Relative stability of zincblende and wurtzite structure in CdX(X = S, Se, Te) series - A NMTO study

Using NMTO-downfolding technique we have revisited the issue of relative stability between zincblende (ZB) and wurtzite (WZ) symmetries in case of CdS, CdSe and CdTe semiconductors. Our computed ionicity factors using accurate NMTO-downfolding successfully brings out the right trend within the CdX series - CdS being most ionic stabilizes in WZ symmetry while CdSe and CdTe being more covalent stabilizes in ZB symmetry. Our NMTO constructed Wannier functions corresponding to only valence bands provide a nice demonstration of this fact. The tendency towards ZB stability is governed by the covalency which prefers isotropic nature of the tetrahedral bonds.Comment: 13 pages, 6 figures, 4 table

Siberian Arctic black carbon sources constrained by model and observation

Black carbon (BC) in haze and deposited on snow and ice can have strong effects on the radiative balance of the Arctic. There is a geographic bias in Arctic BC studies toward the Atlantic sector, with lack of observational constraints for the extensive Russian Siberian Arctic, spanning nearly half of the circum-Arctic. Here, 2 y of observations at Tiksi (East Siberian Arctic) establish a strong seasonality in both BC concentrations (8 ng⋅m−3 to 302 ng⋅m−3) and dual-isotope–constrained sources (19 to 73% contribution from biomass burning). Comparisons between observations and a dispersion model, coupled to an anthropogenic emissions inventory and a fire emissions inventory, give mixed results. In the European Arctic, this model has proven to simulate BC concentrations and source contributions well. However, the model is less successful in reproducing BC concentrations and sources for the Russian Arctic. Using a Bayesian approach, we show that, in contrast to earlier studies, contributions from gas flaring (6%), power plants (9%), and open fires (12%) are relatively small, with the major sources instead being domestic (35%) and transport (38%). The observation-based evaluation of reported emissions identifies errors in spatial allocation of BC sources in the inventory and highlights the importance of improving emission distribution and source attribution, to develop reliable mitigation strategies for efficient reduction of BC impact on the Russian Arctic, one of the fastest-warming regions on Earth

Source apportionment of circum-Arctic atmospheric black carbon from isotopes and modeling

Black carbon (BC) contributes to Arctic climate warming, yet source attributions are inaccurate due to lacking observational constraints and uncertainties in emission inventories. Year-round, isotope-constrained observations reveal strong seasonal variations in BC sources with a consistent and synchronous pattern at all Arctic sites. These sources were dominated by emissions from fossil fuel combustion in the winter and by biomass burning in the summer. The annual mean source of BC to the circum-Arctic was 39 ± 10% from biomass burning. Comparison of transport-model predictions with the observations showed good agreement for BC concentrations, with larger discrepancies for (fossil/biomass burning) sources. The accuracy of simulated BC concentration, but not of origin, points to misallocations of emissions in the emission inventories. The consistency in seasonal source contributions of BC throughout the Arctic provides strong justification for targeted emission reductions to limit the impact of BC on climate warming in the Arctic and beyond

Distributions of bacterial and archaeal membrane lipids in surface sediments reflect differences in input and loss of terrestrial organic carbon along a cross-shelf Arctic transect

Enhanced climate warming affecting the Arctic region could have a dramatic impact on the terrigenous organic carbon (terrOC) stored in the Eurasian permafrost and could increase the amount of OC remobilized to the Arctic shelves. An improved understanding of the fate of this remobilized soil OC is essential for better understanding of the consequences for the Arctic and global carbon cycle. In this study, glycerol dialkyl glycerol tetraethers (GDGTs) and bacteriohopanepolyols (BHPs) in surface sediments along a 500 km cross shelf transect from the mouth of the Kolyma River to the middle of the vast East Siberian Sea were analysed to assess their potential and that of the associated branched and isoprenoid tetraether (BIT) and R′soil indices for tracing terrOC in Arctic systems. Both BHP and GDGT contributions indicated the greatest contribution of terrOC close to the river mouth, while the associated indices showed declining trends in an offshore direction, supporting an increasing marine OC input and/or a decrease in terrOC. However, while the BHPs indicated a dominance of terrOC at the start of the transect, the GDGTs suggested a much larger, almost 50%, marine OC input at this point. In addition, the BIT index displayed an exponential decline, controlled mainly by a substantial contribution of marine GDGTs, while R′soil revealed a linear trend governed primarily by the removal of soil marker BHPs. These field results suggest that both biomarker approaches could be used to trace terrigenous derived OC in the Arctic environment. However, using a single proxy approach is not recommended and may lead to an under or over estimation of the relative importance of terrOC. Using a multi-proxy approach is valuable for fully understanding the fate of terrigenous derived OC along Arctic land-ocean transects

Multiscale molecular dynamics/hydrodynamics implementation of two dimensional “Mercedes Benz” water model

A multiscale Molecular Dynamics/Hydrodynamics implementation of the 2D Mercedes Benz (MB or BN2D) [1] water model is developed and investigated. The concept and the governing equations of multiscale coupling together with the results of the two-way coupling implementation are reported. The sensitivity of the multiscale model for obtaining macroscopic and microscopic parameters of the system, such as macroscopic density and velocity fluctuations, radial distribution and velocity autocorrelation functions of MB particles, is evaluated. Critical issues for extending the current model to large systems are discussed

Signatures of Molecular Unification and Progressive Oxidation Unfold in Dissolved Organic Matter of the Ob-Irtysh River System along Its Path to the Arctic Ocean

The Ob-Irtysh River system is the seventh-longest one in the world. Unlike the other Great Siberian rivers, it is only slightly impacted by the continuous permafrost in its low flow. Instead, it drains the Great Vasyugan mire, which is the world largest swamp, and receives huge load of the Irtysh waters which drain the populated lowlands of the East Siberian Plain. The central challenge of this paper is to understand the processes responsible for molecular transformations of natural organic matter (NOM) in the Ob-Irtysh river system along the South-North transect. For solving this task, the NOM was isolated from the water samples collected along the 3,000?km transect using solid-phase extraction. The NOM samples were further analyzed using high resolution mass spectrometry and optical spectroscopy. The obtained results have shown a distinct trend both in molecular composition and diversity of the NOM along the South-North transect: the largest diversity was observed in the Southern “swamp-wetland” stations. The samples were dominated with humic and lignin-like components, and enriched with aminosugars. After the Irtysh confluence, the molecular nature of NOM has changed drastically: it became much more oxidized and enriched with heterocyclic N-containing compounds. These molecular features are very different from the aliphatics-rich permafrost NOM. They witnesses much more conservative nature of the NOM discharged into the Arctic by the Ob-Irtysh river system. In general, drastic reduction in molecular diversity was observed in the northern stations located in the lower Ob flow

The origin of methane in the East Siberian Arctic Shelf unraveled with triple isotope analysis

The Arctic Ocean, especially the East Siberian Arctic Shelf (ESAS), has been proposed as a significant source of methane that might play an increasingly important role in the future. However, the underlying processes of formation, removal and transport associated with such emissions are to date strongly debated. CH4 concentration and triple isotope composition were analyzed on gas extracted from sediment and water sampled at numerous locations on the shallow ESAS from 2007 to 2013. We find high concentrations (up to 500 µM) of CH4 in the pore water of the partially thawed subsea permafrost of this region. For all sediment cores, both hydrogen and carbon isotope data reveal the predominant occurrence of CH4 that is not of thermogenic origin as it has long been thought, but resultant from microbial CH4 formation. At some locations, meltwater from buried meteoric ice and/or old organic matter preserved in the subsea permafrost were used as substrates. Radiocarbon data demonstrate that the CH4 present in the ESAS sediment is of Pleistocene age or older, but a small contribution of highly 14C-enriched CH4, from unknown origin, prohibits precise age determination for one sediment core and in the water column. Our sediment data suggest that at locations where bubble plumes have been observed, CH4 can escape anaerobic oxidation in the surface sediment

Sonar Estimation of Methane Bubble Flux from Thawing Subsea Permafrost: A Case Study from the Laptev Sea Shelf

Seeps found offshore in the East Siberian Arctic Shelf may mark zones of degrading subsea permafrost and related destabilization of gas hydrates. Sonar surveys provide an effective tool for mapping seabed methane fluxes and monitoring subsea Arctic permafrost seepage. The paper presents an overview of existing approaches to sonar estimation of methane bubble flux from the sea floor to the water column and a new method for quantifying CH4 ebullition. In the suggested method, the flux of methane bubbles is estimated from its response to insonification using the backscattering cross section. The method has demonstrated its efficiency in the case study of single- and multi-beam acoustic surveys of a large seep field on the Laptev Sea shelf

Moire minibands in graphene heterostructures with almost commensurate sqrt3 x sqrt3 hexagonal crystals

We present a phenomenological theory of the low energy moir\'e minibands of Dirac electrons in graphene placed on an almost commensurate hexagonal underlay with a unit cell approximately three times larger than that of graphene. A slight incommensurability results in a periodically modulated intervalley scattering for electrons in graphene. In contrast to the perfectly commensurate Kekul\'e distortion of graphene, such superlattice perturbation leaves the zero energy Dirac cones intact, but is able to open a band gap at the edge of the first moir\'e subband, asymmetrically in the conduction and valence bands