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Polyhedral Serpentine Grains in CM Chondrites

CM chondrites are primitive rocks that experienced aqueous alteration in the early solar system. Their matrices and fine-grained rims (FGRs) sustained the effects of alteration, and the minerals within them hold clues to the aqueous reactions. Sheet silicates are an important product of alteration, and those of the serpentine group are abundant in the CM2 chondrites. Here we expand on our previous efforts to characterize the structure and chemistry of serpentines in CM chondrites and report results on a polyhedral form that is structurally similar to polygonal serpentine. Polygonal serpentine consists of tetrahedral (T) sheets joined to M(2+)-centered octahedral (O) sheets (where (M2+) is primarily Mg(2+) and Fe(2+)), which give rise to a 1:1 (TO) layered structure with a 0.7-nm layer periodicity. The structure is similar to chrysotile in that it consists of concentric lizardite layers wrapped around the fiber axis. However, unlike the rolled-up chrysotile, the tetrahedral sheets of the lizardite layers are periodically inverted and kinked, producing sectors. The relative angles between sectors result in 15- and 30-sided polygons in terrestrial samples.

Zega, Thomas J.↗

The Mid-IR Spectral Effects of Darkening Agents and Porosity on the Silicate Surface Features of Airless Bodies

We systematically measured the mid-IR spectra of different mixtures of three silicates (antigorite, lizardite, and pure silica) with varying effective porosities and amounts of darkening agent (iron oxide and carbon). These spectra have broad implications for interpretation of current and future mission data for airless bodies, as well as for testing the capabilities of new instruments. Serpentines, such as antigorite and lizardite, are common to airless surfaces, and their mid-IR spectra in the presence of darkening agents and different surface porosities would be typical for those measured by spacecraft. Silica has only been measured in the plumes of Enceladus and presents exciting possibilities for other Saturn-system surfaces due to long range transport of E-ring material. Results show that the addition of the IR-transparent salt, KBr, to simulate surface porosity affected silicate spectra in ways that were not predictable from linear mixing models. The strengthening of silicate bands with increasing pore space, even when only trace amounts of KBr were added, indicates that spectral features of porous surfaces are more detectable in the mid-IR. Combining iron oxide with the pure silicates seemed to flatten most of the silicate features, but strengthened the reststrahlen band of the silica. Incorporating carbon with the silicates weakened all silicate features, but the silica bands were more resistant to being diminished, indicating silica may be more detectable in the mid-IR than the serpentines. We show how incorporating darkening agents and porosity provides a more complete explanation of the mid-IR spectral features previously reported on worlds such as Iapetus.

Young, Cindy L.↗

Phyllosilicate Formation on Early Mars Via Open-System Acid Alteration of Basaltic Glass

Smectites are widespread on Mars, but neutral/alkaline conditions favorable for smectite formation have surprisingly not led to abundant carbonates. Smectite formation on Mars could also occur in acidic environments unfavorable for carbonate formation. Acidic smectite formation has been demonstrated in batch (closed hydrologic) systems, however, the mechanisms and octahedral composition of smectite forming in acidic flow-through (open hydrologic) systems are not fully understood. Stapafell basaltic glass was hydrothermally altered (190◦C) at two flow rates corresponding to low and high water to rock ratio (W/R) and initial pH (pH_0) values of 2, 3, 4 and 6, and a batch low W/R experiment was conducted at pH_0 2. Kaolinite, montmorillonite and chlorite formed at pH_0 2 at low W/R; no phyllosilicates formed at pH_0 2 at high W/R; and lizardite formed at pH_0 ≥3 at both W/R ratios. Lizardite, kaolinite, and montmorillonite in these experiments formed by precipitation from solution and chlorite likely formed through alteration of montmorillonite and/or basalt. Saponite formed at pH_0 2 in batch conditions by alteration of basaltic glass. Comparison of experimental data with martian phyllosilicate assemblages indicated that smectite formation on Mars likely occurred under water-limited conditions. Al-rich smectite could form in open-system low W/R subsurface environments under a narrow range of pH (pH <3) while saponite could form in closed low W/R systems under acidic to alkaline conditions. Combined open and closed hydrological regimes could be responsible for development of clay mineral stratigraphies observed on Mars. The acidic conditions required for formation of Al-rich smectite were unfavorable for carbonate precipitation, but carbonate precipitation could occur together with Fe/Mg-smectite in closed systems at pH >4. The lack of carbonates occurring together with Fe/Mg-smectite could be cause by low pCO2 in subsurface closed environments and/or by overall lack of carbonate precipitation despite significant oversaturation.

S J Ralston↗

Infrared spectra of the Orgueil /C-1/ chondrite and serpentine minerals

Infrared spectroscopy of the Orgueil C-1 chondrite and polymorphs of serpentine was performed in order to further define the mineralogy of Orgueil. Spectra of the meteorite and a synthetic serpentine (Mg3(Si2O5)(OH)4) were obtained in the regions from 1400 to 200 and from 4000 to 2500 kayers using a double beam infrared spectrometer. The spectra of Orgueil are found to be incompatible with those of the chrysotile, antigorite and lizardite polymorphs of serpentine, indicating a very low abundance of these minerals in the meteorite. It is suggested that chamosite or minerals related to chamosites may prove to be compatible with the compositional, structural and infrared properties of Orgueil.

Zaikowski, A.↗

Structures and textures of the Murchison and Mighei carbonaceous chondrite matrices

High-resolution transmission electron microscopy has confirmed earlier observations that the character of the Murchison and Mighei fine-grained matrices is complex in mineralogy and texture. Layer structure minerals occur as planar laths, rounded grains or subhedral grains, and range in size from less than 100 A to about 1 micrometer. Serpentine-type and brucite-type structures predominate in the CM matrices. The occurrence of Povlen chrysolite and a vein of disordered mixed-layer and brucite-type material cutting a large lizardite-type grain suggests that at least some of the matrix materials were formed by alteration of preexisting material.

Mackinnon, I. D. R.↗

Mineralogical studies of sulfide samples and volatile concentrations of basalt glasses from the southern Juan de Fuca Ridge

Sulfide samples obtained from Alvin dives on the southern Juan de Fuca Ridge were examined, showing the presence of two previously undiscovered minerals, both formed at low temperatures. The first detection of lizardite, starkeyite, and anatase in such an environment is also reported. Sulfide geothermometry involving the Cu-Fe-S system shows a vent temperature of less than 328 C for one sample. Ice-melting temperatures on inclusions from this sample are about -2.8 C, and fluid inclusion studies on crystals near this sample show pressure-corrected homogenization temperatures of 268 and 285 C. Volatile concentrations from vesicle-free basalt glass from the vent field are found to be about 0.0013 wt pct CO2 and 0.16 wt pct H2O.

Brett, Robin↗

Shock wave equation of state of serpentine to 150 GPa - Implications for the occurrence of water in the earth's lower mantle

The shock wave equation of state of Mg end-member serpentine was determined to 150 GPa by examining the shock properties of three polycrystalline serpentines: (1) a lizardite serpentine found near Globe (Arizona), (2) an antigorite serpentine from Thurman (New York), and (3) a chrysotile serpentine from Quebec (Canada). The shock wave experiments were carried out using either a two-stage light gas gun or a 40-mm bore propellant. The shock equation of state that was obtained is shown to exhibit four distinct regions: a low-pressure phase, a mixed phase region, a high-pressure phase, and a very high-pressure phase. The high-pressure density and sound speed of an H2O-rich magnesium silicate determined from these experiments indicate that the observed seismic properties of the lower mantle allow the existence of several weight percent of water in the lower mantle.

Tyburczy, James A.↗

Signatures of the Impact Histories of Comets and Asteroids within Shocked Phyllosilicates, Enstatite, and Forsterite Minerals

Throughout the lifetime of the solar system, collisions between small bodies and impacts on the surfaces of small bodies in the Kuiper Belt have occured at speeds of 1.5 - 3 km s-1 (Stern, Astron J 124, 2002), typically at 1-10 km s-1 between Trojan asteroids (Marzari et al. Icarus 119, 1996), and at ~4-8 km s-1 in the asteroid belt (Farinella and Davis, Icarus 97, 1992). Shock effects recorded by minerals composing these bodies are one observable legacy of this evolutionary process, whether they were generated through large collisions, micrometeoroid impacts, or processing during the formation of the solar system. Shock metamorphism has been observed in cometary samples such as those from Comet Wild 2 (Keller et al. Geochim. Cosmochim. Acta 72, 2008; Tomeoka et al. MAPS 43, 2008; Jacobs et al. MAPS 44, 2009) as well as in forsterites and enstatites found in meteorites (McCausland et al. AGU, 2010). To investigate the observable signatures of these processes, we have conducted a suite of impact experiments at NASA Johnson Space Center's Experimental Impact Laboratory (EIL). Target materials included Mg-rich forsterite (olivine), Mg-rich enstatite (orthopyroxene), and antigorite and lizardite (both in the serpentine group of phyllosilicates). Alumina-ceramic spheres were launched at speeds ranging from ~2.0 - 2.6 km s-1 into targets at temperatures from 25degC to -100degC. Recent advancements have been made in cooling targets in the EIL's vertical gun. Liquid nitrogen (LN2) is fed through a unique jacket surrounding the metallic sample container to chill the samples. Real-time values from temperature sensors attached to the sample holder are converted to target temperature through predetermined regression relationships, providing the target temperature at the time of impact with sub-degree accuracy. Fourier Transform Infrared Spectrometer (FTIR) data in the near to mid-IR will be presented, along with trends relating temperature and velocity with impact speeds, and thereby peak shock stresses experienced by the impacted minerals.

Lederer, Susan M.↗

Examining Weathering of Magnesite in an Arid Environment: Implications For Jezero Crater

Introduction:Orbiter data indicatethe presence of carbonates in severallocations on the surface of Mars[1],but Jezero crater, landing site of the Perseverancerover,is the only known location where carbonatesap-pear coincident with evidence of fluvialand lacustrineactivity [2].On Earth, carbonates in close proximity to these paleoenvironments mayindicatethe presence of past microbial life,like stromatolites[3], that could re-sult inbiosignatures [2]. However,in other cases,car-bonates can also form throughthe alteration of mafic materialwiththe introductionof carbonic acid[4].Hy-drated magnesites have also been found in evaporative environments along lake shores, and in playas[5,6,7].Correctly interpreting past carbonates on Mars is there-fore critical in the search for past signs of life. In Jezero crater,both thenorthernand western fans haveMg-rich carbonates intermixed with olivine-rich material[8].According to CRISM data, magnesite(MgCO3), along with hydromagnesite(Mg5(CO3)4(OH)2•4H2O), arepotential candidatesfor these Mg-carbonates [2]. Considering the spatial con-text with olivine,there aremultiplepotential explana-tions for the presence ofMg-carbonatesin this locationincludingin-situformation via alterationof olivine-rich materialwith carbonic acid,transportationfrom farther up in the watershed, or precipitation of lacustrine car-bonates[2]. The formation of hydromagnesite rather than magnesite is favored when Mg2+saturated solutions have a high CO32-/HCO3-ratio, which, on Earth, is thought to be caused byinflow of groundwater [4]. Additionally, Mg-carbonates tend to precipitate under high pH condi-tions and are unstable at lower pH conditions [5]. Hy-dromagnesite is stable at atmospheric CO2pressure and temperature conditions common to most Earth surface environments [9]. However, it is subject to transfor-mation to magnesite after dehydration and concomitant brucite formation or dissolution and reprecipitation [10].Previousresearch suggests that hydrated car-bonates, including hydromagnesite, can formas weath-ering productsof mafic minerals in the presenceof H2O and CO2in subfreezing temperatures and would not de-hydrate under Martian atmospheric conditions [11,12].It is critical to understand the formation conditions of Mg-carbonatesbecause of the different implications for the past history of Martian environments. Therefore, in this work we are investigating the weathering of Mg-carbonatesin arid environments to helpbetter understand Mg-carbonates in Jezero crater. Study Area:The Ala-Mar Mines(East and West)near Ely, NVare the site ofmultiple magnesitedepositsfound within a calcareous tuff formationthat overlies Tertiary aged volcanic rocks.Here,magnesiteis formed via the alteration of the calcareous tuff and occurs innodules, veins,and lenses[13]. Previous work suggests magnesite deposits are associated with faults [13]. Within the West Mine, magnesite can be found in two maincontexts: (1) relatively circular zones of cauli-flower-like material found within (2) a more massivelensthat is heavily fractured on the surface.Methods.Samplesof both the cauliflower texture and more massive materialwere collectedat Ala Mar West Mine. Both samples were thenpowdered, sieved and analyzed with an inXitu Terra Portable XRD. The program QualX was used to identify potential mineral phases [14].Both samples were also optically inspected using 10x and 20x hand lenses.Figure 1. XRD patterns for the cauliflower magnesite (top) and massive magnesite (bottom). Ongoing and future work on the samples discussed above includes scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and near-infra-red spectroscopy to determine whether hydromagnesite is present. Separation and analysis of the clay-size frac-tionby XRD will helpto better identify any phyllosili-cate phases present. Results and Discussion:Both textures are a white to light tan with a porcelain luster on weathered sur-faces, along with minor iron staining in some areas. Likewise, both textures are white with a porcelain luster on fresh surfaces. When broken apart, the massive mag-nesite shows macroscopic crystals, unlike the cauli-flower magnesite. XRD analysis shows that both samples have high concentrationsof magnesite with lesser amounts of thecarbonatemineral huntite(Mg3Ca(CO3)4; Figure1).The more massive samplecontainsa serpentine-groupmineral,with lizardite being apotential candidate. The cauliflower sample has several minor peaks that may correspond to hydromagnesite(Figure 1), although more work is needed to confirm this.Additionally, thecauliflower deposits closely resemble hydromagnesite deposits found in southwestern Turkey, formed via mi-crobialites[15].As such, it is likely that moreaqueous alterationor weatheringis occurring at the locations where the cauliflower magnesite is present. However, additional field work will need to be conducted to con-firm this hypothesis. Conclusions and Future Work:Future work will include field mapping of fault locations andadditional samplingof the different magnesite types as well as of the calcareous tuffmaterial.We will also look specifi-cally for potential weathering products of magnesite in this arid location, which may yield important insight into the Mg-carbonates located in Jezero crater. XRD analyses on aPANalytical XRDusing non-ambient stages will be used to investigate the stability of hydro-magnesiteat different humiditiesand temperatures, which has implications for samples to bereturned to Earth in the future. Additionally, thermal and evolved gas analysis of magnesite and hydromagnesite will be compared to results from Gale Craterto help interpret the mineralogy inthat location[16]. The results of this research will further ourunderstanding of carbonate for-mationin volcanic settingsandtheirweathering pro-cessesin arid environments. Acknowledgments:We acknowledge funding for this research from Jacobs Technology at the Johnson Space Center.We would also like to thank Ngoc Luu, Christopher Adcock, Richard Allanson, and the rest of the UNLV Soil Science Teamfor their continued sup-portwith troubleshooting and otherlab work. References:[1] Ehlmann, B.L., and Edwards, C.S. (2014) Annual Review of Earth and Planetary Sci., 42, 291–315. [2] Horgan, B.H.N., et al. (2020) Icarus, 339, 113526. [3] Bosak, T., et al. (2013) Annual Review of Earth and Planetary Sci, 41, 21–44. [4] Pohl, W.L. (1989) Gebriider Borntraege, 28, 1-13. [5] Müller, G., et al. (1972) Die Naturwissenschaften, 59, 158–164. [6] Walter, M.R., et al. (1973) Journal of Sedimentary Pe-trology, 43, 1021–1030. [7] Braithwaite, C.J.R., and Zedef, V. (1994) Sedimentary Geology, 92, 1–5. [8] Goudge, T.A., et al. (2015) JGR: Planets, 120, 775–808. [9] Langmuir, D. (1965) Journal of Geology, 73, 730–754. [10] Zhang, P., et al. (2000) Applied Geo-chem., 286, 1748–1753. [11] Calvin, W.M., et al. (1994) JGR, 99, 14659-14675. [12]Russell, M.J., et al. (1999) Journal of the Geological Society of London, v. 156, p. 869–888. [13] Faust, G.T., and Callaghan, E. (1948) GSA Bulletin, 59, 11–74. [14] Altomare, A., et al. (2015) J. of Applied Crystallography, 48, 598–603. [15] Zedef, V.,et al. (2000) Economic Geology, 95, 429–445. [16] Leshin, L.A. et al., (2013) Science, 341, 1–9

A W Provow↗