small amounts of Fe (1.01–1.61 wt.%), Zn (1.89–4.54 wt.%), and substitution of Zn for Cd. Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of chalcopyrite nearer to and away from siderite micro-veins that host greenockite confirms maximum Cd concentrations of 78 and 144 ppm, respectively, entailing possible derivation of Cd from chalcopyrite. We propose the transport of Cd as bisulfide complex in a low temperature alkaline and reducing fluid and the simultaneous precipitation of greenockite and siderite by reaction with Fe-rich minerals, aided by decrease in pH and/or increase in f_O2.