Determination of mass-dependent chromium isotopic compositions in geological samples by double spike-total evaporation-thermal ionization mass spectrometry (DS-TE-TIMS).

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 53Cr/52Cr. 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.

Organic Matter in the Asteroid Ryugu: What We Know So Far.

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.

Spectroscopic and Biophysical Methods to Determine Differential Salt-Uptake by Primitive Membraneless Polyester Microdroplets.

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.

An investigation of the internal morphology of asbestos ferruginous bodies: constraining their role in the onset of malignant mesothelioma.

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.

Insights into the formation and evolution of extraterrestrial amino acids from the asteroid Ryugu.

All life on Earth contains amino acids and carbonaceous chondrite meteorites have been suggested as their source at the origin of life on Earth. While many meteoritic amino acids are considered indigenous, deciphering the extent of terrestrial contamination remains an issue. The Ryugu asteroid fragments (JAXA Hayabusa2 mission), represent the most uncontaminated primitive extraterrestrial material available. Here, the concentrations of amino acids from two particles from different touchdown sites (TD1 and TD2) are reported. The concentrations show that N,N-dimethylglycine (DMG) is the most abundant amino acid in the TD1 particle, but below detection limit in the other. The TD1 particle mineral components indicate it experienced more aqueous alteration. Furthermore, the relationships between the amino acids and the geochemistry suggest that DMG formed on the Ryugu progenitor body during aqueous alteration. The findings highlight the importance of aqueous chemistry for defining the ultimate concentrations of amino acids in primitive extraterrestrial samples.

Nitrogen Incorporation in Potassic and Micro- and Meso-Porous Minerals: Potential Biogeochemical Records and Targets for Mars Sampling.

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 NH4+ in phyllosilicates is indicated by correlated concentrations of N and the LILEs (i.e., K, Ba, Rb, Cs), with scatter likely related to the presence of exchanged, occluded/trapped, or encapsulated organic/inorganic N occurring within structural cavities (e.g., in zeolites). The phyllosilicates, zeolites, and sulfates analyzed in this study contain between 0 and 99,120 ppm N and have δ15Nair values of -34‰ to +65‰. Most of these minerals, and the few siliceous hydrothermal deposits that were analyzed, have δ15N 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.

On the origin and evolution of the asteroid Ryugu: A comprehensive geochemical perspective.

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 δ18O, Δ17O, and ε54Cr 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.

Novel nickel isolation procedure for a wide range of sample matrices without using dimethylglyoxime for isotope measurements using MC-ICP-MS.

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, 60Ni/58Ni 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 60Ni/58Ni was measured with a 2SD of 0.006-0.084‰ from samples containing 100-200 ng Ni.

Elements for the Origin of Life on Land: A Deep-Time Perspective from the Pilbara Craton of Western Australia.

For decades, deep sea hydrothermal vents have been a preferred setting for the Origin of Life, but "The Water Problem" as relates to polymerization of organic molecules, together with a propensity to dilute critical prebiotic elements as well as a number of other crucial factors, suggests that a terrestrial hot spring field with the capacity for wet-dry cycling and element concentration may represent a more likely candidate. Here, we investigate a 3.5 billion-year-old, anoxic hot spring setting from the Pilbara Craton (Australia) and show that its hydrothermal veins and compositionally varied pools and springs concentrated all of the essential elements required for prebiotic chemistry (including B, Zn, Mn, and K, in addition to C, H, N, O, P, and S). Temporal variability (seasonal to decadal), together with the known propensity of hot springs for wet-dry cycling and information exchange, would lead to innovation pools with peaks of fitness for developing molecules. An inference from the chemical complexity of the Pilbara analogue is that life could perhaps get started quickly on planets with volcanoes, silicate rocks, an exposed land surface, and water, ingredients that should form the backbone in the search for life in the Universe.

The Albedo of Ryugu: Evidence for a High Organic Abundance, as Inferred from the Hayabusa2 Touchdown Maneuver.

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.

A new concept for the genesis of felsic magma: the separation of slab-derived supercritical liquid.

Felsic magmas produced at subduction zones have played an important role in the generation and evolution of the continental crust. For the origin of felsic magmas, processes such as fractional crystallization of mafic magmas, partial melting of crustal materials, partial melting of subducting slabs, and partial melting of pyroxenitic mantle wedge components have been proposed. Recent experimental studies have predicted that felsic melt can also be produced in the mantle wedge by the separation of slab-derived supercritical liquid beyond depths corresponding to the critical point. To date, however, the presence of felsic magma of this origin has not yet been reported. In this study, we investigated dacitic lavas and preceding calc-alkaline andesite lavas from the Rishiri Volcano, located at the rear of the Kuril arc. We show that hydrous felsic melt and aqueous fluid were separated from slab-derived supercritical liquid in the mantle wedge. The former erupted as dacitic magma whilst the aqueous fluid induced the generation of primary basaltic magma involved in creating calc-alkaline andesite magma. We infer that slab-derived supercritical liquid is an efficient transport medium for moving silicate-rich components from subducting slabs to the Earth's surface, and that this process may have contributed to the growth of the continental crust.

Origin of ocean island basalts in the West African passive margin without mantle plume involvement.

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.

Boron Isotopes in the Puga Geothermal System, India, and Their Implications for the Habitat of Early Life.

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 (δ11B = -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 10B 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.

Hypervelocity collision and water-rock interaction in space preserved in the Chelyabinsk ordinary chondrite.

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.

Circa 1 Ga sub-seafloor hydrothermal alteration imprinted on the Horoman peridotite massif.

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 H2O 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 H2O content into the mantle and the size of the mantle H2O reservoir are higher than have been estimated recently.

Determination of 17O-excess of terrestrial silicate/oxide minerals with respect to Vienna Standard Mean Ocean Water (VSMOW).

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.

Space environment of an asteroid preserved on micrograins returned by the Hayabusa spacecraft.

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.

Chemical separation and mass spectrometry of Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial materials using thermal ionization mass spectrometry.

A sequential chemical separation technique for Cr, Fe, Ni, Zn, and Cu in terrestrial and extraterrestrial silicate rocks was developed for precise and accurate determination of elemental concentration by the isotope dilution method (ID). The technique uses a combination of cation-anion exchange chromatography and Eichrom nickel specific resin. The method was tested using a variety of matrixes including bulk meteorite (Allende), terrestrial peridotite (JP-1), and basalt (JB-1b). Concentrations of each element was determined by thermal ionization mass spectrometry (TIMS) using W filaments and a Si-B-Al type activator for Cr, Fe, Ni, and Zn and a Re filament and silicic acid-H3PO4 activator for Cu. The method can be used to precisely determine the concentrations of these elements in very small silicate samples, including meteorites, geochemical reference samples, and mineral standards for microprobe analysis. Furthermore, the Cr mass spectrometry procedure developed in this study can be extended to determine the isotopic ratios of 53Cr/52Cr and 54Cr/52Cr with precision of approximately 0.05epsilon and approximately 0.10epsilon (1epsilon = 0.01%), respectively, enabling cosmochemical applications such as high precision Mn-Cr chronology and investigation of nucleosynthetic isotopic anomalies in meteorites.

Precise elemental and isotopic analyses in silicate samples employing ICP-MS: application of hydrofluoric acid solution and analytical techniques.

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.