Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu

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1. 1

   Aramendia, J.; Gomez-Nubla, L.; Castro, K.; Fdez-Ortiz de Vallejuelo, S.; Arana, G.; Maguregui, M.; Baonza, V.; Medina, J.; Rull, F.; Madariaga, J. Overview of the techniques used for the study of non-terrestrial bodies: Proposition of novel non-destructive methodology. TrAC, Trends Anal. Chem. 2018, 98, 36– 46,  DOI: 10.1016/j.trac.2017.10.018

   Google Scholar

   1

   Overview of the techniques used for the study of non-terrestrial bodies: Proposition of novel non-destructive methodology

   Aramendia, J.; Gomez-Nubla, L.; Castro, K.; Fdez-Ortiz de Vallejuelo, S.; Arana, G.; Maguregui, M.; Baonza, V. G.; Medina, J.; Rull, F.; Madariaga, J. M.

   TrAC, Trends in Analytical Chemistry (2018), 98 (), 36-46CODEN: TTAEDJ; ISSN:0165-9936. (Elsevier B.V.)

   A review. Meteorites and impact glasses have been largely analyzed using different techniques, but most studies have been focused on their geol.-mineralogical characterization and isotopic ratios, mainly of a destructive nature. However, much more information can be gained by applying novel non-destructive anal. procedures and techniques that have been scarcely used to analyze these materials. This overview presents some new methodologies to study these materials and compares these new approaches with the commonly used ones. Techniques such as X-Ray Fluorescence (XRF) and Laser Induced Breakdown Spectroscopy (LIBS), for elemental characterization, the hyphenated Raman spectroscopy-SEM/EDS and the combination of them, allow extg. simultaneous information from elemental, mol. and structural data of the studied sample; furthermore, the spectroscopic image capabilities of such techniques allow a better understanding of the mineralogical distribution.
2. 2

   Tsuji, K.; Matsuno, T.; Takimoto, Y.; Yamanashi, M.; Kometani, N.; Sasaki, Y. C.; Hasegawa, T.; Kato, S.; Yamada, T.; Shoji, T.; Kawahara, N. New developments of X-ray fluorescence imaging techniques in laboratory. Spectrochim. Acta, Part B 2015, 113, 43– 53,  DOI: 10.1016/j.sab.2015.09.001

   Google Scholar

   2

   New developments of X-ray fluorescence imaging techniques in laboratory

   Tsuji, Kouichi; Matsuno, Tsuyoshi; Takimoto, Yuki; Yamanashi, Masaki; Kometani, Noritsugu; Sasaki, Yuji C.; Hasegawa, Takeshi; Kato, Shuichi; Yamada, Takashi; Shoji, Takashi; Kawahara, Naoki

   Spectrochimica Acta, Part B: Atomic Spectroscopy (2015), 113 (), 43-53CODEN: SAASBH; ISSN:0584-8547. (Elsevier B.V.)

   A review. X-ray fluorescence (XRF) anal. is a well-established anal. technique with a long research history. Many applications were reported in various fields, such as in the environmental, archeol., biol., and forensic sciences as well as in industry. This is because XRF has a unique advantage of being a nondestructive anal. tool with good precision for quant. anal. Recent advances in XRF anal. were realized by the development of new x-ray optics and x-ray detectors. Advanced x-ray focusing optics enables the making of a micro x-ray beam, leading to micro-XRF anal. and XRF imaging. A confocal micro-XRF technique was applied for the visualization of elemental distributions inside the samples. This technique was applied for liq. samples and for monitoring chem. reactions such as the metal corrosion of steel samples in the NaCl solns. A principal component anal. was applied for reducing the background intensity in XRF spectra obtained during XRF mapping, leading to improved spatial resoln. of confocal micro-XRF images. In parallel, the authors proposed a wavelength dispersive XRF (WD-XRF) imaging spectrometer for a fast elemental imaging. A new two dimensional x-ray detector, the Pilatus detector was applied for WD-XRF imaging. Fast XRF imaging in 1 s or even less was demonstrated for Euro coins and industrial samples. In this review paper, these recent advances in lab.-based XRF imaging, esp. in a lab. setting, will be introduced.
3. 3

   Smith, J. V. Tutorial review. Synchrotron X-ray sources: instrumental characteristics. New applications in microanalysis, tomography, absorption spectroscopy and diffraction. Analyst 1995, 120, 1231– 1245,  DOI: 10.1039/an9952001231

   Google Scholar

   3

   Synchrotron X-ray source: instrumental characteristics. New applications in microanalysis, tomography, absorption spectroscopy and diffraction

   Smith, Joseph V.

   Analyst (Cambridge, United Kingdom) (1995), 120 (5), 1231-45CODEN: ANALAO; ISSN:0003-2654. (Royal Society of Chemistry)

   A review with 123 refs. on the current state of microanal. using synchrotron x-ray techniques. Particularly important is the concept of combining fluorescence, diffraction, and absorption spectrometry to det. the bulk chem. compn., the at. positions in the unit cell, and the type of chem. bonding in a single crystal. Chem. reactions can be followed on a millisecond scale. The current tech. capabilities and anal. application are described and speculation is made about future anal. capabilities possible through further developments. The topics include: app. and anal. examples (geol., environmental, and cosmic dust).
4. 4

   Wada, K.; Grott, M.; Michel, P.; Walsh, K. J.; Barucci, A. M.; Biele, J.; Blum, J.; Ernst, C. M.; Grundmann, J. T.; Gundlach, B.; Hagermann, A.; Hamm, M.; Jutzi, M.; Kim, M. J.; Kührt, E.; Le Corre, L.; Libourel, G.; Lichtenheldt, R.; Maturilli, A.; Messenger, S. R.; Michikami, T.; Miyamoto, H.; Mottola, S.; Müller, T.; Nakamura, A. M.; Nittler, L. R.; Ogawa, K.; Okada, T.; Palomba, E.; Sakatani, N.; Schröder, S. E.; Senshu, H.; Takir, D.; Zolensky, M. E. and International Regolith Science Group (IRSG) in Hayabusa2 project. Asteroid Ryugu before the Hayabusa2 encounter. Prog. Earth Planet. Sci. 2018, 5, 82,  DOI: 10.1186/s40645-018-0237-y

   Google Scholar

   There is no corresponding record for this reference.
5. 5

   Yada, T.; Abe, M.; Okada, T.; Nakato, A.; Yogata, K.; Miyazaki, A.; Hatakeda, K.; Kumagai, K.; Nishimura, M.; Hitomi, Y. Preliminary analysis of the Hayabusa2 samples returned from C-type asteroid Ryugu. Nat. Astron. 2021, 6, 214– 220,  DOI: 10.1038/s41550-021-01550-6

   Google Scholar

   There is no corresponding record for this reference.
6. 6

   Yokoyama, T.; Nagashima, K.; Nakai, I.; Young, E. D.; Abe, Y.; Aléon, J.; Alexander, C. M. O.; Amari, S.; Amelin, Y.; Bajo, K. i. Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites. Science 2023, 379, eabn7850  DOI: 10.1126/science.abn7850

   Google Scholar

   There is no corresponding record for this reference.
7. 7

   Brearley, A. J. Meteorites and the Early Solar System II; University of Arizona Press; Lauretta, D. S., McSween, H. Y., Eds., 2006; p 584.

   Google Scholar

   There is no corresponding record for this reference.
8. 8

   Fujiya, W.; Kawasaki, N.; Nagashima, K.; Sakamoto, N.; O’D. Alexander, C. M.; Kita, N. T.; Kitajima, K.; Abe, Y.; Aléon, J.; Amari, S. Carbonate record of temporal change in oxygen fugacity and gaseous species in asteroid Ryugu. Nat. Geosci. 2023, 16, 675– 682,  DOI: 10.1038/s41561-023-01226-y

   Google Scholar

   8

   Carbonate record of temporal change in oxygen fugacity and gaseous species in asteroid Ryugu

   Fujiya, Wataru; Kawasaki, Noriyuki; Nagashima, Kazuhide; Sakamoto, Naoya; O'D. Alexander, Conel M.; Kita, Noriko T.; Kitajima, Kouki; Abe, Yoshinari; Aleon, Jerome; Amari, Sachiko; Amelin, Yuri; Bajo, Ken-ichi; Bizzarro, Martin; Bouvier, Audrey; Carlson, Richard W.; Chaussidon, Marc; Choi, Byeon-Gak; Dauphas, Nicolas; Davis, Andrew M.; Di Rocco, Tommaso; Fukai, Ryota; Gautam, Ikshu; Haba, Makiko K.; Hibiya, Yuki; Hidaka, Hiroshi; Homma, Hisashi; Hoppe, Peter; Huss, Gary R.; Ichida, Kiyohiro; Iizuka, Tsuyoshi; Ireland, Trevor R.; Ishikawa, Akira; Itoh, Shoichi; Kleine, Thorsten; Komatani, Shintaro; Krot, Alexander N.; Liu, Ming-Chang; Masuda, Yuki; McKeegan, Kevin D.; Morita, Mayu; Motomura, Kazuko; Moynier, Frederic; Nakai, Izumi; Nguyen, Ann; Nittler, Larry; Onose, Morihiko; Pack, Andreas; Park, Changkun; Piani, Laurette; Qin, Liping; Russell, Sara S.; Schonbachler, Maria; Tafla, Lauren; Tang, Haolan; Terada, Kentaro; Terada, Yasuko; Usui, Tomohiro; Wada, Sohei; Wadhwa, Meenakshi; Walker, Richard J.; Yamashita, Katsuyuki; Yin, Qing-Zhu; Yokoyama, Tetsuya; Yoneda, Shigekazu; Young, Edward D.; Yui, Hiroharu; Zhang, Ai-Cheng; Nakamura, Tomoki; Naraoka, Hiroshi; Noguchi, Takaaki; Okazaki, Ryuji; Sakamoto, Kanako; Yabuta, Hikaru; Abe, Masanao; Miyazaki, Akiko; Nakato, Aiko; Nishimura, Masahiro; Okada, Tatsuaki; Yada, Toru; Yogata, Kasumi; Nakazawa, Satoru; Saiki, Takanao; Tanaka, Satoshi; Terui, Fuyuto; Tsuda, Yuichi; Watanabe, Sei-ichiro; Yoshikawa, Makoto; Tachibana, Shogo; Yurimoto, Hisayoshi

   Nature Geoscience (2023), 16 (8), 675-682CODEN: NGAEBU; ISSN:1752-0894. (Nature Portfolio)

   The Hayabusa2 spacecraft explored asteroid Ryugu and brought its surface materials to Earth. Ryugu samples resemble Ivuna-type (CI) chondrites-the most chem. primitive meteorites-and contain secondary phyllosilicates and carbonates, which are indicative of aq. alteration. Understanding the conditions (such as temp., redox state and fluid compn.) during aq. alteration is crucial to elucidating how Ryugu evolved to its present state, but little is known about the temporal changes in these conditions. Here we show that calcium carbonate (calcite) grains in Ryugu and Ivuna samples have variable 18O/16O and 13C/12C ratios that are, resp., 24-46% and 65-108% greater than terrestrial std. values, whereas those of calcium-magnesium carbonate (dolomite) grains are much more homogeneous, ranging within 31-36% for oxygen and 67-75% for carbon. We infer that the calcite pptd. first over a wide range of temps. and oxygen partial pressures, and that the proportion of gaseous CO2/CO/CH4 mols. changed temporally. By contrast, the dolomite formed later in a more oxygen-rich and thus CO2-dominated environment when the system was approaching equil. The characteristic isotopic compns. of secondary carbonates in Ryugu and Ivuna are not obsd. for other hydrous meteorites, suggesting a unique evolutionary pathway for their parent asteroid(s).
9. 9

   Morse, J. W.; Mackenzie, F. T. Geochemistry of Sedimentary Carbonates, 1st ed.; Elsevier Science Publishers B.V.: AE Amsterdam, The Netherlands, 2003.

   Google Scholar

   There is no corresponding record for this reference.
10. 10

    Endreß, M.; Bischoff, A. Carbonates in CI chondrites: clues to parent body evolution. Geochim. Cosmochim. Acta 1996, 60, 489– 507,  DOI: 10.1016/0016-7037(95)00399-1

    Google Scholar

    10

    Carbonates in CI chondrites: clues to parent body evolution

    Endress, Magnus; Bischoff, Adolf

    Geochimica et Cosmochimica Acta (1996), 60 (3), 489-507CODEN: GCACAK; ISSN:0016-7037. (Elsevier)

    All CI chondrites are regolith breccias consisting of various types of chem. and mineralogically distinct mineral and lithic fragments (or units). In the CI chondrite Ivuna, for example, four different lithol. units were identified and are referred to as lithol. I, II, III, and IV. So far, lithologies III and IV have been identified in Orgueil as well. It appears that at least Ivuna and Orgueil consist of the same basic lithologies in different proportions. Carbonates in CIs occur as individual grains within such lithic units or exist as large fragments between them. Carbonate fragments are remnants of former carbonate veins and, in contrast to individual carbonate grains, are not genetically linked to lithol. units. Four different types of carbonates (dolomite, breunnerite, calcite, siderite) occur in CIs and they constitute, on av., 5 vol% of each studied. In this study, carbonates in the CI chondrites Orgueil, Ivuna, Alais, and Tonk were studied petrog., mineralogically, and chem. The results clearly indicate that, in contrast to most previous studies, compositional differences exist between dolomites within and among CI chondrites. From these differences it can be derived that (1) several episodes of alteration occurred on the CI parent body, (2) physicochem. conditions during carbonate formation must have been different among CIs, and (3) CI carbonates obviously were formed at low temps. in equil. with surrounding fluid(s). While local compositional changes in fluid(s) on a micrometer to millimeter scale (as reflected by dolomite compns. within CI chondrites) were most likely controlled by the availability of Ca2+, Mg2+, Fe2+, and esp. Mn2+ ions in the aq. solns., more widespread compositional changes on a meter (or even larger) scale were controlled by variable pH, Eh, CO2 partial pressure, and, esp., temp. conditions (as reflected by the compositional variability of dolomites among CIs).
11. 11

    Johnson, C. A.; Prinz, M. Carbonate compositions in CM and CI chondrites and implications for aqueous alteration. Geochim. Cosmochim. Acta 1993, 57, 2843– 2852,  DOI: 10.1016/0016-7037(93)90393-B

    Google Scholar

    11

    Carbonate compositions in CM and CI chondrites, and implications for aqueous alteration

    Johnson, Craig A.; Prinz, Martin

    Geochimica et Cosmochimica Acta (1993), 57 (12), 2843-52CODEN: GCACAK; ISSN:0016-7037.

    Carbonate minerals in fourteen CM chondrites and two CI chondrites were analyzed by electron microprobe to provide a better understanding of the aq. processes that affected carbonaceous chondrite parent bodies. Calcites in CM chondrites and dolomites and magnesites in CI chondrites display the compns. expected of stable phases formed at low temps. Dolomites in CM chondrites, identified here for the first time in five members of the group, have small amts. of excess Ca which may reflect metastable growth. The distribution of Fe between dolomite and coexisting serpentine differs in the two chondrite groups. If the distributions reflect an approach to chem. equil., then the difference implies higher alteration temps. for the CI group than the CM group in agreement with the results of previously published oxygen isotope thermometry and mineral soly. modeling of the alteration process. Dolomite Fe contents are relatively uniform in the two chondrite groups. Dolomite Mn contents, by contrast, vary widely. The variations may reflect transport-controlled copptn. of Mn resulting from a heterogeneous distribution of the element in the anhyd. precursor material. If this interpretation is correct, then the altering fluids were essentially immobile while hydration reactions proceeded on the meteorite parent bodies. The near closed-system character of the alteration process, long known from bulk chem. analyses of the meteorites, is a direct consequence of the limited mobility of dissolved species.
12. 12

    Rubin, A. E.; Trigo-Rodríguez, J. M.; Huber, H.; Wasson, J. T. Progressive aqueous alteration of CM carbonaceous chondrites. Geochim. Cosmochim. Acta 2007, 71, 2361– 2382,  DOI: 10.1016/j.gca.2007.02.008

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    12

    Progressive aqueous alteration of CM carbonaceous chondrites

    Rubin, Alan E.; Trigo-Rodriguez, Josep M.; Huber, Heinz; Wasson, John T.

    Geochimica et Cosmochimica Acta (2007), 71 (9), 2361-2382CODEN: GCACAK; ISSN:0016-7037. (Elsevier)

    CM chondrites are aqueously altered rocks that contain ∼9 wt% H2O+ (i.e., indigenous water) bound in phyllosilicates; also present are clumps of serpentine-tochilinite intergrowths (previously called "poorly characterized phases" or PCP), pentlandite and Ni-bearing pyrrhotite. The authors studied 11 CM chondrites that span the known range from least altered to most altered. They made use of various petrol. properties (many previously identified) that provide information regarding the degree of aq. alteration. There are no known unaltered or slightly altered CM chondrites (e.g., rocks contg. numerous chondrules with primary igneous glass). Some CM properties result from processes assocd. with early and intermediate stages of the alteration sequence (i.e., hydration of matrix, alteration of chondrule glass, and prodn. of large PCP clumps). Other petrol. properties reflect processes active throughout the alteration sequence; these include oxidn. of metallic Fe-Ni, alteration of chondrule phenocrysts, changes in PCP compn. (reflecting an increase in the phyllosilicate/sulfide ratio), and changes in carbonate mineralogy (reflecting the development of dolomite and complex carbonates at the expense of Ca carbonate). On the basis of these parameters, a numerical alteration sequence is proposed for CM chondrites. Because there are no known CM samples that display only incipient alteration, the least altered sample was arbitrarily assigned to subtype 2.6. The most altered CM chondrites, currently classified CM1, are assigned to subtype 2.0. These highly altered rocks have essentially no mafic silicates; they contain chondrule pseudomorphs composed mainly of phyllosilicate. However, their bulk compns. are CM-like, and they are closer in texture to other C2 chondrites than to CI1 chondrites (which lack chondrule pseudomorphs). Using several diagnostic criteria, every CM chondrite of the study is assigned to a petrol. subtype: Que 97990, CM2.6; Murchison, CM2.5; Kivesvaara, CM2.5; Murray, CM2.4/2.5; Y 791198, CM2.4; QUE 99355, CM2.3; Nogoya, CM2.2; Cold Bokkeveld, CM2.2; QUE 93005, CM2.1; LAP 02277, CM2.0; MET 01070, CM2.0. The proposed CM numerical alteration sequence improves upon the existing scheme in that it does not require a complicated algorithm applied to electron-microprobe data to det. the av. matrix phyllosilicate compn. The new sequence is more comprehensive and employs petrol. subtypes that are easier to use and remember than mineralogic alteration index values. New neutron-activation analyses of QUE 97990, QUE 93005, MET 01070, Murchison and Crescent, together with literature data, confirm the compositional uniformity of the CM group; different degrees of alteration among CM chondrites do not lead to resolvable bulk compositional differences. This suggests that the textural differences among individual CM chondrites reflect progressive alteration of similar hypothetical CM3.0 starting materials in different regions of the same parent body, with minimal aq. transport of materials over appreciable (e.g., meters) distances.
13. 13

    Morita, M.; Urashima, S.; Komatani, S.; Yui, H. New analytical method for the evaluation of heterogeneity in cation compositions of dolomites by micro-XRF and Raman spectroscopies. Anal. Sci. 2023, 39, 1279,  DOI: 10.1007/s44211-023-00333-5

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    13

    New analytical method for the evaluation of heterogeneity in cation compositions of dolomites by micro-XRF and Raman spectroscopies

    Morita, Mayu; Urashima, Shu-hei; Tsuchiya, Hayato; Komatani, Shintaro; Yui, Hiroharu

    Analytical Sciences (2023), 39 (8), 1279-1285CODEN: ANSCEN; ISSN:1348-2246. (Springer)

    Abstr.: Dolomite (CaMg(CO3)2) is an abundant carbonate mineral contained in sedimentary rocks and plays significant roles in water and carbon cycle in geo/cosmochem. environments. Since the cation compns. of carbonates are sensitive to the aq. environment where they were pptd. and persisted, quant. anal. of their cation compns. provides valuable information on the aq. environments and their changes. The difficulty for the anal. of natural dolomite is that Mg2+ is continuously substituted by Fe2+ or Mn2+, and hence they sometimes possess micrometer-scale heterogeneity. Such heterogeneity carries quite important information on the gradual changes in aq. environments due to changes in thermodn. conditions and/or aq. chem. compns. In the present study, we explored a new quant. scale to assess such heterogeneity of cation compn. in natural dolomite and ferroan dolomite by combining X-ray fluorescence (XRF) and Raman spectroscopy. While the Fe + Mn content differed spot-by-spot, it was found that the Raman wavenumber and Fe + Mn content linearly correlated with each other. Since the spatial resoln. of micro-Raman spectroscopy is as high as 1μm, it does not require vacuum conditions, and is free from so-called matrix effect faced in other methods utilizing X-Rays and electron beams, the proposed qual. anal. scale can provide a useful tool to assess the cation compns. in dolomites found in nature.
14. 14

    Urashima, S.; Morita, M.; Komatani, S.; Yui, H. Non-destructive estimation of the cation composition of natural carbonates by micro-Raman spectroscopy. Anal. Chim. Acta 2023, 1242, 340798,  DOI: 10.1016/j.aca.2023.340798

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    14

    Non-destructive estimation of the cation composition of natural carbonates by micro-Raman spectroscopy

    Urashima, Shu-hei; Morita, Mayu; Komatani, Shintaro; Yui, Hiroharu

    Analytica Chimica Acta (2023), 1242 (), 340798CODEN: ACACAM; ISSN:0003-2670. (Elsevier B.V.)

    Carbonates play a crucial role in the water and carbon cycles of both geochem. and cosmochem. environments. As carbonates do not exist homogeneously with other minerals in rocks and sands of various sizes, an anal. method that simultaneously satisfies non-destructivity and high spatial resoln. has been desired. Further, the ability of semi-quant. anal. with carbonates-selectivity and without any pre-treatments is added, for its applicability would be extended to remote sensing for deep sea and outer spaces. Here, we focused on the application of micro-Raman spectroscopy, where the vibrational wavenumbers of the translational (T) and librational (L) modes of carbonates are sensitively related to their cation compn. By comparing the semi-quant. information obtained by X-ray fluorescence spectroscopy, it was found that these vibrational wavenumbers are approx. linearly related to the cation compn. Consequently, a conversion matrix was proposed to est. the cation compn. from the T and L mode vibrational wavenumbers. This method is universally applicable to any cation compn. in carbonates, with no background information on the analyte required. To improve the accuracy, conversion matrixes were further optimized to three solid-soln. series of carbonates. It is worth noting that the proposed conversion matrixes are free from matrix effects and do not depend on the total amt. of carbonate in a sample. Therefore, the proposed method provides a useful anal. basis for remote sensing of the cation compn. of carbonates, both in terrestrial and extra-terrestrial environments.
15. 15

    Urashima, S.; Nishioka, T.; Yui, H. Micro-Raman spectroscopic analysis on natural carbonates: linear relations found via biaxial plotting of peak frequencies for cation substituted species. Anal. Sci. 2022, 38, 921– 929,  DOI: 10.1007/s44211-022-00119-1

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    15

    Micro-Raman spectroscopic analysis on natural carbonates: linear relations found via biaxial plotting of peak frequencies for cation substituted species

    Urashima, Shu-hei; Nishioka, Tomoya; Yui, Hiroharu

    Analytical Sciences (2022), 38 (7), 921-929CODEN: ANSCEN; ISSN:1348-2246. (Springer)

    Carbonates are ubiquitous minerals carrying important information on aq. environments where they pptd. on the Earth and space. While their ideal chem. formulas are denoted as simple as MCO3 or M1M2(CO3)2 (M: metal cations), natural carbonates generally form solid-soln. series and their compns. deviate from the ideal formulas. Since their cation compn. due to the substitution provides a sensitive indicator for chem. and thermodn. environments of aq. solns. where they pptd., their compn. anal. has been widely carried out from the environmental/geochem./astrochem. aspects. However, in widely used back-scattered electron and energy dispersion X-Ray analyses, samples should be generally sliced and/or their surface be polished prior to the measurements. For analyzing rare samples with small sizes, such as ones sampled from deep-sea and/or meteorites and asteroids, a non-destructive method without any pretreatments has been strongly desired. Here, a novel anal. method for discriminating various carbonates with Raman micro-spectroscopy is demonstrated, showing that the biaxial plot of the peak frequencies of their lattice modes linearly moves upon partial substitution of the cations. The cation substitution leads to linear movement in the biaxial map, and the slopes of the movement were different for Mg2+-Fe2+ and Mn2+-Fe2+ substitutions. This finding suggests that the micro-Raman anal. would be a non-destructive anal. method for evaluating the relative amt. of Mg2+, Fe2+, and Mn2+ in dolomite-ankerite-kutnohorite solid-soln. series, as well as Mg2+/Fe2+ ratio for magnesite-breunnerite-siderite. It would be helpful for analyzing the present and past terrestrial and cosmochem. environments.
16. 16

    Reeder, R. J.; Dollase, W. A. Structural variation in the dolomite-ankerite solid-solution series; an X-ray, Moessbauer, and TEM study. Am. Mineral. 1989, 74, 1159– 1167

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    16

    Structural variation in the dolomite-ankerite solid-solution series: An x-ray, Moessbauer, and TEM study

    Reeder, Richard J.; Dollase, Wayne A.

    American Mineralogist (1989), 74 (9-10), 1159-67CODEN: AMMIAY; ISSN:0003-004X.

    Structural variation of the solid-soln. series that extends from dolomite to ∼70 mol% CaFe(CO3)2 was examd. by using several techniques. Single-crystal x-ray structure refinements for specimens contg. 22, 50, and 68 mol% CaFe(CO3)2 demonstrate essentially full ordering of Ca and the remaining divalent cations. With increasing Fe content, the (Fe,Mg) octahedron dilates at a normal rate while the Ca octahedron shows a small contraction. Both octahedral sites (‾3 symmetry) are trigonally elongated with this small distortion increasing only very slightly with Fe content. 57Fe Moessbauer spectra of 4 ankerites [contg. 17, 29, 54, and 66 mol% CaFe(CO3)2] show only one moderately split quadrupole doublet with isomer shift of 1.24(1) mm/s. Quadrupole splitting decreases only very slightly from 1.48 to 1.44 mm/s over this range of Fe contents. The Moessbauer data are consistent with Fe2+ in a single, slightly trigonally distorted, octahedral site whose degree of distortion remains very nearly const. with compn. TEM images and electron-diffraction patterns are compatible with homogeneous microstructures in these samples, all of which have stoichiometric Ca contents. Domain microstructures suggested previously are not present. The factors that cause natural and synthetic ankerites with compns. exceeding ≈70 mol% CaFe(CO3)2 to be unstable (relative to calcite + siderite solid solns.) cannot be obviously identified with any structural parameters so far investigated.
17. 17

    Chai, L.; Navrotsky, A. Synthesis, characterization, and energetics of solid solution along the dolomite-ankerite join, and implications for the stability of ordered CaFe(CO₃)₂. Am. Mineral. 1996, 81, 1141– 1147,  DOI: 10.2138/am-1996-9-1012

    Google Scholar

    17

    Synthesis, characterization, and energetics of solid solution along the dolomite-ankerite join, and implications for the stability of ordered CaFe(CO3)2

    Chai, L.; Navrotsky, A.

    American Mineralogist (1996), 81 (9-10), 1141-1147CODEN: AMMIAY; ISSN:0003-004X. (Mineralogical Society of America)

    Samples along the dolomite-ankerite join were synthesized using a piston-cylinder app. and the double-capsule method. Some of the ankerite samples may be disordered. Thermal anal. and X-ray diffraction showed that all samples can be completely decompd. to uniquely defined products under calorimetric conditions (770°C, O2), and a well-constrained thermodn. cycle was developed to det. the enthalpy of formation. The energetics of ordered and disordered ankerite solid solns. were estd. using data from calorimetry, lattice-energy calcns., and phase equil. The enthalpies of formation of ordered dolomite and disordered end-member ankerite from binary carbonates, detd. by calorimetry, are -9.29 ± 1.97 and 6.98 ± 2.08 kJ/mol, resp. The enthalpy of formation of ordered ankerite appears to become more endothermic with increasing Fe content, whereas the enthalpy of formation of disordered ankerite becomes more exothermic with increasing Fe content. The enthalpy of disordering in dolomite (approx. 25 kJ/mol) is much larger than that in pure ankerite, CaFe(CO3)2 (approx. 10 kJ/mol), which may explain the nonexistence of ordered CaFe(CO3)2.
18. 18

    Sherman, J. The theoretical derivation of fluorescent X-ray intensities from mixtures. Spectrochim. Acta 1955, 7, 283– 306,  DOI: 10.1016/0371-1951(55)80041-0

    Google Scholar

    18

    The theoretical derivation of fluorescent x-ray intensities from mixtures

    Sherman, Jacob

    Spectrochimica Acta (1955), 7 (), 283-306CODEN: SPACA5; ISSN:0038-6987.

    A mixt. of elements irradiated by a sufficiently energetic x-ray beam absorbs the incident x-rays and reemits other x-rays, the wave lengths of which are characteristic of the elements in the sample, and the intensities of which may be correlated with their concns. The problem is to correlate Ifi, the intensity of the x-ray spectrum emitted by an element of at. no. Zi with c, μ, and τ (concn., absorption coeff., and emission coeff., resp.) of the elements in the sample. The correlation is complicated by the fact that the fluorescent radiation from elements of higher Z will excite addnl. radiation from elements of lower Z. With integral methods, a math. analysis of the absorption-re.ovrddot.emission process yields explicit closed formulas, when the incident beam is monochromatic, for Ifi (c, μ,τ) in terms of logarithms and ψ-functions. A preliminary investigation suggests that the theory of means may offer a theoretical solution when the incident beam is polychromatic. Graphical methods make it possible to invert the formulas and express c in terms of Ifi, which makes chem. analysis possible. The use of a reference sample of known compn. in the same elements as the sample in question makes it possible to derive a close approximation to the chem. analysis when the incident beam is polychromatic. A brief comparison of computed and measured intensities from samples of known compn. shows a good agreement. The report closes with appendixes giving math. details, a numerical table of ψ(x), (0 ≤ x ≤ 1), and the fluorescence yields for some elements.
19. 19

    Shiraiwa, T.; Fujino, N. Theoretical Calculation of Fluorescent X-Ray Intensities in Fluorescent X-Ray Spectrochemical Analysis. Jpn. J. Appl. Phys. 1966, 5, 886,  DOI: 10.1143/JJAP.5.886

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    19

    Theoretical calculation of fluorescent x-ray intensities in fluorescent x-ray spectrochemical analysis

    Shiraiwa, Toshio; Fujino, Nobukatsu

    Japanese Journal of Applied Physics (1966), 5 (10), 886-99CODEN: JJAPA5; ISSN:0021-4922.

    The theoretical formulas of the fluorescent x-ray intensity (the primary, the secondary, and the tertiary fluorescent x-rays) are obtained and actual calcns. are made for Ni-Fe, Fe-Cr, and Ni-Fe-Cr alloys. In the calcn., the continuous intensity distribution of the irradiating x-rays for the wavelength is taken into account. The theoretical results agree with the expts. very well, the deviations being 1% at most; the theoretical estn. of the fluorescent x-ray intensity emitted from samples of various compn. is possible. The matrix effect, absorption effect, and enhancement effect are evaluated from the present theory. In the enhancement effect, secondary fluorescent x-rays are quite significant (for instance, the Cr secondary fluorescent x-rays from Cr 2% and Fe 98% alloy reach the 55% of the Cr primary fluorescent x-rays and they cannot be neglected), but the tertiary fluorescent x-rays are only a few percent. The usual approxn. methods, where the irradiating x-rays are assumed as monochromatic rays and the secondary fluorescent rays are not taken into consideration are also discussed and their meaning is made clear.
20. 20

    Couture, L. Etude des spectres de vibrations de monocristaux ioniques. Ann. Phys. 1947, 12, 5– 94,  DOI: 10.1051/anphys/194711020005

    Google Scholar

    There is no corresponding record for this reference.
21. 21

    White, W. B. The Infrared Spectra of Minerals; Mineralogical Society of Great Britain and Ireland, 1974.

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    There is no corresponding record for this reference.
22. 22

    Rutt, H. N.; Nicola, J. H. Raman spectra of carbonates of calcite structure. J. Phys. C, Solid State Phys. 1974, 7, 4522– 4528,  DOI: 10.1088/0022-3719/7/24/015

    Google Scholar

    22

    Raman spectra of carbonates of calcite structure

    Rutt, H. N.; Nicola, J. H.

    Journal of Physics C: Solid State Physics (1974), 7 (24), 4522-8CODEN: JPSOAW; ISSN:0022-3719.

    Six new Raman spectra of carbonates of calcite structure (D3d6) are presented and compared with the previously reported siderite and calcite spectra. Correction on the assignment of the electronic Raman spectra in siderite was done by this comparative study. In calcite a new line was obsd. and assigned as an Eg + A1g mode. Some samples were prepd. by hydrothermal synthesis and the technique is described.
23. 23

    Rividi, N.; van Zuilen, M.; Philippot, P.; Menez, B.; Godard, G.; Poidatz, E. Calibration of carbonate composition using micro-Raman analysis: application to planetary surface exploration. Astrobiology 2010, 10, 293– 309,  DOI: 10.1089/ast.2009.0388

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    23

    Calibration of Carbonate Composition Using Micro-Raman Analysis: Application to Planetary Surface Exploration

    Rividi, Nicolas; van Zuilen, Mark; Philippot, Pascal; Menez, Benedicte; Godard, Gaston; Poidatz, Emmanuel

    Astrobiology (2010), 10 (3), 293-309CODEN: ASTRC4; ISSN:1531-1074. (Mary Ann Liebert, Inc.)

    Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquant. ests. of solid solns. in the Ca-Mg-Fe(+ Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy anal. was performed on a set of carbonate stds. (calcite, ankerite, dolomite, siderite, and magnesite) of known compn. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solns. display a well-defined pos. correlation (r2 > 0.9) with the Mg# = 100 × Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chem. compn. of carbonates. Raman anal. of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the compn. and structure of carbonates on planetary surfaces.
24. 24

    Spivak, A.; Solopova, N.; Cerantola, V.; Bykova, E.; Zakharchenko, E.; Dubrovinsky, L.; Litvin, Y. Raman study of MgCO3-FeCO3 carbonate solid solution at high pressures up to 55 GPa. Phys. Chem. Miner. 2014, 41, 633– 638,  DOI: 10.1007/s00269-014-0676-y

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    24

    Raman study of MgCO3-FeCO3 carbonate solid solution at high pressures up to 55 GPa

    Spivak, Anna; Solopova, Natalia; Cerantola, Valerio; Bykova, Elena; Zakharchenko, Egor; Dubrovinsky, Leonid; Litvin, Yuriy

    Physics and Chemistry of Minerals (2014), 41 (8), 633-638CODEN: PCMIDU; ISSN:0342-1791. (Springer)

    Magnesite, siderite and ferromagnesites Mg1-xFexCO3 (x = 0.05, 0.09, 0.2, 0.4) were characterized using in situ Raman spectroscopy at high pressures up to 55 GPa. For the Mg-Fe-carbonates, the Raman peak positions of six modes (T, L, ν4, ν1, ν3 and 2ν2) in the dependence of iron content in the carbonates at ambient conditions are presented. High-pressure Raman spectroscopy shows that siderite undergoes a spin transition at ∼40 GPa. The examn. of the solid solns. with compns. Mg0.6Fe0.4CO3, Mg0.8Fe0.2CO3, Mg0.91Fe0.09CO3 and Mg0.95Fe0.05CO3 indicates that with increase in the amt. of the Fe spin transition pressure increases up to ∼45 GPa.
25. 25

    Herman, R. G.; Bogdan, C. E.; Sommer, A. J.; Simpson, D. R. Discrimination among Carbonate Minerals by Raman Spectroscopy Using the Laser Microprobe. Appl. Spectrosc. 1987, 41, 437– 440,  DOI: 10.1366/0003702874448841

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    25

    Discrimination among carbonate minerals by Raman spectroscopy using the laser microprobe

    Herman, Richard G.; Bogdan, Charles E.; Sommer, Andre J.; Simpson, Dale R.

    Applied Spectroscopy (1987), 41 (3), 437-40CODEN: APSPA4; ISSN:0003-7028.

    Raman spectra was used to distinguish the individual carbonate minerals belonging to the calcite, dolomite, and aragonite [14791-73-2] structural groups. When the in situ laser microprobe technique is used, the particle-size effects do not hinder the mineral identification and a high precision in line position is achieved. Spectra can be obtained from samples in any form and provide rapid, nondestructive analyses on a microscopic scale of the hard-to-discriminate carbonate minerals.
26. 26

    Dufresne, W. J. B.; Rufledt, C. J.; Marshall, C. P. Raman spectroscopy of the eight natural carbonate minerals of calcite structure. J. Raman Spectrosc. 2018, 49, 1999– 2007,  DOI: 10.1002/jrs.5481

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    26

    Raman spectroscopy of the eight natural carbonate minerals of calcite structure

    Dufresne, William J. B.; Rufledt, Carson J.; Marshall, Craig P.

    Journal of Raman Spectroscopy (2018), 49 (12), 1999-2007CODEN: JRSPAF; ISSN:0377-0486. (John Wiley & Sons Ltd.)

    To date, only five natural carbonate minerals of calcite structure have been studied by Raman spectroscopy. These include calcite (CaCO3), magnesite (MgCO3), siderite (FeCO3), smithsonite (ZnCO3), and rhodochrosite (MnCO3). Thus far, only synthetic compds. of otavite (CdCO3), spherocobaltite (CoCO3), and gaspeite (NiCO3) have been investigated by Raman spectroscopy. However, the Raman spectra of natural otavite, spherocobaltite, and gaspeite have yet to be interpreted and compared with the Raman spectra of the other five natural carbonate minerals of calcite structure. This work has been undertaken to fill this gap and provide a comparison and interpretation of Raman spectra representative of all the eight natural carbonate minerals of calcite structure. The data here show that the carbonate Eg (T) phonon shifts are due to influences from the nearest neighbor distance; i.e., M-O, and different ionic radii of the divalent metal cation, as shown graphically by a strong correlation (r2 = 0.87 and 0.91, resp.). Using this graphical approach, we have developed a Raman spectroscopic model based on the equation, y = -2.067x + 356.2 (±5 pm) to calc. the ionic radii of the divalent metal cation present within the mineral and hence affording the identification and discrimination of calcite-group minerals based on the band position of the Eg (T) mode.
27. 27

    Kim, Y.; Caumon, M. C.; Barres, O.; Sall, A.; Cauzid, J. Identification and composition of carbonate minerals of the calcite structure by Raman and infrared spectroscopies using portable devices. Spectrochim. Acta, Part A 2021, 261, 119980,  DOI: 10.1016/j.saa.2021.119980

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    27

    Identification and composition of carbonate minerals of the calcite structure by Raman and infrared spectroscopies using portable devices

    Kim, Yonghwi; Caumon, Marie-Camille; Barres, Odile; Sall, Amadou; Cauzid, Jean

    Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (2021), 261 (), 119980CODEN: SAMCAS; ISSN:1386-1425. (Elsevier B.V.)

    A portable Raman device with a 532 nm excitation laser and a portable IR spectrometer with ATR (Attenuated Total Reflection) mode were used to analyze the spectral features assocd. with the identification and compositional variation of Ca-Mg-Fe-Mn natural carbonate minerals with a calcite structure (calcite, ankerite, dolomite, siderite, rhodochrosite, and magnesite). A systematic study of the variations of the peak positions with various compositional ratios was carried out. Most of the band positions were shifted to lower wavenumbers with increasing ionic radius or at. mass of the divalent cations but the band of the translational lattice (T) mode in Raman and the sym. bending (ν4) band in the mid-IR were the most sensitive. Therefore, the elemental variation of the Ca-Mg-Fe-Mn ratio in this carbonate series can be estd. from Raman and IR band positions from spectra acquired with portable spectrometers.
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    Nakamura, T.; Matsumoto, M.; Amano, K.; Enokido, Y.; Zolensky, M. E.; Mikouchi, T.; Genda, H.; Tanaka, S.; Zolotov, M. Y.; Kurosawa, K. Formation and evolution of carbonaceous asteroid Ryugu: Direct evidence from returned samples. Science 2023, 379, eabn8671  DOI: 10.1126/science.abn8671

    Google Scholar

    There is no corresponding record for this reference.
29. 29

    Nakato, A.; Inada, S.; Furuya, S.; Nishimura, M.; Yada, T.; Abe, M.; Usui, T.; Yoshida, H.; Mikouchi, T.; Sakamoto, K.; Yano, H.; Miura, Y. N.; Takano, Y.; Yamanouchi, S.; Okazaki, R.; Sawada, H.; Tachibana, S. Ryugu particles found outside the hayabusa2 sample container. Geochem. J. 2022, 56, 197– 222,  DOI: 10.2343/geochemj.GJ22017

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    29

    Ryugu particles found outside the Hayabusa2 sample container

    Nakato, Aiko; Inada, Shiori; Furuya, Shizuho; Nishimura, Masahiro; Yada, Toru; Abe, Masanao; Usui, Tomohiro; Yoshida, Hideto; Mikouchi, Takashi; Sakamoto, Kanako; Yano, Hajime; Miura, Yayoi N.; Takano, Yoshinori; Yamanouchi, Shinji; Okazaki, Ryuji; Sawada, Hirotaka; Tachibana, Shogo

    Geochemical Journal (2022), 56 (6), 197-222CODEN: GEJOBE; ISSN:0016-7002. (Terra Scientific Publishing Co.)

    The Hayabusa2 spacecraft explored C-type near-Earth asteroid (162173) Ryugu and returned asteroidal materials, collected during two touchdown operations, to the Earth as the first sample from carbonaceous-type asteroid. The sample container, in which ∼5 g of Ryugu sample was enclosed, was safely opened in the clean chamber system with no severe exposure to the terrestrial atm. In the course of prepn. operation of the sample container, two dark-colored millimeter- to sub-millimeter-sized particles were found outside the sealing part of the sample container. Because they look similar to the Ryugu particles inside the sample container, the particles were named as Q particles (Q from questionable). In this study, we investigated Q particles (Q001 and Q002) mineralogically and petrog. to compare them with potential contaminants (the ablator material of the reentry capsule and fine sand particles at the capsule landing site), Ryugu sample, and CI chondrites. The Q particles show close resemblance to Ryugu sample and CI chondrites, but have no evidence of terrestrial weathering that CI chondrites experienced. We therefore conclude that the Q particles are originated from Ryugu and were expelled from the sample catcher (sample storage canister) in space prior to the enclosure operation of the sample catcher in the sample container. The most likely scenario is that the Q particles escaped from the sample catcher during the retrieval of the sample collection reflector, which was the necessary operation for the sample container closing.