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

Transport of carbon, major and trace elements by rivers in permafrost-affected regions is one of the key factors in circumpolar aquatic ecosystem response to climate warming and permafrost thaw. A snap-shot study of major and trace element concentration in the Lena River basin during the peak of spring flood revealed a specific group of solutes according to their spatial pattern across the river main stem and tributaries and allowed the establishment of a link to certain landscape parameters. We demonstrate a systematic decrease of labile major and trace anion, alkali and alkaline-earth metal concentration downstream of the main stem of the Lena River, linked to change in dominant rocks from carbonate to silicate, and a northward decreasing influence of the groundwater. In contrast, dissolved organic carbon (DOC) and a number of low-soluble elements exhibited an increase in concentration from the SW to the NE part of the river. We tentatively link this to an increase in soil organic carbon stock and silicate rocks in the Lena River watershed in this direction. Among all the landscape parameters, the proportion of sporadic permafrost on the watershed strongly influenced 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 the watershed by light (for B, Cl, Na, K, U) and deciduous (for Fe, Ni, Zn, Ge, Rb, Zr, La, Th) needle-leaf forest (pine and larch). Our results also suggest a 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 the 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 stem from changes in the spatial pattern of dominant vegetation as well as the permafrost regime. We argue that comparable studies of large, permafrost-affected rivers during contrasting seasons, including winter baseflow, should allow efficient prediction of future changes in riverine ‘inorganic’ hydrochemistry induced by permafrost thaw.

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.

The carbon (C) cycle in inland waters, including carbon concentrations in and carbon dioxide (CO₂) emissions from water surfaces, are at the forefront of biogeochemical studies, especially in regions strongly impacted by ongoing climate change. Towards a better understanding of C storage, transport and emission in Central Asian mountain regions, an area of knowledge that has been extremely poorly studied until now, here, we carried out systematic measurements of dissolved C and CO₂ emissions in rivers and lakes located along a macrotransect of various natural landscapes in the Sayan–Altai mountain region, from the high mountains of the Western Sayan in the northwest of Tyva to the arid (dry) steppes and semideserts in the intermountain basins in the southeast of Tyva on the border with Mongolia. New data on major hydrochemical parameters and CO₂ fluxes (fCO₂) gathered by floating chambers and dissolved organic and inorganic carbon (DOC and DIC, respectively) concentrations collected over the four main hydrological seasons allowed us to assess the current C biogeochemical status of these water bodies in order to judge possible future changes under climate warming. We further tested the impact of permafrost, river watershed size, lake area and climate parameters as well as ‘internal’ biogeochemical drivers (pH, mineralization, organic matter quality and bacterial population) on CO₂ concentration and emissions in lakes and rivers of this region and compared them with available data from other subarctic and mountain settings. We found strong environmental control of the CO₂ pattern in the studied water bodies, with thermokarst lakes being drastically different from other lakes. In freshwater lakes, pCO₂ negatively correlated with O₂, whereas the water temperature exerted a positive impact on pCO₂ in large rivers. Overall, the large complexity of counteracting external and internal drivers of CO₂ exchange between the water surfaces and the atmosphere (CO₂-rich underground DIC influx and lateral soil and subsurface water; CO₂ production in the water column due to dissolved and particulate OC biodegradation; CO₂ uptake by aquatic biota) precluded establishing simple causalities between a single environmental parameter and the fCO₂ of rivers and lakes. The season-averaged CO₂ emission flux from the rivers of Tyva measured in this study was comparable, with some uncertainty, to the C uptake fluxes from terrestrial ecosystems of the region, which were assessed in other works.