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Goethite and modified goethites have been found as good photocatalysts because their conduction band can mediate electron transfer in various redox processes. Many kinds of metal elements can be incorporated into the structure of goethite to form solid solutions in nature, but their optoelectronic properties have not been well disclosed. Mn-substituted goethite is one of the potential photocatalysts, which can exhibit high-photocatalytic activity in many Earth’s surface processes. Based on the first-principles calculation, pairwise interaction energies and static lattice energies of goethitegroutite solid solution were computed, and the most thermodynamically stable configurations of Mn-substituted goethite were determined. The results indicate that Mn3+ ion tends to distribute within the cation layer parallel to the (001) plane. Phase relations of goethite-groutite solid solution were derived by subsequent configurational statistics with energies of all 232 configurations of a 2 × 1 × 4 supercell with 32 exchangeable cations. The phase diagram shows that no more than 3 mol% Fe of goethite can be substituted by Mn ions. Therefore, Mn-substituted goethite is thermodynamically metastable or bears groutite-like clusters/lamellae. Furthermore, the effects of Mn substitutions on the band gap were experimentally and theoretically investigated. It is found that a small amount of Mn-substitution can reduce the band gap of goethite significantly, and the decrease ceases when the Mn content is higher than 3–4 mol%. Such a decrease in band gap causes red-shift to the photo response wavelength of goethite and improves the responding capability. This improvement was confirmed in the experiments of photocatalytic degradation of methylene blue (MB). Such kind of photocatalytic reaction probably can happen widely in natural environments. Therefore, the contribution of photocatalysis of natural goethites to geochemical processes on Earth’s surface should be considered.

Hydroxyapatite (HAp) has been widely used to remove cadmium (Cd) in contaminated water and soils via Cd-Ca substitution. The Cd incorporation into HAp affects its structure; however, the detailed mechanism remains unclear. In this study, a series of Cd-substituted hydroxyapatites were synthesized and characterized with various techniques. Cd incorporation causes a decrease in a- and c-lattice parameters due to the radius of Cd2+ being slightly smaller than that of Ca2+. As the Cd content increases, the particle sizes of the synthesized samples decrease and their specific surface areas increase. Raman bands shift linearly and the ν1(PO4) peak at 961 cm−1 becomes broadened with increasing Cd content. Change in X-ray absorption near edge structure (XANES) spectra of the P K-edge indicates distortion of phosphate with Cd incorporation. Total electron yield (TEY) spectra of the Ca L2,3-edge show a decrease in the octahedral symmetry, suggesting preferential occupancy of Cd over the Ca2 site. Extended X-ray absorption fine structure (EXAFS) analysis of the Ca K-edge reveals no obvious change in the local environment of Ca induced by Cd incorporation. However, EXAFS analysis of the Cd K-edge indicates that the substituted Cd occupies one Ca2 site in hexagonal Ca2 positions at low-Cd contents [

Fungi actively enhance the local dissolution of nutrient-bearing minerals through the combined biomechanical and biochemical actions of their hyphal tips to obtain mineral-bound inorganic nutrients (MINs). However, little is known about the dynamic processes underlying hyphal tip-mineral interactions. Here, we assess the adhesive force between a single hypha of the common fungus Talaromyces flavus and the Fe-bearing silicate lizardite and quartz (as a control), as well as hyphal tip-induced lizardite weathering and hyphal Fe uptake. We showed that T. flavus hyphae formed their maximal adhesive force with lizardite at the growing tips, reaching 6.11 ± 0.69 nN after a contact time of one minute. The adhesive forces of the tip-lizardite interface within two minutes were > 2.65 times stronger than those of the tip-quartz interface. Examination of the hyphal tip-lizardite interface after 18 h indicated the formation of dissolution channels with a depth of 27.7 ± 8.0 nm. Furthermore, the hyphal tips resulted in an altered lizardite up to 46 nm. The thickness of the altered lizardite increased to ∼130 nm after contact with the mature regions of the hyphae for ∼173 min. And the altered lizardite was found to have depleted Fe levels that increased with increasing contact time. The total content of Fe in T. flavus associated with the lizardite surface after 18 h was 52.98 ± 12.20 nmol mg-1, which was 6 times greater than the total amount of Fe in quartz surface-associated T. flavus after 24 h of culture. These results demonstrate that fungi access MINs by the active development of a strong adhesive force with target minerals through their hyphal tips, effectively enabling fungi to flourish in heterogeneous environments and be major geological agents for biogeochemical transformation.

Birnessite-type MnO

Iron hydroxides are ubiquitous in soils and aquifers and have been adopted as adsorbents for As(V) removal. However, the complexation mechanisms of As(V) have not been well understood due to the lack of information on the reactive sites and acidities of iron hydroxides. In this work, we first calculated the acidity constants (pKas) of surface groups on lepidocrocite (010), (001), and (100) surfaces by using the first-principles molecular dynamics (FPMD)-based vertical energy gap method. Then, the desorption free energies of As(V) on goethite (110) and lepidocrocite (001) surfaces were calculated by using constrained FPMD simulations. The point of zero charges and reactive sites of individual surfaces were obtained based on the calculated pKas. The structures, thermodynamics, and pH dependence for As(V) complexation were derived by integrating the pKas and desorption free energies. The pKa data sets obtained are fundamental parameters that control the charging and adsorption behavior of iron oxyhydroxides and will be very useful in investigating the adsorption processes on these minerals. The pH-dependent complexation mechanisms of As(V) derived in this study would be helpful for the development of effective adsorbent materials and the prediction of the long-term behavior of As(V) in natural environments.

In this paper, we report a first-principles Molecular Dynamics (FPMD) study of interfacial structures and acidity constants of goethite. The pKa values of the groups on (010), (110), and (021) surfaces (space group Pbnm) are derived with the FPMD based vertical energy gap technique. The results indicate that major reactive groups include ≡Fe2OH2 and ≡FeOH2 on (010), ≡FeOH2, ≡Fe3OLH, and ≡Fe3OUH on (110), and ≡FeOhH2 and ≡Fe2OH on (021). The interfacial structures were characterized in detail with a focus on the hydrogen bonding environment. With the calculated pKa values, the point of zero charges (PZCs) of the three surfaces are derived and the overall PZC range of goethite is found to be consistent with the experiment. We further discuss the potential applications of these results in future studies toward understanding the environmental processes of goethite.

Layered double hydroxides (LDHs) are potential low-cost filter materials for use in fluoride removal from drinking water, but molecular-scale defluoridation mechanisms are lacking. In this research, we employed 19F solid-state NMR spectroscopy to identify fluoride sorption products on 2:1 MgAl LDH and to reveal the relationship between fluoride sorption and the LDH structure. A set of six 19F NMR peaks centered at -140, -148, -156, -163, -176, and -183 ppm was resolved. Combining quantum chemical calculations based on density function theory (DFT) and 19F{27Al} transfer of populations in double resonance (TRAPDOR) analysis, we could assign the peaks at -140, -148, -156, and -163 ppm to Al-F (F coordinated to surface Al) and those at -176 and -183 ppm to Mg-F (F coordinated to surface Mg only). Interestingly, the spectroscopic data reveal that the formation of Al-F is the predominant mode of F- sorption at low pH, whereas the formation of Mg-F is predominant at high pH (or a higher Mg/Al ratio). This finding supports the fact that the F- uptake of 2:1 MgAl LDH was nearly six times that of activated alumina at pH 9. Overall, we explicitly revealed the different roles of the surface >MgOH and >AlOH sites of LDHs in defluoridation, which explained why the use of classic activated alumina for defluoridation is limited at high pH. The findings from this research may also provide new insights into material screening for potential filters for F- removal under alkaline conditions.

Fe is a common substituent in palygorskites (Plg), but its effect on the microscopic properties is unclear. In the current study, molecular dynamics (MD) simulations were carried out to investigate the effect of Fe on the properties of the nano-pores in Plg. The structures and dynamics of water and Na+ ions in the pores were computed by analyzing the MD trajectories. The results revealed that for both Fe-containing and ordinary Plg, zeolitic water molecules can diffuse into the pores with very low mobility whereas Mg-coordinated water fails to escape. Na+ ions show no obvious diffusivity because they are fixed above the Si–Osix-membered rings. Detailed comparison indicates that Fe-substitution has no significant influence on the pore properties of Plg.

Microplastics are ubiquitous in the freshwater environment, while its abundance in the sediment profiles has received little attention. The vertical microplastic distribution in the sediment of the North (NTH) and Southwest (SWTH) Taihu Lake were identified and characterized in this study. Microplastics could be detected at all depths (0–50 cm) at the two sites, with the total abundance of 8066 and 5333 particles kg-1 dry weight sediment at NTH and SWTH, respectively. This indicates that the microplastic storage in the sediment of the Taihu Lake may be underestimated, if only the surface sediment is considered. Microplastics composed of various polymer types were identified in the sediment of the two sites, including polyamide (PA), acrylic acid (AA), polyethylene terephthalate (PET) and cellulose acetate (CA), while high density polyethylene (HDPE) and polypropylene (PP) were only detected at NTH. The main type of polymers detected at NTH (42%) and SWTH (43%) were PA. The majority shape of microplastics was fibers, with a ratio of 76% and 78%, respectively at the site NTH and SWTH. The colors of microplastics were mainly white (accounted for 42% and 43% at NTH and SWTH, respectively), which may be caused by the long-term decomposition of dyestuff in the syngenesis of sediment and/or probably the degradation during sample treatments. The textile industry and fishery activities may provide the source. In summary, our findings in the Taihu Lake favors to understand the microplastic pollution and tackle microplastics challenges.

Knowledge of Sn(II) speciation in aqueous and gaseous phases and the corresponding isotope effects are critical for understanding the transport and deposition of Sn in various geological and cosmochemical processes. In this study, we use first principles method to investigate the speciation of stannous (Sn(II)) chloride in fluids under hydrothermal and supercritical conditions. The results show that SnCl3−, SnCl2(H2O) and SnCl(H2O)2+ are stable in hydrothermal solutions at temperatures of up to 300 °C, with SnCl3− being the dominant species, whereas SnCl2 and SnCl2(H2O) are the stable species in vapor phases. Notably, SnCl2 is found to be stable under supercritical conditions. The reduced partition function ratios (β factors) for the stable Sn(II) species and three major Sn minerals (cassiterite, megawite, and romarchite) are also calculated by first principles methods. The calculation results show that under equilibrium, heavy Sn isotopes are preferentially partitioned into stannic (Sn(IV)) species, and gaseous species enrich heavy Sn isotopes relative to aqueous species. Based on the equilibrium Sn isotope fractionation factors derived in this study, we use a transport-precipitation model to evaluate the Sn isotope response to cassiterite precipitation in hydrothermal fluids. The modeling results show that significant Sn isotope variability could be produced during cassiterite precipitation, with temperature and Sn speciation being the primary controlling factors. Furthermore, by comparing the Sn isotope variability in natural cassiterite and those derived from the model, we argue that Sn should occur predominantly as Sn(IV) species in hydrothermal fluids during cassiterite precipitation in tin mineralizing systems.

Fungus-mineral interactions influence a variety of geochemical and biological processes on and near the Earth’s surface. The secondary metabolites produced by fungi during these interactions control mineral weathering and affect geochemical element cycling; however, the extent to which minerals exert their influence on fungal metabolism has not been quantitatively determined in detail. Here, we used mass spectroscopy to investigate the exometabolome of Talaromyces flavus, a serpentine soil-inhabiting fungus, during interactions with antigorite, chlorite, hornblende, lizardite, magnetite, and quartz at 28 °C under aerobic conditions. Our experimental results showed that all the minerals used promoted spore germination and hyphal growth. The glucose consumption rate during the initial stages of the fungus-mineral interactions indicated that the metabolic activity of T. flavus was enhanced by a factor of ∼7 by lizardite, antigorite, chlorite, hornblende, and magnetite and by a factor of ∼3 by quartz. A total of 1198 secondary metabolites were detected at 166 h, and 977 (81.55%) of them were common to the T. flavus interactions with antigorite, chlorite, hornblende, lizardite, and magnetite. Statistical and comparative analyses of the 28 most common organic acids revealed that the production of these secondary metabolites by T. flavus was highly mineral-specific and that their content varied significantly in response to the different minerals. Moreover, the component composition of the secondary metabolites of T. flavus interacting with lizardite was more similar to chlorite and magnetite than to antigorite, hornblende, and quartz. Strong correlations were found between the production of gluconic, oxalic, citric, and itaconic acid and the bioavailability of certain elements. Fumaric and orsellinic acid production were stimulated by magnetite and chlorite, respectively. These results demonstrate that fungi can significantly regulate their metabolic behavior during interactions with minerals and that their metabolic regulation is primarily related to the chemical composition, weatherability, and surface properties of the minerals. Such biotic and abiotic responses have important implications for the fungus-induced geochemical transformation of minerals and metals.

Chiral α-amino acids play critical roles in the metabolic process in nearly all life forms. So far, chiral recognition of α-amino acids has mainly focused on the determination of l/d enantiomers. Herein, selection of planar chiral conformations between water-soluble pillar[5]arene WP5 and pillar[6]arene WP6 was observed due to α-side chain or ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides binding with WP5 and WP6, respectively. Therefore, α-side chain and ethyl ester moieties of l-α-amino acid ethyl ester hydrochlorides were recognized by observing the induced CD signal and its inversion. This is a rare example of being able to detect the chiral region around α-carbon of a chiral α-amino acid molecule.

The expression of specific crystal facets in different nanostructures is known to play a vital role in determining the sensitivity toward the photodegradation of organics, which can generally be ascribed to differences in surface structure and energy. Herein, we report the synthesis of hematite nanoplates with controlled relative exposure of basal (001) and edge (012) facets, enabling us to establish direct correlation between the surface structure and the photocatalytic degradation efficiency of methylene blue (MB) in the presence of hydrogen peroxide. MB adsorption experiments showed that the capacity on (001) is about three times larger than on (012). Density functional theory calculations suggest the adsorption energy on the (001) surface is 6.28 kcal/mol lower than that on the (012) surface. However, the MB photodegradation rate on the (001) surface is around 14.5 times faster than on the (012) surface. We attribute this to a higher availability of the photoelectron accepting surface Fe3+ sites on the (001) facet. This facilitates more efficient iron valence cycling and the heterogeneous photo-Fenton reaction yielding MB-oxidizing hydroxyl radicals at the surface. Our findings help establish a rational basis for the design and optimization of hematite nanostructures as photocatalysts for environmental remediation.

Subduction of atmospheric noble gases has been considered to play an important role in altering the primordial isotopes of Earth’s mantle over geological time. Analysis of natural samples and experiments indicate that large quantities of noble gases can be dissolved in volatile-bearing hydrous minerals in the subduction slabs. To quantitatively investigate the recycling efficiency of noble gases and relevant consequences on the mantle noble gas isotopic evolution, the diffusivities of noble gases in these minerals are needed. In this study, diffusion of He, Ne, Ar, Kr and Xe in lizardite, antigorite and tremolite have been calculated by first-principles methods based on density functional theory. Our results disclose that diffusion is slower with increasing radius of the noble gas atom (DHe > DNe > DAr > DKr > DXe) as expected. The common ring-structures in hydrous silicate minerals provide incorporation sites for the noble gas atoms and control their mobility. The diffusion activation energies are 84.9, 157.3, 287.5, 347.4, 414.9 kJ/mol from He to Xe in lizardite, and despite the very similar lattice structure between lizardite and antigorite, the activation energies are found to be significantly higher in antigorite, which are 120.6, 267.3, 449.6, 497.9 and 550.0 kJ/mol, respectively. In tremolite, the energy barriers are 93.6, 158.2, 266.3, 322.2 and 385.0 kJ/mol, which are also found to be in very good agreement with available experimental values and similar to those in lizardite. We also calculated diffusion activation energies at higher pressures (1 GPa for liazardite, 3 GPa for antigorite and tremolite) to better understand how much noble gases can be preserved against diffusive loss during subduction. Our result show that the oceanic crust and the lithospheric mantle of the subduction slab play different roles in delivering noble gases into the mantle. We find that all Ar, Kr, Xe and possibly part of the Ne can be entrained by the serpentine-dominated lithospheric mantle into the deep mantle due to the high diffusive energy barriers in antigorite. In contrast, noble gases in the amphibole-enriched oceanic crust would be characterized by fractionated noble gas signature, with the concentrations of retained noble gases in the crust following their respective ionic radius (Ne

A better understanding on gas flow in nanopores will advance the knowledge of gas accumulation and preservation in shale as well as development of shale gas exploitation. A modified LB model for na...

In this study, clay-soil organic matters (SOMs) interactions were investigated by combining first principles molecular dynamics (FPMD) and classical molecular dynamics (CMD) techniques. FPMD was employed to quantify the binding mechanisms of reactive SOMs groups on clay surfaces and to derive parameters for the bonding of the reactive groups on edge surfaces. By integrating the derived parameters with CVFF–CLAYFF force fields, CMD simulations were carried out to investigate the structures of large models of clay-SOMs associations. All possible reactive SOMs groups, including carboxylate, phosphate, quinone species and ammonium groups were taken into account. FPMD results showed that all these groups are important to the complexation of SOMs on clay surfaces under dry conditions but only chemical bonding of carboxylate and phosphate and cation bridging are of significance under wet conditions. pH dependence of carboxylate and phosphate and Eh-pH dependence of quinone species are presented. CMD simulations showed that SOMs bound on clay surfaces via direct bonding of carboxylate and Ca2+ bridging and revealed the effect of water on structures of the clay-SOMs association. Based on the computational results, a procedure was proposed for constructing realistic molecular models for soils. Possible applications and further improvements of these models are discussed.

A stoichiometry-controlled chirality induction was successfully achieved through coassemblies of amphiphilic tetraphenylethylene derivative TPEA, γ-cyclodextrin (γ-CD), and water-soluble pillar[5]a...

This research was supported by the Key Research Program of Frontier Sciences CAS [QYZDY-SSW-DQC026] and the National Natural Science Foundation of China [41590853]. SRTM DEM and NASA HMA DEM data were sourced from NASA Earthdata (https://earthdata.nasa.gov/), and the ALOS Global Digital Surface Model (AW3D30) was sourced from JAXA (https://www.eorc.jaxa.jp/ALOS/en/aw3d30/index.htm). ALOS PRISM level-1B1 products were ordered from http://en.alos-pasco.com/alos/prism/ under a 4th ALOS RA data grant awarded to Quincey (PI No. 1008). Landsat-7 and Landsat-8 images can be freely downloaded from http://glovis.usgs.gov. Randolph Glacier Inventory data were acquired from Global Land Ice Measurements from Space (GLIMS) (RGI Consortium, 2017). Lv acknowledges program B for outstanding PhD candidates of Nanjing University and the support from the Chinese Scholarship Council (CSC) for studying at the University of Leeds. Glaciers in the eastern Pamir have reportedly been gaining mass during recent decades, even though glaciers in most other regions in High Mountain Asia have been in recession. Questions still remain about whether the trend is strengthening or weakening, and how far the positive balances extend into the eastern Pamir. To address these gaps, we use three different digital elevation models to reconstruct glacier surface elevation changes over two periods (2000–09 and 2000–15/16). We characterize the eastern Pamir as a zone of transition from positive to negative mass balance with the boundary lying at the northern end of Kongur Tagh, and find that glaciers situated at higher elevations are those with the most positive balances. Most (67% of 55) glaciers displayed a net mass gain since the 21st century. This led to an increasing regional geodetic glacier mass balance from −0.06 ± 0.16 m w.e. a−1 in 2000–09 to 0.06 ± 0.04 m w.e. a−1 in 2000–15/16. Surge-type glaciers, which are prevalent in the eastern Pamir, showed fluctuations in mass balance on an individual scale during and after surges, but no statistical difference compared to non-surge-type glaciers when aggregated across the region. Publisher PDF

A dissipative assembly process is an out-of-equilibrium dynamic process driven by chemical fuels. Such processes play very important roles in different types of biochemical process in nature. Herei...

Although biodiversity and ecosystem functions are strongly shaped by contemporary environments, such as climate and local biotic and abiotic attributes, relatively little is known about how they depend on long-term geological processes. Here, along a 3000-m elevational gradient with tectonic faults on the Tibetan Plateau (that is, Galongla Mountain in Medog County, China), we study the joint effects of geological and contemporary environments on biological communities, such as the diversity and community composition of plants and soil bacteria, and ecosystem functions. We find that these biological communities and ecosystem functions generally show consistent elevational breakpoints at 2000–2800 m, which coincide with Indus-Yalu suture zone fault and are similar to the elevational breakpoints of soil bacteria on another mountain range 1000 km away. Mean annual temperature, soil pH and moisture are the primary contemporary determinants of biodiversity and ecosystem functions, which support previous findings. However, compared with the models excluding geological processes, inclusion of geological effects, such as parent rock and weathering, increases 67.9 and 35.9% of the explained variations in plant and bacterial communities, respectively. Such inclusion increases 27.6% of the explained variations in ecosystem functions. The geological processes thus provide additional links to ecosystem properties, which are prominent but show divergent effects on biodiversity and ecosystem functions: parent rock and weathering exert considerable direct effects on biodiversity, whereas indirectly influence ecosystem functions via interactions with biodiversity and contemporary environments. Thus, the integration of geological processes with environmental gradients could enhance our understanding of biodiversity and, ultimately, ecosystem functioning across different climatic zones.

CO2-Switchable surfactants are of great potential in a wide range of industrial applications related to their ability to stabilize and destabilize emulsions upon command. Molecular dynamics simulations have been performed to reveal the fundamental mechanism of the reversible emulsification/demulsification processes of a dodecane–saline system by a CO2-switchable surfactant that switches between active (i.e., N′-dodecyl-N,N-dimethylacetamidinium (DMAAH+)) and inactive (i.e., N′-dodecyl-N,N-dimethylacetamidine (DMAA)) forms. The density profiles indicate that DMAAH+ could increase the oil–water interfacial thickness to a greater extent compared to DMAA. DMAAH+ could sharply reduce the interfacial tension of the dodecane–saline system, while DMAA only exhibits a limited decrease, which is in accordance with the experimental observation that DMAAH+/DMAA can reversibly emulsify/demulsify alkane–water systems. Our simulations showed that both the number and lifetime of hydrogen bonds (HBs) between DMAA and water are almost equal to those between DMAAH+ and water. In DMAA, the N atom connecting with the alkyl tail acted as a HB acceptor, while the N atom attached by a proton in DMAAH+ acted as a HB donor. Furthermore, the HBs between DMAAH+ and HCO3− at the interfaces are relatively limited. Hence, it is deduced that the HBs are insufficient to achieve the CO2-switchability of DMAA/DMAAH+. The Lennard Jones and coulombic potentials between DMAA/DMAAH+ and other species show that the coulombic potentials between DMAAH+ and water or anions (i.e., Cl− and HCO3−) sharply decrease with the increase of DMAAH+ and are much lower than those in models with DMAA. The enhanced coulombic interactions between DMAAH+ and anions lead to a remarkable reduction in interfacial tension and the emulsification of the alkane–saline system. Therefore, coulombic interactions are of crucial importance to the reversible emulsification/demulsification processes regulated by CO2-switchable surfactants, namely DMAAH+/DMAA.

Silica, water, and hydrogen are known to be the major components of celestial bodies, and have significant influence on the formation and evolution of giant planets, such as Uranus and Neptune. Thus, it is of fundamental importance to investigate their states and possible reactions under the planetary conditions. Here, using advanced crystal structure searches and first-principles calculations in the Si-O-H system, we find that a silica-water compound (SiO_{2})_{2}(H_{2}O) and a silica-hydrogen compound SiO_{2}H_{2} can exist under high pressures above 450 and 650 GPa, respectively. Further simulations reveal that, at high pressure and high temperature conditions corresponding to the interiors of Uranus and Neptune, these compounds exhibit superionic behavior, in which protons diffuse freely like liquid while the silicon and oxygen framework is fixed as solid. Therefore, these superionic silica-water and silica-hydrogen compounds could be regarded as important components of the deep mantle or core of giants, which also provides an alternative origin for their anomalous magnetic fields. These unexpected physical and chemical properties of the most common natural materials at high pressure offer key clues to understand some abstruse issues including demixing and erosion of the core in giant planets, and shed light on building reliable models for solar giants and exoplanets.

The directional hydrogen-bond (HB) network and nondirectional van der Waals (vdW) interactions make up the specificity of water. Directional HBs could construct an ice-like monolayer in hydrophobic confinement even in the ambient regime. Here, we report a water monolayer dominated by vdW interactions confined in a phyllosilicate interlayer under high pressure. Surprisingly, it was in a thermodynamically stable state coupled with bulk water at the same pressure (P) and temperature (T), as revealed by the thermodynamic integration approach on the basis of molecular dynamics (MD) simulations. Both classical and ab initio MD simulations showed water O atoms were stably trapped and exhibited an ordered hexagonal closest-packing arrangement, but OH bonds of water reoriented frequently and exhibited a specific two-stage reorientation relaxation. Strikingly, hydration in the interlayer under high pressure had no relevance with surface hydrophilicity rationalized by the HB forming ability, which, however, determines wetting in the ambient regime. Intercalated water molecules were trapped by vdW interactions, which shaped the closest-packing arrangement and made hydration energetically available. The high pressure-volume term largely drives hydration, as it compensates the entropy penalty which is restricted by a relatively lower temperature. This vdW water monolayer should be ubiquitous in the high pressure but low-temperature regime.

Microbes play a critical role in regulating the size, composition, and turnover of dissolved organic matter (DOM), which is one of the largest pools of carbon in aquatic ecosystems. Global change may alter DOM-microbe associations with implications for biogeochemical cycles, although disentangling these complex interactions remains a major challenge. Here we develop a framework called Energy-Diversity-Trait integrative Analysis (EDTiA) to examine the associations between DOM and bacteria along temperature and nutrient gradients in a manipulative field experiment on mountainsides in contrasting subarctic and subtropical climates. In both study regions, the chemical composition of DOM correlated with bacterial communities, and was primarily controlled by nutrients and to a lesser degree by temperature. At a molecular-level, DOM-bacteria associations depended strongly on the molecular traits of DOM, with negative associations indicative of decomposition as molecules are more biolabile. Using bipartite networks, we further demonstrated that negative associations were more specialized than positive associations indicative of DOM production. Nutrient enrichment promoted specialization of positive associations, but decreased specialization of negative associations particularly at warmer temperatures in subtropical climate. These global change drivers influenced specialization of negative associations most strongly via molecular traits, while both molecular traits and bacterial diversity similarly affected positive associations. Together, our framework provides a quantitative approach to understand DOM-microbe associations and wider carbon cycling across scales under global change.

The solubilization and mobilization of elements from silicate minerals during fungal weathering are predominantly promoted by acidification and complexation reactions. However, stark differences exist in the release rates of different elements driven by fungal-derived low molecular weight organic compounds (LMWOCs) when acidity maintains constant, raising the question of whether the release of individual element during dissolution is ligand-specific. In this work, we investigate this question by characterizing the release of Mg, Si, Fe, and Ni from lizardite [(Mg, Fe, Ni)3Si2O5(OH)4]. Miniaturized batch reactors (microplate wells of 250 µL) were used in dissolution experiments in the presence and absence of the indigenous fungus Talaromyces flavus. Abiotic chemical weathering experiments with metabolically relevant organics and HCl were also carried out to isolate the vital effects of elemental releases. The initial release rates of Mg, Si, Fe, and Ni were obtained from determining the dissolved elemental concentrations. The results show that T. flavus enhances the release of Mg and Si by a factor of ∼2, but that of Fe and Ni by a factor of >10, relative to the rates measured in the control experiment. Additionally, the measurements show an overexcretion of siderophores and oxalic acid, as well as acidification of bulk solution, during bioweathering. Abiotic chemical dissolution of lizardite confirms the release of Fe and Ni proceeds mainly via a ligand-promoted pathway. In addition, the results indicate that siderophores and oxalic acid are responsible for the solubilization of Fe and Ni, respectively. These findings provide direct evidence that the rate and mechanism of elemental release from silicate during bioweathering are ligand-specific, and both synergistic and inhibitory effects may be involved. Given that siderophore- and oxalic acid-producing fungi are highly active in soils, these results may have the potential to advance our understanding of the critical roles of fungi in rhizosphere geochemistry and ecology.

Modern thermodynamic assessment studies of multicomponent systems typically employ the Compound Energy Formalism (CEF) to describe phases of variable composition, which may show effects of chemical ordering. In CEF, the ordering is described by splitting a crystallographic site in which several components can substitute for each other into subsites (sublattices) and by allowing fractional occupancies of these subsites to vary. This type of component redistribution over subsites (sublattices) is classified in solid solution theories as long-range order (LRO). A well-known shortcoming of CEF is the absence of a direct description of the effects of short-range order (SRO), which do not involve a redistribution of components between sublattices, but reveal themselves in various modes of clustering. Here we show that SRO can be taken into account within CEF as an additional (fictive) LRO effect driven by an extra negative excess enthalpy term. We argue that the mathematical form of this term should be constrained such that it ensures its vanishing both in low- and high-temperature limits. Including such a term into CEF allows a significant improvement in the description of phase relations in the system of calcite-magnesite, CaCO3-MgCO3. The modified CEF model with SRO emulation is made available in the GEM-Selektor software.

Crystallization is one of the most fundamental processes for both solid inorganic and organic materials in nature. The classical crystallization model mainly involves the monomer-by-monomer addition of simple chemical species. Recently, nanoparticle attachment has been realized as an important mechanism of crystallization in comparatively low-temperature aqueous natural and synthetic systems. However, no evidence of crystallization by particle attachment has been reported in petrologically important melts. In this study, we described spherical (Mg,Fe)-oxides with a protrusion surface in a shock-induced melt pocket from the martian meteorite Northwest Africa 7755. Transmission electron microscopic observations demonstrate that the (Mg,Fe)-oxides are structure-coherent intergrowth of ferropericlase and magnesioferrite. The magnesioferrite is mainly present adjacent to the interface between (Mg,Fe)-oxides spherules and surrounding silicate glass, but not in direct contact with the silicate glass. Thermodynamic and kinetic considerations suggest that development of the spherical (Mg,Fe)-oxides can be best interpreted with crystallization by particle attachment and subsequent Ostwald ripening. This indicates that crystallization by particle attachment can also take place in high-temperature melts and has potential implications for understanding the nucleation and growth of early-stage crystals in high-temperature melts, such as chondrules in the solar nebula, erupted volcanic melts, and probably even intrusive magmas.