The diversity of ice algal communities on the Greenland Ice Sheet as revealed by oligotyping

The Arctic is being disproportionally affected by climate change compared with other geographic locations, and is currently experiencing unprecedented melt rates. The Greenland Ice Sheet (GrIS) can be regarded as the largest supraglacial ecosystem on Earth, and ice algae are the dominant primary producers on bare ice surfaces throughout the course of a melt season. Ice-algal-derived pigments cause a darkening of the ice surface, which in turn decreases albedo and increases melt rates. The important role of ice algae in changing melt rates has only recently been recognized, and we currently know little about their community compositions and functions. Here, we present the first analysis of ice algal communities across a 100 km transect on the GrIS by high-throughput sequencing and subsequent oligotyping of the most abundant taxa. Our data reveal an extremely low algal diversity with Ancylonema nordenskiöldii and a Mesotaenium species being by far the dominant taxa at all sites. We employed an oligotyping approach and revealed a hidden diversity not detectable by conventional clustering of operational taxonomic units and taxonomic classification. Oligotypes of the dominant taxa exhibit a site-specific distribution, which may be linked to differences in temperatures and subsequently the extent of the melting. Our results help to better understand the distribution patterns of ice algal communities that play a crucial role in the GrIS ecosystem

The Biodiversity and Geochemistry of Cryoconite Holes in Queen Maud Land, East Antarctica

Cryoconite holes are oases of microbial diversity on ice surfaces. In contrast to the Arctic, where during the summer most cryoconite holes are ‘open’, in Continental Antarctica they are most often ‘lidded’ or completely frozen year-round. Thus, they represent ideal systems for the study of microbial community assemblies as well as carbon accumulation, since individual cryoconite holes can be isolated from external inputs for years. Here, we use high-throughput sequencing of the 16S and 18S rRNA genes to describe the bacterial and eukaryotic community compositions in cryoconite holes and surrounding lake, snow, soil and rock samples in Queen Maud Land. We cross correlate our findings with a broad range of geochemical data including for the first time 13C and 14C analyses of Antarctic cryoconites. We show that the geographic location has a larger effect on the distribution of the bacterial community compared to the eukaryotic community. Cryoconite holes are distinct from the local soils in both 13C and 14C and their isotopic composition is different from similar samples from the Arctic. Carbon contents were generally low (≤0.2%) and older (6–10 ky) than the surrounding soils, suggesting that the cryoconite holes are much more isolated from the atmosphere than the soils

Quantifying water diffusion in high-viscosity and glassy aqueous solutions using a Raman isotope tracer method

Recent research suggests that under certain temperature and relative humidity conditions atmospheric aerosol may be present in the form of a glassy solid. In order to understand the impacts that this may have on aerosol–cloud interactions and atmospheric chemistry, knowledge of water diffusion within such aerosol particles is required. Here, a method is described in which Raman spectroscopy is used to observe D2O diffusion in high-viscosity aqueous solutions, enabling a quantitative assessment of water diffusion coefficients, Dwater, as a function of relative humidity. Results for sucrose solutions compare well with literature data at 23.5 ± 0.3 °C, and demonstrate that water diffusion is slow (Dwater ~5 × 10−17 m2 s−1), but not arrested, just below the glass transition at a water activity of 0.2. Room temperature water diffusion coefficients are also presented for aqueous levoglucosan and an aqueous mixture of raffinose, dicarboxylic acids and ammonium sulphate: at low humidity, diffusion is retarded but still occurs on millisecond to second timescales in atmospherically relevant-sized particles. The effect of gel formation on diffusion in magnesium sulfate solutions is shown to be markedly different from the gradual decrease in diffusion coefficients of highly viscous liquids. We show that using the Stokes–Einstein equation to determine diffusion timescales from viscosity leads to values which are more than 5 orders of magnitude too big, which emphasises the need to make measurements of diffusion coefficients. In addition, comparison of bounce fraction data for levoglucosan with measured diffusion data reveals that even when particles bounce the diffusion timescales for water are a fraction of a second for a 100 nm particle. This suggests a high bounce fraction does not necessarily indicate retarded water diffusion

Arsenic removal from natural groundwater using ‘green rust’: Solid phase stability and contaminant fate

Arsenic (As) contamination in groundwater remains a pressing global challenge. In this study, we evaluated the potential of green rust (GR), a redox-active iron phase frequently occurring in anoxic environments, to treat As contamination at a former wood preservation site. We performed long-term batch experiments by exposing synthetic GR sulfate (GRSO4) to As-free and As-spiked (6 mg L−1) natural groundwater at both 25 and 4 °C. At 25 °C, GRSO4 was metastable in As-free groundwater and transformed to GRCO3, and then fully to magnetite within 120 days; however, GRSO4 stability increased 7-fold by lowering the temperature to 4 °C, and 8-fold by adding As to the groundwater at 25 °C. Highest GRSO4 stability was observed when As was added to the groundwater at 4 °C. This stabilizing effect is explained by GR solubility being lowered by adsorbed As and/or lower temperatures, inhibiting partial GR dissolution required for transformation to GRCO3, and ultimately to magnetite. Despite these mineral transformations, all added As was removed from As-spiked samples within 120 days at 25 °C, while uptake was 2 times slower at 4 °C. Overall, we have successfully documented that GR is an important mineral substrate for As immobilization in anoxic subsurface environments

Experimental and simulation results of the adsorption of Mo and V onto ferrihydrite.

This study aims to highlight discrepancies between experimental and simulation linked to the mechanisms of Mo and V adsorption onto ferrihydrite (FHY) nanoparticles. We have measured adsorption capacities and uptake efficiencies and then fitted and compared these with outputs from various geochemical and adsorption models that were run as a function of pH, surface area (SA) and ferrihydrite particles size distributions. Our results revealed that the experimental data for the Mo system could be fitted very well, but this was not the case for the V system, when a model default value for the SA of FHY of 600 m2 g-1 was used. The discrepancy in the results for the V system can be explained by the lack of specific V species and/or associated constants in databases and variation in software versions, which change the outputted chemical species. Our comparative results also confirm that any experimental variables used as modelling inputs need to be checked carefully prior to any modelling exercises

The microbiome of glaciers and ice sheets

Glaciers and ice sheets, like other biomes, occupy a significant area of the planet and harbour biological communities with distinct interactions and feedbacks with their physical and chemical environment. In the case of the glacial biome, the biological processes are dominated almost exclusively by microbial communities. Habitats on glaciers and ice sheets with enough liquid water to sustain microbial activity include snow, surface ice, cryoconite holes, englacial systems and the interface between ice and overridden rock/soil. There is a remarkable similarity between the different specific glacial habitats across glaciers and ice sheets worldwide, particularly regarding their main primary producers and ecosystem engineers. At the surface, cyanobacteria dominate the carbon production in aquatic/sediment systems such as cryoconite holes, while eukaryotic Zygnematales and Chlamydomonadales dominate ice surfaces and snow dynamics, respectively. Microbially driven chemolithotrophic processes associated with sulphur and iron cycle and C transformations in subglacial ecosystems provide the basis for chemical transformations at the rock interface under the ice that underpin an important mechanism for the delivery of nutrients to downstream ecosystems. In this review, we focus on the main ecosystem engineers of glaciers and ice sheets and how they interact with their chemical and physical environment. We then discuss the implications of this microbial activity on the icy microbiome to the biogeochemistry of downstream ecosystems

Formation of calcium sulfate through the aggregation of sub-3 nanometre primary species

The formation pathways of gypsum remain uncertain. Here, using truly in situ and fast time-resolved small-angle X-ray scattering, we quantify the four-stage solution-based nucleation and growth of gypsum (CaSO4 ·2H2O), an important mineral phase on Earth and Mars. The reaction starts through the fast formation of well-defined, primary species of <3 nm in length (stage I), followed in stage II by their arrangement into domains. The variations in volume fractions and electron densities suggest that these fast forming primary species contain Ca-SO4-cores that self-assemble in stage III into large aggregates. Within the aggregates these well-defined primary species start to grow (stage IV), and fully crystalize into gypsum through a structural rearrangement. Our results allow for a quantitative understanding of how natural calcium sulfate deposits may form on Earth and how a terrestrially unstable phase-like bassanite can persist at low-water activities currently dominating the surface of Mars

Xyloglucan is released by plants and promotes soil particle aggregation.

Soil is a crucial component of the biosphere and is a major sink for organic carbon. Plant roots are known to release a wide range of carbon-based compounds into soils, including polysaccharides, but the functions of these are not known in detail. Using a monoclonal antibody to plant cell wall xyloglucan, we show that this polysaccharide is secreted by a wide range of angiosperm roots, and relatively abundantly by grasses. It is also released from the rhizoids of liverworts, the earliest diverging lineage of land plants. Using analysis of water-stable aggregate size, dry dispersion particle analysis and scanning electron microscopy, we show that xyloglucan is effective in increasing soil particle aggregation, a key factor in the formation and function of healthy soils. To study the possible roles of xyloglucan in the formation of soils, we analysed the xyloglucan contents of mineral soils of known age exposed upon the retreat of glaciers. These glacial forefield soils had significantly higher xyloglucan contents than detected in a UK grassland soil. We propose that xyloglucan released from plant rhizoids/roots is an effective soil particle aggregator and may, in this role, have been important in the initial colonization of land

Reaction pathways and textural aspects of the replacement of anhydrite by calcite at 25 °C

The replacement of sulfate minerals by calcium carbonate polymorphs (carbonation) has important implications in various geological processes occurring in Earth surface environments. In this paper we report the results of an experimental study of the interaction between anhydrite (100), (010), and (001) surfaces and Na₂CO₃ aqueous solutions under ambient conditions. Carbonation progress was monitored by glancing incidence X-ray diffraction (GIXRD) and scanning electron microscopy (SEM). We show that the reaction progresses through the dissolution of anhydrite and the simultaneous growth of calcite. The growth of calcite occurs oriented on the three anhydrite cleavage surfaces and its formation is accompanied by minor vaterite. The progress of the carbonation always occurs from the outer-ward to the inner-ward surfaces and its rate depends on the anhydrite surface considered, with the (001) surface being much more reactive than the (010) and (100) surfaces. The thickness of the formed carbonate layer grows linearly with time. The original external shape of the anhydrite crystals and their surface details (e.g., cleavage steps) are preserved during the carbonation reaction. Textural characteristics of the transformed regions, such as the gradation in the size of calcite crystals, from ~2 μm in the outer region to ~17 μm at the calcite-anhydrite interface, the local preservation of calcite crystalographic orientation with respect to anhydrite and the distribution of the microporosity mainly within the carbonate layer without development of any significant gap at the calcite-anhydrite interface. Finally, we compare these results on anhydrite carbonation with those on gypsum carbonation and can explain the differences on the basis of four parameters: (1) the molar volume change involved in the replacement process in each case, (2) the lack/existence of epitactic growth between parent and product phases, (3) the kinetics of dissolution of the different surfaces, and (4) the chemical composition (amount of structural water) of the parent phases

How Short-Lived Ikaite Affects Calcite Crystallization

The pathways of CaCO₃ crystallization are manifold, often involving one or several metastable amorphous or nanocrystalline intermediate phases. The presence of such intermediates is often overlooked, because they are short-lived and/or occur at small molar fractions. However, their occurrence does not just impact the mechanisms and pathways of formation of the final stable CaCO₃ phase, but also affects their crystal size, shape, and structure. Here we document the presence of a short-lived intermediate through in situ and time-resolved small and wide-angle X-ray scattering combined with high resolution electron microscope observations. When ikaite forms concomitant with the dissolution of amorphous calcium carbonate (ACC) but prior to calcite formation, fairly large glendonite-type calcite crystals grow despite the presence of citrate ligands that usually reduce crystal size. These were ideal seeding crystals for further crystallization from supersaturated ions in solution. In contrast, in the absence of ikaite the crystallization of calcite proceeds through transformation from ACC, resulting in fine-grained spherulitic calcite with sizes ∼8 times smaller than when ikaite was present. Noteworthy is that the formation of the intermediate ikaite, although it consumes less than 3 mol % of the total precipitated CaCO₃, still clearly affected the calcite formation mechanism