Mathematics – Logic
Scientific paper
Sep 2008
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2008epsc.conf..905v&link_type=abstract
European Planetary Science Congress 2008, Proceedings of the conference held 21-25 September, 2008 in Münster, Germany. Online a
Mathematics
Logic
Scientific paper
The Phoenix spacecraft will search for organics in the soil and ice in the Martian north polar regions using thermal volatilization (TV) followed by mass spectrometry (MS). This experiment is a combination of a high-temperature furnace and a mass spectrometer that will be use to analyze samples delivered to instrument via a robotic arm. The samples will be heated from ambient to 1000ºC while evolved gases, including organic molecules and fragments, if they are present, will be simultaneously measured by a magnetic sector mass spectrometer (1). Our laboratory has developed a sample characterization method using a pyrolizer integrated to a quadrupole mass spectrometer to support the interpretations of TV data. The Atacama Desert, on northern Chile and southern Peru, has been considered the most arid region over the world (2) and an excellent Mars-like soil analogous (3). These soils contain very low levels to organic matter (10-40 ppm of organic C), and exotic mineralogical composition including iron oxides, which are common characteristics expected on Mars. A previous paper that examined the release of organics from samples soils by flash TV (pyrolisis) coupled to GC-MS (4). This work showed low efficiency of flash TV in soils with low organics or high contents of iron minerals. In addition, other study of agricultural soils showed low correlation between organics concentration and TV response, when levels of total organic matter were below 50000 ppm C or high presence of iron oxides (5). However, the efficiency of gradual heating by TV analysis from hyperarid soils has not been investigated. Here we examine the thermal and evolved gas properties of six types of soils from the two hyperarid core regions from the Atacama Desert: Yungay (northern Chile) and Pampas de La Joya (southern Peru), in order to investigate the effect of soil matrix and low organics contents over TV response. Between 20 to 40 mg of soil was loaded in a capillary quartz tube and it was mounted in the center of platinum coil filament pyrolizer probe. Then sample into de quartz tube was subjected to a thermal treatment from 30°C to 1200°C with a heating rate of 20°C/min. The resulting volatiles evolved from the sample were carried away by helium and transferred into a HP quadrupole mass spectrometer operating in electron ionization mode at 70 eV with a resolution of 1m/z. The mass analyzer was scanned from 10 to 200 m/z at a rate 5.3 scans per second. The nominal sensitivity of the mass analyzer is 0.02 ppb of hexachlorobenzene. Blanks were prepared with no soil added. As expected, there were significant differences in the evolved gas behaviors between soils samples depending of the soil matrix under similar heating conditions. First, the samples belonging to the most arid environments (PE001, PE389) had significant differences compared with less arid soils (PE378, PE386). Carbon in hyperarid soils, in the form of CO2 (ion 44 m/z) began its release to 330±30°C, while the less arid soils to 245±45°C. Volatile ions released from soils during TV-MS analysis were analyzed searching organics fragments. Soil type VI (PE-001), which contains ~11.4 ppm organic C, showed the release of the following mass fragments: 18, 44, 48, 64, and 66. Sources for the release of CO2 in TV analysis of soils comes to oxidation of organic matter (<600ºC), and thermal decomposition of carbonates (>600ºC). Mass 18 originates from water releasing in the course of dehydration processes that is bound in soil minerals, and from oxidation of organics in different temperatures depending the mineral fraction in the soil. The masses 48, 64, and 66 have similar thermal properties, beginning to be released at ~370°C and continue to rise up to 1200°C. These masses are due to the decomposition of sulfates into SO+, SO2 +, and S34O2 +. Mass 66 is detected only if the abundance of mass 64 is very high. TV traces from soils type V (PE-276), type I (PE-361), and type II (PE-388), which contain low organics concentrations (3-23 ppm of organic C), presented similar ions released to soil type VI, but with some variations at times of peak start or maximum release. The TV-MS trace for soil type IV (PE-287) showed the release of the following ions: 16, 18, 36, 44, 48, and 64. In this soil, the mass 44 showed the highest value at >760°C, probably by thermal decomposition of carbonates at higher temperatures; however at 700ºC, CO2 could result from the decomposition oxidation of refractory organics that have been detected by pyrolisis-GC-MS at 750ºC (4). In contrast, the TV-MS trace for sample soil type III (PE-386), which contains 35 ppm of organic C, showed the release of the following major mass fragments (m/z): 18, 30, 36, 44, 48 and 64 (Figure 1). EPSC Abstracts, Vol. 3, EPSC2008-A-00490, 2008 European Planetary Science Congress, Author(s) 2008 Probably, the mass 30 is due to NO that evolves from the thermal oxidation of N-organics at low temperature or degradation of nitrates at high temperatures. Additionally, ion 36 could be due to thermal degradation to chlorides. Our results show interesting ions released from Marslike soils by TV analysis, however soils that have low levels to organic carbon (3-40 ppm), were not detected by this method. If the concentrations of organics in the soils and ice on Mars at the Phoenix landing site are low than 30 ppm, the experiment could fail. Recently, our laboratory investigated the presence of organics in the samples soils by the release of NO (mass 30) at low temperatures using TV-MS (Research submitted). Hence, Phoenix mission could have an option in the searching for organic matter on Mars. These data indicate the importance of the study of Mars-like soils to prevent similar problems in space research.
McKay Chris P.
Navarro-González Rafael
Valdivia-Silva Julio E.
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