Calcium sulfates are known to be potential reservoirs of organic compounds and have been detected on Mars. However, not all data that indicate the presence of sulfates collected by the Mars Exploration Rovers (Spirit and Opportunity) and Curiosity rover can be explained by the different calcium sulfate polymorphs, and therefore, mixtures of calcium sulfates with other single sulfates must be considered. In addition, the presence of mixed calcium sulfates supports the data and indicates that the molar ratio of sulfate/calcium is >1. To obtain adequate spectroscopic information of mixed-cation sulfates to be used in the interpretation of data from Mars in the next few years, the thermodynamically stable syngenite (K2Ca(SO4)2·H2O) and görgeyite (K2Ca5(SO4)6·H2O) mixed-cation sulfates have been studied along with the interrelationships in the gypsum–syngenite–görgeyite system to understand their possible formation on Mars. Raman spectroscopy and Visible–Near Infrared–Shortwave Infrared (VisNIR) spectroscopy have been used for their characterization to increase the databases for the two future Mars exploration missions, Mars2020 and ExoMars2022, where both techniques will be implemented. These VisNIR data can also help with the interpretation of spectral data of salt deposits on Mars acquired by the OMEGA and CRISM spectrometers onboard the Mars Express and Mars Reconnaissance orbiters. This work demonstrates that syngenite (K2Ca(SO4)2·H2O) easily precipitates without the need for hydrothermal conditions, which, depending on the ion concentrations, may precipitate in different proportions with gypsum. Furthermore, in this study, we also demonstrate that, under hydrothermal conditions, görgeyite (K2Ca5(SO4)6·H2O) would also be highly likely to form and may also be identified on Mars together with syngenite and gypsum.
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References
1.
AgeeCB, WilsonNV, McCubbinFM, et al. (2013) Unique meteorite from early amazonian mars: water-rich basaltic breccia Northwest Africa 7034. Science, 339:780–785.
2.
AlexandrowiczZ and MarszałekM (2019) Efflorescences on weathered sandstone tors in the stone town nature reserve in Ciężkowice (the outer Carpathians, Poland)—their geochemical and geomorphological controls. Environ Sci Pollut Res, 26:37254–37274.
3.
AlexandrowiczZ, MarszałekM, and RzepaG (2014) Distribution of secondary minerals in crusts developed on sandstone exposures. Earth Surf Processes Landforms, 39:320–335.
4.
ArvidsonRE, SquyresSW, Bell IIIJF, et al. (2014) Ancient aqueous environments at Endeavour crater, Mars. Science, 343:1248097.
5.
AubreyA, CleavesHJ, ChalmersJH, et al. (2006) Sulfate minerals and organic compounds on Mars. Geology, 34:357–360.
6.
AyalaR and Itzel K (2016) Análisis Geológico de La Región Oxia Planum EnMarte, Sitio Principal de Aterrizaje de La MisiónExoMars . Universidad Nacional Autónoma de México, México DF.
7.
BarbieriR and StivalettaN (2011) Continental evaporites and the search for evidence of life on Mars. Geol J, 46:513–524.
8.
BenedettoC, FortiP, GalliE, et al. (1998) Chemical deposits in volcanic caves of Argentina. Int J Speleol, 27:155–162.
9.
BenisonKC and KarmanockyFJ (2014) Could microorganisms be preserved in Mars gypsum? Insights from terrestrial examples. Geology, 42:615–618.
10.
BorchertH and Muir RO (1964) Salt Deposits: The Origin, Metamorphism and Deformation of Evaporites, Vol VIII. D. Van Nostrand. Co. Ltd, London.
11.
BridgesJC and GradyMM (2000) Evaporite mineral assemblages in the Nakhlite (martian) meteorites. Earth Planet Sci Lett, 176:267–279.
12.
BridgesJC, CatlingDC, SaxtonJM, et al. (2001) Alteration assemblages in martian meteorites: implications for near-surface processes. Space Sci Rev, 96:365–392.
13.
CaiK, ZhaoD, LiaoL, et al. (1985) The mineralogy of gorgeyite. Earth science. J China Univ Geosci, 10:21–28.
14.
CavarrettaG, MottanaA, and TecceF (1983) Gorgeyite and syngenite in the Cesano geothermal field, Latium, Italy. Neues Jahrb Mineral Abh, 147:304–314.
15.
CombsLM, UdryA, HowarthGH, et al. (2019) Petrology of the enriched poikilitic shergottite Northwest Africa 10169: insight into the martian interior. Geochim Cosmochim Acta, 266:435–462.
16.
CousinA, SautterV, PayréV, et al. (2017) Classification of igneous rocks analyzed by ChemCam at Gale Crater, Mars. Icarus, 288:265–283.
17.
CrowleyJK (1991) Visible and near-infrared (0.4–2.5μM) reflectance spectra of playa evaporite minerals. J Geophys Res Solid Earth, 96:16231–16240.
18.
CrowleyJK and Clark RN (1992) AVIRIS study of DeathValley evaporite deposits using least-squares band-fitting methods. Summaries of the Third Annual JPL Airborne Geoscience Workshop. Vol 1, AVIRIS Workshop, pp 29–31.
19.
DeitLL, MangoldN, ForniO, et al. (2016) The potassic sedimentary rocks in Gale Crater, Mars, as seen by ChemCam on board Curiosity. J Geophys Res Planets, 121:784–804.
20.
DownsRT and HallMK (2002) A database of crystal structures. Published in the. American Mineralogist and The Canadian Mineralogist and Its Use as a Resource in the Classroom. 18th Gen. Meet. Int. Mineral. Assoc.
21.
ErikssonG (1979) An algorithm for the computation of aqueous multi-component, multiphase equilibria. Anal Chim Acta, 112:375–383.
22.
FairénAG, DavilaAF, Gago-DuportL, et al. (2009) Stability against freezing of aqueous solutions on early Mars. Nature, 459:401–404.
23.
Fleischer M (1955) New mineral names. Am Mineral 40, 551–554.
24.
FrançoisP, SzopaC, BuchA, et al. (2016) Magnesium sulfate as a key mineral for the detection of organic molecules on Mars using pyrolysis. J Geophys Res Planets, 121:61–74.
25.
GhadimiF and GhomiM (2013) Geochemical and sedimentary changes of the Mighan Playa in Arak, Iran. Iran J Earth Sci, 5:25–32.
26.
GoodrichCA, TreimanAH, FilibertoJ, et al. (2013) K2O-rich trapped melt in olivine in the Nakhla meteorite: implications for petrogenesis of nakhlites and evolution of the martian mantle. Meteorit Planet Sci, 48:2371–2405.
27.
GrotzingerJP, SumnerDY, KahLC, et al. (2014) A habitable fluvio-lacustrine environment at Yellowknife Bay, Gale Crater, Mars. Science, 343:1242777.
28.
Gustafsson JP (2013) MINTEQ, Royal Institute of Technology, Stockholm, Sweden.
29.
IngriN, KakolowiczW, SillénLG, et al. (1967) High-speed computers as a supplement to graphical methods, part V—Haltafall, a general program for calculating the composition of equilibrium mixtures. Talanta, 14:1261–1286.
30.
JohnsonSS, MillanM, GrahamH, et al. (2020) Lipid biomarkers in ephemeral acid salt lake mudflat/sandflat sediments: implications for Mars. Astrobiology, 20:167–178.
31.
KloproggeJT, HickeyL, DuongL, et al. (2004) Synthesis and characterization of K2Ca5(SO4)6· H2O, the equivalent of Görgeyite, a rare evaporite mineral. Am Mineral, 89:266–272.
32.
LiuY (2018) Raman, mid-IR, and NIR spectroscopic study of calcium sulfates and mapping gypsum abundances in Columbus Crater, Mars. Planet Space Sci, 163:35–41.
33.
MatovićV, ErićS, KremenovićA, et al. (2012) The origin of syngenite in black crusts on the limestone monument King's Gate (Belgrade Fortress, Serbia)—the role of agriculture fertiliser. J Cult Heritage, 13:175–186.
34.
MayrhoferH (1953) Gorgeyit. Ein neues mineral aus der ischler salzlagerstatte. Neues Jb Miner Mh, 2:35–44.
35.
McLennanSM, BellJF, CalvinWM, et al. (2005) Provenance and diagenesis of the evaporite-bearing burns formation, Meridiani Planum, Mars. Earth Planet Sci Lett, 240:95–121.
36.
McSweenHY, TaylorGJ, and WyattMB (2009) Elemental composition of the martian crust. Science, 324:736–739.
37.
MeixnerH (1955) Zur Identität von Mikheewit (Micheewit) Mit Görgeyit. Geologie, 6:576–578.
38.
MokievskyVA (1953) The scientific session of the Fedorov institute together with the all-union mineralogical society. Zapiski Vses Mineral Obshchestva, 82:311–317.
39.
MorillasH, MagureguiM, ParisC, et al. (2015) The role of marine aerosol in the formation of (double) sulfate/nitrate salts in plasters. Microchem J, 123:148–157.
40.
MötzingR (1988) Goergyeit Im Zechstein 2. Chem Erde, 48:233–244.
41.
NachonM, CleggSM, MangoldN, et al. (2014) Calcium sulfate veins characterized by ChemCam/Curiosity at Gale Crater, Mars. J Geophys Res Planets, 119:1991–2016.
42.
NefedovEI (1955) Neue minerale. Geologie, 5:526–528.
43.
OnacBP, WhiteWB, ViehmannI (2016) Leonite [K2Mg(SO4)2 ·4H2O], konyaite [Na2Mg(SO4)2 ·5H2O] and syngenite [K2Ca(SO4)2 ·H2O] from Tausoare Cave, Rodnei Mts, Romania. Mineral Mag, 65:103–109.
44.
Prieto-TaboadaN, Fdez-Ortiz de VallejueloS, VenerandaM, et al. (2018) Study of the soluble salts formation in a recently restored house of Pompeii by in-situ Raman spectroscopy. Sci Rep, 8:1613.
45.
Puigdomenech I (2009a) MEDUSA (Make Equilibrium Diagrams Using Sophisticated Algorithms), Dep. Inorg. Chem. R. Inst. Technol. KTH Stockh.: Sweden.
46.
Puigdomenech I (2009b) HYDRA (Hydrochemical Equilibrium-Constant Database), Royal Institute of Technology, Stockholm, Sweden.
47.
RapinW, MeslinP-Y, MauriceS, et al. (2016) Hydration state of calcium sulfates in Gale Crater, Mars: identification of bassanite veins. Earth Planet Sci Lett, 452:197–205.
48.
SalvatoreMR, GoudgeTA, BrambleMS, et al. (2018) Bulk mineralogy of the NE Syrtis and Jezero crater regions of Mars derived through thermal infrared spectral analyses. Icarus, 301:76–96.
49.
SantosAR, AgeeCB, McCubbinFM, et al. (2015) Petrology of igneous clasts in Northwest Africa 7034: implications for the petrologic diversity of the martian crust. Geochim Cosmochim Acta, 157:56–85.
50.
SautterV, ToplisMJ, WiensRC, et al. (2015) In situ evidence for continental crust on early Mars. Nat Geosci, 8:605–609.
51.
SmithGW and WallsR (1980) The crystal structure of görgeyite K2SO4.5CaSO4⋅H2O. Zeitschrift fuer Kristallographie, 151:49–60.
52.
SmithGW, WallsR, WhymanPE (1964) An occurrence of görgeyite in Greece. Nature, 203:1061–1062.
53.
SnowMR, PringA, and AllenN (2014) Minerals of the Wooltana Cave, Flinders Ranges, South Australia. Trans R Soc S Aust, 138:214–230.
54.
SquyresSW, ArvidsonRE, Bell IIIJF, et al. (2012) Ancient impact and aqueous processes at Endeavour crater, Mars. Science, 336:570–576.
55.
StolperEM, BakerMB, NewcombeME, et al. (2013) The petrochemistry of Jake_M: a martian mugearite. Science, 341:1239463.
56.
TanJ, LewisJMT, SephtonMA (2018) The fate of lipid biosignatures in a Mars-analogue sulfur stream. Sci Rep, 8:7586.
57.
ThompsonLM, SchmidtME, SprayJG, et al. (2016) Potassium-rich sandstones within the Gale impact crater, Mars: the APXS perspective: potassium-rich sandstones on Mars. J Geophys Res Planets, 121:1981–2003.
58.
ToscaNJ and McLennanSM (2006) Chemical divides and evaporite assemblages on Mars. Earth Planet Sci Lett, 241:21–31.
59.
TreimanAH, BishDL, VanimanDT, et al. (2016) Mineralogy, provenance, and diagenesis of a potassic basaltic sandstone on Mars: cheMin X-ray diffraction of the Windjana sample (Kimberley Area, Gale Crater). J Geophys Res Planets, 121:75–106.
60.
WangA, KorotevRL, JolliffBL, et al. (2006) Evidence of phyllosilicates in Wooly Patch, an altered rock encountered at West Spur, Columbia Hills, by the Spirit rover in Gusev crater, Mars. J Geophys Res Planets, 111:E02S16.
61.
YenAS, MingDW, VanimanDT, et al.; and the MSL Science Team (2017) Multiple stages of aqueous alteration along fractures in mudstone and sandstone strata in Gale Crater, Mars. Earth Planet Sci Lett, 471:186–198.
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