Workshop on Modern Analytical Methods Applied to Earth, Planetary and Material Sciences II

Program and Abstract Volume

LPI Contribution No. 2021

November 10, 2017 • Budapest, Hungary

Institutional Support

Lunar and Planetary Institute Universities Space Research Association Wigner Research Centre for Physics of the Hungarian Academy of Sciences

Conveners

Timothy Jull University of Arizona Arnold Gucsik Wigner Research Centre for Physics of the Hungarian Academy of Sciences

Scientific Organizing Committee

Timothy Jull University of Arizona Arnold Gucsik Wigner Research Centre for Physics of the Hungarian Academy of Sciences Miklós Veres Wigner Research Centre for Physics of the Hungarian Academy of Sciences

Local Organizing Committee

Arnold Gucsik Wigner Research Centre for Physics of the Hungarian Academy of Sciences Kozmáné Blazsik Valéria Wigner Research Centre for Physics of the Hungarian Academy of Sciences Kerekes Attila Wigner Research Centre for Physics of the Hungarian Academy of Sciences Miklós Veres Wigner Research Centre for Physics of the Hungarian Academy of Sciences

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LPI Contribution No. 2021

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Author A. B. (2017) Title of abstract. In Workshop on Modern Analytical Methods Applied to Earth, Planetary and Material Sciences II, p. XX. LPI Contribution No. 2021, Lunar and Planetary Institute, Houston.

ISSN No. 0161-5297 Preface

This volume contains abstracts that have been accepted for presentation at the Workshop on Modern Analytical Methods Applied to Earth, Planetary and Material Sciences II, November 10, 2017, Budapest, Hungary.

Administration and publications support for this meeting were provided by the staff of the Meeting and Publication Services Department at the Lunar and Planetary Institute.

Contents

Program ...... vii

Planetary Surface Measuring Arrangement According to the Principles of the Onsager Matrix Transports: Complexity and Integrated Simultaneous Sensor Cell-System Sz. Bérczi, P. G. Vizi, Gy. Hudoba, I. Schiller, A. Róka, and I. Gyollai ...... 1

Data Analysis and Simulation of Plasma Flow Vortices in the Magnetotail K. Chargazia, O. Kharshiladze, G. Zimbardo, and J. Rogava ...... 3

On the Mg/Fe Ratio in Silicate Minerals in the Circumstellar Environments I. The Mg/Fe Ratio in Silicate Mineral Constituents of the Kaba Meteorite P. Futó ...... 4

Radiolysis of Murchison Samples — A Photoionization Reflectron Time-of-Flight Study S. Góbi, R. Frigge, M. J. Abplanalp, J. Gillis-Davis, and R. I. Kaiser ...... 6

A Metallographic Study of the Meteorites: Capabilities of EBSD Method V. I. Grokhovsky, K. A. Badekha, E. V. Brusnitsyna, R. F. Muftakhetdinova, and G. A. Yakovlev ...... 8

In-Situ Cathodoluminescence Microscopy and Spectroscopy for the Robotic Missions on Mars: A Review A. Gucsik ...... 10

Space Weathering of Asteroid Itokawa: Micro-Raman Spectroscopy of a Plagioclase Particle from the Hayabusa-1 Sample Return Mission A. Gucsik, H. Nishido, K. Ninagawa, T. Nakmura, and A. Tsuchiyama ...... 12

Characterization of the Ground Paprika Samples Using Raman Spectroscopy A. Gucsik, M. Veres, L. Himics, and I. Rigó ...... 13

IR-Raman Correlation of Shocked Minerals in Csátalja Meteorite — Clues for Shock Stages I. Gyollai, A. Kereszturi, K. Fintor, Zs. Kereszty, M. Szabo, and H. Walter ...... 14

Biosignatures in the Recrystallized Shock Melt Pocket of ALH-77005 Shergottite — Clues to Martian Life I. Gyollai, M. Polgári, Sz. Bérczi, A. Gucsik, and E. Pál-Molnár ...... 16

Terrestrial Ages of Meteorites Determined by 14C and 14C/10Be Using Accelerator Mass Spectrometry A. J. T. Jull, I. Kontul, E. R. Creager, L. Cheng, A. Gucsik, M. Molnar, R. Janovics, and P. P. Povinec ...... 18

Concept and Breadboard of the Planetary Borehole-Wall Imager A. Kereszturi, L. Duvet, Gy. Grof, A. Gyenis, T. Gyenis, B. Kovacs, and Gy. Maros ...... 20

Fe2+ Partitioning Between the M1 and M2 Sites in Silicate Phases from Some Stony and Stony- Iron Meteorites Studied Using X-Ray Diffraction and Mössbauer Spectroscopy A. A. Maksimova, A. V. Chukin, E. V. Petrova, and M. I. Oshtrakh ...... 21

Using the Gas Ion Source Coupled to a MICADAS 200kV AMS for 14C Measurements on Very Small Samples: From Meteorites to Tree Rings M. Molnar, A. J. T. Jull, I. Major, K. Hubay, and R. Janovics ...... 23 Application of Image Analysis in Optical Microscopy of Ordinary Chondrites E. V. Petrova, M. S. Petrov, and V. I. Grokhovsky ...... 25

Complex Organics in the Icy Bodies in Planetary Systems — Accepted Notions and New Ideas I. Simonia and D. P. Cruikshank ...... 26

Luminescence of Cometary Substance I. Simonia and A. Gucsik ...... 28

Mean Atomic Weight of Stubenberg Meteorite M. Szurgot ...... 30

Uncompressed Density of the Moon, Lunar Mantle and Core M. Szurgot ...... 32

Streaming Swarm of Nano Space Probes for Modern Analytical Methods Applied to Planetary Science P. G. Vizi, A. F. Horvath, and Sz. Berczi ...... 34

Modern Analytical Methods II 2017 vii

Program

Friday, November 10, 2017 MORNING SESSION 10:00 a.m.

Chairs: Timothy Jull Akos Kereszturi

10:00 a.m. Gucsik A. * Nishido H. Ninagawa K. Nakmura T. Tsuchiyama A. Space Weathering of Asteroid Itokawa: Micro-Raman Spectroscopy of a Plagioclase Particle from the Hayabusa-1 Sample Return Mission [#6013] This study describes Raman spectral properties of plagioclase from asteroid Itokawa that can be used for the astromineralogical study of the space weathering effects in asteroids.

10:15 a.m. Gyollai I. * Kereszturi A. Fintor K. Kereszty Zs. Szabo M. Walter H. IR-Raman Correlation of Shocked Minerals in Csátalja Meteorite — Clues for Shock Stages [#6004] The analyzed meteorite called Csátalja is an H chondrite (H4, S2, W2), and based on the differences between its certain parts, probably it is a breccia. The aim of methodological testing is characterizing shock deformation and heterogeneity.

10:30 a.m. Simonia I. * Gucsik A. Luminescence of Cometary Substance [#6016] We studied possible photoluminescence and cathodoluminescence of the cometary mineral dust. Obtained results are presented. Different aspects of the problem are discussed.

10:45 a.m. Simonia I. * Cruikshank D. P. Complex Organics in the Icy Bodies in Planetary Systems — Accepted Notions and New Ideas [#6017] We considered physical properties of frozen hydrocarbon substance and refractory organic of icy bodies of the solar system. We proposed main physical properties of potential self-organized substance of icy bodies. Obtained results are presented.

11:00 a.m. Break

11:30 a.m. Gyollai I. * Polgári M. Bérczi Sz. Gucsik A. Pál-Molnár E. Biosignatures in the Recrystallized Shock Melt Pocket of ALH-77005 Shergottite — Clues to Martian Life [#6001] In the spinifex textured, recrystallized shock melt portion in ALH 77005 shergottite mineralized microbially produced texture (MMPT) - in form of pearl necklace-like, vermiform inner signatures - was measured, which we propose to have Martian origin.

11:45 a.m. Gucsik A. * In-Situ Cathodoluminescence Microscopy and Spectroscopy for the Robotic Missions on Mars: A Review [#6019] The purpose of this study is to summarize the potential how to use the Cathodoluminescence microscopy and spectroscopy, which may be applied to the planetary sciences, especially to the robotic explorations on Mars.

12:00 p.m. Jull A. J. T. * Kontul I. Creager E. R. Cheng L. Gucsik A. Molnar M. Janovics R. Povinec P. P. Terrestrial Ages of Meteorites Determined by 14C and 14C/10Be Using Accelerator Mass Spectrometry [#6006] Terrestrial ages of meteorites can be determined from the measurement of the concentration of 14C, 10Be and other radionuclides. We will discuss these applications in this presentation. viii LPI Contribution No. 2021

12:15 p.m. Góbi S. * Frigge R. Abplanalp M. J. Gillis-Davis J. Kaiser R. I. Radiolysis of Murchison Samples — A Photoionization Reflectron Time-of-Flight Study [#6010] Murchison samples were irradiated at 5 K in an ultra-high vacuum simulation chamber. The changes upon irradiation were monitored in situ with FT-IR, UV-VIS, and EI-QMS, whereas the subliming volatile products were detected by the PI-ReTOF-MS method.

12:30 p.m. Lunch

Modern Analytical Methods II 2017 ix

Friday, November 10, 2017 AFTERNOON SESSION 2:00 p.m.

Chairs: Arnold Gucsik Michael Oshtrakh

2:00 p.m. Molnar M. * Jull A. J. T. Major I. Hubay K. Janovics R. Using the Gas Ion Source Coupled to a MICADAS 200kV AMS for 14C Measurements on Very Small Samples: From Meteorites to Tree Rings [#6018] We summarize the use of a gas ion source for analysis of samples down to 10 μg C using a small AMS system.

2:15 p.m. Maksimova A. A. Chukin A. V. Petrova E. V. Oshtrakh M. I. * Fe2+ Partitioning Between the M1 and M2 Sites in Silicate Phases from Some Stony and Stony-Iron Meteorites Studied Using X-Ray Diffraction and Mössbauer Spectroscopy [#6009] In this work we present the results of our approach to estimate the Fe2+ cations distribution between two nonequivalent sites in silicates using XRD and Mössbauer spectroscopy with a high velocity resolution.

2:30 p.m. Chargazia K. * Kharshiladze O. Zimbardo G. Rogava J. Data Analysis and Simulation of Plasma Flow Vortices in the Magnetotail [#6015] Ulf electromagnetic planetary waves can self-organize into vortex structures. They are often detected in the plasma media. Large scale vortices may correspond to the injection scale of turbulence.

2:45 p.m. Vizi P. G. * Horvath A. F. Berczi Sz. Streaming Swarm of Nano Space Probes for Modern Analytical Methods Applied to Planetary Science [#6012] Streaming swarms gives possibilities to collect data from big fields in one time. The whole streaming fleet possible to behave like one big organization and can be realized as a planetary mission solution with stream type analytical methods.

3:00 p.m. Kereszturi A. * Duvet L. Grof Gy. Gyenis A. Gyenis T. Kovacs B. Maros Gy. Concept and Breadboard of the Planetary Borehole-Wall Imager [#6002] A subsurface imaging device to scan the internal wall of drilled boreholes is being developed to support the Earth analogue tests of ExoMars Rover’s drilling activity.

3:15 p.m. Gucsik A. * Veres M. Himics L. Rigó I. Characterization of the Ground Paprika Samples Using Raman Spectroscopy [#6020] Micro-Raman spectroscopy as a powerful technique can be used in food industry, especially in the ground pepper or paprika characterization in order to deter-mine the paprika sample’s origin as well as their quality.

3:30 p.m. Break x LPI Contribution No. 2021

Friday, November 10, 2017 POSTER SESSION 4:00 p.m.

Szurgot M. Uncompressed Density of the Moon, Lunar Mantle and Core [#6007] Relationship between density and Fe/Si ratio was applied to verify Fe/Si atomic ratios, and uncompressed density of the Moon, lunar mantle and core.

Bérczi Sz. Vizi P. G. Hudoba Gy. Schiller I. Róka A. Gyollai I. Planetary Surface Measuring Arrangement According to the Principles of the Onsager Matrix Transports: Complexity and Integrated Simultaneous Sensor Cell-System [#6008] A cell mosaic arrangement (an array) is constructed according to Onsager matrix type sensor units (for 3 of μ1-μ2, T1-T2, P1-P2, U1-U2) for a complex simultaneous measuring of local field parameters at the locality of space probe model Hunveyor.

Futó P. On the Mg/Fe Ratio in Silicate Minerals in the Circumstellar Environments I. The Mg/Fe Ratio in Silicate Mineral Constituents of the Kaba Meteorite [#6003] The moderately high ratio of Mg in the silicates of the solar environment indicates that Mg-rich silicates are likely to be frequent in the interstellar medium and the circumstellar environments in case of chondritic-like composition.

Szurgot M. Mean Atomic Weight of Stubenberg Meteorite [#6005] Mean atomic weight (Amean=23.65), mean atomic number (Zmean=11.70), Amean/Zmean=2.021), and Fe/Si atomic ratio (0.551) of Stubenberg (LL6) meteorite were determined and analysed, and grain density (3.51 ± 0.02 g/cm3) of Stubenberg predicted.

Grokhovsky V. I. Badekha K. A. Brusnitsyna E. V. Muftakhetdinova R. F. Yakovlev G. A. A Metallographic Study of the Meteorites: Capabilities of EBSD Method [#6011] We present the history and results of a metallographic study of meteoritic metal by EBSD method.

Petrova E. V. Petrov M. S. Grokhovsky V. I. Application of Image Analysis in Optical Microscopy of Ordinary Chondrites [#6014] Application of image analysis systems give additional possibilities for estimation, calculation and comparison of optical microscopic images. Different parameters of the texture (phase distribution, porosity, grains shape parameters) can be obtained.

Modern Analytical Methods II 2017 1

PLANETARY SURFACE MEASURING ARRANGEMENT ACCORDING TO THE PRINCIPLES OF THE ONSAGER MATRIX TRANSPORTS: COMPLEXITY AND INTEGRATED SIMULTANEOUS SENSOR CELL-SYSTEM. Sz. Bérczi1, P.G. Vizi2, Gy. Hudoba3, I. Schiller1, A. Róka4, I. Gyollai1, 1Eötvös University, Inst. of Physics, Dept. Materials Physics, Cosmic Materials Space. Res. Group. H-1117, Budapest, Pázmány P. s. 1/a. Hun- gary ([email protected]), 2MTA Wigner RCP H-1121 BUDAPEST, Konkoly Thege M. út 29-33. ([email protected]) 3Óbuda University, Alba Regia Univ. Center, H-6000, Székesfehérvár, Budai út 45, Hungary ([email protected]), 4Eötvös University, Dept. Physical-Chemistry. H-1117, Budapest, Pázmány P. s. 1/a. Hungary, ([email protected]),

Introduction: In a wetland or a field on Earth we can identify soil characteristics by the observation of indicator plants (for example they refer to the pH). This plant indicator arrangement gives a cellular mosaic overview of the surface soils. A similar program should be realized by recognizing a Bell Lab. advertisement from the early 80’s: how to measure simultaneously the compositional gradient and the thermal gradient? [1] (Fig. 1.) (Our program is part of the syn- thesis project in teaching planetary and environmental science at Eötvös University.)

Fig. 2. The Onsager matrix of generalized physical „tensions” (thermodynamical drives, rows) and the transported streams of extensive physical quantities (columns). The Bell Lab. experiment of Fig. 1. realized a representation of the yellow row temperature gradient of T1- T2, and the green row of chemical potential gradient µ -µ , while the image observed in the microscope was 1 2 the visible product of diffusion effect boundaries Fig. 1. The advertisement of Bell Lab (in the 80’s) (phases, pink) by the heat gradient (orange). shows the synchronous measurement of chemical transport and heat transport with a gradient arrangement. The result is a c-T diagram for two compounds while they were in diffusion in the fine capillary cell.

The Onsager principle of transports in a matrix: In Onsager matrix the generalized „strains” (repre- sented by the strains of intensive physical parameters - where pressure difference: P1-P2, chemical potential difference: µ1-µ2, temperature difference: T1-T2, etc. - are triggering the transporting the streams of the extensive physical quantities of volume, of mass, and of energy etc. If a cell mosaic arrangement – an array – is constructed according to such Bell Lab. type sensor units (not only for µ1-µ2, T1-T2, but for P1-P2, U1-U2 etc.) a complex simultaneous measuring array can measure the local field parameters. The benefit of such a system is that physical parameter mapping can be Fig. 3. One measuring unit cell, in a quadrangle cell carried out by one complex measuring unit. representation, with 2 streams and 4 sensors. From our point of view this measuring arrangement gives a representation of the Onsager matrix in a 2x2 form of [2]. (Fig. 2.) 2 LPI Contribution No. 2021

not for a single parameter, but for the observation of joint changes of several parameters.

µ flux d µ /dt dn/dt dm/dt chemical potential FICK’S µ1--µ2 DIFFUSION interdiffusion interdiffusion for µ chemical potential FICK’S n1--n2 interdiffusion DIFFUSION interdiffusion for n chemical potential FICK’S Fig. 4. One measuring unit cell, in a hexagonal cell- m1--m2 interdiffusion interdiffusion DIFFUSION mosaic representation, with 3 streams and 6 sensors. for m The transported streams of extensive physical quantities are (columns). Fig. 5. Interdiffusion transports form a sub-array in the Fick law element of Fig. 2. matrix. The von-Neumann principle of cellular auto- mata [3]: a mosaic system array: This Onsager-array is a future development for The sensorial unit cells can be realized in an array Hunveyor, Husar educational space probe models of of square prisms with two types of transport acting the Competition of Applied Engineering Sciences between the two parallel faces (Fig. 3.) or in a hexago- (magyarokamarson.hu) [5]. After earlier single pH [6], nal prisms form with three types of transport acting single optical heating for gases [7], magnetic carpet [8] between the three parallel faces (Fig. 4.), while the top experiments it applies joint measuring systems [9]. and bottom surface is used for the sensors which ob- References: [1] Bérczi Sz. (1985): Anyagtechnológia serve the streams running between the parallel sides. I. (Technology of Materials) Lecture Note Ser. Eötvös Measurements [4]: The system array can be used: University (J3-1333) Tankönyvk. Budapest [2] Sz. Bér- (1) - Invasive mode (interfering signal is applied) (2) - czi, et al. (2009): Systems Woven by Two Flux- Passive (non-invasive) mode (no interfering signal is Subsystems: One of them is Planetary. Concise Atlas of applied) (3) - Combined mode: passive mode and ac- the Solar System (12): 40. LPSC, #1256, LPI, Houston tive (invasive) signal combined. (transport between (CD-ROM). [3] Sz. Bérczi, S. Józsa, S. Kabai, I. Kubo- side walls through the adjacent cells). A special case to vics, Z. Puskás, Gy. Szakmány. (1999): NASA Lunar measure interdiffusion (cross-diffusion) matrix for 3 Sample Set: Complex Concepts in Petrography and Plane- chemical compounds simultaneously (combined layout tary Petrology. 30. LPSC, #1038, LPI, Houston (CD- with quadratic or hexagonal units) (Fig. 5.). ROM) [4] Bérczi Sz., A. Róka, Z. Nyíri, T. Varga, A. Sz. Fabriczy, Cs. Peták, Gy. Hudoba, S. Hegyi, A. Lang, I. Planetary soil measuring mode: the cell-mosaic Gyollai, A. Gucsik (2014): Chemistry Experiments - for system is placed on the soil surface. Comparative Analyses for Demonstrating Environmental Bottom open, top closed version: the cell-walls Differences on Venus, Earth, Mars and Titan, - Built on form a grid (a frame), and the soil fulfills the cells, Hunveyor and Husar. Workshop: Modern Anal. Methods, which are open at bottom, but closed on the top (on the Earth and Planetary Sci., Sopron, Hungary. LPI Contrib. top wall are the sensors) (Fig. 4.) No. 1821, #4003.; [5] Sipos, A.; Vizi, P. G. 47th Lunar Example situations: The system observes the inter- and Planetary Science Conference, (No 1903), p.2098 diffusion transports (cross-diffusions of the Fick matrix http://www.hou.usra.edu/meetings/lpsc2016/eposter/2098.pdf; element in the Onsager matrix). One sensor array ob- [6] Lang Á., et al. (2009): Chemistry Experiment Measur- serves the pH-changes, other for the optical changes in ing (Ph) of the Planetary Soil by The Husar-5, 40. LPSC soil (or fluid) units. #1325, LPI, Houston (CD-ROM). [7] Lang Á., et al. Conclusion: The simultaneous measuring with ap- (2010): Optical-Chemistry Experiment Measuring Gases plication of the “Onsager matrix array” (square or hex- Liberated by Heating from the “Planetary” Soil. 41. LPSC agonal cell-mosaic arrangement) can encourage stu- #2139, LPI, Houston, [8] Magyar, I. et al (2008): Con- dents to develop new strategy in data collecting in struction of Hunveyor-9 and experiments with its mag- planetary missions. Application of this construction netic carpet observing dust mixtures at Eötvös High School, Tata. Hungary. 39. LPSC, #1361. [9] N. Kocher- method in education of space and planetary science ginsky, M. Gruebele (2016): Mechanical approach to chemi- gives challenges to the students for planning measure- cal transport. PNAS, 113(40), 11116-11121. ments. In this way measurements are not alone, done

Modern Analytical Methods II 2017 3

DATA ANALYSIS AND SIMULATION OF PLASMA FLOW VORTICES IN THE MAGNETOTAIL. Kh. Chargazia1, O. Kharshiladze2, G. Zimbardo3, J, Rogava4, 1Iv. Javakhishvili Tbilisi State University, Chavchavadze ave 2., 0128 Tbilisi, Georgia, 2Iv. Javakhishvili Tbilisi State University, Chavchavadze ave 2., 0128 Tbilisi, Georgia, 3Universita’ della Calabria, 87036 Rende (CS), Italy, 4Iv. Javakhishvili Tbilisi State University, Chavchavadze ave 2., 0128 Tbilisi, Georgia,

Introduction: Ulf electromagnetic planetary waves [5] Aburjania G., Khantadze A., Kharshiladze O. Nonlinear can self-organize into vortex structures (monopole, planetary electromagnetic vortex structures in F region of the dipole or into vortex chains). They are often detected ionosphere. Plasma Phys. Rep. V. 28, N 7, P. 633-638. 2002. in the plasma media, for instance in the magnetosheath, in the magnetotail and in the ionosphere. Large scale vortices may correspond to the injection scale of turbulence, so that understanding their origin is important for understanding the energy transfer processes in the geospace environment. In a recent work, the THEMIS mission has detected vortices in the magnetotail in association with the strong velocity shear of a substorm plasma flow (Keiling et al., J. Geophys. Res., 114, A00C22 (2009), doi:10.1029/2009JA014114), which have conjugate vortices in the ionosphere. By analyzing the THEMIS data for that event, we find that several vortices can be detected together with the main one, and that the vortices indeed constitute a vortex chain. The study is carried out by analyzing both the velocity and the magnetic field measurements for spacecraft C and D, and by obtaining the corresponding hodograms. It is found that both monopolar and bipolar vortices may be present in the magnetotail. The comparison of observations with numerical simulations of vortex formation in sheared flows is also discussed.

References: [1] Keiling, A., Angelopoulos, V., Runov, A., Weygand, J., Apatenkov, S. V., Mende, S., McFadden, J., Larson, D., Amm, O., Glassmeier, K.-H., and Auster, H. U.: Substorm current wedge driven by plasma flow vortices: THEMIS observations, J. Geophys. Res., 114, A00C22, doi:10.1029/2009JA014114, 2009. [2] Baumjohann, W., M. Hesse, S. Kokubun, T. Mukai, T. Nagai, and A. A. Petrukovich. Substorm dipolarization and recovery, J. Geophys. Res., 104, 24,995–25,000, doi:10.1029/1999JA900282. 1991 [3] Birn, J., J. Raeder, Y. Wang, R. Wolf, and M. Hesse. On the propagation of bubbles in the geomagnetic tail, Ann. Geophys., 22, 1773–1786, doi:10.5194/angeo-22-1773-2004. 2004 [4] Aburjania G. ,Chargazia Kh. Self-organization of ULF large-scale electromagnetic wave structures in E region of the ionopshere at interaction with inhomogeneous zonal winds. Plasma Phys. Rep., V. 37, N 2, P. 199-213. 2011. 4 LPI Contribution No. 2021

ON THE Mg/Fe RATIO IN SILICATE MINERALS IN THE CIRCUMSTELLAR ENVIROMENTS I. THE Mg/Fe RATIO IN SILICATE MINERAL CONSTITUENTS OF THE KABA METEORITE. P. Futó1, 1Uni- versity of Debrecen, Hungary, Department of Mineralogy and Geology, Debrecen, Egyetem tér 1. H-4032, Hungary ([email protected])

Introduction: Some important elements such as O, using the measured concerning data by Gucsik et al. Mg, Si and Fe are the cosmically most important (2013) [6]. mineral-forming elements, which may be the dominant The model composition for the examined sample of planet-building elements for terrestrial planets. The Kaba meteorite: The major components of a typical cosmic silicate mineral grains can be categorized into carbonaceous chondrite are the chondrules, the fine- two main groups: the olivines (Ol) (Mg2xFe2x-2xSiO4 grained matrix of minerals, Ca/Al-rich inclusions where x is between 0 and 1) (forsterite-Mg2SiO4,

fayalite-Fe2SiO4) and the pyroxenes (Px) (MgxFe1-xSiO3 (CAIs) and it may even contain amobeoid olivine ag- where x is between 0 and 1) (enstatite-MgSiO3, gregates (AOA) and isolated grains in the matrix. ferrosilite-FeSiO3). In the interstellar medium (ISM) The examined sample is the Kaba meteorite, which is a and in the protoplanetary disks the silicate minerals less metamorphosed CV3 type carbonaceous chondrite may be present in amorphous and/or in crystalline with a relative large-sized chondrules and it had been forms (that can be classified into two cristallographic systems: rhombic -Ol, Px; and monoclinic structure- undergone on a low-grade thermal metamorphosis. Px) [1]. The purpose of this study is to support that the silicates The detailed compositions and origins of crystalline or in the ISM and PPDs are mostly Mg-rich minerals. The amorphous ferromagnesiosilicates are poorly measure results for given mineral compounds are being understood, up to date. Nevertheless, they are likely analyzed based on the examination of Kaba meteorite. derived from supernovae (SN)-nucleosynthesis and the The chondritic composition of terrestrial-type planets atmosphere of metal-rich asymptotic giant stars (AGB). in the Galaxy have been assumed. It is known that the composition of Earth's crust and The quantitative analyses (Gucsik et al. 2013) for the mantle are dominated by Mg-rich silicates with a rela- minor and major elements of olivine were performed tively low Fe-content. The interstellar silicates are Mg- by wavelength-dispersive spectrometry (WDS) linked rich minerals [2], which are being caused by the cos- to a JEOL JXA-8900R SEM (scanning electron micro- mochemically higher abundance of Mg as opposed to scope). that of Fe. Interestingly, Mg-rich (X=0.01±0.001 at a The selected target minerals for the estimation: The

formulation of Mg(2-2x) Fe2xSiO4) crystalline olivine one of the examined minerals is forsterite (Fo1-1) that grains are being found in the disk of β Pictoris [3]. At can be found in a ~1.3 mm sized porphyritic olivine the same time, Fe-rich crystalline olivine grains (Fe/ chondrule on the analyzed area of A1. Two forsterite [Mg + Fe] ~0.2) are also known in several debris disk mineral components (Fo7-1 and Fo7-2) have been in- [4] and iron-rich olivine has also been found by analyz- tentified in an area of amobeoid olivine aggregates. ing the mineral chemistry of Itokawa dust particles [5]. Chondrule is also known, which contains Fe-rich min- The Mg/Fe ratio in silicates may be an important factor eral phases in the analyzed area of A5. The mineral for the material properties in terrestrial planetary man- texture in the area of complex aggregates contains fay- tles. The examination of Mg/Fe ratio in the meteoritic alitic olivine (Fa9-2) and enstatite (En9-4). materials of Solar-System may provide useful informa- The simple applied method for calculating the Mg/Fe ratio tion, which from we may conclude on the plausible in the mineral constituents of target areas is the com- compositional properties of planet-building silicates in parison for the molar masses of the compound elements other planetary systems. According to a likely scenario, in the oxides (FeO, MgO). the terrestrial-like exoplanets are thought to have been Results: The smallest Mg/Fe ratio is calculated in case accreted from undifferentiated protoplanetary disc the sample of A7-Fo7-2, the highest value has been (PPD) materials similarly to the chondritic meteorites. found for the sample A5-FeO, which composed almost entirely of iron-oxide. Therefore, I presents calculated values for Mg/Fe ratio The Mg/Fe ratio in the most of the examined target based on a composition of a carbonaceous chondrite mineral constituents is moderately high, which corrob- Modern Analytical Methods II 2017 5

oratory data also shows that the silicates in the Solar 1113-1116. [6] Gucsik A. et al. (2013) Meteoritics & enviroment are Mg-rich minerals. This statement may Planet. Sci., 48, 2577-2596. extend to the composition of silicate minerals of the ISM by assuming the chondritic-like compositions in the most of the interstellar and circumstellar enviro- Acknowledgements: The author would like to express ments in the Galaxy. his sincere thanks to Mr. Taro Endo (Department of Biosphere-Geosphere system Science, Okayama Target FeO MgO Mg/Fe University of Science) for the measure results. The area (wt%) (wt%) author is also greatful to Mr. Arnold Gucsik (Wigner Research Center for Physics) for his useful comments A1-Fo1-1 0.3 55 Mg Fe 0.993 0.007 and suggestions during the interpretation of the A5-FeO 97.63 0.28 Mg0.002225Fe0.99775 measured results.

A7-Fo7-1 0.41 55.03 Mg0.9904 Fe0.0096

A7-Fo7-2 2.71 52.58 Mg0.93356Fe0.0664

A9-Fa9-2 68.05 0.26 Mg0.9962Fe0.0038

A9-En9-4 1.21 36.3 Mg0.957Fe0.043

Table 1. The ratio of FeO and MgO compounds (wt%) in the given target areas. The Mg/Fe ratios are also calculated. The utilized concerning data of the elements Fe, Mg and O are taken from www.ptable.com.

Results: The smallest Mg/Fe ratio is calculated in case the sample of A7-Fo7-2, the highest value has been found for the sample A5-FeO, which composed almost entirely of iron-oxide. The Mg/Fe ratio in the most of the examined target mineral constituents is moderately high, which corrob- oratory data also shows that the silicates in the Solar enviroment are Mg-rich minerals (Table 1.) This statement may extend to the composition of silicate minerals of the ISM by assuming the chondritic-like compositions in the most of the interstellar and circumstellar enviroments in the Galaxy.

Summary: The moderately high ratio of Mg in the silicates of the Solar enviroment indicates that Mg-rich silicates might be frequent in the interstellar and the circumstellar enviroments for the case of chondritic composition.

References: [1] Henning T. (2010) Annual Review of Astronomy and Astrophysics, 48, 21-46. [2] Min M. et al. (2007) Astronomy and Astrophysics, 462, 667-676. [3] de Vries B. L. et al. (2012) Nature, 490, 74-76. [4] Olofsson J. et al. (2012) Astronomy and Astrophysics, 542, A90. [5] Nakamura T. et al. (2011) Science, 333, 6 LPI Contribution No. 2021

RADIOLYSIS OF MURCHISON SAMPLES – A PHOTOIONIZATION REFLECTRON TIME-OF- FLIGHT STUDY. S. Góbi1,2, R. Frigge1,2, M. J. Abplanalp1,2, J. Gillis-Davis3, R. I. Kaiser1,2 1 Department of Chemistry, University of Hawai’i at Mānoa, Honolulu, HI 96822, USA, 2 W. M. Keck Re- search Laboratory in Astrochemistry, University of Hawaii, 2545 McCarthy Mall, 96822 HI, USA, 3 Universi- ty of Hawai’i at Mānoa, Hawaii Institute of Geophysics and Planetology, Honolulu, HI 96822, USA, e-mail: [email protected]

Introduction. The carbonaceous chondrite Mur- larger than the penetration depth of the electrons. The chison is one of the most well studied meteorite be- same holds true for the sample irradiated with the CO2 longing to the aqueously altered CM2 group. It is es- laser and in the dual irradiation experiments except pecially of great interest because of its relatively high that a new O–H stretching band can be observed water and organic material content, which has spurred emerging at 3 m in the latter experiment at 150 K. a plethora of analytical works so far. Furthermore, This implies the formation of H2O by the destruction radiolysis studies have also been done in order to bet- of the serpentinite content of the meteorite releasing ter understand the space weathering taking place on the chemically bound water. The UV-VIS spectra bodies with astrophysical relevance. Nevertheless, showed darkening of the sample when irradiated with there is still no comprehensive picture on these pro- the CO2 laser, which is in accordance with previous cesses necessitating the conduction of further experi- experimental results. In the EI-QMS spectra of the ments in this topic. dual irradiated samples, signals at m/z values of 18 Experimental details. Thin films of Murchison and at 44 can be detected during the TPD phase of the meteorite samples were prepared on silver wafers with experiment showing the sublimation events of the H2O 2 an area of roughly 1.9 cm . These were mounted on a and CO2 molecules formed during the irradiation. The cold finger and cooled down to 5.5 ± 0.1 K or 150.0 ± latter species originates from the destruction of the 0.1 K in an ultrahigh vacuum chamber operated at a organic compounds that are abundant constituents of base pressure of roughly 10–10 torr using oil-free tur- the Murchison meteorite. Being the PI-ReTOF-MS bomolecular pumps backed by dry scroll pumps. The technique more sensitive than the other used methods samples were then irradiated for 5 hours (i) with 5 makes it capable to detect molecules sublimed into the keV electrons at a current of 10 A, (ii) with CO2 gas phase even in minor concentrations. This allowed laser at the energy of approximately 8 W cm–2, (iii) for the detection of numerous signals that belong to simultaneously with both radiation sources. During smaller, volatile organic molecules that were produced the irradiation, UV-VIS, FT-IR, and EI-QMS (with an during the radiolysis of the non-volatile organic con- ionization energy of 70 eV) spectra were taken on line tent of the Murchison sample. It is also important to and in situ. Blank experiments were also performed by note that the EI-QMS and PI-ReTOF-MS results of conducting the identical experimental sequence, but the dual radiolysis experiments performed at 5.5 and without irradiating the sample. Then, the samples 150 K differ from each other in their signal strengths were kept isothermally for 1 additional hour before only, i.e. in the concentration of the species produced. being heated to 300 K at a rate of 1.0 K min–1, while Namely, the observed formation rate of the products monitoring the volatile products subliming into the are higher at higher temperatures in general. gas phase (temperature programmed desorption or Conclusion, future goals. Radiolysis of Murchison TPD phase). This was done via the EI-QMS and by samples were carried out using different radiation the help of the state-of-the-art single-photon photoion- sources while monitored online and in situ by means ization reflectron time-of-flight mass spectrometric of FT-IR, EI-QMS, and UV-VIS; whereas EI-QMS (PI-ReTOF-MS) methods. The energy of the VUV and PI-ReTOF-MS spectra were collected during the photons used for photoionization were 10.49 eV. The TPD phase. The results of the dual irradiated samples samples were also analyzed by electron microscopy ex imply the production of H2O originating from the re- situ after the experiments. lease of chemically bound water. Besides, formation of Evaluation of results. No observable decrease can CO2 and small volatile organic compounds can also be be identified in the FT-IR spectrum of the electron observed caused by the destruction of the carbona- irradiated samples; neither a decrease in the silicate ceous material indigenous to the Murchison sample. bands at 10 m nor the appearance of a new absorp- Moreover, the electron microscopy confirmed that the tion band in the examined MIR region. The former CO2 laser heating causes the sample to melt and evap- finding can be explained by the thickness of the sam- orate on its surface. Future studies investigating mete- ple, being approximately two orders of magnitude orite samples other than Murchison are required to be Modern Analytical Methods II 2017 7

able to gain a comprehensive picture on the space weathering processes occurring on the surface of bodies with astrophysical relevance. Acknowledgment. The authors acknowledge the support by the National Aeronautics and Space Ad- ministration under Grant NNX14AG39G.

8 LPI Contribution No. 2021

A METALLOGRAPHIC STUDY OF THE METEORITES: CAPABILITIES OF EBSD METHOD. V. I. Grokhovsky, K. A. Badekha, E. V. Brusnitsyna, R. F. Muftakhetdinova, G. A. Yakovlev. Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002, Russian Federation. E-mail: [email protected].

Introduction: A metallographic study of the mete- indicated that roaldite was formed after complete pre- orites structure is useful method of analysis for classifi- cipitation of rhabdite [3]. cation and the cooling rates estimation of an extrater- Haxonite was found in taenite area of the metal restrial metal both in the α→γ transformation tempera- grain near taenite/kamacite boundary in Chelybinsk ture range and at the spinodal decomposition tempera- LL5 meteorite. EBSD analysis confirmed that light ture. Often, new analytical capabilities are tested using particles have taenite lattice and dark matrix have hax- meteoritic metal. Researchers began to use many new onite lattice (fig.1). Earlier, the cubic carbide in iron techniques over the last quarter of a century: FIB, meteorites has been well described [4]. Previously [5], computer tomography, nanoindenting, EBSD, image it was suggested, that graphite and carbides precipitat- analysis. EBSD method provides wide possibilities in ed after finish of crystallization. Carbides formed at acquiring local crystallographic information. Metallo- low temperature after kamacite and schreibersite. In graphic studies of extraterrestrial metal at the Ural our section graphite was not found. Federal University were carried out since 1971. First works described metallic phases in lunar soil. Besides morphology and local chemical composition, one should have diffraction data for good phase identification. Registration of Kossel lines (X-ray diffraction) and Kikuchi lines can provide such information. It was Kossel technique that UrFU’s researchers applied for determination of kamacite lattice parameters in particles of lunar soil from Luna 16 and Luna 20. The first demonstrations of EBSD on meteorites were given in works [1,2]. Here, examples of phase and orientation EBSD analysis for the identification of phases and structural transformations in a meteorite metal are presented. Experimental: Samples were polished using stand- ard metallographic polishing procedure followed by polishing using 0,04μm SiO2 for 2 hr. EBSD studies Fig. 1. Haxonite (H) assosiasted with taenite (T) in were accomplished using FE-SEM SIGMA VP and Chelyabinsk LL5 meteorite. SEM JEOL JSM-6490LV with EDS and EBSD units. Additionally, program CaRIne Crystallography 3.1 for Also, this technique allowed to suggest the origin of obtaining stereographic projec-tions and modeling the the Schlieren bands in ataxites. Schlieren effect in the crystals structure has been used. ataxites was known for a long time, but the origin of Meteorites of various types were investigated: this bands was not clear. Each investigated ataxite Chelyabinsk (LL5), Sikhote-Alin (IIAB), Chinga (Iron- demonstrate a set of three main bcc orientations which ung), Gebel Kamil (Iron-ung), Hoba (IVB), Iquique retained in the neighboring Schlieren bands while the (IVB), Cape of Good Hope (IVB), Bilibino (IIAB), dominant bcc orientation in these bands was different. Aliskerovo (IIIAB). The dominant bcc orientations in the Schlieren bands The EBSD method has a wide range of applications coincided with the orientation of kamacite spindles. for solving problems in the study of various minerals of Therefore, the Schlieren bands were drawn out along meteoritic matter. For example, roaldite (Fe, Ni)4N the Widmanshtätten direction. The presence of retained revealing is too difficult due to similarity of its mor- γ phase after martensite transformation (γR) as well as phology with rhabdite and Neiman bands, especially in exsolved γ phase from martensite (γE) was shown earli- the range size less than 1 µm. However, EBSD allowed er [6, 7]. We observed that orientation of γR phase was to identify thin plates of roaldite in the Sikhote-Alin the same in dark and light bonds. This fact excludes meteorite. The phase contrast map demonstrates the twinning origin of the bands. It was further shown that presence of kamacite, rabdite and roaldite. The charac- planes (111) for γR and (011) for α were parallel. The ter of roaldite morphology in Sikhote-Alin meteorite directions [1Ī0] for γR and [100] for α in both dark and Modern Analytical Methods II 2017 9

light bands were also parallel that was close to Alin iron meteorite (IIAB) after loading by spherically Nashiyama-Vasserman martensite orientation relation- converging shock waves. The results obtained by the ship. These results demonstrated that taenite decompo- method of electron backscatter diffraction, as well as sition in Chinga ataxite was by martensite type reac- the data of local chemical analysis unambiguously in- tion: γR→α2+γR→α′+γE+γR. Thus, we can conclude that dicate the presence of regions experiencing polymor- Schlieren bands appeared due to formation of different phic α→ε and ε→α transitions in the loaded sample crystallographic set of submicroscopic products during [11]. martensite transformation [8, 9]. Structural changes in kamacite were investigated in EBSD analysis serves as an excellent tool for solv- iron meteorites of ancient fall (Aliskerovo IIIAB, ing problems of changing orientation without changing Bilibino IIAB) with EDS and EBSD units. Samples chemical and phase composition. Thus, in the shock- which were significantly affected by climate were cho- induced samples of the Sikhote-Alin meteorite, the sen for research of climatic factors. All of them demon- regions of contact melting at the kamacite–rhabdite strate uncompleted recrystallization. It was noticed that boundary were found around some rhabdites. Concen- recrystallization started from the kamacite-rhabdite tration of Ni was not changed in comparison with the boundaries in the Bilibino meteorite and from the kam- initial kamacite matrix. EBSD analysis demonstrated acite-schreibersite boundaries in the Aliskerovo mete- misorientation of the formed rim around the rhabdite orite. There are strongly etched sites in the recrystal- and the rhabdite itself. The phase map indicates the fcc lized zones. One can suggest that these sites are traces lattice (fig.2, 3). The eutectic liquid in these regions of former boundaries. It is possible to think that the formed during a local heating. EDS analysis of these boundaries were moving with jumps because of the regions revealed a decrease of phosphorus content in position of these sites in the recrystallized zone. Also, comparison with that in rhabdite. The phase and orien- it was noticed that there is a net of cracks before the tation maps demonstrated polycrystalline α-Fe(Ni). The recrystallization reaction front. A possible reason for area of contact melting after heating (above the melting this phenomenon is a wedge of extra material which point of 950°C) and rapid cooling transformed to the generates an elastic stress field in the vicinity of the supersaturated solid solution of P in the kamacite (α- grain boundary [12]. All these phenomena can be ex- Fe(Ni)+P) [10]. plained using the grain boundary Kirkendall effect: the boundary shift is the result of the different concentrations of vacancies between the boundary sides [13]. Acknowledgement: This work was supported in part by the Ministry of Education and Science of the Russian Federation (The projects 5.4825.2017/6.7, 5.3451.2017/4.6) and the Act 211 of the Government of the Russian Federation. Contribution to the study from G.A.Y. was funded by the RFBR according to the Fig.2. SEM image of contact melting zone and EBSD research Project No. 16-38-00532 mol_a. phase mapping. References: [1] Zucolotto M.E. and Pinto A.L. (2000) Meteoritics & Planet. Sci., 35, A180. [2] Zuco- lotto M.E. and Pinto A.L. (2001) Meteoritics & Planet. Sci., 36, A234. [3] Uymina K.A. et al. (2010) Meteorit- ics & Planet. Sci., 45, A205. [4] Scott E. R. D. (1971) Nature Physical science, 229, 6–62. [5] Scott E. R. D. (2012) LPS XXXXIII, Abstract #2671. [6] Nolze G. and Geist V. (2004) Cryst. Res. Technol. 39, 343–352. [7] Goldstein J. I. and Michael J. R. (2006) Meteoritics & Planet. Sci., 41, 553–570. [8] Grokhovsky V. I. et al. Fig.3. Orientation map of contact melting zone accord- (2008) Meteoritics & Planet. Sci., 43, A50. [9] Badekha ing to EBSD data. K. A. (2012) Meteoritics & Planet. Sci., 47, A49. [10] Gizzatullina R. F. et al. (2014) Meteoritics & Planet. EBSD analysis is almost the only method for prov- Sci., 49, A137. [11] Muftakhetdinova R.F. et al. (2016) ing the passage of α→ε transformation. We have stud- Technical Physics, 61(12) 1830–1834. [12] Klinger L., ied microstructural deformation-induced changes and Rabkin E. (2011) Acta Materialia, 59, 1389–1399. phase transformations in the material of the Sikhote- [13] Yakovlev G. A (2013) Meteoritics & Planet. Sci., 48, A382. 10 LPI Contribution No. 2021

IN-SITU CATHODOLUMINESCENCE MICROSCOPY AND SPECTROSCOPY FOR THE ROBOTIC MISSIONS ON MARS: A REVIEW. A. Gucsik, Wigner Research Center for Physics, Hungarian Academy of Sciences, Konkoly Thege Miklós út 29-33, H-1121, Budapest, Hungary ([email protected]).

Introduction: Cathodoluminescence (CL) is an emis- The purpose of this study is to summarize the po- sion of photon in the wavelength range from UV tential how to use the CL microscopy and spectrosco- through visible light to IR stimulated by high energetic py, which may be applied to the planetary sciences, electrons. Further readings for the basics of CL can be especially to the robotic explorations on Mars. found in the reviews and books reported by [1-6]. This is a powerful, non-destructive technique, which allows A prototype of the luminescence device for the us many applications in the geosciences as demonstrat- Mars in-situ microscopy and spectroscopy: It has ed by [1,2,4 and 7]. CL has applied to meteoritics to been clearly demonstrated in the previous paragraphs study of shock metamorphism, hydrothermal alteration of this manuscript that luminescence would be applied products, and high-pressure polymorphs in meteorites for the in-situ study of the Martian rocks. Figure 1 as well as astrobiological aspects (e.g. [8]). However, shows a prototype of a luminescence device, which can the CL properties of planetary materials have not been be used for both cathodoluminescence and thermolu- extensively investigated and characterized up to date. minescence analyses of the samples. A conveyor belt Cathodoluminescence microscopy and spectroscopy transports samples (indicated by a robotic arm) to the applied to the planetary missions, especially for Moon sample holder, which are placed in a turntable with and Mars, were proposed by Götze and Tempe [5], sample cups. This sample holder must be heated (at Gucsik et al. [9] and Götze & Gucsik [10]. around 400 C) for the thermoluminescence measure- Two other luminescence types such as thermolumi- ments. The miniaturized X-ray source, for instance, nescence (TL-light is emitted upon heating of sample) MOXTEK Bullet can be used for the TL [21]. Both CL and Optically Stimulated Luminescence (OSL-light and TL detectors will be equipped by a photomultiplier emission is due to the ionizing radiation, which may be (PMT) unit for the detection of the signal. applied to the Planetary Sciences, as follows. Thermo- Therefore, the luminescence device shows some luminescence (TL) analysis leads to dating of the for- advantages for the in-situ mineralogical studies of Mar- mation or metamorphic ages in meteorites and estimat- tian rocks as follows. This instrument provides infor- ing the depositional environments (e.g. aeolian or wa- mation about the radiation dose (for instance, from the ter) [11] as well as studying thermal effects on meteor- solar wind) on the surface of Mars, which would be ites [12]. This is important for deduction of the rates of used in a preparation of the human exploration. More- solar heating up to 105 years in the past, which can be over, it can give some details of the carbonate or phos- useful to estimate perihelia distance, although the phate minerals as indicators for the fluid-rock interac- thermal effect depends on several properties of the tions on Mars. Furthermore, the combination of TL and given meteorite, including rotation, albedo, heat con- CL methodologies provides prescreening of samples ductivity, as well as potential depth inside the source for sample return missions (e.g., [21]-and references body. Luminescence dating is closely associated with therein). solid-state properties of minerals in a meteorite. Expo- The above-mentioned luminescence techniques do sures of radiation (throughout radiational ionization) not require a complicated sample preparation as fol- can be investigated by CL method [13]. Optically stim- lows. The robotic arm collects a few grams of a bulk ulated luminescence (OSL) technique (blue stimulated sample from the surface and then the conveyor trans- luminescence) has been also applied for evaluation of ports it into the sample chamber. Moreover, the thin the maximum intensity of radiation [11]. TL measure- atmosphere in Mars provides vacuum as one of the ments also can aid to the estimation of certain orbital required conditions for the proposed luminescence elements and therefore possible parent bodies of a giv- analysis above. en meteorite. This method is based on the maximum solar heating of meteorites during perihelia of their orbits [12]. More recently, SEM-CL instrument has been applied for studying Martian meteorites and anal- ogous materials as a powerful technique for the clarifi- cation of the atmospheric-fluid-rock interactions, sedimentary processes as well as their high-pressure minerals (silica and feldspar) [8, 14-20]. Modern Analytical Methods II 2017 11

delberg: Springer. [6] Gucsik A. (2009) (Ed) Cathodo- luminescence and its Application in the Planetary Sci- ences. Springer-Verlag, Heidelberg, 160 pp. [7] Pagel M., Barbin V., Blanck P. Ohnensetter, D. (Eds.) (2000) Cathodoluminescence in Geosciences. Springer Verlag, Heidelberg, 514 p. [8] Thomas R. et al. (2009) In Ca- thodoluminescence and its Application in the Planetary Sciences. Gucsik A. (Ed.), pp. 111-126. Heidelberg: Springer. [9] Gucsik A. et al. (2006) LPS XXXVII, abstract#1543. [10] Götze J. and Gucsik A. (2008) LPS XXXIX, abstract#1140. [11] Banerjee D. et al. (2002) XXXIII Lunar and Planetary Science Conference Ab- stract#1561. [12] Melcher C.L. (1981) EPSL 52, 39- 54. [13] Blair M.V. et al. (2003) VI International Con- ference of Mars, Abstract#3201. [14] Protheroe W. J., JR. and Stirling J.A.R. (1998), LPS XXIX, Ab- stract#1569. [15] Protheroe W.J., JR. and Stirling, J.A.R. (2000) LPS XXXI, Abstract#2021. [16] Protheroe W. J., JR. and Stirling, J.A.R. (2000) LPS XXXI, Abstract#1980. [17] Gucsik A. et al. (2006) Conference on Martian Sulfates as Recorders of At- mospheric-Fluid-Rock Interactions, Abstract#7049. [18] Kayama, M. et al. (2011) LXXIV Annual Meteorit- ical Society Meeting, Abstract#5025. [19] Kayama M.

et al. (2012) JGR 117: E09007. [20] Gavin P. et al.

(2013) Journal of Geophysical Research 118: Figure 1. A schematic figure shows a possible setup of E004185. [21] DeWitt R. and McKeever S.W.S. the CL and TL detector on board of a robotic mission (2013) LPS XLIV, abstract#1665. in Mars.

Conclusions: In conclusion, the combination of CL imaging as well as CL spectroscopy is a potentially useful tool that can be used to characterize the mineralogical consequences of the atmospheric-fluid-rock interactions of Mars. Our results may also give new insight into the cathodoluminecence properties of the phosphate and carbonate minerals that occur in the Martian meteorites, which might be potential carriers of the remnants of primitive life forms. Further research, however, is required before an attempt can be made to sufficiently quantify these results to convert them into an application for the in-situ planetary robotic missions and their astrobiological aspects.

References: [1] Marshall, D.J. (1988) Cathodolumine cence of geological materials. Unwin Hyman, Boston, p. 146. [2] Hayward C.L. (1998) In: Short Course Se- ries, 27, Cabri L.J., Vaughan, D.J. (Eds.), pp. 269-325. [3] Boggs S., et al. (2001) Meteoritics & Planet. Sci 36, 783-793. [4] Götze J. (2002) Analytical & Bional. Chem. 374, 703-708. [5] Götze J. and Kempe U. (2009) In Cathodoluminescence and its Application in the Planetary Sciences. Gucsik A. (Ed.), pp. 1-22. Hei- 12 LPI Contribution No. 2021

SPACE WEATHERING OF ASTEROID ITOKAWA: MICRO-RAMAN SPECTROSCOPY OF A PLAGIOCLASE PARTICLE FROM THE HAYABUSA-1 SAMPLE RETURN MISSION. A. Gucsik1, H. Nishido2, K. Ninagawa3, T. Nakamura4 and A. Tsuchiyama5. 1Wigner Research Center for Physics, Hungarian Academy of Sciences, Konkoly Thege út 29-33., H-1121, Budapest, Hungary; 2Department of Biosphere-Geosphere System Science, Okayama University of Science, 1-1 Ridai-cho, Okayama, 700-0005, Japan; 3Department of Applied Physics, Okayama University of Science, 1-1 Ridai-cho, Okayama, 700-0005, Japan; 4Department of Earth and Planetary Materials Science, Graduate School of Science, Tohoku University, Sendai 980- 8578, Japan; 5Kyoto University, Faculty of Science, Graduate School of Science, Division of Earth and Planetary Sciences, Kitashirakawaoiwake-cho, Sakyu-ku, Kyoto-shi, 606-8502, Japan

Introduction: We report a systematic luminescence data were published in Gucsik et spectroscopical investigation of a plagioclase al. [4]. particle (RA-QD02-0025-01) returned by the References: [1] McKeown et al. 2005. American Hayabusa spacecraft from asteroid Itokawa by Mineralogist 90: 1506-1517. [2] Fritz et al. 2005. means of Micro-Raman Spectroscopy. The Antarctic. Met. Res. 18: 96-116. [3] Tomioka N. et al. 2010. Geophys Res Lett 37: L21301. [4] Gucsik et al. structural properties of that selected sample are 2017. Micros Microanal used to evaluate the crystallization effects and shock wave history as well as the degree of space weathering processes of asteroid Itokawa. Results and Discussion: Only one grain (RA- A QD02-0025-01) was selected for the Raman analysis as it shows the best quality/crystallinity among three available specimens. Raman spectral properties obtained at 514 nm (University of Johannesburg, South Africa) excitation show two Raman vibrations at 476 and 505 cm-1, which are superimposed at a relatively high background fluorescence. This indicates a highly distorted structure. In order to reduce the background fluorescence, Raman

spectra were taken from two spectral regions B such as 400-600 and 1100-1200 cm-1 using LabRam (Jena, Germany) facility at 638 nm excitation. Raman spectral properties exhibit three Raman bands centered at 476, 505 and 1009 cm-1. According to McKeown [1], Raman peaks in albite at 476 cm-1 is related to the tetrahedral ring compression in ab-plane, at 505 cm-1 is assigned to compression of four- membered tetrahedral rings along c and a peak centered at 1009 cm-1 is associated with Si- tetrahedral base breathing (Figs. 1A and B). Shock pressure-induced amorphization such as occurrence of maskelynite and its Raman Figure 1. Raman spectral features of the selected signatures were not observed in the selected Itokawa-particle data from [4]. grain (e.g., [2,3]). Raman as well as

Modern Analytical Methods II 2017 13

CHARACTERIZATION OF THE GROUND PAPRIKA SAMPLES USING RAMAN SPECTROSCOPY. A. Gucsik, M. Veres, L. Himics, I. Rigó Wigner Research Center for Physics, Hungarian Academy of Sciences, Konko- ly Thege Miklós út 29-33, H-1121, Budapest, Hungary ([email protected]).

Introduction: The micro-Raman spectrometer can be of which contain carotionic CH3 groups (methyl used for non-destructive determination of the composi- groups) [1]. tion, contaminants and their distribution even at very low concentrations. Micro-Raman spectroscopy as a powerful technique can be used in food industry, especially in the gound pepper or paprika characterization in order to determine the paprika sample’s origin as well as their quality. Experimental procedure: The instrument used for the measurements was a Renishaw 1000 Raman spectrometer attached to a Leica DM/LM optical microscope. The excitation was done with a diode laser of 785 nm (1.58 eV), with a focused laser beam diameter of 500x using a sample of ~ 2 μm. The resolution of the spectra was 0.5 cm-1, the time of each spectrum was 10x10 seconds. The ground paprika samples including Chinese, Peruvian, Spanish, Hungarian and Szegedi were placed on a Si-plate using a lab spoon such as spatula. Raman measurements were always preceded by optical microscopic observations. By avoiding in- homogeneities and other pollutants within the samples, at least seven measurements were made per sample. Results and Discussion: Optical Microscope Observations: Among the five selected pepper paprika samples, the Szeged/the Hun- garian pepper has the most vivid red color assuming that these samples contain the most aromatic compounds. In contrast to the above, the Chinese sample shows yellowish pale red. In all five samples, relatively Figure 1. Raman spectral properties of five ground high density of irregularly shaped shiny surfaces can be paprika samples (baseline-corrected spectra). found in the translucent v. glassy parts break down. In the Chinese sample, oval and spherical black forms are punctuated in the yellowish reddish matrix material. Their size usually reaches 20 microns. It is assumed Conclusions: Raman spectroscopic measurements that these formations may be mold colonies due to in- (especially at 785 nm excitation) are well suited for the correct storage (relatively high moisture content). determination of origins of the ground paprika samples. In the case of Hungarian samples, it is also possible to Raman Spectral Properties of the Ground Paprika show characteristic features. Some top parameters are Specimens: Samples with 785 nm excited Raman spec- suitable for distinguishing between different samples. tra are shown in Figure 1. It can be seen in the figure that the background fluorescence shows relatively high Reference: values for each sample. Therefore, in some cases laser [1] Di Annibal C. V. et al. (2012) Spectrochim Acta A, power was reduced from 100% to 50%. The common 87, 135-141. feature of the spectra is that they have small intensity broad bands, mainly in the low frequency range (300- 600 cm-1) at the following peak positions: 346, 484 and 631 cm-1, and a weak intensity narrow peak (Fig. 1). Characteristic or dominant strong peak intensity vibra- tional peaks appear in the Hungarian and the Szeged paprika samples: 997, 1150, 1180 and 1515 cm-1, some 14 LPI Contribution No. 2021

IR-Raman correlation of shocked minerals in Csátalja meteorite – clues for shock stages Gyollai I. (1, 2), Kereszturi A.(1), Fintor K. (3), , Kereszty Zs.(4), Szabo M.(2), Walter H. (3) (1) Research Centre for Astronomy and Earth Sciences, Konkoly Thege Miklos Astronomical Institute, H-1121 Bu- dapest, Konkoly Thege Miklós út 15-17, Hungary (2) Research Centre for Astronomy and Earth Sciences, Institute for Geological and Geochemical Research, Hungary (3) Vulcano Petrology and Geochemistry Research Group, De- partment of Mineralogy, Geochemistry and Petrology, University of Szeged, Hungary.(4) International Meteorite Collectors Association (IMCA#6251). E-mail: [email protected]

Introduction: The analyzed meteorite called Csátalja boratory of the Department of Mineralogy, Geochemis- is a H chondrite (H4, S2, W2), and based on the differ- try and Petrology, University of Szeged; and used ences between its certain parts, probably it is a breccia. Bruker Hyperion 20000 FTIR-ATR microscope (tip of The meteorite was found in August of 2012, some km the germanium (Ge) crystal of 100 µm in diameter, east of the village of Csatalja (46.006° N, 18.991°) in ,performed for 30 sec at 4 cm-1 resolution, Bruker Op- Hungary (Kovács et al. 2015). The meteorite shows tics’ Opus 5.5. software) at Research Centre for As- high iron abundance (25-31%), its main minerals are: tronomy and Earth Sciences of Hungarian Academy of orthopyroxene, olivine (fayalite content 16-20 mol%), Sciences. 15-19% reduced Ni-Fe metal and 5% troilite. In this Results: Comparing the shock impact produced min- work we analyse typical meteorite minerals, including eral alterations in two thin sections of the recently shock altered ones in order to demonstrate some useful found Csátalja meteorite indicates that the most signifi- capabilities and also the limits of the methods, by cor- cant differences can be observed in mineral clasts: 1) relating the infrared observations with better estab- the clasts in Csátalja-1 show homogeneous mineral lished Raman measurements for phase identification composition (pyroxene, olivine) and characterized by and characterization (Fintor et al., 2014), as with Ra- mosaic extinction, which indicates shock stage <15 man much more standardized data are available. Opti- GPa. 2), while the Csátalja-2 mineral clasts contain cal analysis was also used mainly to characterize the subgrained pyroxene and olivine with feldspar melt isotropy of mixed phases. The aim besides the method- along subgrain boundaries without any evidence for ological testing is to characterize the shock defor- high pressure transformation (e.g. akimotoite, ring- mation and estimate formation conditions, related small woodite) indicating shock pressure in 15-17 GPa scale heterogeneity and reconstruct shock history. range. With increasing shock stage the peak positions of Raman and infrared spectra of mineral clasts shifted in wavenumber relatively to the unshocked references. We confirmed that both Raman and infrared peak shifts and FWHM values correlate to each other with correlation factors between 0.6-0.9. The best correlation parameter occurred in shocked pyroxene between the two methods (Raman FWHM-shock induced shift, r2=0.97). The Csátalja-1 pyroxenes showed a bit stronger correlation values, than pyroxenes in Csátalja- 2 sample, because of less disordering of structure by less shock stage. In case of feldspars Raman FWHM- shock induced shift showed weak correlation because those occur as mixed melts with Ca-rich pyroxene.

Fig.1: Raman and IR measuring points of Csátalja-1 Pure feldspar spectra could be detected only by FTIR (a, d, e) and Csátalja-2 (b, c) samples. spectroscopy which shows moderate, but weaker corre- 2 lation value than the pyroxenes (r =0.84 infrared shock Materials and Methods: The mineral assemblages drivel peak shift-FWHM, r2=0.91 Raman FWHM- and textures of two 30µm thickness thin sections FTIR FWHM) (Fig. 2). (Csátalja -1, and Csátalja-2, Fig. 1) were characterized In case of mixed mineral clasts formed by selective with a Nikon Eclipse LV100POL optical microscope. melting around subgrain boundaries and fractures by- Phase analytical measurements were made by shock annealing, the IR and Raman FWHM values THERMO Scientific DXR confocal Raman micro- show weaker correlation 0.42 of Csátalja-2 than 0.72 scope (532 nm laser, 10 mW laser power, 100X objec- of Csátalja-1 according to the higher shock level of tive lens, 5 μm pinhole confocal aperture) in the la- Csátalja-2. The FWHM values with shock induced Modern Analytical Methods II 2017 15

shifts correlated well with both in case of FTIR and Raman spectroscopy. In summary the joint usage of Raman and infrared provide deeper insight into the shock produced changes and its spatial inhomogeneity.

Fig. 2: Raman-IR correlation of shocked pyroxenes

Conclusion: The clasts in Csátalja-1 show homogeneous mineralogical composition, separated parallel shock veins, the shock pressure did not exceeded 15 GPa. While the Csátalja-2 mineral clasts have mixed mineralogy, larger shock melt volume, the pyroxene and olivine clasts are surrounded by feldspar melt along the subgrain boundaries, indicating >15- GPa shock pressure – but below 17 GPa as transformation to akimotoite and ringwoodite were not observed. The different shock levels could be observed by the peak shift and FWHM change both in olivine and pyroxene. Acknowledgement: This work was supported by NKFIH with the GINOP-2.3.2-15-2016-00003 fund. We are grateful to University of Szeged, and to Rese- arch Centre for Astronomy and Earth Sciences HAS for instrumental support. References: Fintor, K., Park, C., Nagy, Sz., Pál-Molnár, E., Krot, A., N., 2014. Hydrothermal origin of hexagonal CaAl2Si2Os (dmisteinbergite) in a compact type A CAI from the Northwest Africa 2086 CV3 chondrite. Meteorit. Planet. Sci. 49, 812-823.; Kovács J., Sajó I., Márton Z., Jáger V., Hegedüs T., Berecz T., Tóth T., Gyenizse P., Podobni A., 2015. Csátalja, the largest H4-5 chondrite from Hungary. Planet. Space Sci. 105, 94.

16 LPI Contribution No. 2021

Biosignatures in the Recrystallized Shock Melt Pocket of ALH-77005 Shergottite - Clues to Martian Life I. Gyollai (1,2), M. Polgári (2), Sz. Bérczi (1), A. Gucsik (3), E. Pál-Molnár (4) (1) Eötvös University, Dept. of Ma- terials Physics, Cosmic Materials Space Res. Group, H-1117 Budapest, Pázmány P. str. 1/a, Hungary, e-mail: gy- [email protected]; [email protected]; (2) Research Center for Astronomy and Geosciences, IGG, HAS, 1112 Budapest, Budaörsi str. 45, Hungary, e-mail: [email protected]; (3) Wigner Research Centre for Physics, HAS, H-1121 Budapest, Konkoly-Thege M. str. 29-33, Hungary, e-mail: [email protected]; (4) University of Szeged, 'Vulcano' Petrology and Geochemistry Research Group, Department of Mineralogy, Geochemistry and Petrology 6722 Szeged, Egyetem Str. 2, e-mail: [email protected]

Introduction: The ALH-77005 Martian meteorite melt pocket and is intimately woven in the full cross- (lherzolitic type) was found at around the Allan Hills, section of the melted part. All of recrystallized melt in South Victoria Land on Antarctica in 1977-1978 [1]. pocket sections showed signs of Fe mobilization and Nyquist et al. [2] indicated lherzolitic texture of ALH- oxidation (brown haloes around mineral grains, brown 77005. Moreover, Ikeda [3] suggested this meteorite filaments, Fig. 1/B). and its shergottite formation. The aim of this study is to ATR-FTIR: The iron-oxidizing microbial structures investigate of biosignatures in the spinifex textured have a mixed composition containing iron oxides (fer- melt pockets. rihydrite, goethite) [4], and olivine [5]. Hydrocarbon Samples and Methods: The mineral assemblages compounds were also detected (long chain hydrocar- and textures were characterized with a Nikon Eclipse bon, diene; [6-8], and C-H stretching of aliphatic hy- LV100POL optical microscope. We used Bruker Hy- drocarbons [7] (Fig. 2). The presence and appearance perion 20000 FTIR-ATR microscope for the determi- of ferrihydrite corresponds to bacterial originated re- nation and distribution of micro-mineralogy and or- mobilization of iron from olivine and troilite. IR vibra- ganic compounds. tions of isoprenoids were also detected [8]. Results: Petrography: The ALH-77005 consists of Conclusion: The presence of iron oxidizing bacteria pyroxene, olivine and feldspar. The ALH-77005 has in recrystallized shock melt could be proposed as Mar- coarse-granular texture with locally microgranular and tian origin. In general, the terrestrial weathering is in- poikilitic texture regions and melt pockets with recrys- duced along fractures and rims, but this sample does tallized needle-like crystallites in glassy matrix. In the not contain microbial alterations and weathering fea- environment of melt pockets resorbtion rim can be ob- tures outside of recrystallized melt pocket. Increasing served with toast-like texture in some cases and infil- microbially mediated activity helps to increase the tration of dark melt. The melt pockets are darker (dark- amount of microbes, which first „eat” (consume) and brown-black in plane polarized lights) than its envi- then remineralize the mineral components in the matrix ronment (well-crystallized coarse crystals). In the vi- and in the glass regions [9,10], before the microbial cinity and inside of melt pockets several textures can alteration was stopped. be observed. The needle-like crystals are feldspar and Acknowledgement: We are grateful to H. Kojima for pyroxene in melt pockets. The lengths of needles are the loan of ALH77005 sample, and to RCAG IGG between 10-75 µm, and their width falls into 1-5 µm HAS for instrumental support. range. Near to melt pockets, isotropic lath-shaped plagioclase, maskelynite occur. But, according to presence References: [1] Yanai K. (1979) Mem. NIPR Res. of weak feldspar band Raman FTIR spectra, this altera- Spec. Is., 12, 1–8. [2] Nyquist L. E. (2001) Space Sci. tion is transient, the shock pressure did not exceeded Rev., 96, 105–204. [3] Ikeda Y. (1994) Proc. of NIPR 30GPa. In the olivines, parallel to the fractures, kink- Symp. of Ant. Met. Res., 7, 929, [4] Glotch TD, band system can be observed. The poikilitic fractured Rossman GR (2009) Icarus, 204, 663–671. [5] Matrajt pyroxene grain contains olivine with thick one-set kink G, Muñoz GM, Dartois CE, d’Hendecourt L, Deboe D, bands. Borg J (2005) Astron & Astrophys, 433, 979–995. [6] The recrystallized shock melt with spinifex texture Parikh SJ, Chorover J (2006) Langmuir, 22, 8492- contains microbial features as well, Mineralized mi- 8500. [7] Rajasekar A, Maruthamuthu S, Muthukumar crobially produced texture (MMPT) in the form of N, Mohanan S, Subramanian P, Palaniswamy N (2006) pearl necklace-like, with vermiform inner signatures, is Corros Sci, 47, 257–271. [8] Orlov AS, Mashukov VI, embedded in needles (olivine, pyroxene, feldspar) in Rakitin AR, Novikova ES (2012) J Appl Spectr, 79/3, the rapidly cooled shock melt (Fig. 1/A). The MMPT 484-489. [9]Gyollai et al. 2017 #chondrules 2017 consists of micrometer-sized microbial filamentous (London), [10] Polgári et al. 2017 EANA17 (Aarhus). elements and clusters in their boundary region. The

MMPT is very extensive, reaches 70-80 % of the shock Modern Analytical Methods II 2017 17

A A

B B Fig. 1: (A) Filamentous pearl necklace-like inner Fig. 2: IR spectra of area near troilite (degradation textures (marked by arrows) in shock melt pocket, (B): to ferrihydrite) and pyroxene with organinc compounds Microbially mediated mobilization and mineralization of biosignatures. Spectra were taken in shock melt of iron from opaque minerals and organic material. pocket.

18 LPI Contribution No. 2021

TERRESTRIAL AGES OF METEORITES DETERMINED BY 14C AND 14C/10Be USING ACCELERATOR MASS SPECTROMETRY. A. J. T. Jull1,2,3, I. Kontul4, L. Cheng3, E. R. Creager3, A. Gucsik5, M. Molnar2, R. Ja- novics2 and P. Povinec4 1Department of Geosciences, University of Arizona, Tucson, AZ 85721 USA. 2Isotope Cli- matology Research Centre, Institute of Nuclear Research, 4026 Debrecen, Hungary. 3AMS Laboratory, University of Arizona, Tucson, AZ 85721, USA. 4Faculty of Mathematics, Physics and Informatics, Comenius University, 842 48 Bratislava, Slovakia. 5Wigner Institute of Physics, Budapest, 1121 Budapest, Hungary.

Introduction: Large concentrations of meteorites can spectrometry (AMS). This suite of cosmogenic radio- be recovered from areas of the Earth’s surface where nuclides provides a useful range for potential exposure weathering rates are lower, such as in deserts, or in polar age studies, from thousands to millions of years. The regions, where concentration of the meteorites can oc- distinct and varied chemical properties of each of these cur due to ice flow, such as in Antarctica. Abundant elements also make them well-suited to geochemical recovery locations for meteorites are arid and semi-arid studies. For stable cosmogenic nuclide the units of con- regions. These include Antarctica, the Sahara Desert, centration are expressed as atoms g-1, however for radi- Atacama, Namib and Arabian deserts, the Nullarbor onuclides the most widely used units are given as activ- Plain of Australia, areas in the southwestern USA and ities(dpm/kg = decays minute-1 kg-1). 60 dpm/kg is similar recovery locations. Cosmogenic radionuclides equivalent to 1 Bq/kg. (such as 10Be, 14C, 26Al, 36Cl and 41Ca) provide important information on the exposure time of meteorites Secondary neutrons and protons produced by GCR re- and planetary surfaces in space and also shorter-lived actions have a characteristic depth dependence. The nuclides provide information on the terrestrial-resi- time for a target to become saturated with a particular dence time of meteorites on the surface of the Earth [1- cosmogenic radioisotope is a function of the half-life of 3]. We find that exposure times of meteorites reflect the the radionuclide. A maximum saturation level for a ra- time since the breakup of the larger parent object, which dionuclide occurs within about 5-6 half-lives, since the is typically in the range of 1-50Ma. The terrestrial-resi- radioactivity builds up according to the build-up rela- dence time (or terrestrial age) depends on the environ- tion: ment where a meteorite lands. This age can range from zero (a recent fall) to over 40ka in desert environments [1] and can be hundreds of thousands of years in cold, polar # )*+ 14 𝑁𝑁 = $ (1 − e ) environments. Radionuclides such as C have also been Where P is the production rate (at a given location), λ is used to distinguish between terrestrial and extraterres- the half-life of the radionuclide of interest, and t is the trial sources of carbon by using the very different levels build-up time. The production rate P depends on a com- expected. plex function of the particle flux at the depth of the sample in the body, the energy distribution of nuclear parti- Material in space and on the earth is subject to irradia- cles at this depth, the excitation function for 14C production by cosmic rays. The result is the production of section from oxygen (and other elements) as a function of ondary nuclides, known as “cosmogenic nuclides”. We energy, and the chemical composition of the sample [5]. know that meteorites and lunar material contain signifi- In the case of 14C, we can calculate the terrestrial age if cant radioactivity produced by the action of cosmic ra- we know the production rate, since we can assume that diation in space [1,2]. Since radionuclides decay, they the 14C saturated during the meteorite’s exposure in give us “clocks” on various time-scales that help us to space. The 14C terrestrial age is then calculated from the better understand the duration of the time during which equation: they were exposed to cosmic rays, which we call the cosmic ray exposure time or exposure age, and the length of their residence on the Earth’s surface, which ) [2] we call the terrestrial age. Cosmic ray exposure ages 1 78 ./00 have been reviewed by Eugster et al. [1] and Herzog et 𝑇𝑇 = − $23 ln (79:; 14 -4 Where λ14 is the decay constant for C of 1.21 X 10 , al. [2]. Jull [3] has summarized data for terrestrial ages. 14 Nm is the measured amount of C (in activity, dpm/kg; It has also been recognized that small amount of cosmo- or atoms/g) and N is the saturated activity, which is genic nuclides can be produced on the Earth’s surface sat P /λ [3,6]. as well, although the atmosphere shields this production 14 14 substantially [4]. The radionuclides C (half-life: 14 10 We previously also investigated the ratio C/ Be for 5.7ka), 10Be (1.38Ma), 36Cl(301ka) 26Al (700ka), and dating on the assumption that this production ratio 129I (15.7Ma) can all be measured with accelerator mass should be reasonably constant at ~2.5 to 2.6 [7,8]. Modern Analytical Methods II 2017 19

Since 10Be and 14C are produced by similar nuclear spallation reactions, we expect that the production ratio Acknowledgements: This research was supported of these two nuclides is relatively constant and this is a by the European Union and the State of Hungary, way of correcting for the depth effects. In this case, co-financed by the European Regional Develop- we can calculate the terrestrial age from the ratio of 14 10 ment Fund in the project GINOP-2.3.2.-15-2016- C/ Be, according to the following equation. The ter- 00009 ‘ICER’. We also acknowledge support for restrial age is then calculated from the equation: IK from an IAEA training fellowship and AG for a Fulbright fellowship from the Hungarian-Amer- ican Fulbright Commission. [3] References: [1] Eugster, O. et al. (2006) In Meteorites This assumes that the exposure age of the meteorite in 10 and the Early Solar System (ed. D. Lauretta), Tucson: space was long enough to saturate Be. University of Arizona Press. pp. 829-851. [2] G. F. Herzog et al. 2015. Cosmogenic nuclides in Antarctic Meteorites have been recovered since prehistoric times. meteorites. In: 35 Seasons of U.S. Antarctic Meteor- The length of time they survive on the surface of the ites (1976–2010): A Pictorial Guide to the Collection, Earth has always been of considerable interest. Meteor- AGU Special Publication 68. (eds. Kevin Righter et ites appear to fall equally all over the world and have be al.) New York: Wiley. pp. 153-172.[3] Jull, A. J. T. recovered from all parts of the globe [9]. In general, (2006) Terrestrial ages of meteorites. In “Meteorites the infall rate can been described as a function of mass and the Early Solar System II” (eds. D. Lauretta and H. where: Y. McSween, Jr.), University of Arizona Press, Tuc- son, pp. 889-905. [4] Phillips et al. [5] Halliday et al. log N = a log M + b (1989). [5] Leya I. and Masarik J. (2009) Meteoritics [4] and Planetary Science, 44, 1061, 1086.[6] Jull A. J. T. et al. (2010) Meteoritics and Planetary Science 45, where N is the number of meteorites which fall per 106 2 1271-1283. [7] Welten K. C. et al. (2003) Meteoritics km per year, of greater than mass M in grams. Halli- and Planetary Science 38, 157-173. [8] Welten K. C. et day et al [9] determined the constants a and b to be -0.49 al. (2004) Meteoritics and Planetary Science 39: 481- and -2.41 for M<1030g, and -0.82 and -3.41 for 498. [9] Halliday I. et al. (1989) Meteoritics 24, 173- M>1030g, based on observations of meteoroids. This 178. [10] Bland P. A. et al. (1996) Geochim. Cosmo- would result in an infall rate of M>10g of 83 events per 6 2 2 chim. Acta 60, 2053-2059. [11] Love S. G. and 10 km /yr, or roughly one event per km in 10,000 yr. Brownlee D. (1993) Science 262, 550-553. Bland et al. [10] estimated an infall rate of 36-116 events per 106km2/yr based on meteorite weathering and recovery. The total mass of infalling material from cosmic dust to large objects averages about 40,000 tons/yr [11]. Despite the apparently uniform infall rate, meteorites are easier to locate in some places than in others.

Methods: We extracted 14C from samples using an RF induction system, as described earlier [6]. Sample gas is extracted, cleaned and reduced to graphite for AMS measurement without adding a carrier. Graphites are pressed into a target holder and were measured using the NEC machine at the University of Arizona running at 2.5MV. Recently, we also have experimented with using an AMS gas ion source attached to the 200kV MICADAS AMS in Debrecen for meteorite 14C measurements.

In this paper, we present measurements of terrestrial ages on a number of meteorites from different environments and compare the differences due to various factors. We highlight some recent results on meteorites from central and eastern Europe. 20 LPI Contribution No. 2021

CONCEPT AND BREADBOARD OF THE PLANETARY BOREHOLE-WALL IMAGER. A. Kereszturi1, L. Duvet4, Gy. Grof2, A. Gyenis3, T. Gyenis2, B. Kovacs2, Gy. Maros5 1Research Centre for Astronomy and Earth Sci- ences, Hungary; 2Budapest University of Technology and Economics, Hungary; 3Kolorprint LP. Hungary; 4European Space Agency, ESTEC, 5Mining and Geological Survey of Hungary. (e-mail: [email protected] ).

Introduction: Planetary surface exploration is ef- ment), keep its ideal position and shield against falling fectively supported by laboratory and field tests on the grains inside the borehole (camera house, Fig.2.); data Earth, where concepts and versions of various instru- transfer and recording happens through an USB cable ments could be tested. Below the concept and design of onto a laptop with linking the auxiliary parameters to a borehole-wall imager (BHWI) probe is presented to the individual images, specific software will be used to support the testing and further development of the drill- support the mosaicking, image detorsion, identification ing and sampling facility of the ExoMars (EXM) rover of geological properties, bedding, grain size and other of ESA to be launched in 2020 [1]. spatial sedimentary characteristics. Based on the experiences of some of the authors [2] in drilled core scanning, a partly “inverse” method of boreholewall analysis is being developed to help the interpretation of EXM drilling on Mars. The BHWI aim is to support research work and testing some aspects of the drill based sample acquisition and sample analysis at Earth based Mars analogue site with the specific aims: 1. provide a general overview of the

borehole-wall appearance, 2. support the connection of Figure 1. Two views of the surface stand presenting the original location of the acquired samples and the the main components of the system. The stand is about later laboratory based sample analysis. 30 cm high and 50 cm diameter This work contains some technical aspects of the development are presented toward the building of the breadboard including design aspects too. Concept: Three main specific goals of the development: 1. Support the understanding of methodological issues regarding the drill and the drill based sample acquisition using Earth based analogue tests and partly laboratory tests by providing information on the borehole structure, internal appearance, target material/structural characteristics. 2. Linking samples’ and borehole-wall’s characteristics together with inferred geological context. 3. Support the target identification for drills by providing linked information of borehole characteristics, acquired sample characteristics, Earth based analogue tests regarding methodological issues. Methods: The development supported by background knowledge in Earth and planetary sciences, currently available low cost optical detectors, and also Figure 2. Structural overview of the two cameras (a) Solidworks 2016 software for technical engineering and one cameras (b) containing design. visualization and planning of piece parts. Results: The implementation and first test results Design elements: optical components: detector: 1 will be presented at the meeting, including the realiza- MP CMOS detector with 1600x1200 pixel resolution tion and the laboratory based performance on test tar- and 24 bit true colour with physical CCD chip size of gets of the BHWI’s first version. 2.4x1.6 mm; the objective and mirror support to pro- References: [1] Vago et al. 2015 Solar System Re- ject the borehoe-wall image onto the detector; electron- search 49, 518-528. [2] Maros Gy., Pásztor Sz. 2001. ic components are to drive and adjust the movement European Geologists 12, 40–43. and harmonized image recording; mechanical compo- Acknowledgment: This work was supported by the nents (Fig.1.) to move the system by a metal stripe or EXODRILTECH project (No. 4000119270), and the telescopic boom (for vertical movement) and a small Hungarian Space Agency. sized fixed motor at its bottom (for horizontal move- Modern Analytical Methods II 2017 21

Fe2+ PARTITIONING BETWEEN THE M1 AND M2 SITES IN SILICATE PHASES FROM SOME STONY AND STONY-IRON METEORITES STUDIED USING X-RAY DIFFRACTION AND MÖSSBAUER SPECTROSCOPY. A. A. Maksimova, A. V. Chukin, E. V. Petrova and M. I. Oshtrakh, Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002, Russian Federation. E-Mail: [email protected].

Introduction: Stony and stony-iron meteorites and the system were given elsewhere [1–4]. The consist of various iron-bearing phases with the main 1.8×109 Bq 57Со(Rh) source (Ritverc GmbH, St. Pe- content of silicate phases. These phases are olivine (Fe, tersburg) was used at room temperature. The Mössbau- Mg)2SiO4, orthopyroxene (Fe, Mg)SiO3 and clinopy- er spectra were measured in transmission geometry roxene (Fe, Mg, Ca)SiO3 which have two crystallo- with moving absorber at 295 K and recorded in 4096 graphically non-equivalent positions for Fe2+ and Mg2+ channels. Then spectra were converted into 1024 chan- cations denoted as M1 and M2. The information about nels. The Mössbauer spectra of meteorites were com- the Fe2+ and Mg2+ partitioning between the M1 and M2 puter fitted with the least squares procedure using sites in silicate crystals is important for estimation of UNIVEM-MS program with a Lorentzian line shape. their thermal history. Therefore, evaluation of the Fe2+ The spectral parameters such as: isomer shift, δ, quad- 2+ and Mg occupancies in silicate phases in stony and rupole splitting, ∆EQ, line width, Γ, relative subspec- stony-iron meteorites could be useful for analysis of trum area, A, and statistical quality of the fit, χ2, were their thermal history. determined. Criteria for the best fits were differential X-ray diffraction (XRD) and Mössbauer spectros- spectrum (the difference between experimental and copy are very useful techniques for the study of various calculated spectral points), χ2 and a physical meaning 2+ meteorites including the Fe partitioning between the of the spectral parameters. Values of δ are given rela- M1 and M2 sites in silicate phases. In this work we tive to α-Fe at 295 K. 2+ present the results of our approach to estimate the Fe Results and Discussion: Examples of XRD pat- cations distribution between two nonequivalent sites in tern and the Mössbauer spectrum of NWA 6286 ordi- silicates using XRD and Mössbauer spectroscopy with nary chondrite are shown in Figs. 1 and 2. All XRD a high velocity resolution. The latter technique has patterns were fitted using the Ritvield full profile anal- much more presize reaching the resonance and much ysis with revealing the Fe2+ and Mg2+ occupations of M1 M2 better sensitivity to the absorption lines features than the M1 and M2 sites in silicates (XFe and XFe and M1 M2 conventional Mössbauer spectroscopy (see [1, 2]). XMg and XMg , respectively) shown in Table 1. Materials and Methods: Samples of powdered matter from ordinary chondrites (several fragments of Chelyabinsk LL5, Northwest Africa (NWA) 6286 and 7857 LL6, Annama H5) and stony part from Seymchan main group pallasite (PMG) were prepared for the study. After measurement of XRD patterns samples powders were glued on Fe-free Al foil with a thickness of ~8 mg Fe/cm2 or less for Mössbauer spectra measurements. XRD patterns were measured using XRD-7000 (Shimadzu) operated at 40 kV and 30 mA with CuKα radiation using a monochromator on the secondary beam, scanned over 2Θ from 12° to 80° with a step of Fig. 1. XRD pattern of NWA 6286 LL6 ordinary 0.03° per 10 s, and PANalytical X'Pert PRO MPD dif- chondrite shown in selected 2Θ range. Ol – olivine, fractometer (The Netherlands) with CuKα radiation and OPy – orthopyroxene, CPy - clinopyroxene, Tr – Ni filter in the 2Θ range of 10–90° with a step of troilite, Ch – chromite, Hc – hercynite, α – α-Fe(Ni, 0.013° per 300 s. Mössbauer spectra of meteorites Co) phase, γ – γ-Fe(Ni, Co) phase. were measured using an automated precision Mössbau- er spectrometric system built on the base of the SM- All Mössbauer spectra were better fitted with revealing of the main and minor spectral components. 2201 spectrometer with a saw-tooth shape velocity 57 reference signal formed by the digital-analog converter The components related to the Fe in the M1 and M2 12 sites in all silicates were identified and their relative using discretization of 2 (quantification using 4096 M1 M2 steps). Details and characteristics of this spectrometer areas A and A were obtained for olivine, orthop y- roxene and clinopyroxene (see Table 1). 22 LPI Contribution No. 2021

troscopy with a high velocity resolution. Furthermore, it is possible to estimate the distribution coefficient KD: 1M × XX 2M = Fe Mg , (1) KD 2M 1M Fe × XX Mg and the temperatures of equilibrium cations distribution Teq using the following equations for olivine [5]: TRG ××=∆− ln K , (2) NWA 6286 eq D LL6 where ∆G is the Gibbs energy (∆G=20935 J for olivine), R=8.31 J⋅K–1⋅mol, and for orthopyroxene [6]: 2205 . (3) ln D 391.0K −= Teq However, in contrast to XRD which permits estimation M1 M2 M1 M2 of XFe and XFe and XMg and XMg , Mössbauer M1 M2 spectroscopy cannot estimate XMg and XMg without additional data. It takes to use fayalite Fa and ferro- M1 M2 silite Fs data to obtaine XMg and XMg values from Mössbauer spectroscopy (see [7]). Some estimated Fig. 2. Mössbauer spectrum of NWA 6286 LL6 ordi- values of Teq for olivine are shown in Table 2. The nary chondrite. Indicated components are the result of results obtained using two techniques are consistent. the best fit. The differential spectrum is shown below.

2+ Table 2. Selected values of Teq estimated for olivine Table 1. The Fe partitioning between the M1 and M2 using XRD and Mössbauer data. sites in silicates estimated using XRD and Mössbauer

(MS) data. Teq, K Olivine MS XRD Method of estimation Silicates Chelyabinsk LL5 No 2 1115 1179 XRD MS NWA 6286 LL6 1052 1010 X M1/X M2 AM1/AM2 Fe Fe Seymchan PMG 835 684 Olivine Chelyabinsk LL5 No 2 1.17 1.18 Acknowledgements: This work was supported by NWA 6286 LL6 1.23 1.19 the Ministry of Education and Science of the Russian NWA 7857 LL6 1.16 1.22 Federation (the Project # 3.1959.2017/4.6) and by Act Annama H5 1.2 1.4 211 Government of the Russian Federation, contract № Seymchan PMG 1.38 1.31 02.A03.21.0006. Contribution to the study from Orthopyroxene A.A.M. was funded by the RFBR according to the re- Chelyabinsk LL5 No 2 0.20 0.25 search project № 16-32-00151 mol_a. NWA 6286 LL6 0.25 0.26 References: [1] Oshtrakh M. I. and Semionkin V. NWA 7857 LL6 0.33 0.34 A. (2013) Spectrochim. Acta, Part A: Molec. and Bio- molec. Spectrosc., 100, 78–87. [2] Oshtrakh M. I. and Annama H5 0.1 0.2 Semionkin V. A. (2016) Proceedings of the Interna- Seymchan PMG – – tional Conference “Mössbauer Spectroscopy in Materi- Clinopyroxene als Science 2016”, Eds. J. Tuček, M. Miglierini, AIP Chelyabinsk LL5 No 2 1.78 1.90 Conference Proceedings. AIP Publishing, Melville, NWA 6286 LL6 1.33 1.30 New York, 1781, 020019. [3] Oshtrakh M. I. et. al. NWA 7857 LL6 2.00 2.43 (2009) J. Radioanal. Nucl. Chem., 281, 63–67. Annama H5 – – [4] Semionkin V. A. et. al. (2010) Bull. Rus. Acad. Seymchan PMG 1.6 1.67 Sci.: Phys., 74, 416–420. [5] Malysheva T. V. (1975) Mössbauer effect in geochemistry and cosmochemistry. A comparison of the Fe2+ partitioning between the Moscow: Nauka, pp. 166 (in Russian). [6] Wang L. et M1 and M2 sites in silicates obtained on the basis of al. (2005) Geochim. Cosmochim. Acta, 69, 5777–5788. two techniques appeared to be similar, i.e. indicated a [7] Oshtrakh M. I. et al. (2008) Meteorit. & Planet. good agreement between XRD and Mössbauer spec- Sci., 43, 941–958. Modern Analytical Methods II 2017 23

USING THE GAS ION SOURCE COUPLED TO A MICADAS 200kV ACCELERATOR MASS SPECTROMETER FOR MEASUREMENTS OF 14C ON VERY SMALL SAMPLES: FROM METEORITES TO TREE RINGS. M. Molnar1 , A. J. T. Jull1,2,3, I. Major1, K. Hubay1, R. Janovics1 1Isotope Cli- matology Research Centre, Institute of Nuclear Research, 4026 Debrecen. Hungary 2Department of Geosciences, University of Arizona, Tucson, AZ 85721 USA. 3AMS Laboratory, University of Arizona, Tucson, AZ 85721, USA.

14 Introduction: The concentration of C (t1/2 secondary cosmic-ray neutrons with nitrogen, 5,700 yr) is of great importance in understand- according to the equation 14N(n,p)14C. A ing the terrestrial residence time of meteorites growing field of interest is in short-term fluc- [1,2], planetary surfaces [3] as well as many tuations of 14C production in the terrestrial at- other types of terrestrial materials, as will be mosphere. Rapid excursions could be the re- discussed. The terrestrial age depends on the sult of rapid changes in the cosmic-ray flux environment where a meteorite lands. 14C has due to changes in solar activity. This signal is also been used to distinguish between terres- best recorded in tree-rings which have an an- trial and extraterrestrial sources of carbon by nual record of cosmic-ray fluctuations, since using the very different levels expected. Past rapid changes in 14C have been observed at meteorite studies have used relatively large specific times in the past, including at AD 774- samples or diluted the 14C extracted with a car- 775 and 993-994 [7-12]. These records have rier gas. Recently, we have experimented with been extended to additional events around 14 injecting the CO2 from meteorites directly 5480BC and 660BC [13,14]. The importance into an AMS ion source using a gas-ion source of these rapid events cannot be underesti- interface developed by ETH-Zurich. This al- mated, since a large solar cosmic-ray event or lows the measurement of samples of as low as coronal mass ejection could cause large-scale 10-20µg and a corresponding reduction in damage to our increasingly complicated elec- sample size. Independently, another group [4] tronic infrastructure. has also developed a method for 14C extraction from meteorites using a similar interface. Meteorite Methods: We extracted 14C from These new developments are important as we samples using an RF induction system, as de- move forward to sample-return missions from scribed earlier [3]. Sample gas is extracted, comets (e.g. Hayabusa-2) or asteroids cleaned and reduced to graphite for AMS (OSIRIS-Rex), where sample size will be a measurement without adding a carrier. Tradi- limitation. tionally, graphites are pressed into a target holder and were measured using the NEC ma- Application to terrestrial cosmogenic in- chine at the University of Arizona running at situ 14C: Cosmogenic 14C produced in situ in 2.5MV or the Debrecen machine running at rocks is also important for studies on the sur- 200kV. We will report on new studies using face of the earth, where in combination with the gas-ion source for known-age materials other radionuclides such as 10Be, it can give and meteorites. important information about past surface exposure times and erosion rates [5,6]. We are Tree-ring methods. Samples of known-age developing a new in situ cosmogenic 14C line tree rings were divided and converted to holo- following the Cologne design in collaboration cellulose using established methods. These are with Fülöp et al. [7]. then combusted with CuO to CO2 and then converted to graphite for measurement on the Cosmic-ray Records in Tree Rings: How- Debrecen machine. So far, we have not run ever, 14C is produced directly in the terrestrial many samples using the gas-ion source for tree atmosphere as well, due to the interaction of 24 LPI Contribution No. 2021

rings, but we will report on investigations using the gas-ion source at the conference.

Gas Ion Source: The gas ion source is an interface which mixes CO2 in the sample with a He carrier. The interface allows the gas pressure to be varied to maximize the ion current. The gas mixture flows through a capillary tube into the source over a Ti frit. The gas in- teracts at this surface with a Cs sputtering beam to produce negative ions. Typically, ion currents can be variable but are generally about 10-15µA C-. The transmission of the machine under these conditions to the high- energy C+ charge-state is about 35%.

Acknowledgements: This research was supported by the European Union and the State of Hungary, co-financed by the European Regional Develop- ment Fund in the project GINOP-2.3.2.-15-2016- 00009 ‘ICER’.

References: [1] G. F. Herzog et al. 2015. Cosmogenic nuclides in Antarctic meteorites. In: 35 Seasons of U.S. Antarctic Meteorites (1976–2010): A Pictorial Guide to the Collection, AGU Special Publication 68. (eds. Kevin Righter et al.) New York: Wiley. pp. 153-172. [2] Jull, A. J. T. (2006) Terrestrial ages of meteorites. In Meteorites and the Early Solar System II (eds. D. Lau- retta and H. Y. McSween, Jr.), University of Arizona Press, Tucson, pp. 889-905. [3] Jull A. J. T. et al. (1998) Geochimica et Cosmochimica Acta 62: 3025-3036. [4] Meszaros et al. (2017) Radiocarbon, in press. [5] Lifton N. A. et al. (2001) Geochimica et Cosmochimica Acta 65: 1953-1969. [6] Goehring B. H. et al. (2011) Geology 39: 679-682. [7] Fülöp R. et al. (2015) Nuclear Instru- ments and Methods B 361: 20-24. [8] Miyake F. et al. (2012) Nature 486:240–242. [9] Miyake F., et al. (2013) Nature Communications 4: 1748. [10] Jull A. J. T. et al. (2014) Geophysical Research Letters 41: 3004-3010. [11] Güttler D. et al. (2015) Earth and Planetary Sci- ence Letters 411: 290-297. [12] Fogtmann-Schultz, A. et al. (2017) Geophysical Research Letters 44: 8621- 8628. [13] Miyake, F. et al. (2017a) Proceedings of the National Academy of Sciences USA 114: 881-884. [14] Park, J. et al. (2017) Radiocarbon 59: 1147-1156.

Modern Analytical Methods II 2017 25

APPLICATION OF IMAGE ANALYSIS IN OPTICAL MICROSCOPY OF ORDINARY CHONDRITES. E. V. Petrova, M. S. Petrov, and V.I. Grokhovsky, Institute of Physics and Technology, Ural Federal University, Ekaterinburg, 620002, Russian Federation. E-Mail: [email protected].

Most of meteorite collections contain sections/thin the sample texture instead of traditional qualitative sections and slices of meteoritic material, which are description. Moreover, these characteristics depend on avaliable for the microscopic study. Ordinary chon- the of the processes that took place within the sample drites consist of various mineral phases such as olivine, (flowing of the melt, cooling, shock etc.). orthopyroxene, clinopyroxene, plagioclase, kamasite, As far as optical microscopy images, in contrast to taenite, troilite, chromite, ilmenite. Most of the phases electron microscopy images, provides color infor- can be determined using optical microscopy with mation, additional analysis parameter can be used. In transmitted light (TL) and reflected light (RL). Optical the case of the same image-capture conditions provid- microscopy is a useful non-destructive method, which ed, images of the different zones in monomict breccia give information about as phase composition as distri- can be compared to each other; as images of the heat- bution of grains of different phases within the sample. ed/shocked samples can be compared to the initial Application of image analysis systems give addi- samples texture. It is important, because different phase tional possibilities for estimation, calculation and com- positioning causes different strength properties of the parison of microscopic images. It allows to provide meteoritic material, which means strength properties of measurements on a large area of the section with a high the asteroid/meteoroid material. spatial resolution, up to the scanning of the whole pol- In our laboratory we recently studied samples of ished surface of the fragment at once (see, for example several ordinary chondrite fragments (Chelyabinsk [1]). It demands less complicated sample preparation LL5, Annama H5 and Tsarev L5). Optical images were for the study than, for instance, electron microscopy. obtained using Axiovert 40MAT (Carl Zeiss, RL), Moreover, image analysis of optical microscopy imag- Laboval 2 (Carl Zeiss Jena, TL), Meiji MX 8530 (TL). es can be easily applied using equipment that most of Further image analysis was performed with SIMAGIS laboratories already have. This is method for direct software and Panoramic Microscopy System SIAMS observations. Phase composition can be obtained using MT. indirect methods, while phase distribution – using Application of image analysis in optical microscopy computer tomography or optical microscopy image of ordinary chondrites permitted us: analysis.  to investigate phase distribution in the sample Different integral parameters can be measured for volume (from the one side of the sample to an- the troilite, metal or chromite phase inclusions in the other); section, for instance:  to measure and compare the texture of the dif-  Spatial phase distribution and its size distribu- ferent meteorite zones; tion;  to measure the porosity and jointing of the sam-  Shape and relative situations of the grains; ple texture;  Intergrowings or distinctive inclusions parame-  to measure the color differences between com- ters. parable meteoritic material; Different stereological and morphological characteristics can be measured for individual grain as well as Therefore, image analysis provides additional numeri- for every grain in the section (see [2]). On the basis of cal information about texture, and processes that mete- these data several assumptions concerning phase trans- orite fragment experienced. formations, thermal history or shock metamorphism in Acknowledgements: This work was supported by the meteoritic material can be developed. For instance, the Ministry of Education and Science of the Russian it was noted that amount of large metal grains in the Federation (the Project # 3451, 4825) and by Act 211 thin sections increases with the petrologic type of ordi- Government of the Russian Federation, contract № nary chondrite from 3 to 6 [3]. Besides, increasing of 02.A03.21.0006. the roughness factor value (FR) for both H and L References: [1] Kohout T. et al. (2017) Meteoritics chondrites with the petrologic type was revealed [3]. & Planetary Science 52, Nr 8, 1535-1541. [2] Other textural features of the meteorite fragment, Negashev V. S. and Grokhovsky V. I. 2000. Meteorit- such as porosity and jointing can be measured by im- ics & Planetary Science 35, No 5, A117-118 [3] Zhi- age analysis. It can realize quantitative description of ganova E.V. and Grokhovsky V. I. (2003) Meteoritics & Planetary Science 38, Nr 7, A58. 26 LPI Contribution No. 2021

COMPLEX ORGANICS IN THE ICY BODIES IN PLANETARY SYSTEMS- ACCEPTED NOTIONS AND NEW IDEAS I.Simonia1 and D. P. Cruikshank2, 1School of Natural Sciences and Engineering of Ilia State University, Cholokash- vili str., 3/5,Tbilisi 0162, Georgia, [email protected], 2Astrophysics Branch, NASA Ames Research Center, Moffett Field, CA 94035, USA. [email protected].

Introduction: Comets are widely acknowledged to Frozen hydrocarbon matter in cometary nuclei in the contain some of the most primitive matter in the Solar form of dense clusters of microcrystals similar to snow System, including ices, minerals, and organic material, may be the main source of fine dispersed organic icy both simple and complex. A substantial number of particles of cometary comae. Sources of hydrocarbons previously unidentified spectral emission features ob- irregularly distributed in the inner layers of the cometa- served in comets can be explained as emission by hy- ry nuclei that have not been processed by solar radia- drocarbon molecules enclosed in a Shpolskii matrix tion are cometary relicts – witnesses of Solar System and forming frozen hydrocarbon particles (FHP) that formation. During cometary outbursts or flares certain are nano- to micrometer in size [1]. FHPs contribute portions of such relict matter is injected into cometary both to the emission of spectral lines and bands, and comae where it is subsequently photo-excited. The de- the scattering of sunlight in cometary comae. UV- excitation of previously excited molecules (relict mole- induced luminescence spectra of a number of prebiotic cules) then gives rise to bright luminescence emission. and biotic molecules exhibit spectral emission lines Optical spectra of the cometary bursts could be rich in coincident with unidentified comet lines, and open the unknown emission lines or featureless bands especially possibility of the presence of these complex organic as in the blue range. Photoluminescence spectra of poly- components of the primitive organic inventory of com- cyclic aromatic hydrocarbons at temperatures T > 100 ets. Organics that appear to have originated in a primi- K have a featureless character in the form of extended tive icy body much larger than ordinary comets are blue emission (4000-4900 AA). This extended blue found on three of Saturn's icy satellites. Phoebe, the emission in cometary spectra appears to have been first ~200 km diameter outer satellite of Saturn, originated detected by [3]. In the terminology of Bobrovnikoff, in distant regions of the Solar System, apparently ag- “violet type spectra” were detected in several comets. gregating and sequestering primitive organic matter Archived spectroscopic data of the cometary outbursts from the original solar nebula. Phoebe was later cap- or flares must be reanalyzed in light of this prob- tured as a Saturn satellite, and a relatively recent im- lem.We have also described the cometary FHPs as a pact on its surface dispersed material from its interior molecularly dispersed structure and substitutional solid into circum-Saturn space where it now accumulates on solution structure. Such substance might be abundant in two other Saturn satellites, Iapetus and Hyperion. Fu- terrestrial planets and exoplanetary objects. ture studies may link the Phoebe organics to comet Results: We present here two new perspectives on the organics, although at present the connection is conjec- organic materials in the Solar System. The first con- tural. cerns the form in which organics are held in comet Main Aspects: Frozen hydrocarbons are components nuclei, and when ejected into the coma produce optical of cometary ice. and it can reasonably be expected that spectral bands through the luminescence effects of the different layers of cometary nuclei are rich with com- Shpolskii matrix. In support of this, we show that a plex aromatics and aliphatics. These hydrocarbons number of previously unidentified comet emission consist of unified structures that include solid solu- bands and lines are coincident in optical wavelength tions, polycrystalline mixtures, and substitutional ma- with laboratory measurements of molecules in the trices. As has often been noted [2], there may be a con- Shpolskii matrix, and can therefore identified with nection of the complex organic chemistry of comets sufficient reliability. Several of these molecules might that includes prebiotic and biotic components to the be of prebiological interest. They may constitute part origin of life. Intense solar ultraviolet radiation, the of the ice component of comet nuclei and emerge into flux of charged particles, and the structure of cometary the coma as frozen hydrocarbon particles (FHP). As organics would appear to stimulate luminescence phe- such, they contribute both to the optical (spectral) nomena in organic-rich cometary ice that may be de- emission signature of a comet and to the scattering of tectable. We have suggested that a Shpolskii matrix in sunlight that together characterize the coma surround- the form of polycrystalline mixtures (PAHs in n- ing the nucleus as the comet warms on approach to the alkanes) might be a significant component of the com- Sun in its elliptical (or parabolic) orbit. Parameters of plex organic substance comprising a major fraction of a certain minerals were discussed as well. comet's mass. Modern Analytical Methods II 2017 27

References: [1]Simonia, I. (2011) AJ, 141, 56 -61. [2] Oró, J. et al. (2006) In Comets and the Origin and Evolution of Life. Ed. Thomas, P. J., Hicks, R. D., Chyba, C. F., McKay, C. P. Springer, pp. 1-27. [3]Bobrovnikoff, N.T. (1927) ApJ, 66,439-464.

28 LPI Contribution No. 2021

LUMINESCENCE OF COMETARY SUBSTANCE. I. Simonia 1 and A. Gucsik 2, ,1 The School of Natural Sciences and Engineering, Ilia State University, Cholokashvili str., 3/5, Tbilisi, 0162, Georgia, [email protected], 2 Hungarian Academy of Sciences, Budapest, Hungary, [email protected].

Introduction: It is proposed that under the action of the comets will have a significant importance as under solar, X-ray and UV photons and of the fluxes of low temperature conditions, the quantum yield of pho- charged particles of the solar wind, the cometary and toluminescence of many substances increases signifi- other small bodies mineral substance are display vari- cantly [2]. It is necessary to take into account the fact ous luminescence phenomena. The conditions under that, in contrast to the conditions of laboratory experi- which this luminescence intensity can be compared in ments, the natural cosmic material is subjected to the intensity with the scattered solar radiation are dis- influence of the whole range of the solar shortwave cussed. The mechanisms of luminescence processes electromagnetic radiation spectrum. This, in turn, can and the methods of its identification in the cometary favor a high intensity of photoluminescence of cometa- spectra are considered. It is suggested that the small ry substance.In many cases, photoluminescence intensi- bodies of the Solar System may be sources of a red ty may not be weaker than the scattered solar radiation, luminescence similar to the red luminescence of inters- but can dominate over the latter [3]. Taking into ac- tellar dust, presumably related to the presence of or- count the definite similarity between meteorites and ganic matter. Other plausible materials and in particu- certain comets it seems reasonable to carry out a series lar minerals such as silicates, may also be identified of laboratory experiments for comprehensive studies of from their luminescence spectra. photoluminescence of meteorites and, in particular, of Photo- and Cathodoluminescence of Cometary carbonaceous chondrites in context of cometary sub- Substance: The photoluminescence of comets can be stance luminescence problem. This will allow to collect of fluorescence or phosphorescence character depend- a reliable database for comparative analysis (e.g., mi- ing on the chemical-mineralogical composition of its cro-and nano-minerals from nature and experiment, surface and halo material. It is known that under low [4]. temperature conditions, complex organic molecules Results: In this work the processes of photolumines- such as PAHs can display a bright photoluminescence cence and cathodoluminescence of comets and other with a high quantum yield within 50-90% [1]. The im- small bodies of the solar system are discussed. It is portance of studying the photoluminescence of cometa- suggested that the intensity of the luminescence could ry substance is thus obvious. The photoluminescence be comparable with the scattered solar radiation, and in may provide reliable information on the chemical and some cases, could exceed it. Duration and other cha- mineralogical composition, temperature, and some racteristics of the luminescence of the cometary sub- peculiarities of crystal lattice (point defects) of cometa- stance are estimated. The concept of identification of ry materials including mineral substance. The photoluminescence emissions in the spectra of small bodies luminescence spectra of cometary substance will vary are proposed. However, one must point out that the in intensity, band positions and shapes depending on application of our suggestion to a positive detection of the characteristic properties of the specific materials of luminescence phenomena from comets require to per- their surfaces and halo. The detection of photolumines- form a careful set of laboratory experiments. The most cence from ground-based telescopes will depend (i) on relevant solids to be investigated are meteorites of var- the quantum yield of the photoluminescence of the ious types but other synthetic materials such as material of the given comet and (ii) on the albedo of amorphous carbon as well as organic molecules may be the cometary substance. The minimum, but sufficient also considered. Experiments must provide not only condition for detection of the photoluminescence of the good and interpretable spectra but must also address comets will depend on a combination between a high the efficiency of the processes invoked so as to be able quantum yield of the photoluminescence (ℓ) of the ma- to quantify the respective intensity of the luminescence terial and an as low as possible albedo (A) of the latter. to the scattered light from the surface of the cosmic Numerically this can be expressed as ℓ  50%, A body. Results of laboratory detection of luminescence 0.2.The proposed values may be deduced from careful of minerals of meteorites are presented. Results of the laboratory experiments, mainly based on simulations comparative analysis of mineral luminescence with reproducing the physical characteristics of cometary unidentified cometary emissions are presented as well. substance (composition, temperatures and average ir- Some other aspects of the problem are under consid- radiation in space). The temperature of the material of eration. Modern Analytical Methods II 2017 29

References: [1] D'Hendecourt, L. B. et al. (1986) A& A 170 (1), 91. [2] Gudipati, M. S. et al.(2003), ApJ 583 (1), 514. [3] Simonia, I. (2011) AP&SS 332 (1), 91. [4] Gucsik, A. et al. (2012) MiMic 18,1285.

30 LPI Contribution No. 2021

MEAN ATOMIC WEIGHT OF STUBENBERG METEORITE. M. Szurgot, Lodz University of Technology, Center of Mathematics and Physics, Al. Politechniki 11, 90 924 Lodz, Poland, ([email protected]).

Introduction: Stubenberg meteorite is a very Braunschweig chondrites. Data concern falls and one intersting LL6 chondrite, which fell on March 6th, 2016 find (NWA 7915), and the bulk composition of meteor- in Germany [1]. Mineralogical, chemical, and some ites does not include H2O. physical characteristics of this new meteorite have been recently reported [1]. It was established that Table 1 Mean atomic weight Amean, mean atomic number Stubenberg is a fragmental breccia, weekly shocked Zmean, Amean/Zmean ratio, and Fe/Si atomic ratio of (S3) [1]. The aim of the paper was to determine and Stubenberg, Ensisheim [6], Chelyabinsk [9], Olivenza, Siena analyze mean atomic weight and mean atomic number [10], Hautes Fagnes [10], NWA 7915 [10], Sołtmany [2], of the Stubenberg meteorite, and to predict grain den- and Braunschweig [7] chondrites. sity of the chondrite. Mean atomic weight and mean Meteorite A Z A/Z Fe/Si atomic number, bulk and grain densities are important (class) properties to characterize minerals, rocks, planets, Stubenberg 23.65 11.70 2.021 0.551 moons and asteroids, and are important to classify me- (LL6 S3) teorites, and to characterize meteorite parent bodies [2- Ensisheim 23.32 11.51 2.026 0.509 11]. The bulk composition of Stubenberg, and mineral (LL6 S4) composition determined by Bischoff and co-workers Chelyabinsk [1] was applied in calculations. Light lith. 23.47 11.58 2.027 0.545 Results and discussion: Bulk composition of the Dark lith. 23.63 11.66 2.027 0.571 meteorite has been used to calculate mean atomic Mean* 23.52 11.61 2.026 0.553 weight Amean and mean atomic number Zmean using (LL5 S4) the following formulas: Olivenza 23.29 11.50 2.025 0.493 Amean = ∑wi/ ∑(wi/Ai), (1) (LL5 S3) Zmean = ∑wi/ ∑(wi/Zi), (2) Siena 24.47 12.10 2.022 0.734 where wi(wt%) is the mass fraction of ith element, and (LL5) ith oxide, Ai is atomic weight of ith element, and Zi is atomic number of ith element. Apart from elements and Hautes 23.11 11.44 2.020 0.529 oxides, which concentration (wi) was determined by Fagnes 23.35 11.56 Bischoff and co-workers [1] by inductively coupled (LL5 S1) plasma atomic emission spectroscopy (ICP-AES), and NWA 7915 22.80 11.29 2.019 0.529 inductively coupled plasma sector field mass spec- (LL5 S2) trometry (ICP-SFMS), concentration of certain ele- Sołtmany 23.97 11.85 2.022 0.588 ments such as: Si, S, C, and O was added in calcula- (L6 S2) tions, assuming that Stubenberg meteorite contains the Braunschweig 23.68 11.72 2.021 0.587 mean abundance of Si (19.01 wt%), S (2.05 wt%), C (L6 S4) (0.07 wt%), and O (37.38 wt%) as the other LL6 *2/3 light lithology + 1/3 dark lithology. chondrites falls, according to Jarosewich’s data [12]. Apart from the bulk composition data, also Fe/Si Table 2 Amean values of Stubenberg, determined by bulk ratio, grain density dgrain, and magnetic susceptibility composition (eq.(1)), minerals composition (eq.(1)), and by χ were used to predict Amean values by Amean(Fe/Si), relationships (eqs (3) - (6)). Amean(dgrain), and Amean(logχ) relationships, recent- Bulk Mine- Fe/Si dgrain χ Fe/Si,d,χ ly established by Szurgot (e.g. [2-6, 9-10]): rals Amean(Fe/Si) = 5.72∙Fe/Si + 20.25, (3) 23.65 23.33 23.40* 23.70** 22.09# 23.06 Amean(dgrain) = 7.51∙dgrain - 2.74, (4) *For Stubenberg Fe/Si = 0.551, **for dgrain = 3.52 g/cm3 Amean(logχ) = 1.49∙logχ + 16.6. (5) predicted by eq. (8). #For logχ = 3.683 ± 0.015 [1]. Amean(Fe/Si,d,χ) = [Amean(Fe/Si)+Amean(dgrain)+ + Amean(logχ)]/3. (6) Tables 1 and 2 show that Stubenberg Amean(Bulk Table 1 compiles values of Amean, Zmean and composition) = 23.65 is close to the mean atomic Amean/Zmean ratios calculated for bulk composition weight of Braunschweig (23.68), and to Chelyabinsk of Stubenberg, Ensisheim, Chelyabinsk, Olivenza, Si- Amean (23.47 for light lithology, and 23.63 for dark ena, Hautes Fagnes, NWA 7915, Sołtmany, and Modern Analytical Methods II 2017 31

lithology), and Stubenberg Fe/Si atomic ratio (0.55) is and mean atomic weight dgrain(Amean) is expressed close to Chelyabinsk Fe/Si atomic ratio (0.55). by the equation [2, 3]: In addition, Stubenberg Amean/Zmean ratio (2.021) dgrain(Amean) = 0.133∙Amean + 0.37. (8) and Braunschweig Amean/Zmean ratio (2.021) are Substituting Amean = 23.65 into eq. (8) gives identical, and Stubenberg Zmean (11.7), Braunschweig dgrain = 3.52 ± 0.07 g/cm3 for grain density of Zmean (11.7), and Chelyabinsk Zmean (11.6) are very Stubenberg meteorite. close to each other. Third prediction of dgrain is based on the modal Table 2 reveals that Fe/Si atomic ratio and grain composition of the meteorite, and grain densities of density satisfactorily predict Amean values for Stuben- constituent minerals. It is given by the equation: berg, and magnetic susceptibility leads to too low value dgrain(minerals) = ∑wi/ ∑(wi/di), (9) of Amean. Arithmetic mean Amean(Fe/Si,d,χ) = 23.06 where wi(wt%) is the mass fraction of ith mineral, and ± 0.86 confirms that Stubenberg is one of LL di is grain density of ith mineral. chondrites (AmeanLL = 22.90 [4]), but Amean value Using the same values of wi(wt%) for Stubenberg min- determined by bulk composition (23.65) indicates ra- erals, as previously for Amean(minerals) determina- ther L/LL intermediate group (AmeanL/LL = 23.34 ± tion, and grain densities: 3.58 g/cm3 for olivine, 3.2 0.19 [4]), or even L group (AmeanL = 23.67 [4]), and g/cm3 for both pyroxenes, 2.7 g/cm3 for plagioclase, Fe/Si ratio (0.55) indicates L/LL group (Fe/SiL/LL = 4.74 g/cm3 for troilite, and 7.9 g/cm3 for Fe, Ni metal 0.54 ± 0.03 [4]). (kamacite and taenite) leads to grain density of Second column in Table 2 presents the Stubenberg Stubenberg dgrain(minerals) = 3.49 g/cm3 (Table 3). mean atomic weight Amean(Minerals) calculated by minerals composition (eq. (1)), and wi(wt%) is here the Table 3 Grain density d(g/cm3) of Stubenberg meteorite, mass fraction of ith mineral, and Ai is atomic weight of determined by relationships expressed by eqs. (7) - (9). ith mineral. Using the same modal compostion for d(Fe/Si) d(A) dminerals dmean Stubenberg as that for Ensisheim chondrite [13], and 3.53 3.52 3.49 3.51 mean atomic weights of main minerals of the Stuben- Grain density values predicted for Stubenberg mete- berg: olivine Fa31.4Fo68.6 [1] (wOL = 0.5332, orite: 3.49, 3.52, 3.53, and mean density: 3.51 ± 0.02 AOL=22.928), low Ca pyroxene En72.6Fs25.4Wo2 [1] 3 g/cm are reasonable since they are close to the mean (wOpx = 0.1947, AOpx = 21.743), high Ca pyroxene 3 value for grain density of LL falls (3.52 g/cm [14]). En47.4Fs11.2Wo41.4 [1] (wCpx = 0.0632, ACpx = Conclusions: Mean atomic weight of Stubenberg 22.091), plagioclase Ab83.4An11.1Or5.5 [1] (wPL = LL6 chondrite is close to the mean atomic weight of 0.1027, APL = 20.397), troilite ((wtr = 0.0599, Atr Chelyabinsk LL5 chondrite, and is close to Amean of =43.954), Fe,Ni metal (kamacite Fe90Ni3.9Co6.1 [1], Braunschweig L6 chondrite. Stubenberg Fe/Si ratio is and taenite Fe53.68Ni44.39Co1.8Cu0.22 [1]) (wMe = close to the Chelyabinsk Fe/Si ratio. Predicted grain 0.024, AMe =56.636) leads to Amean(Minerals)= density for Stubenberg meteorite is close to the mean 23.33. Amean’s values of Stubenberg minerals: AOL, grain density of LL falls. AOpx, ACpx, WPL, Atr, and AMe were calculated by References: [1] Bischoff A. et al. (2017) eq. (1), using the mineral composition established by Metoritics & Planet. Sci., 52, 1683-1703. [2] Szurgot Bischoff and co-workers [1]. M. (2015) Acta Societ. Metheor. Polon., 6, 107-128. Bulk density of the Stubenberg chondrite was meas- [3] Szurgot M. (2015) LPSC XLVI, Abstract #1536. [4] ured by Bischoff et al. (dbulk = 3.40 g/cm3) [1]. Grain Szurgot M. (2016) LPSC XLVII, Abstract #2180. [5] density has not been determined so far. To predict Szurgot M. (2017) LPS XLVIII, Abstract #1130. [6] grain density dgrain of the Stubenberg chondrite rela- Szurgot M. (2017) Acta Societ. Metheor. Polon. 8, tionships discovered by Szurgot [2, 3, 9-11] have been 110-122. [7] Szurgot M., Wach R. A., Bartoschewitz used. R. (2017) Metoritics & Planet. Sci., 52 Suppl. S1, First relationship is between density dgrain and #6002.pdf. [8] Szurgot M. (2016) Metoritics & Planet. Fe/Si atomic ratio. It is given by the equation [11]: Sci., 51 Suppl. S1, #6021.pdf. [9] Szurgot M. (2015)

Metoritics & Planet. Sci. 50 Suppl. S1, #5008.pdf. [10] dgrain(Fe/Si) = 0.765∙Fe/Si + 3.11. (7) Szurgot M. (2016) Acta Societ. Metheor. Polon., 7,

133-143. [11] Szurgot M. (2017) Metoritics & Planet. Substituting Fe/Si = 0.551 into eq. (7) gives d = 3.53 Sci., 52 Suppl. S1, #6008.pdf. [12] Jarosewich E. ± 0.07 g/cm3 for grain density of Stubenberg meteorite. (1990) Meteoritics, 35, 323-337. [13] McSween H. Y. Apart from the Fe/Si ratio, also mean atomic weight et al. (1991) Icarus, 90, 107-116. [14] Macke R. J. Amean enables one to predict grain density for ordi- (2010) PhD Thesis, Univ. Central Florida, Orlando. nary chondrites. The relationship between grain density 32 LPI Contribution No. 2021

UNCOMPRESSED DENSITY OF THE MOON, LUNAR MANTLE AND CORE. M. Szurgot, Lodz University of Technology, Center of Mathematics and Physics, Al. Politechniki 11, 90 924 Lodz, Poland ([email protected]).

Introduction: Knowledge of densities, iron to sili- Author’s data reveal that d(Fe/Si) relationship is val- con ratios, and mean atomic weights is important to id not only for rocky planets, asteroids, moons, OC, characterize minerals and rocks, planets, moons, and and EC chondrites, but also for ferromagnesian asteroids. The aim of the paper was to apply relation- chondrules. ship between density and Fe/Si ratio for extraterrestrial Figure 1 shows that Moon’s and Earth’s Fe/Si atom- materials to verify Moon’s uncompressed density, and ic ratios, and uncompressed densities much perfectly Fe/Si atomic ratio. Literature data on chemical compo- the relationship. For example, literature data indicate sition and density of the Moon [1-16] have been used uncompressed density d = 3.27 g/cm3 for the Moon to verify and apply d(Fe/Si) relationship, recently es- [10,12], and substituting Fe/Si values: 0.205 [1], and tablished for planetary materials, chondrules, 0.213 [6] into eq. (4) predicts the same value d = 3.27 chondrites, chondrules, planets, and asteroids by ± 0.04 g/cm3 for uncompressed density of Moon. Szurgot [17]. Results and discussion: Recently relationships be- Table 1. Moon’s Fe/Si atomic ratio, uncompressed density tween mean atomic weight Amean and density d of predicted by d(Fe/Si) dependence (eq. (4)), and atomic meteorites, planets, moon, and asteroids have been weight Amean for various Moon’s models. established [18-21]. They are expressed by the equa- Moon Fe/Si d(Fe/Si) Amean tions: (g/cm3) Amean = (7.51 ± 0.13)∙d - (2.74 ± 0.55), (1) TWM* 0.205 [1] 3.27 21.52 d = (0.133 ± 0.002)∙Amean + (0.37 ± 0.07), (2) BM 1# 0.296 [2] 3.34 22.44 where d(g/cm3) is a planetary uncompressed density, or BM 2 0.063 [3] 3.16 20.96 grain density of meteorites [18-21]. Using eq. (2) we can predict d, if Amean is known. Values of RMSE: BM 3a 0.074 [3] 3.17 21.09 0.54 for eq. (1), and 0.07 for eq. (2). BM 3b 0.135 [3] 3.21 21.37 Another important relationship is between Amean BM 4 0.301 [4,15] 3.34 22.09 and Fe/Si atomic ratio, valid also for chondrules: Interior 0 [5] 3.11 21.61 Amean = (5.72 ± 0.13)∙Fe/Si + (20.25± 0.54), (3) Interior 0.213 [6] 3.27 21.73 for which RMSE = 0.12 [18-21]. Equations (2) and (3) suggest that there exists a relationship between density Mantle 0.186 [7] 3.25 21.31 d and Fe/Si atomic ratio. Mantle+Crust 0.181 [7] 3.25 21.29 The d(Fe/Si) relationship for extraterrestrial matter LPUM## 0.138 [8] 3.22 21.14 has been discovered by the author, and verified for U. Mantle 0.157 [9] 3.23 21.80 Mars, Venus, Earth, Moon, and OC chondrites [17]. L. Mantle 0.307 [9] 3.34 22.32 The d(Fe/Si) dependence is presented in Fig. 1, and is Mantle+Crust 0.193 [16] 3.26 21.75 expressed by the equation [17]: d = (0.765 ± 0.046)∙Fe/Si + (3.11 ± 0.03). (4) Crust 0.119 [7] 3.20 20.93 H. Crust 0.082 [10] 3.17 21.57 Range 0 - 0.30 3.1 - 3.34 21 - 22.4 *TWM = Taylor Whole Moon, #BM = Bulk Moon, LPUM## = Lunar Primitive Upper Mantle, U = upper, L. Mantle = Lower Mantle, H. Crust = Highland Crust.

For Fe/Si ratio established for the upper mantle (0.138) eq. (4) predicts 3.22 g/cm3, the same value which was recently given for the lunar mantle [11]. Predicted density for lunar crust (3.17 g/cm3) is, however too high. Lower bound (3.11 g/cm3) indicated Fig. 1 Relationship between d and Fe/Si atomic ratio (eq. for density by eq. (4) is too high for crustal materials, (4)). It is seen that Earth’s data: d = 3.955 g/cm3 [10,12], and and recent GRAIL data reveal crustal density as low as Fe/Si = 1.104 [14]), and Moon’s data: d = 3.27 g/cm3 [10,12], and Fe/Si = 0.205 [1] verify d(Fe/Si) relationship. Modern Analytical Methods II 2017 33

2.55 g/cm3 [11], that is even lower than the previous Lunar core Amean = 50.3 ± 3.7, mantle Amean = 21.9 estimations for the lunar crust 2.8 - 2.9 g/cm3. ± 0.4, crust Amean = 21.7 ± 0.4, and bulk silicates of Various Moon’s models lead to the range of uncom- mantle and crust Amean = 21.5 ± 0.4 [18]. pressed values: 3.11 – 3.34 g/cm3 for Moon (Table 1). Table 4. Lunar mean atomic weight Amean, Fe/Si atomic This means that d(Fe/Si) relationship (eq. (4)) holds ratio, and uncompressed density d. well for the Moon. Equation (4) and Table 1 data indi- Amean Fe/Si d(Fe/Si) d(g/cm3) cate that relative error in d determination is of the order 21.8±0.4 0.21±0.05 3.27± 0.04 3.27 [10,12] of 1 - 2%. Table 3 presents data on predicted values of un- There exists the inter-dependence between density compressed density of Moon’s bulk silicates and and Fe/Si ratio expressed by Fe/Si(d) relation. It is Moon’s core by d(Amean) (eq. (2)) dependence. Is is described by the equation: seen that uncompressed density of Moon’s silicates is Fe/Si = (d - 3.11)/0.765, (5) 3 3 3.23 g/cm , and lunar core: 7.06 g/cm , and 7.55 g/cm3, for which expected error is Δ(Fe/Si) ≈ 0.02 for Earth’s for mean density, and upper limit of density, respec- Fe/Si ratio: 1.10, and 0.004 for Moon’s Fe/Si ratio: tively. Data collected in Table 4 show values of 0.20. Using eq. (5) we can predict Fe/Si atomic ratio, if Moon’s mean atomic weight Amean, Fe/Si ratio, and d is known. Equation (5) predicts Fe/Si = 0.209 ± uncompressed density d, verified in this paper. 0.004 for the Moon’s uncompressed density d = 3.27 Conclusions: Dependence between density and g/cm3 (Table 2). Relative error is of order of 2%. Fe/Si atomic ratio d(Fe/Si) predicts precisely uncom- Table 2. Uncompressed density of Moon, and Fe/Si atom- pressed density of the Earth, and the Moon, and leads ic ratios predicted by Fe/Si(d) dependence (eq. (5)). to reliable values for uncompressed density of lunar 3 d(g/cm ) (Fe/Si)(d) Fe/Si mantle+crust, and lunar core. Fe/Si ratios are predicted /[reference] /[reference] by Fe/Si(density) relation. Moon’s mean atomic 3.27 [10] 0.209 ±0.004 0.205 [1] weight, uncompressed density, and Fe/Si atomic ratio 3.27 [10] 0.209 ± 0.004 0.213 [6] have been verified. Various Moon’s models lead to various values of References: [1] Taylor S. R. (1982) Planetary Sci- elemental abundance of the Moon, and as a result they ence: A Lunar Perspective, LPI, Houston. [2] predict various values of Fe/Si ratio, various values of Krahenbuhl U. et al. (1973) Science 180, 858-861. [3] mean atomic weight, and various values of uncom- Ganapathy R. and Anders E. (1974) Proc. Lunar Sci. pressed density of the Moon. Moon‘s Fe/Si ratio is in Conf., 5, 1181-1206. [4] Smith J. V. (1979) Mineral. the range of 0–0.30, predicted density d is in the range: Mag. 43, 1-89. [5] Anderson D. L. (1973) Earth Plan- 3.11 - 3.34, and Moon’s range of Amean is: 21.0 – 22.4 et. Sci Lett. 18, 301-316. [6] Ringwood A. E. and Es- [18] (Table 1). sene E., (1970) Geochim. Cosmochim. Acta 1 Data presented in Tables 1 and 2 show that eq. (4) (Suppl.1), 769-799. [7] Kuskov O. L. (1998) Constitu- for Fe/Si = 0.209 ± 0.004 gives the best value for un- tion of the Terrestrial Planets and the Moon, in: Ad- compressed density of Moon: d = 3.27 ± 0.04 g/cm3. vanced Mineralogy 3, 39-46, Springer, Berlin. [8] For this value of Fe/Si ratio we get Amean(Fe/Si) = Longhi J. (2006) Geochem. Cosmochim. Acta 70, 21.4 ± 0.1, i.e. 2% lower value Amean than that result- 5919-5934. [9] Gast P. W. (1972) The Moon, 5, 121- ed from the Moon’s bulk composition. 148. [10] Taylor S. R. and McLennan S. M. (2009) Planetary crusts: Their composition, origin, and evolu- Table 3. Moon’s mean atomic weight Amean, uncom- tion, Cambridge. [11] Wieczorek M. A. et al. (2013) pressed density d (g/cm3) resulted from d(Amean) depend- Science 339, 671-674. [12] Stacey F. D. (2005) Rep. ence (eq. (2)), and Fe/Si ratio predicted by Fe/Si(d) depend- Prog. Phys., 68, 341-383. [13] Brown G.C. and Musset ence (eq. (5)). A.E. (1993) The Inaccessible Earth, An Integrated Amean [18] d(Amean) Fe/Si(d) View to its Structure and Composition, London. [14] Moon 21.8 ± 0.4 3.27 ±0.04 0.21 ± 0.05 Kargel J.S. and Lewis J.S. (1993) Icarus 105, 1-25. Mantle 21.5 ± 0.4 3.23 ±0.05 0.16 ± 006 [15] Morgan J. V. et al. (1978) The Moon and the +Crust Planets 18, 465-478. [16] Kronrod V.A. and Kuskov Core 50.3 ± 3.7 7.06 ±0.49* 5.2 ± 0.5# O. L. (2011) Izv. Phys. Solid Earth 47, 711-730. [17] *d(Amean) range: 6.57-7.55 (g/cm3), #Fe/Si(d) range:4.7-5.7. Szurgot M. (2017) Metoritics & Planet. Sci., 52 For Fe/Si = 5.7 eq. (1) gives d = 7.47 g/cm3, and for Suppl. S1, #6008.pdf. [18] Szurgot M. (2015) LPSC th Amean = 54 eq. (2) gives d = 7.55 g/cm3 for the lunar core. 46 , Abstract #1536. [19] Szurgot M. (2015) Compar- ative Tectonics and Geodynamics, Abstract #5001. Author’s recent data indicate that the whole Moon th bulk composition leads to Amean = 21.8 ± 0.4 [18]. [20] Szurgot M. (2016) LPSC, 47 Abstract #2180. [21] Szurgot M. (2017) LPSC 48th, Abstract #1130. 34 LPI Contribution No. 2021

Streaming Swarm of Nano Space Probes for Modern Analytical Methods Applied to Planetary Sciences Pál Gábor VIZI1 András Horváth2 Szaniszlo Bérczi3 1Wigner RCP, Hungarian Academy of Sciences, H-1121 BU- DAPEST, Konkoly 29-33.Hungary [email protected], 2 Konkoly Observatory 3 ELTE Univ. Hungary

Introduction: The idea described hereby is the munications and radiation. Described concepts and concept of Streaming Swarm of Nano Space Probes possible solutions as communication in Swarm, nega- (SNP) for planetary mission to contain modern analyti- tive feedback to next part of Swarm. cal methods of nowadays applied to planetary sciences. In case of big abundances of elements of the swarm However well-known it isn’t possible to complete we can command a special part of the swarm to do a the mission described here nowadays, maybe it is inter- specific job inside a space interval. Let we divide the esting to thinking about it. space into sectors near the target – a moon, planet or Recent technologies allegedly promise fast speed star. Particular space intervals demand definite activi- space devices - probes - accelerated by a launch base ties. One classical probe is orbiting the target and until to some percent of the speed of light. Some new makes measurements in circulating or near rounding reports talk about big plans to reach really distant tar- orbit. A high speed streaming swarm couldn’t orbit the gets [1]. Several hard challenges are standing before target.But we can command the part of them at just the those plans and let we try to show some of them. target area to make the same measurements at the Author’s earlier works described the Nano, Pico same position where classical probe made. Behaviors Space Devices and Robots (NPSDR) [2-4] and the fleet of the prepared elements of the flowing swarm are turn- of Micro Sized Space-Motherships (MSSM) [5] which ing into the position dependent program branch and type or similar devices maybe can fulfill the require- collecting the data. When the element leaves the posi- ments incidentally. tion turning the behavior to the next program branch, We have tried to describe methods focus not only makes new measures and finally transmit all the col- horizontally available measuring but on vertical 3D lected data to a backward to the relay transmitter. measuring and gives a detailed, layered map on a full The kth parts of the stream make measurements and spectrum of sensors from electromagnetic waves from start to process the data. According to the results, the radio, through light to micro waves and resonating mat- kth part of the stream could send feedback to the k+1th ter by matter so get seismic and sonar like results to part of the stream and so on step by step. It is a theoret- build the complex data of structure of the target from ical possibility to pinpoint the next new specific mea- static and dynamic point of view. suring according to the preprocessed data. Swarm can When a matter hit a similar matter, the depth of im- send back the whole collected data in one time together pact can reach maximum six time deeper as the length to the Earth with the united power of the Stream at cor- of the impact object matter in direction of moving. nerstones of mission. Similar physical law is valid in case of shooting of am- Detailing: During any sensing process in the life, in munition from cannons. industry or in research the serial of results are involv- We will try to introduce a new streaming type of ing the next steps. Streaming NPSDRs have ability to NPSDR and MSSM to distribute and to handle of focus some factors which are become important until them. It will remain a big challenge today to use them then and they can emphasize more significant point of when we want to reach a surface of a planetary object. view and able to weight out the tasks. For example if Streaming Swarm of Nano Space Probes as Mis- we have some useful information about a planet which sion and Instruments Concept [6] described the trou- planet's atmosphere could be clear or cloudy just ex- bles about accelerating, decelerating, relativistic com- actly at that time then the elements of the stream which have arrived earlier can inform the next elements of the stream to set up they sensors to getting ready to use a fitted settings of parameters for the specific measuring. The result must be the same like in case of a single space probe which can turn on and off experiments and they measuring sensors in accordance with the conditions expected. Usually conditions are so rigorous to find the best balance between the available time and electrical power and the importance of significant measuring to achieve the best results for the knowledge. Modern Analytical Methods II 2017 35

Additional considerations: Conclusion: Streaming swarms gives possibilities - More independent manufacturers: more indepen- to collect data from big fields in one time. The problem dent manufacturers giving benefits during test and is to put enough smart measuring devices in small demonstration phase and finally the standardization for enough sizes. The redundancy is also coming from the the best manufacturer. large amount of abundance of the Streaming Swarm of - Telecommunications e.g. slow and fast; laser or Nano Space Probes (SNP). In case of a realistic quantum telemetry. Long term and low power con- streaming swarm mission a weighted distribution of sumption for swarm chain communications tasks necessary to elaborate during developing and the - Single or multi purposes - Combined from one whole streaming fleet necessary to behave like one big task oriented elements of swarm to multi featured sur- organization as one big integrated measuring system face with different sensors on one element of swarm. and perhaps can be realized as a planetary mission so- -Task specific altered devices are necessary at dif- lution with stream type analytical methods. ferent planetary target places. Target objects: Planets with magnetic field: Possible target objects in point of view of space physics are magnetic planets, non-magnetic planets. Planetary object size: Requirements are also different in point of view of size, ranging from asteroids, comets to rocky planets through to the gas giant sized planets. Dusty fields: Dusty places e.g. comets or rings of planets which are around of gas giants usually. References: Combined: Gaseous big planets - according to our [1] Malcolm Ritter: Stephen Hawking joins futuristic bid to ex- knowledge - significantly have moons, magnetosphere, plore outer space, phys.org, April 12 2016, phys.org/news/2016-04- dusty halo with particle shower together with huge par- stephen-hawking-life-tiny-spacecraft.html [2] Vizi P G, Horváth A, ticle streams and massive amount of individual seemly Hudoba Gy, Bérczi Sz, Sík A.: 'Lump Sugar and Salt Shaker'-Like random particles may come from even may come even Nano and Pico Space Devices and Robots, IPM International Work- long distances e.g. the distance of Kuiper Belt or Oort shop on Instrumentation for Planetary Missions. Greenbelt (MD), Cloud or high radiation galactic particles. 2012. www.lpi.usra.edu/meetings/ipm2012/pdf/1122.pdf ssed.gs- Self-Regenerating: According to last few consid- fc.nasa.gov/IPM/IPM2012/PDF/Posters/Vizi-1122.pdf [3] Vizi PG, erations, some self-regeneration is necessary which is et al.: Possible Identification Method for Martian Surface Organism possible in electrical parts of devices according to re- by Using a New Strategy of Nano-Robots, 44th LPSC#2281 2013 search of Center for Nanotechnology, NASA Ames Re- www.lpi.usra.edu/meetings/lpsc2013/pdf/2281.pdf www.lpi.us- search Center [7] By applying voltage to the gate elec- ra.edu/meetings/lpsc2013/eposter/2281.pdf [4] Vizi et al. Modern trode, the gate dielectric and isolation dielectric are an- Analytical Methods Applied to Earth and Planetary Sciences for nealed by the high temperature generated by Joule heat, Micro, Nano and Pico Space Devices and Robots in Landing Site and the damaged device can be recovered to a fresh Selection and Surface Investigation, Workshop on The Modern Ana- state. lytical Methods Applied to Earth and Planetary Science, Sopron, Possible target: Dark Dune Features in the south- Magyarország, 2014. LPI#4007 www.hou.usra.edu/meetings/meth- ern hemisphere of Mars are possible interesting targets. ods2014/pdf/4007.pdf [5] P. G. Vizi: Application of the Fleet of Mi- cro Sized Space-Motherships (MSSM) Deploying Nano, Pico Space Devices and Robots (NPSDR) in Space p. 43-44 of H-SPACE2016, space.bme.hu/sites/default/files/sima_lap/Proceedings_H- SPACE2016.pdf [6] P. G. Vizi: Streaming Swarm of Nano Space Probes as Mission and Instruments Concept, 48th LPSC #3007 2017www.hou.usra.edu/meetings/lpsc2017/pdf/3007.pdf [7] Sus- tainable Electronics for Nano-Spacecraft in Deep Space Missions Center for Nanotechnology, NASA Ames Research Center, Moffett Field, CA, USA, 2016 IEEE nobent.kaist.ac.kr/nobel/data/paper/2016/FC_DIM_sustainable %20electronics NOTES