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.     

Analysis of solar radiation on the surface estimated from GWNU solar radiation model with temporal resolution of satellite cloud fraction

Preliminary analysis with a solar radiation model is generally performed for photovoltaic power generation projects. Therefore, model accuracy is extremely important. The temporal and spatial resolutions used in previous studies of the Korean Peninsula were 1 km × 1 km and 1-h, respectively. However, calculating surface solar radiation at 1-h intervals does not ensure the accuracy of the geographical effects, and this parameter changes owing to atmospheric elements (clouds, aerosol, ozone, etc.). Thus, a change in temporal resolution is required. In this study, one-year (2013) analysis was conducted using Chollian geostationary meteorological satellite data from observations recorded at 15-min intervals. Observation data from the intensive solar site at Gangneung-Wonju National University (GWNU) showed that the coefficient of determination (R²), which was estimated for each month and season, increased, whereas the standard error (SE) decreased when estimated in 15-min intervals over those obtained in 1-h intervals in 2013. When compared with observational data from 22 solar sites of the Korean Meteorological Administration (KMA), R² was 0.9 or higher on average, and over- or under-simulated sites did not exceed 3 sites. The model and 22 solar sites showed similar values of annual accumulated solar irradiation, and their annual mean was similar at 4,998 MJ m^?2 (3.87 kWh m^?2). These results show a difference of approximately ± 70 MJ m^?2 (± 0.05 kWh m^?2) from the distribution of the Korean Peninsula estimated in 1-h intervals and a higher correlation at higher temporal resolution.     

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.     

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.     

Formation of the adakite-like granitoid complex and porphyry copper-gold deposit in Shaxi from southern Tancheng-Lujiang fault belt： A clue to the West Pacific plate subduction

On the basis of the geological and geochemical studies, including chemical analysis of bulk rocks, rare-earth and trace element studies, fluid inclusion, and S and O isotopic analyses, the authors described the geo-logical background of the deposit in detail and presented significant proofs for the conditions of formation of the Shaxi porphyry copper-gold deposit. Compared with other large and supper-large porphyry copper deposits in China and the adjacent Cu-Au mineralized areas, the ore-forming processes and conditions were analyzed; and the possibil-ity of forming large porphyry copper deposits in the Shaxi area was discussed. The present study indicated that the ore-forming fluid and material were mainly of magmatic origin, while meteoric water played a certain role in the ore-forming processes. Interactions between subducting and overriding plates provided a major driving force for the formation of igneous rocks and the deposition of metal elements in East China since Jurassic. Based on the geo-chemical data of the Shaxi intrusive, it is found that the copper (gold) mineralization is closely related to the genesis of adakite-like intrusive in the Shaxi area. This adakite-like intrusive was formed in the subduction environment as a result of the subduction of the West Pacific plate toward the East China continent, where there is a great potential-ity to form a large porphyry copper deposit.     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Glauconites from the Late Palaeocene — Early Eocene Naredi Formation,western Kutch and their genetic implications

Glauconitic minerals are considered as one of the valuable input parameters in sequence stratigraphic analysis of a basin. In the present study glauconitic minerals are reported from subtidal green shale facies in the lower part of the Late Paleocene-Early Eocene Naredi Formation of western Kutch. On the basis of the foraminiferal assemblage the glauconite bearing beds are interpreted to have formed in a mid shelf depositional settings of an unstable marine conditions. XRD studies confirm the glauconite mineralogy of the green pellets and provide an estimation of glauconite maturity. Textural attributes of the glauconites confirm their derivation by different degrees of alteration of precursor feldspar grains. Because of the authigenic origin and autochthonous nature, these glauconites hold promise for understanding sequence stratigraphy of the Palaeogene succession of the western Kutch.