Reassigning CI chondrite parent bodies based on reflectance spectroscopy of samples from carbonaceous asteroid Ryugu and meteorites.

The carbonaceous asteroid Ryugu has been explored by the Hayabusa2 spacecraft to elucidate the actual nature of hydrous asteroids. Laboratory analyses revealed that the samples from Ryugu are comparable to unheated CI carbonaceous chondrites; however, reflectance spectra of Ryugu samples and CIs do not coincide. Here, we demonstrate that Ryugu sample spectra are reproduced by heating Orgueil CI chondrite at 300°C under reducing conditions, which caused dehydration of terrestrial weathering products and reduction of iron in phyllosilicates. Terrestrial weathering of CIs accounts for the spectral differences between Ryugu sample and CIs, which is more severe than space weathering that likely explains those between asteroid Ryugu and the collected samples. Previous assignments of CI chondrite parent bodies, i.e., chemically most primitive objects in the solar system, are based on the spectra of CI chondrites. This study indicates that actual spectra of CI parent bodies are much darker and flatter at ultraviolet to visible wavelengths than the spectra of CI chondrites.

Calibration and performances of the MicrOmega instrument for the characterization of asteroid Ryugu returned samples.

MicrOmega, a miniaturized near-infrared hyperspectral microscope, has been selected to characterize in the laboratory the samples returned from Ryugu by the Hayabusa2 mission. MicrOmega has been delivered to the Extraterrestrial Samples Curation Center of the Japanese Aerospace eXploration Agency at the Institute of Space and Astronautical Science in July 2020 and then mounted and calibrated to be ready for the analyses of the samples returned to Earth on December 6, 2020. MicrOmega was designed to analyze the returned samples within a field of view of 5 × 5 mm2 and a spatial sampling of 22.5 µm. It acquires 3D near-infrared hyperspectral image-cubes by imaging the sample with monochromatic images sequentially covering the 0.99-3.65 µm spectral range, with a typical spectral sampling of 20 cm-1. This paper reports the calibration processes performed to extract scientific data from these MicrOmega image-cubes. The determination of the instrumental response and the spectral calibration is detailed. We meet or exceed the goals of achieving an accuracy of ∼20% for the absolute reflectance level, 1% for the relative wavelength-to-wavelength reflectance, and <5 nm for the peak position of the detected absorption features. For the nominal measurements of Ryugu samples with MicrOmega/Curation, the instrument performance also reaches a signal-to-noise ratio of >100 over the entire spectral range. By characterizing the entire collection of the returned samples at the microscopic scale, MicrOmega/Curation offers the potential to provide unprecedented insights into the composition and history of their asteroid parent body.

Spectrally blue hydrated parent body of asteroid (162173) Ryugu.

Ryugu is a carbonaceous rubble-pile asteroid visited by the Hayabusa2 spacecraft. Small rubble pile asteroids record the thermal evolution of their much larger parent bodies. However, recent space weathering and/or solar heating create ambiguities between the uppermost layer observable by remote-sensing and the pristine material from the parent body. Hayabusa2 remote-sensing observations find that on the asteroid (162173) Ryugu both north and south pole regions preserve the material least processed by space weathering, which is spectrally blue carbonaceous chondritic material with a 0-3% deep 0.7-µm band absorption, indicative of Fe-bearing phyllosilicates. Here we report that spectrally blue Ryugu's parent body experienced intensive aqueous alteration and subsequent thermal metamorphism at 570-670 K (300-400 °C), suggesting that Ryugu's parent body was heated by radioactive decay of short-lived radionuclides possibly because of its early formation 2-2.5 Ma. The samples being brought to Earth by Hayabusa2 will give us our first insights into this epoch in solar system history.

A Mineralogical Context for the Organic Matter in the Paris Meteorite Determined by A Multi-Technique Analysis.

This study is a multi-technique investigation of the Paris carbonaceous chondrite directly applied on two selected 500 × 500 µm² areas of a millimetric fragment, without any chemical extraction. By mapping the partial hydration of the amorphous silicate phase dominating the meteorite sample matrix, infrared spectroscopy gave an interesting glimpse into the way the fluid may have circulated into the sample and partially altered it. The TOF-SIMS in-situ analysis allowed the studying and mapping of the wide diversity of chemical moieties composing the meteorite organic content. The results of the combined techniques show that at the micron scale, the organic matter was always spatially associated with the fine-grained and partially-hydrated amorphous silicates and to the presence of iron in different chemical states. These systematic associations, illustrated in previous studies of other carbonaceous chondrites, were further supported by the identification by TOF-SIMS of cyanide and/or cyanate salts that could be direct remnants of precursor ices that accreted with dust during the parent body formation, and by the detection of different metal-containing large organic ions. Finally, the results obtained emphasized the importance of studying the specific interactions taking place between organic and mineral phases in the chondrite matrix, in order to investigate their role in the evolution story of primitive organic matter in meteorite parent bodies.

Binding of Nucleic Acid Components to the Serpentinite-Hosted Hydrothermal Mineral Brucite.

The adsorption of nucleic acid components onto the serpentinite-hosted hydrothermal mineral brucite has been investigated experimentally by determining the equilibrium adsorption isotherms in aqueous solution. Thermodynamic characterization of the adsorption data has been performed using the extended triple-layer model (ETLM) to establish a model for the stoichiometry and equilibrium constants of surface complexes. Infrared characterization of the molecule-mineral complexes has helped gain insight into the molecular functional groups directly interacting with the mineral surface. Quantum mechanical calculations have been carried out to identify the possible complexes formed on surfaces by nucleic acid components and their binding configurations on mineral surfaces, both in the presence of water molecules and in water-free conditions. The results indicate that brucite favors adsorption of nucleotides with respect to nucleosides and nucleobases from dilute aqueous environments. The surface of this mineral is able to induce well-defined orientations of the molecules through specific molecule-mineral interactions. This result suggests plausible roles of the mineral brucite in assisting prebiotic molecular self-organization. Furthermore, the detection of the infrared spectroscopic features of such building blocks of life adsorbed on brucite at very low degrees of coverage provides important support to life detection investigations.

Determination of aluminum by electrothermal atomic absorption spectroscopy in lubricating oils emulsified in a sequential injection analysis system.

The sequential injection (SIA) technique was applied for the on-line preparation of an "oil in water" microemulsion and for the determination of aluminum in new and used lubricating oils by electrothermal atomic absorption spectrometry (ET AAS) with Zeeman-effect background correction. Respectively, 1.0, 0.5 and 1.0ml of surfactants mixture, sample and co-surfactant (sec-butanol) solutions were sequentially aspirated to a holding coil. The sonication and repetitive change of the flowing direction improved the stability of the different emulsion types (oil in water, water in oil and microemulsion). The emulsified zone was pumped to fill the sampling arm of the spectrometer with a sub-sample of 200mul. Then, 10mul of this sample solution were introduced by means of air displacement in the graphite tube atomizer. This sequence was timed to synchronize with the previous introduction of 15mug of Mg(NO(3))(2) (in a 10mul) by the spectrometer autosampler. The entire SIA system was controlled by a computer, independent of the spectrometer. The furnace program was carried out by employing a heating cycle in four steps: drying (two steps at 110 and 130 degrees C), pyrolisis (at 1500 degrees C), atomization (at 2400 degrees C) and cleaning (at 2400 degrees C). The calibration graph was linear from 7.7 to 120mugAll(-1). The characteristic mass (mo) was 33.2pg/0.0044s and the detection limit was 2.3mugAll(-1). The relative standard (RSD) of the method, evaluated by replicate analyses of different lubricating oil samples varied in all cases between 1.5 and 1.7%, and the recovery values found in the analysis of spiked samples ranged from 97.2 to 100.4%. The agreement between the observed and reference values obtained from two NIST Standard Certified Materials was good. The method was simple and satisfactory for determining aluminum in new and used lubricating oils.

High-performance liquid chromatographic determination of cocaine and benzoylecgonine by direct injection of human blood plasma sample into an alkyl-diol-silica (ADS) precolumn.

A column-switching high-performance liquid chromatographic method with UV detection for the determination of cocaine (COC) and benzoylecgonine (BZE) in human blood plasma samples is described. The method uses an alkyl-diol-silica ADS-C18 extraction precolumn. A 50- micro L plasma sample was introduced to the ADS precolumn in order to separate the analytes from proteins and endogenous compounds. The fraction containing COC and BZE was back-flushed and transferred to an Alltech mixed-mode C(18)/cation-exchange analytical column for final separation. The validation of the method revealed quantitative recoveries from 95.0 to 99.0% for COC at three different concentrations (0.5, 1.0 and 2.0 micro g mL(-1)), and from 96.0 to 99.0% for BZE at the same concentration levels with coefficients of variation <4.00% (n=5). The detection limit (signal to noise ratio (S/N)>3) was 0.03 micro g mL(-1) for all the compounds with an injection volume of 50 micro L. However, it was possible to enhance the sensitivity further by injecting larger plasma volumes, up to 200 micro L, at the same optimal conditions. The overlap of sample preparation, analysis and reconditioning of the extraction column, increase the overall sample throughput to 5 samples h(-1). The developed method has been applied to human blood plasma samples from subjects suspected of cocaine abuse.

Optimum phase-behavior formulation of surfactant/oil/water systems for the determination of chromium in heavy crude oil and in bitumen-in-water emulsion.

An "oil in water" formulation was optimized to determine chromium in heavy crude oil (HCO) and bitumen-in-water emulsion (Orimulsion-400(R)) samples by transversally heated electrothermal atomic absorption spectrometry (TH-ET AAS) using Zeeman effect background correction. The optimum proportion of the oil-water mixture ratio was 7:3 v/v (70 ml of oil as the internal phase) with a non-ionic surfactant concentration (Intan-100) in the emulsion of 0.2% w/w. Chromium was determined in different crude oil samples after dilution of the emulsions 1:9 v/v with a 0.2% w/w solution of surfactant in order to further reduce the viscosity from 100 to 1.6 cP and at the same time to bring the concentration of chromium within the working range of the ET AAS technique. The calibration graph was linear from 1.7 to 100 mug Cr l(-1). The sensitivity was of 0.0069 s l mug(-1), the characteristic mass (m(o)) was of 5.7 pg per 0.0044 s and the detection limit (3sigma) was of 0.52 mug l(-1). The relative standard deviation of the method, evaluated by replicate analyses of three crude oil samples varied in all cases between 1.5 and 2.6%. Recovery studies were performed on four Venezuelan crude oils, and the average chromium recovery values varied between 95.9-104.8, 90.6-107.6, 95.6-104.0 and 98.8-103.9% for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión(R)-400, respectively. The results obtained in this work for the Cerro Negro, Crudo Hamaca and Boscán crude oils and for the Orimulsión(R)-400 following the proposed procedure were of 0.448+/-0.008, 0.338+/-0.004 0.524+/-0.021 and 0.174+/-0.008 mg Cr l(-1), respectively, which were in good agreement with the values obtained by a tedious recommended standard procedure (respectively: 0.470+/-0.05, 0.335+/-0.080, 0.570+/-0.021 and 0.173+/-0.009 mg Cr l(-1)).

Flow analysis-hydride generation-Fourier transform infrared spectrometry. A new analytical technique for the simultaneous determination of antimony, arsenic and tin.

The combination of flow analysis (FA), hydride generation (HG) and Fourier transform infrared (FTIR) spectrometry is proposed as a novel and powerful analytical technique for the individual and simultaneous determination of antimony, arsenic and tin in aqueous samples. The analytes were transformed into the volatile hydride form by on-line reaction with sodium tetrahydroborate in acidic medium. The gaseous analyte hydrides [M(n)H(m), (g)] generated, were transported by means of a carrier gas stream inside the IR gas cell and the corresponding FTIR spectrum was acquired in a continuous mode. The 1893, 1904 and 2115 cm(-1) bands of the SbH3, SnH4, and AsH3 were selected for the determination of antimony, tin and arsenic, respectively. The limit of detection (3sigma) obtained by using a short-path (10 cm) IR gas cell were 0.25, 0.30 and 1.2 mg l(-1) for the determination of antimony, tin and arsenic, respectively; while the precision (relative standard deviation, RSD, n 5) found from a standard solution containing 50 mg l(-1) of each element was, in all cases, less than 0.3%. However, the use of a long-path (7.25 m) IR gas cell improved the figures of merit (sensitivity, limits of detection and quantification) nearly 60-fold. The effect of the main experimental and instrumental variables, such as acidic media, sodium tetraborohydrate concentration, nitrogen flow rate, nominal resolution and the scan accumulation on the analytical signals of the antimony, tin and arsenic hydrides, were studied. Further, the potential of the proposed technique for the simultaneous determination of these elements was tested, analyzing synthetic samples containing different amounts of Sb, Sn and As.