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We investigated the catalytic activity of different coating layers and put forward a selection criterion for surface layers. Al 2 O 3 could effectively suppress HER and enable the cycling of Li 4 Ti 5 O 12 anode in water-in-salt electrolyte, with a capacity of 145 mA h g −1 .
Vapor phase conversion of 3-hydroxybutyric and crotonic acid to propylene in a continuous-flow reactor over silica–alumina and niobium catalysts demonstrates a new strategy for producing renewable fuels and chemicals from wastewater carbon.
Junctions formed from materials that contain mobile charged species and fixed counterions can assist in photo-induced charge separation and lead to photovoltaic action, irrespective of whether the mobile charges are electronic or protonic.
Zinc-MnO2 based batteries have acquired attention for grid-level applications, due to impressive theoretical performance, cost effectiveness and intrinsic safety. However, there are still many challenges that remain elusive due to the complex and controversial mechanisms of operation that hinders commercialization. In this work, the detailed redox processes that occur at the cathode during Zn-MnO2 battery operation are elucidated. Using a blend of structural and electrochemical techniques, the redox pairs that occur during operation are mechanistically studied while also showcasing the true impact of the electrolyte additive (0.1 M MnSO4) in a 1 M ZnSO4 electrolyte. An electrochemical quartz-crystal microbalance (EQCM) has been leveraged to reveal the effect of zinc hydroxy sulfate salt (Zn4SO4(OH)6·nH2O) and zinc manganese oxide (ZnxMnyOz) dissolution/deposition, which are believed to be major components during discharge and charge conditions. . These results provide insight not currently available, allowing a holistic view of the electrochemical reaction mechanisms during battery operation.
A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.
The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.
The geologic processes responsible for aqueous alteration of basaltic materials on Mars are modeled beginning with our knowledge of analog processes on Earth, i.e., characterization of elemental and mineralogical compositions of terrestrial environments where the alteration and weathering pathways related to aqueous activity are better understood. A key ingredient to successful modeling of aqueous processes on Mars is identification of phases that have formed by those processes. The purpose of this paper is to describe what is known about the elemental and mineralogical composition of aqueous alteration products of basaltic materials on Mars and their implications for specific aqueous environments based upon our knowledge of terrestrial systems. Although aqueous alteration has not occurred on the Moon, it is crucial to understand the behaviors of basaltic materials exposed to aqueous environments in support of human exploration to the Moon over the next two decades. Several methods or indices have been used to evaluate the extent of basalt alteration/weathering based upon measurements made at Mars by the Mars Exploration Rover (MER) Moessbauer and Alpha Particle X-Ray Spectrometers. The Mineralogical Alteration Index (MAI) is based upon the percentage of total Fe (Fe(sub T)) present as Fe(3+) in alteration products (Morris et al., 2006). A second method is the evaluation of compositional trends to determine the extent to which elements have been removed from the host rock and the likely formation of secondary phases (Nesbitt and Young, 1992; Ming et al., 2007). Most of the basalts that have been altered by aqueous processes at the two MER landing sites in Gusev crater and on Meridiani Planum have not undergone extensive leaching in an open hydrolytic system with the exception of an outcrop in the Columbia Hills. The extent of aqueous alteration however ranges from relatively unaltered to pervasively altered materials. Several experimental studies have focused upon the aqueous alteration of lunar materials and simulants (e.g., Keller and Huang, 1971; Eick et al., 1996). Lunar basalts are void of water and highly reduced, hence, these materials are initially very reactive when exposed to water under oxidizing conditions.
Over the past three decades we have become increasingly aware of the fundamental importance of water, and aqueous alteration, on primitive solar-system bodies. Some carbonaceous and ordinary chondrites have been altered by interactions with liquid water within the first 10 million years after formation of their parent asteroids. Millimeter to centimeter-sized aggregates of purple halite containing aqueous fluid inclusions were found in the matrix of two freshly-fallen brecciated H chondrite falls, Monahans (1998, hereafter simply "Monahans") (H5) and Zag (H3-6) (Zolensky et al., 1999; Whitby et al., 2000; Bogard et al., 2001) In order to understand origin and evolution of the aqueous fluids inside these inclusions we much measure the actual fluid composition, and also learn the O and H isotopic composition of the water. It has taken a decade for laboratory analytical techniques to catch up to these particular nanomole-sized aqueous samples. We have recently been successful in (1) measuring the isotopic composition of H and O in the water in a few fluid inclusions from the Zag and Monahans halite, (2) mineralogical characterization of the solid mineral phases associated with the aqueous fluids within the halite, and (3) the first minor element analyses of the fluid itself. A Cameca ims-1270 equipped with a cryo-sample-stage of Hokkaido University was specially prepared for the O and H isotopic measurements. The cryo-sample-stage (Techno. I. S. Corp.) was cooled down to c.a. -190 C using liquid nitrogen at which the aqueous fluid in inclusions was frozen. We excavated the salt crystal surfaces to expose the frozen fluids using a 15 keV Cs+ beam and measured negative secondary ions. The secondary ions from deep craters of approximately 10 m in depth emitted stably but the intensities changed gradually during measurement cycles because of shifting states of charge compensation, resulting in rather poor reproducibility of multiple measurements of standard fluid inclusions of +/- 90 0/00(2 sigma) for delta D, and +/- 29 0/00 (2 sigma) for delta O-18. On the other hand, the reproducibility of Delta O-17 is plus or minus 8 /00 (2 sigma ) because the observed variations of isotope ratios follow a mass dependent fractionation law. Variations of delta D of the aqueous fluids range over sog,a 330(90; 2 sigma ) to +1200(90) 0/00 for Monahans and delta 300(96) 0/00 to +90(98)0/00 for Zag. Delta O-17 of aqueous fluids range over delta 16(22) 0/00 to +18(10) 0/00 for Monahans and +3(10) 0/00 to +27(11) 0/00 for Zag. These variations are larger than the reproducibility of standard analyses and suggest that isotope equilibria were under way in the fluids before trapping into halite. The mean values of delta D and Delta O-17 are +290 0/00 and +9 0/00, respectively. The mean values and the variations of these fluids are different from the representative values of ordinary chondrites, verifying our working hypothesis that the fluid inclusion-bearing halites were not indigenous to the H chondrite parent-asteroid but rather represent exogenous material delivered onto the asteroid from a separate cryovolcanically-active body. This initial isotopic work has demonstrated the feasibility of the measurements, but also revealed sample processing and analytical shortcomings that are now being addressed. Examination of solid mineral inclusions within Monahans and Zag halite grains by confocal Raman spectroscopy at the Carnegie Geophysical Laboratory has revealed them to be metal, magnetite, forsteritic olivine (Fo.98), macromolecular carbon (MMC), pyroxenes, feldspar with Raman spectral affinity to anorthoclase and, probably, fine-grained lepidocrocite (FeO(OH)). In addition, one inclusion features aliphatic material with Raman spectral features consistent with a mixture of short-chain aliphatic compounds. We have initiated analyses of the bulk composition of the fluids within the inclusions in Zag and Monahans halites at Virginia Tech by LA ICPMS using angilent 7500ce quadrupole ICPMS and a Lambda Physik GeoLas 193 nm excimer laser ablation system. Preliminary results reveal that the inclusion aqueous fluids contain highly charged cations of Ca, Mg and Fe. The minerals and compounds discovered thus far within Monahans/Zag halites are indicative of an originating body at least partly composed of unequilibrated anhydrous materials (high Fo olivine, pyroxenes, feldspars, possibly the metal) which were subjected to aqueous alteration (the halite parent brine) and containing a light organic component (the short-chain aliphatic compounds). This material was ejected from the originating body with little or no disruption, as evidenced with the presence of fluid inclusions. An actively geysering body similar to modern Enceladus (Postberg et al., 2011) may be a reasonable analogue in this respect. Also, the originating body should have been within close proximity to the H chondrite parent in order to generate the number of halite grains seen in Monahans and Zag. Other candidates for Monahans/Zag halite parent bodie(s) may include a young Ceres with its possible liquid ocean, or Main Belt comets.
Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.
Mineralogical and geochemical data returned by orbiters and landers over the past 15 years have substantially enhanced our understanding of the history of aqueous alteration on Mars. Here, we summarize aqueous processes that have been implied from data collected by landed missions. Mars is a basaltic planet. The geochemistry of most materials has not been “extensively” altered by open-system aqueous processes and have average Mars crustal compositions. There are few examples of open-system alteration, such as Gale crater’s Pahrump Hills mudstone. Types of aqueous alteration include (1) acid-sulfate and (2) hydrolytic (circum-neutral/alkaline pH) with varying water-to-rock ratios. Several hypotheses have been suggested for acid-sulfate alteration including (1) oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials; (3) acid fog weathering of basaltic materials; and (4) near-neutral pH subsurface solutions rich in Fe (sup 2 plus) that rapidly oxidized to Fe (sup 3 plus) producing excess acidity. Meridiani Planum’s sulfate-rich sedimentary deposit containing jarosite is the most “famous” acid-sulfate environment visited on Mars, although ferric sulfate-rich soils are common in Gusev crater’s Columbia Hills and jarosite was recently discovered in the Pahrump Hills. An example of aqueous alteration under circum-neutral pH conditions is the formation of Fe-saponite with magnetite in situ via aqueous alteration of olivine in Gale crater’s Sheepbed mudstone. Circum-neutral pH, hydrothermal conditions were likely required for the formation of Mg-Fe carbonate in the Columbia Hills. Diagenetic features (e.g., spherules, fracture filled veins) indicate multiple episodes of aqueous alteration/diagenesis in most sedimentary deposits. However, low water-to-rock ratios are prominent at most sites visited by landed missions (e.g., limited water for reaction to form crystalline phases possibly resulting in large amounts of short-range ordered materials and little physical separation of primary and secondary materials). Most of the aqueous alteration appears to have occurred early in the planet’s history; however, minor aqueous alteration may be occurring at the surface today (e.g., thin films of water forming carbonates akin to those discovered by Phoenix).
A method of treating an aqueous solution comprises forming a treatment stream comprising a condensable material. The treatment stream is introduced to an aqueous solution comprising water and a solute to fractionally precipitate the solute out of the aqueous solution and form a solids stream comprising the solute and an aqueous liquid stream comprising at least one solute-depleted solution of the water and the condensable material. The condensable material of at least a portion of the aqueous liquid stream is separated from the water of the at least a portion of the aqueous liquid stream to at least partially reform the treatment stream and form an aqueous liquid product stream depleted in the solute. Aqueous solution treatment systems and additional methods of treating an aqueous solution are also described.
Lithium-ion batteries (LIBs) are a widely used energy storage device. For decades, researchers have been studying aqueous electrolytes due to their non-flammability and environmental friendless. However, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) of water greatly limit the voltage window of the aqueous electrolyte. The recent concept of ‘solvent-in-salt’ electrolytes, namely ‘water-in-salt’ electrolytes (WISE) for aqueous batteries and ‘super-concentrated’ electrolytes for non-aqueous batteries, greatly expands the electrochemical window of these battery systems and consequently their energy density. This expansion occurs because the large number of salt aggregates in ‘solvent-in-salt’ electrolytes enables preferential salt decomposition over solvent decomposition to form robust interphase layers on electrodes, thus enhancing their stability in a wide range of operating voltages. However, even when the salt concentration reached 63m, regardless of cost, the cathodic potential of the WISE expanded only to 1.75V with an overall electrochemical stability window of <3.25V. To design the next generation of high energy aqueous LIBs, electrolytes that possess a wider electrochemical stability window and lower cost but still maintain the merit of non-flammability are much needed. In this project, we designed the aqueous LIBs with widened voltage window. We reported a cheap and non-flammable ternary eutectic electrolyte that can form a robust solid electrolyte interface (SEI)so that the cathodic limiting potential can be decreased to <1.5 V for Li 4 Ti 5 O 12 anodes, while maintaining both a high ionic conductivity of >10 -3 S cm –1 and a low viscosity. We demonstrated the super-stable2.5V LiMn 2 O 4 ||Li 4 Ti 5 O 12 pouch cell with mass loading of 2.5 mAh/cm. Further, LiCl-LiBr-Graphite/Li full cells were designed with high energy density. Finally, we use a bi-layer design to enlarge the voltage window of aqueous electrolyte, which can endow the stable cycling of aqueous Lithium metal batteries.
Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.
Aqueous Li-ion batteries (ALIBs) are an important class of battery chemistries owing to the intrinsic non-flammability of aqueous electrolytes. However, water is detrimental to most cathode materials and could result in rapid cell failure. Identifying the degradation mechanisms and evaluating the pros and cons of different cathode materials are crucial to guide the materials selection and maximize their electrochemical performance in ALIBs. Here, in this study, we investigate the stability of LiFePO 4 (LFP), LiMn 2 O 4 (LMO) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC) cathodes, without protective coating, in three different aqueous electrolytes, i.e., salt-in-water, water-in-salt, and molecular crowding electrolytes. The latter two are the widely reported "water-deficient electrolytes." LFP cycled in the molecular crowding electrolyte exhibits the best cycle life in both symmetric and full cells owing to the stable crystal structure. Mn dissolution and surface reduction accelerate the capacity decay of LMO in water-rich electrolyte. On the other hand, the bulk structural collapse leads to the degradation of NMC cathodes. LMO demonstrates better full-cell performance than NMC in water-deficient aqueous electrolytes. LFP is shown to be more promising than LMO and NMC for long-cycle-life ALIB full cells, especially in the molecular crowding electrolyte. However, none of the aqueous electrolytes studied here provide enough battery performance that can compete with conventional non-aqueous electrolytes. This work reveals the degradation mechanisms of olivine, spinel, and layered cathodes in different aqueous electrolytes and yields insights into improving electrode materials and electrolytes for ALIBs.
Aqueous alteration has played a significant role in the geological evolution of almost all the chondrite groups and attests to the importance of water during the earliest history of the solar system. Among the chondrites that show evidence of aqueous alteration the CM chondrites, in particular, have received considerable attention, because of their primitive composition and the fact that they preserve a record of incomplete hydration. Petrologic studies of this group of meteorites have helped provide important insights into aqueous alteration processes and the nature of the alteration products. However, due to the complex history of these chondrites, important details of the alteration remain enigmatic. Among the major problems to be resolved are the location and timing of aqueous alteration as well as the relationship between alteration and brecciation. Although many authors favor aqueous alteration within a parent body environment, there is also evidence that some of the components of CM chondrites may have experienced aqueous alteration prior to accretion. One of the key lines of evidence for alteration in a pre-accretionary environment is the presence of unaltered metal grains associated with hydrated phases. Low-Ni metal (kamacite) is typically one of the first phases in CM chondrites that alters in the presence of water. However, in some CM chondrites, such as Yamato 791198, micron-sized metal grains are present within the hydrated fine-grained rim material around chondrules. In addition, nanometer-sized grains that have been interpreted as being unaltered metal particles have been reported in the relatively heavily altered CM chondrite, ALH 81002. In most cases, these occurrences have been interpreted as being the result of mixing of anhydrous and hydrous materials prior to accretion. According to this hypothesis, the metal grains remain unaltered because little or no post-accretionary alteration took place. Whilst such a scenario is plausible, no alternative explanations such as the presence of submicron protective layers or a minor element chemistry that might inhibit oxidation have been investigated in detail. During a study of the distribution of carbonaceous material in fine-grained rims on chondrules in Murchison, previously unidentified, nanometer-sized metal grains were observed. These grains were characterized in detail using high resolution TEM and energy filtered TEM (EFTEM) and provide important insights into how metal grains in CM chondrites may survive aqueous alteration.
Aqueous alteration is the change in composition of a rock, produced in response to interactions with H2O-bearing ices, liquids, and vapors by chemical weathering. A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Mineralogical indicators for aqueous alteration include goethite (lander), jarosite (lander), kieserite (orbiter), gypsum (orbiter) and other Fe-, Mg-, and Ca-sulfates (landers), halides (meteorites, lander), phyllosilicates (orbiter, meteorites), hematite and nanophase iron oxides (telescopic, orbiter, lander), and Fe-, Mg-, and Ca-carbonates (meteorites). Geochemical indicators (landers only) for aqueous alteration include Mg-, Ca-, and Fe-sulfates, halides, and secondary aluminosilicates such as smectite. Based upon these indicators, several styles of aqueous alteration have been suggested on Mars. Acid-sulfate weathering (e.g., formation of jarosite, gypsum, hematite, and goethite), may occur during (1) the oxidative weathering of ultramafic igneous rocks containing sulfides, (2) sulfuric acid weathering of basaltic materials, and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials. Near-neutral or alkaline alteration occurs when solutions with pH near or above 7 move through basaltic materials and form phases such as phyllosilicates and carbonates. Very low water:rock ratios appear to have been prominent at most of the sites visited by landed missions because there is very little alteration (leaching) of the original basaltic composition (i.e., the alteration is isochemical or in a closed hydrologic system). Most of the aqueous alteration appears to have occurred early in the history of the planet (3 to 4.5 billion years ago); however, minor aqueous alteration may be occurring at the surface even today (e.g., in thin films of water or by acid fog).
A method for extracting rare earth metals (e.g., lanthanides and/or actinides) from aqueous solution, the method comprising: (i) acidifying an aqueous solution containing said rare earth metals with sulfuric acid to result in an acidified aqueous solution containing 1-12 M concentration of sulfuric acid; and (ii) contacting the acidified aqueous solution with an aqueous-insoluble hydrophobic solution comprising a rare earth extractant molecule dissolved in an aqueous-insoluble hydrophobic solvent to result in extraction of one or more of the rare earth metals into the aqueous hydrophobic solution, wherein the rare earth extractant molecule has the following structure: wherein R1, R2, R3, and R4 are independently selected from hydrocarbon groups containing 1-20 carbon atoms, provided that the total carbon atoms in R1, R2, R3, and R4 is at least 12; and R5 and R6 are independently selected from hydrogen atom and hydrocarbon groups containing 1-3 carbon atoms.
Phenolic compounds, which are significant emissions from biomass burning (BB), undergo rapid photochemical reactions in both gas and aqueous phases to form secondary organic aerosol, namely, gasSOA and aqSOA, respectively. The formation of gasSOA and aqSOA involves different reaction mechanisms, leading to different product distributions. In this study, we investigate the gaseous and aqueous reactions of guaiacol a representative BB phenol to elucidate the compositional differences between phenolic aqSOA and gasSOA. Aqueous-phase reactions of guaiacol produce higher SOA yields than gas-phase reactions (e.g., roughly 60 vs 30% at one half-life of guaiacol). These aqueous reactions involve more complex reaction mechanisms and exhibit a more gradual SOA evolution than their gaseous counterparts. Initially, gasSOA forms with high oxidation levels (O/C > 0.82), while aqSOA starts with lower O/C (0.55–0.75). However, prolonged aqueous-phase reactions substantially increase the oxidation state of aqSOA, making its bulk chemical composition closer to that of gasSOA. Additionally, aqueous reactions form a greater abundance of oligomers and high-molecular-weight compounds, alongside a more sustained production of carboxylic acids. AMS spectral signatures representative of phenolic gasSOA have been identified, which, together with tracer ions of aqSOA, can aid in the interpretation of field observation data on aerosol aging within BB smoke. The notable chemical differences between phenolic gasSOA and aqSOA highlighted in this study also underscore the importance of accurately representing both pathways in atmospheric models to better predict the aerosol properties and their environmental impacts.