Preferential Incorporation Research Articles

Azimuthal Anisotropy of Rhombohedral (Corundum Phase) Heterostructures

The corundum structure is rhombohedral/trigonal and thus has lower symmetry than the well‐investigated hexagonal crystals such as wurtzite GaN‐ and ZnO‐based materials. By investigating the growth of α‐phase alloy thin films on various orientations of Al2O3 substrates, the anisotropy around the [00.1]‐axis is investigated. In particular, the pseudomorphic growth on the r plane (01.2) and (10.2) plane substrates is compared. The findings agree with elasticity theory. Also, different growth kinetics are found on these two planes in terms of growth rate and preferential cation incorporation.

Sintering and grain growth behaviour of magnesium aluminate spinel: Effect of lithium hydroxide addition

Lithium hydroxide, LiOH, in the amounts ranging from 0.1 to 1.2 wt% has been used as a sintering aid to improve the densification of MgAl2O4. The addition of 0.3 wt% LiOH promotes densification and limits grain growth. The activation energy of sintering, calculated using master sintering curve approach, decreases from 790 ± 20 kJ.mol−1 to 510 ± 20 kJ.mol−1 with the addition of 0.3 wt% of LiOH. In addition, MgAl2O4 was also mixed with 10 wt% of LiOH to amplify the formation of reaction products. High-temperature XRD results showed that secondary phases (MgO and LiAlO2) are produced above 1040 °C. The secondary phases start to disappear at T > 1200 °C, and MgAl2O4 is produced. While adding small amounts of LiOH, up to ca. 0.3 wt%, is beneficial for densification and suppressing grain growth, there exists a critical concentration of Li+ that is accounted for by the preferential incorporation of lithium ions into MgAl2O4 crystal lattice.

Effect of off-axis substrate angles on β-Ga2O3 thin films and solar-blind ultraviolet photodetectors grown on sapphire by MOCVD

β-Ga2O3 thin films were heteroepitaxially grown on c-plane sapphire substrates with different off-axis angles toward <11‾00> direction by metalorganic chemical vapor deposition (MOCVD), where the crystal quality of the films and the deep-ultraviolet photodetectors (PDs) fabricated on these films were characterized. The effect of sapphire substrates with different off-axis angles on the β-Ga2O3 thin films and the optical performance of β-Ga2O3 PDs are investigated for the first time. (2‾01)-oriented β-Ga2O3 thin films were grown on sapphire substrates with off-axis angles of 0°, 1.5°, 4°, and 6°. The full width at half maxima (FWHM) of rocking curves decreased significantly with the increase of off-axis angles. The β-Ga2O3 thin films grown on the 6° off-axis angle substrate showed a FWHM of 0.55°, indicating excellent crystal quality. Substrate off-axis angles play a critical role in the nucleation process in the growth of β-Ga2O3 thin films. The step edge on the off-axis substrates serves as the preferential incorporation sites for Ga adatoms. The step terrace width is controlled by the off-axis angle and influences the growth modes depending on the relative magnitude of the step terrace width compared with the Ga adatom diffusion length. In addition, β-Ga2O3 photodetectors with a metal-semiconductor-metal (MSM) structure have been fabricated using these β-Ga2O3 thin films. The β-Ga2O3 PDs fabricated on 6° off-axis sapphire substrate showed excellent optical performance with a large photocurrent of 61 μA, an outstanding photo/dark current ratio of 2.3 × 103, and peak responsivity of 74.6 mA/W. These results can provide important guidance on heterogeneous epitaxy of β-Ga2O3 thin films and photodetectors on cost-effective mass-producible sapphire substrates by MOCVD.

The Molybdenum isotope subduction recycling conundrum: A case study from the Tongan subduction zone, Western Alps and Alpine Corsica

Molybdenum isotopes have emerged as novel tracers for high-temperature igneous and metamorphic processes. The debate remains to what extent different subducted slab lithologies, such as oceanic crust and marine sediments, contribute to the Mo isotope signature of arc magmas and, hence, exert different controls on the terrestrial Mo cycle. Here we investigate Mo isotope systematics from input to output at the Tongan subduction zone: Arc lavas from different Tongan islands, pelagic sediments and altered oceanic crust (AOC) samples from DSDP site 595/596 on the subducting Pacific plate. For complementary insights into the fate of Mo and its isotopic signatures during prograde subduction metamorphism, we also present data of metasediments and variably altered AOC-type eclogites from the Zermatt-Saas ophiolite, Switzerland and Italy, and the Schistes Lustrés Complex in Alpine Corsica.Manganese oxide-rich pelagic sediments from DSDP site 595/596 show variable, depth-dependent Mo/Mn ratios and Mo isotope compositions controlled by diagenetic reactions. As subducted equivalents, Mn-rich eclogitic metapelites display lower Mo contents and δ98/95Mo ratios compared to their non-subducted protolith. This indicates prominent loss of Mo along with isotope fractionation during early subduction metamorphism. In comparison to unaltered MORB, low temperature seafloor alteration has shifted Mo/Ce and δ98/95Mo in studied AOC samples towards lower ratios, in the range of most mafic eclogites published so far. However, some mafic eclogites show even lower Mo/Ce and δ98/95Mo ratios compared to AOC, likely due to fluid-related Mo loss upon early subduction and preferential incorporation of light Mo into residual rutile.Our data document a prominent loss of isotopically heavy Mo before and upon early subduction metamorphism at shallow depths in the forearc region. Moreover, when prograde rutile crystallizes at ~30 km depth, it fixes the largest fraction of Mo in the subducting material. This creates an “arc Mo-conundrum” as devolatization of the slab at subarc depths is not able to account for the fluid-mobile Mo source responsible for observed higher Mo/Ce and δ98/95Mo in Tongan arc lavas compared to the mantle. As an alternative scenario, Mo mobilization by slab-derived aqueous fluids during the early stages of subduction into the forearc mantle produces serpentinites enriched in Mo with a possible heavy Mo isotopic signature. Mechanical transport and devolatization of forearc serpentinites at subarc regions is a plausible alternative recycling process accounting for the observed Mo systematics in Tongan arc lavas. This is supported by positive covariations of Mo/Ce and δ98/95Mo with elements such as As, Sb, and Cs, which are thought to be mostly released from the subducting material during early stages of subduction. We propose that a multi-stage recycling of metasomatized forearc mantle can be an important process in recycling of Mo and possibly other elements.

Pb2+ Uptake by Magnesite: The Competition between Thermodynamic Driving Force and Reaction Kinetics

The thermodynamic properties of carbonate minerals suggest a possibility for the use of the abundant materials (e.g., magnesite) for removing harmful divalent heavy metals (e.g., Pb2+). Despite the favourable thermodynamic condition for such transformation, batch experiments performed in this work indicate that the kinetic of the magnesite dissolution at room temperature is very slow. Another set of co-precipitation experiments from homogenous solution in the Mg-PbII-CO2-H2O system reveal that the solids formed can be grouped into two categories depending on the Pb/Mg ratio. The atomic ratio Pb/Mg is about 1 and 10 in the Mg-rich and Pb-rich phases, respectively. Both phases show a significant enrichment in Pb if compared with the initial stoichiometry of the aqueous solutions (Pb/Mg initial = 1 × 10 − 2–1 × 10−4). Finally, the growth of {10.4} magnesite surfaces in the absence and in the presence of Pb2+ was studied by in situ atomic force microscopy (AFM) measurements. In the presence of the foreign ion, a ten-fold increase in the spreading rate of the obtuse steps was observed. Further, the effect of solution ageing was also tested. We observed the nucleation of a secondary phase that quickly grows on the {10.4} surfaces of magnesite. The preferential incorporation of Pb2+ into the solid phase observed during precipitation and the catalytic effect of Pb2+ on magnesite growth are promising results for the development of environmental remediation processes. These processes, different from the transformation of magnesite into cerussite, are not limited by the slow dissolution rate of magnesite. Precipitation and growth require an external carbon source, thus they could be combined with carbon sequestration techniques.

Chemical Composition and Genesis Implication of Garnet from the Laoshankou Fe-Cu-Au Deposit, the Northern Margin of East Junggar, NW China

In order to reveal the formation mechanism of different garnets and its implications for the fluid evolution in the Laoshankou Fe-Cu-Au deposit in the northern margin of East Junggar (NW China), three types of garnet have been investigated in detail in this study. (1) Type 1 grossular, formed at Ca-silicate stage (stage I, the pre-mineralization stage), was replaced by Type 2 garnet and magnetite, and displays a compositional range of Grs44–53Adr44–53, which has relatively lower total REE (rare earth elements) contents (8.14–32.8 ppm) and markedly depleted LREE (light rare earth elements) with distinctive positive Eu anomaly (1.36–9.61). (2) Type 2 Al-rich andradite, formed at the early sub-stage of amphibole-epidote-magnetite stage (stage II, the main magnetite mineralization stage), can be divided into two sub-types, i.e., Type 2a and Type 2b. Type 2a garnets exhibit polysynthetic twinning and relatively narrow compositional variations of Adr63–66Grs31–34 with HREE-(heavy rare-earth elements) enrichment and positive Eu anomalies (3.22–3.69). Type 2b garnets own wide compositional variations of Adr55–77Grs21–43 with relatively higher REE contents (49.1–124 ppm), markedly depleted LREE and a distinctive positive Eu anomaly (2.11–4.61). (3) Type 3 andradite (Adr&gt;91) associated with sulfide stage (stage III, the main copper-gold mineralization stage) is different from other types of garnets in Laoshankou, which are characterized by lowest total REE contents (1.66–91.1 ppm), flat HREE patterns, LREE-enrichment and the strongest positive Eu anomalies (3.31–45.48). Incorporation of REE into garnet is largely controlled by external factors, such as fluid chemistry, pH, ƒO2 and water-rock ratios as well as its crystal chemistry. Type 1 and 2 garnets mainly follow the creation of X2+ (e.g., Ca2+) site vacancy, e.g., [X2+]−3VIII[]+1VIII[REE3+]+2VIII. The REE3+ substitution mechanism for Type 3 garnet is the Na+-REE3+ coupled substitutions, e.g., [X2+]−2VIII[X+]+1VIII[REE3+]+1VIII, without the evaluation of the creation of site vacancy. The compositional variations from Type 1 to Type 3 garnet indicate significant differences of fluid compositions and physicochemical conditions, and can be used to trace the fluid–rock interaction and hydrothermal evolution of garnet. Type 1 grossular was formed by magmatic fluid under low water–rock ratios and ƒO2, and neutral pH environment by diffusion metasomatism in a nearly closed system with the preferential incorporation into the grossular of HREE. As the long fluid pore residence and continuing infiltration metasomatism under nearly closed-system conditions, fluids with high water/rock ratios were characterized by increased ƒO2, more active incorporation of Fe3+ and REE, and formed Type 2 Al-rich andradite. In contrast, Type 3 garnet formed by oxidizing magmatic fluid under a mildly acidic environment with highest ƒO2 and water–rock ratios, and was influenced by externally derived high salinity and Ca-rich fluids in an open system. Thus, the geochemical features of different types and generations of garnets in the Laoshankou deposit can provide important information of fluid evolution, revealing a transition from neutral magmatic fluid to oxidizing magmatic fluid with addition of external non-magmatic Ca-rich fluid from the Ca-silicate stage to the sulfide stage. The above proved the fluid evolution process further indicates that the Laoshankou deposit prefers to be an IOCG-like (iron oxide-copper-gold) deposit rather than a typical skarn deposit.

Mechanism of Formation of Chabazite-K by Fusion of Fly Ash with KOH Followed by Hydrothermal Reaction and Its Cs+ Sorption Properties

Chabazite-K was synthesized from coal fly ash by a two-stage hydrothermal process. Fly ash was fused with KOH and colloidal SiO2, and the resulting material was characterized by x-ray diffraction (XRD) analysis and Raman spectroscopy. The role of KOH in the nucleation of chabazite is explained in terms of uniform incorporation of Al and Si tetrahedra in aluminosilicate rings at the fusion stage. Cocrystallization of phillipsite with chabazite led to the formation of phillipsite–chabazite combined phase along with chabazite-K. The Cs+ sorption capacity of the material was found to be 299 ± 8 mg/g with selectivity for Cs+. Under the same experimental conditions, fusion of fly ash in NaOH led to formation of sodalite, which can be explained in terms of preferential incorporation of Al tetrahedra in aluminosilicate rings at the fusion stage of synthesis.

Analysis of the BAS OH band reveals a non-statistical incorporation of Al into the MOR framework

H-MOR zeolites with different Si/Al ratios were investigated by the combined use of FT-IR spectroscopy, calorimetry, and periodic DFT calculations. Our analysis of 14 different Brønsted acid sites (BAS) was carried out with the ω/r correlation method parameterized to reproduce the OH band shape for the high silica H-MOR(32) sample. The estimated populations clearly show that the Al distribution exhibits non-statistical behavior. The preferential incorporation of Al into the T3 and T4 framework positions is in excellent agreement with the X-ray study of Alberti et al. on natural mordenites. This suggests that the Al distribution is very similar in both high silica and aluminum rich MOR materials. The analysis of H-MOR with lower Si/Al ratios is complicated by the interaction of the adjacent BAS. This effect leads to significant changes in relative energies that determine populations of the individual sites. Our interpretation of the experimental data is further supported by a very good agreement between calculated CO adsorption enthalpies and calorimetric measurements. An anomalously large dispersion stabilization is found for adsorption complexes located in the side pocket of the MOR framework.

Coupled stable chromium and iron isotopic fractionation tracing magmatic mineral crystallization in Archean komatiite-tholeiite suites

Chromium exists in two oxidation states Cr2+ and Cr3+ during high-temperature magmatic processes and changes in Cr redox are often associated with stable isotopic fractionation. Thus, the stable chromium isotope compositions of mantle-derived magmas bear the potential to trace the oxidation states of their mantle sources as well as any post melting changes in Cr redox (e.g. during magmatic differentiation), in a manner similar to magmatic stable Fe isotopic fractionation. However, these stable isotope fractionation effects are less understood for Cr relative to Fe. Komatiites and tholeiitic basalts represent a wide range of mantle-derived partial melts with variable fractional crystallization of phases with different affinity for Cr2+ and Cr3+. Thus, they offer potential archives to better understand high-temperature Cr isotope fractionation processes and mantle redox.Here, we report major and trace elements as well as coupled stable Cr and Fe isotope compositions of two well-characterized Archean komatiite-tholeiite suites from the Barberton Greenstone Belt, South Africa and Eswatini, and Belingwe Greenstone Belt, Zimbabwe. The sample suites range in MgO concentrations from 3.85 to 34.33 wt%, which allows investigation of the impact of large degrees of magmatic differentiation in a komatiite-basalt system. Whole-rock δ53/52CrSRM979 and δ56/54FeIRMM014 values range from −0.390 ± 0.016 to −0.061 ± 0.016‰ and −0.014 ± 0.018 to +0.192 ± 0.018‰, respectively. The komatiites have a very narrow range in their Cr isotopic composition with an average δ53/52CrSRM979 value of −0.122 ± 0.050‰ (2SD; n = 21), which supports previous estimates of the bulk silicate Earth δ53/52CrSRM979 value. However, high-Mg tholeiites and basaltic andesites exhibit significantly lighter δ53/52CrSRM979 and heavier δ56/54FeIRMM014 values than komatiites. These variations can be linked to crystallization and accumulation of mineral phases observed from fractionation trends of the two Archean komatiite-tholeiite suites. In detail, during crystallization and accumulation of olivine the Cr isotope compositions of komatiites stay invariant, whereas at the onset of Cr-bearing spinel and pyroxene crystallization the Cr isotope signatures of komatiitic basalts, high-Mg tholeiites and basaltic andesites become progressively lighter, which is attributed to the preferential incorporation of isotopically heavier Cr3+ in these mineral phases. The gradual increase of δ56/54FeIRMM014 with increasing magmatic differentiation, does not allow identifying the crystallization of particular mineral phases using Fe isotopes alone. Ultimately, this study demonstrates the power of combining stable Cr and Fe isotopic analyses to examine the effects of fractional crystallization on modifying melt source values and thus to ensure accurate mantle redox estimations.

Bismuth based photoelectrodes for solar water splitting

Photoelectrochemical water splitting is a sustainable path to generate valuable hydrogen using sunlight and water as the only inputs. Despite significant efforts to date, it is still a challenge to achieve photoelectrode with superior performance and long-term stability.Many bismuth-based semiconductor materials have demonstrated excellent visible light harvesting capability and suitable band edge for water splitting. Herein, we summarized the latest studies conducted on bismuth-based photoelectrodes for photoelectrochemical water splitting. Specifically, photoelectrochemical properties of copper bismuth oxide (CuBi2O4), bismuth ferrites (BiFeO3, Bi2Fe4O9), bismuth vanadate (BiVO4), bismuth tungstate (Bi2WO6), bismuth molybdate(Bi2MoO6) and bismuth oxyhalids (BiOX, X = I, Cl, Br) are presented. Strategies to achieve high stability and photolectrochemical performance were discussed in the aspects of nanostructure formation, heterostructure assembly, practical defect engineering, preferential facet growth and oxygen evolution catalyst incorporation.

Preliminary exploration of molybdenum isotope fractionation during coprecipitation of molybdate with abiotic and microbial calcite

Molybdenum isotopes in marine carbonates have been proposed to track the redox conditions of oceans through time. Large variations of Mo concentration and isotopic composition were observed in primary biogenic carbonates and shallow-water carbonate sediments from modern oceans. However, it remains unknown whether the abiotic calcium carbonate precipitation process fractionates Mo isotopes and affects Mo isotopic composition in marine carbonates. To better understand carbonate Mo isotope proxy, we conducted abiotic calcite coprecipitation experiment to determine Mo partition coefficient in calcite and Mo isotope fractionation during molybdate incorporation into calcite. We also investigated Mo isotopic compositions in microbial calcite induced by photosynthetic activity of cyanobacteria and diatoms in the surface water of Fayetteville Green Lake (FGL), New York, USA.Our calcite coprecipitation experiment, for the first time, determined the Mo partition coefficient Kd=MoCacalcite/MoO42−CO32−solution = 1.49 × 10−5 in calcite at pH ~8.3. We observed a relatively small Mo isotope fractionation of 0.15 ± 0.06‰ with light Mo isotopes preferentially incorporated into calcite. The Mo isotope fractionation observed in our experiment most likely results from equilibrium isotope fractionation among different Mo species and preferential incorporation of the isotopically light Mo(VI) species (MoO42−) into calcite. Microbial calcite formed in FGL fractionated Mo isotopes in the same direction as abiotic calcite coprecipitation experiment but with significantly larger isotope fractionations (0.82–2.45‰) and significantly higher Mo concentrations (0.04–0.28 ppm vs. the inferred 0.002 ppm Mo from our abiotic calcite coprecipitation experiment). Molybdenum isotopic composition decreased with Mn/Fe ratios from +1.56 to −0.07‰, suggesting that Fe and Mn oxides dominantly control Mo isotope fractionation in these microbial calcite samples. Additionally, isotopically light Mo associated with organic matter (e.g., live or dead microorganisms like cyanobacteria) might also contribute to the light Mo isotopic composition in microbial calcite.The relatively small Mo isotope fractionation (0.15 ± 0.06‰) and Mo partition coefficient (1.49 × 10−5) in our abiotic calcite coprecipitation experiment indicate that calcite precipitation process has negligible effects on Mo isotopic composition in primary biogenic calcite precipitates. In contrast, Mo associated with organic matter, detrital particles, and Fe and Mn oxides, and carbonate diagenesis strongly affect Mo isotopic compositions in calcium carbonate precipitates in nature. Caution should be taken when applying Mo isotopes in ancient carbonates rocks to track seawater redox conditions.

Prunus spinosa Extract Loaded in Biomimetic Nanoparticles Evokes In Vitro Anti-Inflammatory and Wound Healing Activities.

Prunus spinosa fruits (PSF) contain different phenolic compounds showing antioxidant and anti-inflammatory activities. Innovative drug delivery systems such as biomimetic nanoparticles could improve the activity of PSF extract by promoting (i) the protection of payload into the lipidic bilayer, (ii) increased accumulation to the diseased tissue due to specific targeting properties, (iii) improved biocompatibility, (iv) low toxicity and increased bioavailability. Using membrane proteins extracted from human monocyte cell line THP-1 cells and a mixture of phospholipids, we formulated two types of PSF-extract-loaded biomimetic vesicles differing from each other for the presence of either 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) or 1,2-dioleoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (DOPG). The biological activity of free extract (PSF), compared to both types of extract-loaded vesicles (PSF-DOPCs and PSF-DOPGs) and empty vesicles (DOPCs and DOPGs), was evaluated in vitro on HUVEC cells. PSF-DOPCs showed preferential incorporation of the extract. When enriched into the nanovesicles, the extract showed a significantly increased anti-inflammatory activity, and a pronounced wound-healing effect (with PSF-DOPCs more efficient than PSF-DOPGs) compared to free PSF. This innovative drug delivery system, combining nutraceutical active ingredients into a biomimetic formulation, represents a possible adjuvant therapy for the treatment of wound healing. This nanoplatform could be useful for the encapsulation/enrichment of other nutraceutical products with short stability and low bioavailability.

Preferential dipeptide incorporation of Porphyromonas gingivalis mediated by proton-dependent oligopeptide transporter (Pot).

Multiple dipeptidyl-peptidases (DPPs) are present in the periplasmic space of Porphyromonas gingivalis, an asaccharolytic periodontopathic bacterium. Dipeptides produced by DPPs are presumed to be transported into the bacterial cells and metabolized to generate energy and cellular components. The present study aimed to identify a transporter responsible for dipeptide uptake in the bacterium. A real-time metabolic analysis demonstrated that P. gingivalis preferentially incorporated Gly-Xaa dipeptides, and then, single amino acids, tripeptides and longer oligopeptides to lesser extents. Heterologous expression of the P. gingivalis serine/threonine transporter (SstT; PGN_1460), oligopeptide transporter (Opt; PGN_1518) and proton-dependent oligopeptide transporter (Pot; PGN_0135) genes demonstrated that Escherichia coli expressing Pot exclusively incorporated Gly-Gly, while SstT managed Ser uptake and Opt was responsible for Gly-Gly-Gly uptake. Dipeptide uptake was significantly decreased in a P. gingivalis Δpot strain and further suppressed in a Δpot-Δopt double-deficient strain. In addition, the growth of the Δpot strain was markedly attenuated and the Δpot-Δopt strain scarcely grew, whereas the ΔsstT strain grew well almost like wild type. Consequently, these results demonstrate that predominant uptake of dipeptide in P. gingivalis is mostly managed by Pot. We thus propose that Pot is a potential therapeutic target of periodontal disease and P. gingivalis-related systemic diseases.

Oscillatory- and sector-zoned pyrochlore from carbonatites of the Kerimasi volcano, Gregory rift, Tanzania

AbstractThe Quaternary carbonatite–nephelinite Kerimasi volcano is located within the Gregory rift in northern Tanzania. It is composed of nephelinitic and carbonatitic pyroclastic rocks, tuffs, tuff breccias and pyroclastic breccias, which contain blocks of different plutonic (predominantly ijolite) and volcanic (predominantly nephelinite) rocks including carbonatites. The plutonic and volcanic carbonatites both contain calcite as the major mineral with variable amounts of magnetite or magnesioferrite, apatite and forsterite. Carbonatites also contain accessory baddeleyite, kerimasite, pyrochlore and calzirtite. Zr and Nb minerals are rarely observed in rock samples, though they are abundant in eluvial deposits of carbonatite tuff/pyroclastic breccias in the Loluni and Kisete craters. Pyrochlore, ideally (CaNa)Nb2O6F, occurs as octahedral and cubo-octahedral crystals up to 300 μm in size. Compositionally, pyrochlore from Loluni and Kisete differs. The former is enriched in U (up to 19.4 wt.% UO2), light rare earth elements (up to 8.3 wt.% LREE2O3) and Zr (up to 14.4 wt.% ZrO2), and the latter contains elevated Ti (up to 7.3 wt.% TiO2). All the crystals investigated were crystalline, including those with high U content (a= 10.4152(1) Å for Loluni anda= 10.3763(1) Å for Kisete crystals). They have little or no subsolidus alteration nor low-temperature cation exchange (A-site vacancy up to 1.5% of the site), and are suitable for single-crystal X-ray diffraction analysis (R1= 0.0206 and 0.0290; for all independent reflections for Loluni and Kisete crystals, respectively). Observed variations in the pyrochlore composition, particularly Zr content, from the Loluni and Kisete craters suggest crystallisation from compositionally different carbonatitic melts. The majority of pyrochlore crystals studied exhibit exceptionally well-preserved oscillatory- and sometimes sector-type zoning. The preferential incorporation of smaller and higher charged elements into more geometrically constrained sites on the growing surfaces explains the formation of the sector zoning. The oscillatory zoning can be rationalised by considering convectional instabilities of carbonatite magmas during their emplacement.

A global survey of radiogenic strontium isotopes in river sediments

Radiogenic strontium isotopes are routinely used in provenance studies, but their application to sediments is often complicated by various grain size and weathering effects, which can influence measured 87Sr/86Sr ratios. Here, we report Sr isotopic data for a large number of sediment samples (n = 61) from the world's largest rivers and other river catchments draining particular geological and climatic settings; using both clay-rich (<4 μm) and silt-size (4-63 μm) detrital fractions to re-examine the factors controlling their distribution in sediments. In agreement with previous studies, the detrital material transported by world rivers defines general inverse Nd-Sr isotope relationships, which provide further empirical evidence for the utility of radiogenic Sr isotopes in sediment provenance studies. In a novel departure, however, we show that the 87Sr/86Sr difference between paired clay- and silt-size fractions (Δ87Sr/86Sr Clay-Silt) relates to the degree of chemical alteration of river sediments, as inferred from various relationships with weathering indices, such as the CIA, WIP and Na2O/Al2O3. The weathering dependence of Δ87Sr/86Sr Clay-Silt appears to be mainly controlled by temperature. In sub-Arctic and temperate regions, river sediments systematically display positive Δ87Sr/86Sr Clay-Silt indicative of preferential alteration of biotite in soils. In contrast, in sub-tropical watersheds characterized by mean annual temperatures >20 °C, intense feldspar weathering leads to the preferential incorporation of unradiogenic Sr into secondary clay minerals; a process which results in negative Δ87Sr/86Sr Clay-Silt values. In addition to climate forcing, the degree of size-dependent Sr isotope decoupling is also shown to be dependent on the type of weathering regime in watersheds, being more pronounced in low-elevation environments (< 2000 m), where transport-limited conditions and the presence of thick soil sequences can be associated with intense silicate weathering, than in high mountain regions (> 4000 m) dominated by kinetically-limited weathering regimes.While further studies will be required to test the validity of these conclusions at the local scale of weathering profiles, these findings suggest that combined Sr isotopic analyses of separate size fractions could be used as a new weathering proxy in sediment records, ideally complementing the conventional use of radiogenic Sr isotopes as provenance tracers. Finally, our results are also used to re-assess the mean Sr flux and 87Sr/86Sr composition of the suspended sediment exported to the ocean yearly, yielding a global flux-weighted average of 0.7160, identical to that proposed earlier in the seminal study of Goldstein and Jacobsen (1988).

Impact of methane concentration on surface morphology and boron incorporation of heavily boron-doped single crystal diamond layers

The methane concentration dependence of the plasma gas phase on surface morphology and boron incorporation in single crystal, boron-doped diamond deposition is experimentally and computationally investigated. Starting at 1%, an increase of the methane concentration results in an observable increase of the B-doping level up to 1.7×1021 cm−3, while the hole Hall carrier mobility decreases to 0.7±0.2 cm2 V−1 s−1. For B-doped SCD films grown at 1%, 2%, and 3% [CH4]/[H2], the electrical conductivity and mobility show no temperature-dependent behavior due to the metallic-like conduction mechanism occurring beyond the Mott transition. First principles calculations are used to investigate the origin of the increased boron incorporation. While the increased formation of growth centers directly related to the methane concentration does not significantly change the adsorption energy of boron at nearby sites, they dramatically increase the formation of missing H defects acting as preferential boron incorporation sites, indirectly increasing the boron incorporation. This not only indicates that the optimized methane concentration possesses a large potential for controlling the boron concentration levels in the diamond, but also enables optimization of the growth morphology. The calculations provide a route to understand impurity incorporation in diamond on a general level, of great importance for color center formation.

Effects of Preferential Incorporation of Carboxylic Acids on the Crystal Growth and Physicochemical Properties of Aragonite

The preferential incorporation of carboxylic acids into aragonite and its effects on the crystal growth and physicochemical properties of aragonite were systematically investigated using a seeded co-precipitation system with different carboxylic acids (citric, malic, acetic, glutamic, and phthalic). Aragonite synthesized in the presence of citric and malic acids showed a remarkable decrease in the crystallinity and size of crystallite, and the retardation of crystal growth distinctively changed the crystal morphology. The contents of citric acid and malic acid in the aragonite samples were 0.65 wt % and 0.19 wt %, respectively, revealing that the changes in the physicochemical properties of aragonite were due to the preferential incorporation of such carboxylic acids. Speciation modeling further confirmed that citric acid with three carboxyl groups dominantly existed as a metal–ligand, (Ca–citrate)−, which could have a strong affinity toward the partially positively charged surface of aragonite. This indicates why citric acid was most favorably incorporated among other carboxylic acids. Our results demonstrate that the number of carboxyl functional groups strongly affects the preferential incorporation of carboxylic acids into aragonite; however, it could be suppressed by the presence of other functional groups or the structural complexity of organic molecules.

Intestinal inflammation alters mucosal carbohydrate foraging and monosaccharide incorporation into microbial glycans

Endogenous carbohydrates released from the intestinal mucus represent a constant source of nutrients to the intestinal microbiota. Mucus‐derived carbohydrates can also be used as building blocks in the biosynthesis of bacterial cell wall components, thereby influencing host mucosal immunity. To assess the uptake of endogenous carbohydrates by gut microbes in healthy mice and during intestinal inflammation, we applied azido‐monosaccharides that can be tracked on bacterial cell walls after conjugation with fluorophores. In interleukin‐10 deficient mice, changes in the gut microbiota were accompanied by decreased carbohydrate hydrolase activities and increased lumenal concentrations of host glycan‐derived monosaccharides. Tracking of the monosaccharide N‐azidoacetylglucosamine (GlcNAz) in caecum bacteria revealed a preferential incorporation of this carbohydrate by Xanthomonadaceae in healthy mice and by Bacteroidaceae in interleukin‐10 deficient mice. These GlcNAz‐positive Bacteroidaceae fractions mainly belonged to the species B. acidifaciens and B. vulgatus. Growth of Bacteroides species in the presence of specific monosaccharides changed their stimulatory activity toward CD11c+ dendritic cells. Expression of activation markers and cytokine production was highest after stimulation of dendritic cells with B. vulgatus. The variable incorporation of monosaccharides by related Bacteroides species underline the necessity to investigate intestinal bacteria down to the species level when addressing microbiota‐host interactions.

Significant Zr isotope variations in single zircon grains recording magma evolution history

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15‰ for δ94Zr) and high-spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon-melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation.

Effect of silver and strontium incorporation route on hydroxyapatite coatings elaborated by rf-SPS

Hydroxyapatite coatings have been currently used on hip prostheses for their ability to promote faster osseointegration and bone growth. Nevertheless, post-operative infections remain a recurring problem. To overcome this issue, doping with antibacterial elements has become a new trend. In this work, hydroxyapatite coatings elaborated by radio-frequency suspension plasma spraying (rf-SPS) were doped with silver and strontium. Several doping strategies were explored thanks to the versatility offered by SPS compared with conventional spraying. First way: calcium phosphate doped powders were synthesized by coprecipitation and then dispersed into water before plasma spraying; second way: undoped powder was dispersed into aqueous medium in which nitrates or nanoparticles of the dopant(s) were respectively dissolved/dispersed. XRD revealed a high level of crystallinity ratio (ISO 13 779) and hydroxyapatite proportion for most of the coatings, with the presence of Ag/Ag2O nanoparticles whatever the doping route. SEM-EDS and STEM have demonstrated a more homogeneous distribution of the strontium within the coating made from the doped powder. Adherence of the coatings was estimated via a 3-point bending test, while bacteriological tests with S. aureus and proliferation of mesenchymal stem cells (hMSC) were performed. The results indicated a preferential incorporation of strontium into the secondary phases, showed efficient bactericidal properties, excellent mechanical properties in comparison with an APS reference coating, and no evidence of cytotoxic effect. This opens the way of a new type of coatings with a finer structure and a higher homogeneity through a better control of physicochemical properties using a suspension as the precursor.