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Despite recent progress in the understanding of the carbon (C) cycle of Siberian permafrost-affected rivers, spatial and seasonal dynamics of C export and emission from medium-sized rivers (50 000–300 000 km2 watershed area) remain poorly known. Here we studied one of the largest tributaries of the Ob River, the Ket River (watershed = 94 000 km2), which drains through pristine taiga forest of the boreal zone in the West Siberian Lowland (WSL). We combined continuous and discrete measurements of carbon dioxide (CO2) concentration using submersible CO2 sensor and floating chamber flux (FCO2), with methane (CH4), dissolved organic and inorganic C (DOC and DIC, respectively), particulate organic C and total bacterial concentrations over an 800 km transect of the Ket River main stem and its 26 tributaries during spring flood (May 2019) and 12 tributaries during summer baseflow (end of August–beginning of September 2019). The partial pressure of CO2 (pCO2) was lower and less variable in the main stem (2000 to 2500 µatm) compared to that in the tributaries (2000 to 5000 µatm). In the tributaries, the pCO2 was 40 % higher during baseflow compared to spring flood, whereas in the main stem, it did not vary significantly across the seasons. The methane concentration in the main stem and tributaries was a factor of 300 to 1900 (flood period) and 100 to 150 times lower than that of CO2 and ranged from 0.05 to 2.0 µmol L−1. The FCO2 ranged from 0.4 to 2.4 g C m−2 d−1 in the main channel and from 0.5 to 5.0 g C m−2 d−1 in the tributaries, being highest during August in the tributaries and weakly dependent on the season in the main channel. During summer baseflow, the DOC aromaticity, bacterial number, and needleleaf forest coverage of the watershed positively affected CO2 concentrations and fluxes. We hypothesize that relatively low spatial and seasonal variability in FCO2 of the Ket River is due to a flat homogeneous landscape (bogs and taiga forest) that results in long water residence times and stable input of allochthonous dissolved organic matter (DOM), which dominate the FCO2. The open water period (May to October) C emission from the fluvial network (main stem and tributaries) of the Ket River was estimated to 127 ± 11 Gg C yr−1, which is lower than the downstream dissolved and particulate C export during the same period. The estimated fluvial C emissions are highly conservative and contain uncertainties linked to ignoring hotspots and hot moments of emissions, notably in the floodplain zone. This stresses the need to improve the temporal resolution of FCO2 and water coverage across seasons and emphasizes the important role of WSL rivers in the release of CO2 into the atmosphere.

In contrast to the large number of studies on humic waters from permafrost-free regions and oligotrophic waters from permafrost-bearing regions, the bio- and photolability of DOM from the humic surface waters of permafrost-bearing regions has not been thoroughly evaluated. Following standardized protocol, we measured biodegradation (at low, intermediate and high temperatures) and photodegradation (at one intermediate temperature) of DOM in surface waters along the hydrological continuum (depression → stream → thermokarst lake → Pechora River) within a frozen peatland in European Russia. In all systems, within the experimental resolution of 5 % to 10 %, there was no bio- or photodegradation of DOM over a 1-month incubation period. It is possible that the main cause of the lack of degradation is the dominance of allochthonous refractory (soil, peat) DOM in all waters studied. However, all surface waters were supersaturated with CO2. Thus, this study suggests that, rather than bio- and photodegradation of DOM in the water column, other factors such as peat pore-water DOM processing and respiration of sediments are the main drivers of elevated pCO2 and CO2 emission in humic boreal waters of frozen peat bogs.

In contrast to numerous studies on the dynamics of dissolved ( 0.45 µm) matter (RSM) in these regions. In order to test the effect of climate, permafrost and physio-geographical landscape parameters (bogs, forest and lake coverage of the watershed) on RSM and particulate C, N and P concentrations in river water, we sampled 33 small and medium-sized rivers (10–100 000 km2 watershed) along a 1700 km N–S transect including both permafrost-affected and permafrost-free zones of the Western Siberian Lowland (WSL). The concentrations of C and N in RSM decreased with the increase in river watershed size, illustrating (i) the importance of organic debris in small rivers which drain peatlands and (ii) the role of mineral matter from bank abrasion in larger rivers. The presence of lakes in the watershed increased C and N but decreased P concentrations in the RSM. The C : N ratio in the RSM reflected the source from the deep soil horizon rather than surface soil horizon, similar to that of other Arctic rivers. This suggests the export of peat and mineral particles through suprapermafrost flow occurring at the base of the active layer. There was a maximum of both particulate C and N concentrations and export fluxes at the beginning of permafrost appearance, in the sporadic and discontinuous zone (62–64° N). This presumably reflected the organic matter mobilization from newly thawed organic horizons in soils at the active latitudinal thawing front. The results suggest that a northward shift of permafrost boundaries and an increase in active layer thickness may increase particulate C and N export by WSL rivers to the Arctic Ocean by a factor of 2, while P export may remain unchanged. In contrast, within a long-term climate warming scenario, the disappearance of permafrost in the north, the drainage of lakes and transformation of bogs to forest may decrease C and N concentrations in RSM by 2 to 3 times.

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.

This work describes the hydrochemical composition of thermokarst lake and pond ecosystems, which are observed in various sizes with different degrees of permafrost influence and are located in the northern part of western Siberia within the continuous and discontinuous permafrost zones. We analysed the elemental chemical composition of the lake waters relative to their surface areas (from 10 to 106 m2) and described the elemental composition of the thermokarst water body ecosystems in detail. We revealed significant correlations between the Fe, Al, dissolved organic carbon (DOC) and various chemical elements across a latitude gradient covering approximately 900 km. Several groups of chemical elements that reflect the evolution of the studied water bodies were distinguished. Combining the data for the studied latitude profile with the information available in the current literature demonstrated that the average dissolved elemental concentrations in lakes with different areas depend specifically on the latitudinal position, which is presumably linked to (1) the elements leached from frozen peat, which is the main source of the solutes in thermokarst lakes, (2) marine atmospheric aerosol depositions, particularly near the sea border and (3) short-range industrial pollution by certain metals from the largest Russian Arctic smelter. We discuss the evolution of the chemical compositions observed in thermokarst lakes during their formation and drainage and predict the effect that changing the permafrost regime in western Siberia has on the hydrochemistry of the lakes.

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.

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m−2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.

To examine the mechanisms of carbon mobilization and biodegradation during permafrost thawing and to establish a link between organic carbon (OC) and other chemical and microbiological parameters in forming thermokarst (thaw) lakes, we studied the biogeochemistry of OC and trace elements (TEs) in a chronosequence of small lakes that are being formed due to permafrost thawing in the northern part of western Siberia. Twenty lakes and small ponds of various sizes and ages were sampled for dissolved and colloidal organic carbon, metals and culturable heterotrophic bacterial cell number. We observed a sequence of ecosystems from peat thawing and palsa degradation due to permafrost subsidence in small ponds to large, km-size lakes that are subject to drainage to, finally, the khasyrey (drained lake) formation. There is a systematic evolution of both total dissolved and colloidal concentration of OC and TEs in the lake water along with the chronosequence of lake development that may be directly linked to the microbial mineralization of dissolved organic matter and the liberation of the inorganic components (Fe, Al, and TEs) from the organo-mineral colloids. In this chronosequence of lake development, we observed an apparent decrease in the relative proportion of low molecular weight