Origin of organic matter in the early solar system—VII. The organic polymer in carbonaceous chondrites

The insoluble polymer from the Murchison C2 chondrite was studied by a variety of degradation techniques: pyrolysis, depolymerization by Na₄P₂O₇ or CF₃COOH, and oxidation by HNO₃, Na₂Cr₂O₇, or O₂/UV light. Products were identified by IR spectroscopy, gas chromatography, and mass spectrometry (time-of-flight and high-resolution). In some cases, parallel measurements were made on a synthetic polymer produced by the Fischer-Tropsch reaction, a meteoritic polymer from the Allende C3V chondrite, and samples of coal or related materials.Our studies confirm the prevailing view that the meteoritic polymer has a bridged aromatic structure with functional groups such as COOH, OH, and CO, but provides much new detail. Oxidation with HNO₃ shows that the meteoritic and synthetic polymers have a similar degree of condensation, greater than that of high-volatile bituminous coal. Gentler oxidation with Cr₂O^2?₇ or O₂/UV led to the identification of 15 aromatic ring systems as the corresponding carboxylic acids: benzene, biphenyl, naphthalene and phenanthrene and their methyl derivatives, fluoranthene (or pyrene), chrysene, fluorenone, benzophenone, anthraquinone; and the heterocyclics dibenzofuran, benzothiophene, dibenzothiophene, pyridine, quinoline (or isoquinoline), and carbazole. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably are derived from bridging groups or ring substituents.Depolymerization with CF₃COOH yielded some of the same ring systems, as well as alkanes (C₁–C₈) and alkenes (C₂–C₈), alkyl (C₁–C₅) benzenes and naphthalenes, and methyl- or dimethyl-indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200°C, and hence probably were indigenous constituents rather than pyrolysis products.Though the match between the synthetic and meteoritic polymer is only fair, several properties of the latter suggest that it, too, was produced by surface catalysis: the predominance of n-alkyl fragments, its occurrence as a surface coating on specific kinds of mineral grains, and the $\text{C}{}^{13}\text{C}{}^{12}$ fractionation between polymer and coexisting carbonates.     

Karrat Fjord (Greenland) tsunamigenic landslide of 17 June 2017: initial 3D observations

On 17 June 2017, a landslide-generated tsunami reached the village of Nuugaatsiaq, Greenland, leaving four persons missing and presumed dead. Here, we present a preliminary high-resolution analysis of the tsunamigenic landslide scar based on three-dimensional (3D) reconstructions of oblique aerial photographs taken during a post-failure reconnaissance helicopter overflight. Through a 3D quantitative comparison with pre-failure topography, we estimate that approximately 58 million m³ of rock and colluvium (talus) was mobilized during the landslide, 45 million m³ of which reached the fjord, resulting in a destructive tsunami. We classify this event as a “tsunamigenic extremely rapid rock avalanche,” which likely released along a pre-existing metamorphic fabric, bounded laterally by slope-scale faults. Further analysis is required to properly characterize this landslide and adjacent unstable slopes, and to better understand the tsunami generation.     

Postsettlement patterns of habitat use by sciaenid fishes in subtropical seagrass meadows

Spatial and temporal patterns of distribution and abundance were examined for postsettlement sciaenids collected from seagrass meadows in the Aransas Estuary, Texas. Overall, 5443 sciaenid larvae and early juveniles were identified from biweekly epibenthic sled collections taken from August 1994 to August 1995. Eight species were present in seagrass meadows, with five accounting for over 99.9% of sciaenids collected: silver perch (Bairdiella chrysoura), spotted seatrout (Cynoscion nebulosus), spot (Leiostomus xanthurus), Atlantic croaker (Micropogonias undulatus), and red drum (Sciaenops ocellatus). Settlement to seagrass meadows was partitioned temporally with little overlap among the five species. Postsettlers from inshore spawners (B. chrysoura, C. nebulosus, S. ocellatus) inhabited seagrass meadows during the spring and summer, while individuals from offshore spawners (L. xanthurus, M. undulatus) were present in the late fall and winter. Densities ofB. chrysoura, C. nebulosus, S. ocellatus were highest for small individuals (4–8 mm SL) and these taxa remained in seagrass sites through the early juvenile stage. Conversely,L. xanthurus andM. undulatus maintained longer pelagic periods and generally entered seagrass meadows at larger sizes (10–14 mm SL). Moreover, these taxa were only temporary residents of selected seagrass meadows, apparently migrating to alternative habitats shortly after arrival. During peak settlement, mean and maximum densities among species ranged from 0.1 m^?2 to 0.8 m^?2 and 0.7 m^?2 to 23.8 m^?2, respectively. Density and mean size of possettlement sciaenids differed significantly between seagrass species (Halodule wrightii, Thalassia testudinum) and among sites within the estuary.     

Predicting selenite adsorption by soils using soil chemical parameters in the constant capacitance model

The constant capacitance model, a chemical surface complexation model, was applied to selenite, Se(IV), adsorption on 36 soils selected for variation in soil chemical properties. The constant capacitance model was able to fit Se(IV) adsorption by optimizing one monodentate Se(IV) surface complexation constant and the surface protonation constant. A general regression model was developed for predicting these surface complexation constants for Se(IV) from easily measured soil chemical characteristics. These chemical properties were inorganic carbon content, organic carbon content, iron oxide content, aluminum oxide content, and surface area. The prediction equations were used to obtain values for the surface complexation constants for four additional soils, thereby providing a completely independent evaluation of the ability of the constant capacitance model to describe Se(IV) adsorption. The model’s ability to predict Se(IV) adsorption was quantitative on one soil and semi-quantitative on three soils. Incorporation of these prediction equations into chemical speciation-transport models will allow simulation of soil solution Se(IV) concentrations under diverse non-calcareous agricultural and environmental conditions without the requirement of soil specific adsorption data and subsequent parameter optimization.     

Stability and equation of state of post-aragonite BaCO3

At ambient conditions, witherite is the stable form of BaCO₃ and has the aragonite structure with space group Pmcn. Above ~10 GPa, BaCO₃ adopts a post-aragonite structure with space group Pmmn. High-pressure and high-temperature synchrotron X-ray diffraction experiments were used to study the stability and equation of state of post-aragonite BaCO₃, which remained stable to the highest experimental P–T conditions of 150 GPa and 2,000 K. We obtained a bulk modulus K ₀ = 88(2) GPa with $K'$  = 4.8(3) and V ₀ = 128.1(5) ų using a third-order Birch-Murnaghan fit to the 300 K experimental data. We also carried out density functional theory (DFT) calculations of enthalpy (H) of two structures of BaCO₃ relative to the enthalpy of the post-aragonite phase. In agreement with previous studies and the current experiments, the calculations show aragonite to post-aragonite phase transitions at ~8 GPa. We also tested a potential high-pressure post–post-aragonite structure (space group C222 ₁ ) featuring four-fold coordination of oxygen around carbon. In agreement with previous DFT studies, ΔH between the C222 ₁ structure and post-aragonite (Pmmn) decreases with pressure, but the Pmmn structure remains energetically favorable to pressures greater than 200 GPa. We conclude that post–post-aragonite phase transformations of carbonates do not follow systematic trends observed for post-aragonite transitions governed solely by the ionic radii of their metal cations.     

A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25°C

The Raman spectra of thioarsenite and arsenite species in aqueous solution were obtained at room temperature. Solutions at constant ΣAs + ΣS of 0.1 and 0.5 mol kg^-1 were prepared with various ΣS/ΣAs ratios (0.1–9.0) and pH values (~7–13.2). Our data suggest that the speciation of As under the conditions investigated is more complicated than previously thought. The Raman measurements offer evidence for at least six separate S-bearing As species whose principal bands are centered near 365, 385, 390, 400, 415 and 420 cm^-1. The data suggest that at least two different species may give rise to bands at 385 cm^-1, bringing the probable minimum number of species to seven. Several additional species are possible but could not be resolved definitively. In general, the relative proportions of these species are dependent on total As concentration, ΣS/ΣAs ratio and pH. At very low ΣS/ΣAs ratios we also observe Raman bands attributable to the dissociation products of H₃AsO₃(aq). Although we were unable to assign precise stoichiometries for the various thioarsenite species, we were able to map out general pH and ΣS/ΣAs conditions under which the various thioarsenite and arsenite species are predominant. This study provides a basis for more detailed Raman spectroscopic and other types of investigations of the nature of thioarsenite species.     

Geotechnical analysis of paleoseismic shaking using liquefaction features: a major updating

A new methodology is proposed for the geotechnical analysis of strength of paleoseismic shaking using liquefaction effects. The proposed method provides recommendations for selection of both individual and regionally located test sites, provides techniques for validation of field data for use in back-analysis, and presents a recently developed energy-based solution to back-calculate paleoearthquake magnitude and strength of shaking. The proposed method allows investigators to qualitatively assess the influence of post-earthquake density change and aging. The proposed method also describes how the back-calculations from individual sites should be integrated into a regional assessment of paleoseismic parameters.     

Isotopic evidence for widespread cold‐season‐biased groundwater recharge and young streamflow across central Canada

Transformations of precipitation into groundwater and streamflow are fundamental hydrological processes, critical to irrigated agriculture, hydroelectric power generation, and ecosystem health. Our understanding of the timing of groundwater recharge and streamflow generation remains incomplete, limiting our ability to predict fresh water, nutrient, and contaminant fluxes, especially in large basins. Here, we analyze thousands of rain, snow, groundwater, and streamflow δ¹⁸O and δ²H values in the Nelson River basin, which covers 1.2 million km² of central Canada. We show that the fraction of precipitation that recharges aquifers is ~1.3–5 times higher for precipitation falling during cold months with subzero mean monthly temperatures than for precipitation falling during warmer months. The near‐ubiquity of cold‐season‐biased groundwater recharge implies that changes to winter water balances may have disproportionate impacts on annual groundwater recharge rates. We also show that young streamflow—defined as precipitation that enters a river in less than ~2.3 months—comprises ~27% of annual streamflow but varies widely among tributaries in the Nelson River basin (1–59%). Young streamflow fractions are lower in steep catchments and higher in flatter catchments such as the transboundary Red River basin. Our findings imply that flat, lower permeability, heavily tiled landscapes favor more rapid transmission of precipitation into rivers, possibly mobilizing excess soluble fertilizers and exacerbating eutrophication events in Lake Winnipeg.     

Paleosols and the forest border in Keewatin,N.W.T.

The morphology of paleosols and radiocarbon-dated charcoal from buried surface horizons of soils provide evidence to suggest that between periods of northward forest encroachment tundra climate has dominated areas at least 50 km south of the present forest/tundra border in southwest Keewatin. The present forest/tundra border climate is nearly as severe as any climate that has prevailed in the area since deglaciation.     

Chemical fractionation in iron meteorites and its interpretation

Published analyses of trace and minor elements in iron meteorites have been compiled and the distributions interpreted with the chemical groups defined by Wasson. When each element is plotted against Ni on log scales, groups are often clearly resolved with all the members of a group falling within the limits of sampling and analytical error on a straight line. The lines for groups IIIa,b and IVa are generally parallel with IIa,b plotting on a steeper gradient. In contrast to Ga and Qe, many elements show variations within a group which may approach that shown by all the iron meteorites. Group I members have a fairly uniform concentration of elements which are severely fractionated in the other major groups. There are also fewer correlations of elements in group I.