Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.     

Visual extinction towards the Omega Nebula (M17) and the ionization of nitrogen in the nebula

We estimate the absolute intensity of the Hα emission line in M17 based on spectroscopic observations with the 70 cm telescope of the Fesenkov Astrophysical Institute and the 1.25 m telescope of the Sternberg Astronomical Institute’s Crimean Laboratory. The visual extinction, A _v , is derived for about 250 regions in the nebula via a comparison of the optical (Hα) and radio (21 cm continuum) emissions. The A _v values for the eastern, optically bright, part of the nebula are 2–6^m. For the western part, which is covered by a dark cloud, the extinction is A _v = 7?14.5^m. We derived I(Hα)/I([NII] λ6584) ratios and estimated the degree of ionization of nitrogen in the nebula; we find that most nitrogen is in the [NIII] state.     

Fracture mechanics analysis of multiple cracks in anisotropic media

This paper presents a single‐domain boundary element method (BEM) for linear elastic fracture mechanics analysis in the two‐dimensional anisotropic material. In this formulation, the displacement integral equation is collocated on the un‐cracked boundary only, and the traction integral equation is collocated on one side of the crack surface only. A special crack‐tip element was introduced to capture exactly the crack‐tip behavior. A computer program with the FORTRAN language has been developed to effectively calculate the stress intensity factors of an anisotropic material. This BEM program has been verified having a good accuracy with the previous researches. Furthermore, by analyzing the different anisotropic degree cracks in a finite plate, we found that the stress intensity factors of crack tips had apparent influence by the geometry forms of cracks and media with different anisotropic degrees. Copyright © 2010 John Wiley & Sons, Ltd.     

Impacts of groundwater flow on the evolution of a thermokarst lake in the permafrost–dominated region on the Qinghai–Tibet plateau

As a result of global warming induced permafrost degradation in recent decades, thermokarst lakes in the Qinghai–Tibet plateau (QTP) have been regulating local hydrological and ecological processes. Simulations with coupled moisture–heat numerical models in the Beiluhe basin (located in the hinterland of permafrost regions on the QTP) have provided insights into the interaction between groundwater flow and the freeze–thaw process. A total of 30 modified SUTRA scenarios were established to examine the effects of hydrodynamic forces, permeability, and climate on thermokarst lakes. The results indicate that the hydrodynamic condition variables regulate the permafrost degradation around the lakes. In case groundwater recharges to the lake, a low–temperature groundwater flow stimulates the expansion of the surrounding thawing regions through thermal convection. The thawing rate of the permafrost underlying the lake intensifies when groundwater is discharged from the lake. Under different permeability conditions, spatiotemporal variations in the active layer thickness significantly influence the occurrence of an open talik at the lake bottom. A warmer and wetter climate will inevitably lead to a sharp decrease in the upper limit of the surrounding permafrost, with a continual decrease in the duration of open talik events. Overall, our results underscore that comprehensive consideration of the relevant hydrologic processes is critical for improving the understanding of environmental and ecological changes in cold environments.     

Chemical weathering and CO2 consumption in the glaciated Karuxung River catchment,Tibetan Plateau

Climate factors play critical roles in controlling chemical weathering, while chemically weathered surface material can regulate climate change. To estimate global chemical weathering fluxes and CO₂ balance, it is important to identify the characteristics and driving factors of chemical weathering and CO₂ consumption on the Tibetan Plateau, especially in glaciated catchments. The analysis of the hydro-geochemical data indicated that silicate weathering in this area was inhibited by low temperatures, while carbonate weathering was promoted by the abundant clastic rocks with fresh surfaces produced by glacial action. Carbonate weathering dominated the riverine solute generation (with a contribution of 58%, 51%, and 43% at the QiangYong Glacier (QYG), the WengGuo Hydrological Station (WGHS), and the lake estuary (LE), respectively). The oxidation of pyrite contributed to 35%, 42%, and 30% of the riverine solutes, while silicate weathering contributed to 5%, 6%, and 26% of the riverine solutes at the QYG, WGHS, and LE, respectively. The alluvial deposit of easily weathering fine silicate minerals, the higher air temperature, plant density, and soil thickness at the downstream LE in comparison to upstream and midstream may lead to longer contact time between pore water and mineral materials, thus enhancing the silicate weathering. Because of the involvement of sulfuric acid produced by the oxidation of pyrite, carbonate weathering in the upstream and midstream did not consume atmospheric CO₂, resulting in the high rate of carbonate weathering (73.9 and 75.6 t km⁻² yr⁻¹, respectively, in maximum) and potential net release of CO₂ (with an upper constraint of 35.6 and 35.2 t km⁻² yr⁻¹, respectively) at the QYG and WGHS. The above results indicate the potential of the glaciated area of the Tibetan Plateau with pyrite deposits being a substantial natural carbon source, which deserves further investigation.     

A tree‐ring width based drought reconstruction for southeastern China: links to Pacific Ocean climate variability

We present a drought reconstruction for southeastern China based on a tree‐ring width chronology of Cryptomeria fortunei developed from two sampling sites in central Fujian. A reconstruction of July–February drought variability, spanning AD 1855–2011, was developed by calibrating total tree‐ring width data with the self‐calibrating Palmer drought severity index (scPDSI). The reconstruction was verified against an independent data set, and accounts for 36% of the actual scPDSI variance during the period 1955–2011. Relatively dry intervals were reconstructed between AD 1859–1880, 1899–1911, 1927–1933, 1946–1959, 1964–1970 and 1987–1997. Relatively wet conditions prevailed during 1855–1858, 1881–1898, 1912–1926, 1934–1945, 1960–1963, 1971–1986 and 1998–2011. Comparisons between our scPDSI reconstruction and a moisture‐sensitive tree‐ring width record from Vietnam revealed consistencies between the two data sets, suggesting similar drought regimes. Spectral peaks of 2.2–6.4 years may be indicative of El Niño‐Southern Oscillation (ENSO) activity, as also suggested by the significant correlations with sea surface temperatures (SSTs) in the eastern equatorial and southeastern Pacific Ocean and an extreme event analysis. The analysis of links between our scPDSI reconstruction and the large‐scale regional climatic variation shows that there is a relationship between regional drought variation and East Asian summer monsoon (EASM) intensity.     

The influence of coupled physical swelling and chemical reactions on deformable geomaterials

Coupled thermo‐hydro‐mechanical‐chemical modelling has attracted attention in past decades due to many contemporary geotechnical engineering applications (e.g., waste disposal, carbon capture and storage). However, molecular‐scale interactions within geomaterials (e.g., swelling and dissolution/precipitation) have a significant influence on the mechanical behaviour, yet are rarely incorporated into existing Thermal‐Hydro‐Mechanical‐Chemical (THMC) frameworks. This paper presents a new coupled hydro‐mechanical‐chemical constitutive model to bridge molecular‐scale interactions with macro‐physical deformation by combining the swelling and dissolution/precipitation through an extension of the new mixture‐coupling theory. Entropy analysis of the geomaterial system provides dissipation energy, and Helmholtz free energy gives the relationship between solids and fluids. Numerical simulation is used to compare with the selected recognized models, which demonstrates that the swelling and dissolution/precipitation processes may have a significant influence on the mechanical deformation of the geomaterials.