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The vast potential of using sediment adsorbed DNA as a window to past and present biodiversity rely on the ability of solid surfaces to adsorb environmental DNA. However, a comprehensive insight into DNA adsorption at surfaces in general is lacking. Soot and charcoal are carbonaceous materials widespread in the environment where they readily can come in contact with extracellular DNA shed from organisms. Using batch adsorption, we measured DNA adsorption capacity at soot and charcoal as a function of solution composition, time and DNA length. We observed that the adsorption capacity for DNA is highest at low pH, that it increases with solution concentration and cation valency and that the activation energy for DNA adsorption at both soot and charcoal is ~50 kJmol-1, suggesting strong binding. We demonstrate how the interaction between DNA and soot and charcoal partly occurs via terminal base pairs, suggesting that, besides electrostatic forces, hydrophobic interactions play an important role in binding. The large adsorption capacities and strong binding of DNA to soot and charcoal are features important for eDNA research and provide a motivation for use of carbonaceous materials from, e.g., anthropogenic pollution or wildfire as sources of biodiversity information.

The crystal structure and ferroelectric properties of epitaxial ZrO2 films ranging from 7 to 42 nm thickness grown on La0.67Sr0.33MnO3 buffered (110)‐oriented SrTiO3 substrate are reported. By employing X‐ray diffraction, a tetragonal phase (t‐phase) at all investigated thicknesses, with slight in‐plane strain due to the substrate in the thinnest films, is confirmed. Further confirmation of the t‐phase is obtained through infrared absorption spectroscopy with synchrotron light, performed on ZrO2 membrane transferred onto a high resistive silicon substrate. Up to a thickness of 31 nm, the ZrO2 epitaxial films exhibit ferroelectric behavior, at variance with the antiferroelectric behavior reported previously for the t‐phase in polycrystalline films. However, the ferroelectricity is found here to diminish with increasing film thickness, with a polarization of 13 µC cm−2 and down to 1 µC cm−2 for 7 and 31 nm thick ZrO2 films, respectively. Given that the t‐phase is nonpolar, the observations emphasize the influence of external factors, in promoting polarization in t‐ZrO2 thin films. These findings provide new insights into the ferroelectric properties and structure of ZrO2 thin films, and open up new directions to investigate the origin of ferroelectricity in ZrO2 and to optimize this material for future applications. [ABSTRACT FROM AUTHOR]

In the French north‐western Alps, several lakes of glacial origin, such as Aiguebelette and La Thuile, present some mass‐transport deposits within their sedimentary sequences. These event layers can result from lake sediment destabilization eventually triggered by earthquakes. On Lake Aiguebelette, based on sedimentological, geochemical and magnetic analyses, and high‐resolution seismic and bathymetric surveys a ca 1 m thick event layer was identified in the deepest lake basin and a synchronous ca 2 cm thick deposit in the shallow basin. Age‐depth models based on radiocarbon ages reveal that both mass‐transport deposits in Lake Aiguebelette occurred around the Younger Dryas – Early Holocene climatic transition (i.e. 11 700 cal bp) time range. In Lake La Thuile, located 30 km away, unique mass‐transport deposits (translational slide type) were recorded at the same time range in sedimentary records. Additionally, high‐resolution seismic profiles previously acquired in Lake Annecy and Lake Bourget support the hypothesis of significant mass‐transport deposits occurring at the Younger Dryas – Early Holocene time range. These outcomes on four north‐western peri‐Alpine and Alpine lakes highlight the regional occurrence of mass‐transport deposits in the Younger Dryas – Early Holocene time range. Seismic and rockfall events are discussed as potential sources of these significant and similarly aged mass‐transport deposits. Based on this study and a literature review, the authors suggest that mechanisms induced by rapid climate change and glacial retreat, such as crustal rebound and erosional unloading, could favour the triggering of earthquakes and rockfall events. In the case of mass‐transport deposits archived in north‐western Alpine lakes during this time period, this study favours the hypothesis of increased seismicity as the primary source driving process involved. [ABSTRACT FROM AUTHOR]

Kimberlites carry a dense cargo of olivine. Although normally referred to as macrocrysts, much of this olivine is present as multigrain xenoliths of dunite. Because of their well-rounded outlines, we refer to these objects as 'nodules' and apply the term to both multigranular and monogranular varieties. Although compositions within each nodule are very uniform, the entire population displays an enormous variation in Fo content (100*Mg/(Mg + Fe), cation proportions), from close to Fo95 to about Fo82. The change is continuous, and there is no indication of separate Fo-rich and Fo-poor populations. Likewise, the sizes, internal textures and habits of Fo-rich and Fo-poor olivines are indistinguishable. Fo-poor nodules have compositions like those of olivines of the megacryst suite, and they share similar sizes and internal structures. We propose that the dunite nodules in kimberlites and olivines of the megacryst suite have a common origin. In our interpretation, almost all olivines in kimberlites, except for the marginal rims and rinds, are fragments of dunite that was produced during interaction between mantle peridotite and CO2-rich fluid. Analogues of this process can be found in ophiolites where dunite is the product of reaction between basaltic magma and peridotite. In situ reactive crystallization eliminated pyroxene, leaving only olivine with Fo contents ranging from higher to lower Fo than in the host peridotite. This interaction occurred near the base of the lithosphere and not during transit of kimberlite towards the surface. [ABSTRACT FROM AUTHOR]

In laboratory experiments, the precipitation of dolomite at ambient temperature is virtually impossible due to strong solvation shells of magnesium ions in aqueous media and probably also due to the existence of a more intrinsic crystallization barrier that prevents the formation of long-range ordered crystallographic structures at ambient surface conditions. Conversely, dolomite can easily form at high temperature (>100 °C), but its precipitation and growth requires several days or weeks depending on experimental conditions. In the present study, experiments were performed to assess how a single heat-ageing step promotes the formation of dolomite under high-carbonate alkaline conditions via dissolution-precipitation reactions. This reaction pathway is relevant for the so-called hydrothermal dolomite frequently observed in carbonate platforms, but still ill-defined and understood. Our precipitation route is summarized by two main sequential reactions: (1) precipitation of Mg-calcite at low temperature (∼20 °C) by aqueous carbonation of synthetic portlandite (Ca(OH) 2 ) in a highly alkaline medium (1 M of NaOH and 1 M of MgCl 2 ), leading to precipitation of oriented nanoparticles of low- and high-Mg calcite (∼79 wt%) coexisting with aragonite (∼18 wt%) and brucite (∼3 wt%) after 24 h; (2) fast dolomitization process starting from 1 h of reaction by a single heat-ageing step from ∼20 to 200, 250 and 300 °C. Here, the Mg-calcite acts as a precursor that lowers the overall kinetics barrier for dolomite formation. Moreover, it is an important component in some bio-minerals (e.g. corals and seashells). Quantitative Rietveld refinements of XRD patterns, FESEM observations and FTIR measurements on the sequentially collected samples suggest fast dolomite precipitation coupled with dissolution of transient mineral phases such as low-Mg calcite (Mg < 4 mol%), high-Mg calcite (Mg > 4 mol%), proto-dolomite (or disordered dolomite; Mg > 40 mol%) and Ca-magnesite. In this case, the dolomite formation rate and the time-dependent mineral composition strongly depend on reaction temperature. For example, high-purity dolomitic material (87 wt% of dolomite mixed with 13 wt% of magnesite) was obtained at 300 °C after 48 h of reaction. Conversely, a lower proportion of dolomite (37 wt%), mixed with proto-dolomite (43 wt%), Ca-magnesite (16 wt%) and high-Mg calcite (4 wt%), was obtained at 200 °C after 72 h. The present experiments provide an additional mechanism for the massive dolomite formation in sedimentary environments (ex. deep sea organic-rich carbonate-sediments) if such sediments are subjected to significant temperature variations, for example by hot fluid circulations related to volcanic activity. In such systems, organic degradation increases the carbonate alkalinity (HCO 3 − ) necessary to induce the dolomitization process at low and high temperature. [ABSTRACT FROM AUTHOR]

The kinetics of the irreversible reaction Ca(OH)2+MgCO3 → CaCO3+Mg(OH)2 were investigated at high pressures and temperatures relevant to metamorphic petrology, using both in situ synchrotron X-ray diffraction and post-mortem analysis of reaction rim growth on recovered samples. Reaction kinetics are found to strongly depend on water content; comparable bulk-reaction kinetics are obtained under water-saturated (excess water, c. 10 wt %) and under intermediate (0.1-1 wt % water) conditions when temperature is increased by c. 300 K. In contrast, similar reaction kinetics were observed at ~673 K and 823 K between intermediate and dry experiments, respectively, where dry refers to a set of experiments with water activity below 1.0 (no free water), as buffered by the CaO-Ca(OH)2 assemblage. Given the activation energies at play, this gap-- corresponding to the loss of no more than 1 wt % of water by the assemblage--leads to a difference of several orders of magnitude in reaction kinetics at a given temperature. Further analysis, at the microscopic scale, of the intermediate and dry condition samples, shows that intergranular transport of calcium controls the reaction progress. Grain boundary diffusivities could be retrieved from the classic treatment of reaction rim growth rate. In turn, once modeled, this rate was used to fit the bulk kinetic data derived from X-ray powder diffraction, offering an alternative means to derive calcium diffusivity data. Based on a comparison with effective grain boundary data for Ca and Mg from the literature, it is inferred that both dry and intermediate datasets are consistent with a water-saturated intergranular medium with different levels of connectivity. The very high diffusivity of Ca in the CaCO3+Mg(OH)2 rims, in comparison with that of Mg in enstatite rims found by earlier workers, emphasizes the prominent role of the interactions between diffusing species and mineral surfaces in diffusion kinetics. Furthermore, we show that the addition of water is likely to change the relative diffusivity of Mg and Ca in carbonate aggregates. From a qualitative point of view, we confirm, in a carbonate-bearing system, that small water content variations within the 0-1wt % range have tremendous effects on both intergranular transport mechanisms and kinetics. We also propose that the water content dependent diffusivity of major species (Mg, Ca) in low-porosity metamorphic rocks is strongly dependent on the interaction between diffusing species and mineral surfaces. This parameter, which will vary from one rock-type to another, needs also to considered when extrapolating (P, T, t, xH2O) laboratory diffusion data to metamorphic processes. [ABSTRACT FROM AUTHOR]

Herein, we report new insights into the nucleation and growth processes of chrysotile nanotubes by using batch and semi-continuous experiments. For the synthesis of this highly carcinogenic material, the influences of temperature (90, 200, and 300 °C), Si/Mg molar ratio, and reaction time were investigated. From the semi-continuous experiments (i.e., sampling of the reacting suspension over time) and solid-state characterization of the collected samples by XRPD, TGA, FTIR spectroscopy, and FESEM, three main reaction steps were identified for chrysotile nucleation and growth at 300 °C: 1) formation of the proto-serpentine precursor within the first 2 h of the reaction, accompanied by the formation of brucite and residual silica gel; 2) spontaneous nucleation and growth of chrysotile between about 3 and 8 h reaction time, through a progressive dissolution of the proto-serpentine, brucite, and residual silica gel; and 3) Ostwald ripening growth of chrysotile from 8 to 30 h reaction time, as attested to by BET and FESEM measurements. Complementary results from batch experiments confirmed a significant influence of the reaction temperature on the kinetics of chrysotile formation. However, FESEM observations revealed some formation of chrysotile nanotubes at low temperatures (90 °C) after 14 days of reaction. Finally, doubling the Si/Mg molar ratio promoted the precipitation of pure smectite (stevensite-type) under the same P (8.2 MPa)/ T (300 °C)/pH (13.5) conditions. [ABSTRACT FROM AUTHOR]

This paper revisits the clay mineralogy of the "smectite" alteration zone in the Krafla geo-thermal field via the study of an exploratory well in which temperatures range from 40 °C to 215 °C. The clay alteration consists of several mineral assemblages superimposed in time and space, resulting from different stages of water-rock interaction. Trioctahedral clay minerals (chlorite, corrensite and smectite) are observed throughout the studied section. These minerals can form in nearly closed systems as replacements of groundmass minerals/glass after interactions with resident and nearly stagnant fluids not far from chemical equilibrium (neutral to basic pH conditions) or from direct precipitation from geothermal fluids. They are locally superimposed by Al clay phases (smectite, illite/smectite and kaolinite), which result from intense leaching of the host rocks due to their interaction with low pH fluids under strong W/R ratios. The absence of mineralogical zoning is explained by the fact that hydrothermal alteration is strongly dependent on very recent hydrodynamics. The current fluid circulation generates trioctahedral clays at depth that cannot be distinguished from pervasive earlier alteration. The only easily detectable signature of current activity and the most relevant signature for geothermal exploration is the presence of Al dioctahedral phases since it indicates leaching and intense hydrothermal activity. [ABSTRACT FROM AUTHOR]

The microstructural evolution of CaSiO3 wollastonite subjected to carbonation reactions at T = 90 °C and pCO2 = 25 MPa was studied at three different starting conditions: (1) pure water; (2) aqueous alkaline solution (0.44 M NaOH); and (3) supercritical CO2. Scanning and transmission electron microscopy on reacted grains prepared in cross-section always revealed unaltered wollastonite cores surrounded by micrometer-thick pseudomorphic silica rims that were amorphous, highly porous, and fractured. The fractures were occasionally filled with nanometer-sized crystals of calcite and Ca-phyllosilicates. Nanoscale chemical profiles measured across the wollastonite-silica interfacial region always revealed sharp, step-like decreases in Ca concentration. Comparison of the Ca profiles with diffusion modeling suggests that the silica rims were not formed by preferential cation leaching (leached layer), but rather by interfacial dissolution-precipitation. Extents of carbonation as a function of time were determined by quantitative Rietveld refinement of X-ray diffractograms performed on the reacted powders. Comparing the measured extents of carbonation in water (condition 1) with kinetic modeling suggests that carbonation was rate-controlled by chemical reactions at the wollastonite interface, and not by transport limitations within the silica layers. However, at conditions 2 and 3, calcite crystals occurred as a uniform surface coating covering the silica layers, and also within pores and cracks, thereby blocking the connectivity of the originally open nanoscale porosity. These crystals ultimately may have been responsible for controlling transport of solutes through the silica layers. Therefore, this study suggests that pure silica layers were intrinsically non-passivating, whereas silica layers became partially passivating due to the presence of calcite crystallites. [ABSTRACT FROM AUTHOR]

Layer charge deficit is a key crystal-chemical parameter for the classification and nomenclature of 2:1 phyllosilicates that also controls some of their fundamental properties such as cation exchange capacity, expandability, water content, or rheology. The clay community has thus devoted significant efforts to determine this parameter either from the smectite/vermiculite chemical composition (the structural formula method) or experimentally using the alkylammonium method, that theoretically allows the determination of the mean layer charge density and of its distribution. In the present study density functional theory (DFT) and molecular dynamics (MD) simulations are compared to experimental X-ray diffraction data for a series of synthetic saponites with layer charge ranging from medium-charge smectite to medium-charge vermiculite. Consistency of computed and measured layer-to-layer distances confirms the ability of computational approaches to accurately predict the organization of alkylammonium cations in smectite interlayers. Thermalization of DFT-optimized structure models through MD simulations allows probing possible alternative interlayer configurations such as the electrostatically-favored location of ammonium heads above/below Al-substituted tetrahedra. X-ray diffraction results showed that layer-to-layer distances intermediate between those corresponding to the stable h1, h2, etc. interlayer configurations described in the literature result from the interstratification of different stable configurations. The overall consistency of computational and experimental results confirms also the ability of the alkylammonium method to accurately determine a mean value of layer charge density consistent with smectite structural formula when using the revised equations proposed by Laird et al. (1989). The validity of the method appears however limited to smectite-group minerals [layer charge density ranging from ~0.5 to ≤1.2 per O 20 (OH) 4 ] most likely owing to the coexistence of both stable "layered" and paraffin-like interlayer configurations for higher values of layer charge. In addition, this consistency challenges the ability of the method to quantitatively describe distributions of layer charge in expandable phyllosilicates even when using the complete series of alkylammonium cations. • Layer charge of synthetic saponites is assessed using the alkyl ammonium method (AAM). • Variation of layer-to-layer distances with alkyl chain length is compared with simulations. • Consistency of experimental and computational data confirms the robustness of the AAM. • The AAM appears unable to determine distribution of layer charge. • The AAM appears unable to differenciate high values of layer charge (vermiculites). [ABSTRACT FROM AUTHOR]

Global food security concerns have spurred increasing demand for locally sourced and produced K-fertilizers. Various processes have been explored for more than a century; one promising solution is based on the alkaline aqueous alteration of feldspar-rich rocks at elevated temperatures. However, knowledge of the overall physico-chemical reactions comprising dissolution of feldspar and precipitation of secondary phases is still rudimentary, in particular how the feldspar structure evolves at the nm-scale during hydrolysis at alkaline conditions. Here we report on the results of a study aimed at converting potassium feldspars to K-rich fertilizer based on the alteration of sanidine and microcline samples at 190 °C in pH 12 Ca(OH) 2 solutions for 24 h. Based on X-ray diffraction and Rietveld refinement, the secondary authigenic minerals that precipitated are primarily composed of Ca-carbonate (calcite, vaterite), and Ca-(Al)-silicates, such as tobermorite and hydrogrossular. Short-term bench top leaching experiments in water prove that the hydrothermal product releases up to two orders of magnitude more K than the unaltered K-feldspar starting material, pointing to its application as a ready-to-use fertilizer for K-deficient soils. Detailed chemical mapping and energy dispersive X-ray spectroscopy (FESEM- and TEM-EDXS) analyses of the precipitates at the μm to nm-scale show that the distribution of K associated with the secondary phases is very heterogeneous, both spatially and in terms of concentrations. Using various analytical transmission electron microscopy (TEM) techniques, e.g., HRTEM, TEM-EDXS, EFTEM, to investigate the structure and chemistry of the feldspar interface, we find no evidence for a change in chemistry or structure at the nm-scale, even though dissolution continuously decreases the volume of each grain. Our observations also show the existence of an amorphous surface altered layer (SAL) of variable thickness (10–~100 nm) forming at the feldspar interface. Nanometer-scale chemical measurements show that this amorphous SAL is rich in K, and therefore may also be an important reservoir of easily leachable K. We hypothesize that it forms continuously and in situ at the expense of the feldspar by a coupled interfacial dissolution-reprecipitation process (CIDR). • Alkaline hydrothermal alteration of K-feldspars yields K-fertilizer for soils. • SEM and TEM techniques used to measure [K] in secondary phases and interface. • Labile K in hydrothermal product associated with soluble secondary phases. • The K-feldspar structure dissolves stoichiometrically, with no change in chemistry. • Coupled interfacial dissolution-reprecipitation (CIDR) controls dissolution process. [ABSTRACT FROM AUTHOR]

Smectite hydration impacts dynamical properties of interlayer cations and thus the transfer and fate of H 2 O, contaminants, and nutriments in surficial environments where this ubiquitous clay mineral is often one of the main mineral components. The influence of key crystal-chemical parameters, such as the amount of charge or the presence of fluorine, rather than hydroxyl groups, in smectite anionic framework, on hydration, organization of interlayer species, and related properties has been described for tetrahedrally substituted trioctahedral smectites (saponites). Despite the ubiquitous character of octahedrally substituted smectites, that make most of the world bentonite deposits, the influence of charge location on smectite hydration properties has not received similar attention. A set of octahedrally substituted trioctahedral smectites (hectorites) with a common structural formula Na x Mg 6-x Li x Si 8.0 O 20 (OH) 4 and a layer charge (x) varying from 0.8 to 1.6 was thus synthesized hydrothermally. The distribution of charge-compensating Na+ cations and of associated H 2 O molecules was determined experimentally from the modeling of X-ray diffraction data obtained along water vapor desorption isotherms. Consistent distributions of charge-compensating cations and of associated H 2 O molecules were also computed from GCMC simulations as a function of layer charge. Interlayer H 2 O contents [2.5–5.5 and 8.0–10.0 H 2 O molecules per O 20 (OH) 4 for 1W and 2W hydrates, respectively] are similar in all Na-saturated smectite samples, independent of the location and amount of their layer charge. In contrast to synthetic saponite, for which stability of most hydrated layers was increased by increasing layer charge, the stability of synthetic hectorite hydrates is only marginally affected by layer charge. Consistently, the layer-to-layer distance of Na-saturated hectorite 2W (and 1W) layers is independent of layer charge (15.10–15.65 Å and 12.0–12.6 Å, respectively). The contrasting hydration behavior of synthetic Na-saturated saponite and hectorite is likely due to different electrostatic attraction between the 2:1 layer and interlayer cation, the charge undersaturation of O atoms at the surface of hectorite 2:1 layer being more diffuse compared to saponite. Combined with previous results on saponites, the present data and sample set provides key constraints to assess the validity of force fields simulating clay-water interactions for an unmatched variety of smectite with contrasting locations and amounts of layer charge deficits. Unlabelled Image • Hectorites with a layer charge varying from 0.8 to 1.6 were synthesized hydrothermally. • H 2 O contents of 1W and 2W layers are independent of layer charge amount and location. • Hectorite hydration is marginally affected by the amount of layer charge. • Saponite & hectorite different hydration behaviors due to undersaturation of O atoms. [ABSTRACT FROM AUTHOR]