Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.     

An application of a new method in permafrost environment assessment of Muli mining area in Qinghai-Tibet Plateau,China

The permafrost environment in the Muli mining area, an opencast mining site in the Qinghai-Tibet Plateau, China, is now undergoing significant degradation because of the ongoing mining activities. The permafrost environment in this mining site had already been evaluated by previous study, in which analytic hierarchy process was applied. Although this method can roughly characterize the permafrost environment of this mining site, it has limitations by being easily affected by man-made factors. In view of this limitation, this study attempts to employ a new method, the catastrophe progression method, to estimate the current stage of the permafrost environment in this mining area. The results show that, by catastrophe progression method, currently the calculated indexes of the permafrost freezing–thawing disintegration, permafrost thermal stability, permafrost ecological fragility, and the permafrost environment are 0.43 (general situation), 0.77 (general situation), 0.71 (bad situation) and 0.83 (general situation), respectively. These values imply that the permafrost environment has been damaged by anthropologic activities to a certain degree and potentially may be further degenerated. However, at this degree, a new equilibrium stage of permafrost environment could be achieved if the current state of environmental degradation is stabilized and treatments are constructed against further damages.     

REE Geochemistry of the Lead—Zinc Ores from the Jinding Lead—Zinc Deposit,Lanping,Yunnan

Nineteen volcanic and magmatic rock samples were collectecd from the Jinding leadzinc deposit and its surrounding areas in Yunnan.The ICP and AES analyses,feferred to the previous results,show that the metal minerals and altered rocks in the Jinding lead-zinc deposit display a decreasing trend of ∑REE from the early to late stages of mineralization,and similarities in REE distribution patterns,indicating that the ore fluids are characterized by high LREE enrichment,markedly negative δCe anomaly and slight δEu anomaly.These REE distribution paterns exhibit striking similarities to those of the Pliocene trachyte in the study area,both of which are similar in ∑REE,LREE/HREE ratio,δEu and δCe.The ore fluids besides the basin fluids in the deposit are also closely related to those associated with Pliocene trachyte magmas.     

Assessing the vulnerability of social–environmental system from the perspective of hazard,sensitivity, and resilience: a case study of Beijing,China

Despite a recent increase in the number of vulnerability analyses there has been relatively little discussion of vulnerability assessment of social–environment system, especially when they face multiple hazards. In this study, we developed an applicable and convenient method to assess vulnerability of social–environment system at a regional scale. Vulnerability is quantified by measuring three critical elements (i.e. hazards, sensitivity, and resilience) through some key variables. The results showed that vulnerability is high in Miaofeng Mountain in Mengtougou District, the hills of Pinggu County and the riparian zones of the lower courses of the Beiyun and Yongding Rivers; but low in the city of Beijing and the southwestern part of the Fangshan District. Areas of very high, high, medium, and low-vulnerability account for 6.19, 25.48, 33.06, and 35.27% of the total area, respectively. The degree of vulnerability decreases in a northwest direction in mountainous areas and declines from watercourses to riparian zones along a lateral direction in the plain. Some adaptive strategies are also proposed.     

Late Proterozoic older granitoids from the North Eastern desert of Egypt: petrogenesis and geodynamic implications

Major, trace, and REE data for three localities of calc?Calkaline older granitoid rocks exposed in the north Eastern Desert of Egypt are presented. These rocks were selected to cover wide compositional spectrum of the Egyptian older granitoid varieties. They are petrographically represented by granodiorite, tonalite, quartz?Cdiorite, and quartz?Cmonzodiorite. The rocks are comparable with the peraluminous, unfractionated calc?Calkaline suites and fall within the volcanic arc and I-type granite fields. So, they can be regarded as belonging to the volcanic arc collision stage (665?C614?Ma). The granitoids are geochemically similar to other rocks recorded from continental margin arc-systems being exhibit light-REE enriched patterns with variable but chiefly positive Eu anomaly. The latter has reverse relationship with the ??REE, which was attributed to the fractionation of hornblende during partial melting. These patterns are comparable with models involving partial melting of amphibolitic source. This source must represent basalts, gabbros, or volcanics of an island arc system that were transformed to the level of the island arc crust during continental growth where the P?CT conditions are suitable for partial melting. Thus, it is plausible that the studied rocks were derived by partial melting of LREE-enriched, garnet-free, and amphibole-bearing (i.e., hydrated) mafic source. Wadi Milaha granitoids are consistent with the derivation by a high degree of partial melting (30?C40%) of amphibolite protolith in the deep crust. However, the two other localities (Wadi Umm Anab and West Gharib) are matching with 20?C30% partial melting. Within each locality, variation in rock types from granodiorite to tonalite is said to be dominated by variable degree of restite separation during magma ascent. The high water and volatile contents in Wadi Milaha granitoids allowed higher degree of partial melting (30?C40%). Moreover, the lower volatile contents in the other two localities (Wadi Umm Anab and West Gharib) gave lower degrees of partial melting (20?C30%). These processes may resemble important geodynamic features of the Arabo-Nubian Shield evolution in the north Eastern Desert of Egypt.     

Isotope evidence for quantifying river evaporation and recharge processes in the lower reaches of the Yellow River

Evaporation and recharge are important hydrological processes in the water cycle. However, accurately quantifying these two processes of river remains to be difficult due to their spatial heterogeneity and the limitations of traditional methods. In this study, a more reliable method of stable isotopes of δ ¹⁸O and δ ²H based on the Rayleigh distillation equation and mass conservation was used to estimate the evaporation and recharge of the rivers in the lower reaches of the Yellow River, North China Plain. Comprehensive sampling campaigns including 30 surface water samples from 10 rivers, 33 groundwater samples from domestic and observation wells, and two Yellow River water samples were conducted. The results showed that the evaporation proportion of the rivers based on δ ¹⁸O and δ ²H both averaged 14.4%. The evaporation proportions in each river did not completely follow a linear increasing trend along the flow path. This phenomenon could be mainly explained by the different proportions of recharge from groundwater and Yellow River water. With closer to the Yellow river, evaporation of the rivers decreased while the recharge by the Yellow River increased. Regression equations based on δ ¹⁸O, δ ²H, and their average revealed that the evaporation proportion respectively increased by 1.02, 0.79, and 0.90% with the increase in the distance to the Yellow River per 10 km. On the contrary, the recharge proportion decreased by 7.68, 5.51, and 6.59%, respectively. In addition, using δ ¹⁸O rather than δ ²H was more reliable in studying the spatial influence of the Yellow River on evaporation and recharge. Sensitivity analysis showed that the evaporation model was most sensitive to isotopic composition, rather than to air temperature or relative humidity. The results of this study provide insights into the determination of river hydrological processes and the management of water resources.     

XMCD at Fe L<Subscript>2,3</Subscript> edges,Fe and S K edges on Fe<Subscript>7</Subscript>S<Subscript>8</Subscript>

Pyrrhotite (Fe₇S₈) is a natural iron sulphide that can participate in rock magnetisation. Its electronic structure is not yet surely described. X-ray magnetic circular dichroism (XMCD) at Fe L_2,3 edges on Fe₇S₈, coupled with multiplet calculations, shows that iron is present only as Fe²⁺ in this magnetic iron sulphide. It reveals a strong magnetic orbital moment. XMCD at Fe and S K edges shows the quite strong polarization of both Fe and S in Fe₇S₈.     

Provenance,weathering, and paleoenvironment of the Upper Cretaceous Duwi black shales,Aswan Governorate,Egypt

The mineralogy and geochemistry of the Upper Cretaceous Duwi black shales of Nile Valley district, Aswan Governorate, Egypt, have been investigated to identify the source rock characteristics, paleoweathering, and paleoenvironment of the source area. The Duwi Formation consists mainly of phosphorite and black shales and is subdivided into three members. The lower and upper members composed mainly of phosphorite beds intercalated with thin lenses of gray shales, while the middle member is mainly composed of gray shale, cracked, and filled with gypsum. Mineralogically, the Duwi black shales consist mainly of smectite and kaolinite. The non-clay minerals are dominated by quartz, calcite, phosphate, dolomite, feldspar, with little gypsum, anhydrite, iron oxides, and pyrite. Based on the CIA, PIA, and CIW values (average?=?84, 94, 95, respectively), it can be concluded that the litho-components of the studied shales were subjected to intense chemical weathering and reflect warm/humid climatic conditions in the depositional basin. The provenance discrimination diagram indicates that the nature of the source rocks probably was mainly intermediate and mafic igneous sources with subordinate recycled sedimentary rocks (Nubia Formation). Geochemical characteristics indicate that the Duwi black shales in Nile Valley district were deposited under anoxic reducing marine environments.     

Bristen granite: a highly differentiated,fluorite-bearing A-type granite from the Aar massif,Central Alps,Switzerland

Bristen granite is a body of fine-grained leucogranite occurring in the Gotthard rail base tunnel in the Central Alps. During construction of the tunnel, Bristen granite (Brgr) has been drilled along a 600 m long section. The aplite-granite belongs to the suite of Variscan granitoid intrusions of the Aar massif and contains a variety of accessory minerals typical of highly differentiated granites. Rock forming fluorite, partly enriched in yttrium (Y) and rare earth elements (REE), is intergrown with the late Y- and REE-bearing carbonate mineral synchysite. The granite contains a variety of Ti- and Y-REE-niobates, thorite, and zircon. Compared with the calc-alkaline central Aar granite (cAgr), Bristen granite is strongly depleted in Ti, P, Mg, Sr, and Ba and shows a remarkable enrichment in incompatible elements such as Rb, Th, U, Nb, Y, HREE and F. Bristen granite is the most evolved granitoid rock of the Aar massif. The composition of Brgr is typical of post-collisional reduced (ferroan) A-type granites. The Brgr melt formed in the lower crust and crystallized from a highly differentiated melt at the cotectic point in the quartz-feldspar system close to 100 MPa and 700 °C. The Brgr intruded as a small isolated stock pre-Variscan gneisses with sharply discordant contacts. The primary igneous host of Nb, Ta, Y, U, Th and REE is biotite in addition to minor amounts of allanite, and zircon. The presence of Y-REE-fluorite, synchysite, parisite and Y- and Ti-niobates and other REE-minerals can be related to reaction of igneous biotite and primary fluorite with hydrothermal fluids. The reaction is associated with alpine metamorphism, because Y-bearing fluorite and synchysite have been reported from Alpine fissures. The transformation of primary biotite to chlorite and muscovite released the heavy metal oxides under lower greenschist facies conditions that formed the Alpine diagnostic mineral stilpnomelane at about 300 °C.     

Formation Environment of Main Brown Coal Seam in Xi-2 Minefield of Shengli Coalfield Based on Coal Ash Phase Analysis

The formation environment of the main coal seam in Shengli coal mine is analyzed, and the effect of coal ash parameters on the coal-forming environment is mainly discussed according to gray component parameters combined with other coal quality test analysis data. Results show that the hydrodynamic conditions of the main coal during coal accumulation have a general pattern of strong northeast and weak southwest, and lakeside swamp is generally in the retrograde process from south to north. The No.5 coal seam is a water entry cycle, and the No.5_lower coal is a water withdrawal cycle. The No.6 thick coal seam is formed in the peat swamp environment where the water is shallow and the groundwater activity is weak. The input of terrestrial debris material was most abundant in the formation period of No.5_lower coal, followed by No.5 coal, and that in No.6 coal is the least. Vertically, the peat swamp environment changed from weak reduction to weak oxidation to strong reducing environment. The ash yield was low to high to low from bottom to top. The organic sulfur is the main type of sulfur in the main coal seam. The weaker the hydrodynamic condition, the higher the organic sulfur content in the reduction environment, while lower organic sulfur content in the oxidation environment. The peat swamp water of No.5_lower coal is medium alkaline, and the peat swamp water of No.5 and No. 6 coals is weakly alkaline or acidic.