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1.
The Hadamengou gold deposit is located in western part of the northern margin of the North China craton. It is a hydrothermal deposit related to alkaline magmatism. Dissolution of Au, Fe from pyrite and iron oxide （including magnetite and hematite） individual minerals in the three main types of ore shows： in iron oxides （magnetite and hematite）, Au and Fe were dissolved simultaneously and their solubilities are positively correlated, which means Au is mainly chemical-bonded （lattice gold） and/or colloidal-adsorbed in iron oxides; while in pyrite, on the contrary, Au dissolution obviously lags behind Fe and the solubility of Au shows negative relationship with that of Fe, which indicates Au is mainly hosted as grains of elemental gold （or native gold） within pyrite. Previous studies revealed that the Hadamengou gold deposit is characterized by intensive K-feldspathization and holds high content of iron oxides occasionally replaced by sulfides, which was caused by oxidizing K-enriched alkaline fluids under a stretching geodynamic setting. These geological features, together with the high Au-content in iron oxides, comparable with that of the Olympic Dam deposit in South Australia, suggest that this deposit is the first example of iron oxide-type gold deposits in China.  相似文献   

2.
Lakes Baikal （Russia） and Khubsugul （Mongolia） are rift freshwater water bodies. The maximal depth of Baikal is 1642 m, that of Khubsugul -238 m. One of the important aspects in the study of suspended matter is its geochemical composition which depends on mineralogy and granulometry of the suspended matter. As the concentration of suspended matter in the sites of deep lakes is not high - about 1 mg/L, to determine the elements in the suspended matter the monochromatized synchrotron radiation method （SRXFA, Novosibirsk, Russia） was used. Water sampling was conducted in three basins of Lake Baikal and in Lake Khubsugul on central vertical cross-sections and in near-coastal sites. The water samples were collected with 10-liter batometers. The suspension was extracted from the water by filtration under vacuum through ＂Nuclepore＂ filters of 47 mm in diameter with pore size of 0.4 mkm. The mean weight of dry suspension on the filters was about 1 rag. The results of study of lacustrine suspended matter show that such elements as Fe, Ca, Mn, Ti, V, Cr, Cu, Zn, Pb dominate in lakes Baikal and Khubsugul. The concentration of other elements is low. On the whole, the vertical distribution of total amount of suspended matter in open Baikal decreases from the surface to the bottom. As for Lake Khubsugul, it increases.  相似文献   

3.
The bauxites in central Guizhou are hosted by the Lower Carboniferous Jiujialu Formation.Geochemistrial characteristics of the Lindai bauxite deposit indicate that the underlying Shilengshui Formation dolomite is the precursor rock of mineral resources.Weathering simulation experiments show that Si is most likely to migrate with groundwater,the migration rate of which is several magnitude higher than Al and Fe under nature conditions （pH=3-9）.The neutral and acid nonreducing condition is the most conducive to the Al rich and Si removal,while the acid reducing conditions is the most conducive to the Al rich and Fe removal.In the process of bauxite formation,coal beds overlying the Al-bearing rock series or other rock formation rich in organic materials can produce acid reducing groundwater,which are important for the bauxite formation.Finally,propose the metallogenic model of the bauxite in central Guizhou Province and put forward three new words which are ＂original bauxite material＂,＂bauxite material＂ and ＂original bauxite＂.  相似文献   

4.
The Three Gorges are considered to be critical to understand the formation of Yangtze River. Recent research results suggest that the Yangtze Three Gorges was created during the Quaternary but the exact time is debatable. Fe–Ti oxide minerals are seldom used to study sediment provenance, expecially using scanning electron microscopy(SEM), and energy dispersive spectrometer(EDS). In this study, the provenance of Quaternary sediments in Yichang area, which is located to the east of the Yangtze Three Gorges, was investigated by using SEM and EDS to research Fe–Ti oxides. The Panzhihua vanadium titanomagnetite and Emeishan basalt outcrop are located to the west of the Three Gorges. Further, the materials from them are observed in the Quaternary sediments of Yichang area. Fe–Ti oxide minerals from the Huangling granite are observed in the Yunchi and Shanxiyao Formations, which were formed before 0.75 Ma B.P., whereas Fe–Ti oxide minerals from the Huangling granite, Panzhihua vanadium titanomagnetite, and Emeishan basalt are observed in the riverbed and fifth-terrace sediments of the Yangtze River, which were formed after 0.73 Ma B.P.. Thus, we can infer that the Three Gorges formed after the deposition of the Shanxi Formation and before the fifth-terrace; i.e., 0.75–0.73 Ma B.P..  相似文献   

5.
A comprehensive assessment of man-made impact on the environment is much kept behind because of missing unified systems of environmental monitoring. They represent sources of reliable information on the current status of the environment, as well as the absence of approaches to assess the impact of chemical pollution by different anthropogenic sources. Vegetation, being the component of environmental systems, is very sensitive to atmospheric man-made load. However, permissible concentrations of elements in plants, causing deflection in their development are differently estimated in different regions and vegetation species. As to the Baikal region, it is commonly the sanitary state of woods, that is primarily assessed. Coniferous trees, in particular pine, represent the main tree species in the region. In the Olkhon region we investigated the trace element compositions in pine needles to obtain the background contents of toxic metals. This region of the National park lies 300 km away from the industrial sources of pollutants, beyond the zone of wind effect, and has no industry. The research was made on the healthy （green） and dried up （red） pine needles. The elements like Zn, Al, Mn, Fe, Cr, Cu, Co, Ni, Sr, Cd, Pb, Li, Rb, Sb and As were measured by atomic absorption and flame emission photometry. The samples were decomposed in autoclaves with the mixture of nitric acid and hydrogen peroxide. Distinct differences were found in a series of elements contained in the green and dried needles. The red needles are characterized by higher contents of Zn, Al, Cu and low Mn, Fe, Pb with similar contents of other elements.  相似文献   

6.
Antimony （Sb） is a toxic element and belongs to group 15 of the periodic table, under arsenic （As）. The geochemical behavior of Sb in the environment is still largely unknown. Since the behavior of Sb in the environment depends on its oxidation state, Sb analysis in environmental samples requires quantitative measurement of Sb （Ⅲ） and Sb （Ⅴ）. The aim of this study is the speciation of Sb in both solid and water phases to understand the reaction and dynamics of Sb in soil-water system. Accordingly, we employed X-ray absorption fine structure （XAFS） analysis to determine the Sb and As species in soil in laboratory and natural systems, while we also determined the oxidation states in soil water by the conventional HPLC-ICP-MS method. Natural soil and soil water samples containing Sb and As were collected around the Ichinokawa mine pithead, Ehime, Japan. To observe the species under various redox conditions, the soil and soil water samples were collected at four depths. Soil containing Sb and As were incubated for 7 days at 25℃ to observe their oxidation states under various redox condition by changing the total amount of water in the soil. Antimony K-edge XAFS spectra were measured at the beamline BL01B 1 at SPring-8 （Hyogo, Japan） and K-edge XAFS spectra of As, Fe, and Mn at the beamline BL12C in Photon Factory, KEK （Thukuba, Japan）. In the natural soil-water system, Sb was present exclusively as Sb （Ⅴ） over a wide redox range （from Eh=-140 to 360 mV; pH 8）, while As was present as a mixture of As （Ⅲ） and As （Ⅴ）. This trend was confirmed in the laboratory experiments. These results suggest that Sb （Ⅴ） is a very stable form in the environment and that Sb is oxidized under more oxic condition than As. Combining the results of Fe and Mn XAFS analyses and a positive correlation among Sb, As, and Fe abundances in the soil, the host phases of Sb and As in soil were Fe （Ⅲ） hydroxide. EXAFS analyses of Sb and As are also consistent with this fact. Under reducing conditions, the concentrations of As in the soil water increased whereas those of Sb decreased in both the natural and laboratory systems.  相似文献   

7.
Using the long-term ground temperature monitoring data of the permafrost zone along the Qinghai-Tibet Railway from 2006 to 2020,three types of typical roadbed structures were analyzed. Traditional embankment（TE）,U-shaped crushed rock embankment（UCRE）and crushed rock revetment embankment（CRRE）were included the three types of typical roadbed,which were selected to the long-term monitoring sections within the warm permafrost zones. The evolution of ground temperature field,mean annual ground temperature （MAGT）and annual maximum ground temperature（AMGT）in the depth range of 20 m under the embankment were analyzed and studied since 15 years of operation. The monitoring and analysis results show that：the growth rate of MAGT under the left and right shoulders of the TE is always higher than that of the same depth in the natural site. The MAGT under the UCRE is always lower than the natural site and always maintains a certain difference,whereas,the difference in ground temperature under the left and right shoulders is also not negligible. The MAGT of the left shoulder in the CRRE is not much different from that of the natural hole,while the MAGT of the right shoulder is always lower than that of the natural hole,and the differ in ground temperature between the left and right shoulders is smaller than that of the UCRE. The artificial permafrost table（APT）under the TE is always lower than that of in the natural site. Both the UCRE and CRRE,the APT in the left and right shoulders of them has been elevated into the embankment,and the differ of APT between the left and right shoulders is about 1. 0~1. 5 m. the differ of APT between the left and right shoulders in the CRRE is slightly lower than that of UCRE. Overall,because of the influence of thermal disturbance about engineering and climate warming,the TE in the warm permafrost zones cannot keep the thermal stability of permafrost under the embankment. Some active-cooling and reinforcement measures need to be taken. Both of the UCRE and CRRE,have a certain active-cooling effect on the permafrost under embankment,but the differ in ground temperature between the left and right shoulders still needs to be taken seriously. © 2022 Science Press (China).  相似文献   

8.
Hematite is an important iron oxide mineral in loess-paleosol sequences in central China. Investigation of the mineralogical characteristics, genetic mechanism and relationship of hematite with other iron oxides and Fe-bearing minerals will help understand the geochemical process before and after eolian deposit, paleocliamte significance of magnetic susceptibility and reconstruct paleoclimate in central China. So, hematite and related minerals of the loess and paleosol units from Chinese Loess Plateau were investigated using optical microscope, X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, and high-resolution transmission microscopy （HRTEM）. The results show that there are five genetic types of hematite in loess-paleosol sequences of central China： （1） weathering of Fe-bearing silicate minerals, for instance, chlorite, will release iron that is precipitated as aggregates of hematite nano-crystals on mineral surfaces; （2） hematite combined with eolian magnetite grains that resulted from partial oxidation of magnetite, even though the partial oxidation may occur in the original area; （3） phase transformation from eolian goethite to hematite; （4） hematite formed on the edge and surface of maghemite because of dissolution and hematite recrystallization; and （5） eolian detrial hematite. The hematite formed from chemical weathering of Fe-bearing silicates with nanoporous texture because of dehydration from iron hydroxide is the most important genetic mechanism. It is proposed that the fact that hematite was formed from chemical weathering of Fe-bearing silicates is a main reason for the redness in paleosol units. However, too intense pedogenesis and high amounts of precipitation will promote oxidation of eolian magnetite and maghemite dissolution, which may result in the decreasing of magnetic susceptibility.  相似文献   

9.
Lead （Pb） is normally considered as a trace element in soils and sediments for geochemical study. However, the concentration of Pb in firing range soils is generally so high that it should be considered as a major element during the evaluation of the soil geochemical properties. Soil organic matter （SOM） has been reported as one of the major factors to expedite the corrosion of metallic lead （Pb） in acidic and organic-rich soils. The main impacts of SOM on the fate and transport of Pb in firing range soils lie in the following two aspects; （1） the complexation of organic matter with Pb, which has received lots of attention, and; （2） changes in soil redox potential due to the transformation of SOM and its subsequent impact on Pb speciation, which has rarely been investigated. Soils from 6 different firing ranges are selected for this study. These samples have been stored under a closed condition for more than 3 years. The soil moisture contents were well-retained, as all the samples were kept in closed plastic buckets. The analytical data showed that the summation of the soil total organic carbon content （TOC） and inorganic carbon contents （TIC） were consistent with soil total carbon contents （TC） measured in previous years, although the TOC and TIC contents have changed respectively after years of storage. In general, it is observed that the soil TOC decreased against an increase of TIC. The mass balance on such a transformation suggested a major conversion of organic carbon （Corg） to inorganic carbon （CO3^2-） in the stored soils.  相似文献   

10.
Conventional methods for investigating soil heavy metal contamination based on raster sampling and chemical analysis are time consuming and relatively expensive. Reflectance spectroscopy within the visible-near-infrared （VNIR） region is known for being rapid, convenient, and accurate. Due to low abundance, heavy metals in soils cannot exhibit their inherently spectral features. The objective of this study were （1） to examine the possibility of reflectance spectra as a rapid method to assess Ni, Cr, Cu, Hg, Zn, As, Pb, and Cd in soils, and （2） to explore the mechanism by which to predict spectrally featureless heavy metals. Two research areas located in the south （120 samples） and north （61 samples） of Nanjing City were researched. Reflectance spectra of the samples were recorded on a Perkin-Elmer Lambda 900 spectrophotometer. Partial least-square regression （PLSR） approach was used to develop calibration equations between the spectral data and measured values for heavy metals. The prediction results of the two areas were consistent. Except for Cd all the other elements could be successfully predicted using the reflectance spectra. The prediction accuracy for Ni, Cr, and Cu was highest, while that for Hg and Cd was lowest. In order to further explore the physicochemical mechanism behind the relations between reflectance spectra and heavy metals, one more principal component analysis （PCA） was done for nine elements （eight heavy metals and Fe）. The results of PCA for the both areas were also consistent. Loading plot of factors 1 and 2 from the results of PCA showed that Ni, Cr and Cu, the prediction accuracy of which was highest, were clustered together with Fe. For the other elements that were less correlated with Fe, their prediction accuracy was also lower than that of the three elements. Fe is spectrally active and can exhibit its absorption features. Therefore, the inter-correlation between heavy metals and spectrally active total Fe is the major mechanism by which to predict spectrally featureless trace metals. This study for the two areas showed the potential of reflectance spectra to predict microelements in soils.  相似文献   

11.
《Applied Geochemistry》1999,14(5):581-606
Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO3) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO3 dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L−1 of O2, Fe3+, Al3+ and Mn2+. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O2>1 mg·L−1) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and Al(OH)3, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and Al(OH)3 particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO3 dissolution and Fe(OH3) precipitation were associated with the relatively low pH and high Fe3+ concentration near the inflow. The rate of CaCO3 dissolution decreased with increased pH and concentrations of Ca2+ and HCO3− and decreased Pco2. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.  相似文献   

12.
《Geochimica et cosmochimica acta》1999,63(19-20):3417-3427
In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [FeII1−xFeIIIx(OH)2]+x· [x/z A−z]−x, where compensating interlayer anions, A−, can be Cl−, SO42−, CO32− or OH−, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fet, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log Ksp = 28.2 ± 0.8 for the reaction Fe3(OH)7 + e− + 7 H+ = 3 Fe2+ + 7 H2O; log Ksp = 25.4 ± 0.7 for the reaction Fe2(OH)5 + e− + 5 H+ = 2 Fe2+ + 5 H2O; log Ksp = 45.8 ± 0.9 for the reaction Fe3(OH)8 + 2e− + 8 H+ = 3 Fe2+ + 8 H2O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: ΔfG° (Fe3(OH)7, cr, 282.15 K) = −1799.7 ± 6 kJ mol−1, ΔfG° (Fe2(OH)5, cr, 282.15 K) = −1244.1 ± 6 kJ mol−1 and ΔfG° (Fe3(OH)8, cr, 282.15 K) = −1944.3 ± 6 kJ mol−1.  相似文献   

13.
Natural ferrihydrites (Fh) often contain impurities such as aluminum, especially in acid mine drainage, and these impurities can potentially impact the chemical reactivity of Fh with respect to metal (loid) adsorption. In the present study, we have investigated the influence of aluminum on the sorption properties of ferrihydrite with respect to environmentally relevant aqueous arsenic species, arsenite and arsenate. We have conducted sorption experiments by reacting aqueous As(III) and As(V) with synthetic Al-free and Al-bearing ferrihydrite at pH 6.5. Our results reveal that, when increasing the Al:Fe molar ratio in Fh, the sorption density dramatically decreased for As(III), whereas it increased for As(V). Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy analysis at the As K-edge indicated that the AsIIIO3 pyramid binds to FeO6 octahedra on both Al-free Fh and Al-bearing Fh, by forming bidentate mononuclear edge-sharing (2E) and bidentate binuclear corner-sharing (2C) surface complexes characterized by As–Fe distances of 2.9 Å and 3.4 Å, respectively. The decrease in As(III) sorption density with increasing Al:Fe ratio in Fh could thus be explained by a low affinity of the As(OH)3 molecule for Al surface sites compared to Fe ones. In contrast, on the basis of available literature on As(V) adsorption mechanisms, we suggest that, in addition to inner-sphere 2C arsenate surface complexes, outer-sphere arsenate surface complexes forming hydrogen bonds with both Al–OH and Fe–OH surface sites could explain the enhancement of As(V) sorption onto aluminous Fh relative to Al-free Fh, as observed in the present study. The presence of aluminum in Fh may thus enhance the mobility of arsenite with respect to arsenate in Acid Mine Drainage impacted systems, while mixed Al:Fe systems could present an alternative for arsenic removal from impacted waters, provided that As(III) would be oxidized to As(V).  相似文献   

14.
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   

15.
Laboratory studies of the weathering of sulphide ores have centred around using samples of ore as electrodes and accelerating the weathering processes by passing an electric current. The results of reacting 19 different ore types under varying conditions are compared with data from co-precipitating, Fe and Cu, Fe and Ni, Fe and Zn, Fe and Co, and Fe and Pb, over a pH range from 2 to 11. An electrochemical cell specially designed to fit onto an optical microscope has allowed direct observation of the changes in sulphide mineral grains as they are anodically weathered.These experiments are used to demonstrate that the pH of the environment during the weathering of sulphides to sulphates is the most important parameter in determining the initial gossan minerals that form. Factors that will cause the pH to be high are buffering from gangue and wallrock minerals, low iron content in the sulphide and a high metal to sulphur ratio in the sulphide. A low pH is favoured by the converse, namely a sulphide sufficiently massive to override the buffering effects of the wallrocks and any gangue minerals present, a high iron content in the sulphide and a low metal to sulphur ratio in the sulphide.Two mechanisms of iron hydrolysis dominate the weathering processes where iron is a major metal being released from a sulphide.
1. (1) The high pH process. Where there is sufficient buffering for the pH to remain at or above 7, most of the base metals including ferrous iron will be hydrolysed and pyroaurite type of minerals form for Ni, Zn and Co, while mixed Fe-Cu hydroxycarbonates and hydroxysulphates form for Cu, and mixed iron lead hydrocarbonates form for Pb. The iron is located in these initial compounds as a green rust where it is effectively bound as ferrous hydroxide. Subsequent oxidation of this hydroxide produces no further acid. 4Fe(OH)2 + O2 + 2H20 → 4Fe(OH)3
2. (2) The low pH process. Where the buffering is insufficient and the pH is below 7, even though some of the ferrous iron will have precipitated as an equivalent to Fe(OH)2, the solubility is such that sufficient Fe2+ will remain in solution so that further oxidation will produce acid. 4Fe2+ + O2 + 1OH2O → Fe(OH)3 + 8H+ This acid will bring more of the Fe2+ into solution to create more acid and the pH will gradually fall even further, so that the gossan forming environment will be at a pH less than 5 and may be as low as 3. At these low pH values, the base metals are soluble and not prone to co-precipitation or adsorption with the gossan minerals. Only elements present in solution as anions, such as Se, As, Mo and Sb, are likely to be bound into gossans forming at low pH.
The results from weathering tests carried out on gossan minerals formed at higher pH show that these minerals are reasonably stable if treated with solutions that have a pH above 7, but they can break down if treated with a solution of pH 5. Thus they could be expected to be leached by rain water saturated with CO2.When investigating a likely gossan, all aspects — the iron oxides, the silicates, the carbonates and penetrations into the footwall and hanging wall — should be examined carefully, being ever mindful of the effect that pH would have had during the formation and reworking of the minerals. The composition of gossan minerals, their adsorption properties, the solubilities of metal ions, the mechanisms of Fe precipitation, the co-precipitation of other metals with Fe, the stability of carbonates and the binding of humic materials are all pH dependent in the same way. At high pH, metals are immobilized; at low pH, they tend to be in solution.  相似文献   

16.
Lead- and Pb-As-jarosites are minerals common to acidic, sulphate-rich environments, including weathering zones of sulphide ore deposits and acid rock or acid mine drainage (ARD/AMD) sites, and often form on or near galena. The structures of these jarosites are based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, comprised of slightly distorted FeO6 octahedra and SO42− (-AsO43− in Pb-As-jarosites) tetrahedra. To better understand the dissolution mechanisms and products of the break down of Pb- and Pb-As-jarosite, preliminary batch dissolution experiments were conducted on synthetic Pb- and Pb-As-jarosite at pH 2 and 20 °C, to mimic environments affected by ARD/AMD, and at pH 8 and 20 °C, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)2). All four dissolutions are incongruent. Dissolution of Pb-jarosite at pH 2 yields aqueous Pb, Fe and SO42−. The pH 8 Pb-jarosite dissolution yields aqueous Pb, SO42− and poorly crystalline Fe(OH)3, which does not appear to resorb Pb or SO42−, possibly due to the low solution pH (3.44-3.54) at the end of the experiment. The pH 2 and 8 dissolutions of Pb-As-jarosite result in the formation of secondary compounds (poorly crystalline PbSO4 for pH 2 dissolution; poorly crystalline PbSO4 and Fe(OH)3 for pH 8 dissolution), which may act as dissolution inhibitors after 250 to 300 h of dissolution. In the pH 2 dissolution, aqueous Fe, SO42− and AsO43− also form, and in the pH 8 dissolution, Fe(OH)3 precipitates then subsequently resorbs aqueous AsO43−. The dissolutions probably proceed by preferred dissolution of the A- and T-sites, which contain Pb, and SO42− and AsO43−, respectively, rather than Fe, which is sterically remote, within the T-O-T Pb- and Pb-As-jarosite structures. These data provide the foundation necessary for further, more detailed investigations into the dissolution of Pb- and Pb-As-jarosites.  相似文献   

17.
观察了三种吸附剂吸附亚砷酸根离子过程中溶液pH值随时间的变化。氢氧化铁在吸附过程中的pH值变化大致可分为三个阶段，0～6分钟为第一阶段，体系的pH值快速上升，指示亚砷酸根置换了固相中的氢氧根；7～40分钟为第二阶段，pH值变化不大，指示Fe(OH)3凝胶对亚砷酸根离子的吸附达到动态平衡；40分钟后为第三阶段，溶液的pH值呈单边下降趋势，这一阶段吸附剂与被吸附的阴离子之间发生了缩合反应，并释放出H＋。Mg-Al-LDO在吸附亚砷酸根的反应过程中pH值持续上升，它具有从水溶液中获取阴离子以恢复其前驱体结构的能力，这一反应中有氢氧根生成；Mg-Fe-LDO兼有前两者的吸附机理，吸附反应过程pH值的变化趋势此介于二者之间。氢氧化铁在加热前后吸附容量变化不大，25C和90C时分别为69.7mg/g和73.7mg/g，而Mg-Al-LDO和Mg-Fe-LDO的吸附容量在25C时分别为62.4mg/g和82.5mg/g，在90C时分别增加到114.9 mg/g和199.0 mg/g。Mg-Al-LDO和Mg-Fe-LDO在90C条件下吸附容量的大幅增加，可能和溶解CO2的干扰被抑制有关。  相似文献   

18.
Changes in the UV spectra of As(OH)3 solutions with variations in pH and temperature have recently been used to determine the temperature dependence of the pKa of the acid. In previous studies I used quantum mechanical techniques to study changes in structure and vibrational spectra as a function of pH for arsenites and thioarsenites. I previously calculated UV spectra for ``molecular' minerals, like realgar As4S4. Here I use a number of different quantum mechanical methods, both Hartree-Fock and density functional theory based, to calculate the UV spectra for both a related simple well-characterized gas-phase molecule PF3 and for As(OH)3 and As(SH)3 and their conjugate anions and some neutral and anionic oligomers in aqueous solution. For the monomeric species small numbers of water molecules have been explicitly included, in a supermolecule or microsolvation approach. I find that UV absorption energies accurate to a few tenths of an eV can be obtained both for gas- phase PF3 and for neutral arsenious acid in aqueous solution, for which the UV absorption maximum is calculated to occur around 6.5 eV, consistent with experiment. Accurate calculation of the UV energies for arsenite anions in aqueous solution is much more difficult, since basis set size and solvation effects are considerably larger than for the neutral molecules, but fairly reliable results can still be obtained. Deprotonation is found to reduce the lowest calculated UV transition energy by about half an eV. Oligomerization also reduces the lowest calculated UV energy by at least half an eV. Replacement of one or all the –OH groups by –SH groups reduces the lowest calculated UV energies by about 2 eV. UV excitation energies have been calculated for oligomeric species as large as As3E3(EH)3 and As4E6, where E = O, S, and may be useful for identifying such species in solution.  相似文献   

19.
Manganese at equilibrium in seawater occurs dominantly as Mn2+ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O2 and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 108 ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn2+ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)30 and Fe(OH)4?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)3.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.  相似文献   

20.
This study investigated possible geochemical reactions during titration of a contaminated groundwater with a low pH but high concentrations of aluminum, calcium, magnesium, manganese, and trace contaminant metals/radionuclides such as uranium, technetium, nickel, and cobalt. Both Na-carbonate and hydroxide were used as titrants, and a geochemical equilibrium reaction path model was employed to predict aqueous species and mineral precipitation during titration. Although the model appeared to be adequate to describe the concentration profiles of some metal cations, solution pH, and mineral precipitates, it failed to describe the concentrations of U during titration and its precipitation. Most U (as uranyl, UO22+) as well as Tc (as pertechnetate, TcO4−) were found to be sorbed and coprecipitated with amorphous Al and Fe oxyhydroxides at pH below ∼5.5, but slow desorption or dissolution of U and Tc occurred at higher pH values when Na2CO3 was used as the titrant. In general, the precipitation of major cationic species followed the order of Fe(OH)3 and/or FeCo0.1(OH)3.2, Al4(OH)10SO4, MnCO3, CaCO3, conversion of Al4(OH)10SO4 to Al(OH)3,am, Mn(OH)2, Mg(OH)2, MgCO3, and Ca(OH)2. The formation of mixed or double hydroxide phases of Ni and Co with Al and Fe oxyhydroxides was thought to be responsible for the removal of Ni and Co in solution. Results of this study indicate that, although the hydrolysis and precipitation of a single cation are known, complex reactions such as sorption/desorption, coprecipitation of mixed mineral phases, and their dissolution could occur simultaneously. These processes as well as the kinetic constraints must be considered in the design of the remediation strategies and modeling to better predict the activities of various metal species and solid precipitates during pre- and post-groundwater treatment practices.  相似文献   

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