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.     

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.     

Structural improvement of age-hardened gypsum-treated bauxite red mud waste using readily decomposable phyto-organics

Several years (7) after incidental lithification by added gypsum, the effect of crushing and phyto-organics on some physical properties of red mud wastes (RMW) was examined under laboratory conditions. It was hypothesized that mechanically breaking up the hardened masses would increase their permeability. However, on the contrary, crushing these rock-hard masses into <2-mm particles did not increase permeability. A phyto-organic treatment on the other hand greatly improved permeability of the crushed entities such that infiltration rates increased from 0 to 10 cm/h. After 24 weeks of incubation, the structure of the newly formed phyto-organically treated gypsum-hardened RMW aggregates was also substantially improved over that of the controls, as a >3-fold increase in resistance to disintegration during wet sieving was exhibited by the phyto-organically treated samples. The increase in water infiltration by combining crushing with phyto-organic applications was ascribed to a decrease in particle dispersion, creating more stable clay clusters, which in turn stabilized channels and pores. Conversely, it was concluded that the singular crushing of gypsum-hardened bauxite waste in the waste dumps is potentially wasteful and ineffective.     

淮河流域水文随机方法的径流图化(英文)

Theoretical difficulties for mapping and for estimating river regime characteristics in a large-scale basin remain because of the nature of the variable under study: river flows are related to a specific area, i.e. the drainage basin, and are hierarchically organized in space through the river network with upstream-downstream dependencies. Another limitation is there are not enough gauge stations in developing countries. This presentation aims at de-veloping the hydro-stochastic approach for producing choropleth maps of average annual runoff and computing mean discharge along the main river network for a large-scale basin. The approach applied to mean annual runoff is based on geostatistical interpolation proce-dures coupled with water balance and data uncertainty analyses. It is proved by an applica-tion in the upstream at Bengbu in the Huaihe River Basin, a typical large-scale basin in China. Hydro-stochasitic approach in a first step interpolates to a regular grid net and in a second step the grid values are integrated along rivers. The interpolation scheme includes a con-straint to be able to account for the lateral water balance along the rivers. Grid runoff map with 10 km × 10 km resolution and the discharge map along the river with the 1 km basic length unit are the main results in this study. This kind of statistic approach can be widely used be-cause it avoids the complexity of hydrological models and does not depend on the meteoro-logical data.     

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.     

Reconstruction of palaeosalinity using carbon isotopes and benthic associations: a comparison

Carbon and oxygen isotopes were determined on 40 recrystallized shells of Late Jurassic bivalves from the Lusitanian Basin of Portugal. In contrast with the oxygen isotopes, which exhibited considerable diagenetic distortion, the carbon isotopes are thought to preserve a record of the salinity of the Jurassic marginal marine seas in which these bivalves lived. The reconstructed palaeosalinities range from 35%o (euhaline) to 5% (oligohaline). Comparing these values with the palaeosalinity reconstructed from a palaeoecological analysis of 17 stratigraphic levels within the basin, the independently derived values agree in most cases. Strongly differing values are explained as being due to biotic factors and to diagenetic distortion of the isotopic signal; they are less likely to be due to smallscale time-averaging or insufficient microstratigraphic sampling. On the whole, the carbon isotope analyses are thought to produce reasonable palaeosalinity values, although data from infaunal, originally aragonitic bivalves appear to be less reliable than those from epifaunal bivalves with a predominantly or exclusively calcitic shell. As diagenetic alteration of the carbon isotope signal is, however, unpredictable and biotic effects on the isotopic composition are insufficiently known, palaeosalinity reconstructions based on stable isotope data should be supported by palaeoecological data.     

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.     

Chemical composition of rock-forming minerals and crystallization physicochemical conditions of the Middle Eocene I-type Haji Abad pluton,SW Buin-Zahra,Iran

The Haji Abad intrusion is a well-exposed Middle Eocene I-type granodioritc pluton in the Urumieh–Dokhtar magmatic assemblage (UDMA). The major constituents of the investigated rocks are K-feldspar, quartz, plagioclase, pyroxene, and minor Fe–Ti oxide and hornblende. The plagioclase compositions fall in the labradorite, andesine, and oligoclase fields. The amphiboles range in composition from magnesio-hornblende to tremolite–hornblende of the calcic-amphibole group. Most pyroxenes principally plot in the field of diopside. The calculated average pressure of emplacement is 1.9 kbar for the granodioritic rocks, crystallizing at depths of about 6.7 km. The highest pressure estimated from clinopyroxene geobarometry (5 kbar) reflects initial pyroxene crystallization pressure, indicating initial crystallization depth (17.5 km) in the Haji Abad granodiorite. The estimated temperatures using two-feldspar thermometry give an average 724 °C. The calculated average temperature for clinopyroxene crystallization is 1090 °C. The pyroxene temperatures are higher than the estimated temperature by feldspar thermometry, indicating that the pyroxene and feldspar temperatures represent the first and late stages of magmatic crystallization of Haji Abad granodiorite, respectively. Most pyroxenes plot above the line of Fe³⁺?=?0, indicating they crystallized under relatively high oxygen fugacity or oxidized conditions. Furthermore, the results show that the Middle Eocene granitoids crystallized from magmas with H₂O content about 3.2 wt%. The relatively high water content is consistent with the generation environment of HAG rocks in an active continental margin and has allowed the magma to reach shallower crustal levels. The MMEs with ellipsoidal and spherical shapes show igneous microgranular textures and chilled margins, probably indicating the presence of magma mixing. Besides, core to rim compositional oscillations (An and FeO) for the plagioclase crystals serve as robust evidence to support magma mixing. The studied amphiboles and pyroxenes are grouped in the subalkaline fields that are consistent with crystallization from I-type calc-alkaine magma in the subduction environment related to active continental margin. Mineral chemistry data indicate that Haji Abad granodiorites were generated in an orogenic belt related to the volcanic arc setting consistent with the subduction of Neo-Tethyan oceanic crust beneath the central Iranian microcontinent.     

Fragmentation during Rock Falls: Two Italian Case Studies of Hard and Soft Rocks

In recent years, rock fall phenomena in Italy have received considerable attention for risk mitigation through in situ observations and experimental data. This paper reports the study conducted at Camaldoli Hill, in the urban area of Naples, and at Monte Pellegrino, Palermo, Italy. The rocks involved are volcanic Neapolitan yellow tuff (NYT) in the former area and dolomitic limestone in the latter. Both rocks, even though with different strength characteristics, have shown a significant tendency towards rock fragmentation during run out. This behavior was first investigated by comparing the volumes of removable blocks on the cliff faces (V ₀) and fallen blocks on the slopes (V _f). It was assumed that the ratio V _f/V ₀ decreases with the distance (x _f) from the detachment area by an empirical law, which depends on a coefficient α, correlated with the geotechnical properties of the materials involved in the rock fall. Finally, this law was validated by observation of well-documented natural rock falls (Palermo) and by in situ full-scale tests (Naples). From the engineering perspective, consideration of fragmentation processes in rock fall modeling provides a means for designing low-cost mitigation measures.