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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.

Analysis of organic and inorganic carbon (DOC and DIC, respectively), pH, Na, K, Ca, Mg, Cl, SO4 and Si in ~ 100 large and small rivers (< 10 to ≤ 150 000 km2) of western Siberia sampled in winter, spring, and summer over a more than 1500 km latitudinal gradient allowed establishing main environmental factors controlling the transport of river dissolved components in this environmentally important region, comprising continuous, discontinuous, sporadic and permafrost-free zones. There was a significant latitudinal trend consisting in a general decrease in DOC, DIC, SO4, and major cation (Ca, Mg, Na, K) concentration northward, reflecting the interplay between groundwater feeding (detectable mostly in the permafrost-free zone, south of 60° N) and surface flux (in the permafrost-bearing zone). The northward decrease in concentration of inorganic components was strongly pronounced both in winter and spring, whereas for DOC, the trend of concentration decrease with latitude was absent in winter, and less pronounced in spring flood than in summer baseflow. The most significant decrease in K concentration from the southern (< 59° N) to the northern (61–67° N) watersheds occurs in spring, during intense plant litter leaching. The latitudinal trends persisted for all river watershed size, from < 100 to > 10 000 km2. Environmental factors are ranked by their increasing effect on DOC, DIC, δ13CDIC, and major elements in western Siberian rivers as follows: watershed area < season < latitude. Because the degree of the groundwater feeding is different between large and small rivers, we hypothesize that, in addition to groundwater feeding of the river, there was a significant role of surface and shallow subsurface flow linked to plant litter degradation and peat leaching. We suggest that plant-litter- and topsoil-derived DOC adsorbs on clay mineral horizons in the southern, permafrost-free and discontinuous/sporadic permafrost zone but lacks the interaction with minerals in the continuous permafrost zone. It can be anticipated that, under climate warming in western Siberia, the maximal change will occur in small (< 1000 km2 watershed) rivers DOC, DIC and ionic composition and this change will be mostly pronounced in summer.

Despite relatively good knowledge of the biogeochemistry of Siberian thermokarst lakes during summer base flow, their seasonal dynamics remains almost unexplored. This work describes the chemical composition of ~130 thermokarst lakes ranging in size from a few m2 to several km2, located in the discontinuous permafrost zone. Lakes were sampled during spring flood, just after the ice break (early June), the end of summer (August), the beginning of ice formation (October) and during the full freezing season in winter (February). The lakes larger than 1000 m2 did not exhibit any statistically significant control of the lake size on dissolved organic carbon (DOC), the major and trace element concentrations over three major open water seasons. On the annual scale, the majority of dissolved elements including organic carbon increased their concentration from 30 to 500%, with a statistically significant (p < 0.05) trend from spring to winter. The concentrations of most trace elements (TEs) increased in the order spring > summer > autumn > winter. The ice formation in October included several stages: first, surface layer freezing followed by crack (fissure) formation with unfrozen water from the deeper layers spreading over the ice surface. This water was subsequently frozen and formed layered ice rich in organic matter. As a result, the DOC and metal (Mn, Fe, Ni, Cu, Zn, As, Ba and Pb) concentrations were highest near the surface of the ice column (0 to 20 cm) and decreased by a factor of 2 towards the bottom. The main implications of discovered freeze-driven solute concentrations in thermokarst lake waters are enhanced colloidal coagulation and removal of dissolved organic matter and associated insoluble metals from the water column to the sediments. The measured distribution coefficients of a TE between amorphous organo-ferric coagulates and lake water (2) water bodies in spring suggests their strongly heterotrophic status and, therefore, a potentially elevated CO2 flux from the lake surface to the atmosphere.

During the anomalously hot summer in 2012, surface air temperatures in Western Siberia were 5 to 15 °C higher than those observed during the previous period of > 30 yr. This unusual climate phenomenon provided an opportunity to examine the effects of short-term natural heating of water in thermokarst ponds and lakes in discontinuous permafrost zones and compare these observations to previous field results obtained when the temperature was normal during the summer of 2010 in the same region. In 2012, thermokarst bodies of water shrank significantly, water levels dropped approximately 50 cm in large lakes and small (< 10–100 m2) ponds, and shallow soil depressions disappeared. Based on samples from ~ 40 bodies of water collected previously and in 2012, first-order features of changes in chemical composition in response to increased water temperatures (from 14.1 ± 2.2 to 23.8 ± 2.3 °C in 2010 and 2012, respectively) were established. In these thermokarst bodies of water that covered a full range of surface areas, the average conductivity and pH were almost unchanged, whereas dissolved organic carbon (DOC), Cl- and SO42- concentrations were higher by a factor of ~ 2 during summer 2012 compared to periods with normal temperatures. Similarly, most divalent metals and insoluble trivalent and tetravalent elements were more concentrated by a factor of 1.7–2.4 in the summer of 2012 than normal periods. The average concentrations of dissolved CO2 and CH4 during the hot summer of 2012 increased by factors of 1.4 and 4.9, respectively. For most of the trace elements bound to colloids, the degree of colloidal binding decreased by a factor of 1.44 ± 0.33 (for an average of 40 elements) during the hot summer of 2012 compared to normal periods. Increases in CO2 and CH4 concentrations with the decreasing size of the body of water were well-pronounced during the hot summer of 2012. The concentrations of CO2 and CH4 rose by factors of 5 and 150, respectively, in small (≤ 102 m2) compared to large (≥ 104 m2) thermokarst (thaw) lakes. Taken together, these trends suggest that, for a conservative scenario of lake size distribution, lake water warming at high latitudes will produce (1) a significant increase in methane emission capacity from thaw lake surfaces; (2) decreased molecular sizes of trace element complexes and potential bioavailability of metal micronutrients in water columns; and (3) relatively conservative responses by CO2, DOC and trace element concentrations.