End-member Research Articles

Two distinct populations of dark comets delineated by orbits and sizes

Small bodies are capable of delivering essential prerequisites for the development of life, such as volatiles and organics, to the terrestrial planets. For example, empirical evidence suggests that water was delivered to the Earth by hydrated planetesimals from distant regions of the Solar System. Recently, several morphologically inactive near-Earth objects were reported to experience significant nongravitational accelerations inconsistent with radiation-based effects, and possibly explained by volatile-driven outgassing. However, these "dark comets" display no evidence of comae in archival images, which are the defining feature of cometary activity. Here, we report detections of nongravitational accelerations on seven additional objects classified as inactive (doubling the population) that could also be explainable by asymmetric mass loss. A detailed search of archival survey and targeted data rendered no detection of dust activity in any of these objects in individual or stacked images. We calculate dust production limits of [Formula: see text]10, [Formula: see text], and [Formula: see text] kg s[Formula: see text] for 1998 FR[Formula: see text], 2001 ME[Formula: see text], and 2003 RM with these data, indicating little or no dust surrounding the objects during the observations. This set of dark comets reveals the delineation between two distinct populations: larger, "outer" dark comets on eccentric orbits that are end members of a continuum in activity level of comets, and smaller, "inner" dark comets on near-circular orbits that could signify a different different population. These objects may trace various stages in the life cycle of a previously undetected, but potentially numerous, volatile-rich population that may have provided essential material to the Earth.

Contribution of Anthropogenic and Lithogenic Aerosol Fe in the East China Sea

AbstractAerosol deposition is one of the major processes providing bioavailable Fe to the surface ocean. However, the quantification of aerosol Fe flux in the surface ocean is highly challenging operationally. In this study, we measured both Fe isotopic composition and specific elemental ratios in 5 size‐fraction aerosols collected over the East China Sea (ECS) to quantify the relative contribution of lithogenic and anthropogenic aerosol Fe. Both the isotopic and elemental ratios indicate that anthropogenic aerosol Fe mainly originates from high‐temperature combustion activities with the end member of the δ56Fe to be −4.5‰. We found that the Cd/Ti ratio is a much more reliable proxy to quantify the contribution of anthropogenic aerosol Fe in coarse aerosols than δ56Fe in the ECS. Attributed to extremely high deposition velocities and high total Fe concentrations for large size aerosols, lithogenic aerosols are still the dominant dissolved aerosol Fe source in the ECS.

The East Asian monsoon variability in the Nihewan Basin, northern China, during the Early Pleistocene: A grain size end-member modelling analysis

The Pleistocene sediments of the Nihewan Basin in northern China preserve a detailed terrestrial sediment archive for reconstructing the palaeoenvironment and palaeoclimate changes during early times of hominin occupation in E Asia, following the earliest locations outside of Africa. In this study, we investigate the composite 86.2-m long NH-T section of Dachangliang which was formed with an astronomically tuned age between ca. 1.66 and 0.78 Ma. Parameterized grain size end-member modelling analysis is applied for the first time in the Nihewan Basin to unravel the characteristics of sediment sources, transportation dynamics, and climatic signals in the region. The grain-size distributions of the NH-T sediment samples are attributed to a mixture of four distinct end members (EMs 1-4). EM 1 represents a global atmospheric fine silt component (mode at 7.9 μm) which probably resulted from high-altitude westerly transport from distal sources. EM 2, a medium silt component (mode at 27.6 μm) was probably transported by the low-level westerly winds during the spring from a relatively proximal source in comparison to EM 1. EM 3, a coarse silt component (mode at 59.9 μm), represents short distance suspended materials that were blown out by N or NW winds of the East Asian winter monsoon (EAWM). EM 4 is a fine sand component (mode at 221.1 μm), probably representing fluvial deposits carried by overland flow. Therefore, the temporal fluctuations in the abundances of EMs 1-3 are used to infer the history of the East Asian summer monsoon (EASM) (EM 1), of dust-storm outbreaks during springtime (EM 2), and of the EAWM (EM 3). The NH-T climate record shows an overall increase in EM 3 peaks, accompanied by a decrease in EM 1 minima from ca. 1.45 to 0.82 Ma, indicating a long-term aridification and cooling trend in the Nihewan Basin. At ca. 1.25 Ma, the EM patterns transition from short-frequency to longer fluctuations, apparently coinciding with the onset of the Mid-Pleistocene transition (MPT). Periods of stronger EASM with more frequently warm and wet conditions probably occurred in the basin between ca. 1.66-1.62, 1.52-1.25 and after 0.82 Ma. Intensified EAWM conditions probably prevailed in the basin during the intervening periods from ca. 1.62-1.52 and the MPT 1.25-0.82 Ma. The inferred warmer and wetter conditions likely supported hominin activities in the Nihewan Basin, in contrast to mostly colder and drier conditions. Nevertheless, the higher number of discovered Palaeolithic sites and recorded lithic artifacts from the first half of the MPT apparently reflects the successful adaptability of hominins to the prevailing cold climate. The relatively consistent patterns observed between the variations of a median grain-size stack of the Chinese Loess Plateau (CLP MD) and EM 3, and of the magnetic susceptibility stack of the CLP (CLP MS) and EM 1, indicate the climatic sensitivity of these EMs in response to the long-term glacial/interglacial oscillations previously inferred from the CLP. However, significant differences in the CLP MD and CLP MS on the one hand side and in the trends of the EMs 3 and 1 on the other suggest that regional climate conditions varied between the CLP and the Nihewan Basin. Further research is required to explore such regional climate differences and their possibly underlying factors in the Early Pleistocene.

The OH-stretching region in infrared spectra of the apatite OH-Cl binary system

Abstract Polarized Fourier transform infrared (FTIR) microspectroscopy of the OH-stretching region of hydroxylapatite-chlorapatite solid solutions presents novel problems for the assignment of peaks to specific OH-Cl pairs. Crystal structure refinements of Hughes et al. (2016) identified new positions for column anions in synthetic mixed Cl-OH apatites, with three different column anion arrangements depending on composition. These structural refinements, combined with bond-valence calculations, allow for interpretation of the OH-stretching region. A peak at 3574 cm–1 is identified as that from end-member hydroxylapatite. A second major peak at 3548 cm–1 is only found in mixed chlorapatite-hydroxylapatite solid solutions, as is a third peak at 3592 cm–1. Both represent perturbations of the OH-stretching vibration as compared to hydroxylapatite, to lower and higher frequency, respectively. Both of the new peaks are the result of a Clb-OH sequence, with adjacent anions in crystallographically similar positions, both above or both below adjacent mirror planes. One configuration has the hydrogen atom pointed toward the chlorine atom. The second has the hydrogen of the OH group pointed away from the chlorine atom. Both configurations present novel problems. The shift to lower wavenumber at 3548 cm–1 is characteristic of hydrogen bonding in fluorapatite-hydroxylapatite mixtures, yet the distance between O(H) and Clb is too great to allow it. The shift of OH-stretching vibrations to lower wavenumber is produced through changes in polarization of intervening Cl-Ca2′ (or Ca2) and Ca2(′)-O3 bonds, which are affected by the presence of the large chlorine atom. Lowering the OH-stretching vibration mimics the expected effect of chlorine on a neighboring OH group in the apatite c-axis column, though without hydrogen bonding. The shift to higher wavenumbers, i.e., higher frequency at 3592 cm–1, is the opposite of that expected for hydrogen bonding between column anions in the apatite mineral group. It is ascribed to the interaction between an adjacent Clb and the oxygen end of an adjacent OH dipole. This pairing places an oxygen and a chlorine atom in close proximity. Possible means of accommodation are discussed. A ubiquitous peak at 3498 cm–1 represents hydrogen bonding between an OH and the OHa site, with an interoxygen distance of about 2.9 Å. Published modeling supports the hypothesis that the OHa site is occupied by an O rather than an OH. However, no clear counterpart to this pairing is observed in crystal structure refinements for specimens lacking OHa, although the infrared absorbance is present. The existence of oxyapatite is inferred from studies of plasma-sprayed biomaterials, but the crystal-lographic details of the substitution have remained elusive. A minor shoulder at 3517 cm–1 does not have a clear counterpart in the structural refinements. Sequences of three columnar anions (e.g., OH-Cl-OH or Cl-OH-OH) can be ruled out, but an unequivocal assignment awaits further research.

Na5/6[Ni1/3Mn1/6Fe1/6Ti1/3]O2 as an Optimized O3-Type Layered Oxide Positive Electrode Material for Sodium-Ion Batteries.

Layered oxides, such as NaxMeO2 (Me = transition metal, x = 0-1), are believed to be the most promising positive electrode materials for Na-ion batteries because of their high true density, large capacities, high working potentials, and reversibility. This study identified Na5/6[Ni1/3Mn1/6Fe1/6Ti1/3]O2 as an optimal composition for use as an O3-type positive electrode material in Na-ion batteries on the basis of a comprehensive phase diagram, where the end members of the triangular phase diagram were Na2/3[Ni1/32+Mn2/34+]O2, Na2/3[Ni1/32+Ti2/34+]O2, and the hypothetical composition Na4/3[Ni1/32+Fe2/33+]O2. By investigating the effects of the partial substitution of Mn4+ with Fe3+ and Ti4+ within the Na(2/3+x)[Ni1/3Mn(2/3-x-y)FexTiy]O2 system, we optimized the capacity, working potential, and cycle performance. Substitution with Fe enhanced the discharge capacity due to the increased Na+ content in the initial composition, although it also led to a reduced cycling stability derived from irreversible Fe migration to the Na layers. In contrast, substitution with Ti improved the working potential and cycling stability, although an excessive Ti content caused capacity degradation with cycling. We found that the O3-type Na5/6[Ni1/3Mn1/6Fe1/6Ti1/3]O2 demonstrated an excellent cycle stability with minimal capacity loss over 250 cycles, which was attributed to the suppression of irreversible transition metal migration.

Short wavelength infrared (SWIR) spectral and geochemical characteristics of white micas in the Xiaonangou gold deposit, East Qinling: As a hyperspectral tool in exploration

The Xiaoqinling-Xiong’ershan region, a prominent component of the East Qinling Belt, is renowned worldwide for its molybdenum and gold ore fields. Moreover, with gold reserves of at least 1300 tons, it is also China’s major gold mining province, second only to Jiaodong. Seated in eastern center of the Xiong’ershan area, the Xiaonangou gold deposit has an estimated gold reserve of over 60 tons and is characterized by disseminated gold in altered rocks. Based on detailed petrographic investigation, coupled with an analysis of crosscutting relationships, there are three stages of hydrothermal alteration and mineralization: pre-ore K-feldspar + quartz (stage Ⅰ), ore quartz + ankerite + disseminated pyrite + polymetallic sulfide (stage Ⅱ), and post-ore quartz + carbonate (stage Ⅲ). As revealed by a systematic analysis of short wavelength infrared (SWIR) spectroscopy, four main types of alteration minerals exist, including white micas, clay minerals, chlorite, and carbonate minerals. In the ore body, white micas mainly developed in stage Ⅱ, and slightly occurred in stage Ⅰ. The clay minerals and chlorite usually developed in the banded alteration zones outside the orebody. Most of the carbonate minerals, including calcite and dolomite, mainly developed in stage Ⅲ, but the ankerite was associated with disseminated pyrite, quartz and polymetallic sulfides in stage Ⅱ. Of these, white micas were recognized as the most abundant hydrothermal alteration minerals, which were observed to be widely distributed within alteration zones in the Xiaonangou gold deposit. The SWIR parameters and its spatial variation of white mica indicate that the Al-OH absorption positions (Pos2200) exhibit a drifting tendency towards longer (>2205 nm) wavelengths in the ore body vicinity. Additionally, there is a discernible increase in illite crystallinity (IC values) in the same region. The temperature, redox, and pH conditions for associated fluids can be reflected through characterization of these parameters. Furthermore, it demonstrates that the ore-proximal zones are situated in a relatively oxidized, alkaline, and high-temperature environment in the Xiaonangou gold deposit. According to the electron probe microanalysis (EPMA) results, two distinct end members exist in white mica: a Si-poor, Al-rich muscovite and an Al-poor, Si-, Fe-, and Mg-rich phengite. The Si, ivAl, viAl, Mg, Fe, and Ti elements exhibit a linear correlation with the wavelength of Pos2200, demonstrating that the shift in wavelength of white mica is predominantly controlled by Tschermak substitution (ivSivi(Mg，Fe) ↔ivAlviAl). The application of spatial variation in the SWIR spectral parameters along with geochemical properties of white mica facilitates the effective guidance of mineral exploration. In comparison to other deposits, it can be concluded that the longer (>2205 nm) wavelength of the Pos2200 along with the higher IC values (>1.4) of white mica are applicable as valid vectors towards gold mineralization in the Xiaonangou gold deposit.

New insights into Holocene dust activity in eastern Uzbekistan

Central Asia is a substantial source of long-range-transported dust, yet the historical and geological variability of dust activity in this region remains poorly understood. This study presents a Holocene record of dust activity from a 6.2-m loess section located near Tashkent in the westerlies-dominated region of eastern Uzbekistan, Central Asia. Utilizing the quartz optically stimulated luminescence dating protocol, we employed grain-size analysis and trace-element geochemistry to reconstruct Holocene dust activity. Dating indicated that this section was deposited over the last 9.6 ka. Four grain-size end-member (EM) components were identified, each representing different atmospheric circulation patterns and sedimentary environments. End-member 2, with a modal size of 11.2 μm, likely represents particles transported by upper-level westerlies, while EM 3, with a modal size of 28.3 μm, is associated with near-surface winds linked to dust storms. Zirconium is concentrated in coarse particles, whereas Rb is enriched in finer particles during dust deposition. Therefore, higher Zr/Rb ratios indicate stronger or more distant dust transport; hence, the Zr/Rb ratio is a reliable indicator of dust activity. Holocene dust activity was reconstructed using the EM 3 component and Zr/Rb ratio, revealing several extreme dust-storm events. During the early–middle Holocene (9.6–5 ka), dust activity was stronger but less frequent compared with the subsequent shift to lower intensity but higher frequency dust events. The long-term orbital-scale decline in Holocene dust activity can be attributed to reduced solar insolation and weakening of the Siberian High since the early Holocene. On a centennial to millennial scale, extreme dust-storm events are teleconnected with cold ice-rafted debris events in the North Atlantic. Projections for the coming century suggest that dust activity in eastern Uzbekistan may further decline, accompanied by an increase in precipitation. This study provides new insights into understanding and predicting dust storms in Central Asia.

Rational Pathways to Ordered Multianion Chalcogenides Using Retrosynthetic Crystal Chemistry.

Mixed-anion chalcogenides make up a versatile class of materials with properties that can be fine-tuned for specific applications. While chalcogen anions (Q = S, Se, or Te) tend to form solid solutions in simple binary systems, ordering does occur in structures that have more than one unique anion site. Here, we use crystallographic analysis and hard-soft acid-base principles to predict the Wyckoff positions that secondary chalcogens will occupy in a range of single-anion hosts. The analysis serves as a guide for generating ordered sulfoselenide, selenotelluride, and sulfotelluride products in a predictable manner. The study focuses on ternary and quaternary systems with varying compositional and structural features, with an emphasis on 3D CsCu5Q3 (P42/mnm) and 2D NaCuZrQ3 (Pnma) crystal systems. The samples were prepared by using high-temperature solid-state methods and structurally characterized by using single-crystal X-ray diffraction. Ordering in the mixed-anion products is attributed to the size and bonding variance across the chalcogen series. The degree of ordering varies according to the distinctiveness of the local chemistry at the anion sites and additionally the specific combination of chalcogens employed in the reaction. Additionally, we find that mixed-chalcogen products can adopt phases that are distinct from their single-anion end members, including KCuZrTe2S (P21/m), where an alternate arrangement of polyhedral building blocks maximizes favorable bonding interactions. Density-functional theory calculations corroborate the experimental findings and offer additional insights into the ordering trends. We anticipate that the reverse-engineering approach, which is inspired by the retrosynthetic analyses used in molecular chemistry, will help accelerate the discovery and understanding of heteroanionic phenomena.

Quantitative contributions of different atmospheric circulation systems to Holocene aeolian activity in northwestern China: Evidence from a closed interdune lake in the Tengger Desert hinterland

The aeolian deserts of northwestern China are major landscape types in the arid regions of the Northern Hemisphere, and collectively they are one of the largest dust source regions on Earth. However, owing to occurrence of sedimentary hiatuses within aeolian deposits in the deserts, we lack clear knowledge of the history of Holocene aeolian activity and the interaction between aeolian processes and their potential drivers. In this study, we extracted an environmentally sensitive grain-size component from the sediments of a closed interdune lake in the hinterland of the Tengger Desert. Our methodology included the application of End Member Analysis (EMA) of different modern sediment types from catchment to regional scales. We reconstructed aeolian activity over the past 13 cal ka BP and quantified the contributions of environmental factors. The results indicated that the EM 2 fraction of the interdune lake sediments is mainly transported by local winds and reflects changes in the intensity of aeolian activity. Based on EM 2 the strongest aeolian activity occurred during 13.0–7.0 cal ka BP, especially during 8.0–7.0 cal ka BP, and the weakest activity occurred during 7.0–3.5 cal ka BP. Aeolian activity increased after 3.5 cal ka BP, but with a gradually weakening trend. The occurrence of the weakest aeolian activity in the Tengger Desert during the Middle Holocene differs from that on the Asian Summer Monsoonal Boundary and in the area influenced by the Westerlies-dominated climate regime. Thus, there was a clearly defined spatio-temporal differentiation of Holocene aeolian activity across the deserts and dune fields of northern China. Quantitative analysis of the contributions of the potential drivers indicated that wind activity forced by different atmospheric circulation systems, rather than changes in vegetation cover, were the most important driver of regional aeolian activity, although their relative effects varied during the Holocene.

Separations of meltwater discharge in a snowpack by artificial rain-on-snow experiments

In temperate regions, snow and its meltwater constitute primary freshwater resources and snowmelt isotopes offer valuable insights into understanding the snowmelt processes including the timing and contribution of snowmelt to the soil and watershed in spring. Assessing the storage and movement of liquid water within natural snowpacks, a previously unquantified aspect, holds significance for predicting natural hazards and managing water resources for agricultural purposes and ecosystem health. The escalating occurrence of rain-on-snow (ROS) events, attributed to winter warming, has the potential to trigger natural hazards and surface runoff into major river systems in temperate climate regions. End member mixing calculations (EMMC) based on isotopic and chemical tracers were employed to quantify the proportions of rainwater, meltwater, and pore water within the snowpack discharge. In this study, artificial rain-on-snow experiments involving conservative anions and stable water isotopes were conducted at the surface of snowpack to differentiate each component (rainwater, pore water, and snowmelt) within the discharge collected at the bottom of the snowpack. Pore water content exhibited a shift from 1.1 ± 1.1% (± 1σ, N = 23) after the initial artificial ROS event to 2.8 ± 1.2% (± 1σ, N = 19) following the spray in our experiment. Based on the EMMC, the contributions of rainfall, pore water, and snowmelt to the meltwater discharge were 2,620.2 L (63.3%), 829.0 L (20.0%), and 687.4 L (16.6%), respectively. Notably, contrary to prior studies, our experimental results suggest that rainwater reached the bottom through multiple rapid flow channels before matrix flow occurred. This experimental approach provides additional insights into the dynamics of water percolation in snowpacks during rain-on-snow events.

Unveiling the Monoclinic Phase in CsPbBr3-xClx Perovskite Crystals, Phase Transition Suppression and High Energy Resolution γ-Ray Detection.

All-inorganic CsPbBr3 and CsPbCl3 perovskites are promising materials for high-performance solar cells and advanced radiation detection technologies with high stability. Here we report that CsPbBr3-xClx (x = 0-3) crystals exhibit eutectoid behavior for the melting points and phase transition temperatures. The well-known halide perovskite cubic phase transition temperature shifts near room temperature (∼37 °C for CsPbBr2Cl). We conducted an extensive crystallographic analysis on single crystals of 7 different compositions, including the end members CsPbBr3 and CsPbCl3. Contrary to previous beliefs, we discovered they exhibit a monoclinic structure with space group symmetry P21/m at room temperature, rather than the orthorhombic Pnma. This new structural model is more precise and features a unit cell volume that is four times larger than that of the orthorhombic model. From high-quality single crystals of CsPbBr2Cl, grown by the Bridgman method, we constructed γ-ray detectors achieving an energy resolution of 7.2% at 200 V for 57Co radiation. Thermally stimulated current spectroscopy of the CsPbBr2Cl samples revealed that the defect densities in crystals from different regions of the ingot were relatively uniform, with values of ∼4.72 × 1012 and ∼5.09 × 1012 cm-3. These findings indicate that low deep-level defect densities can be achieved that are consistent with the notable performance of the CsPbBr2Cl perovskite as a high-energy γ radiation detector.

Brittle Regime Slip Partitioned Damage and Deformation Mechanisms Along the Eastern Denali Fault Zone in Southwestern Yukon

AbstractRare bedrock exposures of the eastern Denali fault zone in southwestern Yukon allow for the measurement, sampling, and analyses of brittle regime fault slip data and deformation mechanisms to explore relations to far field, oblique plate motions. Host rock lithologies and associated slip surfaces show episodic damage zone‐related deformation and calcite ± hematite ± chlorite related hydrothermal fluid flow. This regional scale network of asymmetric fault damage is spatially and kinematically linked to a discrete and narrow fault core. Fault network observations, orientations, slip data, and strain inversions document a slip partitioned strike‐slip fault system with locally and mutually overprinting strike‐, oblique‐, and dip‐slip components. Microstructural analyses reveal crystal plastic and co‐seismic brittle deformation mechanisms active in a narrow range of upper crustal temperature, pressure, fluid, and chemical conditions. The net damage related slip is not exclusively formed by a single kinematic system, but rather a fully partitioned, time integrated system likely operative for much of the fault's brittle regime evolution temporally constrained by previously published thermochronometric data. Although the fault slip data was collected from outcrop‐scale exposures at sites tens of kilometers apart, results show remarkable correlation between fault kinematics and plate motions along the ∼580 km long eastern Denali fault segment. End member, subhorizontal, northeast directed reverse and north directed dextral strike slip fault strain axes closely reflect relative plate motion interactions over at least the last 30 m.y. and act as a proxy for far‐field stresses compatible with the kinematics of the damage zone network.

Hydrochemical characterization and pCO2 dynamics in the surface waters of Himalayan River: A case study of river Alaknanda.

Chemical weathering processes are becoming increasingly important in studies on carbon cycling because they are responsible for increased solute fluxes in the proglacial zone, can effectively sequester atmospheric CO2 and raise carbon budgets for lateral transport via rivers. Here, we examined the hydrochemical and hydrogeochemical processes, solute sources and factors controlling riverine pCO2 of the Alaknanda River and its tributaries for three sampling seasons, viz. pre-monsoon (May 2021), post-monsoon (October 2021) and winter (January 2022). The surface water is enriched with Ca2+ and Mg2+ as the dominant cations, while HCO3- and SO42- were the major anions. Gibbs's plot confirmed rock weathering as the leading mechanism in controlling the hydrochemistry of the basin. The chemical composition of river water was mainly regulated by the weathering of carbonate end members: dolomite, limestone and feldspar along with small inputs from silicate weathering. The mean pCO2 values in the mainstream (1702.7 µatm), Pindar (2267.9 µatm) and Mandakini (1136.1 µatm) revealed the streams were oversaturated with CO2 having a higher rate of exporting excess CO2 gas to the atmosphere. The study showed the persistence of high pCO2 closed system characteristics associated with increased suspended sediment concentration resulting from carbonate weathering, dominance of HCO3- over SO42- and thereby results in high values of C ratio. Principal component analysis of the water chemistry suggests that weathering contributes about 41%, while humans contribute about 13% of the ionic load to the river. This study is one of its kind to understand the system characteristics of Alaknanda River water.

Phase equilibrium constraints on the pre-eruptive conditions of alkaline basalts of the Main Ethiopian Rift and their bearing on the production of peralkaline rhyolites

Abstract Bimodal magmatism is characteristic of the geodynamic evolution of the Main Ethiopian Rift (MER), which is a reference area for the study of the processes leading to continental break-up before seafloor spreading. There are abundant emissions of basalts and rhyolites, which are in possible parent-daugther relationships. However, the P-T-H2O conditions of production and storage of the basaltic end member remain unclear. Crystallization experiments have been conducted on an alkali basalt from the MER to define its pre-eruptive conditions and shed light on the compositional evolution of derivative liquids and source conditions. The experiments were performed at 100-200 MPa, 975-1080°C, varying H2O/CO2 ratios, corresponding to melt water contents of 1-5 wt%, at fO2 slightly lower than the Fayalite-Magnetite-Quartz (FMQ) solid buffer. Comparison between the petrological attributes of the starting rock and the experiments shows that the basaltic magma was stored at 150-200 MPa, 1050 ± 10°C, with 1-2 wt% H2O in melt, with fO2 near FMQ prior to eruption. Geochemical modelling shows that the corresponding mantle source contained about 0.1 wt% H2O, reflecting a metasomatized source. Extensive crystallization of such basalts produces SiO2-rich liquids, which are not yet peralkaline, however. This underscores that extreme fractionation (>90 wt%) is required in order to produce peralkaline derivatives from mildly alkaline basalts. This extreme fractionation and the water-rich nature of the starting basalt readily explain the H2O-rich condition of peralkaline rhyolites that have fueled caldera forming eruptions in the Rift.

Triple oxygen and hydrogen isotopes of glacial diamictites record crustal maturation and changing surface conditions through geologic time

The triple oxygen and hydrogen stable isotopic compositions of 24 glacial diamictite composites with depositional ages from 2.9 to 0.3 Ga are used to reconstruct the evolution of the continental crust and surface environments. The δ18O of the diamictite composites increases from the Archean to the Phanerozoic by ∼4 ‰ (3–5 ‰ in Mesoarchean to 13.5 ‰ in Neoproterozoic), a trend that is comparable to those seen in shales and granites, although the diamictites plot on the lower δ18O end of the range seen in shales. The Δ’17O0.528 decreases from −0.04 to −0.15 ‰, overlapping with shales and granites. Nine zircon separates extracted from individual diamictites also show a ∼3 ‰ increase in δ18O from 3.75 to 4.5 ‰ to 7 ‰ between 2.9 and 0.6 Ga. The δ18O of diamictites and zircon separates negatively correlates with ɛNd(i) of the diamictites, suggesting that the longer the rocks reside in the upper continental crust (the lower the ɛNd), the more they are subjected to repeated weathering cycles, thus acquiring a higher δ18O and lower Δ’17O0.528 during each cycle. On a triple O isotope plot (δ17O vs δ18O), diamictites define an array with a slope of 0.523, analogous to granites and shales.The δD values of nearly all diamictites overlap with the typical mantle and crustal ranges of −58 ± 12 ‰ and − 69 ± 24 ‰, respectively, but are on the lower end of coeval shale values. Water, contained primarily in sheet silicates, ranges from 2.85 wt% (pre-2.4 Ga) and 2.35 wt% (post-2.4 Ga), showing no temporal change, likely reflecting post-depositional reset. The youngest diamictites (0.3 Ga Dwyka Group) exhibit low δD values of −105 to −111 ‰, lower than the typical crustal values, potentially reflecting the near-polar position of South Africa at the time of their deposition, which is corroborated by the reconstructed δ18O value of −26 ‰ based on triple oxygen isotopic systematics.The chemical index of alteration (CIA) allows inverting measured δ18O and Δ’17O values of diamictite composites into a pure weathering product (wp) end member by subtracting values of coeval unweathered crust based on tzircon δ18O. This reveals that the δ18Owp also increases with time, suggesting that the increase in δ18O (decrease in Δ’17O) of the maturing crust is insufficient to fully explain the trends. Therefore, at least part of the increasing δ18Owp likely reflects increasing δ18O of the hydrosphere. Reconstructed surface temperatures around the time of diamictite deposition using δ18Owp and Δ’17Owp display a general decrease since the Archean. Given the diagenetic and post-diagenetic history experienced by the diamictites, the temporal and global trends should be interpreted with caution. Nonetheless, reconstructed δ18Owater shows an increase from −21 ‰ at 2.9 Ga to −11 ‰ at 0.6 Ga. Thus, diamictites, like shales, broadly monitor the evolution of surface conditions on Earth from warmer to colder and from lower to higher δ18Owater values of the hydrosphere.

Carbon sequestration in a typical mountain lake associated with earthquakes, floods, droughts, and human activities in southern Altay during the late Holocene

Lakes, being key regulators of atmospheric carbon dioxide (CO2), have not yet been intensively explored in the carbon cycle. This study provides an attempt to investigate how carbon sequestration in mountain lakes responds to seismic activities, extreme climate events and human disturbance. The new data of grain-size end members (EMs), TN contents, C/N, concentrations of algal spores, and P and Mn contents, in addition to previously published data of TOC and Ca contents, Zr/Rb, Rb/Sr, and land-pollen assemblages of a well-dated sediment core from Yileimu Lake, depicted a more detailed history of environmental evolution in the region. A great earthquake happened in southern Altay at ∼ 3500 cal yr BP that triggered extensive landslides around the lake, and then frequent floods eroded the catchment between ∼ 3500 and 2300 cal yr BP, subsequently severe drought events occurred within the period of 2300–1000 cal yr BP, finally agricultural and pastoral activities intensified within the last 1000 yrs. Organic carbon accumulation rate (OCAR) in Yileimu Lake was extremely high (an underestimated value of ∼ 370 g m–2 yr–1) during the earthquake event, in response to the rapid accumulation of landslide materials. Regional comparison revealed that summer temperature was unexpected to have determined the OCAR during both flood and drought events (average 4.07 and 3.64 g m–2 yr–1, respectively), because it dominated the production of land- and aquatic plants. Human activities increased the OCAR prominently (averages 6.26 g m–2 yr–1) via changing sediment production and vegetation planting, which decoupled the OCAR from climate factors. These data imply that carbon sequestration in lakes from mountain areas where temperature adversity stress dominated vegetation growth would have the potential to increase under anthropogenic warming. In addition, seismically induced carbon sequestration in lakes from tectonically active regions cannot be ignored.

Magnetic signature of deep pit ovens from Paquimé, ceremonial center of the Casas Grandes culture (Northern Mexico)

The Casas Grandes culture in Northern Mexico and Southwest United States has been characterized by its impressive architecture - unique to desert cultures, with houses and constructions of up to four floors built by adobe. In this study, we report an integrated rock-magnetic and archaeomagnetic study from Paquimé archaeological site, considered as an outstanding testimony of the relationship between the cultures of North America and Mesoamerica. The In Situ structures of Paquimé archaeological zone were magnetically analyzed for the first time. Four up to 2.6 m deep Pit Ovens, commonly used for agave cooking, were sampled. 78 specimens were subjected to stepwise alternating field demagnetizations to retrieve characteristic remanence archaeodirections. The great majority of samples yielded evidence of essentially stable, single component remanent magnetization carried by the end members of titanomagnetite solid solutions (almost magnetite phase). Hematite grains apparently also co-exist, but their contribution in total thermoremanence is minor. The archaeomagnetic dating, based on mean declination and inclination, was performed using the global geomagnetic models and the available regional Paleosecular Variation Curves available for Mesoamerica. Additionally, SW United State paleosecular variation patterns from Four Corner region was also considered. The most probable age interval for one of the studied ovens (around 940 AD) is out of Paquimé’s main occupation phase between 1200 and 1450 AD. The age estimation for the PH1 pit oven, around 1150 AD, could be located near the limit of the beginning of the Medio Period. Remained two analyzed ovens yielded up to three possible ages distributed around 1100, 1320 and 1480 AD. Pit Ovens studied here, were long time considered to correspond to same time interval, while these new results attest that these combustion structures encompassed almost six centuries in agreement with the historical fact that the city of Paquimé was abandoned before the arrival of the Spaniards.

Thermodynamics of the α-FeOOH (goethite)-ScOOH solid solution

Scandium (Sc) is a rare element that finds uses in modern technologies. Thermodynamic properties of Sc phases could help in the development of innovative technologies to extract Sc from mining waste. In this work, we investigated the FeOOH–ScOOH solid solution with the goethite structure. The end members and five intermediate compositions were synthesized and characterized. The lattice parameters show that the solid solution is non-ideal, with complex behavior induced by the Fe–Sc substitution. The excess unit-cell volume deviates negatively for the Sc-rich region, and positively for the Fe-rich region from the ideal behavior (Vegard’s law). Enthalpies of dissolution were determined by acid-solution calorimetry in 5 mol·dm-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\cdot \\hbox {dm}^{-3}$$\\end{document} HCl at T = 343.15 K. Enthalpies of mixing (ΔmixH\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta _{mix}H$$\\end{document}), calculated from the experimental data, are small and positive. The available data allow for fitting the data as ΔmixH=Wx(1-x)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta _{mix}H = W x (1-x)$$\\end{document}, with the mixing parameter W=15.2±\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$W = 15.2\\pm$$\\end{document}1.0 kJ·mol-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\cdot \\hbox {mol}^{-1}$$\\end{document}. Using ΔfGo\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta _fG^o$$\\end{document} of ScOOH from earlier literature, we calculated a Lippmann diagram that shows that Sc should strongly partition into the aqueous phase upon goethite precipitation. The field observations from lateritic profiles show that Sc is primarily harbored by goethite via adsorption. It seems that under weathering conditions, thermodynamically driven partitioning of Sc3+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Sc}^{3+}$$\\end{document} into the aqueous phases and its subsequent adsorption onto goethite surfaces controls the mobility of Sc in the weathering profiles.

Tuning structural modulation and magnetic properties in metal-organic coordination polymers [CH3NH3]CoxNi1-x(HCOO)3.

Three solid solutions of [CH3NH3]CoxNi1-x(HCOO)3, with x = 0.25 (1), x = 0.50 (2) and x = 0.75 (3), were synthesized and their nuclear structures and magnetic properties were characterized using single-crystal neutron diffraction and magnetization measurements. At room temperature, all three compounds crystallize in the Pnma orthorhombic space group, akin to the cobalt and nickel end series members. On cooling, each compound undergoes a distinct series of structural transitions to modulated structures. Compound 1 exhibits a phase transition to a modulated structure analogous to the pure Ni compound [Cañadillas-Delgado, L., Mazzuca, L., Fabelo, O., Rodríguez-Carvajal, J. & Petricek, V. (2020). Inorg. Chem. 59, 17896-17905], whereas compound 3 maintains the behaviour observed in the pure Co compound reported previously [Canadillas-Delgado, L., Mazzuca, L., Fabelo, O., Rodriguez-Velamazan, J. A. & Rodriguez-Carvajal, J. (2019). IUCrJ, 6, 105-115], although in both cases the temperatures at which the phase transitions occur differ slightly from the pure phases. Monochromatic neutron diffraction measurements showed that the structural evolution of 2 diverges from that of either parent compound, with competing hydrogen bond interactions that drive the modulation throughout the series, producing a unique sequence of phases. It involves two modulated phases below 96 (3) and 59 (3) K, with different q vectors, similar to the pure Co compound (with modulated phases below 128 and 96 K); however, it maintains the modulated phase below magnetic order [at 22.5 (7) K], resembling the pure Ni compound (which presents magnetic order below 34 K), resulting in an improper modulated magnetic structure. Despite these large-scale structural changes, magnetometry data reveal that the bulk magnetic properties of these solid solutions form a linear continuum between the end members. Notably, doping of the metal site in these solid solutions allows for tuning of bulk magnetic properties, including magnetic ordering temperature, transition temperatures and the nature of nuclear phase transitions, through adjustment of metal ratios.

Quantitative analysis of spectral properties and composition of primitive achondrites (acapulcoites, lodranites and winonaites)

The establishment of robust meteorite-asteroid links has been a major focus of planetary exploration, and a major driver of asteroid sample return missions. Reflectance spectroscopy has been shown to be a powerful tool for this purpose. For the meteorites dominated by silicate minerals, quantitative analysis of spectral absorption features caused by the Fe2+-bearing minerals (mainly olivine and pyroxene) is a common method to determine mafic silicate mineralogy and end member abundances, and establish the relationship between them and possible parent bodies. In this study, the reflectance spectra of 22 primitive achondrites (acapulcoites, lodranites and winonaites) from NASA RELAB database were analyzed to determine their positions in the plot of the band area ratio (BAR) and 1 μm band center (Band I center). We found that Band I center and BAR of acapulcoites and lodranites are in roughly the same range. Acapulcoite-lodranite partially overlap with the field of H chondrites in the plot of the BAR and Band I center. This overlap means that spectral calibrations (also referred to as mineralogical formulas) based on the two types of meteorites needs to be applied with caution. The 2 μm band center of acapulcoite–lodranite is significantly lower than that of H chondrites, which is consistent with the conclusion of previous studies and provides a means to separate these two groups. In addition, the choice of spectral parameter analysis techniques may be a potential error source in similar studies. We provide generalized spectral fields of primitive achondrites in the plot of the BAR and Band I center derived from two widely used technologies.