Homoleptic Poly(nitrato) Complexes of Group 14 Stable at Ambient Conditions

Using a novel approach in homoleptic nitrate chemistry, Sn(NO3)62− (3c) as well as the previously unknown hexanitrato complexes Si(NO3)62− (1c), Ge(NO3)62− (2c) were synthesized from the element tetranitrates as salt-like compounds which were isolated and characterized using 1H, 14N, and 29Si NMR and IR spectroscopies, elemental and thermal analyses, and single-crystal XRD. All hexanitrates are moderately air-sensitive at 298 K and possess greater thermal stability toward NO2 elimination than their charge-neutral tetranitrato congeners as solids and in solution. The complexes possess distorted octahedral coordination skeletons and adopt geometries that are highly symmetric (3c) or deformed (1c, 2c) depending on the degree of steric congestion of the ligand sphere. As opposed to the κ2O,O′ coordination mode reported for Sn(NO3)4 previously,1 all nitrato ligands of 3c coordinate in κ1O mode. Six geometric isomers of E(NO3)62− were identified as minima on the PES using DFT calculations at the B3LYP/6-311+G(d,p) level of which two were observed experimentally

ETEKOS experimental ecological system

The problem of changes in the ecology resulting, for example, in increases in water temperature because of discharges from large thermal power plants is considered. An experiment creating a model of such an ecological system is described

Carbon emission and export from the Ket River, western Siberia

Despite recent progress in the understanding of the carbon (C) cycle of Siberian permafrost-affected rivers, spatial and seasonal dynamics of C export and emission from medium-sized rivers (50 000–300 000 km2 watershed area) remain poorly known. Here we studied one of the largest tributaries of the Ob River, the Ket River (watershed = 94 000 km2), which drains through pristine taiga forest of the boreal zone in the West Siberian Lowland (WSL). We combined continuous and discrete measurements of carbon dioxide (CO2) concentration using submersible CO2 sensor and floating chamber flux (FCO2), with methane (CH4), dissolved organic and inorganic C (DOC and DIC, respectively), particulate organic C and total bacterial concentrations over an 800 km transect of the Ket River main stem and its 26 tributaries during spring flood (May 2019) and 12 tributaries during summer baseflow (end of August–beginning of September 2019). The partial pressure of CO2 (pCO2) was lower and less variable in the main stem (2000 to 2500 µatm) compared to that in the tributaries (2000 to 5000 µatm). In the tributaries, the pCO2 was 40 % higher during baseflow compared to spring flood, whereas in the main stem, it did not vary significantly across the seasons. The methane concentration in the main stem and tributaries was a factor of 300 to 1900 (flood period) and 100 to 150 times lower than that of CO2 and ranged from 0.05 to 2.0 µmol L−1. The FCO2 ranged from 0.4 to 2.4 g C m−2 d−1 in the main channel and from 0.5 to 5.0 g C m−2 d−1 in the tributaries, being highest during August in the tributaries and weakly dependent on the season in the main channel. During summer baseflow, the DOC aromaticity, bacterial number, and needleleaf forest coverage of the watershed positively affected CO2 concentrations and fluxes. We hypothesize that relatively low spatial and seasonal variability in FCO2 of the Ket River is due to a flat homogeneous landscape (bogs and taiga forest) that results in long water residence times and stable input of allochthonous dissolved organic matter (DOM), which dominate the FCO2. The open water period (May to October) C emission from the fluvial network (main stem and tributaries) of the Ket River was estimated to 127 ± 11 Gg C yr−1, which is lower than the downstream dissolved and particulate C export during the same period. The estimated fluvial C emissions are highly conservative and contain uncertainties linked to ignoring hotspots and hot moments of emissions, notably in the floodplain zone. This stresses the need to improve the temporal resolution of FCO2 and water coverage across seasons and emphasizes the important role of WSL rivers in the release of CO2 into the atmosphere.</p

Designing a model of interaction of economic resources in the quantization conditions of economic area

© 2015, Mediterranean Center of Social and Educational Research. All rights reserved. The article aims to develop a methodology for investigating cyclic recurrence of economic phenomena in the quantization conditions of the modern economy. The article highlights the quantization levels and the adaptive possibilities of stabilizing the economic processes and phenomena. The authors have developed a target model of interaction of economic resources in the quantization conditions, allowing to identify the type and stages of interaction at the current time. The results of the research have a wide range of applications in the development of specific manifestations of economic regularities by researchers, practicians working in the field of economics

Permafrost coverage, watershed area and season control of dissolved carbon and major elements in western Siberian rivers

Analysis of organic and inorganic carbon (DOC and DIC, respectively), pH, Na, K, Ca, Mg, Cl, SO₄ and Si in ~ 100 large and small rivers (< 10 to &le; 150 000 km²) of western Siberia sampled in winter, spring, and summer over a more than 1500 km latitudinal gradient allowed establishing main environmental factors controlling the transport of river dissolved components in this environmentally important region, comprising continuous, discontinuous, sporadic and permafrost-free zones. There was a significant latitudinal trend consisting in a general decrease in DOC, DIC, SO₄, and major cation (Ca, Mg, Na, K) concentration northward, reflecting the interplay between groundwater feeding (detectable mostly in the permafrost-free zone, south of 60° N) and surface flux (in the permafrost-bearing zone). The northward decrease in concentration of inorganic components was strongly pronounced both in winter and spring, whereas for DOC, the trend of concentration decrease with latitude was absent in winter, and less pronounced in spring flood than in summer baseflow. The most significant decrease in K concentration from the southern (< 59° N) to the northern (61–67° N) watersheds occurs in spring, during intense plant litter leaching. The latitudinal trends persisted for all river watershed size, from < 100 to > 10 000 km². Environmental factors are ranked by their increasing effect on DOC, DIC, δ¹³C_DIC, and major elements in western Siberian rivers as follows: watershed area < season < latitude. Because the degree of the groundwater feeding is different between large and small rivers, we hypothesize that, in addition to groundwater feeding of the river, there was a significant role of surface and shallow subsurface flow linked to plant litter degradation and peat leaching. We suggest that plant-litter- and topsoil-derived DOC adsorbs on clay mineral horizons in the southern, permafrost-free and discontinuous/sporadic permafrost zone but lacks the interaction with minerals in the continuous permafrost zone. It can be anticipated that, under climate warming in western Siberia, the maximal change will occur in small (< 1000 km² watershed) rivers DOC, DIC and ionic composition and this change will be mostly pronounced in summer

Landscape, soil, lithology, climate and permafrost control on dissolved carbon, major and trace elements in the Ob River, Western Siberia

In order to foresee possible changes in the elementary composition of Arctic river waters, complex studies with extensive spatial coverage, including gradients in climate and landscape parameters, are needed. Here, we used the unique position of the Ob River, draining through the vast partially frozen peatlands of the western Siberia Lowland and encompassing a sizable gradient of climate, permafrost, vegetation, soils and Quaternary deposits, to assess a snap-shot (8–23 July 2016) concentration of all major and trace elements in the main stem (~3000 km transect from the Tom River confluence in the south to Salekhard in the north) and its 11 tributaries. During the studied period, corresponding to the end of the spring flood-summer baseflow, there was a systematic decrease, from the south to the north, of Dissolved Inorganic Carbon (DIC), Specific Conductivity, Ca and some labile trace elements (Mo, W and U). In contrast, Dissolved Organic Carbon (DOC), Fe, P, divalent metals (Mn, Ni, Cu, Co and Pb) and low mobile trace elements (Y, Nb, REEs, Ti, Zr, Hf and Th) sizably increased their concentration northward. The observed latitudinal pattern in element concentrations can be explained by progressive disconnection of groundwaters from the main river and its tributaries due to a northward increase in the permafrost coverage. A northward increase in bog versus forest coverage and an increase in DOC and Fe export enhanced the mobilization of insoluble, low mobile elements which were present in organo-ferric colloids (1 kDa—0.45 µm), as confirmed by an in-situ dialysis size fractionation procedure. The chemical composition of the sampled mainstream and tributaries demonstrated significant (p < 0.01) control of latitude of the sampling point; permafrost coverage; proportion of bogs, lakes and floodplain coverage and lacustrine and fluvio-glacial Quaternary deposits of the watershed. This impact was mostly pronounced on DOC, Fe, P, divalent metals (Mn, Co, Ni, Cu and Pb), Rb and low mobile lithogenic trace elements (Al, Ti, Cr, Y, Zr, Nb, REEs, Hf and Th). The pH and concentrations of soluble, highly mobile elements (DIC, SO4, Ca, Sr, Ba, Mo, Sb, W and U) positively correlated with the proportion of forest, loesses, eluvial, eolian, and fluvial Quaternary deposits on the watershed. Consistent with these correlations, a Principal Component Analysis demonstrated two main factors explaining the variability of major and trace element concentration in the Ob River main stem and tributaries. The DOC, Fe, divalent metals and trivalent and tetravalent trace elements were presumably controlled by a northward increase in permafrost, floodplain, bogs, lakes and lacustrine deposits on the watersheds. The DIC and labile alkaline-earth metals, oxyanions (Mo, Sb and W) and U were impacted by southward-dominating forest coverage, loesses and eluvial and fertile soils. Assuming that climate warming in the WSL will lead to a northward shift of the forest and permafrost boundaries, a “substituting space for time” approach predicts a future increase in the concentration of DIC and labile major and trace elements and a decrease of the transport of DOC and low soluble trace metals in the form of colloids in the main stem of the Ob River. Overall, seasonally-resolved transect studies of large riverine systems of western Siberia are needed to assess the hydrochemical response of this environmentally-important territory to on-going climate change

USING OF 3D-MICROSCOPY IN MICROSURGERY

Work is executed at RFBR financial support, the project 15-29-04868

Riverine particulate C and N generated at the permafrost thaw front: case study of western Siberian rivers across a 1700&thinsp;km latitudinal transect

In contrast to numerous studies on the dynamics of dissolved ( &lt; 0.45&thinsp;µm) elements in permafrost-affected high-latitude rivers, very little is known of the behavior of river suspended ( &gt; 0.45&thinsp;µm) matter (RSM) in these regions. In order to test the effect of climate, permafrost and physio-geographical landscape parameters (bogs, forest and lake coverage of the watershed) on RSM and particulate C, N and P concentrations in river water, we sampled 33 small and medium-sized rivers (10–100&thinsp;000&thinsp;km2 watershed) along a 1700&thinsp;km N–S transect including both permafrost-affected and permafrost-free zones of the Western Siberian Lowland (WSL). The concentrations of C and N in RSM decreased with the increase in river watershed size, illustrating (i) the importance of organic debris in small rivers which drain peatlands and (ii) the role of mineral matter from bank abrasion in larger rivers. The presence of lakes in the watershed increased C and N but decreased P concentrations in the RSM. The C : N ratio in the RSM reflected the source from the deep soil horizon rather than surface soil horizon, similar to that of other Arctic rivers. This suggests the export of peat and mineral particles through suprapermafrost flow occurring at the base of the active layer. There was a maximum of both particulate C and N concentrations and export fluxes at the beginning of permafrost appearance, in the sporadic and discontinuous zone (62–64°&thinsp;N). This presumably reflected the organic matter mobilization from newly thawed organic horizons in soils at the active latitudinal thawing front. The results suggest that a northward shift of permafrost boundaries and an increase in active layer thickness may increase particulate C and N export by WSL rivers to the Arctic Ocean by a factor of 2, while P export may remain unchanged. In contrast, within a long-term climate warming scenario, the disappearance of permafrost in the north, the drainage of lakes and transformation of bogs to forest may decrease C and N concentrations in RSM by 2 to 3 times.</p