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1.
The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms. 相似文献
2.
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. 相似文献
3.
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. 相似文献
4.
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 [Fe1−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. 相似文献
5.
《Applied Geochemistry》2004,19(8):1255-1293
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. 相似文献
6.
《Chemie der Erde / Geochemistry》2016,76(3):419-428
Tooeleite, nominally Fe63+(As3+O3)4(SO4)(OH)4·4H2O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol−1. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol−1 K−1. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol−1. The log Ksp value, calculated for the reaction Fe6(AsO3)4(SO4)(OH)4·4H2O + 16H+ = 6Fe3+ + 4H3AsO3 + SO42− + 8H2O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe3+ and As3+ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe2+ to Fe3+ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms. 相似文献
7.
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. 相似文献
8.
《Applied Geochemistry》2005,20(5):961-972
The temperature dependence of the self-diffusion of HTO, 22Na+ and 36Cl− in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol−1, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol−1 for 22Na+ and 36Cl−, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol−1). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na+ and Cl−, slightly higher values than in bulk liquid water (Na+: 18.4 kJ mol−1; Cl−: 17.4 kJ mol−1) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA. 相似文献
9.
The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO2 concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO2 varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO3 and Fe(CO3)33−, with formation constants log*β°1,1,1 = 10.76 ± 0.38 and log β°1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO2 and at T = (25 ± 1) °C, as log*Ks,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO2-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers. 相似文献
10.
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; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45 °C (−9.07 mol g−1 s−1), while the lowest log RSi 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. 相似文献
11.
《Applied Geochemistry》2004,19(9):1377-1389
This study investigated P and As sediment remobilisation in Lake Yangebup, a shallow lake with an overlying floc layer that covers the consolidated sediment. This floc is frequently resuspended into the water column, a process that was postulated to produce high P and As lakewater concentrations. Rate investigations using deionised water showed that P and As remobilisation reached steady state after 20 h in the consolidated sediment and within 1 h for the floc. Floc resuspension in lakewater showed no net release of either P and As, indicating that the floc was in constant equilibrium with the water column. A protocol to distinguish between desorption and dissolution was applied to both sediments and the response of remobilisation to varying slurry density and As addition measured. For the consolidated sediment, the concentration of Fe(II), P and As were unaffected above a slurry density ∼30 g L−1 and added arsenate (10–100 μg L−1) did not significantly change As and P remobilisation. It is shown that these results do not fit an adsorption/desorption equilibrium formulation for P and As remobilisation. Instead, the evidence suggests that the solubility of a thin, non-stoichiometric FePxFeAsy oxyhydroxide surface coating determined the remobilisation process. Data scatter lead to some uncertainty in the floc results but suggest that dissolved P is controlled by dissolution, while dissolved As is controlled by adsorption/desorption. The results conclusively show that P and As remobilisation was lower from the floc than from the consolidated sediment and that the removal of the floc would not lower P and As lakewater concentrations. Implications of these results for the management of As in Lake Yangebup are outlined. 相似文献
12.
13.
《Applied Geochemistry》2005,20(3):639-659
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. 相似文献
14.
《Chemie der Erde / Geochemistry》2016,76(1):133-148
The variation of major and rare earth elements and yttrium (REY) in the monomictic hardwater Lake Tiberias during the wet and dry seasons of the hydrological year was studied in two profiles. The average volume and Cl concentration of the known and unknown saline inflows of 1.6 × 107 m3 and 1.2 × 109 mol are derived by closing both balances. This brine corresponds to a mixture of 83% of groundwater from Cretaceous aquifers and 17% of very saline deep brine. Taking cycling of calcite in the hypolimnion into account, the settling rate of authigenic calcite is estimated to be 3.3 mol m−2 a−1.In the stratified lake of the dry season dissolved inorganic carbon increases by 490 μM at the thermo-/chemocline due to microbial reduction of SO42−, NO3−, chemical reduction of Fe(III) and MnO2 colloids, and cycling of calcite in the hypolimnion. REY distribution in the stratified water column is dominantly controlled by coprecipitation with calcite, hydrous ferric oxides and MnO2 in the epilimnion and cycling of these compounds in the hypolimnion. The positive Ce anomaly in the hypolimnetic water is produced by cycling of MnO2. The simulation of the increase of REY in the hypolimnion reveals that hydrous ferric and manganese oxides only play a negligible role except Ce. Only about 10% of REY from cycled matter enhance REY in solution. Most of the released REY are adsorbed by particular matter and thus settling on the floor of the lake.Different from Na, U, SO42− and SiO2, the other elements, in particular REY, increase in the mixed water column from the top to the lower third and mostly decrease thereafter toward the bottom in the mixed lake during the wet season. The behavior of REY is caused by some cycling of calcite and pH-dependent re-equilibration of REY bound to hydrous ferric and manganese oxides adsorbed by particular matter. 相似文献
15.
Woo Chun Lee Soon-Oh Kim James Ranville Seong-Taek Yun Sun Hee Choi 《Environmental Earth Sciences》2014,71(8):3307-3318
Arsenic(V), as the arsenate (AsO4 3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 molAs/molFe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (2C) and bidentate mononuclear edge-sharing (2E) complexes. 相似文献
16.
The concentration and the role of colloids in the transport of elements in the vicinity of a fossil reactor at Bangombé, Gabon, were assessed. Colloid sampling was conducted in seven boreholes around and in the extinguished natural reactor. The ground waters are of Na–Mg–Ca–HCO3 type, with variable salinities, pH 4.6–6.8 and anaerobic Eh values. Filtered ground water and colloid samples were taken from the reactor and the surroundings. Filtered fluids and colloid samples collected on membranes and resuspended in solution were analysed by ICP-MS and ICP-AES in order to examine the element association in the colloid phase within the size range 3000 to 400 to 50 nm. The colloid concentrations for the size 400 to 50 nm range from 80 to 300 ng ml−1. They consist of silica particles associated with ferrihydrite coated with organics. Trace element results show that metals including Pb, Sc, Y, La, Ce, Pr, Nd, Bi, Th and U are associated to various degrees with the colloid phase. The distribution ratios of these trace elements between the water and the colloid phase (Kp) were experimentally determined. The high Pb distribution ratios of 10+7 ml g−1 are specifically discussed. Values range from 10+6 to 10+5 ml g−1for the trivalent elements (Sc, Y, La, Ce, … , Bi). For uranium, a Kp of the order of 10+5 ml g−1 may be calculated and compared with data gained using the surface complexation model. These Kp values suggest that the uranium is partially sorbed or associated with ground water colloids. Measurements from the reactor zone show that about 2–4% of the uranium is associated with the colloid phase, which contributes partially to the uranium transport. The rather low colloid concentrations are due to the relatively high concentrations of Ca, Mg and Na in these quasi-neutral waters. These soluble elements contribute to the attachment of the colloids, restricting their transport. This indicates that the colloid phase may not be an important transport medium for the radionuclides in the Bangombé system if their association is reversible. The Bangombé colloid results are compared with those studied for other systems. 相似文献
17.
《Applied Geochemistry》2006,21(7):1240-1247
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. 相似文献
18.
We report the structure of a novel sunscreen based on the scytoneman skeleton. This pigment, scytonemin-3a-imine, was isolated from cultures of the cyanobacterium, Scytonema hoffmani, only when grown under high to intense (300–1500+ μmol quanta m−2 s−1) light conditions, with or without added UVR (ultraviolet radiation). It was also isolated from samples of natural cyanobacterial mats growing in shallow/short hydroperiod fresh water (Florida Everglades), soils (Loxahatchee, Florida) and saline cyanobacterial mats (Eleuthera, The Bahamas). These natural samples were all growing under intense (e.g. > 1500 μmol quanta m−2 s−1) light conditions. Scytonemin-3a-imine may eventually become a biomarker for such biota.Characterization included UV/Vis spectrophotometry, Fourier transform infrared (FTIR) spectroscopy, matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry (MS and MSn), and both 1- and 2-D 1H nuclear magnetic resonance (NMR) spectrometry. Derivatization (NaBH4 reduction, acetylation, deuterium exchange) were utilized to confirm structural features. The UV/Vis spectrum had maxima at 237, 366, 437 and 564 nm. The absorption of UVR is in line with other scytoneman-based pigments. The strong visible absorption bands (437 and 564 nm) indicate an alternate or additional physiological role for the pigment. We propose that it may protect both the chlorophyll reaction centers and the cytochromes from excess radiation. We speculate that excitation of the cytochromes, potentially leading to excess electron transport, or photo-oxidative destruction of the cytochromes, may enhance reactive oxygen species (ROS) generation. 相似文献
19.
《Applied Geochemistry》2006,21(12):2188-2200
Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca10−xNax(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). 相似文献
20.
Hematite is a common primary/secondary mineral in mine drainage and mine waste settings that can adsorb dissolved metals and metalloids. This study explored the ability of synthetic hematite to retain one such contaminant, molybdate, on its surfaces under highly alkaline (pH = ∼10) conditions. X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), and specific surface area (BET) analyses show that synthetic hematite particles are stable and able to adsorb molybdate. Raman spectra show that the hematite efficiently adsorbs molybdate and retains it on its surfaces via strong inner-sphere surface complexation. Inductively coupled plasma-mass spectrometry (ICP-MS) data indicate that hematite aged (7 and 9 days) at high and room temperatures (75 and 25 °C) retains adsorbed molybdate and that molybdate sorption increases with aging. SEM images show that aged hematite particles with adsorbed molybdate are similar in size and shape to pure hematite and exhibit no significant reduction in surface area. These findings are valuable for understanding the fate of Mo in mine wastes and mill tailings environments where the 2-line ferrihydrite to which it is adsorbed can transform to hematite. 相似文献