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The pursuit of understanding the origins of life (OoL) on and off Earth and the search for extraterrestrial life (ET) are central aspects of astrobiology. Despite the considerable efforts in both areas, more novel and multifaceted approaches are needed to address these profound questions with greater detail and with certainty. The complexity of the chemical milieu within ancient geological environments presents a diverse landscape where biomolecules and non-biomolecules interact. This interaction could lead to life as we know it, dominated by biomolecules, or to alternative forms of life where non-biomolecules could play a pivotal role. Such alternative forms of life could be found beyond Earth, i.e., on exoplanets and the moons of Jupiter and Saturn. Challenging the notion that all life, including ET life, must use the same building blocks as life on Earth, the concept of contingency-when expanded beyond its macroevolution interpretation-suggests that non-biomolecules may have played essential roles at the OoL. Here, we review the possible role of contingency and non-biomolecules at the OoL and synthesize a conceptual model formally linking contingency with non-biomolecular OoL theories. This model emphasizes the significance of considering the role of non-biomolecules both at the OoL on Earth or beyond, as well as their potential as agnostic biosignatures indicative of ET Life.

α-Hydroxy acids are prebiotic monomers that undergo dehydration synthesis to form polyester gels, which assemble into membraneless microdroplets upon aqueous rehydration. These microdroplets are proposed as protocells that can segregate and compartmentalize primitive molecules/reactions. Different primitive aqueous environments with a variety of salts could have hosted chemistries that formed polyester microdroplets. These salts could be essential cofactors of compartmentalized prebiotic reactions or even directly affect protocell structure. However, fully understanding polyester-salt interactions remains elusive, partially due to technical challenges of quantitative measurements in condensed phases. Here, spectroscopic and biophysical methods are applied to analyze salt uptake by polyester microdroplets. Inductively coupled plasma mass spectrometry is applied to measure the cation concentration within polyester microdroplets after addition of chloride salts. Combined with methods to determine the effects of salt uptake on droplet turbidity, size, surface potential and internal water distribution, it was observed that polyester microdroplets can selectively partition salt cations, leading to differential microdroplet coalescence due to ionic screening effects reducing electrostatic repulsion forces between microdroplets. Through applying existing techniques to novel analyses related to primitive compartment chemistry and biophysics, this study suggests that even minor differences in analyte uptake can lead to significant protocellular structural change., (© 2023 The Authors. Small Methods published by Wiley-VCH GmbH.)

Background: Chromium isotopes have been used to trace geochemical and cosmochemical processes in the past. However, the presence of multivalent Cr species has made it difficult to isolate Cr from geological samples, particularly for samples with a low Cr mass fraction., Results: Here, a simple three-step ion exchange chromatography procedure is presented to separate Cr from various sample matrices, ranging from ultramafic to felsic rocks. Throughout each of the column chromatography step, 1 mL of cation exchange resin AG50W-X8 (200-400 mesh) was used as the stationary phase and oxalic acid as a chelating agent, was used in addition to the inorganic acids. This method yielded high recoveries of Cr [93 ± 8% (2SD, N = 7)] regardless of the lithology. The total procedural blank of Cr was <0.5 ng. We also developed a double spike-total evaporation-thermal ionization mass spectrometry (DS-TE-TIMS) technique that significantly reduced sample consumption to ∼20 ng of Cr per each measurement of mass-dependent 53 Cr/ 52 Cr., Significance: This study achieved a 2SD external precision of 0.02‰ for the analysis of NIST NBS3112a and of 0.01-0.07‰ for the geological samples. This study enabled high-precision Cr isotope analysis in geological samples with various matrix and Cr compositions using relatively small sample volumes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The Hayabusa2 mission was tasked with returning samples from the C-complex asteroid Ryugu (1999 JU3), in order to shed light on the formation, evolution and composition of such asteroids. One of the main science objectives was to understand whether such bodies could have supplied the organic matter required for the origin of life on Earth. Here, a review of the studies concerning the organic matter within the Ryugu samples is presented. This review will inform the reader about the Hayabusa2 mission, the nature of the organic matter analyzed and the various interpretations concerning the analytical findings including those concerning the origin and evolution of organic matter from Ryugu. Finally, the review puts the findings and individual interpretations in the context of the current theories surrounding the formation and evolution of Ryugu. Overall, the summary provided here will help to inform those operating in a wide range of interdisciplinary fields, including planetary science, astrobiology, the origin of life and astronomy, about the most recent developments concerning the organic matter in the Ryugu return samples and their relevance to understanding our solar system and beyond. The review also outlines the issues that still remain to be solved and highlights potential areas for future work.

Background: Asbestos is a fibrous mineral that was widely used in the past. However, asbestos inhalation is associated with an aggressive type of cancer known as malignant mesothelioma (MM). After inhalation, an iron-rich coat forms around the asbestos fibres, together the coat and fibre are termed an "asbestos ferruginous body" (AFB). AFBs are the main features associated with asbestos-induced MM. Whilst several studies have investigated the external morphology of AFBs, none have characterised the internal morphology. Here, cross-sections of multiple AFBs from two smokers and two non-smokers are compared to investigate the effects of smoking on the onset and growth of AFBs. Morphological and chemical observations of AFBs were undertaken by transmission electron microscopy, energy dispersive x-ray spectroscopy and selected area diffraction., Results: The AFBs of all patients were composed of concentric layers of 2-line or 6-line ferrihydrite, with small spherical features being observed on the outside of the AFBs and within the cross-sections. The spherical components are of a similar size to Fe-rich inclusions found within macrophages from mice injected with asbestos fibres in a previous study. As such, the spherical components composing the AFBs may result from the deposition of Fe-rich inclusions during frustrated phagocytosis. The AFBs were also variable in terms of their Fe, P and Ca abundances, with some layers recording higher Fe concentrations (dense layers), whilst others lower Fe concentrations (porous layers). Furthermore, smokers were found to have smaller and overall denser AFBs than non-smokers., Conclusions: The AFBs of smokers and non-smokers show differences in their morphology, indicating they grew in lung environments that experienced disparate conditions. Both the asbestos fibres of smokers and non-smokers were likely subjected to frustrated phagocytosis and accreted mucopolysaccharides, resulting in Fe accumulation and AFB formation. However, smokers' AFBs experienced a more uniform Fe-supply within the lung environment compared to non-smokers, likely due to Fe complexation from cigarette smoke, yielding denser, smaller and more Fe-rich AFBs. Moreover, the lack of any non-ferrihydrite Fe phases in the AFBs may indicate that the ferritin shell was intact, and that ROS may not be the main driver for the onset of MM., (© 2023. The Author(s).)

We measured the N concentrations and isotopic compositions of 44 samples of terrestrial potassic and micro- and meso-porous minerals and a small number of whole-rocks to determine the extent to which N is incorporated and stored during weathering and low-temperature hydrothermal alteration in Mars surface/near-surface environments. The selection of these minerals and other materials was partly guided by the study of altered volcanic glass from Antarctica and Iceland, in which the incorporation of N as NH 4 in phyllosilicates is indicated by correlated concentrations of N and the LILEs ( + in phyllosilicates is indicated by correlated concentrations of N and the LILEs ( i.e. , in zeolites). The phyllosilicates, zeolites, and sulfates analyzed in this study contain between 0 and 99,120 ppm N and have δ e.g. , in zeolites). The phyllosilicates, zeolites, and sulfates analyzed in this study contain between 0 and 99,120 ppm N and have δ 15 values of -34‰ to +65‰. Most of these minerals, and the few siliceous hydrothermal deposits that were analyzed, have δ air N consistent with the incorporation of biologically processed N during low-temperature hydrothermal or weathering processes. Secondary ion mass spectrometry on altered hyaloclastites demonstrates the residency of N in smectites and zeolites, and silica. We suggest that geological materials known on Earth to incorporate and store N and known to be abundant at, or near, the surface of Mars should be considered targets for upcoming Mars sample return with the intent to identify any signs of ancient or modern life.15 N consistent with the incorporation of biologically processed N during low-temperature hydrothermal or weathering processes. Secondary ion mass spectrometry on altered hyaloclastites demonstrates the residency of N in smectites and zeolites, and silica. We suggest that geological materials known on Earth to incorporate and store N and known to be abundant at, or near, the surface of Mars should be considered targets for upcoming Mars sample return with the intent to identify any signs of ancient or modern life.

Fluids mediate the transport of subducted slab material and play a crucial role in the generation of arc magmas. However, the source of subduction-derived fluids remains debated. The Kamchatka arc is an ideal subduction zone to identify the source of fluids because the arc magmas are comparably mafic, their source appears to be essentially free of subducted sediment-derived components, and subducted Hawaii-Emperor Seamount Chain (HESC) is thought to contribute a substantial fluid flux to the Kamchatka magmas. Here we show that Tl isotope ratios are unique tracers of HESC contribution to Kamchatka arc magma sources. In conjunction with trace element ratios and literature data, we trace the progressive dehydration and melting of subducted HESC across the Kamchatka arc. In succession, serpentine (<100 km depth), lawsonite (100-250 km depth) and phengite (>250 km depth) break down and produce fluids that contribute to arc magmatism at the Eastern Volcanic Front (EVF), Central Kamchatka Depression (CKD), and Sredinny Ridge (SR), respectively. However, given the Tl-poor nature of serpentine and lawsonite fluids, simultaneous melting of subducted HESC is required to explain the HESC-like Tl isotope signatures observed in EVF and CKD lavas. In the absence of eclogitic crust melting processes in this region of the Kamchatka arc, we propose that progressive dehydration and melting of a HESC-dominated mélange offers the most compelling interpretation of the combined isotope and trace element data., (© 2022. The Author(s).)

Presented here are the observations and interpretations from a comprehensive analysis of 16 representative particles returned from the C-type asteroid Ryugu by the Hayabusa2 mission. On average Ryugu particles consist of 50% phyllosilicate matrix, 41% porosity and 9% minor phases, including organic matter. The abundances of 70 elements from the particles are in close agreement with those of CI chondrites. Bulk Ryugu particles show higher δ 18 O, Δ 17 O, and ε 54 Cr values than CI chondrites. As such, Ryugu sampled the most primitive and least-thermally processed protosolar nebula reservoirs. Such a finding is consistent with multi-scale H-C-N isotopic compositions that are compatible with an origin for Ryugu organic matter within both the protosolar nebula and the interstellar medium. The analytical data obtained here, suggests that complex soluble organic matter formed during aqueous alteration on the Ryugu progenitor planetesimal (several 10's of km), <2.6 Myr after CAI formation. Subsequently, the Ryugu progenitor planetesimal was fragmented and evolved into the current asteroid Ryugu through sublimation.

Nickel isotope ratios have traditionally been used as an important tracer in cosmochemistry, and recently, it has gained attention in geochemistry, biochemistry, and environmental sciences with the development of MC-ICP-MS. Purification of Ni before isotope measurement is mandatory for obtaining precise data, which has been commonly achieved with ion-exchange chromatography, employing dimethylglyoxime (DMG) as a chelating agent for Ni. However, it has been pointed out that the use of DMG can adversely affect the isotope measurement due to insufficient Ni recovery and mass bias during measurement caused by the remaining DMG. Ni isolation procedures without the usage of DMG were innovated, but they have disadvantages such as the necessity of complex separation methods, high Ni blank, and matrix-dependent Ni recovery. Here, we present a simple Ni isolation procedure without using DMG but with the aid of oxalic acid along with common inorganic acids, achieving near-complete recovery of Ni with low blanks [0.7 ± 0.3 ng (2SD, n = 4)] only using three ion exchange column steps. To validate our method and strengthen the Ni isotope database of reference materials, 60 Ni/ 58 Ni of 20 geological reference materials, covering wide matrix compositions, were measured by MC-ICP-MS using the double-spike method. The results have shown that high recovery of Ni, independent of the sample matrix elements was achieved (98 ± 4%) and the 60 Ni/ 58 Ni was measured with a 2SD of 0.006-0.084‰ from samples containing 100-200 ng Ni., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The Hayabusa2 mission successfully collected samples from the asteroid Ryugu last year and will return these to Earth in December 2020. It is anticipated that the samples will enable the analysis of terrestrially uncontaminated organic matter and minerals. Such analyses are in turn expected to elucidate the evolution of organic matter through Solar System history, including the origination and processing of biogenically important molecules, which could have been utilized by the first organisms on Earth. In anticipation, studies have made predictions concerning the properties of Ryugu, including its composition. The spectral characteristics of Ryugu, such as albedo, have been employed to relate the asteroid to members of the carbonaceous chondrite group that have been identified on Earth. However, the recent Hayabusa2 touchdown highlights a disparity between the color of surfaces of displaced platy fragments, indicating a brightening trend for the surface exposed to space compared to that facing into the body. Here we present a mass balance calculation with reference to data from the literature, which indicates that Ryugu may contain a significantly higher abundance of organic matter (likely >50%) than the currently most accepted meteorite analogues. A high organic content may result in high levels of extractable organic matter for the second touchdown site, where the spacecraft sampled freshly exposed material. However, high abundances of insoluble aromatic/graphitic rich organic matter may be present in the first touchdown site, which sampled the surface of Ryugu that had been exposed to space. Moreover, we suggest that the potentially high organic abundance and the rubble-pile nature of Ryugu may originate from the capture of rocky debris by a comet nucleus and subsequent water-organic-mineral interactions and sublimation of water ice.

Boron is associated with several Archean stromatolite deposits, including the tourmaline-rich Barberton stromatolites in South Africa and tourmaline-bearing pyritic laminae associated with stromatolites of the 3.48 Ga Dresser Formation in the Pilbara Craton, Australia. Boron is also a critical element in prebiotic organic chemistry, including in the formation of ribose, a crucial component in RNA. As geological evidence and advances in prebiotic chemistry are now suggesting that hot spring activity may be associated with the origins of life, an understanding of boron and its mobility and isotopic fractionation in geothermal settings may provide important insights into the setting for the origin of life. Here, we report on the boron isotopic compositions and elemental concentrations in a range of fluid, sediment, and mineral samples from the active, boron-rich Puga geothermal system in the Himalayas, India. This includes one of the lowest boron isotope values ever recorded in modern settings: diatom-rich sediments (δ 11 B = -41.0‰) in a multiphase fractionation system where evaporation is not the dominant form of isotope fractionation. Instead, the extreme boron isotopic fractionation is ascribed to the incorporation of tetrahedral 10 B borate anions in precipitating amorphous silica. These findings expand the known limits and drivers of boron isotope fractionation, as well as provide insight into the concentration and fractionation of boron in Archean hot spring environments.

The geochemical variabilities in intraplate basalts (IB) from the West African passive margin (WAPM) region, have generally been employed to indicate the presence of recycled materials in an associated upwelling mantle plume. However, the absence of time-progressive linear hotspot tracks in WAPM-IB make it difficult to explain their genesis solely by the mantle plume hypothesis. Here, we show that the Sr-Nd-Hf-Pb isotopic variations in basalts from most of the WAPM-IB could have mainly attributed to the derivation from two types of fusible regions of the refertilized subcontinental lithospheric mantle (SCLM) and the sub-lithospheric mantle. The locations and magma genesis of WAPM-IB are strongly related to the distance from the Mesozoic rift axis and the structure of the rifted SCLM. The melting of the source region can possibly be attributed to small-scale mantle convection at the base of the SCLM without the involvement of a mantle plume.

Northwest Africa (NWA) 6704 is a unique achondrite characterized by a near-chondritic major element composition with a remarkably intact igneous texture. To investigate the origin of this unique achondrite, we have conducted a combined petrologic, chemical, and 187 Re- 187 Os, O, and Ti isotopic study. The meteorite consists of orthopyroxene megacrysts (En 55-57 Wo 3-4 Fs 40-42 ; Fe/Mn = 1.4) up to 1.7 cm in length with finer interstices of olivine (Fa 50-53 ; Fe/Mn = 1.1-2.1), chromite (Cr# ~ 0.94), awaruite, sulfides, plagioclase (Ab 92 An 5 Or 3 ) and merrillite. The results of morphology, lattice orientation analysis, and mineral chemistry indicate that orthopyroxene megacrysts were originally hollow dendrites that most likely crystallized under high super-saturation and super-cooling conditions (1-10 2 °C/h), whereas the other phases crystallized between branches of the dendrites in the order of awaruite, chromite → olivine → merrillite → plagioclase. In spite of the inferred high supersaturation, the remarkably large size of orthopyroxene can be explained as a result of crystallization from a melt containing a limited number of nuclei that are preserved as orthopyroxene megacryst cores having high Mg# or including vermicular olivine. The Re-Os isotope data for bulk and metal fractions yield an isochron age of 4576 ± 250 Ma, consistent with only limited open system behavior of highly siderophile elements (HSE) since formation. The bulk chemical composition is characterized by broadly chondritic absolute abundances and only weakly fractionated chondrite-normalized patterns for HSE and rare earth elements (REE), together with substantial depletion of highly volatile elements relative to chondrites. The HSE and REE characteristics indicate that the parental melt and its protolith had not undergone significant segregation of metals, sulfides, or silicate minerals. These combined results suggest that a chondritic precursor to NWA 6704 was heated well above its liquidus temperature so that highly volatile elements were lost and the generated melt initially contained few nuclei of relict orthopyroxene, but the melting and subsequent crystallization took place on a timescale too short to allow magmatic differentiation. Such rapid melting and crystallization might occur as a result of impact on an undifferentiated asteroid. The O-Ti isotope systematics (Δ 17 O = -1.052 ± 0.004, 2 SD; ε 50 Ti = 2.28 ± 0.23, 2 SD) indicate that the NWA 6704 parent body sampled the same isotopic reservoirs in the solar nebula as the carbonaceous chondrite parent bodies. This is consistent with carbonaceous chondrite-like refractory element abundances and oxygen fugacity (FMQ = -2.6) in NWA 6704. Yet, the Si/Mg ratio of NWA 6704 is remarkably higher than those of carbonaceous chondrites, suggesting significant nebular fractionation of forsterite in its provenance.

A comprehensive geochemical study of the Chelyabinsk meteorite reveals further details regarding its history of impact-related fragmentation and melting, and later aqueous alteration, during its transit toward Earth. We support an ∼30 Ma age obtained by Ar-Ar method (Beard et al., 2014) for the impact-related melting, based on Rb-Sr isotope analyses of a melt domain. An irregularly shaped olivine with a distinct O isotope composition in a melt domain appears to be a fragment of a silicate-rich impactor. Hydrogen and Li concentrations and isotopic compositions, textures of Fe oxyhydroxides, and the presence of organic materials located in fractures, are together consistent with aqueous alteration, and this alteration could have pre-dated interaction with the Earth's atmosphere. As one model, we suggest that hypervelocity capture of the impact-related debris by a comet nucleus could have led to shock-wave-induced supercritical aqueous fluids dissolving the silicate, metallic, and organic matter, with later ice sublimation yielding a rocky rubble pile sampled by the meteorite.

The chemical compositions of the residues of the mantle melting that produces mid-ocean ridge basalt can be altered by fluid-rock interactions at spreading ridges and, possibly, during seawater penetration along bending-related faults in plates approaching trenches. This chemically modified rock, if subducted deeply and after long-term residence within the deep Earth, is a potential source of chemical heterogeneity in the mantle. Here, we demonstrate that peridotites from the Horoman massif preserve the chemical signatures of sub-seafloor hydrothermal (SSH) alteration at a mid-ocean ridge approximately one billion years ago. These rocks have evolved chemically subsequent to this SSH alteration; however, they retain the SSH-associated enrichments in fluid mobile elements and H 2 O despite their long-term residence within the mantle. Our results indicate that ancient SSH alteration resulting in the production of sulfide leads to Pb enrichment that could affect the present-day Pb isotopic evolution of the silicate earth. Evidence from the Horoman massif of the recycling of hydrous refractory domains into the mantle suggests that both the flux of H 2 O content into the mantle and the size of the mantle H 2 O reservoir are higher than have been estimated recently.

Observed enrichments of N (and the δ 15 N of this N) in volcanic glasses altered on Earth's modern and ancient seafloor are relevant in considerations of modern global N subduction fluxes and ancient life on Earth, and similarly altered glasses on Mars and other extraterrestrial bodies could serve as valuable tracers of biogeochemical processes. Palagonitized glasses and whole-rock samples of volcanic rocks on the modern seafloor (ODP Site 1256D) contain 3-18 ppm N with δ 15 N air values of up to +4.5‰. Variably altered glasses from Mesozoic ophiolites (Troodos, Cyprus; Stonyford volcanics, USA) contain 2-53 ppm N with δ 15 N of -6.3 to +7‰. All of the more altered glasses have N concentrations higher than those of fresh volcanic glass (for MORB, <2 ppm N), reflecting significant N enrichment, and most of the altered glasses have δ 15 N considerably higher than that of their unaltered glass equivalents (for MORB, -5 ± 2‰). Circulation of hydrothermal fluids, in part induced by nearby spreading-center magmatism, could have leached NH 4 + in altering volcanic glasses. Glasses from each site contain possible textural evidence for microbial activity in the form of microtubules, but any role of microbes in producing the N enrichments and elevated δ 4 N remains uncertain. Petrographic analysis, and imaging and chemical analyses by scanning electron microscopy and scanning transmission electron microscopy, indicate the presence of phyllosilicates (smectite, illite) in both the palagonitized cracks and the microtubules. These phyllosilicates (particularly illite), and possibly also zeolites, are the likely hosts for N in these glasses. Key Words: Nitrogen-Nitrogen isotope-Palagonite-Volcanic glass-Mars. Astrobiology 18, 330-342.+ in altering volcanic glasses. Glasses from each site contain possible textural evidence for microbial activity in the form of microtubules, but any role of microbes in producing the N enrichments and elevated δ 15 N remains uncertain. Petrographic analysis, and imaging and chemical analyses by scanning electron microscopy and scanning transmission electron microscopy, indicate the presence of phyllosilicates (smectite, illite) in both the palagonitized cracks and the microtubules. These phyllosilicates (particularly illite), and possibly also zeolites, are the likely hosts for N in these glasses. Key Words: Nitrogen-Nitrogen isotope-Palagonite-Volcanic glass-Mars. Astrobiology 18, 330-342.

Rationale: Oxygen triple isotope compositions give key information for understanding physical processes during isotopic fractionation between the geo-, hydro-, bio-, and atmosphere. For detailed discussion of these topics, it is necessary to determine precise (17)O-excess values of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW)., Methods: Water was fluorinated in an electrically heated Ni-metal tube into which water and BrF(5) were loaded for the quantitative extraction of oxygen. Silicate/oxide minerals were fluorinated by heating with a CO(2) laser in an atmosphere of BrF(5). The extracted oxygen was purified and isotope ratios of the oxygen triple isotope compositions were determined using a Finnigan MAT253 isotope ratio mass spectrometer., Results: The oxygen triple isotope compositions of meteoric water and terrestrial silicate/oxide minerals fall on statistically distinguishable fractionation lines, defined as [ln(δ(17)O + 1) = λln(δ(18) O + 1) + Δ], where λ and Δ correspond to the slope and intercept, respectively. The fractionation line for meteoric water has λ = 0.5285 ± 0.0005 and Δ = 0.03 ± 0.02‰ and for terrestrial silicate/oxide minerals has λ = 0.5270 ± 0.0005 and Δ = -0.070 ± 0.005‰, at the 95% confidence limit., Conclusions: All the analyzed terrestrial silicate/oxide minerals including internationally accepted reference materials (NBS-28, UWG-2, and San Carlos olivine) have a negative (17)O-excess with respect to VSMOW. We propose that it is necessary to specify if the determined δ(17)O values of terrestrial and extraterrestrial samples are expressed as the difference from VSMOW or the terrestrial silicate mineral-corrected value., (Copyright © 2012 John Wiley & Sons, Ltd.)

Records of micrometeorite collisions at down to submicron scales were discovered on dust grains recovered from near-Earth asteroid 25143 (Itokawa). Because the grains were sampled from very near the surface of the asteroid, by the Hayabusa spacecraft, their surfaces reflect the low-gravity space environment influencing the physical nature of the asteroid exterior. The space environment was examined by description of grain surfaces and asteroidal scenes were reconstructed. Chemical and O isotope compositions of five lithic grains, with diameters near 50 μm, indicate that the uppermost layer of the rubble-pile-textured Itokawa is largely composed of equilibrated LL-ordinary-chondrite-like material with superimposed effects of collisions. The surfaces of the grains are dominated by fractures, and the fracture planes contain not only sub-μm-sized craters but also a large number of sub-μm- to several-μm-sized adhered particles, some of the latter composed of glass. The size distribution and chemical compositions of the adhered particles, together with the occurrences of the sub-μm-sized craters, suggest formation by hypervelocity collisions of micrometeorites at down to nm scales, a process expected in the physically hostile environment at an asteroid's surface. We describe impact-related phenomena, ranging in scale from 10(-9) to 10(4) meters, demonstrating the central role played by impact processes in the long-term evolution of planetary bodies. Impact appears to be an important process shaping the exteriors of not only large planetary bodies, such as the moon, but also low-gravity bodies such as asteroids.

In this review, a new classification of elements based on behavior in hydrofluoric acid (HF) solution is presented for the precise quantitative analysis of each element by inductively coupled plasma mass spectrometry (ICP-MS). The elements are divided into 7 groups: (1) "fluorophile" elements; (2) insoluble fluoride-forming elements; (3) "bromophile" or "iodophile" elements; (4) "oxophile" elements; (5) "aquaphile" elements; (6) bare cation elements; and (7) other elements. Especially, the importance of fluorophile and insoluble fluoride-forming elements in elemental analysis is described. Due to the elemental characteristics, these two groups of elements cannot be dissolved simultaneously in the same solution, and thus cannot be measured together. In addition, coprecipitation of the fluorophile elements with the insoluble fluorides occurs in some conditions and hinders accurate analysis. The peculiar conditions when the coprecipitation occurs are discussed, and the "Al-addition" and "Mg-addition" methods for overcoming these problems are described. In addition, some state-of-the-art analytical techniques in ICP-MS are shown, and future directions of the element analysis are presented.

While exposure to fibers and particles has been proposed to be associated with several different lung malignancies including mesothelioma, the mechanism for the carcinogenesis is not fully understood. Along with mineralogical observation, we have analyzed forty-four major and trace elements in extracted asbestos bodies (fibers and proteins attached to them) with coexisting fiber-free ferruginous protein bodies from extirpative lungs of individuals with malignant mesothelioma. These observations together with patients' characteristics suggest that inhaled iron-rich asbestos fibers and dust particles, and excess iron deposited by continuous cigarette smoking would induce ferruginous protein body formation resulting in ferritin aggregates in lung tissue. Chemical analysis of ferruginous protein bodies extracted from lung tissues reveals anomalously high concentrations of radioactive radium, reaching millions of times higher concentration than that of seawater. Continuous and prolonged internal exposure to hotspot ionizing radiation from radium and its daughter nuclides could cause strong and frequent DNA damage in lung tissue, initiate different types of tumour cells, including malignant mesothelioma cells, and may cause cancers.

A precise and accurate determination method of 187Os/188Os, 189Os/188Os, and 185Re/187Re ratios of down to 0.2 pg of Os and 0.08 pg of Re using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) with multiple ion counting has been developed. Os and Re were introduced into MC-ICPMS as 0.5 mol L(-1) HF solutions through the desolvator, and 185Re, 187Os, 188Os, and 189Os ions were detected simultaneously by four channeltrons. The Os and Re ratios were determined by the standard bracketing method, in which channeltron yields and mass discrimination factors are corrected together. Os and Re memories after 800-s wash were <0.1% and negligible, typically 0.02 and 0.03%, respectively. Isotope ratios of 187Os/188Os, 189Os/188Os, and 185Re/187Re were constant within error in the concentration ranges of 1-100, 1-40, and 0.4-5 pg mL(-1) with reproducibility (1sigma) of 2.7-0.14, 0.33-0.10, and 0.41-0.19%, respectively. For analysis of larger amounts of Os and Re, the Faraday cup measurement was employed. The precision and reproducibility obtained in this study are comparable to those of N-TIMS and better than MC-ICPMS achieved so far with a capability of higher sample throughput with simpler sample preparation.

A new group separation method for Re and PGE (Ru, Pd, Os, Ir, Pt) is described using a novel anion exchange chromatographic resin called TEVA. Re and PGEs are converted into bromo complexes by heating with HF-HBr mixture in a Teflon bomb at 518 K, by in situ-generated Br2 formed by reaction of HBr and HNO3. Distribution coefficients (Kd) of the bromo complexes onto TEVA resin in 0.1 M HBr with heating at 353 K for one night were 2,200, 16,000, 1,600, 5,500, 4,000, and 17,000 for Ru, Pd, Re, Os, Ir, and Pt, respectively, thus allowing 97% recovery of Re and PGEs in 5 mL of solution by 0.1 mL of resin. These strongly bound Re and PGE bromo complexes are stripped and recovered >90% by the following three steps: (i) addition of 6 M HCl at 353 K and 2.2 M HCl-5 M HBr at 353 K; (ii) heating the resin in 6 M HCl at 353 K to convert the bromo complexes into the chloro complexes with weaker affinities to the resin; and (iii) sequential addition of the HCl-HBr mixture at room temperature and 7 M HI. Neither the elution profile nor the recovery yield for a 0.2-g geological sample showed significant changes, indicating minimal matrix effects for the geological samples. Total blanks were < 14 pg for Ru, Pd, and Pt and < 10 pg for Re, Os, and Ir. This new technique, therefore, is suitable for simultaneous determination of subnanogram per gram of Ru, Pd, Re, Os, Ir, and Pt and Os isotope analysis in geological, mineralogical, and environmental samples without direct addition of toxic reagents required in distillation/extraction of Os or oxidizing of Ir.

We have developed a new, simple, and accurate method for the determination of total sulfur at microgram per gram levels in milligram-sized silicate materials with isotope dilution high-resolution inductively coupled plasma mass spectrometry equipped with a flow injection system. In this method, sulfur can be quantitatively oxidized by bromine into sulfate with achievement of isotope equilibrium between the sample and spike. Detection limits for 32S+ and 34S+ in the ideal solution and silicate samples were 1 and 6 ng mL(-1) and 0.07 and 0.3 microg g(-1), respectively. The total blank was 46 ng, so that a 40-mg silicate sample containing 10 mirog g(-1) sulfur can be measured with a blank correction of < 10%. This total blank can be lowered to 8 ng if a low-blank air system is used for evaporations. To evaluate the applicability of this method, we analyzed not only silicate reference materials with sulfur content of 5.25-489 microg g(-1) and sample sizes of 13-40 mg but also the Allende meteorite with a sulfur content of 2%. The reproducibility for various rock types was < 9%, even though blank corrections in some samples of low sulfur content were up to 24%. This method is suitable for analyzing geological samples as well environmental samples such as soils, sediments, and water samples.

A new chemical separation technique to isolate Th and U from silicate rocks was established by using two kinds of commercial extraction chromatographic resins. In the first column procedure, with U/TEVA·spec resin, almost all elements except Th and U were eluted by 4 M HNO(3). Th was then separated by using 5 M HCl, and U was finally isolated by successive addition of 0.1 M HNO(3). A significant amount of Zr still remained in the Th fraction, which was then further purified in the second column stage using TEVA·spec resin. In the second procedure, Zr was eluted first by using 2 M HNO(3), and then Th was collected by 0.1 M HNO(3). Both the Th and U fractions obtained by these procedures were sufficiently pure for thermal ionization mass spectrometric (TIMS) analysis. Recovery yields of Th and U exceeded 90%, and total blanks were <19 pg for Th and <10 pg for U. Our method has advantages over previous methods in terms of matrix effects, tailing problems, and degree of isolation. Since Th and U are effectively separated without suffering any matrix interference from coexisting cations and anions, this technique can be used not only for the analysis of igneous rock samples but also for the analysis of soils, marine sediments, carbonates, phosphates and seawater, groundwater, and surface water.