The Role of (Delta)C-13 in the Search for Reduced Organics on the Surface of Mars

The capabilities of the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to detect trace amounts of organic carbon compounds are unprecedented, and MSL may be the first mission to reveal the presence of organic carbon on Mars. The search for reduced organic carbon on Mars is inextricably tied to: a) the preservation potential of the environment from which we take a solid sample, and b) the evolved gas analysis (EGA) techniques used by SAM to release volatiles from this solid sample. Several prospective targets have been identified for sample analysis at Gale Crater. Stratigraphic sequences of phyllosilicates and sulfates at Gale are thought to represent a period of global climate transition from a moderate pH lacustrine environment to an evaporitic environment, both of which could sequester organic carbon (Thomson et al. 2011). The sediment mound in Gale Crater contains a range of lithologies suggesting changes in redox conditions, and evidence of both lacustrine and fluvial depositional processes, which may have transported organic carbon from the layer in which it formed and resulted in its preservation elsewhere within the crater (Anderson and Bell, 2010). Inverted channel fills suggest erosion resistant material that could serve to preserve organics originally deposited in a low energy aqueous environment. The lithology sampled will affect not only the preservation of organics, but also our ability to detect organics during our evolved gas analysis, based on the sample matrix. For example, reduced organics may be trapped in the mineral structure, and thermal evolution of these organics will occur during thermal decomposition of the host mineral. If organics are occluded in minerals that have very high thermal decomposition temperatures, they may be, in effect, "too well preserved," and difficult to detect during EGA. Alternatively, the possible presence of perchlorate, or other strong oxidants in surface regolith, may result in destruction of structural information identifying organic molecules before reaching the QMS on SAM via oxidation to C02 during heating. If this is the case, the stable carbon isotopic composition (delta 13C) of the C02 evolved and measured by the Tunable Laser Spectrometer (TLS) on SAM may help identify the presence of organics. On Earth, biological activity can cause large fractionations of 13C/12C, which can preserved in sedimentary deposits and distinguish the organic products of biotic processes from inorganic atmospheric and geological reservoirs. It is plausible that similar fractionations could occur on Mars and be preserved in reduced organic matter in sediments. Bulk delta 13C measurements alone may not reveal a signature of trace organic carbon that may be present along with inorganic carbon. If both organic and inorganic carbon compounds are present, it may be possible to detect the organic carbon by comparing the 013C of pyrolysis and combustion experiments. The TLS on SAM is capable of obtaining high precision measurements of delta13C from C02 evolved during pyrolysis and combustion of solid regolith samples. Because carbonates are expected to be present at abundances of 0.1-1 % in Martian soil, and organics in the ppb range (Webster and Mahaffy, 2011), analog samples must represent this mix of reduced organic carbon and carbonate. The work presented here will examine the use of delta13C of C02 produced during combustion of bulk Mars analog samples as a proxy for detection of reduced organic carbon

4-[(E)-2-Ferrocenylethen­yl]-1,8-naphthalic anhydride

In the structure of the title compound, [Fe(C5H5)(C19H11O3)], the plane of the substituted ferrocene ring is tilted by 14.17 (6)° with respect to the mean plane through the naphthalene ring system. In the crystal structure, centrosymmetric dimers are formed through π–π inter­actions [centroid–centroid distance = 3.624 (2) Å] between the substituted ferrocene ring and the three fused rings of the naphthalic anhydride unit. Pairs of dimers are held together by further naphthalene–naphthalene π–π interactions [distance between parallel mean planes 3.45 (3) Å]. Each dimer inter­acts with four neighbouring dimers in a herringbone fashion through C—H⋯π inter­actions, so forming a two-dimensional sheet-like structure

Dissolved gas separation for engineered anaerobic wastewater systems

Dissolved gases produced within engineered anaerobic processes subsequently create a fugitive emission which can have financial, environmental and health and safety implications. Whilst desorption technology has been used to control dissolved gases in the drinking water sector, there is considerably less understanding of its deployment in wastewater for which there are numerous existing and emerging challenges. This review therefore focuses on existing and proposed technological approaches to gas desorption in engineered anaerobic wastewater processes, with specific emphasis on technology compatibility and downstream gas phase management. Simplified engineered solutions such as diffused aeration and multi-tray aerators appear robust solutions for implementation into wastewater. However, these processes are characterised by a low mass transfer coefficient and require high gas to liquid ratios (G/L) to achieve reasonable separation, which suggests their suitability is limited to small scale applications, in which gas recovery is not a priority. Packed columns and membrane contactors afford process intensification through increasing interfacial area which favours large scale applications; although both will require prefiltration technology to obviate media clogging. Vacuum or steam is the preferred driving force for separation when gas recovery is sought, while sweep-gas is energetically favoured. Sweep-gas has been used for gas recovery by operating at G/L toward the equilibrium value, which somewhat constrains mass transfer. Process selection must therefore be weighted on whole life cost, but will also be dependent upon process scale, financial (e.g. incentivisation) and non-financial (e.g. carbon) instruments, which are strongly influenced by regional policy

delta C-13 Analysis of Mars Analog Carbonates Using Evolved Gas Cavity - Ringdown Spectrometry on the 2010 Arctic Mars Analog Svalbard Expedition (AMASE)

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two distinct geologic settings on Svalbard, using instrumentation and techniques in development for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return (MSR). The Sample Analysis at Mars (SAM) instrument suite, which will fly on MSL, was developed at Goddard Space Flight Center (GSFC), together with several partners. SAM consists of a quadrupole mass spectrometer (QMS), a gas chromatograph CGC), and a tunable laser spectrometer (TLS), which all analyze gases created by evolved gas analysis (EGA). The two sites studied represent "biotic" and "abiotic" analogs; the "biotic" site being the Knorringfjell fossil methane seep, and the "abiotic" site being the basaltic Sigurdfjell vent complex. The data presented here represent experiments to measure the carbon isotopic composition of carbonates from these two analogs using evolved gas analysis coupled with a commercial cavity ringdown CO2 isotopic analyzer (Picarro) as a proxy for the TLS on SAM

Changing epidemiology of methicillin-resistant Staphylococcus aureus colonization in paediatric intensive-care units

Community-associated methicillin-resistant S. aureus (CA-MRSA) accounts for a growing proportion of hospital-onset infections, and colonization is a risk factor. This study aimed to determine changes in the prevalence of CA-MRSA colonization in paediatric intensive-care units (ICUs). A total of 495 paediatric patients colonized with MRSA from neonatal, medical, surgical, and cardiac ICUs between 2001 and 2009 were identified. Isolates were characterized by spa type, staphylococcal cassette chromosome (SCC) mec type and the presence of the genes encoding Panton–Valentine leukocidin (PVL). The proportion of patients colonized with MRSA remained stable (average 3·2%). The proportion of isolates with spa type 1, SCCmec type IV and PVL increased over time to maximums in 2009 of 36·1% (P < 0·001), 54·2% (P = 0·03) and 28·9% (P = 0·003), respectively. Antibiotic susceptibility patterns showed increasing proportions susceptible to clindamycin, gentamicin, tetracycline and trimethoprim-sulfamethoxazole (P values <0·001). In conclusion, the proportion of MRSA-colonized children in ICUs with CA-MRSA increased significantly over time

Evolved Gas Analysis of Mars Analog Samples from the Arctic Mars Analog Svalbard Expedition: Implications for Analyses by the Mars Science Laboratory

The 2011 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings on Svalbard, using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL). The Sample Analysis at Mars (SAM) instrument suite on MSL consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS), which analyze gases created by pyrolysis of samples. During AMASE, a Hiden Evolved Gas Analysis-Mass Spectrometer (EGA-MS) system represented the EGA-QMS capability of SAM. Another MSL instrument, CheMin, will use x-ray diffraction (XRD) and x-ray fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during AMASE. AMASE 2011 sites spanned a range of environments relevant to understanding martian surface materials, processes and habitability. They included the basaltic Sverrefjell volcano, which hosts carbonate globules, cements and coatings, carbonate and sulfate units at Colletth0gda, Devonian sandstone redbeds in Bockfjorden, altered basaltic lava delta deposits at Mt. Scott Keltie, and altered dolerites and volcanics at Botniahalvoya. Here we focus on SAM-like EGA-MS of a subset of the samples, with mineralogy comparisons to CheMin team results. The results allow insight into sample organic content as well as some constraints on sample mineralogy

Compositional Explanation of Types and Algorithmic Debugging of Type Errors

The type systems of most typed functional programming languages are based on the Hindley-Milner type system. A practical problem with these type systems is that it is often hard to understand why a program is not type correct or a function does not have the intended type. We suggest that at the core of this problem is the difficulty of explaining why a given expression has a certain type. The type system is not defined compositionally. We propose to explain types using a variant of the Hindley-Milner type system that defines a compositional type explanation graph of principal typings. We describe how the programmer understands types by interactive navigation through the explanation graph. Furthermore, the explanation graph can be the foundation for algorithmic debugging of type errors, that is, semi-automatic localisation of the source of a type error without even having to understand the type inference steps. We implemented a prototype of a tool to explore the usefulness of the proposed methods

Visible, Near-Infrared, and Mid-Infrared Spectral Characterization of Hawaiian Fumarolic Alteration Near Kilauea's December 1974 Flow: Implications for Spectral Discrimination of Alteration Environments on Mars

The December 1974 flow in the SW rift zone at Kilauea Volcano, Hawaii, has been established as a Mars analog due to its physical, chemical, and morphological properties, as well as its interaction with the outgassing plume from the primary Kilauea caldera. We focus on a solfatara site that consists of hydrothermally altered basalt and alteration products deposited in and around a passively degassing volcanic vent situated directly adjacent to the December 1974 flow on its northwest side. Reflectance spectra are acquired in the visible/near-infrared (VNIR) region and emission spectra in the mid-infrared (MIR) range to better understand the spectral properties of hydrothermally altered materials. The VNIR signatures are consistent with silica, Fe-oxides, and sulfates (Ca, Fe). Primarily silica-dominated spectral signatures are observed in the MIR and changes in spectral features between samples appear to be driven by grain size effects in this wavelength range. The nature of the sample coating and the thermal emission signatures exhibit variations that may be correlated with distance from the vent. Chemical analyses indicate that most surfaces are characterized by silica-rich material, Fe-oxides, and sulfates (Ca, Fe). The silica and Fe-oxide-dominated MIR/VNIR spectral signatures exhibited by the hydrothermally altered material in this study are distinct from the sulfate-dominated spectral signatures exhibited by previously studied low-temperature aqueous acid-sulfate weathered basaltic glass. This likely reflects a difference in open vs. closed system weathering, where mobile cations are removed from the altered surfaces in the fumarolic setting. This work provides a unique infrared spectral library that includes martian analog materials that were altered in an active terrestrial solfatara (hydrothermal) setting. Hydrothermal environments are of particular interest as they potentially indicate habitable conditions. Key constraints on the habitability and astrobiological potential of ancient aqueous environments are provided through detection and interpretation of secondary mineral assemblages; thus, spectral detection of fumarolic alteration assemblages observed from this study on Mars would suggest a region that could have hosted a habitable environment

Young K-Ar gae of jarosite in the Mojave sample at Gale Crater, Mars.

By combining the Sample Analysis at Mars (SAM) instrument’s capabilities with those of the alpha particle X-ray spectrometer (APXS) on the Curiosity rover, radiometric K-Ar ages and 3He, 21Ne, and 36Ar exposure ages have been measured on two samples as of sol 1430. The Cumberland mudstone was found to have a K-Ar age of 4.21 ± 0.35 Ga (all uncertainties here are reported in 1σ), consistent with crater-counting estimates of the surrounding terrains. A second geochronology experiment was undertaken on the potassium-rich Windjana sandstone, which resulted in the unreasonably young and unrepeatable ages of 627 ± 50 Ma and 1710 ± 110 Ma on two different aliquots. These results were attributed to incomplete Ar extraction arising from the coarse grainsize and Ar-retentive characteristics of sanidine, the major K-bearing mineral in the sample.Recently, a drilled bedrock sample from the Murray mudstone formation (termed Mojave 2) was found by the CheMin instrument to contain approximately 3.1 wt% jarosite. Jarosite is precipitated from acidic, sulfate-rich waters and is a suitable mineral for KAr dating. On a large scale, jarosite has been thought to signal the aridification of Mars and a shift towards a cold, dry environment. The small amount of jarosite in this sample prohibits generalization to a larger Martian context. However, since jarosite forms strictly through interaction with water, the K-Ar age of the jarosite in Mojave 2 puts a maximum age constraint on the last time liquid water was present at the sample site. By extension, it could also indicate the time of the very final stages of evaporation from the lake in Gale Crater.A two-step heating experiment was designed to obtain the K-Ar age of the jarosite, which accounts for about 20% of the K2O in the sample. The remainder of the K2O exists in plagioclase, an amorphous component, and possibly a small amount in K-bearing phyllosilicates