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Thermokarst lakes in the Western Siberian Lowland (WSL) are major environmental factors controlling organic carbon and trace metal storage in inland waters and greenhouse gas emissions to the atmosphere. In contrast to previously published research devoted to lake hydrochemistry, hydrobiology, sedimentary carbon, and processes controlling the lake total dissolved (

A land cover map of two arctic catchments, nearby the Abisko Scientific Research Station, was obtained from a classification of a Sentinel-2 satellite image and a ground survey performed in July 2022. The two contiguous catchments, Miellajokka and Stordalen, are covered by various ecotypes, from boreal forest to alpine tundra and peatland. The Random Forest algorithm correctly identified 83% of polygon pixels reserved for testing. The developed workflow relied solely on open source software and acquired ground observations. Space organization was directed by the altitude as shown by the intersection of the land cover with the topography. Comparison between this new land cover map and previous ones based on data acquired between 2008 and 2011 demonstrates some trends of vegetation cover evolution in response to climate change in the considered area. The potential applications in terms of permafrost modeling (hiperborea.omp.eu) are finally discussed.

International audience; The biomineralization of CO2, in the form of carbonate minerals, is considered as one of the efficient solutions of atmospheric CO2 removal, allowing stable and sustainable storage of this greenhouse gas. Cyanobacteria are among the most powerful microorganisms capable of precipitating carbonate minerals, both in the present and in the past. In the modern environments, high Si concentration during geoengineering biomineralization could occur due to dissolution of Mg-bearing primary silicates such as olivine. However, most of experimental studies aimed to understand the formation of these carbonates were performed in Si-poor solutions. Thus, experimental characterizations of the nature, rate, and stoichiometry of precipitated minerals in Si-rich solutions in the presence of bacteria are lacking. The present study attempted to reproduce, in controlled laboratory experiments, the processes of biomineralization in a carbonate- and Mg-bearing medium having high Si concentrations (2–4 mM, which is below the saturation with respect to amorphous silica). These experiments have been carried out in the presence of three contrasting cyanobacteria: Synechococcus sp., Chroococcidiopsis sp. and Aphanothece clathrata in order to characterize the rate of formation, stoichiometry and mineralogical nature of precipitates. The results demonstrated significant role of cyanobacteria in the precipitation of carbonate and silicate minerals by increasing the pH of the medium during photosynthesis. Magnesium precipitation rates measured between 50 and 150 h of reaction time ranged from 0.05 to 0.5 mmol h−1 gdry1 and decreased (Synechococcus sp. and Chroococcidiopsis sp.) or increased (A. clathrata) with an increase in the Si:Mg ratio in solution. The abiotic instantaneous rates of Mg and Si removal from alkaline solutions were similar to those in the presence of cyanobacteria at the same pH value suggesting that photosynthetically induced pH rise was the main factor of mineral formation. The transmission electron microscopy (TEM) and spectroscopic observations and associated analyses identified an amorphous magnesium silicate together with hydrous Mg carbonates (hydromagnesite). The formation of carbonate solid phase at high Mg: Si ratios indicated the potential for the removal of inorganic carbon at pH > 10. The difference in the degree of C removal between different species was primarily linked to different degree of pH rise during photosynthesis. Taken together, the results obtained in this study allowed an efficient reproduction of combined magnesium hydroxo-carbonates and hydrous silicates precipitation under cyanobacterial activity, suitable for geoengineering of biologically controlled CO2 sequestration in Si-Mg-carbonate-bearing solutions.

Despite the importance of river suspended matter (RSM) for carbon, nutrient, and trace metal transfer from the land to the ocean, the mineralogical control on major and trace element speciation in the RSM remains poorly constrained. To gain a better understanding of environmental and seasonal factors controlling the mineral and chemical composition of riverine suspended load, we studied, over several hydrological seasons, including winter baseflow, the RSM of a large boreal river in Western Siberia (Ob in its middle course) and its two small tributaries. The concentration of RSM increased from 2–18 mg/L in winter to 15–105 mg L−1 during the spring flood. Among the dominant mineral phases of the RSM in the Ob River, quartz (20–40%), albite (4–18%), smectite (2–14%), and chlorite (6–16%) increased their relative proportions with an increase in discharge in the order “winter ≤ summer < spring flood”; illite (5–15%) was not affected by seasons or discharge, whereas the abundance of calcite (0–30%) decreased with discharge, from winter to summer and spring. Seasonal variation of elemental composition of the Ob River’s RSM allowed distinguishing three main groups of elements. Sodium, K, Si, Al, trivalent, and tetravalent hydrolysates increased their concentrations in the RSM with an increase in discharge, reflecting enhanced contribution of lithogenic material during high flow, whereas the concentration of alkaline-earth metals (Ca, Sr, Ba), P, Mn, and As decreased with discharge, reflecting accumulation of these elements in the suspended matter under ice. At the same time, a number of nutrients and trace elements demonstrated progressive accumulation in the RSM during winter (Ca, P, Cu, Zn, Mo, As, Cd, Sb). Micronutrients (V, Co), Fe, and Cr exhibited a minimum during summer, which could reflect both the uptake of these elements by the biota during baseflow (micronutrients) and their enhanced export during winter and spring compared to summer (Fe). The RSM of small tributaries demonstrated quite a different pattern compared to the Ob River main stem. Maximal concentration of suspended matter was observed at low discharges during the winter. During this period, the RSM was dominated by amorphous Fe hydroxides. Overall, the obtained results confirm the overwhelming impact of peatlands on element export in suspended form in small rivers of Western Siberia, and strong seasonal variations of both mineralogy and chemistry of the RSM in the Ob River main stem. Elemental yields (watershed-normalized export), assessed for the first time for the middle course of the Ob River and tributaries, were shifted towards the more important role of particulate vs. dissolved export for a number of trace elements, compared to that of the small and medium-sized rivers of Western Siberia, draining the taiga forest and peatlands of the boreal zone. The contrasting pattern of RSM chemical composition across the year demonstrated the importance of seasonal approach for sampling river suspended matter and calls a need for addressing strongly understudied RSM sources during winter baseflow, under ice.

Riverine particulates dominate the transport of vital nutrients such as Si, Fe or P to the ocean margins, where they may increase primary production by acting as slow-release fertilizer. Furthermore, the supply of particulate surface area to the ocean is considered to be a major control of organic carbon burial. Taken together, these observations suggest a close link between the supply of riverine particulate material and the organic carbon cycle. To explore this link, we conducted microcosm experiments to measure the growth of the marine diatom Thalassiosira weissflogii in the presence and absence of different types and concentrations of riverine particulate material. Results demonstrate a strong positive effect of riverine particulate material on diatom growth with increased total diatom concentrations and slowed post-exponential death rates with increasing particulate concentration. Moreover, SEM and optical microscope investigations confirm that riverine particulates facilitate organic carbon burial through their role in the aggregation and sedimentation of phytoplankton. The supply of riverine particulate material has been shown to be markedly climate sensitive with their fluxes increasing dramatically with increasing global temperature and runoff. This pronounced climate sensitivity implies that riverine particulates contribute substantially in regulating atmospheric CO2 concentrations through their role in the organic carbon cycle.

—: Experiments on modeling the phase fractionation of trace elements (Mn, Co, Ni, Cu, Zn, Cd, Pb, Tl, Ga, Y, REE, V, As, Sb, and U) at interaction between acidic volcanic waters with seawater, accompanied by the sequential precipitation of Fe and Al hydroxides, show that the coprecipitation efficiency of various trace elements with Fe and Al hydroxides differs. The most dramatic differences were found for Ga and REE: Ga is predominantly accommodated by Fe hydroxide, whereas REE are bound mostly to Al hydroxide. It was established that, in addition to pH value, the degree of coprecipitation of trace elements also depends on the relative volume fraction of seawater, with its increase likely leading a shift in the adsorption equilibrium and, as a consequence, to a change in the coprecipitation efficiency of trace elements.

The inland aquatic ecosystems play a significant role in the global carbon cycle, owing to the metabolism of terrestrially derived organic matter as it moves through fluvial networks along the water continuum. During this transport, dissolved organic matter (DOM) is microbial processed and released into the atmosphere, but the degree and intensity of this processing vary greatly both spatially and temporally. The Western Siberian Lowlands is of particular interest for a quantitative assessment of DOM biodegradation potential because the global areal-scale effects of DOM biodegradation in abundant surface organic-rich waters might be the highest in this region. To this end, we collected water samples along a typical aquatic continuum of the Bakchar Bog (the north-eastern part of the Great Vasyugan Mire) and, following standardized protocol, conducted an experimental study aimed at characterizing the seasonal and spatial variability of dissolved organic carbon (DOC) biodegradability. The biodegradable DOC fraction (BDOC) over the exposure incubation period ranged from 2% to 25%. The natural aquatic continuum “mire–forest–stream–river” demonstrated the systematic evolution of biodegradable DOC among the sites and across the seasons. The highest biodegradation rates were measured during spring flood in May and decreased along the continuum. The maximum possible CO2 production from DOM yielded the maximum possible flux in the range of 0.1 and 0.2 g C-CO2 m−2 day−1 d, which is an order of magnitude lower than the actual net CO2 emissions from the inland waters of the WSL. This study suggests that although the biodegradation of the humic waters of the WSL can sizably modify the concentration and nature of the DOM along the aquatic continuum, it plays only a subordinary role in overall C emissions from the lakes and rivers of the region.

We studied two medium size pristine rivers (Taz and Ket) of boreal and subarctic zone, western Siberia, for a better understanding of the environmental factors controlling major and trace element transport in riverine systems. Our main objective was to test the impact of climate and land cover parameters (permafrost, vegetation, water coverage, soil organic carbon, and lithology) on carbon, major and trace element concentration in the main stem and tributaries of each river separately and when considering them together, across contrasting climate/permafrost zones. In the permafrost-bearing Taz River (main stem and 17 tributaries), sizable control of vegetation on element concentration was revealed. In particular, light coniferous and broadleaf mixed forest controlled DOC, and some nutrients (NO2, NO3, Mn, Fe, Mo, Cd, Ba), deciduous needle-leaf forest positively correlated with macronutrients (PO4, Ptot, Si, Mg, P, Ca) and Sr, and dark needle-leaf forest impacted Ntot, Al, and Rb. Organic C stock in the upper 30–100 cm soil positively correlated with Be, Mn, Co, Mo, Cd, Sb, and Bi. In the Ket River basin (large right tributary of the Ob River) and its 26 tributaries, we revealed a correlation between the phytomass stock at the watershed and alkaline-earth metals and U concentration in the river water. This control was weakly pronounced during high-water period (spring flood) and mostly occurred during summer low water period. Pairwise correlations between elements in both river systems demonstrated two group of solutes—(1) positively correlated with DIC (Si, alkalis (Li, Na), alkaline-earth metals (Mg, Ca, Sr, Ba), and U), this link originated from groundwater feeding of the river when the labile elements were leached from soluble minerals such as carbonates; and (2) elements positively correlated with DOC (trivalent, tetravalent, and other hydrolysates, Se and Cs). This group reflected mobilization from upper silicate mineral soil profile and plant litter, which was strongly facilitated by element colloidal status, notably for low-mobile geochemical tracers. The observed DOC vs DIC control on riverine transport of low-soluble and highly mobile elements, respectively, is also consistent with former observations in both river and lake waters of the WSL as well as in soil waters and permafrost ice. A principal component analysis demonstrated three main factors potentially controlling the major and TE concentrations. The first factor, responsible for 26% of overall variation, included aluminum and other low mobile trivalent and tetravalent hydrolysates, Be, Cr, Nb, and elements strongly complexed with DOM such as Cu and Se. This factor presumably reflected the presence of organo-mineral colloids, and it was positively affected by the proportion of forest and organic C in soils of the watershed. The second factor (14% variation) likely represented a combined effect of productive litter in larch forest growing on carbonate-rich rocks and groundwater feeding of the rivers and acted on labile Na, Mg, Si, Ca, P, and Fe(II), but also DOC, micronutrients (Zn, Rb, Ba), and phytomass at the watershed. Via applying a substituting space for time approach for south-north gradient of studied river basins, we predict that climate warming in northern rivers may double or triple the concentration of DIC, Ca, Sr, U, but also increase the concentration of DOC, POC, and nutrients.

Due to its insulating and draining role, assessing ground vegetation cover properties is important for high-resolution hydrological modeling of permafrost regions. In this study, morphological and effective hydraulic properties of Western Siberian Lowland ground vegetation samples (lichens, Sphagnum mosses, peat) are numerically studied based on tomography scans. Porosity is estimated through a void voxels counting algorithm, showing the existence of representative elementary volumes (REVs) of porosity for most samples. Then, two methods are used to estimate hydraulic conductivity depending on the sample's homogeneity. For homogeneous samples, direct numerical simulations of a single-phase flow are performed, leading to a definition of hydraulic conductivity related to a REV, which is larger than those obtained for porosity. For heterogeneous samples, no adequate REV may be defined. To bypass this issue, a pore network representation is created from computerized scans. Morphological and hydraulic properties are then estimated through this simplified representation. Both methods converged on similar results for porosity. Some discrepancies are observed for a specific surface area. Hydraulic conductivity fluctuates by 2 orders of magnitude, depending on the method used. Porosity values are in line with previous values found in the literature, showing that arctic cryptogamic cover can be considered an open and well-connected porous medium (over 99 % of overall porosity is open porosity). Meanwhile, digitally estimated hydraulic conductivity is higher compared to previously obtained results based on field and laboratory experiments. However, the uncertainty is less than in experimental studies available in the literature. Therefore, biological and sampling artifacts are predominant over numerical biases. This could be related to compressibility effects occurring during field or laboratory measurements. These numerical methods lay a solid foundation for interpreting the homogeneity of any type of sample and processing some quantitative properties' assessment, either with image processing or with a pore network model. The main observed limitation is the input data quality (e.g., the tomographic scans' resolution) and its pre-processing scheme. Thus, some supplementary studies are compulsory for assessing syn-sampling and syn-measurement perturbations in experimentally estimated, effective hydraulic properties of such a biological porous medium.

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.

The bivalve genus Galatea Bruguière, 1797 (Venerida: Donacidae) was thought to contain exclusively brackish-water clams, the ranges of which are confined to estuaries and lower tidal parts of large rivers in West Africa. This genus was therefore included to the global freshwater bivalve checklists (Bogan 2013; Graf 2013) as a largely estuarine group. Conversely, a review of published data alongside our field surveys indicate that at least three populations of Galatea spp. largely occur in freshwater environment, i.e. those from the Sanaga (Cameroon), Niger (Nigeria), and Volta (Ghana) rivers. The systematic placement of these populations is unclear, as are the taxonomic status and validity of numerous nominal taxa described in this genus from a variety of localities throughout the Atlantic Coast of Africa (Angola to Senegal). We tentatively assign the populations from Niger and Volta to Galatea paradoxa (Born, 1778), while the Sanaga’s population is considered here as Galatea schwabi (Clench, 1929). However, these taxa do not share clear morphological differences and may belong to a single widespread species. In this study, we present the first DNA sequence data for a Galatea member, i.e. G. schwabi. Our COI phylogeny supports its placement within the family Donacidae suggesting sister relationships between Galatea and Donax Linnaeus, 1758. Most Galatea populations play a vital role for local riparian communities in West Africa as an intensively exploited food source. Furthermore, the clams are heavily threaten by anthropogenic impacts such as dam construction, riverbed substrate mining, and river pollution. The fishing loads and habitat degradation altogether lead to the rapid decreasing of Galatea populations in several water bodies, e.g. the Volta River in Ghana. It is impossible to develop conservation and management plans for these clams due to the lack of reliable species-level taxonomic concept of the genus. It is clear that the Galatea taxonomy and ecology need a thorough revision in the future based on DNA sequences of newly collected samples from all West African rivers, in which these remarkable clams occur.

According to experimental modeling data, the quantitative characteristics of macro and trace elements phase fractionation in the process of ice formation from fresh surface waters were obtained. Significant variations in the values of the integral distribution coefficient were established, apparently due to processes not associated with the entering of elements into the ice crystal lattice. It was suggested that such processes may include ice adhesive uptake of suspended and colloidal particles, sorption of organic and inorganic components on the surface of growing ice, formation of chemogenic solid phases at the water–ice boundary, and flocculation and coagulation of colloids near the boundary between the liquid and solid phases.

Published data and research results from the authors on the concentrations of dissolved trace elements (P, Si, Li, Rb, Cs, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd, Tl, Pb, Al, Ga, Y, Ti, Zr, Hf, Th, U, rare earth elements, B, F, V, Cr, Ge, As, Mo, W, and Sb) in the rivers discharging into the catchment areas of the White and Kara seas have been synthesized. The mean concentrations of the vast majority of trace elements are found to be not much different from the values of the global runoff, and only some of them (P, Fe, Zn, Cd, Y, Zr, B, and W for the rivers of the White Sea catchment area and Cs, Fe, Zn, and Cd for the rivers of the Kara Sea catchment area) differ threefold in concentrations. The lack of significant differences in the mean concentrations could be a result of their spatial variability smoothed out over the extent of large catchment areas.

Small lakes of the boreal zone are highly sensitive indicators of both global environmental change and local anthropogenic pressure. This work presents the results of multidisciplinary study of three small, seasonally stratified lakes of NW Russia, conducted since 2002 to the present time. These lakes were subjected to various degree of impact by rural population and agricultural activity since the beginning of twentieth century but the population and anthropogenic pressure have decreased since 1990s. To monitor the recovering of these lakes from human impact and to relate the evolution of their hydrochemical parameters to short-term weather events and global climatic trend, we measured the lake water temperature and chemical composition (carbon, macro- and micronutrients, trace elements) in summer and winter over full depth of the water column. The pH and concentration of DIC, SO4 and H2S decreased over past decade. Concentrations of Si and nitrite increased over past 15 years, probably linked to progressive replacement of diatoms by cyanobacteria. We also recorded an increase in concentration of Cl and major cations in all lakes, likely linked to increasing connection to groundwater reservoirs. Some trace elements (Fe, Mn, Al, Zn, As, Pb) can serve as suitable indicators of on-going natural processes controlling lake response to external factors. Unlike widely reported global trend of DOC and Fe concentration increase in boreal surface waters of Europe and Northern America, such trend was not discernable in studied Fe-rich humic lakes. We conclude on the necessity of complex, multidisciplinary studies of small humic lakes in the boreal zone, because these “model” lakes can serve as important proxies of on-going environmental changes in highly abundant aquatic ecosystems of poorly characterized regions of NW Russia.

Olivine is an important mineral that controls the sequestration of atmospheric CO2 in the form of secondary carbonate minerals during chemical and biological weathering of mafic rocks on Earth. Despite significant efforts in characterization of olivine reactivity and coupled secondary mineral precipitation both in abiotic and biotic systems, little is known on olivine behavior in the presence of bacterial consortia, which are the dominant forms of microbial life impacting mineral reactivity in natural settings. To address this gap, we studied the interaction of olivine with a bacterial consortium composed of typical freshwater cyanobacterium Synechococcus sp. and heterotrophic aerobic Pseudomonas reactans, isolated from a CO2 storage site in Icelandic basalts. We quantified the impact of this consortium on the dissolution rate of olivine and we characterized the precipitation of secondary mineral phases while monitoring various biological (number of cells, bacterial biomass) and physicochemical (pH, Si, Mg, Ca, alkalinity, dissolved organic and inorganic carbon) parameters of the medium over a period of ∼21 days. Heterotrophic bacteria and their organic exometabolites enhanced the release of Mg and Si and produced leaching features (etch pits) at the olivine surface whereas cyanobacterial photosynthesis raised the pH and favored precipitation of hydrous Mg carbonates and silicates in the vicinity of the cells. During microbially-induced transformation of aquatic carbon, the latter was sequestered in the form of cyanobacterial biomass (about 66%) and their soluble organic exometabolites (11%), and stored as secondary Mg carbonates (23%). Overall, the impact of bacterial consortium is higher than that of individual species and may represent important and understudied biotically-controlled mechanism of CO2 sequestration in natural waters.

The fate of organic carbon (OC), nutrients and metals accumulated in thawing permafrost ice is at the forefront of environmental studies in the Arctic. In contrast to a fairly good understanding of the chemical nature of dissolved OC (DOC) and metals in surface Arctic waters, the speciation and colloidal status of solutes accommodated in the dispersed ground ice remain virtually unknown. Here we used a size fractionation procedure (centrifugal ultrafiltration) to quantify the proportion of colloidal (3 kDa to 0.45 μm) and conventionally dissolved low molecular weight (LMW

To better understand freezing - thawing cycles operating in peat soils of permafrost landscapes, we experimentally modelled bi-directional freezing and thawing of the three sections of 90-cm long peat core collected from a discontinuous permafrost zone in western Siberia. We measured translocation of microorganisms and changes in porewater chemistry (pH, UV absorbance, dissolved organic carbon (DOC), and major and trace element concentrations) after thawing and two-way freezing of peat cores. We demonstrate that bi-directional freezing and thawing of a peat core is capable of strongly modifying the vertical pattern of bacteria, DOC, nutrients, and trace element concentrations. Sizeable enrichment (a factor of 2 to 5) of DOC, macro- (P, K, Ca) and micro-nutrients (Ni, Mn, Co, Rb, B) and some low-mobile trace elements in several horizons of ice and peat porewater after freeze/thaw experiment may stem from physical disintegration of peat particles, leaching of peat constituents and opening of isolated (non-connected) pores during freezing front migration. However, due to the appearance of multiple maxima of element concentration after a freeze-thaw event, the use of peat ice chemical composition as environmental archive for paleo-reconstructions is unwarranted.

Bacterially-induced sequestration of atmospheric CO2 is at the forefront of geomicrobiological research due to high potential of this process in the mitigation of climate warming. Cyanobacteria have been known to form stromatolites since the Precambrian and could be used to enhance this process by sequestering carbon via the biomineralization of Mg and Ca carbonates. Currently, olivine (MgSiO4) is considered as one of the most efficient silicate minerals suitable for CO2 capture in the form of secondary Mg carbonates. However, the role of dissolved Si on the efficiency of biomineralization is not sufficiently well understood. The present study intended to reproduce in the laboratory the processes of biomineralization by Synechococcus sp. cyanobacteria extracted from modern stromatolites in a carbonate- and Mg-bearing medium containing various Si concentrations, in order to characterize the rates and stoichiometry of reactions as well as mineralogical nature of precipitates. The results demonstrated the dominant role of cyanobacterial metabolism in the precipitation of carbonate minerals by increasing the pH of the medium via photosynthesis and providing a template in the form of cell walls and their EPS for mineral nucleation. Transmission electron microscopy and other microscopic and spectroscopic observations and analyses identified magnesium carbonates and silicates, such as nesquehonite (MgCO3·3H2O) and/or hydromagnesite (Mg5(CO3)4(OH)2·4(H2O) together with amorphous analogue of sepiolite (Mg4Si6O15(OH)2·6H2O) as dominant precipitated minerals. Apparent inorganic C precipitation rates were not affected by the concentration of Mg and Si in the initial solution. However, the carbon sequestration potential was 20–40% higher in the presence of Si. Overall, the experimental approach developed in this study allows efficient reproduction of combined Mg hydroxy‑carbonate and hydrous silicate precipitation under cyanobacterial activity and helps to constrain optimal conditions of cyanobacteria-induced CO2 sequestration.

International audience; Phytoliths are microscopic structures made of amorphous opal (opal-A), an amorphous hydrated silica, dispersed within plant tissues and persisting after the decay of the plant. Silicon is known to alleviate metal toxicity in plants, but the role of phytoliths in metal sequestration and detoxification is unclear. Dry ashing, the most common protocol for phytolith extraction, was previously shown to lead to sequestration of metals by the phytoliths; however, the mechanisms of this process remained elusive. The purpose of this study was to evaluate whether the association between metals and phytoliths results from dry ashing or pre-exists in plant tissues. Thus, we compared phytoliths extracted by dry ashing at 700°C and plant leaves before and after dry ashing. A combination of ICP-MS, XRD, SEM-EDX and Zn-K-edge EXAFS spectroscopy was used to assess elemental concentrations, morphology and crystallography of silica, and chemical status of Zn. Results demonstrated a phase transition from amorphous opal (opal-A) to opal-CT and -cristobalite, and the sequestration of metal in phytoliths during dry ashing. For Zn, Mn and Pb, a linear relationship was found between the concentration in phytoliths and in leaves. In the phytoliths, Zn was sequestered in silica in tetrahedral configuration. We hypothesize that this association results form a solid-state reaction during ashing, involving a redistribution of Zn from the organic material to the silica, possibly promoted by the release of structural water from amorphous opal throughout the heating procedure. This study improves our understanding of the impact of high temperature treatments on plant biomass and phytoliths. It suggests that Zn toxicity alleviation in plants by silicon does not rely on its sequestration by phytoliths. In natural settings, wild fire events and biomass burning may lead to metal sequestration in low-soluble form, which should be considered in modeling of biogeochemical cycles and in paleoenvironmental studies.

Snow cover is known to be an efficient and unique natural archive of atmospheric input and an indicator of ecosystem status. In high latitude regions, thawing of snow provides a sizable contribution of dissolved trace metals to the hydrological network. Towards a better understanding of natural and anthropogenic control on heavy metals and metalloid input from the atmosphere to the inland waters of Siberian arctic and subarctic regions, we measured chemical composition of dissolved (

Colloidal (size 1 nm to 1 μm) transport of major and trace elements, notably micronutrients and low-solubility geochemical tracers, is a ubiquitous and well-established feature for all surface and soil waters in boreal and subarctic regions. However, little is known on the colloidal associations of organic carbon (OC) and major and trace elements in atmospheric precipitation such as snow. This is despite significant efforts devoted to distinguishing the soluble and particulate transport of trace metals and contaminants by atmospheric aerosols. To acquire a snap-shot of major and trace element size fractionation in the snow cover of western Siberia, we sampled snow cores integrated over the entire depth (0–50 cm until bottom) across a sizable (2800 km) south - north transect in the Ob River watershed (western Siberia). A number of trace metal pollutants (Cr, Ni, Zn, Cd) exhibited significant linkage, pronounced over the first 20 km, to sources of local pollution. Some elements (P, Mn, Zn, Ba) also demonstrated an increase in their colloidal fraction in the proximity of pollution centers, possibly reflecting input from industrial centers and gas flares. Following centrifuginal ultrafiltration, we analyzed total dissolved (< 0.22 μm), two colloidal (high molecular weight, HMW50 kDa ̶ 0.22 μm; medium molecular weight MMW3 kDa ̶ 50 kDa) and low molecular weight (LMW < 3 kDa) fractions in the melted snow for all major and trace elements. We discovered sizable (20 to 70%) proportion of some major (Ca, SO4) and many trace (Fe, Y, Zn, Sb, La, Ce, Yb, Pb) elements in the colloidal (3 kDa - 0.22 μm) form, without significant link to latitude, type of biome, or the concentration of possible colloidal carrier (DOC, Fe, Al, Ca, SO4). The origin of snow water colloids in snow can be hypothesized to stem from solute freezing on lake surfaces (Fe, OC), frost flowers of the Arсtic ice (Ca, SO4), clays dispersion (Al, Si) and sulphur dioxide oxidation particles (SO4, oxyanions). Via hydrochemical mass balance calculations, we demonstrate an overwhelming impact of snow melt on spring-time riverine export of Cd, Pb, Zn, As, Sb and Cs. These preliminary results call for further studies of atmospheric colloids including those originating from rainwater.

Extensive studies have been performed on wildfire impact on terrestrial and aquatic ecosystems in the taiga biome, however consequences of wildfires in the tundra biome remain poorly understood. In such a biome, permafrost peatlands occupy a sizable territory in the Northern Hemisphere and present an extensive and highly vulnerable storage of organic carbon. Here we used an experimental approach to model the impact of ash produced from burning of main tundra organic constituents (i.e., moss, lichen and peat) on surrounding aquatic ecosystems. We studied the chemical composition of aqueous leachates produced during short-term (1 week) interaction of ash with distilled water and organic-rich lake water at 5 gsolid L−1 and 20 °C. The addition of ash enriched the fluid phase in major cations (i.e., Na, Ca, Mg), macro- (i.e., P, K, Si) and micronutrients (i.e., Mn, Fe, Co, Ni, Zn, Mo). This enrichment occurred over

Trace elements in freshwater bivalve shells are widely used for reconstructing long-term changes in the riverine environments. However, Northern Eurasian regions, notably the European Russian North, susceptible to strong environmental impact via both local pollution and climate warming, are poorly studied. This work reports new data on trace elements accumulation by widespread species of freshwater mussels Unio spp. and Anodonta anatina in the Severnaya Dvina and the Onega River Basin, the two largest subarctic river basins in the Northeastern Europe. We revealed that iron and phosphorous accumulation in Unio spp. and Anodonta anatina shells have a strong relationship with a distance from the mouth of the studied river (the Severnaya Dvina). Based on multiparametric statistics comprising chemical composition of shells, water, and sediments, we demonstrated that the accumulation of elements in the shell depends on the environment of the biotope. Differences in the elemental composition of shells between different taxa are associated with ecological preferences of certain species to the substrate. The results set new constraints for the use of freshwater mussels’ shells for monitoring riverine environments and performing paleo-reconstructions.

Lake sediments accumulate various pollutants and act as efficient natural archives suitable for reconstruction the environmental conditions of the past. In contrast to fairly good knowledge of mineral sediments in lakes of European and North America boreal lakes, Siberian lakes of the boreal zone remain quite poorly studied. In this work, two cores of lake sediments of the Ob River valley were investigated. Elemental analyses were carried out on the sediments, losses on ignition were determined, and the rate of sedimentation was measured from the activity of Pb-210 and Cs-137. According to the content of organic matter, bottom sediments belong to different types: clastic (Lake Inkino, located in the Ob River floodplain) and organogenic (Lake Shchuchie on the second terrace). The rate of sedimentation in Lake Shchuchie is several times higher than that in Lake Inkino. The sediments of Lake Inkino are similar in composition (including the pattern of rare earth elements) to the suspended particulate matter of the Ob River as well as to average detrital matter of the upper continental crust. Sediments of Lake Shchuchie (sapropels) are enriched in a number of heavy metals. Based on the elemental composition, signs of diagenetic processes and authigenic mineral formation were determined, such as accumulation of carbonates and the formation of manganese oxides and hydroxides. There is an enhanced recent input of Cr, Co, Cu, Zn, Cd, Sb, Pb, and Bi in the upper layers of sediments as a result of atmospheric anthropogenic pollutant deposition.

SF and the Si isotope measurements at STAiG were supported by NERC grant NE/R002134/1 to PS; PS would also like to cite the support of a Carnegie Trust Research Incentive Grant, which helped the setup of various isotope techniques in the St Andrews Isotope Geochemistry (STAiG) laboratories. C.D. Coath is thanked for laboratory support and the European Research Council is acknowledged for funding (ICY-LAB, grant agreement 678371). The use of silicon (Si) isotopes has led to major advances in our understanding of Si cycling in modern and past environments. This inter‐laboratory comparison exercise provides the community with the first set of soil and plant reference materials with an analytically challenging matrix containing organic material that is known to induce isotopic bias, for use as secondary reference materials in Si isotope measurement. Seven laboratories analysed four soil reference materials (GBW‐07401, GBW‐07404, GBW‐07407, TILL‐1) and one plant reference material (ERM‐CD281). Participating laboratories employed a range of chemical preparation methods and analytical setups but all analyses were performed by MC‐ICP‐MS. Irrespective of the chemical preparation method or analytical conditions, the results show excellent agreement among laboratories within 2s for at least three replicates. Data were combined together to calculate δ29Si and δ30Si mean values (relative to NBS 28) and their expanded uncertainties (U, coverage factor k = 2). The δ30Si values are as follow: GBW‐07401: ‐0.27 ± 0.06 ‰, GBW‐07404: ‐0.76 ± 0.12 ‰, GBW‐07407: ‐1.82 ± 0.17 ‰, TILL‐1: ‐0.16 ± 0.06 ‰ and ERM‐CD281: ‐0.28 ± 0.11 ‰. Also, a compilation of published data provides an up‐to‐date mean δ30Si for BHVO‐2 of ‐0.28 ± 0.08 ‰. Postprint

Shallow thaw (thermokarst) lakes abundant in regions of permafrost-affected peatlands represent important sources of carbon dioxide and methane emission to the atmosphere, however the quantitative parameters of phytoplankton communities which control the C cycle in these lakes remain poorly known. This is especially true considering the roles of permafrost, hydrochemical composition of lakes, lake sizes and season as major governing factors on phytoplankton abundance and biodiversity. In this work, we quantified phytoplankton characteristics of 27 thermokarst lakes (sizes ranging from 115 m2 to 1.24 km2) sampled in spring, summer and autumn across a permafrost gradient (isolated, sporadic, discontinuous and continuous zone) in the Western Siberia Lowland (WSL). The biodiversity indices were highest during all seasons in lakes of the continuous permafrost zone and rather similar in lakes of isolated, sporadic and discontinuous permafrost zone. Considering all seasons and permafrost zones, the biomass and cell number of phytoplankton correlated with Dissolved Organic Carbon (DOC), phosphate, and some metal micro-nutrients (Ni, Zn). The strongest correlations were observed for Cyanophycea during summer, with pH, Ni, Cu, Zn, Sr, Ba (cell number) and Cu, Zn, Ba (biomass), and during autumn, with DOC, K, Cr, Cu, Zn, Ba, Cd, Pb (biomass). Using a substituting space for time approach for climate warming and permafrost thaw and suggesting a shift in permafrost boundaries northward, we foresee an increase in cell number and biomass in continuous permafrost zone in spring and summer, and a decrease in phytoplankton abundance in the discontinuous and sporadic permafrost zones. The biodiversity of phytoplankton in the continuous permafrost zone might decrease whereas in other zones, it may not exhibit any sizably change. However, in case of strong deepening of the active layer down to underlaying mineral horizons, and the release of some limiting nutrients (Si, P) due to enhanced connectivity of the lake with groundwater, the share of cyanobacteria and diatoms may increase.

In order to better understand the biogeochemical cycle of nitrogen in meromictic lakes, which can serve as a model for past aquatic environments, we measured dissolved concentrations of nitrate, nitrite, ammonium and organic nitrogen in deep (39 m maximal depth) subarctic Lake Svetloe (NW Russia). The lake is a rare type of freshwater meromictic water boy with high concentrations of methane, ferrous iron, manganese and low concentrations of sulfates and sulfides in the monimolimnion. In the oligotrophic mixolimnion, the concentration of mineral forms of nitrogen decreased in summer compared to winter, likely due to phytoplankton bloom. The decomposition of the bulk of organic matter occurs under microaerophilic/anaerobic conditions of the chemocline and accompanied by the accumulation of nitrogen in the form of N-NH4 in the monimonimlion. We revealed a strong relationship between methane and nitrogen cycles in the chemocline and monimolimnion horizons. The nitrate concentrations in Lake Svetloe varied in the range from 9 to 13 μM throughout the water column. This fact is rare for meromictic lakes, where nitrate concentrations up to 13 µM are found in the monimolimnion zone down to the bottom layers. We hypothesize, in accord with available data for other stratified lakes, that under conditions of high concentrations of manganese and ammonium at the boundary of redox conditions and below, anaerobic nitrification with the formation of nitrates occurs. Overall, most of organic matter in Lake Svetloe undergoes biodegradation essentially under microaerophilic/anaerobic conditions of the chemocline and the monimolimnion. Consequently, the manifestation of the biogeochemical nitrogen cycle is expressed in these horizons in the most vivid and complex relationship with other cycles of elements.

Transport of carbon, major and trace element by rivers in permafrost-affected regions is one of the key factor of circumpolar aquatic ecosystem response to climate warming and permafrost thaw. While seasonal and annual export fluxes (yields) of carbon (C) and inorganic solutes are fairly well known for all large Arctic rivers, spatial variations in elementary concentration along the river length and among its tributaries remain poorly understood. Moreover, the landscape factors controlling riverine element concentration in permafrost-affected regions are still poorly constrained. This is especially true for the largest river of Eastern Siberia, the Lena River, which drains through continuous permafrost zones with highly variable lithology and vegetation. Here we present the results of C, major and trace element measurements over a 2600-km transect of the Lena River main stem (upper and middle reaches) including its 30 tributaries, conducted at the peak of the spring flood. There were two main group of solutes in the main stem depending on their spatial pattern: i) elements that decreased their concentrations downstream, from SW to NE (Cl, SO4, DIC, Li, B, Na, Mg, K, Ca, As, Sr, Mo, Sb, Ba and U), which probably reflected a decrease in the proportion of carbonate rocks in the watershed and the degree of groundwater feeding, and ii) elements that increased their concentrations downstream (Al, Ti, Cr, Fe, Ga, Rb, Y, Zr, Nb, Cs, REEs, Hf and Th), which was tentatively linked to an increase in organic C stock in soils, larch forest coverage and enhanced mobilization of lithogenic elements from silicate soil minerals. Based on landscape parameters of Lena tributaries, we tested the impact of major environmental factors on major and trace element spatial pattern. Among all the variables, the proportion of sporadic permafrost on the watershed strongly controlled concentrations of soluble highly mobile elements (Cl, B, DIC, Li, Na, K, Mg, Ca, Sr, Mo, As and U). Another important factor of element concentration control in the Lena River tributaries was the coverage of watershed by light (B, Cl, Na, K, U) and deciduous (Fe, Ni, Zn, Ge, Rb, Zr, La, Th) needle-leaf forest (pine and larch). The latter, however, could also reflect the DOC-enhanced transport of low-soluble trace elements in the NW part of the basin. This part of the basin is dominated by silicate rocks and continuous permafrost, as compared to carbonate rock-dominated and groundwater-affected SW part of the Lena River basin. Overall, the impact of rock lithology and permafrost on major and trace solutes of the Lena River basin during the peak of spring flood was mostly detected at the scale of the main stem. Such an impact for tributaries was much less pronounced, because of the dominance of surface flow and lower hydrological connectivity with deep groundwater in the latter. Future changes in the river water chemistry linked to climate warming and permafrost thaw at the scale of the whole river basin are likely to be linked to changes in spatial pattern of dominant vegetation, rather than to the permafrost regime. We argue that comparable studies of large, permafrost-impacted rivers during most contrasting seasons, including winter baseflow, should allow efficient prediction of future changes in riverine ‘inorganic’ hydrochemistry induced by permafrost thaw.

The distribution of dissolved matter (major ions, nutrients, and trace elements) in the Yenisei River estuary and adjacent water area was studied according to the natural observations data from 20092016. These results were compared to the literature data of hydrochemical researches of this region. It was shown that transport of major ions (Na, K, Mg, Ca, SO4) and some trace elements (Li, Rb, Cs, Sr, B, F, Cr, Ge, As, Mo, U) is described by the stable in the long-term period equations of conservative mixing between riverine and seawater masses. Alkalinity also belongs to conservative components; however this parameter exhibits substantial spatiotemporal variability of the distribution caused by complex hydrological structure of the Yenisei Bay and adjoining part of the Kara Sea. Concentrations of Pmin, Si, and V in the desalinized waters of photic layer decreases seaward during vegetation period owing to uptake by phytoplankton. The losses of these elements reach 3057, 30, and 9% of their supply by river runoff, respectively. The content of dissolved Pmin and V in the intermediate and near-bottom layers of the Yenisei River estuary strongly increases with increase of salinity due to regeneration of precipitated organic matter, whereas silica remineralization is much less pronounced. Barium in the all estuary is intensively desorbed from river suspended matter in the quantity reaching 20100% of its dissolved forms input with river runoff depending on seasonal variations of chemical composition of the last. The transport of dissolved forms of heavy metals (Mn, Fe, Pb) and elements-hydrolyzates (Al, Ti, Y, La, Ce, Pr) in the mixing zone between the riverine and seawater masses is probably controlled by the coagulation and flocculation of organic and organomineral colloids, which is indicated by decrease in the concentrations of these elements at the beginning of salinization (for 2061%) with subsequent approximation to the seawater mass characteristics.

In contrast to fairly good knowledge of dissolved ( 0.45 µm) fluxes of carbon, nutrients and metals from the land to the ocean, colloidal (1 kDa−0.45 µm) forms of solutes are rarely quantified. This is especially true for Siberian rivers draining into the Arctic Ocean: because of organic-rich soils, colloidal fractions of elements are high and may sizably impact coastal biological processes. However, the main environmental parameters such as seasons, river size, climate, permafrost distribution and landscape parameters of the watershed controlling colloidal distribution of organic carbon (OC) and metals remain totally unknown. Here we used on-site centrifugation combined with ultrafiltration via 3, 30 and 100 kDa pore size membranes and 1 kDa dialysis to characterize colloidal size fractionation of OC and metals in 32 western Siberian rivers, ranging in size from 10 to 150,000 km2 watershed area, across a climate and permafrost gradient (from absent to continuous permafrost). The dominant forms of OC and metals was low molecular weight LMW