Chloride-, sulfate-, and perchlorate-exchanged forms of hydrotalcite have been prepared and their layer spacings determined after equilibration in hydrous atmospheres and after heat-treatments up to the temperature of decomposition in the range 300–400°C. The initial carbonate form of hydrotalcite and also brucite, for purposes of comparison, have been similarly studied. Only chloride-hydrotalcite and brucite exhibit a single phase stable to the decomposition temperature. The other anionic forms exhibit various phases with different layer spacings which are interpreted in terms of the size, orientation, and stability of the anions and, in some cases, the presence of additional water. A regularly interstratified form of sulfate-hydrotalcite (layer spacing = 19.80 Å) is obtained at room temperature and relative humidity <50%; at higher humidities, a fully hydrated phase is obtained, and at 50°C a collapsed form is obtained. In the preparation of perchlorate-hydrotalcite, an interstratified phase (layer spacing = 17.0 Å) was recognized with alternating carbonate and Perchlorate layers, although the evidence is less certain.

The presence of perchlorate in the Martian soil may limit in-situ resource utilization (ISRU) technologies to support human outposts. In order to exploit the desiccation, radiation-tolerant cyanobacterium Chroococcidopsis in Biological Life Support Systems based on ISRU, we investigated the perchlorate tolerance of Chroococcidopsis sp. CCMEE 029 and its derivative CCMEE 029 P-MRS. This strain was obtained from dried cells mixed with Martian regolith simulant and exposed to Mars-like conditions during the BIOMEX space experiment. After a 55-day exposure of up to 200 mM perchlorate ions, a tolerance threshold value of 100 mM perchlorate ions was identified for both Chroococcidopsis strains. After 40-day incubation, a Mars-relevant perchlorate concentration of 2.4 mM perchlorate ions, provided as a 60 and 40% mixture of Mg- and Ca-perchlorate, had no negative effect on the growth rate of the two strains. A proof-of-concept experiment was conducted using Chroococcidopsis lysate in ISRU technologies to feed a heterotrophic bacterium, i.e. an Escherichia coli strain capable of metabolizing sucrose. The sucrose content was fivefold increased in Chroococcidopsis cells through air-drying and the yielded lysate successfully supported the bacterial growth. This suggested that Chroococcidopsis is a suitable candidate for ISRU technologies to support heterotrophic BLSS components in a Mars-relevant perchlorate environment that would prove challenging to many other cyanobacteria, allowing a ‘live off the land’ approach on Mars.

The experiments reported in this research paper aimed to investigate differences in the levels of chlorate (CHLO), perchlorate (PCHLO), trichloromethane (TCM) and iodine residues in bulk tank (BT) milk produced at different milk production periods, and to monitor those levels throughout a skim milk powder (SMP) production chain (BTs, collection tankers [CTs], whole milk silo [WMS] and skim milk silo [SMS]). Chlorate, PCHLO and iodine were measured in SMP, while TCM was measured in the milk cream. The CHLO, TCM and iodine levels in the mid-lactation milk stored in the WMS were lower than legislative and industrial specifications (0.0100 mg/kg, 0.0015 mg/kg and 150 µg/l, respectively). However, in late-lactation, these levels were numerically higher than the mid-lactation levels and specifications. Trichloromethane accumulated in the cream portion after separation. Perchlorate was not detected in any of the samples. Regarding iodine, the levels in mid-lactation reconstituted SMP were higher than that required by manufacturers (100 µg/l), indicating that the levels in milk should be lower than 142 µg/l. The higher residue levels observed in late-lactation could be related to the low milk volume produced during that period and changes in sanitation practices, while changes in feed management could have affected iodine levels. This study could assist in controlling and setting limits for CHLO, TCM and iodine levels in milk, ensuring premium quality dairy products.

The Phoenix lander at Mars polar cap found appreciable levels of (per)chlorate salts, a mixture of perchlorate and chlorate salts of Ca, Fe, Mg and Na at levels of ~0.6% in regolith. These salts are highly hygroscopic and can form saturated brines through deliquescence, likely producing aqueous solutions with very low freezing points on Mars. To support planetary protection efforts, we have measured bacterial growth tolerance to (per)chlorate salts. Existing bacterial isolates from the Great Salt Plains of Oklahoma (NaCl-rich) and Hot Lake in Washington (MgSO4-rich) were tested in high concentrations of Mg, K and Na salts of chlorate and perchlorate. Strong growth was observed with nearly all of these salinotolerant isolates at 1% (~0.1 M) (per)chlorate salts, similar to concentrations observed in bulk soils on Mars. Growth in perchlorate salts was observed at concentrations of at least 10% (~1.0 M). Greater tolerance was observed for chlorate salts, where growth was observed to 2.75 M (>25%). Tolerance to K salts was greatest, followed by Mg salts and then Na salts. Tolerances varied among isolates, even among those within the same phylogenetic clade. Tolerant bacteria included genera that also are found in spacecraft assembly facilities. Substantial microbial tolerance to (per)chlorate salts is a concern for planetary protection since tolerant microbes contaminating spacecraft would have a greater chance for survival and proliferation, despite the harsh chemical conditions found near the surface of Mars.

This paper describes strategies to search for, detect, and identify organic material on the surface and subsurface of Mars. The strategies described include those applied by landed missions in the past and those that will be applied in the future. The value and role of ESA's ExoMars rover and of her key science instrument Mars Organic Molecule Analyzer (MOMA) are critically assessed.

Mars landed and orbiter missions have instrumentation capable of detecting oxychlorine phases (e.g. perchlorate, chlorate) on the surface. Perchlorate (~0.6 wt%) was first detected by the Wet Chemistry Laboratory in the surface material at the Phoenix Mars Landing site. Subsequent analyses by the Thermal Evolved Gas Analyser aboard the same lander detected an oxygen release (~465°C) consistent with the thermal decomposition of perchlorate. Recent thermal analysis by the Mars Science Laboratory's Sample Analysis at Mars instrument has also indicated the presence of oxychlorine phases (up to 1.2 wt%) in Gale Crater materials. Despite being at detectable concentrations, the Chemistry and Mineralogy (CheMin) X-ray diffractometer has not detected oxychlorine phases. This suggests that Gale Crater oxychlorine may exist as poorly crystalline phases or that perchlorate/chlorate mixtures exist, so that individual oxychlorine concentrations are below CheMin detection limits (~1 wt%). Although not initially designed to detect oxychlorine phases, reinterpretation of Viking Gas Chromatography/Mass Spectrometer data also suggest that oxychlorine phases are present in the Viking surface materials. Remote near-infrared spectral analyses by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument indicate that at least some martian recurring slope lineae (RSL) have spectral signatures consistent with the presence of hydrated perchlorates or chlorates during the seasons when RSL are most extensive. Despite the thermal emission spectrometer, Thermal Emission Imaging System, Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité and CRISM detection of hundreds of anhydrous chloride (~10–25 vol%) deposits, expected associated oxychlorine phases (>5–10 vol%) have not been detected. Total Cl and oxychlorine data sets from the Phoenix Lander and the Mars Science Laboratory missions could be used to develop oxychlorine versus total Cl correlations, which may constrain oxychlorine concentrations at other locations on Mars by using total Cl determined by other missions (e.g. Viking, Pathfinder, MER and Odyssey). Development of microfluidic or ‘lab-on-a-chip’ instrumentation has the potential to be the next generation analytical capability used to identify and quantify individual oxychlorine species on future landed robotic missions to Mars.

Various Mars missions have detected Cl atoms, chlorides and perchlorates in martian surface materials. The global soils, in particular, always contain significant levels of observable Cl. Direct evidence points to this Cl being in the form of both chlorides and perchlorates, and possibly also chlorates and other oxychlorines. The most widespread measurements have been of Cl atoms, and cannot discern the chemical form. However, from separate evidence of perchlorate obtained at high latitudes (Phoenix lander) and low latitudes (Curiosity rover), it is likely that perchlorates are widespread, albeit in varying proportions relative to the total amount of ubiquitous Cl.