共查询到20条相似文献，搜索用时 31 毫秒
1.
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 CrIII potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic CrIII into hazardous CrVI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of CrVI from the easily soluble CrIII and 2) the potential bioavailability of CrIII and that of CrVI species produced in the oxidation of CrIII in agricultural soil (fine sand, organic carbon 3.2%). The amount of CrVI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of CrIII into CrVI by manganese oxide (MnIVO2) and 2) the subsequent reduction of CrVI by organic matter back to CrIII. The effect of pH on this net-oxidation of CrIII and on the chemical availability of both CrIII and CrVI 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 CrIII into CrVI (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 CrIII was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of CrVI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of CrVI back to CrIII. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of CrIII, which lowered the overall amount of CrIII 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 CrIII differed from that of the CrVI formed. At elevated pHs the chemical availability of CrIII decreased, whereas that of CrVI produced increased. However, the risk of CrVI formation through oxidation of the easily soluble inorganic CrIII was considered to be low in agricultural soils high in organic matter and low in innate MnO2. 相似文献
2.
重点阐述环境矿物材料基本性能，包括矿物表面吸附、孔道过滤、结构调整、离子交换、化学活性、物理效应、纳米效应及与生物交互作用等，旨在发掘、凝炼并新提出物理方法和化学方法之后与有机界生物同效的无机界矿物天然自净化功能的基础理论与应用方法，以发展和完善无机矿物与有机生物所共同构筑的自然界中存在的天然自净化系统，并就目前笔者在黄铁矿、锰钾矿、金红石、蛭石、蒙脱石、苋铁铁钒等天然矿物方面已经完成和正在开展的一系列环境矿物材料研究工作进行了举例说明。 相似文献
3.
M. N. Taran F. Parisi D. Lenaz A. A. Vishnevskyy 《Physics and Chemistry of Minerals》2014,41(8):593-602
Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4 A 2g → 4 T 2g and 4 A 2g → 4 T 1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions 4 A 2g → 2 E g and 4 A 2g → 2 T 1g of Cr3+, intensified by exchange-coupled interaction between Cr3+ and Fe3+ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm?1. A vague broad band in the range from ca. 15,000 to 12,000 cm?1 in synthetic spinels is tentatively attributed to IVCr2+ + VICr3+ → IVCr3+ + VICr2+ intervalence charge-transfer transition. Iron, mainly as octahedral Fe3+, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O2? → Fe3+, Fe2+ transitions). As tetrahedral Fe2+, it appears as a strong infrared absorption band at around 4,850 cm?1 caused by electronic spin-allowed 5 E → 5 T 2 transitions of IVFe2+. From the composition shift of the U-band in natural and synthetic MgCr2O4 spinels, the coefficient of local structural relaxation around Cr3+ in spinel MgAl2O4–MgCr2O4 system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O6 polyhedra known so far. The octahedral modulus of Cr3+ in MgCr2O4, derived from pressure-induced shift of the U-band of Cr3+, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr3+ in natural and synthetic MgCr2O4 spinels indicates that Cr–O-bonding in octahedral sites of MgCr2O4 has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl2O4 spinel, B does not much depend on pressure. 相似文献
4.
矿物环境属性与无机界天然自净化功能 总被引：7，自引：11，他引：7
鲁安怀 《矿物岩石地球化学通报》2002,21(3):192-197
本将矿物学研究从岩石圈拓展到水圈、大气圈、生物圈与土壤圈之间交互作用的矿物环境属性范畴，研究表明，矿物可成为记录环境演变信息的载体；防止矿物的破坏与分解有可能减少甚至避免由此所造成的对人体健康的影响与生态环境的破坏；矿物与生物交互作用的研究与天然矿物治理污染物的是建立在充分利用自然规律的基础之上，体现了天然自净化作用的特色。天然矿物对污染物的净化功能主要体现在环境矿物材料基本性能方面。天然铁的硫化物，铁的氧化物，锰的氧化物、钛的氧化物。蛭石，有机蒙脱石和含高价阳离子蒙脱石，以及黄钾铁矾等均在处理无机与有机污染物方面展现出良好效果，矿物与其环境界面原子尺度相互作用过程研究，矿物内部结构缺陷影响矿物表面活性规律研究，矿物晶体结构中不同维次连通性孔道效应研究,矿物化学活性作发化污染物方法研究，以及矿物晶芽与生物细胞层次上交互作用净化污染物机理研究等，将是近期着力开发无机界矿物天然自净化功能的重点研究内容。 相似文献
5.
Si K- and L-edge ELNES spectroscopy and multiple-scattering (MS) calculations are used to examine mixed Si coordination compounds
varying in SiVI:SiIV ratio. As in previous studies, the edges are influenced mainly by silicon coordination (tetrahedral vs. octahedral), as supported
by the MS calculations. We demonstrate two methods semi-quantitatively to extract the value of SiVI/(SiVI+SiIV): (1) A linear relationship between the L2,3-L1 splitting and SiVI/(SiVI+SiIV) is observed, (2) a fitting method based on the coaddition of reference tetrahedral and octahedral Si spectra is applied
to both Si K- and L-edge ELNES spectra.
Received: February 10, 1997 / Revised, accepted: May 23, 1997 相似文献
6.
Robert M Weaver Michael F Hochella Jr.Eugene S Ilton 《Geochimica et cosmochimica acta》2002,66(23):4119-4132
The complex interaction between CrIIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10−4 to 10−2 M CrOH2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of CrIII and the surface-catalyzed microprecipitation of CrIII-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of CrIIIaq to highly toxic CrVIaq. CrIII-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither MnII nor CrVI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, CrIIIaq was effectively removed from solution to form CrIII-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and CrVIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites. 相似文献
7.
矿物法--环境污染治理的第四类方法 总被引：26，自引：0，他引：26
总结介绍了近10年开展环境矿物材料研究所取得的较为系统的研究成果。新提出环境矿物材料基本性能,包括矿物表面效应、孔道效应、结构效应、离子交换效应、结晶效应、溶解效应、水合效应、氧化还原效应、半导体效应、纳米效应及矿物生物交互效应等。展示环境矿物材料开发应用方面的崭新成就,包括利用天然铁的硫化物矿物强还原性,发明一步法还原Cr(Ⅵ)与沉淀Cr(Ⅲ)废水处理新工艺;利用天然锰的氧化物矿物强氧化性,发明处理高浓度与强污染的印染和酚类废水新方法;利用天然钛的氧化物矿物日光催化性,发明光催化降解卤代有机污染物新方法;利用天然蛭石高温脱水膨胀热效应,发明能大幅度提高型煤固硫率与除尘新方法;利用天然钙基蒙脱石低成本制备出同时防止水体与无机和有机污染物渗漏的自愈性强的填埋场衬层建造用新型防渗材料,发明生活垃圾尤其是危险废物填埋场衬层建造新工艺;发现凝灰岩与花岗岩中长石类矿物发育有良好的孔道结构,核素进入可发生固定化作用,成为有效阻滞核素迁移的天然屏障;利用天然纳米管状纤蛇纹石成功制备二氧化硅纳米管,接枝有机物可由亲水性变为疏水性;利用黄钾铁矾的胶体特征作为多金属矿山废石堆隔离防渗层,防止金属硫化物矿物氧化分解与矿山酸性废水污染等。着重指出今后环境矿物? 相似文献
8.
An innovative setup of a permeable reactive barrier (PRB) was installed in Willisau, Switzerland to remediate chromate contaminated groundwater. Instead of a conventional continuous barrier, this PRB consists of cylinders installed in rows: a single row for lower expected CrVI-concentrations and an offset double row for higher expected CrVI-concentrations. The cylinders are filled with reactive grey cast-Fe shavings mixed with gravel to prevent extensive precipitation of secondary phases in the pore space. The treatment of the contaminants takes place both within the cylinders and in the dissolved FeII plume generated downstream of the barrier. Monitoring of the contamination situation over a period of 3 a provided evidence of the mobilization, transport and behavior of the contaminants in the aquifer. Groundwater and reactive material were sampled upstream, within and downstream of the barrier by a Multi-Port Sampling System (MPSS) that revealed the geochemical processes as a function of time and space. Comprehensive chemical analyses included sensitive parameters such as CrVI, FeII/FeIII, redox potential, dissolved O2 and pH. Several campaigns using multiple optical tracers revealed a rather complex hydrological regime at different scales, thereby complicating the barrier performance. 相似文献
9.
We have investigated a well-ordered sample of natural Cr-bearing dickite from Nowa Ruda (Lower Silesia, Poland) using electron
paramagnetic resonance (EPR) at X- and Q-band frequencies (9.42 and 33.97 GHz, respectively) and optical diffuse reflectance
spectroscopy. The observation of the spin-forbidden transitions at 15500 and 14690 cm−1 allows us to unambiguously identify the major contribution of octahedrally coordinated Cr3+ ions in the optical spectrum. The X- and Q-band EPR spectra show two superposed Cr3+ signals. The corresponding fine-structure parameters were determined at room temperature and 145 K. These results suggest
the substitution of Cr3+ for Al3+ in equal proportions in the two unequivalent octahedral sites of the dickite structure. In kaolin group minerals, the distortion
around Cr3+ ions (λ≈ 0.2–0.4) in Al sites is significantly less rhombic than that observed around Fe3+ ions (λ≈ 0.6–0.8).
Received: 29 June 2001 / Accepted: 22 October 2001 相似文献
10.
Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (ZnIV) and octahedral (ZnVI) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn3O7·3H2O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized density functional theory (DFT) to examine the ZnIV-TCS and ZnVI-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron overlap populations obtained by DFT for isolated ZnIV-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is ZnVI-TCS. Comparison between geometry-optimized ZnMn3O7·3H2O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn3O7·H2O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO2, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 Å, while surface O bordering the vacancy move away from it by 0.16-0.21 Å, in agreement with recent X-ray absorption spectroscopic analyses. 相似文献
11.
In order to determine whether Li+ cations penetrate into the octahedral layers of montmorillonites upon mild heating (Hofmann-Klemen effect) 57Fe Mössbauer spectra of Na+ and Li+ exchanged montmorillonite were obtained before and after treatment at 220 ° C. The 57Fe nucleus was used as a remote probe to detect electronic perturbations which would occur if a Li cation was to move into the octahedral layer from the interlayer after heating. The ambient Mössbauer spectra showed that a high charge density interlayer cation such as Li+ is effective in reducing the phonon energy of VIFe2+. In addition the EFG at octahedral sites can be significantly modified by interlayer cations as evidenced by the larger quadrupole splitting value measured for the Li+-exchanged sample with respect to the Na+-sample. Interlayer collapse and migration of exchange cations into the montmorillonite lattice after heating to 220 ° C resulted in the oxidation of the VIFe2+ and a decrease in site distortion for IVFe3+. Similar spectral parameters for the Fe3+ resonances of both Na+ — and Li+-heated samples suggested the interlayer cations do not penetrate as far as the octahedral layers. In order to utilize the enhanced sensitivity of VIFe2+ Δ values to changes in EFG the Fe3+ in the heated montmorillonites was reduced to Fe2+ with hydrazine. Similar spectral parameters for both the Na+ — and Li+-exchanged montmorillonite were observed giving further evidence that Li cations do not migrate into vacant octahedral sites. 相似文献
12.
The interaction between minerals and heavy metals has been a hot object of study in environmental science,mineralogy and soil science,Through the selective adsorption experiment of Ca-montomorillonite,illite and kaolinite to Cu2 ,Pb^2 ,Zn^2 ,Cd^2 ,and Cr^3 ions at certain conditions,it could be concluded that Cr^3 is most effectively sorbed by all the three minerals.Also,it can be found that Pb^2 shows a strong affinity for illite and kaolinite while cu^2 for montmorillonite .Based on the adsorption experiment at varying pH of solution,it can be found that the amount of heavy etals sorbed by minerals increases with increasing pH of the solution. 相似文献
13.
本文在简要阐明了环境矿物材料对污染物的净化机理与净化功能的基础上,明确了环境矿物材料的应用领域,重点展望了在土壤重金属污染防治、地表水和地下水水质改善及燃煤固硫除尘等三类状态污染控制与环境保护领域中应用的前景。认为经济、简便、有效地用于污染治理与环境修复的无机界矿物学方法类似于有机界生物学方法,均是自然界地球系统中天然自净化作用的反映。 相似文献
14.
Roger G. Burns 《Geochimica et cosmochimica acta》1973,37(11):2395-2403
Interrelationships between chemical compositions and crystal structures of minerals pioneered by Goldschmidt have been overlooked by modern geochemists. While analytical techniques and data for trace elements have become more sophisticated, progress has been slow in relating abundance data of individual elements to their relative enrichments in specific sites in mineral structures. The concept of diadochy has degenerated into an analytical relationship between major and trace elements, instead of its original crystallographic basis of replacement of one atom by another at a specific site in a crystal structure. Future interpretations of trace element data must consider the partitioning of atoms between different coordination sites in multisite mineral structures.The well-known partitioning of nickel and chromium into the earliest minerals during magmatic crystallization is extended to magma evolution in the mantle. The strong preference of Ni2+ and Cr3+ for octahedral sites in minerals leads to their enrichment in certain Iherzolites which are refractory residua during partial fusion of the mantle. 相似文献
15.
Reduction of octahedral Fe in the crystalline structure of smectites influences, possibly controls, surface-sensitive physical and chemical properties. The purpose of this study was to investigate if reduction of structural Fe by Na-dithionite or bacteria affects the chemical environment of constituent cations in montmorillonite, employing solid state multinuclear (29Si and 27Al) magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Reduction of structural Fe resulted in a positive (down field) chemical shift of the main Si Q3 (Q3(0Al)) site which was strongly correlated with Fe(II) content and inferred that distortions in Si-OT (T=Si, Al) bond angles and Si-O bond lengths occur with increasing layer charge. The line width (W) of the 29Si Q3 signal also increased with increasing levels of reduction. No change occurred in the position of the peak maximum for the octahedral Al (27AlVI) signal; however, an increased W was observed for this peak with increasing Fe(II) content. These results are attributed to decreases in Si-O-T bond angles and Si-O bond distances, corresponding to a better fit between the tetrahedral and octahedral sheets brought about by the presence of Fe(II) in the clay structure. The increased 27AlVI signal width (W) may also be due to a lessening of the paramagnetic influence of Fe(III) nuclei and enhancement of 27AlVI signals with different quadrupole coupling constants (QCC). Multinuclear MAS NMR analyses of dithioniteand microbially-reduced montmorillonite indicate that reduction of structural Fe caused reversible changes in the smectite structure, at least as far as this method could discern. 相似文献
16.
The behaviour of tetrahedrally coordinated and octahedrally coordinated Cr3+ ions in diopside is discussed from the study on the join CaMg-Si2O6-CaCrCrSiO6. The molecule CaCrCrSiO6 decomposes into uvarovite+eskolaite and its maximum solubility in diopside is 6.7 wt percent at 940 ° C. Crystalline phases are diopside ss (ss is abbreviation of solid solution), uvarovite ss, wollastonite ss, spinel and eskolaite. The diopside ss is blue in colour. Its optical spectra were measured in the wavelenght range of 325–2600 nm, and assigned after tetrahedral configuration Td and octahedral configuration Oh. It is estimated that octahedral Cr3+ ions are in high spin state, while tetrahedral Cr3+ ions may be probably in low spin state. The t and B are 10,300–10,370 cm–1 and 429–432 cm–1. The CFSE for tetrahedral low spin Cr3+ ions is nearly the same as that for octahedral high spin Cr3+ ions. The ionic radii of tetrahedral low spin Cr3+ ions calculated are 0.47–0.53 Å, shrinked from the radius of octahedral high spin Cr3+ ion (0.615 Å) as much as 14–24 percent. Petrologic implications of the result are also discussed.The first half of the D. Sc. dissertation of K. Ikeda presented to Hokkaido University in June, 1976 相似文献
17.
Yen-Hong Shau Donald R. Peacor Eric J. Essene 《Contributions to Mineralogy and Petrology》1990,105(2):123-142
Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess AlVI relative to AlIV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high AlVI/AlIV and low FeVI/(Fe+Mg)VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low AlIV/SiIV and low FeVI/(Fe+Mg)VI, while chlorite has high AlIV/SiIV and high FeVI/(Fe+Mg)VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower AlIV/SiIV and FeVI/(Fe+Mg)VI. The ratios of FeVI/(Fe+Mg)VI and AlIV/SiIV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite. 相似文献
18.
Reginaldo Bertolo Christine Bourotte Leonardo Marcolan Sonia Oliveira Ricardo Hirata 《Journal of South American Earth Sciences》2011,31(1):69-80
Anomalous and natural concentrations of Cr6+, occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of São Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urânia, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr2O3. Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr6+ detected in groundwater. 相似文献
19.
D. A. Khanin I. V. Pekov A. V. Pakunova I. A. Ekimenkova V. O. Yapaskurt 《Moscow University Geology Bulletin》2016,71(5):330-336
Based on the results of more than 600 electron microprobe analyses of 25 minerals the distribution pattern of the Cr6+ impurity in vanadates, phosphates, and arsenates collected in oxidation zones of six ore deposits of the Urals was studied. Among them are Pb minerals of the brackebuschite, apatite, adelite, and tsumcorite groups and alunite supergroup, as well as carminite, cornwallite, and bayidonite. Vanadates and arsenates with brackebuschite-type structures show a high affinity to Cr6+. The maximum content of the Cr6+ impurity is characteristic of minerals with specified Fe3+ trivalent cations (ferribushmakinite, arsenbrackebuschite, and gartrellite) or Al3+ (plumbogummite and bushmakinite). The prevailing scheme of isomorphous substitution, according to which chromium enters into the compositions of these minerals, is heterovalent: Cr6+ + M 2+ → Т 5+ + M 3+ (where Т = V, As, P; M 3+ = Fe, Al; M 2+ = Сu, Zn), whereas the role of isovalent substitutions Cr6+ → S6+ and Cr6+ → Mo6+ in oxosalts that formed in mineral occurrences of the Urals is insignificant. 相似文献
20.
V. S. Urusov N. A. Gromalova S. V. Vyatkin V. S. Rusakov V. V. Maltsev N. N. Eremin 《Moscow University Geology Bulletin》2011,66(2):102-107
Data on the structural and valence distribution of Cr and Fe in chrysoberyl and in alexandrite, its gem variety, are given.
It is shown that the Cr3+ line in the natural Ural and Tanzania samples is the strongest in the M1 site and for the synthetic stones, in the M2 site.
During the annealing of the alexandrite crystals, Cr3+ passes from the smaller M1 site into the larger M2 site. The M?ssbauer spectroscopy quantitatively determined the distribution
of different valence Fe ions. The various proportions of both Fe2+ and Fe3+ ions isomorphically entering the octahedral sites in the BeAl2O4 crystal structure were established. 相似文献