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Analyses by the CheMin X-ray diffraction instrument on Mars Science Laboratory show that gypsum, bassanite, and anhydrite are common minerals at Gale crater. Warm conditions (∼6 to 30 °C) within CheMin drive gypsum dehydration to bassanite; measured surface temperatures and modeled temperature depth profiles indicate that near-equatorial warm-season surface heating can also cause gypsum dehydration to bassanite. By accounting for instrumental dehydration effects we are able to quantify the in situ abundances of Ca-sulfate phases in sedimentary rocks and in eolian sands at Gale crater. All three Ca-sulfate minerals occur together in some sedimentary rocks and their abundances and associations vary stratigraphically. Several Ca-sulfate diagenetic events are indicated. Salinity-driven anhydrite precipitation at temperatures below ∼50 °C may be supported by co-occurrence of more soluble salts. An alternative pathway to anhydrite via dehydration might be possible, but if so would likely be limited to warmer near-equatorial dark eolian sands that presently contain only anhydrite. The polyphase Ca-sulfate associations at Gale crater reflect limited opportunities for equilibration, and they presage mixed salt associations anticipated in higher strata that are more sulfate-rich and may mark local or global environmental change. Mineral transformations within CheMin also provide a better understanding of changes that might occur in samples returned from Mars.

Determining the shape of plant cellulose microfibrils is critical for understanding plant cell wall molecular architecture and conversion of cellulose into biofuels. Only recently has it been determined that these cellulose microfibrils are composed of 18 cellulose chains rather than 36 polymers arranged in a diamond-shaped pattern. This study uses density functional theory calculations to model three possible habits for the 18-chain microfibril and compares the calculated energies, structures, 13 C NMR chemical shifts and WAXS diffractograms of each to evaluate which shape is most probable. Each model is capable of reproducing experimentally-observed data to some extent, but based on relative theoretical energies and reasonable reproduction of all variables considered, a microfibril based on 5 layers in a 34443 arrangement is predicted to be the most probable. A habit based on a 234432 arrangement is slightly less favored, and a 6 × 3 arrangement is considered improbable.

Biomaterials are synthetic compounds and composites that replace or assist missing or damaged tissue or organs. This review paper addresses Ca phosphate biomaterials that are used as aids to or substitutes for bones and teeth. The viewpoint taken is that of mineralogists and geochemists interested in (carbonated) hydroxylapatite, its range of compositions, the conditions under which it can be synthesized, and how it is used as a biomaterial either alone or in a composite. Somewhat counter-intuitively, the goal of most medical or materials science researchers in this field is to emulate the properties of bone and tooth, rather than the hierarchically complex materials themselves. The absence of a directive to mimic biological reality has permitted the development of a remarkable range of approaches to apatite synthesis and post-synthesis processing. Multiple means of synthesis are described from low-temperature aqueous precipitation, sol-gel processes, and mechanosynthesis to high-temperature solid-state reactions and sintering up to 1000°C. The application of multiple analytical techniques to characterize these apatitic, frequently nanocrystalline materials is discussed. An online supplement details the specific physical and chemical forms in which synthetic apatite and related Ca phosphate phases are used in biomaterials. The implications from this overview are the enhanced recognition of the structurally and chemically accommodating nature of the apatite phase, insight into the effects of synthesis techniques on the specific properties of minerals (specifically apatite), and the importance of surface chemistry of apatite nanocrystals. The wide range of synthesis techniques, types of analytical characterization, and applications to human health associated with apatite are a non-geological demonstration of the power of mineralogy.

Here we present a study on the quenchability of hydrous mafic melts. We show via hydrothermal experiments that the ability to quench a mafic hydrous melt to a homogeneous glass at cooling rates relevant to natural samples has a limit of no more than 9 ± 1 wt% of dissolved H2O in the melt. We performed supra-liquidus experiments on a mafic starting composition at 1-1.5 GPa spanning H2O-undersaturated to H2O-saturated conditions (from ∼1 to ∼21 wt%). After dissolving H2O and equilibrating, the hydrous mafic melt experiments were quenched. Quenching rates of 20 to 90 K/s at the glass transition temperature were achieved, and some experiments were allowed to decompress from thermal contraction while others were held at an isobaric condition during quench. We found that quenching of a hydrous melt to a homogeneous glass at quench rates comparable to natural conditions is possible at water contents up to 6 wt%. Melts containing 6-9 wt% of H2O are partially quenched to a glass, and always contain significant fractions of quench crystals and glass alteration/devitrification products. Experiments with water contents greater than 9 wt% have no optically clear glass after quench and result in fine-grained mixtures of alteration/devitrification products (minerals and amorphous materials). Our limit of 9 ± 1 wt% agrees well with the maximum of dissolved H2O contents found in natural glassy melt inclusions (8.5 wt% H2O). Other techniques for estimating pre-eruptive dissolved H2O content using petrologic and geochemical modeling have been used to argue that some arc magmas are as hydrous as 16 wt% H2O. Thus, our results raise the question of whether the observed record of glassy melt inclusions has an upper limit that is partially controlled by the quenching process. This potentially leads to underestimating the maximum amount of H2O recycled at arcs when results from glassy melt inclusions are predominantly used to estimate water fluxes from the mantle.

Contamination of water by Pb[sup.2+] and the threat of invasive vegetation affects the quality and quantity of water accessible to all life forms and has become a primary concern to South Africa and the world at large. This paper synthesized, characterized, and evaluated the resins from tannin-rich invasive Acacia species as an environmentally benign Pb[sup.2+] adsorbent. The analysis of the pore volume and surface area of the resins reveals a small pore dimension of 9 × 10[sup.−3] cc/g and large surface area (2.31–8.65 m[sup.2]/g), presenting suitable physical parameters for adsorption of Pb[sup.2+]. Langmuir model offers the best correlation data at pH 6 with maximum monolayer coverage capacity of 189.30, 105.70 and 98.82 mg/g for silver, black and green wattle tannin resins in aqueous solutions, respectively. The kinetic data suitably fits into a pseudo-second-order model, with the Dubinin–Radushkevich adsorption energy (E) ≤ 7.07 KJ/mol and intra-particle diffusion model confirming an associated physisorption process within the bio-sorption system. The thermogravimetric analysis (TGA) and Fourier-transform infrared (FT-IR) data of the resins were informative of the high thermal stability and chelating functionality such as -OH and -NH[sub.2] responsible for the removal of Pb[sup.2+]. All the resins showed good adsorption characteristics while silver wattle tannin resin has the best adsorption capacity compared to black and green wattle tannin resins. This study provides a prototype adsorbent from invasive plants for the removal of Pb[sup.2+] in water.

The wood apple shell s ( Limonia acidissima ) are often discarded as waste creating environmental hazards due to the limited knowledge of the beneficiaries of functional compounds. The current research aims to develop a process methodology to enhance the extraction efficacy of the bioactive compounds from wood apple shell using specific and combined multi-pin discharge atmospheric cold plasma (CP) and pulse ultrasound–assisted (US) extraction techniques. The numerically optimized process parameters for individual treatment of CP (15 kV voltage and 20 min time) and US (50% amplitude, 5 ml/g solvent/feed ratio) has been considered for the combined process. The CP treatment (20 min) prior to US extraction (15 min) has a significantly higher enhancement of antioxidant activity (90 DPPH% and 93 ABTS%), phenols (63.84 mg GAE/g DW), and flavonoids (6.03 mg quecertine/g DW) content compared to specific extraction techniques, i.e., CP (37.34 mg GAE/g extract DW and 77.97 DPPH%) and US (41.39 mg GAE/g extract DW and 83.56 DPPH%) that are elucidated by numerous pores and cracks noticed on the surface of CP-US extract in the scanning electron microscope (SEM) analysis. The characterization of shell extract detected better thermal stability (DSC), relative crystallinity (XRD), and diverse significant peaks (FTIR), corresponding to functional groups like polyphenol, flavonoid, and antioxidant compounds for combined process. The combined CP-US is an eco-friendly and sustainable extraction method for byproduct utilization of wood apple shell with maximum antioxidant potential that is advantageous in functional, pharmaceutical, and nutraceuticals formulations. Graphical abstract

The mineralogy of manganese nodules from the German license area in the eastern Clarion and Clipperton Zone (CCZ) of the central Pacific Ocean was studied using X-ray diffraction. Their individual nanometer to micrometer thick genetically different (hydrogenetic/diagenetic) layer growth structures were investigated using high-resolution transmission electron microscopy. Relationships between the mineral phases and metal content (e.g., Ni+Cu) were assessed with electron microprobe analyzer. The main manganese phase detected in nodules of this study was vernadite, a nanocrystalline and turbostratic phyllomanganate with hexagonal layer symmetry. In layer growth structures of hydrogenetic origin, Fe-vernadite dominates. Layer growth structures of suboxic-diagenetic origin contain three vernadite forms, which are the main Ni and Cu carriers. These Mn-phases were identified on the basis of their structural layer-to-layer distances (7 and 10 Å) and on their capacity to retain these distances when heated. The first form is 7 Å vernadite, which is minor component of the nodules. The second is a thermally unstable ∼10 Å vernadite collapsing between room temperature and 100°C, and the third is a thermally stable ∼10 Å vernadite collapsing between 100 and 300°C. Todorokite was neither detected in bulk nodules nor in any of the individual suboxic-diagenetic growth structures. Because the mineralogical composition of the nodule is quite homogeneous (only different vernadite-types), it is suggested that the content of Ni and Cu in the individual growth structures is controlled by their availability in the environment during individual growth phases. A profile through a CCZ nodule revealed that the thermal stability of the vernadites change from younger (thermally unstable vernadites, collapsing <100°C) to older growth structures (thermally stable 10 Å vernadites, collapsing >100°C) of the nodule accompanied with changes in type and amount of interlayer cations (e.g., Mg, Na, Ca, K). The stability of the vernadites is probably due to re-organization and incorporation of metals within the interlayer of the crystal structure.

We report on a systematic study on the physicochemical attributes of synthetic Fe-Cu-sulfide nanoparticles (NPs) precipitated under conditions similar to the anoxic, low-temperature aqueous, sedimentary, soil, and subsurface environments where these NPs have been repeatedly identified. Characterizing the basic attributes of these NPs is the first step in understanding their behaviors in various processes including in the bio-availability of essential and toxic metals, environmental remediation, and resource recovery. Abiotic experiments are compared to biotic experiments in the presence of the sulfate-reducer Desulfovibrio vulgaris to elucidate biological controls on NP formation. First, the single-metal end-member NPs are determined by precipitation in a solution containing either aqueous Fe(II) or Cu(II). Limited differences are observed between biogenic and abiogenic precipitates aged for up to one month; the Fe-only experiments resulted in 4-10 nm mackinawite (FeS) NPs that aggregate to form nanosheets up to ∼1000 nm in size, while the Cu-only experiments resulted in mixtures of covellite (CuS) NPs comprised of <10 nm fine nanocrystals, 20-40 × 6-9 nm nanorods, and ∼30 nm nanoplates. The crystal sizes of biogenic mackinawite and covellite are, respectively, larger and smaller than their abiogenic counterparts, indicating a mineral-specific response to biological presence. Structural defects are observable in the fine nanocrystals and nanorods of covellite in both biogenic and abiogenic experiments, indicative of intrinsic NP instability and formation mechanism via particle attachment. In contrast, covellite nanoplates are defect free, indicating high stability and potentially rapid recrystallization following particle attachment. Next, mixed-metal sulfide NPs are precipitated at variable initial aqueous Fe-to-Cu ratios (2:1, 1:1, and 1:5). With an increasing ratio of Fe-to-Cu, Fe-rich covellite, nukundamite (Cu5.5FeS6.5), chalcopyrite (CuFeS2), and Cu-rich mackinawite are formed. The Fe-rich covellite NPs are larger (100-200 nm) than covellite precipitated in the absence of Fe, indicating a role for Fe in promoting crystal growth. Chalcopyrite and nukundamite are formed through the incorporation of Fe into precursor covellite NPs while retaining the original crystal morphology, as confirmed by doping a covellite suspension with aqueous Fe(II), resulting in the formation of chalcopyrite and nukundamite within days. Additionally, in the biological systems, we observe the recrystallization of mackinawite to greigite (Fe3S4) after six months of incubation in the absence of Cu and the selective formation of chalcopyrite and nukundamite at lower initial Fe-to-Cu ratios compared to abiotic systems. These observations are consistent with NP precipitation that are influenced by the distinct (sub)micro-environments around bacterial cells compared to the bulk solution. Comparative TEM analyses indicate that the synthetic NPs are morphologically similar to NPs identified in natural environments, opening ways to studying behaviors of natural NPs using experimental approaches.

As iron sulfide mineral phases are important sedimentary sinks for naturally occurring or contaminant metals, it is important to know the fate of metals during the diagenetic transformation of primary sulfide minerals into more stable phases, such as pyrite (FeS2). Furthermore, the trace metal content of pyrite has been proposed as a marine paleoredox proxy. Given the diverse low-temperature diagenetic formation pathways for pyrite, this use of pyrite requires validation. We, therefore, studied nickel (Ni) and cobalt (Co) incorporation into freshly precipitated mackinawite (FeSm), and after experimental diagenesis to pyrite (FeS2) using S0 as an oxidant at 65 °C. Metal incorporation was quantified on bulk digests using ICP-OES or ICP-AES. Bulk mineralogy was characterized with micro-X-ray diffraction (micro-XRD), documenting the transformation of mackinawite to pyrite. Epoxy grain mounts were made anoxically of mackinawite and pyrite grains. We used synchrotron-based micro-X-ray fluorescence (µXRF) to map the distribution of Co and Ni, as well as to collect multiple energy maps throughout the sulfur (S) K-edge. Iron (Fe) and S K-edge micro-X-ray absorption near edge spectroscopy (µXANES) was used to identify the oxidation state and mineralogy within the experimentally synthesized and diagenetically transformed minerals, and map end-member solid phases within the grain mounts using the multiple energy maps. Metal-free FeSm transformed to pyrite, with residual FeSm detectable. Co- and Ni-containing FeSm also transformed to pyrite, but with multiple techniques detecting FeSm as well as S0, implying less complete transformation to pyrite as compared to metal-free FeSm. These results indicate that Co and Ni may inhibit transformation for FeSm to pyrite, or slow it down. Cobalt concentrations in the solid diminished by 30% during pyrite transformation, indicating that pyrite Co may be a conservative tracer of seawater or porewater Co concentrations. Nickel concentrations increased several-fold after pyrite formation, suggesting that pyrite may have scavenged Ni from the dissolution of primary FeSm grains. Nickel in pyrites thus may not be a reliable proxy for seawater or porewater metal concentrations.

Understanding clay mineral transformation is of fundamental importance to grasping phyllosilicate crystal chemistry and unraveling geochemical processes. In this study, hydrothermal experiments were conducted on lizardite and antigorite, to investigate the possibility of the transformation from serpentine to smectite, the effect of precursor minerals' structure on the transformation and the transformation mechanism involved. The reaction products were characterized using XRD, TG, HRTEM, and 27Al MAS NMR. The results show that both lizardite and antigorite can be converted to smectite, but such conversion is much more difficult than that of kaolinite group minerals. The successful transformation is mainly evidenced by the occurrence of the characteristic (001) reflection of smectite at 1.2-1.3 nm in the XRD patterns and smectite layers with a thickness of 1.2-1.3 nm in HRTEM images of hydro-thermal products as well as the dehydroxylation of the newly formed smectite at a higher temperature in comparison to that of the starting minerals. The difficulty for the transformation of serpentine to smectite may be due to the lack of enough available Al in the reaction system, in which the substitution of Al3+ for Si4+ in the neo-formed tetrahedral sheet is critical to control the size matching between the neo-formed tetrahedral sheet and octahedral sheet in starting minerals. Since the neighboring layers in antigorite are linked by the strong Si-O covalent bonds, the transformation only takes place at the edges of an antigorite layer rather than the whole layer, and the neo-formed smectite is non-swelling due to the inheritance of such Si-O covalent bonds. The conversion of lizardite to smectite is more feasible than that of antigorite, accompanied by exfoliation. This leads to a prominent decrease of the particle size in the hydrothermal products and the number of phyllosilicate layers contained therein. Two dominant pathways were observed for the transformation of lizardite and antigorite into smectite, i.e., conversion of one serpentine layer to one smectite layer via attachment of Si-O tetrahedra onto the octahedral sheet surface of the starting minerals and two adjacent serpentine layers merging into one smectite layer. In the case of the latter, dissolution of octahedra and inversion of tetrahedral sheets took place during the transformation. Besides these two dominant pathways, precipitation and epitaxial growth of smectite were also observed in the cases of lizardite and antigorite, respectively. The present study suggests that solid-state transformation is the main mechanism for conversion of serpentine minerals to smectite, similar to the transformation of kaolinite group minerals to beidellite.