Interactions between cadmium and lead with acidic soils: Experimental evidence of similar adsorption patterns for a wide range of metal concentrations and the implications of metal migration

The importance of high- and low-affinity surface sites for cadmium and lead adsorption in typical European and Asian soils was investigated. Adsorption experiments on surface and deep horizons of acidic brown (Vosges, France) and red loess soils (Hunan, China) were performed at 25 ◦C as a function of the pH (3.5–8) and a large range of metal concentrations in solution (10−9–10−4 mol l−1). We studied the adsorption kinetics using a Cd2+-selective electrode and desorption experiments as a function of the solid/solution ratio and pH. At a constant solution pH, all samples exhibited similar maximal adsorption capacities (4.0 ± 0.5 µmol/g Cd and 20 ± 2 µmol/g Pb). A constant slope of adsorbed–dissolved concentration dependence was valid over 5 orders of magnitude of metal concentrations. Universal Langmuir and Freundlich equations and the SCM formalism described the adsorption isotherms and the pH-dependent adsorption edge over very broad ranges of metal concentrations, indicating no high- or low-affinity sites for metal binding at the soil surface under these experimental conditions. At pH 5, Cd and Pb did not compete, in accordance with the SCM. The metal adsorption ability exceeded the value for soil protection by two orders of magnitude, but only critical load guarantees soil protection since metal toxicity depends on metal availability

Elemental composition of plankton exometabolites (mucous macroaggregates): Control by biogenic and lithogenic components

Among the various exometabolitic effects of marine microorganisms, massive mucilage events in the coastal zones of temperate and tropical seas are the most spectacular and environmentally important. Abundant mucilage material in the form of aggregates appears in late spring/early summer in the water column of the Adriatic Sea. These macroaggregate biopolymers originate mainly from plankton exometabolites, with both autochthonous and allochthonous components, and strongly impact the tourism, fisheries, and economy of coastal countries. In contrast to extensive studies on the structural and chemical nature of macroaggregates performed over past decades, the full elemental composition of these substances remains poorly known, which does not allow for a complete understanding of their origin, evolution, and necessary remediation measures. Here, we report the results of comprehensive analyses of 55 major and trace elements in the composition of macro aggregates collected at the surface and in the water column during massive mucilage events. Through normalization of the elemental chemical composition of the upper earth crust (UCC), river suspended material (RSM), mean oceanic plankton, and mean oceanic particulate suspended material, we demonstrate that the water column macroaggregates reflect a superposition of the signal from plankton and marine particulate matter. The surface macroaggregates were preferentially enriched in lithogenic component, and carried the signature of planktonic material. The rare earth element (REE) signal was strongly dominated by plankton and, to a lesser degree, by oceanic particulate matter, while at the same time being strongly (>80 times) impoverished compared with UCC and RSM. Taken together, the elemental composition of macroaggregates allows for distinguishing the lithogenic and biogenic impacts on the occurrence of these unique large-scale mucilage events, linked to the exometabolism of marine plankton combined with the input of allochthonous inorganic material

Element transport in the Taz River, western Siberia

The riverine export fluxes of dissolved carbon, nutrient and metals from the land to the Arctic Ocean are fairly well quantified for five large Arctic rivers but remain virtually unknown for mid-sized Eurasian rivers, notably those draining through the permafrost zone. Because such rivers can most rapidly respond to on-going climate warming and permafrost thaw in the Arctic, their current hydrochemical composition and elemental yields are badly needed for judging the level of changes in the very near future. Towards quantifying the annual export fluxes and assessing the mechanisms of seasonal variability of river solutes, we monitored the pristine subarctic Taz River (Swatershed = 150,000 km2), which drains through boreal forest and peatlands in the discontinuous and continuous permafrost zone, on a weekly to monthly basis over a 3 year period. Based on seasonal pattern of riverine solutes (70% of annual Mn flux occurred in winter. A number of elements present in the snowpack exhibited sizable (> 45%) export during spring flood (Zn, Cu, Pb, Cd, Sb and Cs). The 3 years mean export fluxes (yields) of dissolved components were comparable to or 30–50% lower than those of other large and medium sized Arctic rivers. This was due mostly to a lack of fresh unaltered rocks and a dominance of peatlands within the Taz River watershed. Elevated concentrations of redox-sensitive micro-nutrients (such as Fe and Mn) occurring during winter baseflow can be linked to disproportionally large floodplain zone of this river which can act, especially in the river's lower reaches, as a stratified lake thereby releasing high amounts of redox-sensitive elements from the sediments. The role of suboxic zones in the Arctic boreal riverine landscape may be more important than previously thought, and may allow explaining anomalously high concentrations of some metals (i.e., Mn) reported in Arctic Ocean surface waters. It is anticipated that climate warming in the region may increase the contribution of winter flow and enhance the export of soluble elements and some nutrients (such as Si, Mn and Co)

Partitioning of dissolved organic carbon, major elements, and trace metals during laboratory freezing of organic leachates from permafrost peatlands

Climate change is likely to modify the freezing–thawing cycles in soils and surface waters of permafrost-affected and subarctic regions. However, the change of solution chemical composition during ice formation and the evolution of the remaining fluids remain very poorly known. Towards a better understanding of dissolved (<0.45 µm) organic carbon, as well as major and trace element behavior in permafrost peatland environments, here we performed laboratory freezing of peat leachates, from complete freezing to complete thawing, in order to quantify the partitioning of solutes between the aqueous solution and the remaining ice. Freezing experiments were conducted, with and without polyurethane insulation. Two main types of experiments involved (i) progressive freezing, when we started from liquid leachates (filtered <0.45 µm) and allowed them to freeze at −18 ◦C, and (ii) progressive thawing, where first, we froze solid a series of <0.45 µm filtered leachates and then monitored their thawing at room temperature, 20 ◦C. We hypothesized the existence of two main groups of solutes, behaving conservatively or non-conservatively during freezing, depending on their incorporation into the ice or their ability to coagulate in the form of insoluble minerals or amorphous materials in the fluid phase. An unexpected result of this work was that, despite a sizable degree of element concentration in the remaining fluid and possible coagulation of organic, organo-mineral, and inorganic compounds, the freezing and subsequent thawing produced final concentrations of most solutes which were not drastically different from the initial concentrations in the original leachates prior to freezing. This demonstrates the high stability of dissolved (<0.45 µm) organic carbon, iron, aluminum, and some trace metals to the repetitive freezing and thawing of surface waters in permafrost peatlands

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 microcomponents 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

Can Mg isotopes be used to trace cyanobacteria-mediated magnesium carbonate precipitation in alkaline lakes?

The fractionation of Mg isotopes was determined during the cyanobacterial mediated precipitation of hydrous magnesium carbonate precipitation in both natural environments and in the laboratory. Natural samples were obtained from Lake Salda (SE Turkey), one of the few modern environments on the Earth's surface where hydrous Mg-carbonates are the dominant precipitating minerals. This precipitation was associated with cyanobacterial stromatolites which were abundant in this aquatic ecosystem. Mg isotope analyses were performed on samples of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments. Laboratory Mg carbonate precipitation experiments were conducted in the presence of purified Synechococcus sp cyanobacteria that were isolated from the lake water and stromatolites. The hydrous magnesium carbonates nesquehonite (MgCO3·3H2O) and dypingite (Mg5(CO3)4(OH)25(H2O)) were precipitated in these batch reactor experiments from aqueous solutions containing either synthetic NaHCO3/MgCl2 mixtures or natural Lake Salda water, in the presence and absence of live photosynthesizing Synechococcus sp. Bulk precipitation rates were not to affected by the presence of bacteria when air was bubbled through the system. In the stirred non-bubbled reactors, conditions similar to natural settings, bacterial photosynthesis provoked nesquehonite precipitation, whilst no precipitation occurred in bacteria-free systems in the absence of air bubbling, despite the fluids achieving a similar or higher degree of supersaturation. The extent of Mg isotope fractionation (?26Mgsolid-solution) between the mineral and solution in the abiotic experiments was found to be identical, within uncertainty, to that measured in cyanobacteria-bearing experiments, and ranges from ?1.4 to ?0.7 ‰. This similarity refutes the use of Mg isotopes to validate microbial mediated precipitation of hydrous Mg carbonate

A snap-shot assessment of carbon emission and export in a pristine river draining permafrost peatlands (Taz River, Western Siberia)

Mobilization of dissolved organic carbon (DOC) and CO2 from the frozen peat to surface waters in the permafrost zone of high latitude regions is expected to enhance under on-going permafrost thaw and active layer thickness deepening. Here we explored one of the most remote, pristine, unregulated and yet environmentally important rivers in western Siberia (Taz). This subarctic river drains through forested and tundra peat bogs over a gradient of permafrost and climate and likely acts as an important conduit of CO2 to the atmosphere and carbon and nutrient exporter to the Arctic Ocean. In a snapshot study during end of spring flood–beginning of summer baseflow (July 2019), we monitored daytime CO2 and CH4 concentrations and measured CO2 emissions using floating chambers in the main stem (700 km from the upper reaches to the mouth) and 16 main tributaries and we also assessed day/night variations in the emissions. We further tested the impact of land cover parameters of the watershed and tributaries. Based on regular monitoring of the terminal (gauging) station, we quantified the C export to the Arctic Ocean during the study period. We revealed sizable CO2 emissions from the main stem and tributaries (1.0 ± 0.4 and 1.8 ± 0.6 g C-CO2 m−2 d−1, respectively). The CO2 concentrations positively correlated with dissolved organic carbon (DOC), whereas the CH4 concentrations could be partially controlled by dissolved nutrients (N, P) and proportion of light coniferous forest at the watershed. The overall C emission from the water surfaces (4,845 km2) of the Taz basin (150,000 km2) during open water period (6 months, May to October) was estimated as 0.92 Tg C (>99.5% C-CO2, <0.5% C-CH4) which is twice higher than the total dissolved C (organic and inorganic) riverine export flux during the same period. Applying a “substituting space for time” approach for northern and southern parts of the river basin, we suggest that the current riverine CO2 emission may increase 2 to 3 fold in the next decades due to on-going climate warming and permafrost thaw. When integrating the obtained results into global models of C and biogeochemical cycle in the Arctic and subarctic region, the use of the Taz River as a representative example of continental planes should help to estimate the consequences of frozen peatland thaw on CO2 cycle in the Arctic and subarctic regions

Thermodynamics of Two - Band Superconductors: The Case of MgB2_{2}

Thermodynamic properties of the multiband superconductor MgB$_{2}$ have often been described using a simple sum of the standard BCS expressions corresponding to $\sigma$- and $\pi$-bands. Although, it is \textit{a priori} not clear if this approach is working always adequately, in particular in cases of strong interband scattering. Here we compare the often used approach of a sum of two independent bands using BCS-like $\alpha$-model expressions for the specific heat, entropy and free energy to the solution of the full Eliashberg equations. The superconducting energy gaps, the free energy, the entropy and the heat capacity for varying interband scattering rates are calculated within the framework of two-band Eliashberg theory. We obtain good agreement between the phenomenological two-band $\alpha$-model with the Eliashberg results, which delivers for the first time the theoretical verification to use the $\alpha$-model as a useful tool for a reliable analysis of heat capacity data. For the thermodynamic potential and the entropy we demonstrate that only the sum over the contributions of the two bands has physical meaning.Comment: 27 pages, 10 figures, 1 table, submitted to Phys. Rev.