Chemical Evolution Research Articles

Influence of synchronized pulse bias on the Microstructure and Properties of CrSiN nano-composite ceramic films deposited by MIS-HiPIMS

In this study, CrSiN nano-composite ceramic films with optimized structure were prepared at low temperature using MIS-HiPIMS technique, owing to improved utilization of the high ionization characteristic of HiPIMS under specially designed synchronized pulsed-bias working mode. The correlations of the synchronized pulsed-bias width, the chemical composition, microstructure evolution, mechanical properties and tribological behaviors were studied systematically. According to the results, the waveforms of the pulsed bias experienced obvious fluctuating periods, indicating fluctuating intensities of positive ions arrived at the substrates. Meanwhile, the fluctuating duration increased with increasing synchronized pulse-width, providing an effective way of adjusting the energetic-ion flux for improved bombardment of the growing film. Therefore, obvious microstructure refinement of the as-deposited CrSiN films had been achieved. Due to optimized ion bombardment, the CrSiN films evolved from a coarse and transgranular columnar structure to a more densified columnar structure with the mixture phases of hcp-Cr2N, fcc-CrN as well as a-Si3N4. Moreover, the hardness and elastic modulus of the CrSiN films were also elevated significantly, to the maximum values of 20.2 GPa and 348.3 GPa, respectively. Furthermore, with the best mechanical properties as well as the highest density, the optimized CrSiN film deposited at 400 μs also displayed the most excellent wear resistance, with the wear rate as low as 9.1 × 10−16 m3/N.m. This study not only proposes a method of optimizing the structure and tribological properties of CrSiN nano-composite ceramic films at relatively low temperature, and also enriches the property database of CrSiN films which could expand their application in fields involving thermal-sensitivity materials.

The Heavy Metal Survey: The Evolution of Stellar Metallicities, Abundance Ratios, and Ages of Massive Quiescent Galaxies since z ∼ 2

We present the elemental abundances and ages of 19 massive quiescent galaxies at z ∼ 1.4 and z ∼ 2.1 from the Keck Heavy Metal Survey. The ultradeep LRIS and MOSFIRE spectra were modeled using a full-spectrum stellar population fitting code with variable abundance patterns. The galaxies have iron abundances between [Fe/H] = −0.5 and −0.1 dex, with typical values of −0.2 [−0.3] at z ∼ 1.4 [z ∼ 2.1]. We also find a tentative logσv –[Fe/H] relation at z ∼ 1.4. The magnesium-to-iron ratios span [Mg/Fe] = 0.1–0.6 dex, with typical values of 0.3 [0.5] dex at z ∼ 1.4 [z ∼ 2.1]. The ages imply formation redshifts of z form = 2–8. Compared to quiescent galaxies at lower redshifts, we find that [Fe/H] was ∼0.2 dex lower at z = 1.4–2.1. We find no evolution in [Mg/Fe] out to z ∼ 1.4, though the z ∼ 2.1 galaxies are 0.2 dex enhanced compared to z = 0–0.7. A comparison of these results to a chemical evolution model indicates that galaxies at higher redshift form at progressively earlier epochs and over shorter star formation timescales, with the z ∼ 2.1 galaxies forming the bulk of their stars over 150 Myr at z form ∼ 4. This evolution cannot be solely attributed to an increased number of quiescent galaxies at later times; several Heavy Metal galaxies have extreme chemical properties not found in massive galaxies at z ∼ 0.0–0.7. Thus, the chemical properties of individual galaxies must evolve over time. Minor mergers also cannot fully account for this evolution as they cannot increase [Fe/H], particularly in galaxy centers. Consequently, the buildup of massive quiescent galaxies since z ∼ 2.1 may require further mechanisms, such as major mergers and/or central star formation.

Astrochemical effect of the fundamental grain surface processes

Context. Thermal diffusion is one of the basic processes for the mobility and formation of species on cosmic dust grains. The rate of thermal diffusion is determined by the grain surface temperature, a pre-exponential factor, and an activation energy barrier for diffusion. Due to the lack of laboratory measurements on diffusion, prior astrochemical models usually assume that the diffusion pre-exponential factor is the same as that for desorption. This oversimplification may lead to an uncertainty in the model predictions. Recent laboratory measurements have found that the diffusion pre-exponential factor can differ from that for desorption by several orders of magnitude. However, the newly determined pre-exponential factor has not been tested in astrochemical models so far. Aims. We aim to evaluate the effect of the newly experimentally measured diffusion pre-exponential factor on the chemistry under cold molecular cloud conditions. Methods. We ran a set of parameters with different grain temperatures and diffusion barrier energies using the NAUTILUS astro-chemical code and compared the molecular abundance between the models with the abundance obtained using the experimentally determined pre-exponential factor for diffusion and with the abundance obtained using the values commonly adopted in prior models. Results. We found that statistically, more than half of the total gas-phase and grain surface species are not affected by the new pre-exponential factor after a chemical evolution of 105 yr. The most abundant gas-phase CO and grain surface water ice are not affected by the new pre-exponential factor. For the grain surface species that are affected, compared to the commonly adopted value of the pre-exponential factor for diffusion used in the chemical models, they could be either overproduced or underproduced with the lower diffusion pre-factor used in this work. The former case applies to radicals and the species that serve as reactants, while the latter case applies to complex organic molecules (COMs) on the grain and the species that rarely react with other species. Gas-phase species could also be affected due to the desorption of the grain surface species. The abundance of some gas-phase COMs could be varied by over one order of magnitude depending on the adopted grain surface temperature and/or the ratio of diffusion to desorption energy in the model. Key species whose diffusion pre-exponential factor significantly affects the model predictions were also evaluated, and these species include CH3OH, H2CO, and NO. Conclusions. The results presented in this study show that the pre-exponential factor is one of the basic and important parameters in astrochemical models. It strongly affects the chemistry and should be determined carefully. More experiments to determine the diffusion of grain surface species are helpful for constraining their properties.

Grain growth and its chemical impact in the first hydrostatic core phase

Context. The first hydrostatic core (FHSC) phase is a brief stage in the protostellar evolution that is difficult to detect. Its chemical composition determine that of later evolutionary stages. Numerical simulations are the tool of choice to study these objects. Aims. Our goal is to characterize the chemical evolution of gas and dust during the formation of the FHSC. Moreover, we are interested in analyzing, for the first time with 3D magnetohydrodynamic (MHD) simulations, the role of grain growth in its chemistry. Methods. We postprocessed 2 × 105 tracer particles from a RAMSES non-ideal MHD simulation using the codes NAUTILUS and SHARK to follow the chemistry and grain growth throughout the simulation. Results. Gas-phase abundances of most of the C, O, N, and S reservoirs in the hot corino at the end of the simulation match the ice-phase abundances from the prestellar phase. Interstellar complex organic molecules such as methyl formate, acetaldehyde, and formamide are formed during the warm-up process. Grain size in the hot corino (nH > 1011 cm−3) increases forty-fold during the last 30 kyr, with negligible effects on its chemical composition. At moderate densities (1010 < nH < 1011 cm−3) and cool temperatures 15 < T < 50 K, increasing grain sizes delay molecular depletion. At low densities (nH ~ 107 cm−3), grains do not grow significantly. To assess the need to perform chemo-MHD calculations, we compared our results with a two-step model that reproduces well the abundances of C and O reservoirs, but not the N and S reservoirs. Conclusions. The chemical composition of the FHSC is heavily determined by that of the parent prestellar core. Chemo-MHD computations are needed for an accurate prediction of the abundances of the main N and S elemental reservoirs. The impact of grain growth in moderately dense areas delaying depletion permits the use of abundance ratios as grain growth proxies.

Fractionation in young cores: Direct determinations of nitrogen and carbon fractionation in HCN

Context. Nitrogen fractionation is a powerful tracer of the chemical evolution during star and planet formation. It requires robust determinations of the nitrogen fractionation across different evolutionary stages. Aims. We aim to determine the 14N/15N and 12C/13C ratios for HCN in six starless and prestellar cores and to compare the results between the direct method using radiative transfer modeling and the indirect double isotope method, assuming a fixed 12C/13C ratio. Methods. We present IRAM observations of the HCN 1–0, HCN 3–2, HC15N 1–0 and H13CN 1–0 transitions toward six embedded cores. The 14N/15N ratio was derived using both the indirect double isotope method and directly through non-local thermodynamic equilibrium (NLTE) 1D radiative transfer modeling of the HCN emission. The latter also provides the 12C/13C ratio, which we compared to the local interstellar value. Results. The derived 14N/15N ratios using the indirect method are generally in the range of 300-550. This result could suggest an evolutionary trend in the nitrogen fractionation of HCN between starless cores and later stages of the star formation process. However, the direct method reveals lower fractionation ratios of around ~250, mainly resulting from a lower 12C/13C ratio in the range ~20–40, as compared to the local interstellar medium value of 68. Conclusions. This study reveals a significant difference between the nitrogen fractionation ratio in HCN derived using direct and indirect methods. This can influence the interpretation of the chemical evolution and reveal the pitfalls of the indirect double isotope method for fractionation studies. However, the direct method is challenging, as it requires well-constrained source models to produce accurate results. No trend in the nitrogen fractionation of HCN between earlier and later stages of the star formation process is evident when the results of the direct method are considered.

The evolution and impact of ∼3000 M⊙ stars in the early Universe

We present evolutionary models of massive, accreting population III stars with constant and variable accretion rates until the end of silicon burning, with final masses of ~ 1000–3000 M⊙. In all our models, after the core-hydrogen-burning phase, the star expands towards the red side of the Hertzsprung-Russell diagram is where it spends the rest of its evolution. During core helium burning, the models exhibit an outer convective envelope as well as many large intermediate convective zones. These intermediate zones allow for strong internal mixing to occur which enriches the surface in helium. The effect of increasing metallicity at a constant accretion rate of 10−3 M⊙yr−1 shows an increase in the lifetime, final mass and distribution of helium in the envelope. Our fiducial model with mass of 3000 M⊙ has a final surface helium abundance of 0.74 and 9% of its total mass or 50% of the core mass, has a value of Γ1 < 4/3 at the end of core silicon burning. If the collapse of the core is accompanied by the ejection of the envelope above the carbon-oxygen core, this could have a significant impact on the chemical evolution of the surroundings and subsequent stellar generations. The model has a final log(N/O) ≈ 0.45, above the lower limit in the recently detected high-redshift galaxy GN-z11. We discuss the impact of a single 3000 M⊙ star on chemical, mechanical and radiative feedback, and present directions for future work.

Contribution of very massive stars to the sulfur abundance in star-forming galaxies: Role of pair-instability supernovae

Context. Recent work presented increasing evidence of high non-constant S/O abundance ratios observed in star-forming metal-poor galaxies that deviated from the constant canonical S/O across a wide range of O/H abundances. Similar peculiarly high Fe/O ratios have also recently been detected. Aims. We investigate whether these high S/O ratios at low metallicities could be explained when the process of pair-instability supernovae (PISN) in chemical modelling is included, through which a similar behaviour of the Fe/O ratios was reproduced successfully. Methods. We used chemical evolution models that considered the stages of PISN in the previously published yields and adopted a suitable initial mass function (IMF) to characterize this evolutionary stage appropriately. Results. The peculiarly high values and the behaviour of the observed S/O versus O/H relation can be reproduced when the ejecta of very massive stars that go through the process of PISN are taken into account. Additionally, a bimodal top-heavy IMF and an initial strong burst of star formation are required to reach the reported high S/O values. Conclusions. We show that the role of very massive stars going through the process of PISN should be taken into account to explain the chemical enrichment of sulphur and oxygen in metal-poor star-forming regions.

Ion Depletion Microenvironments Mapped at Active Electrochemical Interfaces with Operando Freezing Cryo-Electron Microscopy.

Interfacial structural and chemical evolution underpins safety, energy density, and lifetime in batteries and other electrochemical systems. During lithium electrodeposition, local nonequilibrium conditions can arise that promote heterogeneous lithium morphologies but are challenging to directly study, particularly at the nanoscale. Here we map chemical microenvironments at the active copper/electrolyte interface during lithium electrodeposition, presenting operando freezing cryogenic electron microscopy (cryo-EM), a new method, to lock in structures arising in coin cells. We find local ion depletion is correlated with lithium whiskers but not planar lithium, and we hypothesize that depletion stems from root-growing whiskers consuming ions at the growth interface while also restricting ion transport through local electrolyte. This can allow dangerous lithium morphologies to propagate, even in concentrated electrolytes, as ion depletion favors dendritic growth. Operando freezing cryo-EM thus reveals local microenvironments at active electrochemical interfaces to enable direct investigation of site-specific, nonequilibrium conditions that arise during operation of energy devices.

Probability distributions of initial rotation velocities and core-boundary mixing efficiencies of γ Doradus stars

Context. The theory of rotational and chemical evolution is incomplete, thereby limiting the accuracy of model-dependent stellar mass and age determinations. The γ Doradus (γ Dor) pulsators are excellent points of calibration for the current state-of-the-art stellar evolution models, as their gravity modes probe the physical conditions in the deep stellar interior. Yet, individual asteroseismic modelling of these stars is not always possible because of insufficient observed oscillation modes. Aims. This paper presents a novel method to derive distributions of the stellar mass, age, core-boundary mixing efficiency, and initial rotation rates for γ Dor stars. Methods. We computed a grid of rotating stellar evolution models covering the entire γ Dor instability strip. We then used the observed distributions of the luminosity, effective temperature, buoyancy travel time, and near-core rotation frequency of a sample of 539 stars to assign a statistical weight to each of our models. This weight is a measure of how likely the combination of a specific model is. We then computed weighted histograms to derive the most likely distributions of the fundamental stellar properties. Results. We find that the rotation frequency at zero-age main sequence follows a normal distribution, peaking at around 25% of the critical Keplerian rotation frequency. The probability-density function for extent of the core-boundary mixing zone, given by a factor of fCBM times the local pressure scale height (assuming an exponentially decaying parameterisation), decreases linearly with increasing fCBM. Conclusions. Converting the distribution of fractions of critical rotation at the zero-age main sequence to units of d−1, we find most F-type stars start the main sequence with a rotation frequency between 0.5 d−1 and 2 d−1. Regarding the core-boundary mixing efficiency, we find that it is generally weak in this mass regime.

Heavy element abundances in galactic globular clusters

Context. Globular clusters are considered key objects for understanding the formation and evolution of the Milky Way. In this sense, the characterisation of their chemical and orbital parameters can provide constraints on chemical evolution models of the Galaxy. Aims. We use the heavy element abundances of globular clusters to trace their overall behaviour in the Galaxy, with the aim to analyse potential relations between the hot H-burning and s-process elements. Methods. We measured the content of Cu I and s- and r-process elements (Y II, Ba II, La II, and Eu II) in a sample of 210 giant stars in 18 galactic globular clusters from high-quality UVES spectra. These clusters span a broad metallicity range and the sample is the largest that has been uniformly analysed to date, with respect to heavy elements in globular clusters. Results. The Cu abundances did not show a considerable spread in the sample, nor any correlation with Na, indicating that the Na nucleosynthesis process does not affect the Cu abundance. Most GCs closely follow the Cu, Y, Ba, La, and Eu field stars’ distribution, revealing a similar chemical evolution. The Y abundances in mid-metallicity regime GCs (−1.10 dex < [Fe/H] < −1.80 dex) display a mildly significant correlation with the Na abundance, which ought to be further investigated. Finally, we do not find any significant difference between the n-capture abundances among GCs with either Galactic and extragalactic origins.

Mineral chemistry evolution of magmatic Li-bearing micas and Li-loss during postmagmatic phengitization in an A-type sieno-monzogranite: A mass balance approach at La Chinchilla pluton, Sierra de Velasco, La Rioja, Argentina

La Chinchilla granite (∼3.75 km2) is an epizonal pluton intruded during the Lower Carboniferous in Sierra de Velasco, Sierras Pampeanas, northwestern Argentina. Three facies have been distinguished in the pluton (equigranular, porphyritic and fine-grained border zone facies), being equigranular and porphyritic the main two granite types, which host abundant millimeter to < 2 m sized miarolitic pegmatites and pockets of simple granitic mineralogy (quartz + albite + microcline + micas) ± beryl. Micrometer-sized accessory magmatic species are monazite-(Ce), several high field strength element oxide species, ilmenite, cassiterite (1), fluorapatite and fluorite. Primary Li-bearing micas with variable degrees of late to postmagmatic replacement occur in abundances that range from ∼2 to 7 %. Textural evidence and mineral chemistry allow to distinguish between early granitic and late bladed miarolitic micas. The mineral chemistry composition of the primary micas shows members of the siderophyllite-polylithionite series. Replacing phases are Li-muscovite (phengite). Electron probe microanalyses of primary micas of both main granite types suggest that these are compositionally distinct intrusives. According to mica chemistry, the porphyritic unit is more enriched in Li than the equigranular granite. The equigranular unit with interconnected miarolitic texture was more intensely affected by fluid-rock interaction processes and is significantly richer in U and Be. An F–Na rich fluid phase caused strong albitization during late miarolitic stages, along with crystallization of polylithionite, fluorite, pyrochlore group species and cassiterite (2). In terms of mass balance, the phengite replacement process is characterized by the conservation of Si, Al and K, a slight gain of Na and Ba, and a systematic loss of orderly decreasing Fe > F > Li > Mn > Ti > Mg > Zn. Likely, the muscovite-forming fluid was the same simultaneously involved in the hydrothermal alteration of high field strength element accessory species, largely included in primary micas, which generated secondary U- and Nb-rich species such as carlosbarbosaite. The hydrothermal late miarolitic to postmagmatic fluid-mineral replacement of primary magmatic micas released significant amounts of Li, of which about 59 wt % of the Li2O content of protholithic micas (i.e., 1 to 2.4 wt % Li2O) was inherited by replacing Li-bearing muscovite and the remaining 41 wt % was released from the system. It is calculated that ∼1.5 km3 of La Chinchilla body would have expelled ∼0.38 million tons of Li2O, just considering than only 30 % of primary siderophyllite-polylithionite was muscovitized. Such a Li2O tonnage was likely transferred to the paleohydrological cycle during Carboniferous times, when the La Chinchilla stock was still undergoing its cooling down path. Currently, evidence of the final fate of mobilized Li is lacking.

Probing the Stellar Populations and Star Formation History of Early-type Galaxies at 0 < z < 1.1 in the Rest-frame Ultraviolet

We measure the evolution of the rest-frame near-ultraviolet (NUV)−V colors for early-type galaxies in clusters at 0 < z < 1.1 using data from the Hyper Suprime-Cam Subaru Strategic Program, CFHT Large Area U-band Deep Survey, and local Sloan Digital Sky Survey clusters observed with Galaxy Evolution Explorer. Our results show that there is an excess in the ultraviolet spectrum in most quiescent galaxies (compared to the expectations from models fitting their optical/infrared colors and spectra) below z ∼ 0.6, beyond which the excess UV emission fades rapidly. This evolution of the UV color is only consistent with the presence of a highly evolved, hot horizontal branch subpopulation in these galaxies (among the majority of cool and optically bright stars), comprising on average 10% of the total stellar mass and forming at z > 3. The blue UV colors of early-type galaxies at low–intermediate redshifts are likely driven by this subpopulation being enriched in helium up to ∼44%. At z > 0.8 (when the extra UV component has not yet appeared) the data allow us to constrain the star formation histories of galaxies by fitting models to the evolution of their UV colors: we find that the epoch at which the stellar populations formed lies in the range 3 < z form < 10 (corresponding to 0.5–2.2 Gyr after the Big Bang) with a star formation e-folding timescale of τ = 0.35–0.7 Gyr, suggesting that these galaxies formed the majority of stars at very high redshift, with a brief yet intense burst of star formation activity. The star formation history and chemical evolution of early-type galaxies resemble those of globular clusters, albeit on much larger scales.

Enceladus: Astrobiology Revisited

AbstractAstrobiology research seeks to understand how life begins and evolves, and to determine whether life exist elsewhere in the universe. The discovery of diverse ocean worlds has significantly expanded the number of planetary bodies in the Solar System that could potentially contain life. Of the recognized ocean worlds, Saturn's moon Enceladus stands out because it appears to meet all requirements to sustain life. For that reason, robotic mission concepts are being developed to determine whether Enceladus' ocean is inhabited. The theory of organic chemical evolution (OCE) represents an ideal framework to guide this exploration strategy, articulating investigations and associated measurements of organic matter in the subsurface ocean. Within this reference frame, the immediate priority with the lowest science risk would be to understand molecular and structural properties of bulk organic matter in the ocean, and search for metabolic precursors and biochemical building blocks, both free and bound. This could be supplemented with “high‐risk, high‐reward” searches for functional polymers, catalytic activity, and cell‐like objects with traits indicative of evolutionary adaptations. The theory of OCE provides a robust scientific foundation for the astrobiological exploration of ocean worlds, fostering a productive path to discovery with lower mission risk that could be implemented with existing technology. Strong synergies between astrobiology and Earth‐bound research could ensue from this exploration strategy particularly in the context of terrestrial analog studies and laboratory simulations.

Electron-capture supernovae in NS + He star systems and the double neutron star systems

ABSTRACT Electron-capture-supernovae (EC-SNe) provide an alternative channel for producing neutron stars (NSs). They play an important role in the formation of double NS (DNS) systems and the chemical evolution of galaxies, and contribute to the NS mass distribution in observations. It is generally believed that EC-SNe originate from e-captures on $\rm ^{24}Mg$ and $\rm ^{20}Ne$ in the massive degenerate oxygen–neon (ONe) cores with masses close to the Chandrasekhar limit (MCh). However, the origin of EC-SNe is still uncertain. In this paper, we systematically studied the EC-SNe in NS + He star systems by considering the explosive oxygen burning that may occur in the near-MCh ONe core. We provided the initial parameter spaces for producing EC-SNe in the initial orbital period − initial He star mass (log$P_{\rm orb}^{\rm i}-M_{\rm He}^{\rm i}$) diagram, and found that both $M_{\rm He}^{\rm i}$ and minimum $P_{\rm orb}^{\rm i}$ for EC-SNe increase with metallicity. Then, by considering NS kicks added to the newborn NS, we investigated the properties of the formed DNS systems after the He star companions collapse into NSs, such as the orbital periods, eccentricities, and spin periods of recycle pulsars (Pspin), etc. The results show that most of the observed DNS systems can be produced by NS kicks of $\lesssim$50 km s−1. In addition, we found that NSs could accrete more material if the residual H envelope on the He star companions is considered, which can form the mildly recycled pulsars (Pspin ∼ 20 ms) in DNS systems.

Experimental research on the influence of acid on the chemical and pore structure evolution characteristics of Wenjiaba tectonic coal.

The chemical and pore structures of coal play a crucial role in determining the content of free gas in coal reservoirs. This study focuses on investigating the impact of acidification transformation on the micro-physical and chemical structure characteristics of coal samples collected from Wenjiaba No. 1 Mine in Guizhou. The research involves a semi-quantitative analysis of the chemical structure parameters and crystal structure of coal samples before and after acidification using Fourier Transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) experiments. Additionally, the evolution characteristics of the pore structure are characterized through high-pressure mercury injection (HP-MIP), low-temperature nitrogen adsorption (LT-N2A), and scanning electron microscopy (SEM). The experimental findings reveal that the acid solution modifies the structural features of coal samples, weakening certain vibrational structures and altering the chemical composition. Specifically, the asymmetric vibration structure of aliphatic CH2, the asymmetric vibration of aliphatic CH3, and the symmetric vibration of CH2 are affected. This leads to a decrease in the contents of -OH and -NH functional groups while increasing aromatic structures. The crystal structure of coal samples primarily dissolves transversely after acidification, affecting intergranular spacing and average height. Acid treatment corrodes mineral particles within coal sample cracks, augmenting porosity, average pore diameter, and the ratio of macro-pores to transitional pores. Moreover, acidification increases fracture width and texture, enhancing the connectivity of the fracture structure in coal samples. These findings provide theoretical insights for optimizing coalbed methane (CBM) extraction and gas control strategies.

Mineral chemistry and melt evolution of the mantle wedge peridotites in the Late Cretaceous Zagros Belt ophiolites (Iran): clues for the subduction initiation-induced forearc magmatism

We investigate in this paper mineral compositions and geochemical evolution of the mantle wedge peridotites preserved in the Late Cretaceous Zagros ophiolites of SW Iran. Mantle peridotites above subduction zones commonly experience distinct melting, depletion and refertilization processes as a result of the circulation of fluids derived from subducting slabs and flux melting. Our results reveal that the mantle wedge peridotites in the Zagros ophiolites are characterized mainly by residual and impregnated types. Residual peridotites resulted from early depletion and later refertilization processes, whereas impregnated peridotites developed due to episodic melt impregnations within and across the mantle. Mg#s and NiO contents, spinel Cr#, Mg#, and TiO 2 in olivines, Mg# and Al 2 O 3 contents of orthopyroxenes, and Mg#, TiO 2 and Al 2 O 3 contents in clinopyroxenes of dunites, harzburgites and lherzolites indicate the significant role of re-equilibration processes among different mineral phases and interactions with basaltic melts percolating within the host peridotites. The observed geochemical variations in the mineral chemistry of the Zagros peridotites reflect changes in magma chemistry and fluctuations in the degree of melt extraction and melt–rock interactions within the mantle peridotites. However, our data suggest that Mg–Fe distribution in the spinels of some dunites and harzburgites might also have resulted from subsolidus redistribution and exchange with surrounding olivine grains. Spinel and clinopyroxene phases in gabbroic rocks and ultramafic cumulates within the Zagros ophiolites also show significant variations in their compositions, suggesting that their magmas evolved from MORB-like to IAT, calc–alkaline and boninite suites, typical of subduction initiation-generated melts. Hence, the Zagros ophiolites present a case study of time-progressive melt evolution of the forearc oceanic lithosphere. Supplementary material: Datasets of the mineral chemistry and melt evolution of the mantle wedge peridotites in the Late Cretaceous Zagros Belt ophiolites (Iran) are available in tabular and figurative form at https://doi.org/10.6084/m9.figshare.c.7093528 . Thematic collection: This article is part of the Ophiolites, melanges and blueschists collection available at: https://www.lyellcollection.org/topic/collections/ophiolites-melanges-and-blueschists

Ice chemistry modeling of active phase comets: Hale–Bopp

We present a chemical kinetics model of the solid-phase chemical evolution of a comet, beginning with a long period of cold-storage in the Oort Cloud, followed by five orbits that bring the comet close to the Sun. Current orbital parameters for Hale–Bopp are used for all orbits. The chemical model is based on an earlier treatment (Garrod 2019) that considered only the cold-storage phase, and which was based on the interstellar ice chemical kinetics model MAGICKAL. The comet is treated as 25 chemically distinct layers, whose thicknesses increase with depth; each layer has a dust component, and the chemical network includes a further 200 atomic/molecular species. The new model includes several key updates to the previous treatment: (i) Time- and depth-dependent temperature profiles based on heat transfer according to heliocentric distance; (ii) a rigorous treatment of back-diffusion (random walk) for species capable of diffusing through the thick bulk-ice layers; (iii) adoption of recent improvements in the kinetic treatment of nondiffusive chemical reaction rates in the ice and on the ice surface. Starting from an initially simple ice composition, interstellar UV photons drive a rapid chemistry in the upper micron of material, but diminished by absorption of the UV by the dust component. Galactic cosmic rays (GCRs) drive a much slower chemistry in the deeper ices over the long cold-storage period, to depths on the order of 10 m. The first solar approach drives off the upper layers of ice material via thermal desorption and/or dissociation (the model does not include a treatment for the more complex cometary outbursts), bringing closer to the surface the deeper material that previously underwent long-term processing by GCRs. Subsequent orbits are more uniform in their chemical behavior after the upper layers are lost. Loss of molecular material leads to concentration of the dust in the upper layers, with a large dust fraction extending to depths on the order of 10 cm after all orbits are complete. Substantial quantities of complex organic molecules (COMs) are formed in the upper 10 m during the cold storage phase, with some of this material released during solar approach; however, their abundances with respect to water appear too low to account for the observed gas-phase values for comet Hale–Bopp, indicating that the majority of complex molecular material observed, at least in comet Hale–Bopp, is an inheritance of primordial material.

Gas-phase hydrogenation of large, astronomically relevant PAH cations

ABSTRACT To investigate the gas-phase hydrogenation processes of large, astronomically relevant cationic polycyclic aromatic hydrocarbon (PAH) molecules under the interstellar environments, the ion–molecule collision reaction between six PAH cations and H-atoms is studied. The experimental results show that the hydrogenated PAH cations are efficiently formed, and no even–odd hydrogenated mass patterns are observed in the hydrogenation processes. The structure of newly formed hydrogenated PAH cations and the bonding energy for the hydrogenation reaction pathways are investigated with quantum theoretical calculations. The exothermic energy for each reaction pathway is relatively high, and the competition between hydrogenation and dehydrogenation is confirmed. From the theoretical calculation, the bonding ability plays an important role in the gas-phase hydrogenation processes. The factors that affect the hydrogenation chemical reactivity are discussed, including the effect of carbon skeleton structure, the side-edged structure, the molecular size, the five- and six-membered C-ring structure, the bay region structure, and the neighbouring hydrogenation. The infrared spectra of hydrogenated PAH cations are also calculated. These results we obtain once again validate the complexity of hydrogenated PAH molecules, and provide the direction for the simulations and observations under the co-evolution interstellar chemistry network. We infer that if we do not consider other chemical evolution processes (e.g. photoevolution), then the hydrogenation states and forms of PAH compounds are intricate and complex in the interstellar medium.

Natural radioactivity of the crust as an important factor of the chemical evolution of the early Earth

The long-lived (billions of years) 40K, 235U, 238U, and 232Th isotopes have a high energy capacity and represent a potent internal source of energy. Together with the external action of the Sun, the natural radioactivity was apparently an important component of evolution of the early Earth and development of Earth's life. The decay of isotopes initiated radiation chemical reactions involving water, which were accompanied by the formation of hydrogen and oxygen and the transformation of Earth's inorganic matter into organic compounds, including prebiotic molecules. Water radiolysis in the Earth's crust continuously produces H2, which is now considered as the main electron donor (food) for microorganisms several kilometers below the Earth's surface. Here we calculate the initial radioactivity of the early Earth's crust from the relative abundances of elements and dynamics of variation of the radioactivity and energy release upon the decay of particular radioactive isotopes. The energy released upon the decay of heavy 235U, 238U, and 232Th throughout the existence of the Earth (4.6 billion years) was 4.5 × 1030 J, while the energy released upon the decay of 40K was approximately 1.0 × 1030 J. The energy release per year during the first billion years decreased from 3.0 × 1021 J to 1.5 × 1021 J for heavy isotopes and from 0.70 × 1021 J to 0.45 × 1021 J for 40K. Over the last billion years, the energy decreased approximately threefold. Analysis of the data on the radiation chemical formation of hydrogen in the wet components of the Earth's crust (cements, zeolites, geopolymers, and other) and bottom sediments indicates that hydrogen is formed upon direct action of radiation on water in yields characteristic of pure water. According to calculations, over the past 4 billion years, approximately 1.7 × 1022 M of hydrogen was formed. Furthermore, ∼93 % of H2 was due to the decay of uranium and thorium, while the contribution of 40K did not exceed 7 %. The global rate of hydrogen formation in the Earth's crust is ∼ 1.5 × 1012 mol per year. A mechanism involving ionic and radical products of water radiolysis was proposed to describe the formation of prebiotic molecules (amino acids, sugars, etc.) from carbon-, nitrogen-, and sulfur-containing inorganic compounds.

Corrosion Mechanism and Electrochemical Reactions on Alloy 690 in Simulated Primary Coolant of Water-Water Energy Reactors.

During the power operation of the primary loop of a water cooled-water moderated energy reactor (WWER), the water chemistry evolves from a high-boron high-potassium composition to significantly lower concentrations of both constituents at the end of a campaign, and the Li concentration reaches ca. 0.7-0.9 ppm. In the present paper, the effect of primary water chemistry evolution during operation on the corrosion rate and conduction mechanism of oxides on Alloy 690 is studied by in situ impedance spectroscopy at 300 °C/9 MPa during 1-week exposures in an autoclave connected to a re-circulation loop. At the end of exposure, the samples were anodically polarized at potentials -0.8 to -0.1 V vs. SHE to evaluate the stability of the passive oxide. Simultaneously exposed samples of Alloy 690 were subsequently analyzed by XPS to estimate the thickness and in-depth composition of oxides. Impedance data were quantitatively interpreted using the mixed-conduction model (MCM) for oxide films. The effect of water chemistry evolution on the corrosion rate and conduction mechanism in the oxide on Alloy 690 in a primary coolant is discussed based on the obtained parameters.