Development of on-line FTIR spectroscopy for siloxane detection in biogas to enhance carbon contactor management

Activated carbon filters are used to limit engine damage by siloxanes when biogas is utilised to provide electricity. However, carbon filter siloxane removal performance is poorly understood as until recently, it had not been possible to measure siloxanes on-line. In this study, on-line Fourier Transform Infrared (FTIR) spectroscopy was developed to measure siloxane concentration in real biogas both upstream (86.1–157.5 mg m−3) and downstream (2.2–4.3 mg m−3) of activated carbon filters. The FTIR provided reasonable precision upstream of the carbon vessel with a root mean square error of 10% using partial least squares analysis. However, positive interference from volatile organic carbons was observed in downstream gas measurements limiting precision at the outlet to an RMSE of 1.5 mg m−3 (47.8%). Importantly, a limit of detection of 3.2 mg m−3 was identified which is below the recommended siloxane limit and evidences the applicability of on-line FTIR for this application

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

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

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

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

Repetitive task training for improving functional ability after stroke

<p><b>Objectives:</b> The objective of this review was to determine if repetitive task training after stroke improves global, upper, or lower limb function and if treatment effects are influenced by the amount, type, or timing of practice.</p> <p><b>Search Strategy:</b> We searched the Cochrane Stroke Trials Register (to October 2006); The Cochrane Library, MEDLINE, EMBASE, CINAHL, AMED, SportDiscus, Science Citation Index, Index to Theses, ZETOC, PEDro, and OT Seeker (all to September 2006); and OT search (to March 2006). We also searched for unpublished/non-English language trials; combed conference proceedings and reference lists; requested information on bulletin boards; and contacted trial authors.</p> <p><b>Selection Criteria:</b> Selection criteria included randomized/quasirandomized trials in adults after stroke, of interventions that included an active motor sequence performed repetitively within a single training session, a clear functional goal, and a quantifiable level of practice.</p> <p><b>Data Collection and Analysis:</b> Two authors independently screened abstracts, extracted data, and appraised trial quality. Further information was obtained from study authors. Results from individual trials were combined using meta-analytic techniques appropriate to the data extracted and the level of between-trial heterogeneity.</p> <p><b>Main Results:</b> Fourteen trials with 17 intervention-control pairs and 659 participants were included. Primary outcomes showed that treatment effects were statistically significant for walking distance (see the Figure); walking speed (standardized mean difference, 0.29; 95% CI, 0.04 to 0.53); and sit-to-stand (standardized effect estimate, 0.35; 95% CI, 0.13 to 0.56). Treatment effects were of borderline statistical significance for functional ambulation.</p&gt

Base-mediated cascade rearrangements of aryl-substituted diallyl ethers.

Two base-mediated cascade rearrangement reactions of diallyl ethers were developed leading to selective [2,3]-Wittig-oxy-Cope and isomerization-Claisen rearrangements. Both diaryl and arylsilyl-substituted 1,3-substituted propenyl substrates were examined, and each exhibits unique reactivity and different reaction pathways. Detailed mechanistic and computational analysis was conducted, which demonstrated that the role of the base and solvent was key to the reactivity and selectivity observed. Crossover experiments also suggest that these reactions proceed with a certain degree of dissociation, and the mechanistic pathway is highly complex with multiple competing routes.We thank Eli Lilly (Dr Magnus Walter and Dr Maria Whatton) for a CASE award to C.A.M. and Queen’s University Belfast for funding. We also thank Girton College, Cambridge (Research Fellowship to M.N.G.) and Unilever for support.This is the accepted manuscript of a paper published in The Journal of Organic Chemistry, 2015, 80 (3), pp 1472–1498, DOI: 10.1021/jo502403n, Publication Date (Web): December 16, 201

Analysis of Organic Molecules Extracted from Mars Analogues and Influence of Their Mineralogy Using N-Methyl-N-(tert-butyldimethylsilyl)Trifluoroacetamide Derivatization Coupled with Gas Chromatography Mass Spectrometry in Preparation for the Sample Analysis at Mars Derivatization Experiment on the Mars Science Laboratory Mission

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids will require a chemical extraction and derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed, a one-pot extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment on the Mars Science Laboratory (MSL). The temperature and duration the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 C for several minutes of a variety of terrestrial Mars analogue materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analogue materials that contained high abundances of hydrated minerals and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA, The combination of pyrolysis and two different chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars

Evolved Gas Analysis and X-Ray Diffraction of Carbonate Samples from the 2009 Arctic Mars Analog Svalbard Expedition: Implications for Mineralogical Inferences from the Mars Science Laboratory

The 2009 Arctic Mars Analog Svalbard Expedition (AMASE) investigated several geologic settings using methodologies and techniques being developed or considered for future Mars missions, such as the Mars Science Laboratory (MSL), ExoMars, and Mars Sample Return (MSR). AMASE-related research comprises both analyses conducted during the expedition and further analyses of collected samples using laboratory facilities at a variety of institutions. The Sample Analysis at Mars (SAM) instrument suite, which will be part of the Analytical Laboratory on MSL, consists of a quadrupole mass spectrometer (QMS), a gas chromatograph (GC), and a tunable laser spectrometer (TLS). An Evolved Gas Analysis Mass Spectrometer (EGA-MS) was used during AMASE to represent part of the capabilities of SAM. The other instrument included in the MSL Analytical Laboratory is CheMin, which uses X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) to perform quantitative mineralogical characterization of samples. Field-portable versions of CheMin were used during the AMASE 2009. Here, we discuss the preliminary interpretation of EGA and XRD analyses of selected AMASE carbonate samples and implications for mineralogical interpretations from MSL. Though CheMin will be the primary mineralogical tool on MSL, SAM EGA could be used to support XRD identifications or indicate the presence of volatile-bearing minerals which may be near or below XRD detection limits. Data collected with instruments in the field and in comparable laboratory setups (e.g., the SAM breadboard) will be discussed