北京地区铬的土壤化学地理

本文以化学地理学的观点，讨论了铬在土壤中的来源，分布规律，迁移和残留累积，生态和环境效应，循环与平衡，预测和评价。     

Pressure dependence of color of natural uvarovite: the barochromic effect

The electronic absorption spectra of natural uvarovite containing 62 mole% of the Cr³⁺ end-member were studied at pressures between 10⁻⁴ and ca. 13 GPa using DAC techniques combined with microscope spectrometric device. With increasing pressure, a barochromic effect with change from green to red color of the garnet specimen was observed. This change could be interpreted on the basis of the spectra and the data points derived in an ICE color card. The evaluation of crystal field data from the spectra showed that 10Dq of chromium increases on pressure while the Racah parameter B, and thus the nature of the chemical bond of Cr–O does not change significantly.     

Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of Cr^III potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic Cr^III into hazardous Cr^VI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of Cr^VI from the easily soluble Cr^III and 2) the potential bioavailability of Cr^III and that of Cr^VI species produced in the oxidation of Cr^III in agricultural soil (fine sand, organic carbon 3.2%). The amount of Cr^VI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of Cr^III into Cr^VI by manganese oxide (Mn^IVO₂) and 2) the subsequent reduction of Cr^VI by organic matter back to Cr^III. The effect of pH on this net-oxidation of Cr^III and on the chemical availability of both Cr^III and Cr^VI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO₂, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO₂, the net-oxidation of Cr^III into Cr^VI (1 mM CrCl₃ in soil suspensions, 1:10 w/V) was negligible. As for the MnO₂-treated soils, at maximum only 4.7% of added Cr^III was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of Cr^VI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of Cr^VI back to Cr^III. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of Cr^III, which lowered the overall amount of Cr^III susceptible for oxidation. Moreover, the oxidation reactions by MnO₂ were inhibited by formation of Cr(OH)₃ coverage on its surface. The pH-dependent chemical bioavailability of added Cr^III differed from that of the Cr^VI formed. At elevated pHs the chemical availability of Cr^III decreased, whereas that of Cr^VI produced increased. However, the risk of Cr^VI formation through oxidation of the easily soluble inorganic Cr^III was considered to be low in agricultural soils high in organic matter and low in innate MnO₂.     

Sources and extractibility of chromium and nickel in soil profiles developed on Czech serpentinites

Soil profiles developed on serpentinites from several localities in the Czech Republic were investigated by a combination of geochemical and mineralogical methods (selective extractions, XRD, SEM/EDS) to determine the partitioning and mobility of chromium (Cr) and nickel (Ni). Whereas Cr is released from pyroxenes, amphiboles and Cr-spinels present in the bedrock, Ni is primarily mobilized from olivines and small Fe-Ni sulphide inclusions. The results of extraction methods indicated significant differences in the availability and mobility of Cr and Ni in soils. Chromium is almost not phytoavailable, as indicated by the DTPA extractions. The selective extractions showed that Cr is tightly bound to well-crystallised Fe-oxides and primary rock-derived phases. In contrast, Ni is substantially more mobile in soil, being mainly controlled by Mn-oxides and amorphous/less crystallised Fe-oxides. The DTPA extraction indicated that up to 10% of total Ni might be phytoavailable.     

大陆科学钻探CCSD-PP3钻孔超镁铁岩岩石学和矿物学特征及其意义

PP3超镁铁岩在钻孔中出露厚度达480米,包括纯橄岩、石榴橄榄岩和闪石化金云母橄榄岩等岩石类型。岩石主要组成矿物橄榄石、铬尖晶石、石榴子石、单斜辉石和斜方辉石等。橄榄石为镁橄榄石(Fo在88.7-93.1之间),SiO2含量在38.8wt.%-42.4wt.%;石榴子石为钙饱和的镁铝榴石(Py65.945Alm18.095Uv7.518Gr4.695And3.605Sp0.142),MgO含量在16.77wt.%-20.04wt.%,CaO含量在5.4到6.4wt.%之间,Cr2O3含量在0.3到3.3wt.%,FeO含量在2.48wt.%-11.78wt.%,TiO2含量小于0.04wt.%,代表早期矿物组合;两类斜方辉石的成分都为顽火辉石(OpxⅠ:En91.86Fs7.80Wo0.34,OpxⅡ:En91.83Fs7.91Wo0.21Ac0.06)。斜方辉石Mg#(Mg/(Mg Fe)×100)在91.7-92.5间,Cr2O3含量低于0.32wt.%,CaO含量在0.102-0.199wt.%间,Al2O3含量为0.32-1.06wt.%,均值在0.72wt.%;单斜辉石可分为早期透辉石(Wo45.98En47.89Fs2.73Ac3.39)和晚期顽透辉石(Wo27.61En68.78Fs2.27Ac1.34)两种。铬尖晶石的Cr#(Cr/(Cr Mg)×100)从51到89变化,TiO2和MnO2含量分别低于0.26wt%和0.46wt%。橄榄石、铬尖晶石和单斜辉石等矿物组合表现为3-4期次的特点。     

对铬铁磨球组织选择的理论探讨

通过对磨球运动、受力状况和磨损机制及其影响因素的分析，提出了对磨球使用性能的要求；应用材料科学基本理论，重点探讨了铝铁磨球组织选择的方法、原则和依据。结论是：根据磨球的工况条件，准确判断磨球的磨损机制是合理选择磨球组织的前提。     

Chemical Reduction of Hexavalent Chromium Present in Contaminated Soil using a Packed-bed Column Reactor

Soil samples extracted from a contaminated landfill with hexavalent chromium, Cr(VI), were treated in a packed-bed column reactor applying different reductant solutions under controlled flow conditions. In all cases, the kinetic study concerning removal of Cr(VI) from packed soil revealed the overall process (leaching and redox reaction) is described by pseudo-first order kinetics. The complexity of the process taking place in non-isotropic medium (packed soil) was evidenced by dependence of the overall pseudo-first order kinetic rate constant, k*, on treatment time, volumetric flow rate, and composition and concentration of the reductant solution. A phenomenological equation was proposed in order to represent k* in non-ideal conditions. The comparative study concerning the use of different reductants revealed application of ferrous sulphate, Fe(II), under flow conditions furnished the best results, since in this case the redox process reached a considerable extent and the reduced chromium, Cr(III), was immobilized in packed soil as an insoluble mixed compound.     

Proposed Adsorption–Diffusion Model for Characterizing Chromium(VI) Removal Using Dried Water Hyacinth Roots

Experiments have been carried out to characterize the adsorption of chromium(VI) in the aqueous phase onto dried roots of water hyacinth. Results revealed a very high degree of removal efficiency (∼100%). Theoretical analyzes are also made for describing the sorption and diffusion processes. The effective pore diffusivity of chromium(VI) in the water hyacinth roots is determined by a suitable global optimization technique. The depth of penetration, on the other hand, has been estimated for various initial concentrations of chromium(VI). Theoretically predicted concentration profiles are in excellent agreement with the experimental values.     

Removal of Cr(VI) by Zero‐valent,Iron‐encapsulated Alginate Beads

Zero‐valent, iron‐encapsulated alginate beads were synthesized and were applied for the removal of Cr(VI) from aqueous solutions. The effects of several important parameters including solution pH, contact time, initial concentration and reaction temperature on Cr(VI) removal levels were investigated in batch studies. An initial solution pH of 1.0 was seen to be most favorable for Cr(VI) removal. The removal process was quick and almost 80% of the removal was attained within 60 min. The kinetic data followed the second‐order equation well. The Cr(VI) removal was almost reaction temperature‐independent and decreased with an increase in Cr(VI) initial concentration. The removal of Cr(VI) by iron‐encapsulated alginate beads was found to be significantly higher than that of non‐encapsulated alginate beads.     

Changes of chromium concentration in alluvial sediments of the Obra river valley

In this research work, changes in concentration of the chosen chemical element in alluvial sediments have been used to estimate the relative age of floodplain deposits. The research concerning changes of chromium concentration in alluvial deposits was done in the Obra river valley near Międzyrzecz (Western Poland). Chromium was chosen because of its low ability to migrate in groundwater environment. Moreover, this chemical element was used in the process of dyeing textures in Międzyrzecz between the sixteenth and the nineteenth century. Confrontation of changes in chromium concentration and age of alluvial sediments (age estimated in years BP using radiocarbon method) have shown that the sediments with higher chromium contents are much older than the period of development of the weaving industry in Międzyrzecz. Therefore, it is not possible to use changes in chromium concentration to estimate relative age of floodplain sediments. Despite information in the literature about low migration ability of this chemical component (Macioszczyk and Dobrzyński in Hydrogeochemia: strefy aktywnej wymiany wód podziemnych. PWN, Warszawa, 2002; Ball and Izbicki in Appl Geochem 19:1123–1135, 2004) migration of chromium is so intensive that distinct changes in its concentration are observed even before the period of increased human activity.