Investigation of acidic dissolution of mixed clays between pH 1.0 and −3.0 using Si and Al X-ray absorption near edge structure

Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H₂SO₄) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H₂SO₄ from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L_2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO₄-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.     

A possible glacially-forced tectonic mechanism for late Neogene surface uplift and subsidence around the North Atlantic

Analysis of old erosion surfaces and estimates of exhumation from apatite fission track data can be used to infer late Neogene surface uplift of Britain, Greenland, Norway and Svalbard of 1–2 km. Subsidence and sedimentation in adjacent offshore basins can be found from interpretation of seismic and well log data. Various mechanisms for surface uplift have been proposed but the underlying cause remains unexplained. Since the multiple glaciations that took place during the late Neogene were a common factor, a possible glacially-forced tectonic mechanism to thicken the crust and produce surface uplift has been investigated. This could result from the relatively slow accumulation of ice that loads the crust as an ice sheet grows during a glacial period, followed by relatively rapid retreat and unloading around its periphery at the end. Unloading could create transient stresses that induce lateral flow in a ductile lower crust to thicken it onshore and produce surface uplift, with associated thinning beneath adjacent offshore basins, producing subsidence. Simple calculations show that the proposed mechanism is feasible and indicate that crustal thickening and surface uplift accumulated from a number of glacial cycles can account for the observed surface uplift, with an acceptable flow rate in the lower crust at the end of each cycle if the viscosity of ductile flow is sufficiently low.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.     

N-body simulations of cohesion in dense planetary rings: A study of cohesion parameters

We present results from a large suite of simulations of Saturn’s dense A and B rings using a new model of particle sticking in local simulations (Perrine, R.P., Richardson, D.C., Scheeres, D.J. [2011]. Icarus 212, 719–735). In this model, colliding particles can be incorporated into or help fragment rigid aggregations on the basis of certain user-specified parameters that can represent van der Waals forces or interlocking surface frost layers.Our investigation is motivated by laboratory results that show that interpenetration of surface layers can allow impacting frost-covered ice spheres to stick together. In these experiments, cohesion only occurs below specific impact speeds, which happen to be characteristic of impact speeds in Saturn’s rings. Our goal is to determine if weak bonding is consistent with ring observations, to constrain cohesion parameters in light of existing ring observations, to make predictions about particle populations throughout the rings, and to discover other diagnostics that may constrain bonding parameters.We considered the effects of five parameters on the equilibrium characteristics of our ring simulations: speed-based merge and fragmentation limits, bond strength, ring surface density, and patch orbital distance (i.e., the A or B ring), some with both monodisperse and polydisperse comparison cases. In total, we present data from 95 simulations.We find that weak cohesion is consistent with observations of the A and B rings (e.g., French, R.G., Nicholson, P.D. [2000]. Icarus 145, 502–523), and we present a range of simulation parameters that reproduce the observed size distribution and maximum particle size. It turns out that the parameters that match observations differ between the A and B rings, and we discuss the potential implications of this result. We also comment on other observable consequences of cohesion for the rings, such as optical depth and scale height effects, and discuss whether very large objects (e.g., “propeller” source objects) are grown bottom-up from cohesion of smaller ring particles.     

Numerical simulations of granular dynamics II: Particle dynamics in a shaken granular material

Surfaces of planets and small bodies of our Solar System are often covered by a layer of granular material that can range from a fine regolith to a gravel-like structure of varying depths. Therefore, the dynamics of granular materials are involved in many events occurring during planetary and small-body evolution thus contributing to their geological properties.We demonstrate that the new adaptation of the parallel N-body hard-sphere code pkdgrav has the capability to model accurately the key features of the collective motion of bidisperse granular materials in a dense regime as a result of shaking. As a stringent test of the numerical code we investigate the complex collective ordering and motion of granular material by direct comparison with laboratory experiments. We demonstrate that, as experimentally observed, the scale of the collective motion increases with increasing small-particle additive concentration.We then extend our investigations to assess how self-gravity and external gravity affect collective motion. In our reduced-gravity simulations both the gravitational conditions and the frequency of the vibrations roughly match the conditions on asteroids subjected to seismic shaking, though real regolith is likely to be much more heterogeneous and less ordered than in our idealised simulations. We also show that collective motion can occur in a granular material under a wide range of inter-particle gravity conditions and in the absence of an external gravitational field. These investigations demonstrate the great interest of being able to simulate conditions that are to relevant planetary science yet unreachable by Earth-based laboratory experiments.     

Macroseepage of methane and light alkanes at the La Brea tar pits in Los Angeles

Geologic seepage of methane and light (C₂-C₅) alkanes was measured at the La Brea Tar Pits in Los Angeles. Samples were collected using flux chambers with stainless steel canisters and analyzed using gas chromatography. Average seepage rates from individual seepage sites were 970 ± 330 mg/h of methane, 14.0 ± 5.5 mg/h of ethane, 9.1 ± 3.7 mg/h of propane, 3.7 ± 1.6 mg/h of i-butane, 0.33 ± 0.16 mg/h of n-butane, 260 ± 120 μg/h of i-pentane, and 5.3 ± 1.9 μg/h of n-pentane, while maximum seepage rates exceeded 17 g/h of methane, 270 mg/h of ethane, 190 mg/h of propane, 95 mg/h of i-butane, 10 mg/h of n-butane, 7 mg/h of i-pentane, and 0.1 mg/h of n-pentane. These absolute fluxes have an additional unknown amount of error associated with them due to sampling methodology, and should be taken as the lower limit of emissions. Samples collected revealed generally dry gas, with high methane emissions relative to the light alkanes. Overall emissions from the tar pits were found to come not only from the active geologic seepage, but also from the outgassing of the standing asphalt at the site. Using the gas ratios, which are negligibly affected by errors introduced by sampling methodology, observed in this study, daily emissions of C₂ – C₅ alkanes from the La Brea area were estimated to be 4.7 ± 1.6 Mg, which represents 2–3 % of total emissions in the entire Los Angeles region.     

Permeable Asphalt: A New Tool to Reduce Road Salt Contamination of Groundwater in Urban Areas

Chloride contamination of groundwater in urban areas due to deicing is a well‐documented phenomenon in northern climates. The objective of this study was to evaluate the effects of permeable pavement on degraded urban groundwater. Although low impact development practices have been shown to improve stormwater quality, no infiltration practice has been found to prevent road salt chlorides from entering groundwater. The few studies that have investigated chlorides in permeable asphalt have involved sampling directly beneath the asphalt; no research has looked more broadly at surrounding groundwater conditions. Monitoring wells were installed upgradient and downgradient of an 860 m² permeable asphalt parking lot at the University of Connecticut (Storrs, Connecticut). Water level and specific conductance were measured continuously, and biweekly samples were analyzed for chloride. Samples were also analyzed for sodium (Na), calcium (Ca), and magnesium (Mg). Analysis of variance analysis indicated a significantly (p < 0.001) lower geometric mean Cl concentration downgradient (303.7 mg/L) as compared to upgradient (1280 mg/L). Concentrations of all alkali metals increased upgradient and downgradient during the winter months as compared to nonwinter months, indicating that cation exchange likely occurred. Despite the frequent high peaks of chloride in the winter months as well as the increases in alkali metals observed, monitoring revealed lower Cl concentrations downgradient than upgradient for the majority of the year. These results suggest that the use of permeable asphalt in impacted urban environments with high ambient chloride concentrations can be beneficial to shallow groundwater quality, although these results may not be generalizable to areas with low ambient chloride concentrations.