Microstructural analysis of slag properties associated with calcite precipitation due to passive CO2 mineralization.

CO2 mineralization in slag has gained significant attention since it occurs with minimal human intervention and energy input. While the amount of theoretical CO2 that can be captured within slag has been quantified based on slag composition in several studies, the microstructural and mineralogical effects of slag on its ability to capture CO2 have not been fully addressed. In this work, the CO2 uptake within legacy slag samples is analyzed through microstructural characterization. Slag samples were collected from the former Ravenscraig steelmaking site in Lanarkshire, Scotland. The collected samples were studied using X-ray Computed Tomography (XCT) to understand the distribution and geometry of pore space, as well as with scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) to visualize the distribution of elements within the studied samples. Electron backscatter diffraction (EBSD) was used to study the minerals distribution. The samples were also characterized through X-ray diffraction (XRD) and X-ray fluorescence (XRF), and the amount of captured CO2 was quantified using thermogravimetric analysis (TGA). Our results demonstrate that CO2 uptake occurs to the extent of ∼9-30 g CO2/ kg slag. The studied samples are porous in nature, with pore space occupying up to ∼30% of their volumes, and they are dominated by åkermanite-gehlenite minerals which interact with the atmospheric CO2 slowly at ambient conditions. EDS and EBSD results illustrate that the precipitated carbonate in slag is calcite, and that the precipitation of calcite is accompanied by the formation of a Si-O-rich layer. The provided analysis concludes that the porous microstructure as well as the minerals distribution in slag should be considered in forecasting and designing large-scale solutions for passive CO2 mineralization in slag.

A dehydrated space-weathered skin cloaking the hydrated interior of Ryugu.

Without a protective atmosphere, space-exposed surfaces of airless Solar System bodies gradually experience an alteration in composition, structure and optical properties through a collective process called space weathering. The return of samples from near-Earth asteroid (162173) Ryugu by Hayabusa2 provides the first opportunity for laboratory study of space-weathering signatures on the most abundant type of inner solar system body: a C-type asteroid, composed of materials largely unchanged since the formation of the Solar System. Weathered Ryugu grains show areas of surface amorphization and partial melting of phyllosilicates, in which reduction from Fe3+ to Fe2+ and dehydration developed. Space weathering probably contributed to dehydration by dehydroxylation of Ryugu surface phyllosilicates that had already lost interlayer water molecules and to weakening of the 2.7 µm hydroxyl (-OH) band in reflectance spectra. For C-type asteroids in general, this indicates that a weak 2.7 µm band can signify space-weathering-induced surface dehydration, rather than bulk volatile loss.

Dorsomedial prefrontal hypoexcitability underlies lost empathy in frontotemporal dementia.

Empathic function is essential for the well-being of social species. Empathy loss is associated with various brain disorders and represents arguably the most distressing feature of frontotemporal dementia (FTD), a leading form of presenile dementia. The neural mechanisms are unknown. We established an FTD mouse model deficient in empathy and observed that aged somatic transgenic mice expressing GGGGCC repeat expansions in C9orf72, a common genetic cause of FTD, exhibited blunted affect sharing and failed to console distressed conspecifics by affiliative contact. Distress-induced consoling behavior activated the dorsomedial prefrontal cortex (dmPFC), which developed profound pyramidal neuron hypoexcitability in aged mutant mice. Optogenetic dmPFC inhibition attenuated affect sharing and other-directed consolation in wild-type mice, whereas chemogenetically enhancing dmPFC excitability rescued empathy deficits in mutant mice, even at advanced ages when substantial cortical atrophy had occurred. These results establish cortical hypoexcitability as a pathophysiological basis of empathy loss in FTD and suggest a therapeutic strategy.

Rubble pile asteroids are forever.

Rubble piles asteroids consist of reassembled fragments from shattered monolithic asteroids and are much more abundant than previously thought in the solar system. Although monolithic asteroids that are a kilometer in diameter have been predicted to have a lifespan of few 100 million years, it is currently not known how durable rubble pile asteroids are. Here, we show that rubble pile asteroids can survive ambient solar system bombardment processes for extremely long periods and potentially 10 times longer than their monolith counterparts. We studied three regolith dust particles recovered by the Hayabusa space probe from the rubble pile asteroid 25143 Itokawa using electron backscatter diffraction, time-of-flight secondary ion mass spectrometry, atom probe tomography, and 40Ar/39Ar dating techniques. Our results show that the particles have only been affected by shock pressure of ca. 5 to 15 GPa. Two particles have 40Ar/39Ar ages of 4,219 ± 35 and 4,149 ± 41 My and when combined with thermal and diffusion models; these results constrain the formation age of the rubble pile structure to ≥4.2 billion years ago. Such a long survival time for an asteroid is attributed to the shock-absorbent nature of rubble pile material and suggests that rubble piles are hard to destroy once they are created. Our results suggest that rubble piles are probably more abundant in the asteroid belt than previously thought and provide constrain to help develop mitigation strategies to prevent asteroid collisions with Earth.

The Winchcombe meteorite, a unique and pristine witness from the outer solar system.

Direct links between carbonaceous chondrites and their parent bodies in the solar system are rare. The Winchcombe meteorite is the most accurately recorded carbonaceous chondrite fall. Its pre-atmospheric orbit and cosmic-ray exposure age confirm that it arrived on Earth shortly after ejection from a primitive asteroid. Recovered only hours after falling, the composition of the Winchcombe meteorite is largely unmodified by the terrestrial environment. It contains abundant hydrated silicates formed during fluid-rock reactions, and carbon- and nitrogen-bearing organic matter including soluble protein amino acids. The near-pristine hydrogen isotopic composition of the Winchcombe meteorite is comparable to the terrestrial hydrosphere, providing further evidence that volatile-rich carbonaceous asteroids played an important role in the origin of Earth's water.

Using Organic Contaminants to Constrain the Terrestrial Journey of the Martian Meteorite Lafayette.

A key part of the search for extraterrestrial life is the detection of organic molecules since these molecules form the basis of all living things on Earth. Instrument suites such as SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) onboard the NASA Perseverance rover and the Mars Organic Molecule Analyzer onboard the future ExoMars Rosalind Franklin rover are designed to detect organic molecules at the martian surface. However, size, mass, and power limitations mean that these instrument suites cannot yet match the instrumental capabilities available in Earth-based laboratories. Until Mars Sample Return, the only martian samples available for study on Earth are martian meteorites. This is a collection of largely basaltic igneous rocks that have been exposed to varying degrees of terrestrial contamination. The low organic molecule abundance within igneous rocks and the expectation of terrestrial contamination make the identification of martian organics within these meteorites highly challenging. The Lafayette martian meteorite exhibits little evidence of terrestrial weathering, potentially making it a good candidate for the detection of martian organics despite uncertainties surrounding its fall history. In this study, we used ultrapure solvents to extract organic matter from triplicate samples of Lafayette and analyzed these extracts via hydrophilic interaction liquid chromatography-mass spectrometry (HILIC-MS). Two hundred twenty-four metabolites (organic molecules) were detected in Lafayette at concentrations more than twice those present in the procedural blanks. In addition, a large number of plant-derived metabolites were putatively identified, the presence of which supports the unconfirmed report that Lafayette fell in a semirural location in Indiana. Remarkably, the putative identification of the mycotoxin deoxynivalenol (or vomitoxin), alongside the report that the collector was possibly a student at Purdue University, can be used to identify the most likely fall year as 1919.

Image-Based Analysis of Weathered Slag for Calculation of Transport Properties and Passive Carbon Capture.

Weathering of silicate-rich industrial wastes such as slag can reduce emissions from the steelmaking industry. During slag weathering, different minerals spontaneously react with atmospheric CO2 to produce calcite. Here, we evaluate the CO2 uptake during slag weathering using image-based analysis. The analysis was applied to an X-ray computed tomography (XCT) dataset of a slag sample associated with the former Ravenscraig steelworks in Lanarkshire, Scotland. The element distribution of the sample was studied using scanning electron microscopy (SEM), coupled with energy-dispersive spectroscopy (EDS). Two advanced image segmentation methods, namely trainable WEKA segmentation in the Fiji distribution of ImageJ and watershed segmentation in Avizo ® 9.3.0, were used to segment the XCT images into matrix, pore space, calcite, and other precipitates. Both methods yielded similar volume fractions of the segmented classes. However, WEKA segmentation performed better in segmenting smaller pores, while watershed segmentation was superior in overcoming the partial volume effect presented in the XCT data. We estimate that CO2 has been captured in the studied sample with an uptake between 20 and 17 kg CO2/1,000 kg slag for TWS and WS, respectively, through calcite precipitation.

The scale of a martian hydrothermal system explored using combined neutron and x-ray tomography.

Nakhlite meteorites are igneous rocks from Mars that were aqueously altered ~630 million years ago. Hydrothermal systems on Earth are known to provide microhabitats; knowledge of the extent and duration of these systems is crucial to establish whether they could sustain life elsewhere in the Solar System. Here, we explore the three-dimensional distribution of hydrous phases within the Miller Range 03346 nakhlite meteorite using nondestructive neutron and x-ray tomography to determine whether alteration is interconnected and pervasive. The results reveal discrete clusters of hydrous phases within and surrounding olivine grains, with limited interconnectivity between clusters. This implies that the fluid was localized and originated from the melting of local subsurface ice following an impact event. Consequently, the duration of the hydrous alteration was likely short, meaning that the martian crust sampled by the nakhlites could not have provided habitable environments that could harbor any life on Mars during the Amazonian.

The utilization of alkaline wastes in passive carbon capture and sequestration: Promises, challenges and environmental aspects.

Alkaline wastes have been the focus of many studies as they act as CO2 sinks and have the potential to offset emissions from mining and steelmaking industries. Passive carbonation of alkaline wastes mimics natural silicate weathering and provides a promising alternative pathway for CO2 capture and storage as carbonates, requiring marginal human intervention when compared to ex-situ carbonation. This review summarizes the extant research that has investigated the passive carbonation of alkaline wastes, namely ironmaking and steelmaking slag, mine tailings and demolition wastes, over the past two decades. Here we report different factors that affect passive carbonation to address challenges that this process faces and to identify possible solutions. We identify avenues for future research such as investigating how passive carbonation affects the surrounding environment through interaction with the biosphere and the hydrosphere. Future research should also consider economic analyses to provide investors with an in-depth understanding of passive carbonation techniques. Based on the reviewed materials, we conclude that passive carbonation can be an important contributor to climate change mitigation strategies, and its potential can be intensified by applying simple waste management practices.

Impact and habitability scenarios for early Mars revisited based on a 4.45-Ga shocked zircon in regolith breccia.

After formation of a primordial crust, early impacts influenced when habitable conditions may have occurred on Mars. Martian meteorite Northwest Africa (NWA) 7034 is a regolith breccia that contains remnants of the earliest Martian crust. The paucity of shock deformation in NWA 7034 was previously cited as recording a decline in giant impacts by 4.48 billion years and evidence for habitable Mars by 4.2 billion years ago. We present new evidence of high-pressure shock effects in a 4.45-billion year-old zircon from the matrix of NWA 7034. The zircon contains {112} shock twins formed in the central uplift of a complex impact structure after 4.45 billion years and records impact pressures of 20 to 30 gigapascals. The zircon represents the highest shock level reported in NWA 7034 and paired rocks and provides direct physical evidence of large impacts, some potentially life-affecting, that persisted on Mars after 4.48 billion years.

Atom Probe Tomography of a Cu-Doped TiNiSn Thermoelectric Material: Nanoscale Structure and Optimization of Analysis Conditions.

Cu-doping and crystallographic site occupations within the half-Heusler (HH) TiNiSn, a promising thermoelectric material, have been examined by atom probe tomography. In particular, this investigation aims to better understand the influence of atom probe analysis conditions on the measured chemical composition. Under a voltage-pulsing mode, atomic planes are clearly resolved and suggest an arrangement of elements in-line with the expected HH (F-43m space group) crystal structure. The Cu dopant is also distributed uniformly throughout the bulk material. For operation under laser-pulsed modes, the returned composition is highly dependent on the selected laser energy, with high energies resulting in the measurement of excessively high absolute Ti counts at the expense of Sn and in particular Ni. High laser energies also appear to be correlated with the detection of a high fraction of partial hits, indicating nonideal evaporation behavior. The possible mechanisms for these trends are discussed, along with suggestions for optimal analysis conditions for these and similar thermoelectric materials.

Shock metamorphism in plagioclase and selective amorphization.

Plagioclase feldspar is one of the most common rock-forming minerals on the surfaces of the Earth and other terrestrial planetary bodies, where it has been exposed to the ubiquitous process of hypervelocity impact. However, the response of plagioclase to shock metamorphism remains poorly understood. In particular, constraining the initiation and progression of shock-induced amorphization in plagioclase (i.e., conversion to diaplectic glass) would improve our knowledge of how shock progressively deforms plagioclase. In turn, this information would enable plagioclase to be used to evaluate the shock stage of meteorites and terrestrial impactites, whenever they lack traditionally used shock indicator minerals, such as olivine and quartz. Here, we report on an electron backscatter diffraction (EBSD) study of shocked plagioclase grains in a metagranite shatter cone from the central uplift of the Manicouagan impact structure, Canada. Our study suggests that, in plagioclase, shock amorphization is initially localized either within pre-existing twins or along lamellae, with similar characteristics to planar deformation features (PDFs) but that resemble twins in their periodicity. These lamellae likely represent specific crystallographic planes that undergo preferential structural failure under shock conditions. The orientation of preexisting twin sets that are preferentially amorphized and that of amorphous lamellae is likely favorable with respect to scattering of the local shock wave and corresponds to the "weakest" orientation for a specific shock pressure value. This observation supports a universal formation mechanism for PDFs in silicate minerals.

Novel Applications of FIB-SEM-Based ToF-SIMS in Atom Probe Tomography Workflows.

Atom probe tomography (APT) is used to quantify atomic-scale elemental and isotopic compositional variations within a very small volume of material (typically <0.01 µm3). The small analytical volume ideally contains specific compositional or microstructural targets that can be placed within the context of the previously characterized surface in order to facilitate a correct interpretation of APT data. In this regard, careful targeting and preparation are paramount to ensure that the desired target, which is often smaller than 100 nm, is optimally located within the APT specimen. Needle-shaped specimens required for atom probe analysis are commonly prepared using a focused ion beam scanning electron microscope (FIB-SEM). Here, we utilize FIB-SEM-based time-of-flight secondary ion mass spectrometry (ToF-SIMS) to illustrate a novel approach to targeting <100 nm compositional and isotopic variations that can be used for targeting regions of interest for subsequent lift-out and APT analysis. We present a new method for high-spatial resolution targeting of small features that involves using FIB-SEM-based electron deposition of platinum "buttons" prior to standard lift-out and sharpening procedures for atom probe specimen manufacture. In combination, FIB-ToF-SIMS analysis and application of the "button" method ensure that even the smallest APT targets can be successfully captured in extracted needles.

Changes in body position on the bike during seated sprint cycling: Applications to bike fitting.

Dynamic bike fitting often includes the optimisation of lower limb joint kinematics while participants undertake sub-maximal intensity cycling; however, this practice might not be appropriate for sprint cycling. This study aimed to determine if trained cyclists maintain lower limb angles, defined during dynamic sub-maximal bike fitting, while completing seated sprint cycling. Fifteen competitive cyclists completed two testing sessions. Dynamic bike fitting was undertaken during the first session, where handlebar positions were identified to produce pre-determined hip flexion angles (70°-110°) during sub-maximal cycling using an inertial-based motion tracking system. In the second session, full body kinematics were determined during two 6-s sprints performed at each of the pre-determined handlebar positions. During sprinting, measured right hip angles were only different at 110°, when compared with 90° (p < 0.01, d = 0.95), and 80° (p < 0.01, d = 1.49). For the left leg, measured hip angles differed between 110° vs. 90° (p < 0.01, d = 1.52), 110° vs. 80° (p < 0.01, d = 2.09), and 100° vs. 80° (p = 0.04, d = 1.06). Even though changes in bike configuration resulted in 10° increments of hip flexion during dynamic sub-maximal bike fitting, these hip angles were not replicated during sprinting. Therefore, dynamic sub-maximal bike fitting leading to changes in handlebar positions that produce hip angles of 80°-100° might not influence cycling performance due to acute changes in the body position of cyclists on the bicycle during a sprint.

Muscle force adaptation to changes in upper body position during seated sprint cycling.

Sprint cycling performance depends upon the balance between muscle and drag forces. This study assessed the influence of upper body position on muscle forces and aerodynamics during seated sprint cycling. Thirteen competitive cyclists attended two sessions. The first session was used to determine handlebar positions to achieve pre-determined hip flexion angles (70-110° in 10° increments) using dynamic bicycle fitting. In the second session, full body kinematics and pedal forces were recorded throughout 2x6-s seated sprints at the pre-determined handlebar positions, and frontal plane images were used to determine the projected frontal area. Leg work, joint work, muscle forces and frontal area were compared at three upper body positions, being optimum (maximum leg work), optimal+10° and optimal-10° of hip flexion. Larger hip (p = 0.01-0.02) and reduced knee (p = 0.02-0.03) contribution to leg work were observed at the optimal+10° position without changes at the ankle joint (p = 0.39). No differences were observed in peak muscle forces across the three body positions (p = 0.06-0.48). Frontal area was reduced at optimum+10° of hip flexion when compared to optimum (p = 0.02) and optimum-10° (p < 0.01). These findings suggest that large changes in upper body position can influence aerodynamics and alter contributions from the knee and hip joints, without influencing peak muscle forces.

Coastal acidification impacts on shell mineral structure of bivalve mollusks.

Ocean acidification is occurring globally through increasing CO 2 absorption into the oceans creating particular concern for calcifying species. In addition to ocean acidification, near shore marine habitats are exposed to the deleterious effects of runoff from acid sulfate soils which also decreases environmental pH. This coastal acidification is being exacerbated by climate change-driven sea-level rise and catchment-driven flooding. In response to reduction in habitat pH by ocean and coastal acidification, mollusks are predicted to produce thinner shells of lower structural integrity and reduced mechanical properties threatening mollusk aquaculture. Here, we present the first study to examine oyster biomineralization under acid sulfate soil acidification in a region where growth of commercial bivalve species has declined in recent decades. Examination of the crystallography of the shells of the Sydney rock oyster, Saccostrea glomerata, by electron back scatter diffraction analyses revealed that the signal of environmental acidification is evident in the structure of the biomineral. Saccostrea glomerata, shows phenotypic plasticity, as evident in the disruption of crystallographic control over biomineralization in populations living in coastal acidification sites. Our results indicate that reduced sizes of these oysters for commercial sale may be due to the limited capacity of oysters to biomineralize under acidification conditions. As the impact of this catchment source acidification will continue to be exacerbated by climate change with likely effects on coastal aquaculture in many places across the globe, management strategies will be required to maintain the sustainable culture of these key resources.

Effectiveness and kinetics of ferrate as a disinfectant for ballast water.

This study examined whether ferrate could meet the international standards for successful ballast water treatment, including final concentrations of less than 1 CFU/mL of Enterococci, less than 2.5 CFU/mL of Escherichia coli, and less than 1 CFU/100 mL of Vibrio cholerae. Pure cultures of E. coli, Klebsiella pneumoniae, and V. cholerae, and a mixed culture of Enterococcus faecium and E. faecilis were grown in saline solution to simulate ballast water and were treated with dosages of ferrate ranging from 0.25 to 5.0 mg/L. A ferrate dose of 5 mg/L resulted in complete disinfection of all organisms tested, and smaller dosages were also very effective. Tailing was consistently observed, and the Hom's model (1972) appeared to most accurately represent the action of ferrate on these organisms. Salinity and pH did not adversely affect results, and regrowth was not a problem. Ferrate shows good potential as an effective disinfectant in the treatment of ballast water.