Elemental composition of grass phytoliths: Environmental control and effect on dissolution.

Plant phytoliths, which represent the main pool of silica (Si) in the form of hydrous Si oxide, are capable of providing valuable information on different aspect of environmental issues including paleo-environmental reconstruction and agricultural sustainability. Phytoliths may have different chemical composition, which, in turn, affects their preservation in soils ad impacts terrestrial cycle of the occluded elements including micro-nutrients and environmental toxicants. Yet, in contrast to sizable work devoted to phytoliths formation, dissolution and physico-chemical properties, the mechanisms that control total (major and trace) elemental composition and the impact that various elements exert on phytolith reactivity and preservation in soils remains poorly known. In order to fil this gap in knowledge, here we combined two different approaches - analytical trace element geochemistry and experimental physical chemistry. First, we assessed full elemental composition of phytoliths from different plants via measuring major and trace elements in 9 samples of grasses collected in northern Eurasia during different seasons, 18 grasses from Siberian regions, and 4 typical Si-concentrating plants (horsetail, larch, elm and tree fern). We further assessed the dissolution rates of phytoliths exhibiting drastically different concentrations of trace metals. In the European grasses, the variations of phytolith chemical composition among species were highly superior to the variations across vegetative season. Compared to European samples, Siberian grass phytoliths were impoverished in Ca and Sr, exhibited similar concentrations of Li, B, Na, Mg, K, V, Zn, Ni, Mo, As, Ba, and U, and were strongly enriched (x 100-1000) in lithogenic elements (trivalent and tetravalent hydrolysates), P, Mn, Fe and divalent metals. Overall, the variations in elemental composition between different species of the same region were lower compared to variations of the same species from distant regions. The main factors controlling phytoliths elemental composition are the far-range atmospheric (dust) transfer, climatic conditions (humidity), and, in a lesser degree, local lithology and anthropogenic pollution. Despite significant, up to 3 orders of magnitude, difference in TE composition of grass and other plant phytoliths, the dissolution rates of grass phytoliths measured in this study were similar, within the experimental uncertainty, to those of other plants studied in former works. Therefore, elemental composition of phytoliths has relatively minor impact on their preservation in soils.

Fractionation of organic C, nutrients, metals and bacteria in peat porewater and ice after freezing and thawing.

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.

Experimental assessment of tundra fire impact on element export and storage in permafrost peatlands.

Extensive studies have been performed on wildfire impact on terrestrial and aquatic ecosystems in the taiga biome, however consequences of wildfires in the tundra biome remain poorly understood. In such a biome, permafrost peatlands occupy a sizable territory in the Northern Hemisphere and present an extensive and highly vulnerable storage of organic carbon. Here we used an experimental approach to model the impact of ash produced from burning of main tundra organic constituents (i.e., moss, lichen and peat) on surrounding aquatic ecosystems. We studied the chemical composition of aqueous leachates produced during short-term (1 week) interaction of ash with distilled water and organic-rich lake water at 5 gsolid L-1 and 20 °C. The addition of ash enriched the fluid phase in major cations (i.e., Na, Ca, Mg), macro- (i.e., P, K, Si) and micronutrients (i.e., Mn, Fe, Co, Ni, Zn, Mo). This enrichment occurred over <2 days of experiment. Among 3 studied substrates, moss ash released the largest amount of macro- and micro-components into the aqueous solution. To place the obtained results in the environmental context of a peatbog watershed, we assume a fire return interval of 56 years and that the entire 0-10 cm of upper peat is subjected to fire impact. These mass balance calculations demonstrated that maximal possible delivery of elements from ash after soil burning to the hydrological network is negligibly small (<1-2 %) compared to the annual riverine export flux and element storage in thermokarst lakes. As such, even a 5-10 fold increase in tundra wildfire frequency may not sizably modify nutrient and metal fluxes and pools in the surrounding aquatic ecosystems. This result requires revisiting the current paradigm on the importance of wildfire impact on permafrost peatlands and calls a need for experimental work on other ecosystem compartments (litter, shrubs, frozen peat) which are subjected to fire events.

Organic carbon, and major and trace elements reside in labile low-molecular form in the ground ice of permafrost peatlands: a case study of colloids in peat ice of Western Siberia.

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.

Dispersed ground ice of permafrost peatlands: Potential unaccounted carbon, nutrient and metal sources.

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.

Lichen, moss and peat control of C, nutrient and trace metal regime in lakes of permafrost peatlands.

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, CO2, 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 CO2 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 pCO2 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 CO2 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.

Enhanced particulate Hg export at the permafrost boundary, western Siberia.

Arctic permafrost soils contain large amounts of organic carbon and the pollutant mercury (Hg). Arctic warming and associated changes in hydrology, biogeochemistry and ecology risk mobilizing soil Hg to rivers and to the Arctic Ocean, yet little is known about the quantity, timing and mechanisms involved. Here we investigate seasonal particulate Hg (PHg) and organic carbon (POC) export in 32 small and medium rivers across a 1700 km latitudinal permafrost transect of the western Siberian Lowland. The PHg concentrations in suspended matter increased with decreasing watershed size. This underlines the significance of POC-rich small streams and wetlands in PHg export from watersheds. Maximum PHg concentrations and export fluxes were located in rivers at the beginning of permafrost zone (sporadic permafrost). We suggest this reflects enhanced Hg mobilization at the permafrost boundary, due to maximal depth of the thawed peat layer. Both the thickness of the active (unfrozen) peat layer and PHg run-off progressively move to the north during the summer and fall seasons, thus leading to maximal PHg export at the sporadic to discontinuous permafrost zone. The discharge-weighed PHg:POC ratio in western Siberian rivers (2.7 ±â€¯0.5 µg Hg: g C) extrapolated to the whole Ob River basin yields a PHg flux of 1.5 ±â€¯0.3 Mg y-1, consistent with previous estimates. For current climate warming and permafrost thaw scenarios in western Siberia, we predict that a northward shift of permafrost boundaries and increase of active layer depth may enhance the PHg export by small rivers to the Arctic Ocean by a factor of two over the next 10-50 years.