Bulk Chemistry Research Articles

The impact of chemical composition of halide surface ligands on the electronic structure and stability of lead sulfide quantum dot materials.

There is a high fundamental interest in the surface and bulk chemistry of quantum dot (QD) solids, as they have proven to be very promising materials in optoelectronic devices. The choice of surface ligands for quantum dots in solid devices determines many of the film properties, as the ligands influence for example the doping density, chemical stability and charge transport. Lead halide ligands have developed as the main ligand of choice for lead sulfide quantum dots, as they have been shown to passivate quantum dot surfaces and enhance the chemical stability. In this study, we successfully varied the ligand composition on the surface of PbS quantum dot films from pure lead iodide to pure lead bromide and investigated its influence on the chemical and electronic structure of the QD solids using hard X-ray photoelectron spectroscopy (HAXPES). Furthermore, we developed a surface treatment to prevent the surface oxidation of a bulk PbS reference sample. Through measurements of this sample and of lead halide reference samples, we were able to assign the contributions of different chemical bonding to the Pb 4f core level and of different atomic orbitals to the valence band spectral shape of the QD materials. Overall, we found that the valence band edge position was very similar for all different iodide:bromide ratios and that all investigated compositions were able to protect the quantum dot surfaces within solid films from oxidation. However, the ligand composition significantly influences the sample stability under X-rays. The iodide rich QD solids showed the highest stability with very little to no chemical changes over several hours of X-ray exposure, while the bromide rich QD solids changed already within the first hour of exposure.

Nanoscale mineralogy and organic structure in Orgueil (CI) and EET 92042 (CR) carbonaceous chondrites studied with AFM‐IR spectroscopy

AbstractMeteorite matrices from primitive chondrites are an interplay of ingredients at the sub‐µm scale, which requires analytical techniques with the nanometer spatial resolution to decipher the composition of individual components in their petrographic context. Infrared spectroscopy is an effective method that enables the probing of vibrations at the molecule atomic scale of organic and inorganic compounds but is often limited to a few micrometers in spatial resolution. To efficiently distinguish spectral signatures of the different constituents, we apply here nano‐infrared spectroscopy (AFM‐IR), based on the combination of infrared and atomic force microscopy, having a spatial resolution beyond the diffraction limits. Our study aims to characterize two chosen meteorite samples to investigate primitive material in terms of bulk chemistry (the CI chondrite Orgueil) and organic composition (the CR chondrite EET 92042). We confirm that this technique allows unmixing the IR signatures of organics and minerals to assess the variability of organic structure within these samples. We report an investigation of the impact of the widely used chemical HF/HCl (hydrogen fluoride/hydrochloric acid) extraction on the nature of refractory organics (insoluble organic matter [IOM]) and provide insights on the mineralogy of meteorite matrices from these two samples by comparing to reference (extra)terrestrial materials. These findings are discussed with a perspective toward understanding the impact of post‐accretional aqueous alteration and thermal metamorphism on the composition of chondrites. Last, we highlight that the heterogeneity of organic matter within meteoritic materials extends down to the nanoscale, and by comparison with IOMs, oxygenated chemical groups are not affected by acid extractions.

Recent developments in reactivity testing of supplementary cementitious materials

Identification and rapid characterization of novel supplementary cementitious materials (SCMs) is a critical need, driven by shortfalls in conventional SCMs. In this study, we present a discussion of recently developed reactivity tests – the R3 test, the modified R3 test, the lime strength test, and the bulk resistivity index test. These tests measure reactivity parameters such as heat release, bound water, calcium hydroxide consumption, strength, and bulk resistivity. All tests can screen inert from reactive materials. To additionally differentiate pozzolanic and latent hydraulic materials, two parameters, for example, calcium hydroxide consumption and heat release, are needed. The influences of SCM bulk chemistry, amorphous content, and fineness on measured reactivity are outlined. Reactivity test outputs can predict strength and durability of cement paste/mortar/concrete; however, caution must be exercised as these properties are influenced by a variety of other factors independent of reactivity. Thoughts are provided on using reactivity tests to screen materials for concrete durability.

Mineralogical, geochemical, and magnetic susceptibility variations in the loess-paleosol sequence from Pattan, Kashmir Valley, India record an enhanced Indian summer monsoon around 35 ka

We present multi-proxy records of bulk chemistry, clay mineralogy, stable isotope composition of soil organic matter (δ13CSOM) and pedogenic carbonate (δ18OSC), and mineral magnetic parameters of a loess-paleosol sequence from Kashmir Valley, India, to infer paleoclimate and paleovegetation during Late Pleistocene. 14C AMS dating brackets the age of paleosols between 40 and 19.6 ka and suggests loess to be > 40 ka. Our study shows that a cold/dry climate prevailed at >40 ka (Late Pleistocene), during which the loess accumulation took place, and a warm/humid climate after that led to the development of soil units, with a prominent warm/humid phase around 35 ka. The range of Chemical Index of Alteration (72–78) and significant amounts of illite and chlorite in the section indicate moderate weathering. High kaolinite content, low chlorite, increased K/C, I/C, K/(I + C) ratio, and presence of poorly crystalline and Al-rich illite by ∼36 ka indicates increasing weathering intensity, likely due to an enhanced Indian Summer Monsoon (ISM). High magnetic susceptibility during 35–32 ka indicates enhanced pedogenesis due to a warm-humid climate. Paleotemperature estimates reveal a relatively warmer (by ∼7 °C) climate during pedogenesis than that at >40 ka. δ13CSOM values (−17‰ to −22.2‰) suggest C3 plants dominated the Kashmir Valley through the Late Pleistocene, however, a short period of enhanced summer monsoon at ∼35 ka favored C4 plant growth. The paleoclimate variability in the loess-paleosol sequence presented here agrees with the Guliya Ice Core δ18O record and high lake water levels in the Tibetan Plateau.

Nucleation mechanisms in a SiO2-Li2O-P2O5-ZrO2 biomedical glass-ceramic: Insights on crystallisation, residual glasses and Zr4+ structural environment

In manufacturing reliable glass-ceramics, bulk chemistry and appropriate thermal treatments are critical points. To better understand the influence of nucleation parameters on the crystallisation behaviour and mechanical properties of multicomponent glass-ceramics, we studied the effects of time and temperature on phase stabilisation, the evolution of the crystal phases and physical properties of a Zr-rich lithium-silicate having a SiO2/Li2O molar ratio < 2. Here, we also provide insights into the structural environment of Zr4+ at the early stage of nucleation by Anomalous X-ray Scattering (AXS). By reverse-engineering a commercial material through remelting and sequential thermal treatments, we observed the strong effect of the nucleation temperature on the final mineral assemblage and of the volume fractions of the lithium-disilicate phase on the fracture toughness (KIc). Indeed, the KIc value was increased from ∼0.8 MPa.m½ in the pristine glass up to ∼ 2 MPa.m½, if compared to the original commercial material exhibiting a KIc value of 1.6 MPa.m½. Furthermore, the synthesis of residual glasses at different stages of the thermal treatments allowed us to observe the changes in the glass network structure and properties. AXS was used to extract the contribution exclusively coming from Zr for different nucleation steps. The differential pair distribution functions ΔZrg(r) show two distinct peaks at ∼2.10 Å and 3.44 Å, respectively associated with Zr-O and Zr-Zr/Zr-Si correlations with the formation of edge sharing in addition to corner sharing polyhedra. It was discerned the occurrence of (sub)nano-sized clusters enriched in Zr. These local clusters do not show changes during the different thermal treatments, either for higher temperatures or longer times. No Zr phases are stabilised in the crystallised materials, suggesting that these clusters do not evolve above the critical nucleus size. All evidence points to a highly heterogeneous environment and the coexistence of three structural regions i) (sub)nano Zr-clusters, ii) P enriched μ-areas, iii) residual silicate glass. The evolution and spatial distribution of these units influence the final properties.

An investigation of Fe‐Ti, V in the north‐east Karbi Hills, Shillong Plateau, north‐east India: Implication for mineralization

The Kulamati gabbro‐anorthosite complex in the Karbi Hills of the Shillong Plateau, north‐east India is a newly discovered stratified Fe‐Ti‐V‐bearing magmatic body that has been classified as a titano‐magnetite ore. The host gabbro‐anorthosite is found intruded into the Mesoproterozoic Shillong Group. The stratified Fe‐Ti‐V oxide body consists mostly of magnetite‐rich and magnetite‐poor layers. The magnetite‐rich bands are composed of titanomagnetite, haematite, ilmenite, and coulsonite with minor Al‐spinel, while the mineral constituents of silicate bands contain plagioclase, clinopyroxene, olivine, apatite, and chlorite. Titaniferous magnetites display a wide variety of subsolvus features, including Al‐spinel–magnetite–ulvöspinel exsolutions and crystallographically oriented ilmenite exsolutions, but magnetites are exclusively vanadiferous. Comprehensive chemical analyses show that the ore is rich in TiO2 (10.98–12.78 wt%) and V2O5 (1.32–1.47 wt%). Ti is attributed by the presence of rutile, titanite, and ilmenite, while V is attributed by coulsonite as a solid solution component in the titanomagnetite. It records moderate to high Al2O3 (4.51–5.46 wt%), with enrichment of FeO and Fe2O3 (26.22–28.32 wt% and 39.34–42.86 wt%, respectively), which can be attributed to the presence of magnetite‐spinel‐ulvospinel. Higher Fe2O3 and lower FeO are indicative of oxidizing conditions of the ore‐forming environment. The rare earth element (REE) patterns have (La/Yb)N and (Ce/Yb)N ratios comparable to an evolved basaltic melt, with light REE being enriched compared to heavy REE and a positive Eu anomaly. The electron probe micro analyser data of magnetite is conformable with the bulk chemistry, and shows consistently high FeO (70.87–88.06 wt%), Cr2O3 (1.02–2.44 wt%), TiO2 (0.16–6.20 wt%), and V2O3 (1.47–2.26 wt%), with trace amounts of Al, Si, Mg, Mn, and PGE. As per targeted parameters, the ore occurrence distinctly belongs to a stratified Fe‐Ti‐V class, where alternate thick (&gt;1.0 m) and thin (&lt;20 cm) strata resulted from the late magmatic crystallization of the original tholeiitic composition.

Abundance and importance of petrological type 1 chondritic material

AbstractWe review the mineralogy, petrology, and abundance of petrological type 1 extraterrestrial material. Such material has been completely altered by aqueous processing on its parent bodies. As well as the four meteorite groups that contain type 1 members (CI, CM, CR, and CY), we summarize data from the 2019 fall Flensburg and a recent reanalysis of the “meteorite” Bench Crater found on the Moon, along with fine‐grained micrometeorites, interplanetary dust particles, and xenoliths in meteorites. Type 1 materials exhibit a remarkably high diversity of alteration conditions (temperature, water‐to‐rock [W/R] ratios, and fluid composition) and starting mineralogy. Type 1 material comprises a significant component of the modern extraterrestrial flux to the Earth and was likely common throughout the solar system during the whole course of its history, pointing to both widespread accretion with ices and heating of parent bodies. Type 1 materials are composed predominantly of various phyllosilicates, carbonates, sulfides, and magnetite. Some type 1 materials appear to be part of a “CM clan” typified by serpentine‐rich phyllosilicate compositions and an oxygen isotope composition that falls in the 16O‐rich part of the CM field. Others span a wide range in δ18O (&gt;30‰) and fall on or above the terrestrial fractionation line (+ve Δ17O). Positive Δ17O values are unusual for carbonaceous meteorites but are relatively common in type 1 materials. The wide variation in oxygen isotopes, as well as in textures, mineralogy, and bulk chemistry, points to multiple parent bodies that may originate in the inner and/or outer solar system. Cometary materials, or transition objects such as Main Belt comets or type D asteroids, are likely the source of much of the type 1 materials on Earth but relating them to specific parents requires more study.

Late Holocene Mongolian climate and environment reconstructions from brGDGTs, NPPs and pollen transfer functions for Lake Ayrag: Paleoclimate implications for Arid Central Asia

A coupled pollen-brGDGT paleoclimate reconstruction approach has been tested to provide independent and robust estimates of Holocene climate and environment changes in the extremely arid environment of the mountainous areas ranging from northern Arid Central Asia (ACA) to the Mongolian Plateau. The two proxies were calibrated for both global and local modern data sets (NMSDB). This multi-proxy approach was then applied to a sediment core collected from Lake Ayrag, Arkhangai, covering the Late Holocene. In addition to brGDGTs and pollen, we also performed magnetic susceptibility, micro-XRF, elemental and isotopic bulk chemistry, and Non-Pollen Palynomorph (NPP) analyses on the Lake Ayrag sediments in order to better understand the lake system and human impact dynamics. While the globally calibrated record (both for pollen and brGDGTs) displayed a slight millennial-scale cooling, the locally calibrated results exhibit centennial-scale climate oscillations such as the 4.2 and 3.5 kyr events, the Roman Warm Period (RWP), Dark Ages Cold Period (DACP), Medieval Warm Period (MWP) and Little Ice Age (LIA). These climate oscillations and vegetation changes are discussed with regard to the main Mongolian human historical occupation events documented by pastoralism proxies, especially the Xiongnu, Mongol Empire, Mandchou and Soviet periods. The climate systems currently dominating the Mongolian Plateau are difficult to resolve because inter-annual climate variability is pronounced. However, precipitation mainly occurs in summer (easterly monsoon driven) when the winter Westerlies lead the air mass movement. In the past, both pollen and biomarkers exhibited anti-correlated trends with annual precipitation and temperature: over the last 4000 kcal yr BP, the warm periods (MWP, RWP) were dry and the cold periods (LIA, DACP, 3.5 kyrs) were humid. Thus, the East Asian Summer Monsoon (i.e., warm and wet conditions dominant during summer) seems not to have influenced central Mongolian climate during the Late Holocene, which could have remained dominated by the Westerlies/Siberian High cells conflict. A comparison between the Ayrag record and other paleoclimate records from the Baikal area (Dulikha), Mongolian Plateau (D3L6, D1L1, NRX, ATM), and continental China (Kesang, Baluk and Tonnel caves, XRD section) to the Loess Plateau (Huangye and Xianglong caves) suggests that the monsoon front has oscillated since the Early Holocene. A climate synthesis following strictly the same approach (locally calibrated brGDGTs vs. pollen-inferred climate) for all the ACA records available for the Late Holocene helps us to resolve the climate systems paced by centennial to millennial-scale oscillations and their consequences for human societies.

Surface Reconstruction of Perovskites for Water Oxidation: The Role of Initial Oxides’ Bulk Chemistry

Developing highly active electrocatalysts for oxygen evolution reaction (OER) is crucial for the scalable production of renewable hydrogen fuels by water electrolysis. Perovskite oxides are extensively studied as OER catalysts as they can have high activity and also offer considerable flexibility in composition and structure. Recently, there are increasingly numerous reports regarding dynamic surface reconstruction of perovskite oxides under OER conditions, with claims that the reconstruction‐derived species are the actual catalysts responsible for the measured OER activity. To enable rational design of perovskite oxides as precatalysts to generate actual active components in situ, gaining essential understanding of their reconstruction behaviors is crucial. This perspective discusses the roles of initial bulk chemistry in the surface evolution process of perovskite oxides during OER, including the dependency of surface stability on electronic structure of the precatalyst and the possibility of occurrence of lattice oxygen evolution reaction and cation leaching on the surface of a perovskite oxide precatalyst. It is reasonably argued that tailoring the bulk properties of perovskite precatalysts, such as electronic structure, crystallographic structure, and ion stoichiometry, can influence the occurrence of surface reconstruction and the formation of actual active surface species.

Comment on “Biogeochemical cycling of iron (hydr-)oxides and its impact on organic carbon turnover in coastal wetlands: A global synthesis and perspective” [Earth-Science Reviews (2021) 103658

Models for a xenocryst origin for kimberlite olivines emphasise the similarity between their core compositions and those in mantle peridotites. While this permits a xenocryst origin, it does not provide proof, as magmas generated in equilibrium with mantle olivines could, in principle, crystallize initial olivines matching those in the source region. Further, in several kimberlites, there is a striking disparity between the compositional range of olivine cores and that in associated mantle peridotite xenoliths from the same locality. Olivine-liquid Mg-Fe exchange coefficients and Ni partition coefficients permit equilibrium between Mg-rich mantle olivines (Mg # ~ 94–93) and magmas matching kimberlite bulk rock compositions. Glass inclusions in olivine megacrysts from the Monastery kimberlite, with compositions which overlap the range of archetypal Group I kimberlites, were interpreted to represent original liquids trapped at pressures of 4.5–6 GPa. These glass inclusions provide direct petrographic support for primitive melts matching kimberlite bulk chemistry in the lower SCLM.A majority of kimberlitic olivines show normal (decreasing Mg #) core to rim zonation. Cores of normal-zoned kimberlitic olivines are typically homogeneous, but collectively define a field with a range in Mg # and invariant or slightly decreasing Ni towards more Fe-rich compositions. The most Mg-rich cores of normal-zoned olivines typically have Mg # in the range 94–93, but there are marked differences in the Fe-rich extreme of the normal-zoned population between different kimberlite clusters. Olivine rims typically define a field characterized by steeply decreasing Ni, coupled with invariant or slightly increasing or decreasing Mg #, which invariably overlaps the Fe-extreme of core compositions of the relatively Mg-rich, normal-zoned olivines. Consequently, while there is a sharp inflection in chemical gradient between the respective fields of cores and rims, they nevertheless define a continuous compositional field. Trace element modelling demonstrates that these zonation patterns can be explained in terms of a Raleigh crystallization model.Most, if not all kimberlites are characterized by a subordinate group of olivine macrocrysts with cores that are Fe-rich relative to the field for rims, and thus show reverse zonation, which are interpreted to be linked to the Cr-poor megacryst suite. Rare Mg-rich olivines (relative to rims), have high-pressure inclusions of garnet, clinopyroxene and orthopyroxene. When present, such inclusions often show disequilibrium features such as internal chemical zonation. This points to a very short mantle residence time prior to entrainment by the host kimberlite, indicating a link to the Cr-rich megacryst suite rather than mantle peridotites. In addition to a variable, but generally subordinate proportion of olivines derived from Cr-poor and Cr-rich megacrysts, xenocrysts derived from disaggregated mantle peridotites will undoubtedly be present. While their proportions are difficult to quantify, the collective evidence points to a cognate origin for a majority of kimberlitic olivines. A kimberlite magma ascent model is proposed which provides a framework for understanding both olivine compositional variation and apparently enigmatic internal and external olivine morphology.

Cognate versus xenocrystic olivines in kimberlites – A review

Models for a xenocryst origin for kimberlite olivines emphasise the similarity between their core compositions and those in mantle peridotites. While this permits a xenocryst origin, it does not provide proof, as magmas generated in equilibrium with mantle olivines could, in principle, crystallize initial olivines matching those in the source region. Further, in several kimberlites, there is a striking disparity between the compositional range of olivine cores and that in associated mantle peridotite xenoliths from the same locality. Olivine-liquid Mg-Fe exchange coefficients and Ni partition coefficients permit equilibrium between Mg-rich mantle olivines (Mg # ~ 94–93) and magmas matching kimberlite bulk rock compositions. Glass inclusions in olivine megacrysts from the Monastery kimberlite, with compositions which overlap the range of archetypal Group I kimberlites, were interpreted to represent original liquids trapped at pressures of 4.5–6 GPa. These glass inclusions provide direct petrographic support for primitive melts matching kimberlite bulk chemistry in the lower SCLM. A majority of kimberlitic olivines show normal (decreasing Mg #) core to rim zonation. Cores of normal-zoned kimberlitic olivines are typically homogeneous, but collectively define a field with a range in Mg # and invariant or slightly decreasing Ni towards more Fe-rich compositions. The most Mg-rich cores of normal-zoned olivines typically have Mg # in the range 94–93, but there are marked differences in the Fe-rich extreme of the normal-zoned population between different kimberlite clusters. Olivine rims typically define a field characterized by steeply decreasing Ni, coupled with invariant or slightly increasing or decreasing Mg #, which invariably overlaps the Fe-extreme of core compositions of the relatively Mg-rich, normal-zoned olivines. Consequently, while there is a sharp inflection in chemical gradient between the respective fields of cores and rims, they nevertheless define a continuous compositional field. Trace element modelling demonstrates that these zonation patterns can be explained in terms of a Raleigh crystallization model. Most, if not all kimberlites are characterized by a subordinate group of olivine macrocrysts with cores that are Fe-rich relative to the field for rims, and thus show reverse zonation, which are interpreted to be linked to the Cr-poor megacryst suite. Rare Mg-rich olivines (relative to rims), have high-pressure inclusions of garnet, clinopyroxene and orthopyroxene. When present, such inclusions often show disequilibrium features such as internal chemical zonation. This points to a very short mantle residence time prior to entrainment by the host kimberlite, indicating a link to the Cr-rich megacryst suite rather than mantle peridotites. In addition to a variable, but generally subordinate proportion of olivines derived from Cr-poor and Cr-rich megacrysts, xenocrysts derived from disaggregated mantle peridotites will undoubtedly be present. While their proportions are difficult to quantify, the collective evidence points to a cognate origin for a majority of kimberlitic olivines. A kimberlite magma ascent model is proposed which provides a framework for understanding both olivine compositional variation and apparently enigmatic internal and external olivine morphology.

Wet magmatic processes during the accretion of the deep crust of the Oman Ophiolite paleoridge: Phase diagrams and petrological records

The Oman Ophiolite is regarded as an analogue to modern fast-spreading ocean ridge systems in an environment of subduction zone initiation. In contrast to recent mid-ocean ridge basalts from the East Pacific Rise, parental melts at the Oman paleoridge are assumed to be hydrous in nature. In order to constrain the role of water during magmatic accretion processes in the deep crust at the Oman paleoridge, we evaluated several experimental studies in hydrous tholeiitic systems performed at shallow pressures. We concluded that the wehrlitic phase assemblage (olivine coexisting with clinopyroxene but without plagioclase) is the most significant feature indicative of high prevailing water activities. The stability of the wehrlitic assemblage decreases with decreasing pressure (not stable in the upper plutonic crust) and depends on the chemical system (only stable in primitive MORB systems).We applied these results to plutonic rocks from cores drilled as part of the Oman Drilling Project (OmanDP). A key observation is the presence of coherent wehrlitic layers within the layered gabbro series, which are frequent in the lowermost gabbros (20%), relative sparse in the mid-crust (6%), and absent from the top of the plutonic crust at the dike/gabbro transition. Based on the combined phase relations for hydrous MORB-type systems at shallow pressures, we interpret this as a direct consequence of the presence of a significant water activity during the accretion of the plutonic crust of the Oman paleoridge, and not as a local phenomenon related to variations in temperature or bulk chemistry. These findings have implications for the mechanism of accretion of the lower crust at the Oman paleoridge, supporting a model that significant parts of the plutonic crust were produced by in-situ crystallization of primitive melt sills.

Petrogenesis of amphibole-rich ultramafic rocks in the Hida metamorphic complex, Japan: Its role in arc crust differentiation

Amphibole controls major and trace element chemistry of arc magma via fractionation, therefore its formation process is the key to understand arc crustal evolution. Amphibole-rich cumulates, occasionally found associated with felsic plutons or metamorphic rocks, provide complementary insights into the arc magma differentiation. In this study, we conducted a petrological examination of amphibole-rich ultramafic rocks from the Hida metamorphic complex in Japan to better understand its role in arc crust evolution. The studied samples are characterized by large poikilitic amphibole and orthopyroxene enclosing olivine grains with corroded margins. Amphibole showed high Cr2O3 and TiO2 contents (up to 0.9 and 1.2 wt%) and light rare earth element enrichment relative to heavy rare earth elements. Microscopic and geochemical features of amphibole and olivine suggest that the amphibole formed at the expense of early crystalized olivine (± clinopyroxene) from hydrous juvenile magma at a deep crustal level, which is consistent with the estimated crystallization pressure of 0.7–1.0 GPa based on an empirical Al-in-hornblende geobarometer. Considering the arc affinity of parental magma and the amphibole-fractionation trend in bulk chemistry of the Mesozoic plutonic rocks from the Hida Belt, it is implied the formation of amphibole-rich plutonic rocks contributed to arc crustal evolution as amphibole-rich residue complementary to differentiated magma.

Iron Mineralogy and Sediment Color in a 100 m Drill Core From Lake Towuti, Indonesia Reflect Catchment and Diagenetic Conditions

AbstractIron is the most abundant redox‐sensitive element on the Earth's surface, and the oxidation state, mineral host, and crystallinity of Fe‐rich phases in sedimentary systems can record details of water‐rock interactions and environmental conditions. However, we lack a complete understanding of how these Fe‐rich materials are created, maintained, and oxidized or reduced in sedimentary environments, particularly those with mafic sources. The catchment of Lake Towuti, Indonesia, is known to contain a wide range of abundant crystalline Fe oxide, and the lake has a long sedimentary history. Here, we study a ∼100 m long drill core from the lake to understand patterns of sedimentation and how young iron‐rich sediments are affected by diagenesis through geologic time. We use visible/near infrared and Mössbauer spectroscopy, X‐ray diffraction, bulk chemistry measurements, and statistical cluster analysis to characterize the core sediment. We find that the core sediment can be divided into three statistically different zones dominated by Mg serpentine, Al clay minerals, and Fe2+ carbonate, respectively. The entire core is rich in nanophase Fe, and elemental correlations and Fe mineralogy vary between these zones. The nanophase Fe is highly complex with both ferrous and ferric components, and contributes to, but does not dictate, variations in sediment color. We propose that the distinctive zones are the result of structural basin changes (notably river capture and shifting drainage patterns), and diagenetic overprinting caused by deep burial of reactive Fe. This complex record has implications for disentangling depositional and diagenetic trends in other mafic lacustrine systems.

Electroless Ag films for ionic liquid lubricated electrical contact

Two kinds of plating solutions, i.e. a standard plating solution and a commercially available plating solution, are employed for the preparation of electroless Ag film. The commercially available plating solution enables fast film deposition within several minutes and is highly selective for deposition onto Cu substrate, and cost-effective (reusable solution, and much less Ag consumption) compared to the standard plating solution. Both electroless Ag films prepared have distinct microstructure, surface chemistry, and bulk chemistry. The film from standard plating solution is composed of nano-grains with an average grain size of 300 nm and homogeneity. The film prepared with commercially available plating solution is composed of equiaxed grains (140 nm in size), and ribbon fish-like grains (80 nm in size and 0.5-2 μm in length) and shows microstructural inhomogeneity. The tribological properties of these electroless Ag films in presence of flooded 1-methyl-3-octylimidazolium hexafluorophosphate are investigated on a reciprocating tribometer with a pin-on-disk configuration under electrical contact. The results demonstrate that both electroless Ag films show better tribological property than Cu-on-Cu contact. Due to their dissimilar microstructure the tribological properties of the two electroless Ag films are quite different. For the standard plated film, local adhesion and tear-up in an annular shape on pin result in many plate-like wear debris in the early stage of the sliding test. For commercially the plated film from a commercial solution, compact and thin tribo-film on the worn surfaces of pin and disk as well as little or no wear debris are observed. The microstructural effect also has an influence on the design of the tribo-interface.

Geochemistry, Mineralogy and Textural Properties of the Lower Globigerina Limestone Used in the Built Heritage

The Lower Globigerina Limestone Member, the oldest member of the Globigerina Limestone Formation, outcrops over most of the Maltese archipelago, notably Malta. It has provided the islands’ main building material since the Neolithic period. This paper makes available a corpus of findings relating to the geochemistry, mineralogy and textural properties of this limestone—mostly unpublished and undertaken nearly three decades ago—which provide a useful source to understand its behavior. Bulk chemistry and mineralogy showed that non-carbonate and clay content is higher in limestone of inferior quality. Textural analyses gave insight into the fabric of the matrix, including inter- and intra-particle porosity. These analyses were supplemented by an array of petrophysical tests, including color (a parameter which has a correlation with density and Fe2O3 content), ultrasonic pulse velocity and compressive strength. The findings not only give insight into the composition of the limestone, using insoluble residue content of ≥5% as the threshold of inferior quality lithotype, but provided an insight into the physico-mechanical bonding present, a characteristic which has a bearing on the deterioration of this limestone.

Naphthalene‐Derived Secondary Organic Aerosols Interfacial Photosensitizing Properties

AbstractWe investigated the photosensitizing properties of secondary organic aerosol (SOA) formed during the hydroxyl radical (OH) initiated oxidation of naphthalene. This SOA was injected into an aerosol flow tube and exposed to UV radiation and gaseous volatile organic compounds or sulfur dioxide (SO2). The aerosol particles were observed to grow in size by photosensitized uptake of d‐limonene and β‐pinene. In the presence of SO2, a photosensitized production (0.2–0.3 µg m−3 h−1) of sulfate was observed at all relative humidity (RH) levels. Some sulfate also formed on particles in the dark, probably due to the presence of organic peroxides. The dark and photochemical pathways exhibited different trends with RH, unraveling different contributions from bulk and surface chemistry. As naphthalene and other polycyclic aromatics are important SOA precursors in the urban and suburban areas, these dark and photosensitized reactions are likely to play an important role in sulfate and SOA formation.

Exposure history, petrology, and shock‐induced sulfidization reaction of Alatage Mountain 001 strewn field samples

AbstractSeveral hundred meteorites with a total mass of over 100 kg were collected as the Alatage Mountain (AM) strewn field located in the Kumtag desert, Xinjiang Province, China. Twelve AM meteorites were studied in this work. Petrography, mineralogy, bulk chemistry, bulk oxygen isotopic compositions, and light noble gas concentrations and isotopic compositions were determined for all or for a selection of the meteorites. The studied meteorites are L‐chondrites that suffered a very strong impact; impact melt veins and melt pockets are widely distributed. More than 50% of the troilite exists in the form of blebs and veins in olivine and pyroxene. Some of these meteorites are impact melt recrystallized rocks (e.g., AM 037). The strong impact caused the decomposition of troilite, which led in AM 034 to the sulfidization reaction of olivine. The metal in most meteorites is almost completely altered, and the troilite has been significantly oxidized. Weathering resulted in the depletion of Mg, Fe, Co, and Ni, and the enrichment of Sr, Ba, Pb, and U in these meteorites. The cosmic ray exposure (CRE) ages measured for these specimens range between 6.2 ± 1.9 Ma and 9.0 ± 2.7 Ma, depending on the cosmogenic nuclide used. The average CRE age is 7.6 ± 1.3 Ma. Both 4He and 40Ar gas retention ages indicate that the strong impact which caused the shock effects occurred about 320 Ma ago.

T-P-fO2 conditions of sulfide saturation in magmatic enclaves and their host lavas

Physicochemical conditions under which early sulfide saturation occurs and the role of this process in the mineralising potential of magmas in different geodynamic settings have been the subject of interest in many recent studies. Here we present new temperature-pressure-fO2 data on sulfide-saturated magmatic enclaves and host lavas from volcanic systems in subduction, post-subduction and intraplate geodynamic settings, some of which are associated with porphyry and epithermal deposits. Petrographic investigations coupled with mineral chemistry of sulfide inclusions and their host minerals and with bulk chemistry of amphibole, plagioclase and pyroxene-rich enclaves and their host lavas indicate that sulfide occurrence, abundance, and composition depend on magma evolution. Sulfides are more abundant and have higher Ni/Cu bulk ratios when found in mafic enclaves compared to sulfide inclusions occurring in more evolved lavas. Thermo-oxibarometry estimates indicate that mafic hornblende-rich cumulates (SiO2 < 45 wt%) occurring at the studied intraplate setting evolve and reach sulfide saturation already in the mantle (61 ± 7 km) at high temperature and pressure conditions (17 kbar and 1135 ± 28 °C) and low ΔNNO (< −1). These cumulates are associated with a greater sulfide abundance (up to 0.23 area %) compared to other types of enclaves and have Cu-poor sulfides (mostly pyrrhotite, with Cu median = 0.16 wt%) with high Ni/Cu values (up to 65). In contrast, more evolved (SiO2 > 50 wt%) gabbroic plutonic enclaves found in arc settings saturate sulfides at shallower crustal levels (~26 ± 10 km, i.e. ≤ 7 kbar) and at lower temperature (1014 ± 28 °C) and higher ΔNNO (> +1), and are characterised by a lower sulfide abundance (down to 0.01 area %), dominated by Cu-rich sulfides (mostly chalcopyrite and bornite with Cu median = 50 wt%). By accounting for the sulfide volume, our results suggest that sulfides can retain significantly higher amounts of metals in the enclaves (Cu = 32–113 ppm) compared to sulfides in the host lavas (Cu < 8 ppm). Considered altogether, our results indicate that alkaline mafic, less oxidised, and barren magmas corresponding to intraplate and back-arc settings saturated in sulfides in the upper mantle. In contrast, calc-alkaline-felsic, oxidised and ore-related magmas corresponding to convergent margins started to be saturated in sulfides at the expected depth of the MASH zone and at shallower crustal levels. This seems to be a consequence of the investigated alkaline systems not forming shallow crustal magma chambers allowing magma differentiation, rather than the fact that late and shallow sulfide saturation is necessary for porphyry formation.

Cavezzo—The double face of a meteorite: Mineralogy, petrography, and geochemistry of a very unusual chondrite

AbstractThe Cavezzo meteorite, which fell on January 1, 2020, is the first meteorite detected and recovered by the Italian PRISMA Fireball Network. Two specimens, weighing 3.12 g (specimen 1) and 52.19 g (specimen 2), were collected 3 days after the bolide was observed, thanks to an effective media campaign that encouraged the involvement of local people. The two specimens of this meteorite have not only completely different lithological characteristics but also a different geochemistry and oxygen isotopic composition as well. Specimen 1 is anomalous both for the textural–structural features, varying seamlessly from chondritic to “achondritic,” and a very unusual modal mineralogy—such as the relatively high amount of olivine (63.1 vol%), plagioclase (18.2 vol%), high‐Ca pyroxene (10.3 vol%), and chlorapatite (2.1 vol%); and the unusually low content of low‐Ca pyroxene (5.8 vol%), metal (0.1 vol%), and troilite (much lesser than 0.1 vol%)—although the compositional values for olivine (Fa 24.24 mol%) and low‐Ca pyroxene (Fs 20.41 mol%) appear to be similar to those of the L chondrite group. Conversely, in specimen 2, not only the texture and the crystal chemistry but also the modal mineralogy (low‐Ca pyroxene much more abundant than high‐Ca pyroxene and occurrence of metal and sulfides) look like those of an ordinary L chondrite. The differences between the two specimens are also confirmed by geochemistry. The oxygen isotope composition of specimen 1 plots at the boundary between the H and L groups (δ17O‰ 3.250; δ18O‰ 4.736; Δ17O‰ 0.788) whereas specimen 2 plots at the boundary of the L and LL fields (δ17O‰ 3.737; δ18O‰ 4.957; Δ17O‰ 1.159). The bulk chemistry shows a different content of many minor and trace elements (including rare earth elements), such as a strong depletion of siderophile and chalcophile elements in specimen 1. The two specimens then do not contain fragments of each other, thus preventing us from classifying this “double face” meteorite as an ordinary chondrite breccia. In detail, specimen 1 can be considered a “xenolith” in which chondritic structure and igneous texture coexist without discontinuity, and therefore, it represents a previously unsampled portion of the L parent body. In summary, these findings support the classification of Cavezzo as an L5 anomalous chondrite.