The observed fall and rapid recovery of the Tissint Mars meteorite has provided minimally contaminated samples of the Martian surface. We report analyses of Tissint for organic compounds by pyrolysis‐gas chromatography‐mass spectrometry and for soluble salts by ion chromatography. Pyrolysis‐gas chromatography‐mass spectrometry analysis shows the presence of organic compounds similar to those in the Mars EETA79001 and Nakhla meteorites. The organic profile is dominated by aromatic hydrocarbons, including oxygen and nitrogen‐containing aromatics, and sulfur‐containing species including thiophenes. The soluble salts in Tissint are dominated by sulfate and various oxidation states of chlorine, including perchlorate. The organic compounds and salts in the soils from the Tissint recovery strewn field differ significantly from those found in Tissint suggesting minimal terrestrial contamination. Our results support the hypothesis that the soluble inorganic components of Tissint are most likely a result of indigenous fluid inclusion, thus providing a glimpse into the composition of early Martian fluids.

The detection of chlorinated hydrocarbons by Curiosity on Mars has been attributed to the presence of unidentified indigenous organic matter. Similarly, oxychlorines on Earth have been proposed to be responsible for the apparent lack of organics in the Atacama Desert. The presence of perchlorate (ClO 4 -) poses a unique challenge to the measurement of organic matter due to the oxidizing power of oxychlorines during commonly used pyrolysis-gas chromatography-mass spectrometry (py-GC-MS) methods. Here, we show that perchlorates and other oxyanion salts inhibit the detection of organic compounds, but that removing these problematic species prior to pyrolysis by using an optimal sample extraction duration and suitable ratios of water to sample mass enables analysis. We have characterized leached and unleached samples containing perchlorates from the Atacama Desert and have found that after leaching, the py-GC-MS chromatograms of the dried mineral residues show identifiable biomarkers associated with indigenous cyanobacteria. Samples which were pyrolyzed without leaching showed no detectable organic matter other than background siloxane and very weak or no trace of detectable polychlorinated benzenes Dried sample residues remaining after leaching, the mineral matrix and water-insoluble organic matter, showed a strong organic response in all cases when analyzed by py-GC-MS. These residues are most likely the product of the pyrolysis of water insoluble organics originally present in the samples. In addition, our results imply that previous soil analyses which contained high levels of oxyanions and concluded that organics were either not present, or at extremely low levels, should be re-examined.

The search for life on Mars targets the detection of organic matter from extant or extinct organisms. Current protocols use thermal extraction procedures to transfer organic matter to mass spectrometer detectors. Oxidizing minerals on Mars, such as perchlorate, interfere with organic detection by thermal extraction. Thermal decomposition of perchlorate releases oxygen, which promotes combustion of organic carbon. We have assessed the minimum mass ratio of organic carbon to perchlorate required to detect organic matter by thermal extraction and mass spectrometry. Locations on Mars with organic carbon to perchlorate ratios above 4.7-9.6 should be targeted. Because habitability is enhanced by the presence of liquid water and because perchlorate is a water-soluble salt, locations on Mars with evidence of past or recent liquid water are high priority targets.Plain Language Summary Missions to Mars look for evidence of organic molecules using thermal extraction techniques. Certain minerals on the Martian surface, such as perchlorate salts, break down during heating, releasing oxygen and causing the combustion of any organic matter, which may have been present. In this event organic carbon is lost to analysis as CO and CO 2 . We used the ratio of CO: CO 2 produced as a proxy for the completeness of combustion when various ratios of organic matter and perchlorate where thermally decomposed together. This allowed us to find a minimum organic carbon: perchlorate mass ratio (~5 times) for the survival of organic molecules. Carbon monoxide can only be produced if there is an excess of carbon to oxygen, which could enable the survival of unoxidized organic molecules for their subsequent detection. Applying these findings to Mars suggests that we would not expect to be able to detect organic molecules in average Martian soil. Consequently, future life detection missions to Mars must search for areas that exceed this ratio, either by having more organic matter or less perchlorate, and locations with evidence of recent water activity or in the subsurface are most likely to fulfill both of these criteria.

To ensure that scientific investments in space exploration are not compromised by terrestrial contamination of celestial bodies, special care needs to be taken to preserve planetary conditions for future astrobiological exploration. Significant effort has been made and is being taken to address planetary protection in the context of inner Solar System exploration. In particular for missions to Mars, detailed internationally accepted guidelines have been established. For missions to the icy moons in the outer Solar System, Europa and Enceladus, the planetary protection requirements are so far based on a probabilistic approach and a conservative estimate of poorly known parameters. One objective of the European Commission-funded project, Planetary Protection of Outer Solar System, was to assess the existing planetary protection approach, to identify inherent knowledge gaps, and to recommend scientific investigations necessary to update the requirements for missions to the icy moons.

All missions to Mars which have attempted to detect organic molecules have detected simple chlorohydrocarbons, the source of which has yet to be firmly established. This study assessed the likelihood of these chlorinated molecules being indigenous to the sedimentary units in which they were detected or if they were chlorinated during analysis. The survivability of 1‐chloronapthalene was examined via hydrous pyrolysis experiments and its dechlorination kinetics were determined. The results of these experiments were used to model the survivability of this simple chlorohydrocarbon under Mars‐relevant diagenetic conditions using the Sheepbed mudstone unit as a case study. It was found that 1‐chloronapthalene was rapidly dechlorinated under Noachian conditions, and thus, the detected Martian chlorohydrocarbons are unlikely to be ancient and probably formed within the rover's sample handling chain during analysis.

The search for, and characterisation of, organic matter on Mars is central to efforts in identifying habitable environments and detecting evidence of life in the martian surface and near surface. Iron oxides are ubiquitous in the martian regolith and are known to be associated with the deposition and preservation of organic matter in certain terrestrial environments, thus iron oxide-rich sediments are potential targets for life detection missions. The most frequently used protocol for martian organic matter characterisation (also planned for use on ExoMars) has been thermal extraction for the transfer organic matter to gas chromatography-mass spectrometry detectors. For the effective use of thermal extraction for martian

Recent and sub-recent laminated tufa stromatolites can contain high resolution δ 18 O records of in stream temperature change. Fossil tufa stromatolites are therefore key targets for reconstructing terrestrial palaeoclimatic, but so far only a few examples have been published.In this research we studied a 2.5 cm-radius tufa stromatolite from the Eemian of the Somme Basin, Northern France. We show; (1) that high resolution sampling of fossil laminated tufas is highly reproducible. We demonstrate; (2) that within the limitations of the δ 18 O method, NW European Eemian seasonality was essentially similar to the present day. Perhaps most important we show; (3) that precise observations from thin section that match the position of 1 Present address: GéoArchÉon, 30 rue de la Victoire, 55210 Viéville-sous-les-Côtes, France A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPT

Conclusively detecting, or ruling out the possibility of, life on the icy moons of the outer solar system will require spacecraft missions to undergo rigorous planetary protection and contamination control procedures to achieve detectable compounds, SPME can also be used in conjunction with high performance liquid chromatography/liquid chromatography-mass spectrometry systems suitable for polar analytes [Kataoka et al., 2000]. Thus, our SPME method presents an opportunity to monitor organic contamination in a relatively rapid and routine way that produces information-rich data sets.