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

Bayesian fitting of probabilistic maturation reaction norms to population-level data

Probabilistic maturation reaction norms (PMRNs) are an important tool for studying fisheries-induced evolution and environmental effects on life history. To date there has been no way to fit a PMRN to population-level fisheries data; instead individual-level data must be used. This limits the stocks and time periods that can be studied.We introduce a Bayesian method for fitting PMRNs to population-level data. The method is verified against both an existing result and simulated data, and applied to historical Barents Sea cod data which combines observations of population-level variation in age, size and maturity status from Russia and Norway.The method shows a clear and rapid trend towards greater probability of maturation at smaller lengths in the Barents Sea cod.The new model fitting algorithm allows us to study historic changes in life history despite the lack of individual-level data seen in much long term data. Access to more data will aid the study of evolutionary hypotheses in a wide range of organisms

Gas to liquid mass transfer in rheologically complex fluids

The increase of studies relaying on gas to liquid mass transfer in digested sludge (shear thinning fluid) necessitates a better understanding of the impact of apparent viscosity (μa) and rheology in process performance. Mass transfer retardation due to μa variations was investigated in a pilot scale absorption bubble column for Newtonian and shear thinning fluids with varied superficial gas velocities (UG). A non-linear reduction of mass transfer efficiency with increasing μa was observed, being the impact higher at low μa ranges and high UG. An increase of 114 cPo in μ from 1.01 to 115 cPo in glycerol solutions saturated with UG = 1.73 cm s−1 led to a reduction of 96% in kLa (α = 0.04), while a comparable raise from 115 to 229 cPo implied a reduction of 52% (α = 0.02). Slug–annular flow regime was identified for shear thinning fluids of high μa (1.0% and 1.5% carboxymethyl cellulose sodium salt solutions), where bubble buoyancy was conditioned by the μ of the fluid at rest and the active volume for mass transfer was reduced because of the presence of stagnant areas. Conditions imitating the rheological variability of anaerobically digested sewage sludge were included within those tested, being a reduction in gas transfer efficiency of 6 percentage points (from 7.6 ± 0.3% to 1.6 ± 0.1%) recorded when increasing μa from 130 to 340 cPo. It is thus recommended that rheology and μa variability are accounted for within the design of gas to liquid mass transfer systems involving digested sewage sludge, in order to avoid reductions in process performance and active volume

The cost of a small membrane bioreactor

The individual cost contributions to the mechanical components of a small membrane bioreactor (MBR) (100–2,500 m3/d flow capacity) are itemised and collated to generate overall capital and operating costs (CAPEX and OPEX) as a function of size. The outcomes are compared to those from previously published detailed cost studies provided for both very small containerised plants (<40 m3/day capacity) and larger municipal plants (2,200–19,000 m3/d). Cost curves, as a function of flow capacity, determined for OPEX, CAPEX and net present value (NPV) based on the heuristic data used indicate a logarithmic function for OPEX and a power-based one for the CAPEX. OPEX correlations were in good quantitative agreement with those reported in the literature. Disparities in the calculated CAPEX trend compared with reported data were attributed to differences in assumptions concerning cost contributions. More reasonable agreement was obtained with the reported membrane separation component CAPEX data from published studies. The heuristic approach taken appears appropriate for small-scale MBRs with minimal costs associated with installation. An overall relationship of net present value = (a tb)Q(−c lnt+d) was determined for the net present value where a = 1.265, b = 0.44, c = 0.00385 and d = 0.868 according to the dataset employed for the analysis

Ethyl 5-hy­droxy-6-oxo-4-phenyl-5,6-dihydro-4H-cyclo­penta­[b]thio­phene-5-carboxyl­ate

In the title mol­ecule, C16H14O4S, the dihydro­cyclo­penta­thio­phenone ring system is almost planar, with an r.m.s. deviation of 0.060 Å from the best fit plane through all nine non-H atoms. The cyclo­penta­none ring adopts a severely flattened envelope conformation with the C atom carrying the OH and ethylcarboxylate substituents at the flap. This atom lies only 0.185 (3) Å from the plane through the other four C atoms. The phenyl substituent is inclined at 43.37 (5)° to the dihydro­cyclo­penta­thio­phenone mean plane. In the crystal, mol­ecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with R 2 2(10) ring motifs. Weak C—H⋯O hydrogen bonds also link mol­ecules into chains along c, while an approximately orthogonal set of C—H⋯O contacts form chains along b, resulting in layers lying parallel to (100). Inversion dimers also form through weaker R 2 2(12) C—H⋯S contacts, which combine with C—H⋯O contacts to form stacks along b

Tube-side mass transfer for hollow fibre membrane contactors operated in the low Graetz range

Transformation of the tube-side mass transfer coefficient derived in hollow fibre membrane contactors (HFMC) of different characteristic length scales (equivalent diameter and fibre length) has been studied when operated in the low Graetz range (Gz < 10). Within the low Gz range, mass transfer is generally described by the Graetz problem (Sh=3.67) which assumes that the concentration profile comprises a constant shape over the fibre radius. In this study, it is experimentally evidenced that this assumption over predicts mass transfer within the low Graetz range. Furthermore, within the low Gz range (below 2), a proportional relationship between the experimentally determined mass transfer coefficient (Kov) and the Graetz number has been identified. For Gz numbers below 2, the experimental Sh number approached unity, which suggests that mass transfer is strongly dependent upon diffusion. However, within this diffusion controlled region of mass transfer, tube-side fluid velocity remained important. For Gz numbers above 2, Sh could be satisfactorily described by extension to the Lévêque solution, which can be ascribed to the constrained growth of the concentration boundary layer adjacent to the fibre wall. Importantly this study demonstrates that whilst mass transfer in the low Graetz range does not explicitly conform to either the Graetz problem or classical Lévêque solution, it is possible to transform the experimentally derived overall mass transfer coefficient (Kov) between characteristic length scales (dh and L). This was corroborated by comparison of the empirical relationship determined in this study (Sh=0.36Gz) with previously published studies operated in the low Gz range. This analysis provides important insight for process design when slow tube-side flows, or low Schmidt numbers (coincident with gases) constrain operation of hollow fibre membrane contactors to the low Gz range

1,4-Bis(iodo­meth­yl)benzene

The centrosymmetric title compound, C8H8I2, was prepared by metathesis from the dibromo analogue. In the crystal structure, weak C—H⋯I inter­actions link the mol­ecules into stacks down the b axis. The structure is further stabilized by short I⋯I contacts [3.8433 (2) Å], forming undulating sheets in the (101) plane

The preparation and characterisation of monomeric and linked metal carbonyl clusters containing the closo-Si2Co4 pseudo-octahedral core

PhSiH3 reacts with [Co₄(CO)₁₂] at 50 °C in hydrocarbon solvents to give [(µ₄-SiPh)₂Co₄(CO)₁₁], 2c, shown by an X-ray crystal structure determination to have a pseudo-octahedral Si₂Co₄ core. Substituted aryl-silanes behaved similarly. Mixtures of PhSiH₃, H₃SiC₆H₄SiH₃ and [Co₄(CO)₁₂] in a ca. 2 1 2 ratio gave the dimeric cluster [{Co₄(µ₄-SiPh)(CO)₁₁Si}₂C₆H₄], 3a, which has the two Si₂Co₄ cores linked by a C₆H₄ group to give a rigid molecule which an X-ray structure analysis shows to be over 23 Å long. Related dimers linked by –(CH₂)₈– groups were isolated from mixtures of PhSiH₃, α ,ω-(H₃Si)₂(CH₂)₈ and [Co₄(CO)₁₂]. Electrochemical studies show the two cluster units in 3a do not interact electronically

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