Background concentrations of elements in surface soils and their changes as affected by agriculture use in the desert-oasis ecotone in the middle of Heihe River Basin,North-west China

The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg^− 1, Al 49.4 g kg^− 1, Fe 19.1 g kg^− 1, Ca 29.4 g kg^− 1, Mg 8.9 g kg^− 1, K 20.1 g kg^− 1, Na 17.5 g kg^− 1 and P 0.338 g kg^− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg^− 1, Mn 404.8 mg kg^− 1, Ni 17.7 mg kg^− 1, Cu 5.1 mg kg^− 1, Zn 33.7 mg kg^− 1, Pb 15.5 mg kg^− 1 and As 5.2 mg kg^− 1) and (c) other trace elements (Ti 2.0 mg kg^− 1, V 55.3 mg kg^− 1, Co 5.7 mg kg^− 1, Rb 82.4 mg kg^− 1, Sr 232.9 mg kg^− 1, Y 14.7 mg kg^− 1, Zr 194.9 mg kg^− 1, Nb 7.8 mg kg^− 1 and Ba 720.6 mg kg^− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.     

Particulate-associated potentially harmful elements in urban road dusts in Xi’an,China

Sixty five urban road dust samples were collected from different land use areas of ∼240 km² in Xi’an, China. The concentrations of Ag, As, Cr, Cu, Hg, Pb, Sb and Zn were determined to investigate potentially harmful element (PHE) contamination, distribution and possible sources. In addition, the concentrations in different size fractions were measured to assess their potential impact on human health. The highest concentrations were found in the fraction with particle diameters between 80 μm and 101 μm, the finest particles (<63 μm) were not the most important carriers for Ag, As, Cd, Cr, Cu, Hg, Pb and Zn. The percentages of these elements in particles with diameters less than 63 μm (PM₆₃) and less than 101 μm (PM₁₀₁) were in the range of 7–15%, and 30–55%, respectively. Three main factors influencing element distributions have been identified: (a) industrial activities; (b) prior agricultural land use; and (c) other activities commonly found in urban areas, such as traffic, coal combustion, waste dumping, and building construction/renovation. The highest concentrations were found in industrial areas for As (20 mg kg⁻¹), Cr (853 mg kg⁻¹), Cu (1071 mg kg⁻¹), Pb (3060 mg kg⁻¹) and Zn (2112 mg kg⁻¹), and in previous agricultural areas for Ag and Hg, indicating significant contributions from industrial activities and prior agricultural activities.     

Preliminary investigations on the defluoridation of water using fired clay chips

The adsorption of fluoride ions on ground fired clay pot has been investigated. The maximum efficiency of the adsorbent for defluoridating 1–2 litres of water was found to be 200 mg fluoride kg⁻¹ adsorbent. The investigation showed that 5–20 mg l⁻¹ fluoride, from 1 litre of water, could be reduced to less than 1.5 mg l⁻¹ using 120–240 g of the adsorbing medium. The effects of the dose of the medium, the pH, the contact time and the initial fluoride content were studied in relation to defluoridation efficiency. Comparison of fluoride removal capacity of the adsorbent was also made with those of fired brick, clay soil and red ash. The latter exhibited practically no adsorption. A packed column of the same ground clay pot was saturated with 285 mg fluoride kg⁻¹ of adsorbent when 20 litres of water containing 10 mg l⁻¹ F was allowed to pass through it. This column defluoridated 6 litres of tap water containing 10 ppm F⁻ to below 1.5 mg l⁻¹.     

Environmental geochemistry of an active Hg mine in Xunyang,Shaanxi Province,China

The Xunyang Hg mine (XMM) situated in Shaanxi Province is an active Hg mine in China. Gaseous elemental Hg (GEM) concentrations in ambient air were determined to evaluate its distribution pattern as a consequence of the active mining and retorting in the region. Total Hg (HgT) and methylmercury (MeHg) concentrations in riparian soil, sediment and rice grain samples (polished) as well as Hg speciation in surface water samples were measured to show local dispersion of Hg contamination. As expected, elevated concentrations of GEM were found, ranging from 7.4 to 410 ng m⁻³. High concentrations of HgT and MeHg were also obtained in riparian soils, ranged from 5.4 to 120 mg kg⁻¹ and 1.2 to 11 μg kg⁻¹, respectively. Concentrations of HgT and MeHg in sediment samples varied widely from 0.048 to 1600 mg kg⁻¹ and 1.0 to 39 μg kg⁻¹, respectively. Surface water samples showed elevated HgT concentrations, ranging from 6.2 to 23,500 ng L⁻¹, but low MeHg concentrations, ranging from 0.022 to 3.7 ng L⁻¹. Rice samples exhibited high concentrations of 50–200 μg kg⁻¹ in HgT and of 8.2–80 μg kg⁻¹ in MeHg. The spatial distribution patterns of Hg speciation in the local environmental compartments suggest that the XMM is the source of Hg contaminations in the study area.     

Alteration of As-bearing phases in a small watershed located on a high grade arsenic-geochemical anomaly (French Massif Central)

At a watershed scale, sediments and soil weathering exerts a control on solid and dissolved transport of trace elements in surface waters and it can be considered as a source of pollution. The studied subwatershed (1.5 km²) was located on an As-geochemical anomaly. The studied soil profile showed a significant decrease of As content from 1500 mg kg⁻¹ in the 135–165 cm deepest soil layer to 385 mg kg⁻¹ in the upper 0–5 cm soil layer. Directly in the stream, suspended matter and the <63 μm fraction of bed sediments had As concentrations greater than 400 mg kg⁻¹. In all these solid fractions, the main representative As-bearing phases were determined at two different observation scales: bulk analyses using X-ray absorption structure spectroscopy (XAS) and microanalyses using scanning electron microscope (SEM) and associated electron probe microanalyses (EPMA), as well as micro-Raman spectroscopy and synchrotron-based micro-scanning X-ray diffraction (μSXRD) characterization. Three main As-bearing phases were identified: (i) arsenates (mostly pharmacosiderite), the most concentrated phases As in both the coherent weathered bedrock and the 135–165 cm soil layer but not observed in the river solid fraction, (ii) Fe-oxyhydroxides with in situ As content up to 15.4 wt.% in the deepest soil layer, and (iii) aluminosilicates, the least concentrated As carriers. The mineralogical evolution of As-bearing phases in the soil profile, coupled with the decrease of bulk As content, may be related to pedogenesis processes, suggesting an evolution of arsenates into As-rich Fe-oxyhydroxides. Therefore, weathering and mineralogical evolution of these As-rich phases may release As to surface waters.     

Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

Rhizosphere and flooding regime as key factors for the mobilisation of arsenic and potentially harmful metals in basic,mining-polluted salt marsh soils

The occurrence of mining areas in the vicinities of salt marshes may affect their ecological functions and facilitate the transfer of pollutants into the food chain. The mobilisation of metals in salt marsh soils is controlled by abiotic (pH, redox potential) and biotic (influence of rhizosphere) factors. The effect of the rhizosphere of two plant species (Sarcocornia fruticosa and Phragmites australis) and different flooding regimes on potentially harmful metals and As mobilisation from salt marsh soil polluted by mining activities were investigated (total concentrations: 536 mg kg⁻¹ As, 37 mg kg⁻¹ Cd, 6746 mg kg⁻¹ Pb, 15,320 mg kg⁻¹ Zn). The results show that the changes in redox conditions (from 300 mV to −100 mV) and pH after flooding and rewetting periods may mobilise the contaminant elements into soil solution (e.g., 100 μg L⁻¹ Cd, 30 μg L⁻¹ Pb, 7 mg L⁻¹ Zn), where they are available for plants or may be leached from the soil. Drying periods generated peaks of concentrations in the soil solution (up to 120 μg L⁻¹ Cd and 50 μg L⁻¹ Pb). The risk assessment of As and metal-polluted salt marshes should take into account flood dynamics in order to prevent metal(loid) mobilisation.     

Estimating specific surface area of fine stream bed sediments from geochemistry

Specific surface area (SSA) of headwater stream bed sediments is a fundamental property which determines the nature of sediment surface reactions and influences ecosystem-level, biological processes. Measurements of SSA – commonly undertaken by BET nitrogen adsorption – are relatively costly in terms of instrumentation and operator time. A novel approach is presented for estimating fine (<150 μm) stream bed sediment SSA from their geochemistry – after removal of organic matter – for agricultural headwater catchments across 15,400 km² of central England, UK. From a regional set of 1972 stream bed sediment sites with common characteristics for which geochemical data were available, 60 samples were selected – based on maximising their variation in Al concentrations – and their BET SSA measured by N₂ adsorption. After careful selection of potential regression predictors following a principal component analysis and removal of a subset of samples with the largest Mo concentrations (>2.5 mg kg⁻¹), four elements were identified as significant predictors of SSA (ordered by decreasing predictive power): V > Ca > Al > Rb. The optimum model from these four elements accounted for 73% of the variation in bed sediment SSA (range 6–46 m² g⁻¹) with a root mean squared error of prediction – based on leave-one-out cross-validation – of 6.3 m² g⁻¹. It is believed that V is the most significant predictor because its concentration is strongly correlated both with the quantity of Fe-oxides and clay minerals in the stream bed sediments, which dominate sediment SSA. Sample heterogeneity in SSA – based on triplicate measurements of sub-samples – was a substantial source of variation (standard error = 2.2 m² g⁻¹) which cannot be accounted for in the regression model.     

Effects of anthropopressure and soil properties on the accumulation of polycyclic aromatic hydrocarbons in the upper layer of soils in selected regions of Poland

Fifty soil samples collected from agricultural land in four regions of Poland with different anthropopressure were analysed for their content of 16PAHs by GC/MS. The regions correspond to Polish administrative units (voievodeships): Podlaskie and Lubelskie are situated in the rural East part of the country and more industrialised Slaskie and Dolnoslaskie voievodeships – in the South-West part. Basic physicochemical properties as well as the content of selected potentially harmful metals (Pb and Zn) were included in the soil analysis. Overall accumulation of Σ16PAHs in the upper soil layer was within the range 73–1800 μg kg⁻¹ with a geometric mean (GM) of 252 μg kg⁻¹, while the mean benzo(a)pyrene (BaP) load was 20 μg kg⁻¹. This corresponds with data for other European countries. Carcinogenic compounds contributed nearly in 50% to the total PAHs loads. In uncontaminated rural regions the mean Σ16PAHs and BaP contents were 113–159 μg kg⁻¹ and 11–13 μg kg⁻¹, respectively. Regional conditions strongly influenced the accumulation of PAHs ?4-rings, which were highly dependent (over 95%) on local anthropopressure expressed as dust and 4PAHs emission indexes. Soil acidity was the main soil parameter related to the accumulation of higher molecular weight PAHs in soils. In more contaminated regions a significant link between soil OM and PAH loads was noted. The same regions were characterised by associations between PAHs and potentially harmful metals implying common sources of pollution. Those relationships were not observed in the uncontaminated part of the country. The lower molecular weight PAHs contributed to a smaller extent (about 20%) to the total PAHs content in soils, and were less affected by anthropogenic factors.     

Zinc mobility and speciation in soil covered by contaminated dredged sediment using micrometer-scale and bulk-averaging X-ray fluorescence, absorption and diffraction techniques

The mobility and solid-state speciation of zinc in a pseudogley soil (pH = 8.2-8.3) before and after contamination by land-disposition of a dredged sediment ([Zn] = 6600 mg kg⁻¹) affected by smelter operations were studied in a 50 m² pilot-scale test site and the laboratory using state-of-the-art synchrotron-based techniques. Sediment disposition on land caused the migration of micrometer-sized, smelter-related, sphalerite (ZnS) and franklinite (ZnFe₂O₄) grains and dissolved Zn from the sediment downwards to a soil depth of 20 cm over a period of 18 months. Gravitational movement of fine-grained metal contaminants probably occurred continuously, while peaks of Zn leaching were observed in the summer when the oxidative dissolution of ZnS was favored by non-flooding conditions. The Zn concentration in the <50 μm soil fraction increased from ∼61 ppm to ∼94 ppm in the first 12 months at 0-10 cm depth, and to ∼269 ppm in the first 15 months following the sediment deposition. Higher Zn concentrations and enrichments were observed in the fine (<2 μm) and very fine (<0.2 μm) fractions after 15 months (480 mg kg⁻¹ and 1000 mg kg⁻¹, respectively), compared to 200 mg kg⁻¹ in the <2 μm fraction of the initial soil. In total, 1.2% of the Zn initially present in the sediment was released to the environment after 15 months, representing an integrated quantity of ∼4 kg Zn over an area of 50 m². Microfocused X-ray fluorescence (XRF), diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques were used to image chemical associations of Zn with Fe and Mn, and to identify mineral and Zn species in selected points-of-interest in the uncontaminated and contaminated soil. Bulk average powder EXAFS spectroscopy was used to quantify the proportion of each Zn species in the soil. In the uncontaminated soil, Zn is largely speciated as Zn-containing phyllosilicate, and to a minor extent as zincochromite (ZnCr₂O₄), ^IVZn-sorbed turbostratic birnessite (δ-MnO₂), and Zn-substituted goethite. In the upper 0-10 cm of the contaminated soil, ∼60 ± 10% of total Zn is present as ZnS inherited from the overlying sediment. Poorly-crystalline Zn-sorbed Fe (oxyhydr)oxides and zinciferous phyllosilicate amount to ∼20-30 ± 10% each and, therefore, make up most of the remaining Zn. Smaller amounts of franklinite (ZnFe₂O₄), Zn-birnessite and Zn-goethite were also detected. Further solubilization of the Zn inventory in the sediment, and also remobilization of Zn from the poorly-crystalline neoformed Fe (oxyhydr)oxide precipitates, are expected over time. This study shows that land deposition of contaminated dredged sediments is a source of Zn for the covered soil and, consequently, presents environmental hazards. Remediation technologies should be devised to either sequester Zn into sparingly soluble crystalline phases, or remove Zn by collecting leachates beneath the sediment.     

Phosphorus status and sorption characteristics of some calcareous soils of Hamadan,western Iran

Phosphorus (P) application in excess of plant requirement may result in contamination of drinking water and eutrophication of surface water bodies. The phosphorous buffer capacity (PBC) of soil is important in plant nutrition and is an important soil property in the determination of the P release potential of soils. Phosphorus sorption greatly affects both plant nutrition and environmental pollution. For better and accurate P fertilizer recommendations, it is necessary to quantify P sorption. This study was conducted to investigate available P and P sorption by calcareous soils in a semi-arid region of Hamadan, western Iran. The soil samples were mainly from cultivated land. Olsen’s biocarbonate extractable P (Olsen P) varied among soils and ranged from 10 to 80 mg kg⁻¹ with a mean of 36 mg kg⁻¹. Half of the soils had an Olsen P > 40 mg kg⁻¹ and >70% of them had a concentration >20 mg kg⁻¹, whereas the critical concentration for most crops is <15 mg P kg⁻¹. Greater average Olsen P in soils occurred under garlic (56 mg kg⁻¹) and potato (44 kg kg⁻¹) fields than in dry-land wheat farming (24 mg kg⁻¹), pasture (30 mg kg⁻¹), and wheat (24 mg P kg⁻¹) fields. A marked increase in fertilizer P rates applied to agricultural soils has caused P to be accumulated in the surface soil. Phosphate sorption curves were well fitted to the Freundlich equation. The standard P requirement (SPR) of soils, defined as the amount of P sorbed at an equilibrium concentration of 0.2 mg l⁻¹ ranged from 4 to 102 mg kg⁻¹. Phosphorus buffer capacity was relatively high and varied from 16 to 123 l kg⁻¹ with an average of 58 l kg⁻¹. In areas of intensive crop production, continual P applications as P fertilizer and farmyard manure have been used at levels exceeding crop requirements. Surface soil accumulations of P are high enough that loss of P in surface runoff and a high risk for P transfer into groundwater have become priority management concerns.     

Spatial distribution and source diagnosis of polycyclic aromatic hydrocarbons in soils from Chengdu Economic Region,Sichuan Province,western China

Surface soils from the Chengdu Economic Region (CER) were analyzed for sixteen United States Environment Protection Agency priority polycyclic aromatic hydrocarbons (PAHs) to study the spatial distribution and to identify the sources of PAHs. Relatively high concentrations (more than 1500 ngg^− 1) of high molecular weight PAHs were found in Chengdu Plain, in the middle of CER, while high concentrations (more than 500 ng g^− 1) of low molecular weight PAHs were detected in the surrounding mountains. The concentrations of ∑₁₆-PAHs in topsoil samples from CER (12.52–75,431.47 ngg^− 1, average value was 3233.92 ngg^− 1) were higher than that from the southern China (21.91–3077 ngg^− 1, average value was less than 500 ngg^− 1), and they were comparable to concentrations in soils from the northern China (366–254,080 ngg^− 1, mean value was more than 3000 ngg^− 1). The concentrations from CER were also much higher than the concentrations of some world clean regions such as Antarctic (34.9–171 ngg^− 1), European high mountains (9–11,000 ngg^− 1, mean value was 158 ngg^− 1) and some Europe residential (736 ngg^− 1) and arable soils (60–145 ngg^− 1, mean value was 66 ngg^− 1). The ratio of tracer compounds (BaA/(BaA + Chr), Flo/(Flo + Pyr), and IcdP/(IcdP + BghiP)) indicated that the high concentrations of PAHs in soils were mainly derived from fossil fuels combustion in mountain region and from the incomplete combustion of petroleum in developed plain area (such as Chengdu and Deyang). From the above distribution characteristics and ratios of tracer compounds, we inferred the reasons for the distribution pattern of PAHs in CER were the domestic heating, emissions, and the physicochemical properties of PAHs.     

Natural radioactivity in sediment of Wei River,China

The concentrations of natural radionuclides in sediment of Wei River of China were measured using γ-ray spectrometry with the aim of estimating the radiation hazard as establishing a database for radioactivity levels of river sediment of China. The activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in sediment samples ranged from 10.4 to 39.9 Bq kg⁻¹, 15.3 to 54.8 Bq kg⁻¹ and 514.8 to 1,175.5 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil and Shaanxi soil. Radium equivalent activity (Ra_eq), external hazard index (H _ex) and representative level index (I _γr) were calculated for the samples to assess the radiation hazards arising due to the use of these sediment samples in the construction of dwellings. All the sediment samples have Ra_eq lower than the limit of 370 Bq kg⁻¹, H _ex less than unity and I _γr close to 1 Bq kg⁻¹. The overall mean outdoor terrestrial gamma dose rate is 64.8 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.079 mSv. None of the studied location is considered a radiological risk and sediment can be safely used in construction.     

50-year record and solid state speciation of mercury in natural and contaminated reservoir sediment

Contaminated fluvial sediments represent both temporary sinks for river-borne pollutants and potential sources in case of natural and/or anthropogenic resuspension. Reservoir lakes play a very important role in sediment dynamics of watersheds and may offer great opportunities to study historical records of river-borne particles and associated elements transported in the past. The fate and potential environmental impact of Hg depends on its abundance, its carrier phases and its chemical speciation. Historical Hg records and solid state Hg speciation were compared in sediments from two contrasting reservoirs of the Lot River (France) upstream and downstream from a major polymetallic pollution (e.g. Cd, Zn) source. Natural (geochemical background) and anthropogenic Hg concentrations and their relationships with predominant carrier phases were determined. The results reveal important historical Hg contamination (up to 35 mg kg⁻¹) of the downstream sediment, reflecting the historical evolution of industrial activity at the point source, i.e. former coal mining, Zn ore treatment and post-industrial remediation work. Single chemical extractions (ascorbate, H₂O₂, KOH) suggest that at both sites most (∼75%) of the Hg is bound to organic and/or reactive sulphide phases. Organo-chelated (KOH-extracted) Hg, representing an important fraction in the uncontaminated sediment, shows similar concentrations (∼0.02 mg kg⁻¹) at both sites and may be mainly attributed to natural inputs and/or processes. Although, total Hg concentrations in recent surface sediments at both sites are still very different, similar mono-methylmercury concentrations (up to 4 μg kg⁻¹) and vertical distributions were observed, suggesting comparable methylation-demethylation processes. High mono-methylmercury concentrations (4–15 μg kg⁻¹) in 10–40 a-old, sulphide-rich, contaminated sediment suggest long-term persistence of mono-methylmercury. Beyond historical records of total concentrations, the studied reservoir sediments provided new insights in solid state speciation and carrier phases of natural and anthropogenic Hg. In case of sediment resuspension, the major part of the Hg historically stored in the Lot River sediments will be accessible to biogeochemical recycling in the downstream fluvial-estuarine environment.     

Temporal and spatial variability of geochemical backgrounds in the Windmill Islands,East Antarctica: Implications for climatic changes and human impacts

To establish a natural background and its temporal and spatial variability for the area around Casey Station in the Windmill Islands, East Antarctica, the authors studied major and trace element concentrations and the distribution of organic matter in marine and lacustrine sediments. A wide range of natural variability in trace metal concentrations was identified between sites and within a time scale of 9 ka (e.g., Ni 5–37 mg kg⁻¹, Cu 20–190 mg kg⁻¹, Zn 50–300 mg kg⁻¹, Pb 4.5–34 mg kg⁻¹). TOC concentrations are as high as 3 wt.% at the marine sites and 20 wt.% at the lacustrine sites, and indicate highly productive ecosystems. These data provide a background upon which the extent of human impact can be established, and existing data indicate negligible levels of disturbance. Geochemical and lithological data for a lacustrine sediment core from Beall Lake confirm earlier interpretation of recent climatic changes based on diatom distribution, and the onset of deglaciation in the northern part of the Windmill Islands between 8.6 and 8.0 ka BP. The results demonstrate that geochemical and lithological data can not only be used to define natural background values, but also to assess long-term climatic changes of a specific environment. Other sites, however, preserve a completely different sedimentary record. Therefore, inferred climatic record, and differences between sites, can be ascribed to differences in elevation, distance from the shore, water depth, and local catchment features. The extreme level of spatial variability seems to be a feature of Antarctic coastal areas, and demonstrates that results obtained from a specific site cannot be easily generalized to a larger area.     

Gold(I) complexing in aqueous sulphide solutions to 500°C at 500 bar

The solubility of gold has been measured in aqueous sulphide solutions from 100 to 500°C at 500 bar in order to determine the stability and stoichiometry of sulphide complexes of gold(I) in hydrothermal solutions. The experiments were carried out in a flow-through system. The solubilities, measured as total dissolved gold, were in the range 3.6 × 10⁻⁸ to 6.65 × 10⁻⁴ mol kg⁻¹ (0.007-131 mg kg⁻¹), in solutions of total reduced sulphur between 0.0164 and 0.133 mol kg⁻¹, total chloride between 0.000 and 0.240 mol kg⁻¹, total sodium between 0.000 and 0.200 mol kg⁻¹, total dissolved hydrogen between 1.63 × 10⁻⁵ and 5.43 × 10⁻⁴ mol kg⁻¹ and a corresponding pH_{T, p} of 1.5 to 9.8. A non-linear least squares treatment of the data demonstrates that the solubility of gold in aqueous sulphide solutions is accurately described by the reactions

Au(s)+H₂S(aq)=AuHS(aq)+0.5H₂(g) K_s,100     

Environmental geochemistry of toxic heavy metals in soils around Sarcheshmeh porphyry copper mine smelter plant,Rafsanjan, Kerman,Iran

The Sarcheshmeh copper mine smelter plant is one of the biggest copper producers in Iran. Long-time operation of about 25 years of the smelter plant causes release of potentially toxic heavy metals into the environment. In this paper, geochemical distribution of toxic heavy metals in 28 soil samples was evaluated around the Sarcheshmeh smelter plant. Soils developed over the nonmineralized and uncontaminated areas have an average background concentration of 41.25 mg kg⁻¹ Cu, 26.6 mg kg⁻¹ As, 12.7 mg kg⁻¹ Pb, 0.9 mg kg⁻¹ Sb, 1.9 mg kg⁻¹ Mo, 1.7 mg kg⁻¹ Sn, 0.2 mg kg⁻¹ Cd, 0.15 mg kg⁻¹ Bi, 235 mg kg⁻¹ S and 73.4 mg kg⁻¹ Zn, respectively. As a result of smelting process, the upper soil layers (0–5 cm) were polluted by Cu (>1,397 mg kg⁻¹), Cd (>3.42 mg kg⁻¹), S (>821 mg kg⁻¹), Mo (>10.3 mg kg⁻¹), Sb (>11.7 mg kg⁻¹), As (>120.6 mg kg⁻¹), Pb (>83.8 mg kg⁻¹), Zn (>214.9 mg kg⁻¹), and Sn (>3.7 mg kg⁻¹), respectively. These values are much higher than the normal concentration of the elements in the uncontaminated soil layers. The elemental values decrease with distance travelled away of the smelter plant, especially at minimum wind direction. Furthermore, high contaminated values of Cu (8,430 mg kg⁻¹), As (500 mg kg⁻¹), Pb (331 mg kg⁻¹), Mo (61 mg kg⁻¹), Sb (56.2 mg kg⁻¹), Zn (664 mg kg⁻¹), Cd (17.2 mg kg⁻¹), Bi (13.4 mg kg⁻¹), and S (3,780 mg kg⁻¹) were observed in the upper soil layers close to the smelting waste dumps. Sequential extraction analysis shows that about 270 mg kg⁻¹ Cu, 28 mg kg⁻¹ Pb, 50.33 mg kg⁻¹ Zn, and 47.84 mg kg⁻¹ As were adsorbed by Fe and Mn oxides. The carbonate phases include 151 mg kg⁻¹ Cu, 28 mg kg⁻¹ Pb, 25 mg kg⁻¹ Zn, and 32.99 mg kg⁻¹ As. Organic matter adsorbed 314.6 mg kg⁻¹ Cu and 29.18 mg kg⁻¹ Zn.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

Enrichment of metals in soils subjected to different land uses in a typical Mediterranean environment (Murcia City, southeast Spain)

Industrialization, urbanization, and agricultural practices are 3 of the most important sources of metal accumulations in soils. Concentrations of Cr, Mn, Ni, Cu, Pb, Zn and Cd were determined in surface soils collected under different land uses, including urban (UR), industrial (IN-1 and IN-2), agricultural (AG), abandoned unused (AB), and natural (NA) sites to examine the influence of anthropogenic activities on metals in soils formed in a typical Mediterranean environment. The highest concentrations of Cr, Cd, and Pb observed in the NW industrial area (IN-2) were 63.7, 3.34 and 2330 mg metal kg⁻¹ soil, for each metal, respectively. The SW industrial area (IN-1) contained the highest Zn content at 135 mg kg⁻¹. However, soils with the highest concentrations of Ni and Cu were located in AG sites at 30.9 and 64.9 mg kg⁻¹ soil, respectively. Sampling locations with the highest concentrations of Mn were identified in AB sites. Using the concentrations of metals at the NA sites as the baseline levels, soils collected from all other land uses in the study area exhibited significantly higher total contents of Zn, Mn, Cr and Ni. Metal enrichment was attributed to fertilizer and pesticide applications, industrial activities, and metal deposition from a high volume of vehicular traffic (for Pb and Cd). High concentrations of Mn in some samples were attributed to parent materials. The study demonstrated that anthropogenic activities associated with various land uses contribute to metal accumulation in soils and indicated a need to closely monitor land management practices to reduce human and ecological risks from environmental pollution.     

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.