Thermal decomposition of ammonium perchlorate

[1] A single scoop of the Rocknest aeolian deposit was sieved (<150 μm), and four separate sample portions, each with a mass of ~50mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover’ ss ample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of ~0.01 to 2.3nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactionsofMartian chlorine released during pyrolysiswith terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

/pdf/evidence-for-perchlorates-and-the-origin-of-chlorinated-82uz165by2.pdf

Evidence for perchlorates and the origin of chlorinated hydrocarbons detected by SAM at the Rocknest aeolian deposit in Gale Crater

[1] The most comprehensive search for organics in the Martian soil was performed by the Viking Landers. Martian soil was subjected to a thermal volatilization process to vaporize and break organic molecules, and the resultant gases and volatiles were analyzed by gas chromatography-mass spectrometry. Only water at 0.1–1.0 wt% was detected, with traces of chloromethane at 15 ppb, at Viking landing site 1, and water at 0.05–1.0 wt% and carbon dioxide at 50–700 ppm, with traces of dichloromethane at 0.04–40 ppb, at Viking landing site 2. These chlorohydrocarbons were considered to be terrestrial contaminants, although they had not been detected at those levels in the blank runs. Recently, perchlorate was discovered in the Martian Arctic soil by the Phoenix Lander. Here we show that when Mars-like soils from the Atacama Desert containing 32 ± 6 ppm of organic carbon are mixed with 1 wt% magnesium perchlorate and heated, nearly all the organics present are decomposed to water and carbon dioxide, but a small amount is chlorinated, forming 1.6 ppm of chloromethane and 0.02 ppm of dichloromethane at 500°C. A chemical kinetics model was developed to predict the degree of oxidation and chlorination of organics in the Viking oven. Reinterpretation of the Viking results therefore suggests ≤0.1% perchlorate and 1.5–6.5 ppm organic carbon at landing site 1 and ≤0.1% perchlorate and 0.7–2.6 ppm organic carbon at landing site 2. The detection of organics on Mars is important to assess locations for future experiments to detect life itself.

/pdf/reanalysis-of-the-viking-results-suggests-perchlorate-and-3o5fyinxs1.pdf

Patrick W. M. Jacobs

Papers

Sublimation of ammonium perchlorate

The thermal decomposition of magnesium perchlorate and of ammonium perchlorate and magnesium perchlorate mixtures