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Sphagnum moss, lichen and peat are widely present in arctic regions, covering millions of km² in permafrost-dominated regions. This multi-component low vegetation strata plays a key role in surfaces fluxes in these areas, as they are the most widespread interface between the atmosphere and the geosphere. Therefore, characterizing their transfer properties such as hydraulic and thermal conductivities is crucial for climate change impacts forecasting in arctic regions. In this work, 12 samples were collected in a discontinuous permafrost arctic area (Khanymey Research Station, Russian Federation) and dried to ensure their conservation. Collected samples have been digitally reconstructed by X-ray scanning. After having assessed morphological and hydraulic properties using numerical analysis of the obtained 3D digital tomographies (Cazaurang et al, submitted), we aim here at developing and using both experimental and numerical methodologies to characterize thermal properties of these samples of Sphagnum, lichen and peat. This new study consist in comparisons of numerically and experimentally estimated thermal properties for contributing to the existing knowledge on Sphagnum, lichen and peat transfer properties. Experiments consist of a steady-state thermal conductivity estimation using a hot plate source on real arctic vegetation cover samples. For this purpose, samples are placed in a confined thermal atmosphere and a constant heat flux is applied at sample base. Thermal conductivity is then retrieved with the resolution of Fourier’s heat conduction law. Similarly, numerical computations are conducted on the same digital reconstructions than those used for hydraulic properties determination. Simulations consist of a numerical reproduction of previously described experiments, allowing to strengthen the analysis of the experimental data. Additionally, the definition of representative elementary volumes of the studied samples is also undertaken using the numerical results.Compiling these assessments of transfer properties will represent essential information to simulate the dynamics of the permafrost underneath the arctic bryophytic layers with a devoted catchment-scale permafrost models. For instance in the framework of the HiPerBorea project (hiperborea.omp.eu), this approach will be used to forecast the impacts of climate warming on boreal permafrost-dominated catchments.

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

To better understand freezing - thawing cycles operating in peat soils of permafrost landscapes, we experimentally modelled bi-directional freezing and thawing of peat 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 the three sections of 90-cm-long peat core. 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.

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

Barium sulfate solubility in diluted Na2SO4–NaNO3 solutions and seawater of 35‰ salinity at 22°C was studied in experiments. The value obtained for the thermodynamic solubility product of barium sulfate was $$L_{{{\text{BaSO}}_{4}^{0}}}^{0}$$ = (7.57 ± 0.87) × 10–11. It was shown that equilibrium concentration of dissolved barium in seawater was 30.7 μg/L and the water mass of the World Ocean was slightly undersaturated in BaSO4. The experimental data were used to determine the values of the mean ionic activity coefficient of BaSO4, total activity coefficient, and fractions of free Ва2+ ions in seawater: 0.108, 0.131, and 0.59, respectively.

The distribution of dissolved matter (major ions, nutrients, and trace elements) in the estuary of the Yenisei River and nearby areas of the Kara Sea was studied based on natural observations data acquired in 2009–2016. These results were compared with literature hydrochemical data on the area. It was demonstrated that the transport of major ions (Na, K, Mg, Ca, and SO4) and some trace elements (Li, Rb, Cs, Sr, B, F, Cr, Ge, As, Mo, and U) is described by equations (which remain unchanging during long periods of time) of conservative mixing between riverine and marine waters. Although alkalinity is a conservative component, its distribution exhibits a significant spatiotemporal variability, which is caused by the 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 the photic layer decrease seaward during the vegetation period owing to uptake by phytoplankton. The losses of these elements reach 30–57, 30, and 9%, respectively, of their supply with riverine runoff. The contents of dissolved Pmin and V in the intermediate and bottom water layers of the Yenisei estuary strongly increase with increasing salinity due to the regeneration of the precipitated organic matter, whereas silica remineralization is much less intense. As much as 20–100% dissolved Ba in the riverine runoff is intensely desorbed from suspended matter, depending on seasonal variations in chemical composition of the runoff, throughout the whole estuary. The transport of dissolved forms of heavy metals (Mn, Fe, and Pb) and hydrolysate elements (Al, Ti, Y, La, Ce, and Pr) in the mixing zone of riverine and marine water masses is likely controlled by the coagulation and flocculation of organic and organomineral colloids, as follows from the decrease (by 20–61%) in the concentrations of these elements during initial salinization and subsequent approach to the characteristics of the seawater.

Detailed knowledge of the flood period of Arctic rivers remains one of the few factors impeding rigorous prediction of the effect of climate change on carbon and related element fluxes from the lan ...

Several rivers of Chile from the latitude 30 degrees-38 degrees have been sampled during a stable anticyclonic period (October 2008). Firstly, our aim was to evaluate the dissolved chemical composition (major and trace elements) of poorly known central Chilean rivers. Secondly, we used a co-inertia analysis (see Doledec and Chessel in Freshw Biol 31:277-294, 1994) to explore the possible relationships between the concentrations of elements and the environmental parameters [surface of the basin (km(2))/mining activity (%)/average height (m)/watershed mean slope (%)/% of the surface covered by vegetation, sedimentary rocks, volcano-sedimentary rocks, volcanic rocks, granitoid rocks/erosion rate (mm/year)]. Globally, the major elements concentration could be explained by a strong control of mixed silicate and carbonate and evaporate lithology. The statistical treatment reveals that the highest metal and metalloids loads of Tinguiririca, Cachapoal, Aconcagua, Choapa, Illapel and Limari could be explained by the contribution of the mining activities in the uppermost part of these watersheds and/or by the higher geochemical background. Indeed, it remains difficult to decipher between a real mining impact and a higher geochemical background. Even if these rivers could be impacted by AMD process, the size of these watersheds is capable of diluting AMD waters by the alkaline character of tributaries that induce acid neutralization and decrease the level of metals and metalloids.

The spatial and temporal variability of the transformation of dissolved matter runoff in the Mezen River estuary is studied from data on comprehensive hydrological–hydrochemical research in 2009 and 2015. The conservative behavior of major ions and dissolved forms of Li, Rb, Cs, Sr, B, F, As, Sb, and Mo has been revealed. The additional input of phosphates and silicon to solution (to 93% and 32–38% of their content in river water, respectively) is apparently caused by the transport of these nutrients from pore waters, which are regularly muddled by inflow of bottom sediments and vertical mixing of the water column. The desorption flux of barium and uranium due to long-term interaction of terrigenous material with saline water exceeds their input with continental runoff (180–380% and 90–150%, respectively, of their content in river waters). Up to 50, 43, 29, 32, 44, 50, and 45% of Fe, Pb, Y, La, Ce, Pr, and Nd, respectively, supplied by river runoff as stable organic complexes are removed from solution upon entering sea water due coagulation of colloids. It is concluded that transformation regularities of dissolved matter in the Mezen River estuary are spatially homogeneous and temporally stable. The specifics of migration of dissolved phosphates, silicon, barium, and uranium is caused by the hydrological features of the estuary.

WOS:000464851100069; International audience; The mangrove ecosystems are known to efficiently sequester trace metals both in sediments and plant biomass. However, less is known about the chemistry of rare earth elements (REE) in the coastal environments, especially in the world's largest mangrove province, the Sundarban. Here, the concentration of REE in the sediment and plant organs of eight dominant mangrove species (mainly Avicennia sp.) in the Indian Sundarban was measured to assess REE sources, distribution, and bioaccumulation state. Results revealed that light REE (LREE) were more concentrated than the heavy REE (HREE) (128-144 mg kg(-1) and 12-15 mg kg(-1), respectively) in the mangrove sediments, with a relatively weak positive europium anomaly (Eu/Eu* = 1.03-1.14) with respect to North American shale composite. The primary source of REE was most likely linked to aluminosilicate weathering of crustal materials, and the resultant increase in LREE in the detritus. Vertical distribution of REE in one of the long cores from Lothian Island was altered by mangrove root activity and dependent on various physicochemical properties in the sediment (e.g., Eh, pH, organic carbon, and phosphate). REE uptake by plants was higher in the below-ground parts than in the above-ground plant tissues (root = 3.3 mg kg(-1), leaf + wood = 1.7 mg kg(-1)); however, their total concentration was much lower than in the sediment (149.5 mg kg(-1)). Species-specific variability in bioaccumulation factor and translocation factor was observed indicating different REE partitioning and varying degree of mangrove uptake efficiency. Total REE stock in plant (above + live below ground) was estimated to be 168 g ha(-1) with LREE contributing similar to 90% of the stock. This study highlighted the efficiency of using REE as a biological proxy in determining the degree of bioaccumulation within the mangrove environment.

The role of mangroves in sequestering metal and nutrients in sediment has been described in the past, but knowledge gaps still exist on storage capacity and recycling fluxes of elements in plant biomass, notably concerning their magnitude in root uptake and loss by litterfall. This study addresses the storage and transport pathways of 16 elements, classified as macro-nutrients (Ca, Mg, Na, K), micro-nutrients (Fe, Mn, Ni, Co, Cu, Cr, Zn, Mo), and potential toxicants (Al, Cd, Sn, Pb) in the world's largest mangroves, the Sundarbans. Elemental concentrations in plant organs were generally lower than in the sediment. The stock of macro and micro-nutrients in plant biomass varied from 60 to 2717 and 0.003 to 37.7 Mg ha−1 respectively, with highest values observed for Na and lowest for Cd. The Avicennia species exhibited the maximal accumulation of all elements. Translocation of major elements to different plant organs increased with increasing their concentrations in the sediment. Elemental loss via litterfall indicated that Sundarbans mangrove could act as a source, particularly of Mn, to the Bay of Bengal. Moreover, belowground uptake of the 16 elements showed 2–3 fold higher fluxes than their loss via litterfall. There was a significant retention of some trace elements (notably Mo, Cd, and Sn) in plant biomass, which might allow one to use these mangroves for phytoremediation and restoration purposes. We conclude that mangroves efficiently store and remobilize major and trace elements from the sediments by root uptake and recycle back to sediment surface via litterfall.

Permafrost thaw in continental lowlands produces large number of thermokarst (thaw) lakes, which act as a major regulator of carbon (C) storage in sediments and C emission in the atmosphere. Here we studied thaw lakes of the NE European permafrost peatlands - shallow water bodies located within frozen peat bogs and receiving the majority of their water input from lateral (surface) runoff. We also conducted mesocosm experiments via interacting lake waters with frozen peat and dominant ground vegetation - lichen and moss. There was a systematic decrease in concentrations of dissolved C, CO2, nutrients and metals with an increase in lake size, corresponding to temporal evolution of the water body and thermokarst development. We hypothesized that ground vegetation and frozen peat provide the majority of C, nutrients and inorganic solutes in the water column of these lakes, and that microbial processing of terrestrial organic matter controls the pattern of CO2 and nutrient concentrations in thermokarst lakes. Substrate mass-normalized C, nutrient (N, P, K), major and trace metal release was maximal in moss mesocosms. After first 16 h of reaction, the pCO2 increased ten-fold in mesocosms with moss and lichen; this increase was much less pronounced in experiments with permafrost peat. Overall, moss and lichen were the dominant factors controlling the enrichment of the lake water in organic C, nutrients, and trace metals and rising the CO2 concentration. The global significance of obtained results is that the changes in ground vegetation, rather than mere frozen peat thawing, may exert the primary control on C, major and trace element balance in aquatic ecosystems of tundra peatlands under climate warming scenario.

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 &lt, 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.

Greenhouse gas (GHG) emission from inland waters of permafrost-affected regions is one of the key factors of circumpolar aquatic ecosystem response to climate warming and permafrost thaw. Riverine systems of central and eastern Siberia contribute a significant part of the water and carbon (C) export to the Arctic Ocean, yet their C exchange with the atmosphere remains poorly known due to lack of in situ GHG concentration and emission estimates. Here we present the results of continuous in situ pCO2 measurements over a 2600 km transect of the Lena River main stem and lower reaches of 20 major tributaries (together representing a watershed area of 1 661 000 km2, 66 % of the Lena's basin), conducted at the peak of the spring flood. The pCO2 in the Lena (range 400–1400 µatm) and tributaries (range 400–1600 µatm) remained generally stable (within ca. 20 %) over the night–day period and across the river channels. The pCO2 in tributaries increased northward with mean annual temperature decrease and permafrost increase; this change was positively correlated with C stock in soil, the proportion of deciduous needleleaf forest, and the riparian vegetation. Based on gas transfer coefficients obtained from rivers of the Siberian permafrost zone (k=4.46 m d−1), we calculated CO2 emission for the main stem and tributaries. Typical fluxes ranged from 1 to 2 gCm-2d-1 (>99 % CO2, % CH4), which is comparable with CO2 emission measured in the Kolyma, Yukon, and Mackenzie rivers and permafrost-affected rivers in western Siberia. The areal C emissions from lotic waters of the Lena watershed were quantified by taking into account the total area of permanent and seasonal water of the Lena basin (28 000 km2 ). Assuming 6 months of the year to be an open water period with no emission under ice, the annual C emission from the whole Lena basin is estimated as 8.3±2.5 Tg C yr−1, which is comparable to the DOC and dissolved inorganic carbon (DIC) lateral export to the Arctic Ocean.

Arctic sea-ice loss is emblematic of an amplified Arctic water cycle and has critical feedback implications for global climate. Stable isotopes (δ18O, δ2H, d-excess) are valuable tracers for constraining water cycle and climate processes through space and time. Yet, the paucity of well-resolved Arctic isotope data preclude an empirically derived understanding of the hydrologic changes occurring today, in the deep (geologic) past, and in the future. To address this knowledge gap, the Pan-Arctic Precipitation Isotope Network (PAPIN) was established in 2018 to coordinate precipitation sampling at 19 stations across key tundra, subarctic, maritime, and continental climate zones. Here, we present a first assessment of rainfall samples collected in summer 2018 (n = 281) and combine new isotope and meteorological data with sea ice observations, reanalysis data, and model simulations. Data collectively establish a summer Arctic Meteoric Water Line where δ2H = 7.6⋅δ18O–1.8 (r2 = 0.96, p < 0.01). Mean amount-weighted δ18O, δ2H, and d-excess values were −12.3, −93.5, and 4.9‰, respectively, with the lowest summer mean δ18O value observed in northwest Greenland (−19.9‰) and the highest in Iceland (−7.3‰). Southern Alaska recorded the lowest mean d-excess (−8.2%) and northern Russia the highest (9.9‰). We identify a range of δ18O-temperature coefficients from 0.31‰/°C (Alaska) to 0.93‰/°C (Russia). The steepest regression slopes (>0.75‰/°C) were observed at continental sites, while statistically significant temperature relations were generally absent at coastal stations. Model outputs indicate that 68% of the summer precipitating air masses were transported into the Arctic from mid-latitudes and were characterized by relatively high δ18O values. Yet 32% of precipitation events, characterized by lower δ18O and high d-excess values, derived from northerly air masses transported from the Arctic Ocean and/or its marginal seas, highlighting key emergent oceanic moisture sources as sea ice cover declines. Resolving these processes across broader spatial-temporal scales is an ongoing research priority, and will be key to quantifying the past, present, and future feedbacks of an amplified Arctic water cycle on the global climate system. © Copyright © 2021 Mellat, Bailey, Mustonen, Marttila, Klein, Gribanov, Bret-Harte, Chupakov, Divine, Else, Filippov, Hyöky, Jones, Kirpotin, Kroon, Markussen, Nielsen, Olsen, Paavola, Pokrovsky, Prokushkin, Rasch, Raundrup, Suominen, Syvänperä, Vignisson, Zarov and Welker. We gratefully acknowledge all participating PAPIN stations. Tarja T?rm?nen and Aino Erkinaro assisted with sample analysis at the Stable Isotope Laboratory, University of Oulu. Shawn Marriott, Patrick Duke and Polar Knowledge Canada are acknowledged for their support with the Canadian High Arctic Research Station. Sergey Serikov and Aleksandr Sokolov assisted with Russian precipitation sampling. The NOAA Air Resources Laboratory (ARL) is gratefully acknowledged for provision of the HYSPLIT transport model used in this study. NCEP/NCAR data were obtained from the National Oceanic and Atmospheric Administration (NOAA) Earth System Research Laboratory?s (ESRL) Physical Sciences Laboratory database. Funding. The Pan-Arctic Precipitation Isotope Network (PAPIN) received funding from the European Union?s Horizon 2020 Project INTERACT, under Grant Agreement No.730938 (JW PI). An Academy of Finland Grant (316014-JW PI). Support was also provided by a University of the Arctic Research Chairship to JW that funded isotope analyses and provided postdoctoral support for HB and K-RM and postgraduate research support for MM. A Russian Science Foundation Grant (No. 18-11-00024) to KG funded isotope analyses. SK was thankful to Russian Science Foundation (No. 20-67-46018). Russian Foundation for Basic Research (BFBR) supported isotopic analyses conducted by AP (#18-05-60203-Arktika).

International audience; Despite the importance of soil and surface waters freezing in permafrost landscapes, the behaviour of dissolved organic carbon (DOC), nutrients and metals during periodic freezethaw cycles (FTC) remains poorly known. The ongoing climate warming is likely to increase the frequency of FTC in continental aquatic settings, which could modify the chemical composition of waters. In this study, we conducted 9 repetitive cycles of overnight freezing (-20 °C) and 5 hours thawing (4°C) in the laboratory using representative 0.22 µm-filtered waters from NE European permafrost peatland: leachates of vegetation and soil, and natural surface waters (depression, thermokarst lake and river). Only minor (< 5%-15%) changes of DOC concentrations, SUVA254 and molecular weight were observed in all leachates and the depression water. In contrast, several trace elements (Fe, Al, P, Mn, As, and REE) exhibited sizable variations during FTC (> 10%). The leachates and the depression water were enriched in trace elements, whereas the thermokarst lake and the river demonstrated a decrease in concentration of Fe (-39 and-94 %, respectively), Al (-9 and-85 %), and Mn (-10 and-79 %) during FTC. Overall, the observations demonstrated an increase in aliphatic low molecular weight organic matter (OM), and the precipitation of Fe, Al hydroxides and organo-mineral particles. Therefore, enhanced of frequency of FTC can favour the release of metals and toxicants from acidic OM-rich surface waters and maintain stable OM-metals-colloids in large lakes and rivers, thus regulating aquatic transport of DOC and metals from soils to the Arctic Ocean.

The majority of organic carbon (OC), nutrients, and dissolved trace elements in soil porewaters are present in the form of colloids which determine element transport, bioavailability, and overall impact on ecosystems. Climate warming and permafrost thaw in high latitudes will primarily affect the soil liquid phase thereby modifying delivery of colloids to the hydrological network and their role in C transport and emission. Here we studied colloids in peat porewaters across a natural gradient of sporadic, isolated, discontinuous and continuous permafrost zone in the Western Siberian Lowland (WSL), the largest peatland in the world. The depth of sampling and the microrelief (mounds and hollows) had a generally weak impact on the proportion of colloidal forms (3kDa 0.45 μm) of OC, major (Fe, Al, P, alkali and alkaline-earth metals) and trace elements (TE) including micronutrients (Zn, Mn, Ni, Co, Cu), toxicants (Sb, As, Cd, Pb) and geochemical tracers (trivalent and tetravalent cations). Considering all micro-landscapes together, there was no sizable change in the proportion of colloidal fraction of OC, Fe, Al, P, micronutrients and toxicants across the permafrost zones. The majority of colloidal forms of all elements of these groups were represented by a size fraction between 3 and 30 kDa and were essentially Fe-Al-organic compounds with an average Fe:Al:OC molar ratio of 1.9:1:308. Overall, the degree of impact from environmental factors on OC and metal distribution among various colloidal fractions can be classified as depth ≤ permafrost type < microlandscape. Applying a substitution “space for time scenario” for the climate warming and permafrost thaw in Western Siberia, we do not expect sizable changes in C and element colloidal status during active layer thickness increase and permafrost boundary shift northward. Future studies of colloids in peat ice (below the active layer) are needed to assess possible changes in delivery of C and metals from soil to rivers and onward into the Arctic Ocean under massive permafrost thawing in the WSL.

International audience; Quantifying the link between cyanobacterial activity and the carbon isotope signature of precipitated carbonate minerals is crucial for reconstructing the environmental conditions present at the time of carbonate mineral formation. In this study, calcite was precipitated in the presence and absence of Synechococcus sp. cyanobacteria in batch reactors. The temporal evolution of the carbon isotope composition of calcite (δ13CCalcite) and dissolved inorganic carbon (δ13CDIC) was monitored to evaluate the rate and degree to which the carbon isotope compositions in calcite are modified during and after its precipitation. The presence of cyanobacteria promoted calcium carbonate formation by increasing fluid pH and the CaCO3 saturation state. It also changed significantly the carbon isotope composition of dissolved inorganic carbon due to the preferential incorporation of 12C into the biomass. This generated an isotope disequilibrium between the calcite and the aqueous fluid phase over time after the calcite precipitated. The carbon isotope composition of the calcite evolved continuously towards mineral-fluid isotope equilibrium after its precipitation, at geometric surface area normalized rates ranging from 1.75 × 10−14 to 1.71 × 10−13 mol 13C/m2/s. These rates are sufficiently fast such that the δ13CDIC value of aqueous fluids in calcite-rich rocks would be buffered by the δ13CCalcite value of the co-existing calcite. Mass balance calculations suggest that the carbon isotope composition of calcite could change noticeably when the calcite is in isotope disequilibrium with its co-existing fluid, for example through the presence of a local 12C sink such as photosynthetic microorganisms or 12C source such as decomposition of organic material.

Emission of greenhouse gases (GHGs) from inland waters is recognized as highly important and an understudied part of the terrestrial carbon (C) biogeochemical cycle. These emissions are still poorly quantified in subarctic regions that contain vast amounts of surface C in permafrost peatlands. This is especially true in NE European peatlands, located within sporadic to discontinuous permafrost zones which are highly vulnerable to thaw. Initial measurements of C emissions from lentic waters of the Bolshezemelskaya Tundra (BZT; 200,000 km2) demonstrated sizable CO2 and CH4 concentrations and fluxes to the atmosphere in 98 depressions, thaw ponds, and thermokarst lakes ranging from 0.5 × 106 to 5 × 106 m2 in size. CO2 fluxes decreased by an order of magnitude as waterbody size increased by > 3 orders of magnitude while CH4 fluxes showed large variability unrelated to lake size. By using a combination of Landsat‐8 and GeoEye‐1 images, we determined lakes cover 4% of BZT and thus calculated overall C emissions from lentic waters to be 3.8 ± 0.65 Tg C yr−1 (99% C‐CO2, 1% C‐CH4), which is two times higher than the lateral riverine export. Large lakes dominated GHG emissions whereas small thaw ponds had a minor contribution to overall water surface area and GHG emissions. These data suggest that, if permafrost thaw in NE Europe results in disappearance of large thermokarst lakes and formation of new small thaw ponds and depressions, GHG emissions from lentic waters in this region may decrease.

The Ob River floodplain is the second largest floodplain in the world. Despite its vast area, estimates of carbon (C) emissions from the Ob River floodplain are largely absent. Here we present seasonal C emission and water area extent from the main channel and the floodplain along a similar to 4 km reach in the boreal zone of the Ob River. We found strong seasonality in water area extent of the Ob main channel (similar to 1.8 km(2)) and floodplain (similar to 3 km(2)) with water covering 34% of land during flood and subsequently declining to similar to 16% and similar to 14% during summer and autumn baseflow, respectively. The C emissions also varied seasonally over the open water period, ranging from -0.1 to 0.6 g C m(-2) d(-1) for the Ob main channel and from 0 to 9 g C m(-2) d(-1) for the floodplain. The dissolved organic carbon positively affected CO2 concentrations and fluxes in the floodplain during all seasons, whereas pH and oxygen concentration negatively impacted CO2 concentrations and fluxes. Some nutrients (ammonia and phosphate) positively correlated with CO2 and CH4 concentrations in summer. The total C emission from the study reach (1.8 km(2) main channel, 3 km(2) floodplain) during moderate flooding was 236 +/- 51 tons C yr(-1) (99% CO2

Although mosses are widely used for active biomonitoring of air pollution, a unified protocol for their treatment before exposure in bags is still lacking. Here we used field- and laboratory-grown Sphagnum palustre L. moss, respectively, treated by EDTA and devitalized by oven drying at 100 °C, to elaborate a consistent procedure of metal and proton adsorption on moss surfaces. Acid-base titrations and Pb2+ adsorption experiments at different pH values and Pb2+ concentrations in solution were performed with both field-collected and laboratory cloned mosses. Devitalization and EDTA treatments did not produce any measurable difference in terms of H+ and Pb2+ adsorption capacities of moss surfaces. The stability constants for Pb2+ adsorption onto moss surfaces as a function of pH (pH-dependent adsorption edge) and at constant pH (5.5 and 6.5) as a function of Pb2+ concentration (“langmuirian” adsorption isotherm) were rather similar between different treatments. A Linear Program Modeling (LPM) of adsorption reactions revealed high similarity of adsorption constants regardless of treatments for both field-grown and cloned mosses. Therefore, in view of the use of S. palustre clone for biomonitoring lead in the environment, we recommend devitalization at 100 °C as unique treatment to perform with the aim to preserve the biomonitor before and after its exposure in bags.

International audience; The solubility of calcite was measured at 100, 120, 140 and 160°C at 1-50 bar pCO2 in10-3-0.1 mol·kg-1 NaCl solutions using a new experimental setup involving in situ pH measurements with high-temperature solid-contact H-selective glass and two types of reference electrodes: i) Ag/AgCl in 3.5 M KCl, saturated AgCl placed in a Teflon extensible container with liquid junction, and ii) solid-contact high-T Na-selective glass electrode in the cell without liquid junction. The stability constants of NaHCO3° and NaCO3-aqueous complexes formation were determined in NaCl-Na2CO3/NaHCO3 solutions in CO2-free media and under 10 bar pCO2 from 100 to 160 °C. These values allowed calculation of the pH of the calibration solution in the system NaCl-CO2-H2O used in the cell without liquid junction with Na+-selective electrode as a reference. This highly stable, low-cost electrode system can be recommended for routine pH measurements at 4 < pH < 10 in sodium-bearing solutions up to 160°C and the critical point of CO2. The values of the stability constants of CaCO3° and CaHCO3+ aqueous complexes and calcite solubility product were generated at 100, 120, 140 and 160 °C allowing a description of the solubility of calcite in a wide range of pH and pCO2.

Arctic regions contain large amounts of organic carbon (OC) trapped in soil and wetland permafrost. With climate warming, part of this OC is released to aquatic systems and degraded by microorganisms, thus resulting in positive feedback due to carbon (C) emission. In wetland areas, water bodies are spatially heterogenic and separated by landscape position and water residence time. This represents a hydrological continuum, from depressions, smaller water bodies and lakes to the receiving streams and rivers. Yet, the effect of this heterogeneity on the OC release from the soil and its processing in waters is largely unknown and not accounted for in C cycle models of Arctic regions. Here we investigated the dissolved OC (DOC) biodegradation of aquatic systems along a hydrological continuum located in two discontinuous permafrost sites: in western Siberia and northern Sweden. The biodegradable dissolved OC (BDOC15; % DOC lost relative to the initial DOC concentration after 15 days incubation at 20 °C) ranged from 0 to 20% for small water bodies located at the beginning of the continuum (soil solutions, small ponds, fen and lakes) and from 10 to 20% for streams and rivers. While the BDOC15 increased, the removal rate of DOC decreased along the hydrological continuum. The potential maximum CO2 production from DOC biodegradation was estimated to account for only a small part of in-situ CO2 emissions measured in peatland aquatic systems of northern Sweden and western Siberia. This suggests that other sources, such as sediment respiration and soil input, largely contribute to CO2 emissions from small surface waters of permafrost peatlands. Our results highlight the need to account for large heterogeneity of dissolved OC concentration and biodegradability in order to quantify C cycling in arctic water bodies susceptible to permafrost thaw.

Snowpack exhibits properties that make it a unique natural archive of airborne pollution. The data on insoluble particles in the Ob River catchment (Western Siberia) snowpack are limited. Insoluble particles in the snowpack of Western Siberia were studied at 36 sites on a 2800 km submeridional profile from the city of Barnaul to Salekhard in February 2020. Snow samples were collected over the full depth of the snow core, from the surface of the snow cover to the boundary with soil, except for the lower 1&ndash, 2 cm. After the filtration of melted snow through a 0.45-&micro, m membrane, the particle composition was studied using a scanning electron microscope with an energy microprobe. In the background areas, the concentration of insoluble particles in the snow was below 2 mg/L. Significantly higher particle concentrations were encountered near cities and hydrocarbon production areas. Particulate matter in snow mainly consists of biogenic and lithogenic particles mixed with anthropogenic particles (ash and black carbon aggregates). The proportion of anthropogenic particles increases near cities and areas of active hydrocarbon production.

International audience; Bioerosion is a process with a high socioeconomic impact that contributes to coastal retreat, and likely to increase with climate change. Whereas limestone bioerosion is well explained by a combination of mechanical and chemical pathways, the bioerosion mechanisms of silicates, which are harder and chemically more resistant, remain elusive. Here we investigated the interface between siltstone and freshwater rock-boring bivalves Lignopholas fluminalis (Bivalvia: pholadidae). Remains of a microbial biofilm were observed only in the poorly consolidated part of the rock within the macroborings created by bivalves. Secondary Mn-bearing minerals identified in the biofilm suggest that microbes promoted silicate rock weathering by dissolving Mn-rich chlorites. Moreover, hard mineral debris found in a biofilm attached to the shells likely contributed to the abrasion of the rock substrate. thus, beyond the classical view of chemical and/or mechanical action(s) of macroborers, silicate bioerosion may also be facilitated by an unexpected synergistic association between macro-and microorganisms. Bioerosion is a commonplace strategy developed by living organisms, which consists in boring hard substrates of various origins, including biological materials (e.g., wood, shells, and bones) 1 , mud 2 , rocks 3 and even synthetic materials. Depending on the nature of the substrate and the borer, bioerosion ensures a wide range of metabolic activities and ecosystem services, ranging from nutrition 4 to the creation of microhabitats protected from predators for themselves as well as for secondary dwellers 5. Gaining knowledge into the occurrence, rates and mechanisms of boring is of fundamental importance for a series of reasons. First and historically, mankind has been confronted with macroborers through the damages caused by shipworms on vessels, wooden wharfs and docks 5,6. More broadly, bioerosion has socioeconomic impacts whenever manufactured materials are damaged, including plastic, metals and concrete materials such as levees or coastal defences 3,6. Second, bioerosion contributes to element recycling, shaping landscapes through the weakening of rocky shorelines and participating to coastal retreat 5 , for which the current rates are likely to be modified drastically as a result of climate change 6. Third, the creation of microhabitats by macroborers such as bivalves is correlated with a significant increase of the abundance of species assemblages, thus partly contributing to local faunal biodiversity 7. Finally, fossil records of macro-bioerosion may be used as a biological proxy to estimate the paleo-location of intertidal and shallow subtidal marine environments, marking ancient shorelines 8. The mechanisms of rock bioerosion associated to macroborers and especially bivalves have been a source of lively debate for decades, and can be schematically divided into two main pathways. First, rock boring can open

The physical and chemical consequences of massive ground ice (wedges) melt upon permafrost thaw is one of the central issues of environmental research linked to climate warming in the Arctic. Little is known about the chemical properties of dispersed ground ice abundant throughout permafrost peatlands that can easily melt with increasing active layer thickness (ALT). This is especially pertinent in continental lowlands, that account for sizeable areas of the Arctic, and contain high amount of organic carbon in both solid (peat) and liquid (porewater) phases. Here we studied 8 peat cores (0–130 cm depth)—comprised of porewater from the active layer (0–45 cm) as well as ice dispersed in frozen peat (40–130 cm)—across a latitudinal profile of Western Siberia Lowland (WSL) extending from discontinuous into continuous permafrost zones. Dissolved Organic Carbon (DOC), alkali and alkaline-earth metals (Ca, Mg, Sr, Ba, Li, Rb, Cs), sulfate, phosphorus, some trace elements (Al, Fe, Mn, Zn, Ni, Co, V, As, Y, REE, Zr, Hf, U) were sizably [more than 3 times] enriched in peat ice compared to peat porewaters from the active layer. In most sampled cores, there was a local maximum of strong enrichment (up to factors between 14 and 58) in DOC, P, Ca, Mg, Mn, Fe, Sr, As located 30–50 cm below the active layer. This maximum likely occurred due to solute concentration during full freezing of the soil column during winter. There was a sizable correlation between DOC, Al, Fe and other major and trace element concentrations that suggests strong control of organic complexes and organo-mineral (Al, Fe) colloids on element migration throughout the peat profile. The pool of C, major cations and trace metals in peat ice (40–130 cm) was approximately 3–55 times higher than the pool of these elements in porewaters from the active layer (0–40 cm). A 1-m increase of the ALT over the next 100 years is capable of mobilizing 58 ± 38 Tg of DOC from soil ice into the rivers and lakes of the WSL latitudinal belt (63–67 °N). This fast lateral export of C (3.7 ± 2.7 t C km−2 y−1) may double current C yields in WSL rivers (3.4 ± 1.3 t C km−2 y−1). A strong increase (150–200%) in riverine export of Zn, P and Cs may also occur while other micronutrients (Fe, Ni, Co, Ba, Mo, Rb) and toxicants (Cd, As, Al) may be affected to a lesser degree (20–30% increase). We propose a global peat ice inventory in permafrost regions is essential for assessing the consequences of permafrost thaw on surface aquatic systems.

Peatlands cover 3% of the land, occur in 169 countries, and have—by sequestering 600 Gt of carbon—cooled the global climate by 0.6 °C. After a general review about peatlands worldwide, this paper describes the importance of the Great Vasyugan Mire and presents suggestions about its protection and future research. The World’s largest peatland, the Great Vasyugan Mire in West-Siberia, forms the border between the Taiga and the Forest-Steppe biomes and harbours rare species and mire types and globally unique self-organizing patterns. Current oil and gas exploitation may arguably be largely phased out by 2050, which will pave the way for a stronger focus on the mire’s role in buffering climate change, maintaining ecosystem diversity, and providing other ecosystem services. Relevant new research lines will benefit from the extensive data sets that earlier studies have gathered for other purposes. Its globally unique character as the ‘largest life form on land’ qualifies the Great Vasyugan Mire in its entirety to be designated as a UNESCO World Heritage Site and a Ramsar Wetland of International Importance.

Thermokarst lakes and ponds formed due to thawing of frozen peat in high-latitude lowlands are very dynamic and environmentally important aquatic systems that play a key role in controlling C emission to atmosphere and organic carbon (OC), nutrient, and metal lateral export to rivers and streams. However, despite the importance of thermokarst lakes in assessing biogeochemical functioning of permafrost peatlands in response to climate warming and permafrost thaw, spatial (lake size, permafrost zone) and temporal (seasonal) variations in thermokarst lake hydrochemistry remain very poorly studied. Here, we used unprecedented spatial coverage (isolated, sporadic, discontinuous, and continuous permafrost zone of the western Siberia Lowland) of 67 lakes ranging in size from 102 to 105 m&sup2, for sampling during three main hydrological periods of the year: spring flood, summer baseflow, and autumn time before ice-on. We demonstrate a systematic, all-season decrease in the concentration of dissolved OC (DOC) and an increase in SO4, N-NO3, and some metal (Mn, Co, Cu, Mo, Sr, U, Sb) concentration with an increase in lake surface area, depending on the type of the permafrost zone. These features are interpreted as a combination of (i) OC and organically bound metal leaching from peat at the lake shore, via abrasion and delivery of these compounds by suprapermafrost flow, and (ii) deep groundwater feeding of large lakes (especially visible in the continuous permafrost zone). Analyses of lake water chemical composition across the permafrost gradient allowed a first-order empirical prediction of lake hydrochemical changes in the case of climate warming and permafrost thaw, employing a substituting space for time scenario. The permafrost boundary shift northward may decrease the concentrations and pools of dissolved inorganic carbon (DIC), Li, B, Mg, K, Ca, Sr, Ba, Ni, Cu, As, Rb, Mo, Sr, Y, Zr, rare Earth elements (REEs), Th, and U by a factor of 2&ndash, 5 in the continuous permafrost zone, but increase the concentrations of CH4, DOC, NH4, Cd, Sb, and Pb by a factor of 2&ndash, 3. In contrast, the shift of the sporadic to isolated zone may produce a 2&ndash, 5-fold decrease in CH4, DOC, NH4, Al, P, Ti, Cr, Ni, Ga, Zr, Nb, Cs, REEs, Hf, Th, and U. The exact magnitude of this response will, however, be strongly seasonally dependent, with the largest effects observable during baseflow seasons.

Rivers play a key role in the water cycle on the earth via integrating all hydrological channels to return terrestrial precipitations back to the oceans. In addition, rivers, together with groundwater, are powerful transformers of the surface lithosphere, responsible for chemical weathering of rocks and the removal of solute into the ocean. Tracing the dynamics of surface water and groundwater versus atmospheric feeding of rivers presents important issues in Arctic regions due to the ongoing change of the structure of hydrological runoff. In this study, stable water isotopes were used to reveal the temporal dynamics of water sources and to predict their possible change under the conditions of ongoing climate warming of the largest European Arctic river, the Severnaya Dvina, and adjacent groundwater. The isotopic composition of the river waters of the studied region is formed by the mixing of atmospheric precipitation with groundwater. The isotopic depletion in the springtime is mainly due to the recharge of thawed snow waters. A less pronounced effect in the autumn-winter period is provided by the discharge of groundwater into rivers, including the meltwater of the Last Glacial Period. This depletion is partially offset due to discharge of isotopically light thawed snow waters and is linked to evaporation in headwater streams, reservoirs, and wetlands. The isotopic composition of groundwater with low mineralization was formed throughout the Holocene and to a large extent depends on paleoclimatic conditions in the study area. In addition to fresh groundwater, brackish groundwater also takes part in the river's recharge. These brackish waters are associated with ancient and modern marine transgressions on the estuarine site and with the dissolution of Ca sulfate rocks in a karst region located in the middle reaches of the river. According to isotope data, the average annual input of the underground source to the total river flow is 25%. The results of this work will serve as the basis for continuing monitoring of the isotopic composition of river waters with an assessment of hydrological processes and observation of short as well as long-term climatic and anthropogenic impacts.

The assessment of riverine fluxes of carbon, nutrients, and metals in surface waters of permafrost-affected regions is crucially important for constraining adequate models of ecosystem functioning under various climate change scenarios. In this regard, the largest permafrost peatland territory on the Earth, the Western Siberian Lowland (WSL) presents a unique opportunity of studying possible future changes in biogeochemical cycles because it lies within a south&ndash, north gradient of climate, vegetation, and permafrost that ranges from the permafrost-free boreal to the Arctic tundra with continuous permafrost at otherwise similar relief and bedrocks. By applying a &ldquo, substituting space for time&rdquo, scenario, the WSL south-north gradient may serve as a model for future changes due to permafrost boundary shift and climate warming. Here we measured export fluxes (yields) of dissolved organic carbon (DOC), major cations, macro- and micro- nutrients, and trace elements in 32 rivers, draining the WSL across a latitudinal transect from the permafrost-free to the continuous permafrost zone. We aimed at quantifying the impact of climate warming (water temperature rise and permafrost boundary shift) on DOC, nutrient and metal in rivers using a &ldquo, approach. We demonstrate that, contrary to common expectations, the climate warming and permafrost thaw in the WSL will likely decrease the riverine export of organic C and many elements. Based on the latitudinal pattern of riverine export, in the case of a northward shift in the permafrost zones, the DOC, P, N, Si, Fe, divalent heavy metals, trivalent and tetravalent hydrolysates are likely to decrease the yields by a factor of 2&ndash, 5. The DIC, Ca, SO4, Sr, Ba, Mo, and U are likely to increase their yields by a factor of 2&ndash, 3. Moreover, B, Li, K, Rb, Cs, N-NO3, Mg, Zn, As, Sb, Rb, and Cs may be weakly affected by the permafrost boundary migration (change of yield by a factor of 1.5 to 2.0). We conclude that modeling of C and element cycle in the Arctic and subarctic should be region-specific and that neglecting huge areas of permafrost peatlands might produce sizeable bias in our predictions of climate change impact.

Climate warming, increased precipitation, and permafrost thaw in the Arctic are accompanied by an increase in the frequency of full or partial drainage of thermokarst lakes. After lake drainage, highly productive plant communities on nutrient-rich sediments may develop, thus increasing the influencing greening trends of Arctic tundra. However, the magnitude and extent of this process remain poorly understood. Here we characterized plant succession and productivity along a chronosequence of eight drained thermokarst lakes (khasyreys), located in the low-Arctic tundra of the Western Siberian Lowland (WSL), the largest permafrost peatland in the world. Based on a combination of satellite imagery, archive mapping, and radiocarbon dating, we distinguished early (&lt, 50 years), mid (50&ndash, 200 years), and late (200&ndash, 2000 years) ecosystem stages depending on the age of drainage. In 48 sites within the different aged khasyreys, we measured plant phytomass and productivity, satellite-derived NDVImax, species composition, soil chemistry including nutrients, and plant elementary composition. The annual aboveground net primary productivity of the early and mid khasyrey ranged from 1134 and 660 g&middot, m&minus, 2&middot, y&minus, 1, which is two to nine times higher than that of the surrounding tundra. Late stages exhibited three to five times lower plant productivity and these ecosystems were distinctly different from early and mid-stages in terms of peat thickness and pools of soil nitrogen and potassium. We conclude that the main driving factor of the vegetation succession in the khasyreys is the accumulation of peat and the permafrost aggradation. The soil nutrient depletion occurs simultaneously with a decrease in the thickness of the active layer and an increase in the thickness of the peat. The early and mid khasyreys may provide a substantial contribution to the observed greening of the WSL low-Arctic tundra.

Constraining the mechanisms controlling the riverine flux of major cations and their isotopes including that of Mg to the World Ocean is one of the challenges in Earth surface isotope geochemistry. In an attempt to identify the main factors affecting the Mg isotopic composition of large rivers including vegetation, climate and lithology of the watershed, we studied the largest, in terms of discharge, Siberian river, Yenisey, and 20 of its main tributaries, during spring flood, summer flow and winter. The working hypothesis was that the influence of bedrock composition is most pronounced in winter, when the soils are frozen and the rivers are fed by deep underground waters. Thus, we anticipated that the presence of permafrost will help to distinguish the impact of surface processes, linked to biological uptake and release, and deep soil/underground transport of Mg from mineral sources. In contrast to these expectations, no sizable differences in the Mg isotope composition of the river water (±0.1‰) for both the Yenisey tributaries and its main channel has been observed between the spring flood (May) and the winter (March) period. Those two periods are characterized by the differences of discharge and degree of lithological impact on element source in the river water. Regardless of the season, there was no straightforward control of lithology (relative abundance of carbonates, basalts, granites and sedimentary rocks) on δ26Mg in the main tributaries of the Yenisey river. Our findings suggest that the use of riverine Mg isotope signature for tracing weathering mechanisms and dominant lithological impact is not straightforward at the scale of large rivers whose watersheds present multiple lithologies, variable climatic conditions and vegetation types.

The response in metal concentrations and isotopic composition to variations in photosynthetic activity of aquatic micro-organisms is crucially important for understanding the environmental controls on metal fluxes and isotope excursions. Here we studied the impacts of two successive diel cycles on physicochemical parameters, Cu and Zn concentrations, and isotopic composition in solution in the presence of mature phototrophic biofilm in a rotating annular bioreactor. The diel cycles induced fluctuations in temperature, pH, and dissolved oxygen concentration following the variation in the photosynthesis activity of the biofilm. Diel variations in metal concentrations were primarily related to the pH variation, with an increase in metal concentration in solution related to a pH decrease. For both metals, δ(66Zn) and δ(65Cu) in solution exhibited complex but reproducible diel cycles. Diel variations in photosynthetic activity led to alternatively positive and negative isotope fractionation, producing the sorption of light Zn (Δ(66Znsorbed-solution) = -0.1 ± 0.06‰) and heavy Cu isotopes (Δ(65Cusorbed-solution) = +0.17 ± 0.06‰) during the day at high pH and the excretion of lighter Zn isotopes (-0.4‰ < Δ(66Znexcreted-biofilm) < +0.14‰) and heavy Cu isotopes (Δ(65Cuexcreted-biofilm) = +0.7 ± 0.3‰) during the night at lower pH. We interpreted Zn and Cu diel cycles as a combination of a desorption of exopolymeric substance-metal complexes and a small active efflux during the night with adsorption and incorporation via an active uptake during the day. The hysteresis of metal concentration in solution over the diel cycle suggested the more important role of uptake compared to desorption and efflux from the biofilm. The phototrophic biofilm presents a non-negligible highly labile metal pool with important potential for contrasting isotopic fractionation at the diel scale.