Quantifying hydrogen‐deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

Abstract— Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen‐deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound‐specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2‐methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in δD values of the dicarboxylic acids were measured following the reflux experiments. A pseudo‐first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2‐methyl glutaric acids with a δD of 1800%***_o would experience isotope changes of 38_o, 10_o, and 6_o, respectively during the extraction process. Therefore, the overall change in δD values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral α‐carbon in 2‐methyl glutaric acid. The results suggest that the racemic mixture of 2‐methyl glutaric acid in the Tagish Lake meteorite could result from post‐synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.     

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2

We report the astronomical identification of the cyanomethyl radical, CH2CN, the heaviest nonlinear molecular radical to be identified in interstellar clouds. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1, where the abundance appears to be about 5 x 10(-9) relative to that of H2. This is significantly greater than the observed abundance of CH3CN (methyl cyanide) in TMC-1. In Sgr B2 the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident. Preliminary searches in other sources indicate that the distribution of CH2CN is similar to that for such carbon chain species as HC3N or C4H.     

Geochemistry of the Uintjiesberg kimberlite, South Africa: petrogenesis of an off-craton, group I, kimberlite

The Uintjiesberg kimberlite diatreme occurs within the Proterozoic Namaqua–Natal Belt, South Africa, approximately 60 km to the southwest of the Kaapvaal craton boundary. It is a group I, calcite kimberlite that has an emplacement age of 100 Ma. Major and trace element data, in combination with petrography, are used to evaluate its petrogenesis and the nature of its source region. Macrocryst phases are predominantly olivine with lesser phlogopite, with very rare garnet and Cr-rich clinopyroxene. Geochemical variation amongst the macrocrystic samples (Mg# 0.85–0.87, SiO₂=27.0–29.3%, MgO=26.1–30.5%, CaO=10.9–13.5%) is shown to result from 10% to 40% entrainment and partial assimilation of peridotite xenoliths, whereas that shown by the aphanitic samples (Mg# 0.80–0.83, SiO₂=19.1–23.0%, MgO=17.9–23.9%, CaO=16.5–23.7%) is consistent with 7–25% crystal fractionation of olivine and minor phlogopite. Changing trajectories on chemical variation diagrams allow postulation of a primary magma composition with 25% SiO₂, 26% MgO, 2.3% Al₂O₃, 5%H₂O, 8.6% CO₂ and Mg#=0.85.

Forward melting models, assuming 0.5% melting, indicate derivation of the primary Uintjiesberg kimberlite magma from a source enriched in light rare earth elements (LREE) by 10× chondrite and heavy REE (HREE) by 0.8–2× chondrite, the latter being dependent on the proportion of residual garnet. Significant negative Rb, K, Sr, Hf and Ti anomalies present in the inferred primary magma composition are superimposed on otherwise generally smooth primitive mantle-normalized trace element patterns, and are inferred to be a characteristic of the primary magma composition. The further requirement for a source with chondritic or lower HREE abundances, residual olivine with high Fo content (Fo₉₄) suggests derivation from a mantle previously depleted in mafic melt but subsequently enriched in highly incompatible elements prior to kimberlite genesis. These requirements are interpreted in the context of melting of continental lithospheric mantle previously enriched by metasomatic fluids derived from a sublithospheric (plume?) source.     

Response of low‐angle dunes to variable flow

Current understanding of bedform dynamics is largely based on field and laboratory observations of bedforms in steady flow environments. There are relatively few investigations of bedforms in flows dominated by unsteadiness associated with rapidly changing flows or tides. As a consequence, the ability to predict bedform response to variable flow is rudimentary. Using high‐resolution multibeam bathymetric data, this study explores the dynamics of a dune field developed by tidally modulated, fluvially dominated flow in the Fraser River Estuary, British Columbia, Canada. The dunes were dominantly low lee angle features characteristic of large, deep river channels. Data were collected over a field ca 1·0 km long and 0·5 km wide through a complete diurnal tidal cycle during the rising limb of the hydrograph immediately prior to peak freshet, yielding the most comprehensive characterization of low‐angle dunes ever reported. The data show that bedform height and lee angle slope respond to variable flow by declining as the tide ebbs, then increasing as the tide rises and the flow velocities decrease. Bedform lengths do not appear to respond to the changes in velocity caused by the tides. Changes in the bedform height and lee angle have a counterclockwise hysteresis with mean flow velocity, indicating that changes in the bedform geometry lag changes in the flow. The data reveal that lee angle slope responds directly to suspended sediment concentration, supporting previous speculation that low‐angle dune morphology is maintained by erosion of the dune stoss and crest at high flow, and deposition of that material in the dune trough.     

Tailings composition effects on shear strength behavior of co-mixed mine waste rock and tailings

The objective of this study was to evaluate the effect of mine tailings composition on shear behavior and shear strength of co-mixed mine waste rock and tailings (WR&T). Crushed gravel was used as a synthetic waste rock and mixed with four types of tailings: (1) fine-grained garnet, (2) coarse-grained garnet, (3) copper, and (4) soda ash. Co-mixed WR&T specimens were prepared to target mixture ratios of mass of waste rock to mass of tailings (R) such that tailings “just filled” interparticle void space of the waste rock (i.e., optimum mixture ratio, R _opt). Triaxial compression tests were conducted on waste rock, tailings, and mixed waste at effective confining stresses (\(\sigma_{\text{c}}^{{\prime }}\)) ranging from 5 to 40 kPa to represent stresses anticipated in final earthen covers for waste containment facilities. Waste rock and co-mixed WR&T specimens were 150 mm in diameter by 300 mm tall, whereas tailings specimens were 38 mm in diameter by 76 mm tall. Shear strength was quantified using effective stress friction angles (?′) from undrained tests: ?′ for waste rock was 37°, ?′ for tailings ranged from 34° to 41°, and ?′ for WR&T mixtures ranged from 38° to 40°. Thus, shear strength of co-mixed WR&T was comparable to waste rock regardless of tailings composition. Shear behavior of WR&T mixtures was a function of R and tailings composition. Tailings influenced shear behavior for R < R _opt and when tailings predominantly were silt. Shear behavior was influenced by waste rock for R ≥ R _opt and when tailings predominantly were sand or included clay particles.     

The role of social capital,personal networks,and emergency responders in post-disaster recovery and resilience: a study of rural communities in Indiana

The factors that explain the speed of recovery after disaster remain contested. While many have argued that physical infrastructure, social capital, and disaster damage influence the arc of recovery, empirical studies that test these various factors within a unified modeling framework are few. We conducted a mail survey to collect data on household recovery in four small towns in southern Indiana that were hit by deadly tornadoes in March 2012. The recovery effort is ongoing; while many of the homes, businesses, and community facilities were rebuilt in 2013, some are still under construction. We investigate how households in these communities are recovering from damage that they experienced and the role of social capital, personal networks, and assistance from emergency responders on the overall recovery experience. We used an ordered probit modeling framework to test the combined as well as relative effects of (a) damage to physical infrastructures (houses, vehicles, etc.); (b) recovery assistance from emergency responders (FEMA) as well as friends and neighbors; (c) personal network characteristics (size, network density, proximity, length of relationship); (d) social capital (civic engagement, contact with neighbors, trust); and (e) household characteristics. Results show that while households with higher levels of damage experienced slower recovery, those with recovery assistance from neighbors, stronger personal networks, and higher levels of social capital experienced faster recovery. The insights gained in this study will enable emergency managers and disaster response personnel to implement targeted strategies in facilitating post-disaster recovery and community resilience.