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In order to foresee the impact of permafrost thaw on CO 2 emissions by high-latitude rivers, in-situ measurements across a permafrost and climate/vegetation gradient, coupled with assessment of possible physico-chemical and landscape controlling factors are necessary. Here we chose 34 catchments of variable stream order (1 to 9) and watershed size (1 to >10 5  km 2 ) located across a permafrost and biome gradient in the Western Siberian Lowland (WSL), from the permafrost-free southern taiga to the continuous permafrost zone of tundra. Across the south-north transect, maximal CO 2 emissions (2.2 ± 1.1 g C-CO 2 m -2 d -1 ) occurred from rivers of the discontinuous/sporadic permafrost zone, i.e., geographical permafrost thawing boundary. In this transitional zone, fluvial C emission to downstream export ratio was as high as 8.0, which greatly (x 10) exceeded the ratio in the permafrost free and continuous permafrost zones. Such a high evasion at the permafrost thawing front can stem from an optimal combination of multiple environmental factors: maximal active layer thickness, sizable C stock in soils, and mobilization of labile organic nutrients from dispersed peat ice that enhanced DOC and POC processing in the water column, likely due to priming effect. Via a substituting space for time approach, we foresee an increase in CO 2 and CH 4 fluvial evasion in the continuous and discontinuous permafrost zone, which is notably linked to the greening of tundra increases in biomass of the riparian vegetation, river water warming and thermokarst lake formation on the watershed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Humic thermokarst lakes of permafrost peatlands in Western Siberia Lowland (WSL) are major environmental controllers of carbon and nutrient storage in inland waters and greenhouse gases emissions to the atmosphere in the subarctic. In contrast to sizable former research devoted to hydrochemical and hydrobiological (phytoplankton) composition, zooplankton communities of these thermokarst lakes and thaw ponds remain poorly understood, especially along the latitudinal gradient, which is a perfect predictor of permafrost zones. To fill this gap, 69 thermokarst lakes of the WSL were sampled using unprecedented spatial coverage, from continuous to sporadic permafrost zone, in order to assess zooplankton (Cladocera, Copepoda, Rotifera) diversity and abundance across three main open water physiological seasons (spring, summer and autumn). We aimed at assessing the relationship of environmental factors (water column hydrochemistry, nutrients, and phytoplankton parameters) with the abundance and diversity of zooplankton. A total of 74 zooplankton species and taxa were detected, with an average eight taxa per lake/pond. Species richness increased towards the north and reached the maximum in the continuous permafrost zone with 13 species found in this zone only. In contrast, the number of species per waterbody decreased towards the north, which was mainly associated with a decrease in the number of cladocerans. Abundance and diversity of specific zooplankton groups strongly varied across the seasons and permafrost zones. Among the main environmental controllers, Redundancy Analysis revealed that water temperature, lake area, depth, pH, Dissolved Inorganic and Organic Carbon and CO 2 concentrations were closely related to zooplankton abundance. Cladocerans were positively related to water temperature during all seasons. Copepods were positively related to depth and lake water pH in all seasons. Rotifers were related to different factors in each season, but were most strongly associated with DOC, depth, CH 4 , phytoplankton and cladoceran abundance. Under climate warming scenario, considering water temperature increase and permafrost boundary shift northward, one can expect an increase in the diversity and abundance of cladocerans towards the north which can lead to partial disappearance of copepods, especially rare calanoid species., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Despite the importance of structural control on metal stable isotope fractionation in inorganic and abiotic systems, the link between metal structural changes and related isotopic fractionation during reactions with organic surfaces and live cells remains poorly established. We conducted reversible adsorption of Fe(II) and Fe(III) on the surface of exopolysaccharide (EPS)-rich and EPS-poor Pseudomonas aureofaciens , and we allowed Fe intracellular uptake by growing cells. We analyzed the Fe isotopic composition of the remaining fluid and cell biomass, and compared the isotopic fractionation during adsorption and assimilation reaction with relative changes in Fe structural status between aqueous solution and bacterial cells, based on available and newly collected X-ray absorption spectroscopy (XAS) observations. Iron(III) adsorption onto P. aureofaciens at 2.8 ≤ pH ≤ 6.0 produced an enrichment of the cell surface in heavier isotopes with Δ 57 Fe cell-solution ranging from +0.7 to +2.1‰, without a link to pH in EPS-rich cultures. In contrast, the magnitude of isotopic fractionation increased with pH in EPS-poor cultures. Iron(II) adsorption produced an even larger enrichment of the cell surface in heavier isotopes, by up to 3.2‰, tentatively linked to Fe(III) hydroxide precipitation. Intracellular assimilation of Fe(II) favored heavier isotopes and led to Δ 57 Fe cell-solution of +0.8‰. In addition, Fe(III) cellular uptake produced an enrichment of the bacterial biomass in lighter isotopes with Δ 57 Fe cell-solution of -1‰. The XAS analyses demonstrated the dominance of Fe(III)-phosphate complexes both at the cell surface and in the cell interior. We suggest that heavier isotope enrichment of the cell surface relative to the aqueous solution is due to strong Fe(III)-phosphoryl surface complexes and Fe complexation to ligands responsible for metal transfer from the surface to the inner cell. In case of Fe(II) adsorption or assimilation, its partial oxidation within the cell compartments may lead to cell enrichment in heavier isotopes. In contrast, loss of symmetry of assimilated Fe(III) relative to the aqueous Fe 3+ ion and longer bonds of intracellular ions relative to aqueous Fe(III)-citrate or hydroxo-complexes could produce an enrichment of cells in lighter isotopes. The versatile nature of Fe(II) and Fe(III) fractionation without a distinct effect of pH and surface exopolysaccharide coverage suggests that, in natural soil and sedimentary environments, Fe isotope fractionation during interaction with heterotrophic bacteria will be primarily governed by Fe complexation with DOM and Fe redox status in the soil pore water.

High altitude (alpine) lakes are efficient sentinels of environmental processes, including local pollution and long-range atmospheric transfer, because these lakes are highly vulnerable to ongoing climate changes and increasing anthropogenic pressure. Towards improving the knowledge of trace element geochemistry in the water column of alpine lakes, we assessed 64 physico-chemical parameters, including macro- and micronutrients, major and trace element concentrations in the water column of 18 lakes in the Pyrenees, located along the border between France and Spain. Lake depth, morphology, retention time and watershed rock lithology did not exhibit sizable impact on major and trace element concentrations in the water column. However, acidic (pH = 4.7 ± 0.2) lakes were distinctly different from circumneutral lakes (pH = 6.8 ± 0.5) as they exhibited >10 times higher concentrations of SO 4 2- and trace metals (Fe, Mn, Zn, Cd, Pb, Co, Ni, Be, Al, Ga and REEs). While some of these elements clearly mark the presence of sulphide-rich minerals within the watershed (Fe, Zn, Cd and Pb), the increased mobility of lithogenic elements (Be, Al, Ga and REEs) in acidic lakes may reflect the leaching of these elements from silicate dust derived from atmospheric deposits or surrounding granites. At the same time, compared to circumneutral lakes, acidic lake water displayed lower concentrations of dissolved oxyanions (As, Mo, V, B and W) and elevated SO 4 2- concentrations. The latter could lead to efficient Ba removal from the water column. The exploitation of metal ores within the watershed of three lakes clearly impacted high Zn and Cd concentrations observed in their water column, despite two of these lakes not being acidic. We conclude that local impacts have a greater effect on the water column than long-range atmospheric inputs and that dissolved trace element concentration measurements can be used for revealing sulphide-rich minerals or acid mine drainage within the lakes' watershed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Within a global warming trend, invasive cyanobacteria, abundant in tropical and temperate regions, can migrate northward and colonize thermokarst lakes in permafrost-affected territories. For a better understanding of the cyanobacterial proliferation mechanism in those lakes, we performed laboratory growth of typical invasive cyanobacteria, Microcystis aeruginosa , onto various organic-rich solutions representative of permafrost peatlands. Aqueous leachates of lichen, moss and peat were the most favorable substrates for massive growth. The growth in the presence of all organic substrates produced an increase in solution pH by two units and a sizable (30-50%) decrease in the concentration of dissolved organic carbon. The observed increase in the dissolved organic carbon aromaticity degree likely reflected preferential cyanobacterial uptake of aliphatic, optically transparent organic substances. Cyanobacterial growth over a bloom period can create a carbon sink (uptake of 2.5 and 8.3 g C-CO 2 m -2 d -1 ) that can offset the net heterotrophic status of thermokarst lakes in permafrost peatlands, thus switching the lake status from a C source to a C sink. Therefore, predictions of future carbon exchanges with the atmosphere in surface waters of permafrost peatlands require explicit accounting for the possibility of invasive cyanobacterial growth.

Despite the importance of small and medium size rivers of Siberian boreal zone in greenhouse gases (GHG) emission, major knowledge gaps exist regarding its temporal variability and controlling mechanisms. Here we sampled 11 pristine rivers of the southern taiga biome (western Siberia Lowland, WSL), ranging in watershed area from 0.8 to 119,000 km 2 , to reveal temporal pattern and examine main environmental controllers of GHG emissions from the river water surfaces. Floating chamber measurements demonstrated that CO 2 emissions from water surface decreased by 2 to 4-folds from spring to summer and autumn, were independent of the size of the watershed and stream order and did not exhibit sizable (>30 %, regardless of season) variations between day and night. The CH 4 concentrations and fluxes increased in the order "spring ≤ summer < autumn" and ranged from 1 to 15 μmol L -1 and 5 to 100 mmol m -2 d -1 , respectively. The CO 2 concentrations and fluxes (range from 100 to 400 μmol L -1 and 1 to 4 g C m -2 d -1 , respectively) were positively correlated with dissolved and particulate organic carbon, total nitrogen and bacterial number of the water column. The CH 4 concentrations and fluxes were positively correlated with phosphate and ammonia concentrations. Of the landscape parameters, positive correlations were detected between riparian vegetation biomass and CO 2 and CH 4 concentrations. Over the six-month open-water period, areal emissions of C (>99.5 % CO 2 ; <0.5 % CH 4 ) from the watersheds of 11 rivers were equal to the total downstream C export in this part of the WSL. Based on correlations between environmental controllers (watershed land cover and the water column parameters), we hypothesize that the fluxes are largely driven by riverine mineralization of terrestrial dissolved and particulate OC, coupled with respiration at the river bottom and riparian sediments. It follows that, under climate warming scenario, most significant changes in GHG regimes of western Siberian rivers located in permafrost-free zone may occur due to changes in the riparian zone vegetation and water coverage of the floodplains., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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 <3 kDa ) fractions of DOC, and major and trace elements in the porewater and ice of 5 peat cores sampled along a 400 km permafrost and climate gradient in the largest peatland in the world, the Western Siberian Lowland (WSL). We discovered that the strong (a factor of 2 to 10) increase in the total dissolved (<0.45 μm) concentration of DOC and most major and trace elements in the peat ice relative to the peat porewater from the thawed layer was essentially linked to an increase in the LMW <3 kDa fraction. This increase in the potentially bioavailable fraction in the peat ice relative to the porewater was especially pronounced for DOC, P and many trace elements including metal micronutrients, and was observed throughout all permafrost zones. This contrasted with element distribution in the upper (thaw) layer, where the majority of these elements were present in the colloidal pool. Following previous experiments on permafrost peatland surface waters, we hypothesized that the freeze-thaw cycles of peat porewater were responsible for generation of the LMW fraction in the bottom part of the peat core. Results of this study demonstrate that carbon, and macro- and micro-nutrients as well as trace metals in ground ice of permafrost peatlands are essentially present in a low molecular weight (<3 kDa) and potentially bioavailable form that can strongly impact the riverine export fluxes of solutes during permafrost thaw.

The biomineralization of CO 2 , in the form of carbonate minerals, is considered as one of the efficient solutions of atmospheric CO 2 removal, allowing stable and sustainable storage of this greenhouse gas. Cyanobacteria are among the most powerful microorganisms capable of precipitating carbonate minerals, both in the present and in the past. In the modern environments, high Si concentration during geoengineering biomineralization could occur due to dissolution of Mg-bearing primary silicates such as olivine. However, most of experimental studies aimed to understand the formation of these carbonates were performed in Si-poor solutions. Thus, experimental characterizations of the nature, rate, and stoichiometry of precipitated minerals in Si-rich solutions in the presence of bacteria are lacking. The present study attempted to reproduce, in controlled laboratory experiments, the processes of biomineralization in a carbonate- and Mg-bearing medium having high Si concentrations (2-4 mM, which is below the saturation with respect to amorphous silica). These experiments have been carried out in the presence of three contrasting cyanobacteria: Synechococcus sp., Chroococcidiopsis sp. and Aphanothece clathrata in order to characterize the rate of formation, stoichiometry and mineralogical nature of precipitates. The results demonstrated significant role of cyanobacteria in the precipitation of carbonate and silicate minerals by increasing the pH of the medium during photosynthesis. Magnesium precipitation rates measured between 50 and 150 h of reaction time ranged from 0.05 to 0.5 mmol h -1 g dry 1 and decreased (Synechococcus sp. and Chroococcidiopsis sp.) or increased (A. clathrata) with an increase in the Si:Mg ratio in solution. The abiotic instantaneous rates of Mg and Si removal from alkaline solutions were similar to those in the presence of cyanobacteria at the same pH value suggesting that photosynthetically induced pH rise was the main factor of mineral formation. The transmission electron microscopy (TEM) and spectroscopic observations and associated analyses identified an amorphous magnesium silicate together with hydrous Mg carbonates (hydromagnesite). The formation of carbonate solid phase at high Mg: Si ratios indicated the potential for the removal of inorganic carbon at pH > 10. The difference in the degree of C removal between different species was primarily linked to different degree of pH rise during photosynthesis. Taken together, the results obtained in this study allowed an efficient reproduction of combined magnesium hydroxo-carbonates and hydrous silicates precipitation under cyanobacterial activity, suitable for geoengineering of biologically controlled CO 2 sequestration in Si-Mg-carbonate-bearing solutions., (© 2022 John Wiley & Sons Ltd.)

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 km 2 ) 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Despite the importance of soil and surface waters freezing in permafrost landscapes, the behaviour of dissolved organic carbon (DOC), nutrients and metals during periodic freeze-thaw cycles (FTC) remains poorly known. The on-going 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 h 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, SUVA 254 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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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, CO 2 , 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 CO 2 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 pCO 2 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 CO 2 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., Competing Interests: Declaration of competing interest We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no significant financial support for this work that could have influenced its outcome., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The chemical composition of thermokarst lake ecosystem components is a crucial indicator of current climate change and permafrost thaw. Despite high importance of macrophytes in shallow permafrost thaw lakes for control of major and trace nutrients in lake water, the trace element (TE) partitioning between macrophytes and lake water and sediments in the permafrost regions remains virtually unknown. Here we sampled dominant macrophytes in thermokarst lakes of discontinuous and continuous permafrost zones in the Western Siberia Lowland (WSL) and measured major and trace elements in plant biomass, lake water, lake sediments and sediment porewater. All six plant species (Hippuris vulgaris L., Glyceria maxima (Hartm.) Holmb., Comarum palustre L., Ranunculus spitzbergensis Hadac, Carex aquatilis Wahlenb s. str., Menyanthes trifoliata L.) sizably accumulated macronutrients (Na, Mg, Ca), micronutrients (B, Mo, Nu, Cu, Zn, Co) and toxicants (As, Cd). Accumulation of other trace elements, including rare earth elements (REE), in macrophytes relative to pore waters and sediments was highly variable among species. Using miltiparametric statistics, we described the behavior of ТЕ across two permafrost zones and identified several group of elements depending on their sources in the lake ecosystems and their affinity to sediments and macrophytes. Under future climate warming and shifting the permafrost border to the north, we anticipate an increasing uptake of heavy metals and lithogenic low mobile elements such as Ti, Al, Cr, As, Cu, Fe, Ni, Ga, Zr, and REEs by macrophytes in the discontinuous permafrost zone and Ba, Zn, Pb and Cd in the continuous permafrost zone. This may eventually diminish transport of metal micronutrients and geochemical tracers from soils to lakes and rivers and further to the Arctic Ocean., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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 (BDOC 15 ; % 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 BDOC 15 increased, the removal rate of DOC decreased along the hydrological continuum. The potential maximum CO 2 production from DOC biodegradation was estimated to account for only a small part of in-situ CO 2 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 CO 2 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Despite the importance of surface waters of permafrost landscapes in carbon (C) emission and dissolved C and metal storage and export, the majority of available observations in high latitude aquatic systems deal with punctual or seasonal sampling without accounting for diurnal variations in temperature and primary productivity-respiration cycles. Towards providing comprehensive understanding of diel variations in CO 2 emission, organic C and element concentrations in lakes of frozen peatlands, we monitored, each 2 h over 2 days, the water temperature, pH, CO 2 fluxes, CO 2 , CH 4 , dissolved organic and inorganic carbon (DOC and DIC, respectively), nutrients, carboxylic acids, bacterial number, and major and trace elements in two acidic (pH = 3.6 and 4.0) and humic (DOC = 15 and 35 mg L -1 ) thermokarst lakes of discontinuous permafrost zone in Western Siberia. We discovered a factor of 2 to 3 higher CO 2 concentrations and fluxes during the night compared to daytime in the high-DOC lake. The emission fluxes in the low-DOC lake increased from zero to negative values during the day to highly positive values during the end of night and early morning. The methane concentration varied within a factor of 5 without any link to the diurnal cycle. The bulk of dissolved (< 0.45 μm) hydrochemical parameters remained highly stable with ±10% variation in concentration over 2 days of observation (DOC, DIC, SUVA 254nm , carboxylates (formate, oxalate, puryvate and glutarate), Mn, Fe, Al, other trace elements). Concentrations of Si, P, K, Cu varied within ±20% whereas those of Zn and Ni ranged by a factor of 2 to 4 without any link to diurnal pattern. Overall, the impact of diel cycle on CH 4 , DOC, nutrient and metal concentration was below 10%. However, neglecting night-time period may underestimate net CO 2 emission by ca. 30 to 50% in small organic-rich thaw ponds and switch the CO 2 exchange from uptake/zero to net emission in larger thermokarst lakes. Given the dominance of large lakes in permafrost regions, the global underestimation of the emission flux may be quite high. As such, monitoring CO 2 concentrations and fluxes in thermokarst lakes during months of extended night time (August to October) is mandatory for assessing the net emissions from lentic waters of frozen peatlands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Biodegradation and photolysis of dissolved organic matter (DOM) in boreal high-latitude waters are the two main factors controlling not only the aquatic fluxes and residence time of carbon but also metal nutrients associated with DOM such as Fe. The DOM is usually present in the form of organic and organomineral colloids, which also account for the majority of dissolved Fe. Here, we use the stable Fe isotope approach to unravel the processes controlling Fe behavior during bio- and photodegradation of colloids in boreal Fe- and DOM-rich humic waters (a stream and a fen). The adsorption of Fe colloids onto heterotrophic bacteria Pseudomonas aureofaciens produced enrichment in +0.4‰ (δ 57 Fe) in the heavier isotopes of the cell surface relative to the remaining solution. In contrast, long-term assimilation of Fe by live cells yielded preferential incorporation of lighter isotopes into the cells (-0.7‰ relative to aqueous solution). The sunlight-induced oxidation of Fe(II) in fen water led to the removal of heavier Fe isotopes (+1.5 to +2.5‰) from solution, consistent with Fe(III) hydroxide precipitation from Fe(II)-bearing solution. Altogether, bio- and photodegradation of organoferric colloids, occurring within a few days of exposure time, can produce several per mil isotopic excursions in shallow lentic and lothic inland waters of high-latitude boreal regions. Considerable daily scale variations of Fe isotopic composition should therefore be taken into account during the interpretation of the riverine flux of Fe isotopes to the ocean or tracing weathering processes using Fe isotopes in surface waters at high latitudes.

Little is known about the sources and processing of selenium, an important toxicant and essential micronutrient, within boreal and sub-arctic environments. Upon climate warming and permafrost thaw, the behavior of Se in northern peatlands becomes an issue of major concern, because a sizable amount of Se can be emitted to the atmosphere from thawing soils and inland water surfaces and exported to downstream waters, thus impacting the Arctic biota. Working toward providing a first-order assessment of spatial and temporal variation of Se concentration in thermokarst waters of the largest frozen peatland in the world, we sampled thaw lakes and rivers across a 750-km latitudinal profile. This profile covered sporadic, discontinuous, and continuous permafrost regions of western Siberia Lowland (WSL), where we measured dissolved (<0.45 μm) Se concentration during spring (June), summer (August), and autumn (September). We found maximum Se concentration in the discontinuous permafrost zone. Considering all sampled lakes, Se exhibited linear relationship ( R 2 = 0.7 to 0.9, p < 0.05, n ≈ 70) with dissolved organic carbon (DOC) concentration during summer and autumn. Across the permafrost gradient, the lakes in discontinuous permafrost regions demonstrated stronger relationship with DOC and UV-absorbance compared to lakes in sporadic/isolated and continuous permafrost zones. Both seasonal and spatial features of Se distribution in thermokarst lakes and ponds suggest that Se is mainly released during thawing of frozen peat. Mobilization and immobilization of Se within peat-lake-river watersheds likely occurs as organic and organo-Fe, Al colloids, probably associated with reduced and elemental Se forms. The increase of active layer thickness may enhance leaching of Se in the form of organic complexes with aromatic carbon from the deep horizons of the peat profile. Further, the northward shift of permafrost boundaries in WSL may sizably increase Se concentration in lakes of continuous permafrost zone.

Soil pore waters are a vital component of the ecosystem as they are efficient tracers of mineral weathering, plant litter leaching, and nutrient uptake by vegetation. In the permafrost environment, maximal hydraulic connectivity and element transport from soils to rivers and lakes occurs via supra-permafrost flow (i.e. water, gases, suspended matter, and solutes migration over the permafrost table). To assess possible consequences of permafrost thaw and climate warming on carbon and Green House gases (GHG) dynamics we used a "substituting space for time" approach in the largest frozen peatland of the world. We sampled stagnant supra-permafrost (active layer) waters in peat columns of western Siberia Lowland (WSL) across substantial gradients of climate (-4.0 to -9.1°C mean annual temperature, 360 to 600mm annual precipitation), active layer thickness (ALT) (>300 to 40cm), and permafrost coverage (sporadic, discontinuous and continuous). We analyzed CO 2 , CH 4 , dissolved carbon, and major and trace elements (TE) in 93 soil pit samples corresponding to several typical micro landscapes constituting the WSL territory (peat mounds, hollows, and permafrost subsidences and depressions). We expected a decrease in intensity of DOC and TE mobilization from soil and vegetation litter to the supra-permafrost water with increasing permafrost coverage, decreasing annual temperature and ALT along a latitudinal transect from 62.3°N to 67.4°N. However, a number of solutes (DOC, CO 2 , alkaline earth metals, Si, trivalent and tetravalent hydrolysates, and micronutrients (Mn, Co, Ni, Cu, V, Mo) exhibited a northward increasing trend with highest concentrations within the continuous permafrost zone. Within the "substituting space for time" climate change scenario and northward shift of the permafrost boundary, our results suggest that CO 2 , DOC, and many major and trace elements will decrease their concentration in soil supra-permafrost waters at the boundary between thaw and frozen layers. As a result, export of DOC and elements from peat soil to lakes and rivers of the WSL (and further to the Arctic Ocean) may decrease., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Photo-induced degradation of dissolved organic matter (DOM) and organo-mineral colloids is one of the major factor responsible for transformation of DOM and dissolved metals in boreal and subarctic waters. In contrast to fairly good understanding of this process in inland waters of high latitude zone, the transformation of riverine DOM and associated trace element (TE) colloids in the Arctic estuaries remains virtually unknown. We incubated, under sunlight in outdoor pools, quartz reactors filled with mixtures of sterile filtered riverine and estuarine water. The water samples were collected in the estuarine zone of the largest European Arctic river, Severnaya Dvina. After 1month of exposure to sunlight, ≤5% change of dissolved organic carbon (DOC) concentration and specific ultraviolet (254nm) absorption occurred. This decrease was within the experimental uncertainty and it implies quite high resistance of river dissolved organic matter to photo-degradation in this estuary. Moreover, very low photodegradability of DOM in the freshwater point of the Severnaya Dvina River may require revisiting the current paradigm of the importance of DOC photolysis in large Arctic rivers. A novel finding was that the percentages of overall removal of Fe and some insoluble elements were quite similar across the full range of studied salinities, whereas the apparent rate of metal removal decreased with the increase of salinity. Overall, the salinity weakly impacted the removal of riverine DOC and metals in the estuarine water via photolysis and coagulation under sunlight. As a result, photoreactivity of DOM and dissolved metals in riverine end members corrected for estuarine dilution can be used to approximate the photolytic transformation of riverine material in the Arctic coastal zone., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The heterotrophic mineralization of dissolved organic matter (DOM) controls the CO 2 flux from the inland waters to the atmosphere, especially in the boreal waters, although the mechanisms of this process and the fate of trace metals associated with DOM remain poorly understood. We studied the interaction of culturable aquatic (Pseudomonas saponiphila) and soil (Pseudomonas aureofaciens) Gammaproteobacteria with seven different organic substrates collected in subarctic settings. These included peat leachate, pine crown throughfall, fen, humic lake, stream, river, and oligotrophic lake with variable dissolved organic carbon (DOC) concentrations (from 4 to 60mgL -1 ). The highest removal of DOC over 4days of reaction was observed in the presence of P. aureofaciens (33±5%, 43±3% and 53±7% of the initial amount in fen water, humic lake and stream, respectively). P. saponiphila degraded only 5% of DOC in fen water but did not affect all other substrates. Trace elements (TE) were essentially controlled by short-term (0-1h) adsorption on the surface of cells. Regardless of the nature of organic substrate and the identity of bacteria, the degree of adsorption ranged from 20 to 60% for iron (Fe 3+ ), 15 to 55% for aluminum (Al), 10 to 60% for manganese (Mn), 10 to 70% for nickel (Ni), 20 to 70% for copper (Cu), 10 to 60% for yttrium (Y), 30 to 80% for rare earth elements (REE), and 15 to 50% for uranium (U VI ). Rapid adsorption of organic and organo-mineral colloids on bacterial cell surfaces is novel and potentially important process, which deserves special investigation. The long-term removal of dissolved Fe and Al was generally consistent with solution supersaturation degree with respect to Fe and Al hydroxides, calculated by visual Minteq model. Overall, the biomass-normalized biodegradability of various allochthonous substrates by culturable bacteria is much lower than that of boreal DOM by natural microbial consortia., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Thaw of frozen peat in discontinuous permafrost zone produces a significant number of thermokarst lakes, which are known to contribute to Green House Gases (GHG) emission in the atmosphere. In palsa peatland of western Siberia, the thermokarst lake formation includes soil subsidences, lichen submergence and peat abrasion, leading to lateral spreading of the lake border, often intensified by ground fires. Mesocosm experiments were conducted during 3weeks on two thermokarst lake waters interacting in 30-L tanks with surface horizon of peat, the dominant ground vegetation (lichen Cladonia sp.) and the ash produced by lichen burning at 450°C. The obtained results allowed a better understanding of physico-chemical factors controlling the enrichment of thermokarst lake water in organic carbon and metals, and evaluating CO 2 sequestration/emission potential. The changes of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC), major element and divalent metal concentration in response to peat and lichen biomass addition were less than a factor of 2 over full duration of the experiment. Iron (Fe) concentration in the lake water decreased by a factor of 2 to 3 after the addition of peat and lichen biomass. The concentration of low-soluble trivalent and tetravalent hydrolysates decreased by ca. 30 to 50%, presumably due to their co-precipitation with Fe hydroxide. The dissolved carbon dioxide (CO 2 ) in tank with lichen increased by a factor of 5.5±0.5, likely due to respiration of algal component in closed environment. Strong enrichment of the lake water in DIC, P, K, Ca, Mg, Si, Al, Ti, Mn, Mo, Rb, As, Sb and U upon the ash addition persisted over full duration of experiments and was significant (p<0.0001) compared to peat and lichen biomass treatments. These elements may serve as indicators of ground fire impact on thermokarst lake water's chemistry. The overall effect of ash leaching on aquatic ecosystems after ground fire of frozen Siberian peatland is predicted to be much stronger than that currently recognized for non-permafrost regions., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The adsorption of Zn onto the humic and illuvial horizons of the podzol soil in the presence of soil bacteria was studied using a batch-reactor technique as a function of the pH (from 2 to 9) and the Zn concentration in solution (from 0.076mM to 0.760mM). Exopolysaccharides-forming aerobic heterotrophs Pseudomonas aureofaciens were added at 0.1 and 1.0gwetL(-1) concentrations to two different soil horizons, and Zn adsorption was monitored as a function of the pH and the dissolved-Zn concentration. The pH-dependent adsorption edge demonstrated more efficient Zn adsorption by the humic horizon than the mineral horizon at otherwise similar soil concentrations. The Zn adsorption onto the EPS-poor strain was on slightly lower than that onto EPS-rich bacteria. Similar differences in the adsorption capacities between the soil and bacteria were also detected by "langmuirian" constant-pH experiments conducted in soil-Zn and bacteria-Zn binary systems. The addition of 0.1gwetL(-1)P. aureofaciens to a soil-bacteria system (4gdryL(-1)soil) resulted in statistically significant decrease in the adsorption yield, which was detectable from both the pH-dependent adsorption edge and the constant-pH isotherm experiments. Increasing the amount of added bacteria to 1gwetL(-1) further decreased the overall adsorption in the full range of the pH. This decrease was maximal for the EPS-rich bacteria and minimal for the EPS-poor bacteria (a factor of 2.8 and 2.2 at pH=6.9, respectively). These observations in binary and ternary systems were further rationalized by linear-programming modeling of surface equilibria that revealed the systematic differences in the number of binding sites and the surface-adsorption constant of zinc onto the two soil horizons with and without bacteria. The main finding of this work is that the adsorption of Zn onto the humic soil-bacteria system is lower than that in pure, bacteria-free soil systems. This difference is statistically significant (p<0.05). As such, EPS-rich bacteria are capable of efficiently shielding the soil particles from heavy-metal adsorption. The removal efficiency of heavy metals in an abiotic organic-rich soil system should therefore be significantly higher than that in the presence of bacteria. This effect can be explained by the shielding of strongly bound metal sites on the organic-rich soil particles by inert bacterial exopolysaccharides., (Copyright © 2014 Elsevier Inc. All rights reserved.)

The colloidal distribution and size fractionation of organic carbon (OC), major elements and trace elements (TE) were studied in a seasonally stratified, organic-rich boreal lake, Lake Svyatoe, located in the European subarctic zone (NW Russia, Arkhangelsk region). This study took place over the course of 4 years in both winter and summer periods using an in situ dialysis technique (1 kDa, 10 kDa and 50 kDa) and traditional frontal filtration and ultrafiltration (5, 0.22 and 0.025 μm). We observed a systematic difference in dissolved elements and colloidal fractions between summer and winter periods with the highest proportion of organic and organo-ferric colloids (1 kDa-0.22 μm) observed during winter periods. The anomalously hot summer of 2010 in European Russia produced surface water temperatures of approximately 30°C, which were 10° above the usual summer temperatures and brought about crucial changes in element speciation and size fractionation. In August 2010, the concentration of dissolved organic carbon (DOC) decreased by more than 30% compared to normal period, while the relative proportion of organic colloids decreased from 70-80% to only 20-30% over the full depth of the water column. Similarly, the proportion of colloidal Fe decreased from 90-98% in most summers and winters to approximately 60-70% in August 2010. During this hot summer, measurable and significant (>30% compared to other periods) decreases in the colloidal fractions of Ca, Mg, Sr, Ba, Al, Ti, Ni, As, V, Co, Y, all rare earth elements (REEs), Zr, Hf, Th and U were also observed. In addition, dissolved (<0.22 μm) TE concentrations decreased by a factor of 2 to 6 compared to previously investigated periods. The three processes most likely responsible for such a crucial change in element biogeochemistry with elevated water temperature are 1) massive phytoplankton bloom, 2) enhanced mineralization (respiration) of allochthonous dissolved organic matter by heterotrophic aerobic bacterioplankton and 3) photo-degradation of DOM and photo-chemical liberation of organic-bound TE. While the first process may have caused significant decreases in the total dissolved concentration of micronutrients (a factor of 2 to 5 for Cr, Mn, Fe, Ni, Cu, Zn and Cd and a factor of >100 for Co), the second and third factors could have brought about the decrease of allochthonous DOC concentration as well as the concentration and proportion of organic and organo-mineral colloidal forms of non-essential low-soluble trace elements present in the form of organic colloids (Al, Y, Ti, Zr, Hf, Th, Pb, all REEs). It can be hypothesized that climate warming in high latitudes capable of significantly raising surface water temperatures will produce a decrease in the colloidal fraction of most trace elements and, as a result, an increase in the most labile low molecular weight LMW(<1 kDa) fraction., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This work describes variation of element concentration in surface water of a subarctic organic-rich lake during the diurnal cycle of photosynthesis. An unusually hot summer 2010 in European part of subarctic Russia produced elevated surface water temperature (28-30 °C) and caused massive cyanobacterial bloom. Diurnal variation of ~40 dissolved macro and trace elements and organic carbon were recorded in the humic Lake Svyatoe in the White Sea drainage basin. Two days continuous measurements with 3 h sampling steps at the surface (0.5 m) allowed tracing cyanobacterial activity via pH and O₂ measurement and revealed constant concentrations (within ±20-30%) of all major elements (Na, Mg, Cl, SO₄, K, Ca), organic and inorganic carbon and most trace elements (Li, B, Sc, Ti, Ni, Cu, Ga, As, Rb, Sr, Y, Zr, Mo, Sb, medium and heavy REEs, Hf, Pb, Th, U). The concentration of Mn demonstrated a factor of 3 decrease during the day following Mn adsorption onto cyanobacterial cells due to ~1 pH unit raise during the photosynthesis and Mn release during the night due to desorption from the cell surface. The role of Mn(II) photo-oxidation by reactive oxygen species could be also pronounced, although its contribution to Mn diurnal variation was much smaller than the adsorption at the cell surfaces. Similar pattern, but with much lesser variations (c.a., 10-20%), was recorded for Ba and Fe. On-site ultrafiltration technique allowed to distinguish between low molecular weight (LMW) complexes (<1 kDa) and high molecular weight (HMW) colloids (1 kDa-0.22 μm) and to assess their diurnal pattern. Colloidal Al and Fe were the highest during the night, when the contribution of HMW allochthonous colloids was maximal. Typical insoluble trivalent and tetravalent elements exhibited constant complexation (>80-90%) with HMW allochthonous organics, independent on the diel photosynthetic cycle. Finally, biologically-relevant metals (Cu, Co, Cr, V, and Ni) demonstrated significant variations of colloidal fractions (from 10 to 60%) not directly related to the photosynthesis. The majority of possible metal nutrients, being strongly associated with organic and organo-mineral colloids do not exhibit any measurable concentration variation during photosynthesis. The two types of element behavior during cyanobacterial bloom in the water column--constant concentration and sinusoidal variations--likely depend on element speciation in solution and their relative affinity to surfaces of aquatic microorganisms and complexation with authochthonous and allochthonous organic matter., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Copper adsorption on the surface and intracellular uptake inside the cells of four representative taxons of soil and aquatic micro-organisms: aerobic rhizospheric heterotrophs (Pseudomonas aureofaciens), anoxygenic (Rhodovulum steppense) and oxygenic (cyanobacteria Gloeocapsa sp. and freshwater diatoms Navicula minima) phototrophs were studied in a wide range of pH, copper concentration, and time of exposure. Chemical status of adsorbed and assimilated Cu was investigated using in situ X-ray absorption spectroscopy. In case of adsorbed copper, XANES spectra demonstrated significant fractions of Cu(I) likely in the form of tri-coordinate complexes with O/N and/or S ligands. Upon short-term reversible adsorption at all four studied micro-organisms' cell surface, Cu(II) is coordinated by 4.0 ± 0.5 planar oxygens at an average distance of 1.97 ± 0.02 Å, which is tentatively assigned to the carboxylate groups. The atomic environment of copper incorporated into diatoms and cyanobacteria during long-term growth is similar to that of the adsorbed metal with slightly shorter distances to the first O/N neighbor (1.95 Å). In contrast to the common view of Cu status in phototrophic micro-organisms, XAFS failed to detect sulfur in the nearest atomic environment of Cu assimilated by freshwater plankton (cyanobacteria) and periphyton (diatoms). The appearance of S in Cu 1st coordination shell at 2.27-2.32 Å was revealed only after long-term interaction of Cu with anoxygenic phototrophs (and Cu uptake by soil heterotrophs), suggesting Cu scavenging in the form of sulfhydryl, histidine/carboxyl or a mixture of carboxylate and sulfhydryl complexes. These new structural constraints suggest that adsorbed Cu(II) is partially reduced to Cu(I) already at the cell surface, where as intracellular Cu uptake and storage occur in the form of both Cu(I)-S linked proteins and Cu(II) carboxylates. Obtained results allow to better understand how, in the course of biological evolution, micro-organisms elaborated various mechanisms of Cu uptake and storage, from passive adsorption and uptake to active, protein-controlled surface reduction, and intracellular storage., (© 2011 Blackwell Publishing Ltd.)

Electrophoretic mobility measurements and surface adsorption of Ca on living, inactivated, and heat-killed haloalkaliphilic Rhodovulum steppense, A-20s, and halophilic Rhodovulum sp., S-17-65 anoxygenic phototrophic bacteria (APB) cell surfaces were performed to determine the degree to which these bacteria metabolically control their surface potential equilibria. Zeta potential of both species was measured as a function of pH and ionic strength, calcium and bicarbonate concentrations. For both live APB in 0.1M NaCl, the zeta potential is close to zero at pH from 2.5 to 3 and decreases to -30 to -40 mV at pH of 5-8. In alkaline solutions, there is an unusual increase of zeta potential with a maximum value of -10 to -20 mV at a pH of 9-10.5. This increase of zeta potential in alkaline solutions is reduced by the presence of NaHCO(3) (up to 10 mM) and only slightly affected by the addition of equivalent amount of Ca. At the same time, for inactivated (exposure to NaN(3), a metabolic inhibitor) and heat-killed bacteria cells, the zeta potential was found to be stable (-30 to -60 mV, depending upon the ionic strength) between pH 5 and 11 without any increase in alkaline solutions. Adsorption of Ca ions on A-20s cells surface was more significant than that on S-17-65 cells and started at more acidic pHs, consistent with zeta potential measurements in the presence of 0.001-0.01 mol/L CaCl(2). Overall, these results indicate that APB can metabolically control their surface potential to electrostatically attract nutrients at alkaline pH, while rejecting/avoiding Ca ions to prevent CaCO(3) precipitation in the vicinity of cell surface and thus, cell incrustation., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Adsorption of copper on exopolysaccharide (EPS)-rich and (EPS)-poor soil rhizospheric Pseudomonas aureofaciens cells was studied as a function of pH and copper concentration at different exposure time in order to assess the effect of cell exopolysaccharides on parameters of adsorption equilibria. The surface properties of bacteria were investigated as a function of pH and ionic strength using potentiometric acid-base titration and electrophoresis that permitted the assessment of the excess surface proton concentration and zeta-potential of the cells, respectively. For adsorption experiments, wide range of Cu concentration was investigated (0.1-375 microM) in order to probe both weak and strong binding sites at the surface. Experimental results were successively fitted using a Linear Programming Model approach. The groups with pK(a) of 4.2-4.8 and from 5.2 to 7.2, tentatively assigned as carboxylates and phosphoryl respectively, are the most abundant at the surface and thus essentially contribute to the metal binding. The presence of exopolysaccharides on the surface decreases the amount of copper adsorbed on the bacterial cell wall apparently via screening the underlining functional groups of the cell wall. At the same time, dissolved EPS substances do not contribute to Cu binding in aqueous solution. Results of this study allow quantification of the role played by the surface EPS matrix as a protective barrier for metal adsorption on bacterial cell walls., (Copyright 2010 Elsevier Inc. All rights reserved.)