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.     

Late Holocene estuarine–inner shelf interactions; is there evidence of an estuarine retreat path for Tampa Bay, Florida?

The purpose of this study was to determine if and how a large, modern estuarine system, situated in the middle of an ancient carbonate platform, has affected its adjacent inner shelf both in the past during the last, post-glacial sea-level rise and during the present. An additional purpose was to determine if and how this inner shelf seaward of a major estuary differed from the inner shelves located just to the north and south but seaward of barrier-island shorelines. Through side-scan sonar mosaicking, bathymetric studies, and ground-truthing using surface grab samples as well as diver observations, two large submarine sand plains were mapped – one being the modern ebb-tidal delta and the other interpreted to be a relict ebb-tidal delta formed earlier in the Holocene. The most seaward portion of the inner shelf studied consists of a field of lobate, bathymetrically elevated, fine-sand accumulations, which were interpreted to be sediment-starved 3D dunes surrounded by small 2D dunes composed of coarse molluscan shell gravel. Additionally, exposed limestone hardbottoms supporting living benthic communities were found as well. This modern shelf sedimentary environment is situated on a large, buried shelf valley, which extends eastward beneath the modern Tampa Bay estuary. These observations plus the absence of an incised shelf valley having surficial bathymetric expression, and the absence of sand bodies normally associated with back-tracking estuarine systems indicate that there was no cross-shelf estuarine retreat path formed during the last rise in sea level. Instead, the modern Tampa Bay formed within a mid-platform, low-relief depression, which was flooded by rising marine waters late in the Holocene. With continued sea-level rise in the late Holocene, this early embayment was translated eastward or landward to its present position, whereby a larger ebb-tidal delta prograded out onto the inner shelf. Extensive linear sand ridges, common to the inner shelves to the north and south, did not form in this shelf province because it was a low-energy, open embayment lacking the wave climate and nearshore zone necessary to create such sand bodies. The distribution of bedforms on the inner shelf and the absence of seaward-oriented 2D dunes on the modern ebb-tidal delta indicate that the modern estuarine system has had little effect on its adjacent inner shelf.     

Solar and stellar chromospheric contrast

Positions of active regions estimated from observations of the whole solar disk in Caii K _iv during the period 1977–1989 at the Coimbra Astronomical Observatory are compared with the time-dependent latitudinal distribution of background solar magnetic fields and with the latitudinal shifts of boundaries of their polarities. We confirm that the sunspot groups are located near the zonal boundaries between the opposite polarities of the solar background magnetic field during different phases of the two recent consecutive cycles of activity. We demonstrate a probable connection between the increased number of groups and the commencement of poleward migration of zonal boundaries in both hemispheres. But the influence of the dominant convective rolls seems to he still unclear. A new problem of interrelation between the zonal and sector boundaries has also appeared.     

The solar surface differential rotation from disk-integrated chromospheric fluxes

Disk-integrated solar chromospheric Caii K-line (3933.68 ) fluxes have been measured almost daily at Sacramento Peak Observatory since 1977. Using observing windows selected to mimic seasonal windows for chromospheric measurements of lower Main-Sequence stars such as those observed by Mount Wilson Observatory's HK Project, we have measured the solar rotation from the modulation of the Caii K-line flux. We track the change of rotation period from the decline of cycle 21 through the maximum of cycle 22. This variation in rotation period is shown to behave as expected from the migration of active regions in latitude according to Maunder's butterfly diagram, including an abrupt change in rotation period at the transition from cycle 21 to cycle 22. These results indicate the successful detection of solar surface differential rotation from disk-integrated observations. We argue that the success of our study compared to previous investigations of the solar surface differential rotation from disk-integrated fluxes lies primarily with the choice of the length of the time-series window. Our selection of 200 days is shorter than in previous studies whose windows are typically on the order of one year. The 200-day window is long enough to permit an accurate determination of the rotation period, yet short enough to avoid complications arising from active region evolution. Thus, measurements of the variation of rotation period in lower Main-Sequence stars, especially those that appear to be correlated with long-term changes in chromospheric activity (i.e., cycles), are probably evidence for stellar surface differential rotation.     

Ionospheric models of Saturn,Uranus, and Neptune

Model ionospheres are calculated for Saturn, Uranus, and Neptune. Protons are the major ions above 150 km altitude measured from a reference level where the hydrogen density is 1 × 10¹⁶ molecules cm^?3, while below 150 km quick conversion of protons to H₃⁺ ions by a three-body association mechanism leads to a rapid removal of ionization in dissociative recombination of H₃⁺. Electron density maxima are found at about 260 km for Saturn and Uranus and 200 km for Neptune. Present knowledge of the physical and chemical processes in the atmospheres of these planets suggests that their ionospheres probably will not be Jupiter-like.     

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.