Mobilization of dissolved organic carbon (DOC) and related trace elements (TEs) from the frozen peat to surface waters in the permafrost zone is expected to enhance under ongoing permafrost thaw and active layer thickness (ALT) deepening in high-latitude regions. The interstitial soil solutions are efficient tracers of ongoing bio-geochemical processes in the critical zone and can help to decipher the intensity of carbon and metals migration from the soil to the rivers and further to the ocean. To this end, we collected, across a 640 km latitudinal transect of the sporadic to continuous permafrost zone of western Siberia peatlands, soil porewaters from 30 cm depth using suction cups and we analyzed DOC, dissolved inorganic carbon (DIC), and 40 major elements and TEs in 0.45 µm filtered fraction of 80 soil porewaters. Despite an expected decrease in the intensity of DOC and TE mobilization from the soil and vegetation litter to the interstitial fluids with the increase in the permafrost coverage and a decrease in the annual temperature and ALT, the DOC and many major and trace elements did not exhibit any distinct decrease in concentration along the latitudinal transect from 62.2 to 67.4° N. The DOC demonstrated a maximum of concentration at 66° N, on the border of the discontinuous/continuous permafrost zone, whereas the DOC concentration in peat soil solutions from the continuous permafrost zone was equal to or higher than that in the sporadic/discontinuous permafrost zone. Moreover, a number of major (Ca, Mg) and trace (Al, Ti, Sr, Ga, rare earth elements (REEs), Zr, Hf, Th) elements exhibited an increasing, not decreasing, northward concentration trend. We hypothesize that the effects of temperature and thickness of the ALT are of secondary importance relative to the leaching capacity of peat, which is in turn controlled by the water saturation of the peat core. The water residence time in peat pores also plays a role in enriching the fluids in some elements: the DOC, V, Cu, Pb, REEs, and Th were a factor of 1.5 to 2.0 higher in mounds relative to hollows. As such, it is possible that the time of reaction between the peat and downward infiltrating waters essentially controls the degree of peat porewater enrichments in DOC and other solutes. A 2° northward shift in the position of the permafrost boundaries may bring about a factor of 1.3 ± 0.2 decrease in Ca, Mg, Sr, Al, Fe, Ti, Mn, Ni, Co, V, Zr, Hf, Th, and REE porewater concentration in continuous and discontinuous permafrost zones, and a possible decrease in DOC, specific ultraviolet absorbency (SUVA), Ca, Mg, Fe, and Sr will not exceed 20 % of their current values. The projected increase in ALT and vegetation density, northward migration of the permafrost boundary, or the change of hydrological regime is unlikely to modify chemical composition of peat porewater fluids larger than their natural variations within different micro-landscapes, i.e., within a factor of 2. The decrease in DOC and metal delivery to small rivers and lakes by peat soil leachate may also decrease the overall export of dissolved components from the continuous permafrost zone to the Arctic Ocean. This challenges the current paradigm on the increase in DOC export from the land to the ocean under climate warming in high latitudes.

Towards a better understanding of trace element (TE) transport in permafrost-affected Earth surface environments, we sampled ∼ 60 large and small rivers (< 100 to ≤ 150 000 km² watershed area) of the Western Siberian Lowland (WSL) during spring flood and summer and winter baseflow across a 1500 km latitudinal gradient covering continuous, discontinuous, sporadic and permafrost-free zones. Analysis of ∼ 40 major and TEs in the dissolved (< 0.45 µm) fraction allowed establishing main environmental factors controlling the transport of metals and TEs in rivers of this environmentally important region. No statistically significant effect of the basin size on most TE concentrations was evidenced. Two groups of elements were distinguished: (1) elements that show the same trend throughout the year and (2) elements that show seasonal differences. The first group included elements decreasing northward during all seasons (Sr, Mo, U, As, Sb) marking the underground water influence of river feeding. The elements of the second group exhibited variable behavior in the course of the year. A northward increase during spring period was mostly pronounced for Fe, Al, Co, Zn and Ba and may stem from a combination of enhanced leaching from the topsoil and vegetation and bottom waters of the lakes (spring overturn). A springtime northward decrease was observed for Ni, Cu, Zr and Rb. The increase in element concentration northward was observed for Ti, Ga, Zr and Th only in winter, whereas Fe, Al, rare earth elements (REEs), Pb, Zr, and Hf increased northward in both spring and winter, which could be linked to leaching from peat and transport in the form of Fe-rich colloids. A southward increase in summer was strongly visible for Fe, Ni, Ba, Rb and V, probably due to peat/moss release (Ni, Ba, Rb) or groundwater feeding (Fe, V). Finally, B, Li, Cr, V, Mn, Zn, Cd, and Cs did not show any distinct trend from S to N. The order of landscape component impact on TE concentration in rivers was lakes > bogs > forest. The lakes decreased export of Mn and Co in summer and Ni, Cu, and Rb in spring, presumably due to biotic processes. The lakes enriched the rivers in insoluble lithogenic elements in summer and winter, likely due to TE mobilization from unfrozen mineral sediments. The rank of environmental factors on TE concentration in western Siberian rivers was latitude (three permafrost zones) > season > watershed size. The effect of the latitude was minimal in spring for most TEs but highly visible for Sr, Mo, Sb and U. The main factors controlling the shift of river feeding from surface and subsurface flow to deep underground flow in the permafrost-bearing zone were the depth of the active (unfrozen) seasonal layer and its position in organic or mineral horizons of the soil profile. In the permafrost-free zone, the relative role of carbonate mineral-bearing base rock feeding versus bog water feeding determined the pattern of TE concentration and fluxes in rivers of various sizes as a function of season. Comparison of obtained TE fluxes in WSL rivers with those of other subarctic rivers demonstrated reasonable agreement for most TEs; the lithology of base rocks was the major factor controlling the magnitude of TE fluxes. Climate change in western Siberia and permafrost boundary migration will essentially affect the elements controlled by underground water feeding (DIC, alkaline earth elements (Ca, Sr), oxyanions (Mo, Sb, As) and U). The thickening of the active layer may increase the export of trivalent and tetravalent hydrolysates in the form of organo-ferric colloids. Plant litter-originated divalent metals present as organic complexes may be retained via adsorption on mineral horizon. However, due to various counterbalanced processes controlling element source and sinks in plant–peat–mineral soil–river systems, the overall impact of the permafrost thaw on TE export from the land to the ocean may be smaller than that foreseen with merely active layer thickening and permafrost boundary shift.

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–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 “substituting space for time” 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 “substituting space for time” 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 2–5. The DIC, Ca, SO₄, Sr, Ba, Mo, and U are likely to increase their yields by a factor of 2–3. 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.

In order to better understand the chemical composition of snow and its impact on surface water hydrochemistry in the poorly studied Western Siberia Lowland (WSL), the surface layer of snow was sampled in February 2014 across a 1700 km latitudinal gradient (ca. 56.5 to 68° N). We aimed at assessing the latitudinal effect on both dissolved and particulate forms of elements in snow and quantifying the impact of atmospheric input to element storage and export fluxes in inland waters of the WSL. The concentration of dissolved+colloidal (< 0.45 µm) Fe, Co, Cu, As and La increased by a factor of 2 to 5 north of 63° N compared to southern regions. The pH and dissolved Ca, Mg, Sr, Mo and U in snow water increased with the rise in concentrations of particulate fraction (PF). Principal component analyses of major and trace element concentrations in both dissolved and particulate fractions revealed two factors not linked to the latitude. A hierarchical cluster analysis yielded several groups of elements that originated from alumino-silicate mineral matrix, carbonate minerals and marine aerosols or belonging to volatile atmospheric heavy metals, labile elements from weatherable minerals and nutrients. The main sources of mineral components in PF are desert and semi-desert regions of central Asia. The snow water concentrations of DIC, Cl, SO₄, Mg, Ca, Cr, Co, Ni, Cu, Mo, Cd, Sb, Cs, W, Pb and U exceeded or were comparable with springtime concentrations in thermokarst lakes of the permafrost-affected WSL zone. The springtime river fluxes of DIC, Cl, SO₄, Na, Mg, Ca, Rb, Cs, metals (Cr, Co, Ni, Cu, Zn, Cd, Pb), metalloids (As, Sb), Mo and U in the discontinuous to continuous permafrost zone (64–68° N) can be explained solely by melting of accumulated snow. The impact of snow deposition on riverine fluxes of elements strongly increased northward, in discontinuous and continuous permafrost zones of frozen peat bogs. This was consistent with the decrease in the impact of rock lithology on river chemical composition in the permafrost zone of the WSL, relative to the permafrost-free regions. Therefore, the present study demonstrates significant and previously underestimated atmospheric input of many major and trace elements to their riverine fluxes during spring floods. A broader impact of this result is that current estimations of river water fluxes response to climate warming in high latitudes may be unwarranted without detailed analysis of winter precipitation.

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 m² 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 2–5 in the continuous permafrost zone, but increase the concentrations of CH₄, DOC, NH₄, Cd, Sb, and Pb by a factor of 2–3. In contrast, the shift of the sporadic to isolated zone may produce a 2–5-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.

Identifying the landscape and climate factors that control nutrient export by rivers in high latitude regions is one of the main challenges for understanding the Arctic Ocean response to ongoing climate change. This is especially true for Western Siberian rivers, which are responsible for a significant part of freshwater and solutes delivery to the Arctic Ocean and are draining vast permafrost-affected areas most vulnerable to thaw. Forty-nine small- and medium-sized rivers (10–100,000 km²) were sampled along a 1700 km long N–S transect including both permafrost-affected and permafrost-free zones of the Western Siberian Lowland (WSL) in June and August 2015. The N, P, dissolved organic and inorganic carbon (DOC and DIC, respectively), particular organic carbon (POC), Si, Ca, K, Fe, and Mn were analyzed to assess the role of environmental parameters, such as temperature, runoff, latitude, permafrost, bogs, lake, and forest coverage on nutrient concentration. The size of the watershed had no influence on nutrient concentrations in the rivers. Bogs and lakes retained nutrients whereas forests supplied P, Si, K, Ca, DIC, and Mn to rivers. The river water temperature was negatively correlated with Si and positively correlated with Fe in permafrost-free rivers. In permafrost-bearing rivers, the decrease in T northward was coupled with significant increases in PO₄, P_tot, NH₄, pH, DIC, Si, Ca, and Mn. North of the permafrost boundary (61° N), there was no difference in nutrient concentrations among permafrost zones (isolated, sporadic, discontinuous, and continuous). The climate warming in Western Siberia may lead to a permafrost boundary shift northward. Using a substituting space for time scenario, this may decrease or maintain the current levels of N, P, Si, K, Ca, DIC, and DOC concentrations in rivers of continuous permafrost zones compared to the present state. As a result, the export flux of nutrients by the small- and medium-sized rivers of the Western Siberian subarctic to the Arctic Ocean coastal zone may remain constant, or even decrease.