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.     

Mercury and methylmercury in riparian soil,sediments, mine-waste calcines,and moss from abandoned Hg mines in east Guizhou province,southwestern China

Concentrations of total Hg and methylmercury (MMHg) in riparian soil, mine-waste calcine, sediment, and moss samples collected from abandoned Hg mines in Wanshan district, Guizhou province, China, were measured to show regional dispersion of Hg-contamination. High total Hg and MMHg concentrations obtained in riparian soils from mined areas, ranged from 5.1 to 790 mg kg⁻¹ and 0.13 to 15 ng g⁻¹, respectively. However, total Hg and MMHg concentrations in the soils collected from control sites were significantly lower varying from 0.1 to 1.2 mg kg⁻¹ and 0.10 to 1.6 ng g⁻¹, respectively. Total Hg and MMHg concentrations in sediments varied from 90 to 930 mg kg⁻¹ and 3.0 to 20 ng g⁻¹, respectively. Total Hg concentrations in mine-waste calcines were highly elevated ranging from 5.7 to 4400 mg kg⁻¹, but MMHg concentrations were generally low ranging from 0.17 to 1.1 ng g⁻¹. Similar to the high Hg concentrations in soil and sediments, moss samples collected from rocks ranged from 1.0 to 95 mg kg⁻¹ in total Hg and from 0.21 to 20 ng g⁻¹ in MMHg. Elevated Hg concentrations in mosses suggest that atmospheric deposition might be an important pathway of Hg to the local terrestrial system. Moreover, the spatial distribution patterns of Hg contamination in the local environment suggest derivation from historic Hg mining sites in the Wanshan area.     

The use of vetiver grass (Vetiveria zizanioides) in the phytoremediation of soils contaminated with heavy metals

Recent research has shown that phytoextraction approaches often require soil amendments, such as the application of EDTA, to increase the bioavailability of heavy metals in soils. However, EDTA and EDTA–heavy metal complexes can be toxic to plants and soil microorganisms and may leach into groundwater, causing further environmental pollution. In the present study, vetiver grass (Vetiveria zizanioides) was studied for its potential use in the phytoremediation of soils contaminated with heavy metals. In the pot experiment, the uptake and transport of Pb by vetiver from Pb-contaminated soils under EDTA application was investigated. The results showed that vetiver had the capacity to tolerate high Pb concentrations in soils. With the application of EDTA, the translocation ratio of Pb from vetiver roots to shoots was significantly increased. On the 14th day after 5.0 mmol EDTA kg⁻¹ of soil application, the shoot Pb concentration reached 42, 160, 243 mg kg⁻¹ DW and the root Pb concentrations were 266, 951, and 2280 mg kg⁻¹ DW in the 500, 2500 and 5000 mg Pb kg⁻¹ soils, respectively. In the short soil leaching column (9.0-cm diameter, 20-cm height) experiment, about 3.7%, 15.6%, 14.3% and 22.2% of the soil Pb, Cu, Zn and Cd were leached from the artificially contaminated soil profile after 5.0 mmol EDTA kg⁻¹ of soil application and nearly 126 mm of rainfall irrigation. In the long soil leaching experiment, soil columns (9.0-cm diameter, 60-cm height) were packed with uncontaminated soils (mimicking the subsoil under contaminated upper layers) and planted with vetiver. Heavy metal leachate from the short column experiment was applied to the surface of the long soil column, the artificial rainwater was percolated, and the final leachate was collected at the bottom of the soil columns. The results showed that soil matrix with planted vetiver, could re-adsorb 98%, 54%, 41%, and 88% of the initially applied Pb, Cu, Zn, and Cd, respectively, which may reduce the risk of heavy metals flowing downwards and entering the groundwater.     

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.     

Arsenic accumulation in the roots of Helianthus annuus and Zea mays by irrigation with arsenic-rich groundwater: Insights from synchrotron X-ray fluorescence imaging

The aim of this study was to investigate the accumulation of arsenic (As) in and on roots of Zea mays (maize) and Helianthus annuus (sunflower) by means of synchrotron-based micro-focused X-ray fluorescence imaging (μ-XRF). Plant and soil samples were collected from two field sites in the Hetao Plain (Inner Mongolia, China) which have been regularly irrigated with As-rich groundwater. Detailed μ-XRF element distribution maps were generated at the Fluo-beamline of the Anka synchrotron facility (Karlsruhe Institute of Technology) to assess the spatial distribution of As in thin sections of plant roots and soil particles. The results showed that average As concentrations in the roots (14.5–27.4 mg kg⁻¹) covered a similar range as in the surrounding soil, but local maximum root As concentrations reached up to 424 mg kg⁻¹ (H. annuus) and 1280 mg kg⁻¹ (Z. mays), respectively. Importantly, the results revealed that As had mainly accumulated at the outer rhizodermis along with iron (Fe). We therefore conclude that thin crusts of Fe-(hydr)oxides cover the roots and act as an effective barrier to As, similar to the formation of Fe plaque in rice roots. In contrast to permanently flooded rice paddy fields, regular flood irrigation results in variable redox conditions within the silty and loamy soils at our study site and fosters the formation of Fe-(hydr)oxide plaque on the root surfaces.     

Weathering versus atmospheric contributions to mercury concentrations in French Guiana soils

This work focuses on two possible sources of Hg in tropical soils, (i) lithogenic Hg from in situ weathering of soil parental material, and (ii) exogenic Hg from natural long-term atmospheric inputs and anthropogenic input from past and present industrial activities. The concentration of lithogenic Hg [Hg]_lithogenic was based on comparison of measured Hg concentration with those of elements resistant to weathering such as Nb, U, Zn, Fe. Exogenic Hg was quantified by subtracting [Hg]_lithogenic from total Hg concentrations. This calculation was applied to 4 French Guiana soil profiles, 3 profiles on the same toposequence (ferralsol, acrisol, hydromorphic soil) and one acrisol close to a Au mine, where elemental Hg is used. In all profiles, [Hg]_lithogenic varied slightly and was always below 40 μg kg⁻¹, whereas [Hg]_exogenic varied considerably and reached 500 μg kg⁻¹. The highest [Hg]_exogenic was calculated for the upper horizon of the acrisol close to Au mining activity, but also in the ferralsol. Concentrations of Hg were insignificant in the compact alterite in acrisols. It was concluded that pedogenesis processes that affect the natural Hg supply, combined with anthropogenic sources, explain the Hg concentrations in these tropical soils.     

The Diavik waste rock project: Initial geochemical response from a low sulfide waste rock pile

Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L⁻¹ when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L⁻¹ (as total CaCO₃), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L⁻¹, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L⁻¹), Ni (<7.0 mg L⁻¹), Co (<1.5 mg L⁻¹), Zn (<0.5 mg L⁻¹), Cd (<0.008 mg L⁻¹) and Cu (<0.05 mg L⁻¹) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe_1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS₂] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO₄, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock.     

Release,transport and attenuation of metals from an old tailings impoundment

The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO₄ and metals and As in the tailings pore water (pH < 1, 129,000 mg L⁻¹ Fe, 280,000 mg L⁻¹ SO₄, 55,000 mg L⁻¹ Zn, 7200 mg L⁻¹ Al, 1600 mg L⁻¹ Cu, 260 mg L⁻¹ Mn, 110 mg L⁻¹ Co, 97 mg L⁻¹ Cd, 40 mg L⁻¹ As, 15 mg L⁻¹ Ni, 8 mg L⁻¹ Pb, and 3 mg L⁻¹ Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO₄, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO₄ sharply decline in concentration. Although dissolved concentrations of metals and SO₄ decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L⁻¹ Fe and 91,600 mg L⁻¹ SO₄ observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO₄ to the environment for decades to centuries.     

Dissolved and particulate zinc and nickel in the Yangtze River (China): Distribution,sources and fluxes

Dissolved and particulate Zn and Ni concentrations were determined at 76 locations along the Yangtze River basin from the headwaters to the estuary during flood and dry seasons. Spatial and temporal variations of Zn and Ni were investigated and six major source zones were identified. The Three Gorges Dam (TGD) blocked most of the suspended loads and extremely low concentration of Zn and Ni were observed downstream of the dam. Dissolved (ranging from 0.062 to 8.0 μg L⁻¹) and particulate (ranging from 12 to 110 mg kg⁻¹) Ni showed similar levels of concentrations during flood and dry seasons, whereas dissolved (ranging from 0.43 to 49 μg L⁻¹) and particulate (ranging from 54 to 1100 mg kg⁻¹) Zn were slightly and much lower in the flood season than dry season, respectively. This was attributed to the increased water discharge during the flood season causing a dilution effect and sediment resuspension. In the flood season, average concentrations of Zn and Ni were higher in the main channel than in tributaries, due to soil erosion and mining activities providing the dominant inputs. The situation was opposite in the dry season, attributed to the contribution of municipal sewage, industrial activities, and waste disposal. During the flood season, dissolved Zn and Ni concentrations were negatively correlated with pH. Water and suspended particulate matter (SPM) from the upper reaches, middle reaches, and lower reaches of the Yangtze River were characterized by their Zn and Ni concentrations. The Panzhihua, Nanling and Tongling mining areas were considered as the most important source zones of particulate Zn and Ni. The Chongqing region, Wuhan region and the Yangtze River Delta provided most of the dissolved Zn and Ni inputs into the river. Annual net flux of Zn (10–72 × 10⁵ kg a⁻¹) and Ni (5.0–19 × 10⁵ kg a⁻¹) in each source zone were estimated according to their respective influent and effluent fluxes. Contributions of the source zones to Zn and Ni transport decreased from the upper reaches to the lower reaches.     

Arsenic associations in sediments from the loess aquifer of La Pampa,Argentina

Groundwater from the Quaternary loess aquifer of La Pampa, central Argentina, has significant problems with high concentrations of As (up to 5300 μg L⁻¹) as well as other potentially toxic trace elements such as F, B, Mo, U, Se and V. Total As concentrations in 45 loess samples collected from the aquifer have a range of 3–18 mg kg⁻¹ with a mean of 8 mg kg⁻¹. These values are comparable to world-average sediment As concentrations. Five samples of rhyolitic ash from the area have As concentrations of 7–12 mg kg⁻¹. Chemical analysis included loess sediments and extracted porewaters from two specially cored boreholes. Results reveal a large range of porewater As concentrations, being generally higher in the horizons with highest sediment As concentrations. The displaced porewaters have As concentrations ranging up to 7500 μg L⁻¹ as well as exceptionally high concentrations of some other oxyanion species, including V up to 12 mg L⁻¹. The highest concentrations are found in a borehole located in a topographic depression, which is a zone of likely groundwater discharge and enhanced residence time. Comparison of sediment and porewater data does not reveal unequivocally the sources of the As, but selective extract data (acid-ammonium oxalate and hydroxylamine hydrochloride) suggest that much of the As (and V) is associated with Fe oxides. Primary oxides such as magnetite and ilmenite may be partial sources but given the weathered nature of many of the sediments, secondary oxide minerals are probably more important. Extract compositions also suggest that Mn oxide may be an As source. The groundwaters of the region are oxidising, with dissolved O₂, NO₃ and SO₄ normally present and As(V) usually the dominant dissolved As species. Under such conditions, the solubility of Fe and Mn oxides is low and As mobilisation is strongly controlled by sorption–desorption reactions. Desorption may be facilitated by the relatively high-pH conditions of the groundwaters in the region (7.0–8.8) and high concentrations of potential competitors (e.g. V, P, HCO₃). PHREEQC modelling suggests that the presence of V at the concentrations observed in the Pampean porewaters can suppress the sorption of As to hydrous Fe(III) oxide (HFO) by up to an order of magnitude. Bicarbonate had a comparatively small competitive effect. Oxalate extract concentrations have been used to provide an upper estimate of the amount of labile As in the sediments. A near-linear correlation between oxalate-extractable and porewater As in one of the cored boreholes investigated has been used to estimate an approximate K_d value for the sediments of 0.94 L kg⁻¹. This low value indicates that the sediments have an unusually low affinity for As.     

Arsenic immobilization in water and soil using acid mine drainage sludge

Adsorption onto Fe-containing minerals is a well-known remediation method for As-contaminated water and soil. In this study, the use of acid mine drainage sludge (AMDS) to adsorb As was investigated. AMDS is composed of amorphous particles and so has a large surface area (251.2 m² g⁻¹). Here, adsorption of both arsenite and arsenate was found to be almost 100%, under various initial AMDS dosages, with the arsenate adsorption rate being faster. The optimum pH for As adsorption onto AMDS was pH 7.0 and the maximum adsorption capacities for arsenite and arsenate were 58.5 mg g⁻¹ and 19.7 mg g⁻¹ AMDS, respectively. In addition, experiments revealed that AMDS dosages decreased As release from contaminated soil. Therefore, the AMDS used in this study was confirmed to be a suitable candidate for immobilizing both arsenite and arsenate in contaminated soils.     

Spatial variations in water composition at a northern Canadian lake impacted by mine drainage

Release of acid drainage from mine-waste disposal areas is a problem of international scale. Contaminated surface water, derived from mine wastes, orginates both as direct surface runoff and, indirectly, as subsurface groundwater flow. At Camp Lake, a small Canadian Shield lake that is in northern Manitoba and is ice-covered 6 months of the year, direct and indirect release of drainage from an adjacent sulfide-rich tailings impoundment has severely affected the quality of the lake water. Concentrations of the products from sulfide oxidation are extremely high in the pore waters of the tailings impoundment. Groundwater and surface water derived from the impoundment discharge into a semi-isolated shallow bay in Camp Lake. The incorporation of this aqueous effluent has altered the composition of the lake water, which in turn has modified the physical limnology of the lake. Geochemical profiles of the water column indicate that, despite its shallow depth (6 m), the bay is stratified throughout the year. The greatest accumulation of dissolved metals and SO₄ is in the lower portion of the water column, with concentrations up to 8500 mg L⁻¹ Fe, 20,000 mg L⁻¹ SO₄, 30 mg L⁻¹ Zn, 100 mg L⁻¹ Al, and elevated concentrations of Cu, Cd, Pb and Ni. Meromictic conditions and very high solute concentrations are limited to the bay. Outside the bay, solute concentrations are lower and some stratification of the water column exists. Identification of locations and composition of groundwater discharge relative to lake bathymetry is a fundamental aspect of understanding chemical evolution and physical stability of mine-impacted lakes.     

Evaluation of the influence of urbanization processes using mangrove and fecal markers in recent organic matter in a tropical tidal flat estuary

Three sediment cores (50 cm depth) were collected at three different sites from a tidal flat estuary at Passagem Channel (Vitória, Espírito Santo State-Brazil) to evaluate the influence of recent urbanization processes on the deposition of organic matter (OM) in a complex polluted tropical estuary. In addition to geochronology (by excess ²¹⁰Pb), the sources of natural and anthropogenic OM to the sediments were evaluated by total organic C (TOC – 14.29 ± 8.73, 30.43 ± 14.71 and 48.70 mg g⁻¹ ± 25.46, respectively, for P1, P2 and P3), C/N molar ratio and lipid biomarkers (sterols and terpenoids). Taraxerol (3.10 ± 4.85, 9.71 ± 3.85 and 16.10 mg gTOC⁻¹ ± 32.48 for P1, P2 and P3, respectively) and sitosterol (1.71 ± 2.72, 2.94 ± 6.41 and 4.07 mg gTOC⁻¹ ± 4.41 for P1, P2 and P3, respectively) were the most abundant compounds in all cores, suggesting a major contribution of terrestrially-derived OM to the study region. Coprostanol levels and selected sterol index indicated significant contamination by fecal material. The organic geochemical indicators suggest that changes of OM reflect occupation and urbanization alteration processes around the Passagem Channel over the last 70 a, mainly the conversion of mangrove forest into urban areas, bridge building and Treatment Plant Station installation.     

Assessing soil erosion and control factors by radiometric technique in the source region of the Yellow River,Tibetan Plateau

Measurements of ¹³⁷Cs concentration in soils were made in a representative catchment to quantify erosion rates and identify the main factors involved in the erosion in the source region of the Yellow River in the Tibetan Plateau. In order to estimate erosion rates in terms of the main factors affecting soil loss, samples were collected taking into account the slope and vegetation cover along six selected transects within the Dari County catchment. The reference inventory for the area was established at a stable, well-preserved, site of small thickness (value of 2324 Bq·m^− 2). All the sampling sites had been eroded and ¹³⁷Cs inventories varied widely in the topsoil (14.87–25.56 Bq·kg^− 1). The effective soil loss values were also highly variable (11.03–28.35 t·km^− 1·yr^− 1) in line with the vegetation cover change. The radiometric approach was useful in quantifying soil erosion rates and examining patterns of soil movement.     

Evolution of groundwater chemistry in and around Vaniyambadi Industrial Area: Differentiating the natural and anthropogenic sources of contamination

Groundwaters in the crystalline aquifers are the major source of drinking water in Vaniyambadi area of Vellore district. Geochemical methods in collaboration with statistical methods were applied in this industrial area to understand the natural and anthropogenic influences on groundwater quality. To accomplish this objective, groundwater samples were collected and analyzed for physicochemical parameters and the results showed a dominance in the order of Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ and HCO₃⁻ > Cl⁻ > SO₄²⁻ > NO₃⁻ for anions and cations, respectively. In contrast to this anion dominance were changed to Cl⁻ > HCO₃⁻ > SO₄²⁻ > NO₃⁻ in samples collected near the tannery industries. Groundwater quality evaluation using TDS and TH suggested that 57% of the total samples are hard-brackish type, indicating its unsuitability for drinking purpose. Generally the water type is Na⁺Cl⁻ to Ca²⁺Mg²⁺HCO₃⁻ type with an intermediate Ca²⁺Mg²⁺Cl⁻, suggesting the mixing of fresh groundwater with tannery effluent and cation exchange. Factor analysis and bivariate plots of major ions suggests that both natural and anthropogenic inputs are equally influencing the groundwater quality. Further investigations proved that silicate weathering is the dominant geogenic source of groundwater solute content, whereas tannery effluent is the anthropogenic source. Saline water mixing index (SWMI) and Cl⁻ vs NO₃⁻ bivariate plot were employed to differentiate the tannery contamination from the other anthropogenic inputs such as agricultural fertilizers, municipal sewages, etc. This analysis shows that samples 2, 4, 8 and 9 (located within the tannery cluster) have a SWMI value greater than 1, representing the groundwater–tannery effluent mixing. This study infers that groundwater in the Vaniyambadi area is under serious threat from both natural and anthropogenic contamination. However, the controlling discharge of untreated tannery effluents must be regulated to reduce the further deterioration of this vital resource in this part of the country.     

Gold mining related mercury contamination in Tongguan,Shaanxi Province,PR China

Elemental Hg–Au amalgamation mining practices are used widely in many developing countries resulting in significant Hg contamination of surrounding ecosystems. The authors examined for the first time Hg contamination in air, water, sediment, soil and crops in the Tongguan Au mining area, China, where elemental Hg has been used to extract Au for many years. Total gaseous Hg (TGM) concentrations in ambient air in the Tongguan area were significantly elevated compared to regional background concentrations. The average TGM concentrations in ambient air in a Au mill reached 18,000 ng m⁻³, which exceeds the maximum allowable occupational standard for TGM of 10,000 ng m⁻³ in China. Both total and methyl-Hg concentrations in stream water, stream sediment, and soil samples collected in the Tongguan area were elevated compared to methyl-Hg reported in artisanal Au mining areas in Suriname and the Amazon River basin. Total Hg concentrations in vegetable and wheat samples ranged from 42 to 640 μg kg⁻¹, all of which significantly exceed the Chinese guidance limit for vegetables (10 μg kg⁻¹) and foodstuffs other than fish (20 μg kg⁻¹). Fortunately, methyl-Hg was not significantly accumulated in the crops sampled in this study, where concentrations varied from 0.2 to 7.7 μg kg⁻¹.     

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.     

Soil-geochemical factors controlling the distribution and oral bioaccessibility of nickel,vanadium and chromium in soil

Geogenic nickel (Ni), vanadium (V) and chromium (Cr) are present at elevated levels in soils in Northern Ireland. Whilst Ni, V and Cr total soil concentrations share common geological origins, their respective levels of oral bioaccessibility are influenced by different soil-geochemical factors. Oral bioaccessibility extractions were carried out on 145 soil samples overlying 9 different bedrock types to measure the bioaccessible portions of Ni, V and Cr. Principal component analysis identified two components (PC1 and PC2) accounting for 69% of variance across 13 variables from the Northern Ireland Tellus Survey geochemical data. PC1 was associated with underlying basalt bedrock, higher bioaccessible Cr concentrations and lower Ni bioaccessibility. PC2 was associated with regional variance in soil chemistry and hosted factors accounting for higher Ni and V bioaccessibility. Eight percent of total V was solubilised by gastric extraction on average across the study area. High median proportions of bioaccessible Ni were observed in soils overlying sedimentary rock types. Whilst Cr bioaccessible fractions were low (max = 5.4%), the highest measured bioaccessible Cr concentration reached 10.0 mg kg⁻¹, explained by factors linked to PC1 including high total Cr concentrations in soils overlying basalt bedrock.     

Mercury in the Lot–Garonne River system (France): Sources,fluxes and anthropogenic component

Dissolved and particulate Hg fluxes in the Lot–Garonne–Gironde fluvial-estuarine system were obtained from observation of daily discharge and suspended particulate matter (SPM) concentrations. In addition to the measurements of the total dissolved (<0.45 μm) and particulate Hg (>0.45 μm), called HgT_D and HgT_P respectively, the dissolved inorganic Hg species (HgR_D) were determined monthly. Geochemical background values for HgT_P in sediments and SPM were similar to crustal values and to typical concentrations in SPM of non-contaminated river systems, respectively. The Riou Mort watershed already known as the origin of important historical polymetallic (e.g., Cd, Zn) pollution was identified as an important Hg point source. In the downstream Lot River, Hg concentrations were clearly higher than those in other moderately contaminated systems. The mean relative contribution of HgR_D to HgT_D in the Lot River and in the Garonne River was close to 25% and 50%, respectively, and showed no correlation with water discharge or SPM concentration. Depending on the origin and nature of SPM, HgT_P concentrations were correlated or not with particulate organic C (POC). Maximum HgT_P concentrations were measured in samples containing low POC concentrations and were attributed to sediment resuspension. In contrast, high POC concentrations (6–17%) during algal blooms were associated with low/moderate HgT_P concentrations (<0.5 mg kg⁻¹) at different sites, suggesting that Hg concentrations in fluvial phytoplankton may be limited by bioavailability of dissolved Hg and/or physiologically controlled Hg accumulation. Mercury was mostly (up to 98%) transported in the particulate phase with estimated annual Hg fluxes at the outlet of the Lot River system ranging from 35 to 530 kg a⁻¹ for the past decade. The minimum anthropogenic component (58–84% of total Hg fluxes) could not be explained by present Riou Mort point source contributions, suggesting important Hg release from contaminated sediment as a major source and from downstream point sources (e.g., coal-fired power plants and/or metal processing industries). HgT_P concentrations and fluxes were strongly related to hydrologic variations and were clearly increased by riverbed dredging during lock construction. Therefore, the estimated Hg stocks in the Lot River sediment (5–13 tons) represent an important potential Hg source for the downstream fluvial-estuarine system.     

Mercury exchange between the atmosphere and low mercury containing substrates

Mercury is emitted to the air from Hg-enriched and low Hg-containing (natural background) substrates. Emitted Hg can be geogenic, or can be derived from the re-emission of Hg that was previously deposited to the soil from the atmosphere. Atmospheric Hg can be derived from natural and/or anthropogenic sources and can be deposited by wet or dry processes. It is important to understand the relative magnitude of emission, deposition, and re-emission of Hg associated with terrestrial ecosystems with natural background soil Hg concentrations because these landscapes cover large terrestrial surface areas. This information is also important for developing biogeochemical mass balances, assessing the impacts of atmospheric Hg sources, and predicting the effectiveness of regulatory controls at local, regional, and global scales.The major focus of this paper is to discuss air–substrate Hg exchange for low Hg-containing soils (<0.1 μg Hg g⁻¹) from two areas in Nevada and one in Oklahoma, USA. Data collected with field and laboratory gas exchange systems are presented. Results indicate that in order to adequately characterize substrate–air Hg exchange, diel and seasonal data must be collected under a variety of environmental conditions. Field and laboratory data showed that dry deposition of gaseous Hg to substrates with low Hg concentrations is an important process. Environmental parameters important in influencing emissions include soil water content, incident light, temperature, atmospheric oxidants, and air Hg concentrations. There are synergistic and antagonistic effects between these parameters complicating prediction of flux.