Sulfate Minerals and Organic Compounds on Mars

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Sulfate Minerals and Organic Compounds on Mars Sulfate minerals and organic compounds on Mars Andrew Aubrey Scripps Institution of Oceanography, University of California at San Diego, La Jolla, California H. James Cleaves 92093-0212, USA John H. Chalmers Alison M. Skelley Department of Chemistry, University of California, Berkeley, California 94720, USA Richard A. Mathies Frank J. Grunthaner Jet Propulsion Laboratory, 4800 Oak Grove Drive, Pasadena, California 91109, USA Pascale Ehrenfreund Leiden Observatory, 2300 RA Leiden, Netherlands Jeffrey L. Bada* Scripps Institution of Oceanography, University of California at San Diego, La Jolla, California 92093-0212, USA ABSTRACT as 3±5 Ma (Remeika and Lindsay, 1992). Strong evidence for evaporitic sulfate minerals such as gypsum and jarosite has recently Gypsum from the Haughton impact crater is been found on Mars. Although organic molecules are often codeposited with terrestrial assumed to date from the time of the impact evaporitic minerals, there have been no systematic investigations of organic components crater, 23 Ma (Parnell et al., 2004). The age in sulfate minerals. We report here the detection of organic material, including amino of the host rock of the Panoche Valley sam- acids and their amine degradation products, in ancient terrestrial sulfate minerals. Amino ples is 75±65 Ma (Presser and Ohlendorf, acids and amines appear to be preserved for geologically long periods in sulfate mineral 1987), but the age of the sulfate minerals is matrices. This suggests that sulfate minerals should be prime targets in the search for estimated as 40 Ma (middle Tertiary); this is organic compounds, including those of biological origin, on Mars. when the coastal ranges were raised in this area during the Sierra Nevada uplift, which Keywords: Mars, sulfates, evaporites, amino acids, gypsum, jarosite, anhydrite, kerogen. caused ocean water to withdraw and deposit evaporitic minerals in California's Central INTRODUCTION not conclusively disprove that there are organ- Valley. Strontium isotope analyses were con- The search for evidence of water and or- ic compounds present on the surface of Mars. ducted to verify the geologically deduced ages ganic compounds, including those of possible The only other opportunity to analyze samples of the Panoche Valley samples. The Panoche biological origin, is one of the major goals of from Mars has been provided by meteorites Valley gypsum 87Sr/86Sr ratio was 0.707745 the Mars exploration programs of both the Na- ejected from its surface and delivered to Earth. (60.000005). Comparing this ratio to the tional Aeronautics and Space Administration However, contamination of these meteorites strontium isotope history of seawater (Hess et (NASA) and the European Space Agency by terrestrial organic material during their res- al., 1986) gives an age 40 Ma, consistent with (ESA). The NASA Mars Exploration Rovers idence times on Earth (102±104 yr) compro- the inferred geologic age. The Panoche Valley and the ESA OMEGA/Mars Express have mises their use in assessing whether organic anhydrite was estimated to be roughly the provided the best evidence to date that liquid compounds are present on Mars (Jull et al., same age because anhydrite forms by dehy- water was once present on Mars. Abundant 1998). dration of gypsum. The jarosite from Panoche sulfate minerals such as gypsum and jarosite Organic matter is often codeposited in ter- Valley was likely formed by aqueous alter- suggest that large acidic water basins were restrial evaporites, and similar deposition pro- ation of pyrite, and it is thus dif®cult to de- once present and that as they evaporated sul- cesses should occur on Mars if organic mol- termine its actual age of the alteration veins, fate minerals were precipitated (Squyres et al., ecules were present in the early oceans but it is probably somewhat younger than 40 2004; Langevin et al., 2005; Gendrin et al., (Mancinelli et al., 2004). To our knowledge, Ma. The modern gypsum sample is from the 2005). Although it is unknown how long these there have been no systemic investigations of South Bay salt works in Chula Vista. The area bodies of water existed, they could potentially organic compounds in sulfate minerals on is rich in marshes and tidal ¯ats, and there is have provided an environment capable of sup- Earth. We report here the determination of the continuous evaporite formation during tidal porting life. organic carbon and nitrogen contents of sev- ¯uctuations. Because of the poor water quality The presence of organic compounds on eral sulfate minerals, as well as the abundance in this region of San Diego Bay, the salts typ- Mars is uncertain. The Viking missions in of amino acids and their degradation products. ically include signi®cant amounts of organic 1976 detected no organic compounds above a material. threshold level of a few parts per billion in METHODS The surface of each sample was thoroughly near-surface Martian soils (Biemann et al., The samples investigated included gypsum rinsed with doubly distilled water (ddH2O) 1976). However, key biomolecules such as from the Anza-Borrego Desert, California (4 followed by 1M ddHCl, then again with amino acids would not have been detected by Ma), gypsum from the Haughton impact cra- ddH2O. The identity of each mineral was ver- the Viking Gas chromatograph and mass spec- ter, Canada (23 Ma), and gypsum, anhydrite, i®ed by X-ray diffraction (XRD) analyses us- trometer (GCMS) even if several million bac- and jarosite samples from Panoche Valley ing a Scintag XDS-2000 powder diffractom- terial cells per gram were present (Glavin et (California) (40 Ma). A modern gypsum sam- eter. Samples were analyzed for total organic al., 2001). In addition, oxidation reactions in- ple from a salt evaporation pond in Chula Vis- carbon and nitrogen using a Costech elemental volving organic compounds on the Martian ta (California) was also analyzed. Sample ages combustion C-N analyzer. Carbon and nitro- surface would likely produce nonvolatile were estimated based on the geology of their gen isotopic ratios were determined with a products such as mellitic acid salts that also respective localities. Thermo®nnigan Delta-XP Plus stable isotope would not have been detected by Viking (Ben- The evaporite formations from the Anza- ratio mass spectrometer. In order to remove ner et al., 2000). Thus, the Viking results did Borrego Desert have been studied extensively. carbonate from the samples, they were pre- The gypsum investigated here was collected treated with an excess of 3N ddHCl and dried *E-mail: [email protected]. from the Fish Creek area and has been dated down on a vacuum centrifuge at 45 8C for 1 q 2006 Geological Society of America. For permission to copy, contact Copyright Permissions, GSA, or [email protected]. Geology; May 2006; v. 34; no. 5; p. 357±360; doi: 10.1130/G22316.1; 1 ®gure; 3 tables. 357 TABLE 1. TOTAL ORGANIC CARBON (TOC), TOTAL ORGANIC NITROGEN (TON), AND rosite was showed a much higher value of ISOTOPIC ANALYSES 1.28 mg´C/g. The nitrogen trends were similar Location (Ma) TOC TON d13C d15NAA1Amines AA1Amines in that the gypsum and anhydrite samples (mg/g) (mg/g) (½) (½) TOC TON ranged from 0.01 to 0.03 mg´N/g. The jarosite (%) (%) was signi®cantly more nitrogen rich with a South Bay Gypsum (0) 6.91 1.01 217.3 111.0 0.041 0.117 content of 0.15 mg´N/g. Anza-Borrego Gypsum (4)* 0.29 0.02 234.9 11.7 0.042 0.265 The organic C/N ratios in old gypsum and Haughton Crater Gypsum (23)² 0.77 0.03 231.3 10.1 0.007 0.105 jarosite range from 9 to 30, indicating that the Panoche Gypsum (40)§ 0.12 0.01 230.0 113.1 0.110 0.399 Panoche Anhydrite (40)§ 0.09 0.02 229.0 14.2 0.359 0.718 major organic component present in the sul- Panoche Jarosite (;40)# 1.28 0.15 226.2 13.9 0.012 0.038 fate minerals is likely a humic acid- and/or Note: The last two columns represent the mass percent of the TOC and TON accounted for by amino acids kerogen-like material (Ertel and Hedges, and amines. The uncertainties are roughly 65% for TOC, 610% for TON and 6 0.5±1.0½ for the isotopic values. 1983), a conclusion that is consistent with the *338009N, 1168109W; (Remeika and Lindsay, 1992) measured carbon and nitrogen isotopic values. ²758229N, 898419W; (Cockell and Lee, 2002). §368359N, 1208429W; (Presser and Ohlendorf, 1987). The exceptions are the Chula Vista gypsum #368279N, 1208399W. with a C/N ratio of ;7 and the Panoche an- hydrite with a ratio of ;5. These numbers are more indicative of recent biological material. h before analyses for total organic carbon and Extracts were analyzed for amino acids and Even though amino acids and amines consti- total organic nitrogen. amines by reverse-phase high performance tute only a fraction of the total organic carbon Amino acids were isolated by vapor-phase liquid chromatography (RP-HPLC) using pre- and nitrogen present in the sulfate minerals acid hydrolysis (6 N HCl, 24 h, 100 8C) of column derivatization with o-phthalaldehyde/ (Table 1), they are readily detected and char- ground samples followed by desalting (Ame- N-acetyl L-cysteine using a Shimadzu RF-530 acterized (Fig. 1; Table 2). lung and Zhang, 2001). Amines were isolated ¯uorescence detector (Zhao and Bada, 1995) The detected levels of amino acids and their by microdiffusion from the powdered mineral and a Phenomenex Synergi Hydro-RP column enantiomers, as well as methylamine (MA) treated with 1N NaOH, into a 0.01N HCl so- (250 3 4.6 mm). Quanti®cation of amino ac- and ethylamine (EA), the decarboxylation lution at 40 8C for 6 days (Conway, 1963).
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