Significance of trace elements in syntaxial quartz cement,Haushi Group sandstones,Sultanate of Oman

Trace element contents and distributions in authigenic quartz cement in deeply buried (2500–4000 m) Haushi Group sandstones from wells in Oman have been investigated in order to determine the factors that control trace element uptake during precipitation.Scanning electron microscope-cathodoluminescence images show well developed growth zones within the quartz cement, which correlate with chemical zonations observed in electron microprobe Al distribution maps. The most abundant trace elements are Al (50–3000 μg g^?1), Li (1–100 μg g^?1), Na (1–40 μg g^?1), and Ge (0.3–5 μg g^?1) with a strong linear correlation between Li and Al and a weaker one between Ge and Al. The molar concentration of Li (+ Na) accounts only for ~ 15% of the charge compensation for Al³⁺ substitution of Si⁴⁺. Though H was not measured in this study, these data indicate a major role of H in charge balancing Al³⁺. The samples belong to the same stratigraphic unit and have similar petrography, but show considerable variability in absolute trace element concentrations between different wells. This variability does not correlate with either sample depth or temperature and shows no regional pattern, but seems to reflect petrophysical and tectonic differences within the sedimentary basin.Petrographic observations of the cogenetic mineral assemblages and hydrochemical modelling indicate that a change from the equilibrium assemblage quartz–kaolinite (–dolomite) to quartz–illite (–dolomite) reflects a decrease in the CO₂ concentration and concurrent variations of the Al concentration. It is concluded that changes in the CO₂ concentrations are responsible for fluctuations in fluid Al concentrations and thus likely also in the investigated quartz cements.     

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.     

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.     

Mobilization of arsenic from acid deposition – The Elbe River catchment,Czech Republic

Temporal changes of As concentration in surface waters were observed in some areas of the Czech Republic. Mobilized As originates from past atmospheric deposition. To understand the factors influencing As aqueous concentration and mobility the chemistry and runoff generation of a number of brooks, springs and rivers in the central part of the Elbe River catchment, Czech Republic, were monitored. Seasonal variations of As (from 0.5 to 10.5 μg L⁻¹), Fe (from 0.05 to 3.9 mg L⁻¹) and DOC (dissolved organic C – from 1.2 to 17.5 mg L⁻¹) were observed in monitored stream waters with maximum values of As and Fe in the summer months at pH values 7.6–7.8. The concentration of As in particles with a diameter < 60 μm correlates with the Fe concentration. There is no correlation between Fe and As in filtered samples (<0.45 μm). The As concentration in stream water colloids depends on an increase in DOC concentration and a decrease in ionic strength. The DOC stabilizes As in solution and reduces its re-adsorption on Fe colloids and consequently As concentration in the stream increases.     

Selenium speciation,distribution, and transport in a river catchment affected by mercury mining and smelting in Wanshan,China

Selenium (Se) is an important co-existing elemental component of the mineral matrix of mercury (Hg) ore deposits. The hazards associated with Se contamination of the aquatic ecosystems in Hg mining areas; however, are often overlooked by environmental researchers due to a preoccupation with Hg. Selenium may also pose a long-term risk to the local ecosystem, and further complicate the situation as Se may also play an important antagonistic role against Hg. Furthermore, most studies on Se pollution have focused only on total Se, whereas the toxicity, bioavailability, and bioaccumulation of Se in aquatic ecosystems is primarily determined by its site-specific individual species. In this study, the concentrations of total Se, inorganic Se (tetravalent and hexavalent), and organic Se were determined in water samples collected from 41 typical sites selected in rivers, tributaries, and springs in Wanshan, China, where Hg and Se co-occur due to historic Hg mining and retorting activities. Se concentrations were observed to decrease with distance from mine-waste calcines, which indicated that mine-waste calcines may be significant sources of the elevated Se in the rivers, especially in downstream areas within 8 km from the mine-waste calcines. The concentration of total aqueous Se throughout the study area was highly variable (3.8 ± 6.0 μg L⁻¹) and on average was one order of magnitude greater than that in natural river systems worldwide (0.1–0.3 μg L⁻¹). The majority of the Se was hexavalent (3.1 ± 4.9 μg L⁻¹; 65%), followed by tetravalent (0.53 ± 0.86 μg L⁻¹; 15%) and organic forms (0.85 ± 1.5 μg L⁻¹; 20%), possibly due to the generally alkaline conditions. Se concentrations in some sampling sites exceeded certain recommended limit of values. However, the existing criteria for Se in aquatic system are mainly based on total Se and the recommended limit of values in different countries or organizations are inconsistent with one another. Therefore, the need to consider Se speciation rather than only total Se is highlighted for future studies.     

Elemental sulfur in drain sediments associated with acid sulfate soils

This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe²⁺ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g⁻¹). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g⁻¹), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g⁻¹, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O₂ and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes.     

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.     

Metal mobility by de-icing salt from an infiltration trench for highway runoff

Soil from an infiltration trench for highway runoff was leached in columns alternately with NaCl and de-ionised water to simulate the runoff of de-icing salt into the trench followed by snowmelt or rainwater. Simultaneously, two columns with the same soil were leached with de-ionised water throughout the experiment. In addition, the groundwater below the infiltration trench was sampled on some occasions. The column leachate and groundwater were split into two sub samples, one was filtered though a 0.45 μm filter; both were analysed for Pb, Cd, Zn, Fe and total organic carbon (TOC). The column experiment showed clearly that an extensive mobilisation of Pb occurred in low electrolyte water leaching following NaCl leaching. The high Pb concentration coincided with peaks in Fe and TOC concentrations and implied colloid-assisted transport. Conversely, Cd and Zn concentrations were raised in the NaCl leachate and a high correlation with Cl showed that Cl complexes are important for the mobilisation, although a pH effect and ionic exchange cannot be excluded. Only 0.15% and 0.06% of the total amount of Pb was leached from the columns leached with alternating NaCl and deionised water confirming the usual hypotheses about the high immobility of Pb in soils. However, on one occasion when the ionic strength and pH was the lowest measured the concentration of Pb in groundwater sampled from 2.5 m depth was 27 μg L⁻¹ in the dissolved phase (<0.45 μm) and 77 μg L⁻¹ in the particle phase (>0.45 μm). These Pb concentrations are almost 3 and 8 times above the Swedish limit for drinking water quality. Accordingly, in spite of the immobility of Pb the accumulation in roadside soils is so large that groundwater quality is threatened. In conclusion, the study suggests that roadside soils impacted by NaCl from de-icing operations contribute Pb to groundwater by colloid-assisted transport.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.     

An Apatite II permeable reactive barrier to remediate groundwater containing Zn,Pb and Cd

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca_10−xNa_x(PO₄)_6−x(CO₃)_x(OH)₂], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO₄ and NO₃. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO₄ reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb₁₀(PO₄)₆(OH,Cl)₂] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L⁻¹), has reduced Zn to near background in this region (about 100 μg L⁻¹), and has reduced SO₄ by between 100 and 200 mg L⁻¹ and NO₃ to below detection (50 μg L⁻¹). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).     

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.     

An Apatite II permeable reactive barrier to remediate groundwater containing Zn,Pb and Cd

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca_10−xNa_x(PO₄)_6−x(CO₃)_x(OH)₂], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO₄ and NO₃. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO₄ reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb₁₀(PO₄)₆(OH,Cl)₂] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L⁻¹), has reduced Zn to near background in this region (about 100 μg L⁻¹), and has reduced SO₄ by between 100 and 200 mg L⁻¹ and NO₃ to below detection (50 μg L⁻¹). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).     

Natural organic matter in sedimentary basins and its relation to arsenic in anoxic ground water: the example of West Bengal and its worldwide implications

In order to investigate the mechanism of As release to anoxic ground water in alluvial aquifers, the authors sampled ground waters from 3 piezometer nests, 79 shallow (<45 m) wells, and 6 deep (>80 m) wells, in an area 750 m by 450 m, just north of Barasat, near Kolkata (Calcutta), in southern West Bengal. High concentrations of As (200–1180 μg L⁻¹) are accompanied by high concentrations of Fe (3–13.7 mg L⁻¹) and PO₄ (1–6.5 mg L⁻¹). Ground water that is rich in Mn (1–5.3 mg L⁻¹) contains <50 μg L⁻¹ of As. The composition of shallow ground water varies at the 100-m scale laterally and the metre-scale vertically, with vertical gradients in As concentration reaching 200 μg L⁻¹ m⁻¹. The As is supplied by reductive dissolution of FeOOH and release of the sorbed As to solution. The process is driven by natural organic matter in peaty strata both within the aquifer sands and in the overlying confining unit. In well waters, thermo-tolerant coliforms, a proxy for faecal contamination, are not present in high numbers (<10 cfu/100 ml in 85% of wells) showing that faecally-derived organic matter does not enter the aquifer, does not drive reduction of FeOOH, and so does not release As to ground water.Arsenic concentrations are high (≫50 μg L⁻¹) where reduction of FeOOH is complete and its entire load of sorbed As is released to solution, at which point the aquifer sediments become grey in colour as FeOOH vanishes. Where reduction is incomplete, the sediments are brown in colour and resorption of As to residual FeOOH keeps As concentrations below 10 μg L⁻¹ in the presence of dissolved Fe. Sorbed As released by reduction of Mn oxides does not increase As in ground water because the As resorbs to FeOOH. High concentrations of As are common in alluvial aquifers of the Bengal Basin arise because Himalayan erosion supplies immature sediments, with low surface-loadings of FeOOH on mineral grains, to a depositional environment that is rich in organic mater so that complete reduction of FeOOH is common.     

Mercury in water and biomass of microbial communities in hot springs of Yellowstone National Park,USA

Ultra-clean sampling methods and approaches typically used in pristine environments were applied to quantify concentrations of Hg species in water and microbial biomass from hot springs of Yellowstone National Park, features that are geologically enriched with Hg. Microbial populations of chemically-diverse hot springs were also characterized using modern methods in molecular biology as the initial step toward ongoing work linking Hg speciation with microbial processes. Molecular methods (amplification of environmental DNA using 16S rDNA primers, cloning, denatured gradient gel electrophoresis (DGGE) screening of clone libraries, and sequencing of representative clones) were used to examine the dominant members of microbial communities in hot springs. Total Hg (THg), monomethylated Hg (MeHg), pH, temperature, and other parameters influential to Hg speciation and microbial ecology are reported for hot springs water and associated microbial mats.Several hot springs indicate the presence of MeHg in microbial mats with concentrations ranging from 1 to 10 ng g⁻¹ (dry weight). Concentrations of THg in mats ranged from 4.9 to 120,000 ng g⁻¹ (dry weight). Combined data from surveys of geothermal water, lakes, and streams show that aqueous THg concentrations range from l to 600 ng L⁻¹. Species and concentrations of THg in mats and water vary significantly between hot springs, as do the microorganisms found at each site.     

Dissolution kinetics and biodurability of tremolite particles in mimicked lung fluids: Effect of citrate and oxalate

The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L⁻¹ of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g⁻¹ s⁻¹ and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L⁻¹ citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L⁻¹) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers.     

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.     

Mercury in sediments from gold and copper exploitation areas in the Camaquã River Basin,Southern Brazil

Mercury concentrations were determined in stream sediments from the Camaquã River Basin, located in the shield region of the state of Rio Grande do Sul, southern Brazil. The resulting geochemical data show that overbank floodplain deposits exhibit higher concentrations than sediments collected from the active channel bed. In addition, higher Hg concentrations were measured in the fine(<63 μm) sediment fraction of the samples. Total Hg concentrations in the fine fraction of active stream sediments from Lavras do Sul County, which have been influenced by past gold mining activities, have decreased during the last five years to values ≤142 ng g⁻¹. However, in a settling pond containing abandoned mine wastes, the Hg concentration of a bulk sample remained exceptionally high (5220 ng g⁻¹). Preliminary speciation results show that Hg⁰ is the predominant species in most of the samples. This was the form of Hg released by the gold amalgamation activities in the area, and appears to be relatively stable under the existing E_h and pH conditions.     

Temporal dynamics of AVS and SEM in sediment of shallow freshwater floodplain lakes

Acid volatile sulfide (AVS) is an operationally defined sulfide fraction, which is considered important for trace metal fate in reduced sediments. Understanding AVS formation rates is important for the management of metal polluted sediment. However, little is known about the fate and dynamics of AVS in spatially and seasonally variable freshwater environments. The authors monitored in situ AVS formation and degradation and simultaneously extracted metals (SEM) in two floodplain lakes and compared this to AVS formation rates in laboratory experiments with the same sediment. In the laboratory experiments, the formation rates of AVS were studied at 20 °C for initially oxidized sediments that were: (a) untreated; (b) enriched with extra ${\mathrm{SO}}_4^{2-}$; and (c) treated with sodium-azide (biocide). In the field, AVS concentrations were highly variable and were significantly correlated to surface water temperature and O₂ concentrations as well as to sediment composition. Between February and August, AVS formation was approximately linear at a rate of 0.07 μmol g⁻¹ d⁻¹. Degradation rates differed drastically between the lakes due to different degradation mechanisms. In one lake AVS removal was caused by reworking and oxygenation of the sediments by bream (Abrami brama), at a rate of 0.25 μmol g⁻¹ d⁻¹. In the other lake AVS removal was caused by desiccation, at a rate of ±2.6 μmol g⁻¹ d⁻¹. This illustrates the large differences that can be found between similar lakes, and the importance of biological processes. In the laboratory, concentrations of AVS with and without ${\mathrm{SO}}_4^{2-}$ addition were similar during the first weeks, and increased at a rate of 0.15 μmol g⁻¹ d⁻¹. However, ${\mathrm{SO}}_4^{2-}$ addition increased the AVS concentration at the end of the experiment, whereas sodium-azide eliminated AVS formation, as expected. This suggests that AVS formation was ${\mathrm{SO}}_4^{2-}$-limited in the laboratory as well as in these shallow freshwater lakes.     

The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

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.