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.     

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.     

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.     

Absorption properties of urban/suburban aerosols in China

The broadband diffuse radiation method is improved to retrieve the aerosol refractive index imaginary part （AIP） and broadband （400-1000 nm mean） single scattering albedo （SSA）. In this method, four sets of SSA selection criteria are proposed for quality control. The method is used to retrieve AIP, SSA and absorptive optical thickness （AbOT） from routine hourly-exposed pyrheliometer and paranometer measurements over 11 sites （meteorological observatories） in China during 1998-2003. Apart from one suburban site （Ejin Qi）, the other urban sites are all located around big or medium cities. As shown in the retrieval results, annual mean SSA during 1998-2003 changes from 0.941 （Wuhan） to 0.849 （Lanzhou）, and AIP from 0.0054 to 0.0203. The 11-site average annual mean SSA and AIP are 0.898 and 0.0119, respectively. SSA during winter is smaller for most sites. There is an evidently positive correlation between SSA and aerosol optical thickness （AOT） for all sites. There is also a positive correlation between SSA and relative humidity for most sites, but a negative correlation for a few sites, such as Kashi and ǚrǚmqi in Northwest China.     

How effective is the new generation of GPM satellite precipitation in characterizing the rainfall variability over Malaysia?

We investigated the potential of the new generation of satellite precipitation product from the Global Precipitation Mission (GPM) to characterize the rainfall in Malaysia. Most satellite precipitation products have limited ability to precisely characterize the high dynamic rainfall variation that occurred at both time and scale in this humid tropical region due to the coarse grid size to meet the physical condition of the smaller land size, sub-continent and islands. Prior to the status quo, an improved satellite precipitation was required to accurately measure the rainfall and its distribution. Subsequently, the newly released of GPM precipitation product at half-hourly and 0.1° resolution served an opportunity to anticipate the aforementioned conflict. Nevertheless, related evidence was not found and therefore, this study made an initiative to fill the gap. A total of 843 rain gauges over east (Borneo) and west Malaysia (Peninsular) were used to evaluate the rainfall the GPM rainfall data. The assessment covered all critical rainy seasons which associated with Asian Monsoon including northeast (Nov. - Feb.), southwest (May - Aug.) and their subsequent inter-monsoon period (Mar. - Apr. & Sep. - Oct.). The ability of GPM to provide quantitative rainfall estimates and qualitative spatial rainfall patterns were analysed. Our results showed that the GPM had good capacity to depict the spatial rainfall patterns in less heterogeneous rainfall patterns (Spearman’s correlation, 0.591 to 0.891) compared to the clustered one (r = 0.368 to 0.721). Rainfall intensity and spatial heterogeneity that is largely driven by seasonal monsoon has significant influence on GPM ability to resolve local rainfall patterns. In quantitative rainfall estimation, large errors can be primarily associated with the rainfall intensity increment. 77% of the error variation can be explained through rainfall intensity particularly the high intensity (> 35 mm d^-1). A strong relationship between GPM rainfall and error was found from heavy (~35 mm d^-1) to violent rain (160 mm d^-1). The output of this study provides reference regarding the performance of GPM data for respective hydrology studies in this region.     

Climatic regime shift and decadal anomalous events in China

Climatic time series from historical documents and instrumental records from China showed temporal and regional patterns in the last two to three centuries, including two multidecadal oscillations at quasi-20-year and quasi-70-year timescales revealed by signal analysis from wavelet transform. Climatic anomalous events on the decadal timescale were identified based on the two oscillations when their positive (or negative) phases coincide with each other to amplify amplitude. The coldest event occurred in the decade of 1965–1975 in eastern China, while the periods of 1920–1930, 1940–1950, and 1988–2000 appeared to be warmer in most parts of China. For the precipitation series in northern China, the dry anomalous event was found in the late 1920s, while the wet anomalous event occurred in the 1950s. A severe drought in 1927–1929 in northern China coincided with the anomalous warm and dry decade, caused large-scale famine in nine provinces over northern China. Climatic anomalous events with a warm-dry or cold-wet association in the physical climate system would potentially cause severe negative impacts on natural ecosystem in the key vulnerable region over northern China. The spatial pattern of summer rainfall anomalies in the eastern China monsoon region showed an opposite variations in phase between the Yellow River Valley (North China) and the mid-low Yangtze River Valley as well as accompanied the shift of the northernmost monsoon boundary. Climatic regime shifts for different time points in the last 200 years were identified. In North China, transitions from dry to wet periods occurred around 1800, 1875, and 1940 while the transitions from wet to dry periods appeared around 1840, 1910, and the late 1970s. The reversal transition in these time points can also be found in the lower Yangtze River. Climatic regime shifts in China were linked to the interaction of mid- and low latitude atmospheric circulations (the westerly flow and the monsoon flow) when they cross the Tibetan Plateau in East Asia.     

Atmospheric chemistry of hydrogen fluoride

Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500 m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.