Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

Adsorption of aluminium by a latosol as affected by phosphate and glutamic acid

The effect of phosphate and glutamic acid on adsorption of aluminium onto a latosol was investigated as a function of pH and ligand concentrations through batch equilibrium experiments. The results showed that adsorption of aluminium by the soil was enhanced after addition of phosphate at low pH, and this promotive effect was gradually eliminated with the increase in pH. The positive effect of phosphate on aluminium adsorption onto latosol was attributed to phosphate-induced surface negative charge and formation of ternary surface complexes involving aluminium and phosphate. While using silica as adsorbent, the inactive surfaces for phosphate, promotion of adsorption of aluminium by phosphate was also found. Then it was proposed that additional aluminium might bind to the phosphate adsorbed onto the silica in the form of surface complexes silica–aluminium–phosphate again, and the mechanism might operate in the soil systems as well. Glutamic acid exhibited no influence on the adsorption of aluminium by the soil at low pH. After increasing the pH, adsorption of aluminium was inhibited especially with the highest addition of glutamic acid, probably owing to weak affinity of complexes between glutamic acid and aluminium to the soil.     

Uranium (VI) sorption on colloidal magnetite under anoxic environment: experimental study and surface complexation modelling

Magnetite is one of the most important end member of iron corrosion products under a reducing environment; therefore, it may be one of the first products interacting with radionuclides in a radioactive waste disposal after the canister failure.Nanocrystalline magnetite was synthetised in the laboratory and its main physico-chemical properties (microstructure, surface area, surface charge) were analysed. The stability of the oxide was also investigated under the experimental conditions used in sorption studies. The sorption behaviour of U^VI onto magnetite was analysed under O₂- and CO₂-free conditions in a wide range of pH, ionic strengths and radionuclide concentrations.The uranyl binding to magnetite is characterised by a sorption edge between pH 4 and 5.5, and sorption was found to be independent on the electrolyte concentration, which indicates the formation of inner sphere complexes. The sorption isotherms showed a linear behaviour up to the saturation of the sorption sites with a Langmuir-type behaviour.One of the aims of this work was to find the simplest model capable to reproduce the experimental data. Sorption data were fitted using a classical approximation (diffuse double layer model), considering only one type of surface site and evaluating two different options: the first one involving two different monodentate complexes, and the second one a single binuclear bidentate complex. A highly satisfactory fit of the experimental data was obtained by both approaches in the range of the experimental conditions investigated.     

Mechanisms of galena dissolution in oxygen-saturated solutions: Evaluation of pH effect on apparent activation energies and mineral-water interface

This work describes a laboratory investigation of processes ruling the dissolution of galena (PbS) under conditions that mimic oxidising Earth surface environments. Freshly cleaved (001) galena surface was partially dissolved in solutions at different pH (HCl, pH between 1.2 and 5.8) and temperature (298 K) levels for several weeks in a flow-through reactor. Analysis of the galena surface after exposure to oxygen-saturated solutions was performed by XPS. The estimated thickness of surface layer formed after interaction for four weeks with solution at pH 5.8 was ∼0.5 nm. After the same time of interaction with solution at pH 1, the surface layer was at least 9 nm thick. Stationary dissolution rates were measured at different pH (between 1 and 5.8) and temperatures (298, 323, 348 K). Reaction order with respect to hydrogen ion averages 0.6 and slightly decreases with temperature. Dissolution rates, plotted vs. the reciprocal values of temperature, follow Arrhenius behaviour. Activation energies show a sharply discontinuous variation with pH. They are 13.5 ± 2 kJmol⁻¹ at pH = 1.2 and 2.87, whereas at pH of 4.08, 4.7, and 5.8, they show, respectively, values of 48.8 ± 3.5, 45 ± 4, and 51 ± 4 kJmol⁻¹. The apparent activation energy was also investigated by starting the experiment from pH 5.8 and then decreasing to pH 1.2. In this case, the apparent activation energies were 44 ± 4 kJmol⁻¹ and 21 ± 4 kJmol⁻¹, respectively.Apparent activation energies indicate a diffusion-controlled kinetic regime for pH <3, and a mixture of surface and diffusion control for pH between ∼4 and 5.8. A strong effect of solution pH on the mineral-water interface is revealed also by the observed pH dependence of surface-layer thickness. On the basis of the high-resolution XPS signals, the dependence of activation energies on solution pH should reflect a change of structure, and also chemical composition, of the mineral-water interface.     

Adsorption of copper onto goethite in aqueous systems

The adsorption of copper(II) onto goethite was studied as a function of pH, total dissolved copper concentration, surface area of goethite, and ionic strength. The adsorption of copper was similar to that of other hydrolyzable metals. A tenfold increase in goethite surface area had a significant effect on the adsorption edge, but a tenfold increase in the ionic strength of the medium did not effect the adsorption edge. The distribution coefficients increase sharply with increase in pH and ranged from 10 to 60,000 ml/g over a range of two and half pH units, depending on the goethite surface area and copper concentration. A tenfold decrease in ionic strength as well as a tenfold increase in surface area of goethite did not have any effect on the magnitude of distribution coefficients. Distribution coefficients were used to calculate the number of protons released per mole of copper adsorbed during the adsorption process. The average number of protons released per mole of copper adsorbed was estimated to be 1.40 ± 0.10.Managed by Martin Marietta Energy System, Inc., for the U.S. Department of Energy under contract no. DE-AC05-840R21400.     

广西全州县富硒土壤地球化学特征

依据广西全州县土地质量地球化学调查数据,研究了表层土壤中硒的总体分布特征、受控因素及生态效应.结果表明,广西全州县存在大面积的富硒土壤,土壤硒平均含量为0.60×10-6,足硒和富硒土壤面积分别占17.38%和81.88%.土壤硒含量的分布明显受成土母质、土壤质地、pH值等影响,主要受控于成土母质,具有明显的继承性.研究区土壤环境质量良好,富硒农产品丰富,富硒土地资源具有良好的开发前景.     

合成碲金矿及其热液蚀变实验研究初探

通过实验合成出了碲金矿 ,并对其进行了 2 0 0℃、80℃温度下不同 p H溶液中的蚀变实验。对碲金矿及蚀变产物分别进行了 X-射线粉晶衍射、矿相显微镜鉴定及电子探针和光电子能谱分析。实验结果表明 ,在中性、偏酸性和碱性溶液的实验条件下碲金矿基本保持稳定 ,而在碱性稀溶液实验条件下可观测到少量含 Fe、 Te、 Au新相的生成及碲金矿表面氧化态碲的明显增加。     

Experimental investigation of aqueous corrosion of R7T7 nuclear glass at 90°C in the presence of organic species

The initial dissolution kinetics of the French “R7T7” inactive LWR reference glass was investigated in organic media at 90°C by static experiments at imposed pH values. Tests were conducted with various organic acids or acid salts (formic acid, citric acid, humic acids, sodium citrate and sodium formate) at different concentrations and at pH values ranging from 3 to 9. The leachates were submitted to ICP-AES analysis, and the alteration films on the glass specimens were examined by SEM (equipped with an energy-dispersive chemical analysis systm) and XRD. Results are discussed for the following areas.Effect of pH: different mechanisms are involved at pH 2.5 and pH 9, but in both cases, the R7T7 glass dissolution kinetics are always controlled by a surface reaction mechanism. The most significant effects of the organic acids on the glass dissolution kinetics were observed at pH 3, which was not unexpected.Nature of the acid (or acid salt): this is an essential parameter. Formic acid (monoacid) and sodium formate had no effect on the initial glass dissolution rate nor on the nature of the alteration film; conversely, citric acid (triacid) and sodium citrate significantly affected glass dissolution. The role of citric acid in the surface reaction mechanism has been demonstrated experimentally at pH 2.5; it is also known to favor that extraction of Si (directly or indirectly) and Zr and probably of Fe. The humic acids are strong catalysts of the R7T7 glass dissolution reaction. The conclusions drawn from these observations corroborate other published findings, suggesting that the catalytic effect is appreciable only for species with at least two carboxylic acid functions.Effect of concentration: the effect of the concentration was observed at basic pH values in the presence of sodium citrate and humic acids. This parameter may thus be quantified and incorporated in the glass dissolution kinetic law.     

溶液pH对自然水体中多种固相介质吸附铅、镉、铜影响的比较

采用实验室内模拟吸附方法,研究不同溶液pH下沉积物、悬浮颗粒物和生物膜吸附重金属的热力学特征。结果表明：在不同pH下,Langmuir方程均可以很好地描述自然水体三种固相介质吸附重金属的热力学过程。在相同pH条件下,三种固相介质对重金属的吸附能力从大到小依次为悬浮颗粒物、生物膜、沉积物,它们对重金属的吸附能力为铅>铜>镉;这三种固相介质对重金属的吸附能力都随着pH值的升高而增大,其中悬浮颗粒物对重金属的吸附能力受溶液pH影响最大;另外,相对于铜和镉,三种固相介质对铅的吸附受溶液pH影响较大。     

锰钾矿光催化降解苯酚及其影响因素研究

利用回流法合成隧道结构的锰钾矿,并研究其光化学降解苯酚的效果及影响因素。分别采用X射线衍射、原子吸收光谱、扫描电镜、透射电镜和BET氮气吸附法对锰钾矿的晶体结构(包括晶型、晶胞参数和结晶度)、化学组成、微观形貌和比表面积进行了表征。研究表明,非光照时锰钾矿对苯酚的降解效果较差,光照能显著促进锰钾矿对苯酚的降解;光照条件下,p H值减小能显著促进锰钾矿对苯酚的降解;锰钾矿用量增加至1.00 g/L时能显著促进锰钾矿降解苯酚,但继续增加矿物用量却显著降低苯酚降解率;非光照条件下,p H值减小和矿物用量增加不能显著促进锰钾矿降解苯酚。     

The solubility of aragonite in seawater—I. Effect of pH and water chemistry at one atmosphere

The effect of water chemistry on the solubility of aragonite in seawater has been defined experimentally as a series of apparent solubility products measured with respect to pH at one atmosphere.The dominant control of the apparent solubility product of aragonite is the carbonate ion concentration, and this is primarily a function of pH. In the light of this fact, we have reconciled our data with 81 other reported values of aragonite solubility by simply examining the water chemistry of the waters in which they were determined.     

A new preparation process of coal-based magnetically activated carbon

Fe/C-based magnetically activated carbon （MAC） was obtained by carbonizing and activating its precursor, that was prepared by co-precipitation of anthracite coal impregnated in ferric chloride solution. The effect of the concentrations of FeC13 and pH of solution on BET surface area, pore volume and magnetic properties of the MAC was studied by BET N2 adsorption and VSM method. The results indicated that the magnetization of MAC gradually increases with increasing concentration of FeC13 and pH value of solution, and BET surface area was inclined to fluctuation. The largest BET surface area and magnetization of MAC were 1327.5 m2/g and 35.56 emu/g, respec- tively. The form of magnetic matter in the magnetically activated carbon was mainly Fe3C by X-ray powder diffrac- tion （XRD） and magnetic attraction test.     

热活化胶状黄铁矿去除酸性溶液中的Cd(Ⅱ)

利用XRD和SEM测试方法表征了热活化胶状黄铁矿结构和微观形貌,考察了溶液pH、溶解氧和热活化温度对热活 化胶状黄铁矿去除水中Cd（Ⅱ）的影响,并探讨了除Cd（Ⅱ）反应动力学和作用机理。胶状黄铁矿在N2氛围下650℃热活化 5 min可完全分解生成多孔结构化单斜磁黄铁矿（PMPyr）。在pH 2~6的无氧水溶液中PMPyr除Cd（Ⅱ）效率均达到88%以 上,除Cd（Ⅱ）效率受pH影响较小;PMPyr表面氧化会抑制其与Cd（Ⅱ）的反应。PMPyr除Cd（Ⅱ）动力学可用准二级动力学模型拟合（R2> 0.9992）,结合溶液pH变化趋势、Fe（Ⅱ）和SO42-浓度变化推测,PMPyr除Cd（Ⅱ）机理主要是Fe1-xS和CdS溶度积差异推动了PMPyr与Cd（Ⅱ）交换反应,表面络合属于次要作用。     

Surface oxidation of chalcopyrite (CuFeS2) under ambient atmospheric and aqueous (pH 2-10) conditions: Cu, Fe L- and O K-edge X-ray spectroscopy

X-ray absorption and emission spectra were used to characterize the surface of chalcopyrite after oxidation both in air and in air-saturated aqueous solution (pH = 2-10). For chalcopyrite oxidized in aqueous solution, the Cu and Fe L-edge spectra show that the surface oxidation layer is copper deficient. As the pH increases, O K-edge spectra reveal a change in the nature of the oxidation layer. An iron (hydroxy)sulfate is dominant at low pH, whereas FeOOH is the major surface phase under alkaline conditions. Fe₂O₃ may be present at intermediate pH. The surfaces of chalcopyrite samples oxidized in air consist of a mixture of copper oxides, FeOOH, and sulfate phases. Sulfate is much more abundant on the surface of air-oxidized chalcopyrite because of its high solubility in aqueous solution. Likewise, copper oxidation products can be observed in the O K-edge spectra of air-oxidized chalcopyrite in contrast to the aqueous samples.     

Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

The nature of the surface oxidation phase on pyrite, FeS₂, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L_III edge, and iron L_II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS₂ can be detected in the X-ray absorption spectra. In a 1.667 × 10⁻³ mol/L Fe³⁺ solution with ferric iron present as FeCl₃ in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.     

锰矿石脱硫产物处理含铜废水动态实验研究

氧化型锰矿石脱硫产物含大量硫化锰,利用这种材料装填固定床进行净化水中铜离子的动态试验.在材料粒径0.45～0.9mm、进水pH=5.8、进水滤速4.58 m/h条件下,1 t锰矿石脱硫产物可以处理923 tρ(Cu~(2+))=50 mg/L的含铜废水,出水ρ(Cu~(2+))<0.5 mg/L,低于国家一级排放标准.控制进水pH在4～9之间、降低进水滤速、采用较小粒径的材料有利于提高锰矿石脱硫产物处理含铜废水的容量.利用X射线粉末衍射(XRD)和扫描电镜-能谱分析(SEM-EDS)对材料和产物进行表征,证明锰矿石脱硫产物去除水中铜离子是基于离子交换反应的原理.     

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

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.     

A vibrational spectroscopic study of the oxidation of pyrite by molecular oxygen

In situ flow-through attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to investigate the formation, and step-wise oxidation, of sulfoxyanions at the pyrite surface during oxidation by molecular oxygen. The surface was studied under two different pH regimes (pH 2.5 and pH 5.6) and under two light conditions (dark and ultraviolet light). It was experimentally observed that multiple sulfoxyanions were present at the pyrite surface during oxidation by molecular oxygen, spectroscopically illustrating the concept of sulfur step-wise oxidation. The results from photochemical experiments were complex and suggest a dependence on both pH and surface speciation.     

生物炭对磷石膏中磷的固化作用

磷石膏中的磷在雨水淋滤作用下浸出,将污染堆场附近水体。本研究采用生物炭固化磷石膏中的磷,以减少其对周遭水体的污染。主要通过模拟固化实验和对照浸出实验,分析生物炭用量、反应时间和温度、初始pH值对固化效果的影响,通过XRD、SEM-EDS分析固化后的生成物。实验结果显示,在生物炭用量为25 mg时,单位固化量达到最大值13.20 mg/g;在反应温度T=293 K、初始pH=7条件下,反应平衡时间72 h时浸出液的磷平衡浓度C_e= 1.40 mg/L;温度提升有助于提高生物炭的固化效果,当T=308 K时,浸出液的磷平衡浓度C_e=0.167 mg/L;碱性条件有利于固化反应持续进行,在pH=11条件下,浸出液的磷平衡浓度C_e=0.153 mg/L。实验结果表明生物炭对磷石膏中的磷具有明显的固化效果。磷石膏中的二水硫酸钙溶解后,Ca²⁺与表面带负电的生物炭结合,在生物炭显微结构的凹陷处,化学吸附溶液中的磷酸根生成了絮状、团簇状的羟基磷灰石(HAP)沉淀,从而使浸出磷得到有效控制。