Landed XRD/XRF analysis of prime targets in the search for past or present Martian life.

Mars landers seeking evidence for past or present life will be guided by information from orbital mapping and from previous surface exploration. Several target options have been proposed, including sites that may harbor extant life and sites most likely to preserve evidence of past life These sites have specific mineralogic characteristics. Extant life might be gathered around the sinters and associated mineral deposits of rare active fumaroles, or held within brine pockets and inclusions in a few evaporite-mineral deposits. Possibilities for fossilization include deltaic and lake-bottom sediments of once-flooded craters, sinters formed by ancient hot-spring deposits, and the carbonate deposits associated with some evaporite systems. However, the highly varied mineralogy of fossil occurrences on Earth leads to the inference that Mars, an equally complex planet, could host a broad variety of potential fossilizing deposits. The abundance of volcanic systems on Mars and evidence for close associations between volcanism and water release suggest possibilities of organism entrapment and mineralization in volcaniclastic deposits, as found in some instances on Earth. Thus the targets being considered for exploration include a wide variety of unique deposits that would be characterized by silica or various nonsilicate minerals. Beyond these "special" deposits and in the most general case, an ability to distinguish mineralized from uncemented volcanic detritus may be the key to success in finding possible fossil-bearing authigenic mineralogies. A prototype miniaturized X ray diffraction/X ray fluorescence (XRD/XRF) instrument has been evaluated with silica, carbonate, and sulfate minerals and with a basalt, to examine the capabilities of this tool in mineralogic and petrologic exploration for exobiological goals. This instrument. CHEMIN (chemical and mineralogical analyzer), is based on an innovative low-power X ray tube, transmission geometry, and CCD collection and discrimination of diffracted and fluoresced X rays. The ability to accumulate and integrate the entire circumference of each complete Debye diffraction ring compensates for poor powder preparations, as might be produced by robotic sampling systems. With CHEMIN, a wide range of minerals can be uniquely identified. Using Rietveld analysis of the XRD results, mineral quantification is also possible. Expanded capabilities in phase analysis and constrained data solutions using quantitative XRD and XRF are within reach.

Enzymatic reaction rate limits with constraints on equilibrium constants and experimental parameters.

A general methodology is presented for estimating maximum rates of enzymatic reactions based on general characteristics of enzymatic reaction mechanisms, kinetic limits and thermodynamics. The useful range of experimentally derived kinetic parameters can also be extended by the methodology. The methodology divides the reaction mechanism into physical and chemical steps. Maximum rates that comply with kinetic and thermodynamic constraints are calculated by setting the physical rate constants to their diffusion limits and optimising the chemical rate constants subject to constraints of the reaction mechanism and overall equilibrium constant. Rate estimates from this methodology can be subject to additional constraints from experimental data, and thus conform to the distinctive features of the enzymatic reaction. The methodology is demonstrated using a reversible enzymatic reaction model involving ordered binding of two reactants and ordered release of two products (bi-bi mechanism). Numerical results are shown for alcohol dehydrogenase (EC 1.1.1.1), which has a bi-bi mechanism. Pyrophosphatase (EC 3.6.1.1) with a uni-bi mechanism and triosephosphate isomerase (EC 5.3.1.1) with a uni-uni mechanism are also examined.

Mineralogy of a mudstone at Yellowknife Bay, Gale crater, Mars.

Sedimentary rocks at Yellowknife Bay (Gale crater) on Mars include mudstone sampled by the Curiosity rover. The samples, John Klein and Cumberland, contain detrital basaltic minerals, calcium sulfates, iron oxide or hydroxides, iron sulfides, amorphous material, and trioctahedral smectites. The John Klein smectite has basal spacing of ~10 angstroms, indicating little interlayer hydration. The Cumberland smectite has basal spacing at both ~13.2 and ~10 angstroms. The larger spacing suggests a partially chloritized interlayer or interlayer magnesium or calcium facilitating H2O retention. Basaltic minerals in the mudstone are similar to those in nearby eolian deposits. However, the mudstone has far less Fe-forsterite, possibly lost with formation of smectite plus magnetite. Late Noachian/Early Hesperian or younger age indicates that clay mineral formation on Mars extended beyond Noachian time.

Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars.

H2O, CO2, SO2, O2, H2, H2S, HCl, chlorinated hydrocarbons, NO, and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H2O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO2. Concurrent evolution of O2 and chlorinated hydrocarbons suggests the presence of oxychlorine phase(s). Sulfides are likely sources for sulfur-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic carbon sources may be preserved in the mudstone; however, the carbon source for the chlorinated hydrocarbons is not definitively of martian origin.

X-ray diffraction results from Mars Science Laboratory: mineralogy of Rocknest at Gale crater.

The Mars Science Laboratory rover Curiosity scooped samples of soil from the Rocknest aeolian bedform in Gale crater. Analysis of the soil with the Chemistry and Mineralogy (CheMin) x-ray diffraction (XRD) instrument revealed plagioclase (~An57), forsteritic olivine (~Fo62), augite, and pigeonite, with minor K-feldspar, magnetite, quartz, anhydrite, hematite, and ilmenite. The minor phases are present at, or near, detection limits. The soil also contains 27 ± 14 weight percent x-ray amorphous material, likely containing multiple Fe(3+)- and volatile-bearing phases, including possibly a substance resembling hisingerite. The crystalline component is similar to the normative mineralogy of certain basaltic rocks from Gusev crater on Mars and of martian basaltic meteorites. The amorphous component is similar to that found on Earth in places such as soils on the Mauna Kea volcano, Hawaii.

Soil diversity and hydration as observed by ChemCam at Gale crater, Mars.

The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.

Curiosity at Gale crater, Mars: characterization and analysis of the Rocknest sand shadow.

The Rocknest aeolian deposit is similar to aeolian features analyzed by the Mars Exploration Rovers (MERs) Spirit and Opportunity. The fraction of sand <150 micrometers in size contains ~55% crystalline material consistent with a basaltic heritage and ~45% x-ray amorphous material. The amorphous component of Rocknest is iron-rich and silicon-poor and is the host of the volatiles (water, oxygen, sulfur dioxide, carbon dioxide, and chlorine) detected by the Sample Analysis at Mars instrument and of the fine-grained nanophase oxide component first described from basaltic soils analyzed by MERs. The similarity between soils and aeolian materials analyzed at Gusev Crater, Meridiani Planum, and Gale Crater implies locally sourced, globally similar basaltic materials or globally and regionally sourced basaltic components deposited locally at all three locations.

Short- and long-term olivine weathering in Svalbard: implications for Mars.

Liquid water is essential to life as we know it on Earth; therefore, the search for water on Mars is a critical component of the search for life. Olivine, a mineral identified as present on Mars, has been proposed as an indicator of the duration and characteristics of water because it dissolves quickly, particularly under low-pH conditions. The duration of olivine persistence relative to glass under conditions of aqueous alteration reflects the pH and temperature of the reacting fluids. In this paper, we investigate the utility of 3 methodologies to detect silicate weathering in a Mars analog environment (Sverrefjell volcano, Svalbard). CheMin, a miniature X-ray diffraction instrument developed for flight on NASA's upcoming Mars Science Laboratory, was deployed on Svalbard and was successful in detecting olivine and weathering products. The persistence of olivine and glass in Svalbard rocks was also investigated via laboratory observations of weathered hand samples as well as an in situ burial experiment. Observations of hand samples are consistent with the inference that olivine persists longer than glass at near-zero temperatures in the presence of solutions at pH approximately 7-9 on Svalbard, whereas in hydrothermally altered zones, glass has persisted longer than olivine in the presence of fluids at similar pH at approximately 50 degrees C. Analysis of the surfaces of olivine and glass samples, which were buried on Sverrefjell for 1 year and then retrieved, documented only minor incipient weathering, though these results suggest the importance of biological impacts. The 3 types of observations (CheMin, laboratory observations of hand samples, burial experiments) of weathering of olivine and glass at Svalbard show promise for interpretation of weathering on Mars. Furthermore, the weathering relationships observed on Svalbard are consistent with laboratory-measured dissolution rates, which suggests that relative mineral dissolution rates in the laboratory, in concert with field observations, can be used to yield valuable information regarding the pH and temperature of reacting martian fluids.

Using in vitro iron deposition on asbestos to model asbestos bodies formed in human lung.

Recent studies have shown that iron is an important factor in the chemical activity of asbestos and may play a key role in its biological effects. The most carcinogenic forms of asbestos, crocidolite and amosite, contain up to 27% iron by weight as part of their crystal structure. These minerals can acquire more iron after being inhaled, thereby forming asbestos bodies. Reported here is a method for depositing iron on asbestos fibers in vitro which produced iron deposits of the same form as observed on asbestos bodies removed from human lungs. Crocidolite and amosite were incubated in either FeCl(2) or FeCl(3) solutions for 2 h. To assess the effect of longer-term binding, crocidolite was incubated in FeCl(2) or FeCl(3) and amosite in FeCl(3) for 14 days. The amount of iron bound by the fibers was determined by measuring the amount remaining in the incubation solution using an iron assay with the chelator ferrozine. After iron loading had been carried out, the fibers were also examined for the presence of an increased amount of surface iron using X-ray photoelectron spectroscopy (XPS). XPS analysis showed an increased amount of surface iron on both Fe(II)- and Fe(III)-loaded crocidolite and only on Fe(III)-loaded amosite. In addition, atomic force microscopy revealed that the topography of amosite, incubated in 1 mM FeCl(3) solutions for 2 h, was very rough compared with that of the untreated fibers, further evidence of Fe(III) accumulation on the fiber surfaces. Analysis of long-term Fe(III)-loaded crocidolite and amosite using X-ray diffraction (XRD) suggested that ferrihydrite, a poorly crystallized hydrous ferric iron oxide, had formed. XRD also showed that ferrihydrite was present in amosite-core asbestos bodies taken from human lung. Auger electron spectroscopy (AES) confirmed that Fe and O were the only constituent elements present on the surface of the asbestos bodies, although H cannot be detected by AES and is presumably also present. Taken together for all samples, the data reported here suggest that Fe(II) binding may result from ion exchange, possibly with Na, on the fiber surfaces, whereas Fe(III) binding forms ferrihydrite on the fibers under the conditions used in this study. Therefore, fibers carefully loaded with Fe(III) in vitro may be a particularly appropriate and useful model for the study of chemical characteristics associated with asbestos bodies and their potential for interactions in a biosystem.