Toti Larson

A Porous Metal−Organic Replica of α-PbO2 for Capture of Nerve Agent Surrogate

A novel metal-organic replica of α-PbO(2) exhibits high capacity for capture of nerve agent surrogate.

Characterization of reaction intermediate aggregates in aniline oxidative polymerization at low proton concentration.

Aggregates of reaction intermediates form during the early stages of aniline oxidative polymerization whenever the initial mole ratio of proton concentration to aniline monomer concentration is low ([H(+)](0)/[An](0) <or= 1.0). Detailed characterization is carried out on those aggregates. The intermediate aggregates show a UV-Vis absorption peak at around 410 nm when dispersed in aqueous solution, whereas the peak is centered on 370 nm when dissolved in an organic solvent such as N-methylpyrrolidone. The electronic band gap decreases when the intermediates aggregate to form a solid, and thus, the absorption peak is red-shifted. Gel permeation chromatography (GPC) shows the aggregates contain a major low molecular weight peak with a long tail. The oligoanilines with low molecular weights consistently show a UV-Vis absorption peak at around 370 nm. Mass spectrometry confirms that the intermediate aggregates contain mainly a component with mass number 363 (M + H(+)), likely a tetramer. UV-Vis, GPC, mass spectrometry, NMR, FTIR, and XRD characterization results are presented and chemical structures for the tetramer are proposed. The major components of the intermediate aggregates are likely highly symmetric phenazine- and dihydrophenazine-containing structures. These particular organic compounds have not been identified before as intermediates. The aggregation and precipitation of the tetramers apparently stabilizes these intermediates. The aggregates are highly crystalline, as evidenced by powder X-ray diffraction. A new reaction mechanism for the formation of these intermediates is proposed.

Profile of a paleo-orogen: High topography across the present-day Basin and Range from 40 to 23 Ma

Records of past topography connect Earth’s deep interior to the surface, reflecting the distribution of heat and mass, past crustal structure, and plate interactions. Many tectonic reconstructions of the North American Cordillera suggest the presence of an Altiplano-like plateau in the location of the modern Basin and Range, with conflicting timing and mechanisms for the onset of surface-lowering extension and orogen collapse. Here we show, through a paleotopographic profile, that from the Eocene to the Oligocene a high, broad orogen stretched across Nevada, with a distinct crest that divided a continuous westward-draining slope extending to central California from an internally drained eastern Nevada plateau. This paleo-orogen maintained demonstrably higher-than-modern elevations, reaching 3500 m in the late Oligocene. Despite the long-term high gravitational potential energy of the crust supporting this topography, surface-lowering extension did not occur until the transition to a transform margin changed the external kinematic framework of the system. Maximum surface lowering was spatially decoupled from brittle upper crustal extension, requiring a large component of mid-crustal flow.

Pretreatment technique for siderite removal for organic carbon isotope and C:N ratio analysis in geological samples

A method for the removal of siderite from geological samples to determine organic carbon isotope compositions using elemental analysis isotope ratio mass spectrometry is presented which includes calculations for % organic carbon in samples that contain diagenetic carbonate. The proposed method employs in situ acidification of geological samples with 6 N HCl and silver capsule sample holders and was tested on modern peach leaf samples (NIST 1547) and ancient lacustrine samples from Valles Caldera, New Mexico. The in situ acidification technique eliminates potential errors associated with the removal of soluble organic material using standard acid decanting techniques and allows for removal of the less soluble siderite, which is not efficiently removed using vapor acidification techniques.

Methane Occurrences in Aquifers Overlying the Barnett Shale Play with a Focus on Parker County, Texas

Clusters of elevated methane concentrations in aquifers overlying the Barnett Shale play have been the focus of recent national attention as they relate to impacts of hydraulic fracturing. The objective of this study was to assess the spatial extent of high dissolved methane previously observed on the western edge of the play (Parker County) and to evaluate its most likely source. A total of 509 well water samples from 12 counties (14,500 km2 ) were analyzed for methane, major ions, and carbon isotopes. Most samples were collected from the regional Trinity Aquifer and show only low levels of dissolved methane (85% of 457 unique locations <0.1 mg/L). Methane, when present is primarily thermogenic (δ13 C 10th and 90th percentiles of -57.54 and -39.00‰ and C1/C2+C3 ratio 10th, 50th, and 90th percentiles of 5, 15, and 42). High methane concentrations (>20 mg/L) are limited to a few spatial clusters. The Parker County cluster area includes historical vertical oil and gas wells producing from relatively shallow formations and recent horizontal wells producing from the Barnett Shale (depth of ∼1500 m). Lack of correlation with distance to Barnett Shale horizontal wells, with distance to conventional wells, and with well density suggests a natural origin of the dissolved methane. Known commercial very shallow gas accumulations (<200 m in places) and historical instances of water wells reaching gas pockets point to the underlying Strawn Group of Paleozoic age as the main natural source of the dissolved gas.

Kinetic hysteresis in gas adsorption behavior for a rigid MOF arising from zig-zag channel structures

A new porous MOF, Zn(TBC)2·{guest}, is synthesized and studied by the single crystallography, N2 isothermal adsorption and GC separation of CO2 from air. This MOF shows large hysteresis on N2 adsorption at 77 K up to a P/Po of 0.9, which arises from the unique zig-zag channel structures of the framework. The MOF shows promising separation ability for CO2 from air.

Fracturing and fluid flow in a sub-décollement sandstone; or, a leak in the basement

Crack-seal texture within fracture cements in the Triassic El Alamar Formation, NE Mexico, shows that the fractures opened during precipitation of quartz cements; later, overlapping calcite cements further occluded pore space. Previous workers defined four systematic fracture sets, A (oldest) to D (youngest), with relative timing constrained by crosscutting relationships. Quartz fluid inclusion homogenization temperatures are higher within Set B (148 ± 20°C) than in Set C (105 ± 12°C). These data and previous burial history modelling are consistent with Set C forming during exhumation. Fluid inclusions in Set C quartz have higher salinity than those in Set B (22.9 v. 14.2 wt% NaCl equivalent, respectively), and Set C quartz cement is more enriched in 18O (20.2 v. 18.7‰ VSMOW). Under most assumptions about the true temperature during fracture opening, the burial duration, the amount of cement precipitated and fluid-flow patterns, it appears that the fracture fluid became depleted in 18O and enriched in 13C. This isotopic evolution, combined with increasing salinity, suggests that throughout fracture opening there was a gravity-driven influx of fluid from upsection Jurassic evaporites, which form a regional décollement. Fracture opening amid downward fluid motion suggests that fracturing was driven by external stresses such as tectonic stretching or unloading, rather than increases in fluid pressure.

Characterizing the Noble Gas Isotopic Composition of the Barnett Shale and Strawn Group and Constraining the Source of Stray Gas in the Trinity Aquifer, North-Central Texas

This study presents the complete set of stable noble gases for Barnett Shale and Strawn Group production gas together with stray flowing gas in the Trinity Aquifer, Texas. It places new constraints on the source of this stray gas and further shows that Barnett and Strawn gas have distinct crustal and atmospheric noble gas signatures, allowing clear identification of these two sources. Like stray gas, Strawn gas is significantly more enriched in crustal 4He*, 21Ne*, and 40Ar* than Barnett gas. The similarity of Strawn and stray gas crustal noble gas signatures suggests that the Strawn is the source of stray gas in the Trinity Aquifer. Atmospheric 22Ne/36Ar ratios of stray gas mimic also that of Strawn, further reinforcing the notion that the source of stray gas in this aquifer is the Strawn. While noble gas signatures of Strawn and stray gas are consistent with a single-stage water degassing model, a two-stage oil modified groundwater exsolution fractionation model is required to explain the light atmospheric noble gas signature of Barnett Shale production gas. These distinct Strawn and Barnett noble gas signatures are likely the reflection of distinct evolution histories with Strawn gas being possibly older than that of Barnett Shale.

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play, South Texas

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo-Wilcox Aquifer (250-1200 m depth range) and Queen City-Sparta Aquifer (150-900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ13 Cmethane (>-55‰) and δDmethane (>-180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ13 Cmethane and δDmethane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs.

Estimates of dietary overlap for six species of Amazonian manakin birds using stable isotopes

We used stable isotope ratios to determine the metabolic routing fraction of carbon and nitrogen in feathers in addition to faecal analysis to estimate diet overlap of six sympatric species of manakins in the eastern lowland forest of Ecuador. Collectively, all species varied from−23.7 to−32.7 ‰ for δ13C, and from 6.0 to 9.9‰ for δ15N, with Machaeropterus regulus showing isotopic differences from the other species. We developed a mixing model that explicitly addresses the routing of carbon and nitrogen to feathers. Interestingly, these results suggest a higher proportion of nitrogen and carbon derived from insects than anticipated based on feeding observations and faecal analysis. A concentration-dependent mixing isotopic model was also used to look at dietary proportions. While larvae and arachnids had higher δ15N values, these two groups may also be preferred prey of manakins and may be more assimilated into tissues, leading to a potential overestimation of the contribution to diet. This study supports the finding that manakin species, previously thought be primarily frugivorous, contain a significant amount of arthropods in their diet.