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.     

Medical geology：new relevance in the earth sciences

The interdisciplinary fieldresponds to the need to betterof “Medical Geology“ understand the relationships between human health and our surrounding environment. The influence of earth resources, natural environmental factors and land-use on human health has long been recognized, dating back to ancient Rome and Peru‘s Inca civilization. Today links between the natural environment and health can be found throughout the world. This review introduces the historical context of this particular type of research, contrasts the direct geological and indirect natural hazard influences on healthas a framework of study, elaborates on pathways of elemental accumulation in the body and provides examples of specific geochemical behaviours and diseases that are often associated with either too much or not enough of certain elements which comprise the Earth.     

Sediment–water interactions of natural oestrogens under estuarine conditions

The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol⁻¹ was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (K_p^true) and colloidal particles (K_c^true) have been calculated, and a K_p^true value of 141 and 102 ml g⁻¹ was obtained for oestrone and 17β-oestradiol, respectively. In addition, K_c^true values for oestrone (222×10² ml g⁻¹) and 17β-oestradiol (135×10² ml g⁻¹) were two orders of magnitude higher than their respective K_p^true values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.     

Efficacy of beach dewatering — Alassio,Italy

The goal of this study is to estimate the efficiency of dewatering operations in Alassio Beach, north Italy by following an integrated approach which included beach volume calculations, daily mapping of the shoreline position, examination of specific beach widening events and daily comparisons of morphodynamic characteristics of the drained beach versus a control section which included wave run-up, bar patterns, rip migration, evolution of the berm and cusp morphology.     

Analysis of mean elements of three U.S. Navy navigation satellites for the period 1974–1976

Analysis of high precision 2-day mean orbital elements of several U.S. Navy navigation satellites is presented. The combined analytical-numerical method for the computation of the elements from the Defense Mapping Agency precision ephemerides is described. The precision of the semimajor axis and the inclination orbital elements are determined to be 2 cm and 0.016 respectively. The 28th degree and 27th order terms of the geopotential field are determined with the mean elements.     

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.