Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.     

Nonhydrostatic effects and the determination of icy satellites’ moment of inertia

We compare the moment of inertia (MOI) of a simple hydrostatic, two layer body as determined by the Radau–Darwin Approximation (RDA) to its exact hydrostatic MOI calculated to first order in the parameter q = Ω²R³/GM, where Ω, R, and M are the spin angular velocity, radius, and mass of the body, and G is the gravitational constant. We show that the RDA is in error by less than 1% for many configurations of core sizes and layer densities congruent with those of solid bodies in the Solar System. We then determine the error in the MOI of icy satellites calculated with the RDA due to nonhydrostatic effects by using a simple model in which the core and outer shell have slight degree 2 distortions away from their expected hydrostatic shapes. Since the hydrostatic shape has an associated stress of order ρΩ²R² (where ρ is density) it follows that the importance of nonhydrostatic effects scales with the dimensionless number σ/ρΩ²R², where σ is the nonhydrostatic stress. This highlights the likely importance of this error for slowly rotating bodies (e.g., Titan and Callisto) and small bodies (e.g., Saturn moons other than Titan). We apply this model to Titan, Callisto, and Enceladus and find that the RDA-derived MOI can be 10% greater than the actual MOI for nonhydrostatic stresses as small as ∼0.1 bars at the surface or ∼1 bar at the core–mantle boundary, but the actual nonhydrostatic stresses for a given shape change depends on the specifics of the interior model. When we apply this model to Ganymede we find that the stresses necessary to produce the same MOI errors as on Titan, Callisto, and Enceladus are an order of magnitude greater due to its faster rotation, so Ganymede may be the only instance where RDA is reliable. We argue that if satellites can reorient to the lowest energy state then RDA will always give an overestimate of the true MOI. Observations have shown that small nonhydrostatic gravity anomalies exist on Ganymede and Titan, at least at degree 3 and presumably higher. If these anomalies are indicative of the nonhydrostatic anomalies at degree 2 then these imply only a small correction to the MOI, even for Titan, but it is possible that the physical origin of nonhydrostatic degree 2 effects is different from the higher order terms. We conclude that nonhydrostatic effects could be present to an extent that allows Callisto and Titan to be fully differentiated.     

Developing coastal adaptation to climate change in the New York City infrastructure-shed: process, approach, tools, and strategies

While current rates of sea level rise and associated coastal flooding in the New York City region appear to be manageable by stakeholders responsible for communications, energy, transportation, and water infrastructure, projections for sea level rise and associated flooding in the future, especially those associated with rapid icemelt of the Greenland and West Antarctic Icesheets, may be outside the range of current capacity because extreme events might cause flooding beyond today??s planning and preparedness regimes. This paper describes the comprehensive process, approach, and tools for adaptation developed by the New York City Panel on Climate Change (NPCC) in conjunction with the region??s stakeholders who manage its critical infrastructure, much of which lies near the coast. It presents the adaptation framework and the sea-level rise and storm projections related to coastal risks developed through the stakeholder process. Climate change adaptation planning in New York City is characterized by a multi-jurisdictional stakeholder?Cscientist process, state-of-the-art scientific projections and mapping, and development of adaptation strategies based on a risk-management approach.     

Modelling the effect of changing precipitation inputs on deep soil water utilization

Forests in the Southeastern United States are predicted to experience future changes in seasonal patterns of precipitation inputs as well as more variable precipitation events. These climate change‐induced alterations could increase drought and lower soil water availability. Drought could alter rooting patterns and increase the importance of deep roots that access subsurface water resources. To address plant response to drought in both deep rooting and soil water utilization as well as soil drainage, we utilize a throughfall reduction experiment in a loblolly pine plantation of the Southeastern United States to calibrate and validate a hydrological model. The model was accurately calibrated against field measured soil moisture data under ambient rainfall and validated using 30% throughfall reduction data. Using this model, we then tested these scenarios: (a) evenly reduced precipitation; (b) less precipitation in summer, more in winter; (c) same total amount of precipitation with less frequent but heavier storms; and (d) shallower rooting depth under the above 3 scenarios. When less precipitation was received, drainage decreased proportionally much faster than evapotranspiration implying plants will acquire water first to the detriment of drainage. When precipitation was reduced by more than 30%, plants relied on stored soil water to satisfy evapotranspiration suggesting 30% may be a threshold that if sustained over the long term would deplete plant available soil water. Under the third scenario, evapotranspiration and drainage decreased, whereas surface run‐off increased. Changes in root biomass measured before and 4 years after the throughfall reduction experiment were not detected among treatments. Model simulations, however, indicated gains in evapotranspiration with deeper roots under evenly reduced precipitation and seasonal precipitation redistribution scenarios but not when precipitation frequency was adjusted. Deep soil and deep rooting can provide an important buffer capacity when precipitation alone cannot satisfy the evapotranspirational demand of forests. How this buffering capacity will persist in the face of changing precipitation inputs, however, will depend less on seasonal redistribution than on the magnitude of reductions and changes in rainfall frequency.     

Changes in the content and composition of pedogenic iron oxyhydroxides in a chronosequence of soils in southern California

Studies of the pedogenic iron oxyhydroxides in suites of latest Holocene to middle Pleistocene soils formed on fluvial deposits of the transverse ranges, southern California, indicate that the content and composition of iron oxyhydroxide change in a systematic manner. Analysis of total secondary free iron oxides (dithionite extractable, Fe₂O₃d) and ferrihydrite (oxalate extractable, Fe₂O₃o) shows that (1) a single-logarithmic model (Y = a + b log X) or double logarithmic model (log Y = a + b log X), where Y is the total mass of pedogenic Fe oxides (g/cm²-soil column) and X is soil age, describes the rate of increase in Fe₂O₃d with time; (2) the Fe₂O₃d content correlates linearly with soil reddening and clay content; (3) the $\text{Fe}{}_2\text{O}{}_3\text{o}\text{Fe}{}_2\text{O}{}_3\text{d}$ ratio, which indicates the degree of Fe oxide crystallinity, is moderately high to very high (0.22–0.58) in middle Holocene to latest Pleistocene soils and progressively decreases to less than 0.10 in older soils; (4) the value of the $\text{Fe}{}_2\text{O}{}_3\text{o}\text{Fe}{}_2\text{O}{}_3\text{d}$ ratio also appears to be infuenced by climate; and (5) temporal changes in Fe oxide content and mineralogy are accompanied by related, systematic changes in clay mineralogy and organic matter content. These relationships are attributed to a soil environment that must initially favor ferrihydrite precipitation and/or organic matter-Fe complexation. Subsequent transformation to hematite causes increasingly intense reddening and a concomitant decrease in the $\text{Fe}{}_2\text{O}{}_3\text{o}\text{Fe}{}_2\text{O}{}_3\text{d}$ ratio. The results demonstrate that iron oxide analysis is useful for numerical age studies of noncalcic soils and shows potential as an indicator of paleoclimates.     

Low‐temperature concentration of tellurium and gold in continental red bed successions

There is very little understanding of tellurium (Te) distribution and behaviour in sedimentary rocks. A suite of 15 samples of reduction spheroids (centimetre‐scale pale spheroids in otherwise red rock), including samples from eight localities in Triassic red beds across the British Isles, were mapped for Te using Laser Ablation–Inductively Coupled Plasma–Mass Spectrometry. Almost all showed enrichment in Te in the cores of the spheroids relative to background red bed concentrations, by up to four orders of magnitude. Some were also enriched over background in gold and/or mercury. In one case, discrete telluride minerals were recorded. The data show that Te is mobile and can be concentrated in low‐temperature sedimentary environments, controlled by redox variations. The consistency in enrichment across widely separate localities implies that the enrichment is a normal aspect of red bed diagenesis and so likely to be controlled by a ubiquitous process, such as microbial activity.     

Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

Using unmanned underwater vehicles as research platforms in coastal ocean studies

The advantages of using unmanned underwater vehicles in coastal ocean studies are emphasized. Two types of representative vehicles, remotely operated vehicle (ROV) and autonomous underwater vehicle (AUV) from University of South Florida, are discussed. Two individual modular sensor packages designed and tested for these platforms and field measurement results are also presented. The bottom classification and albedo package, BCAP, provides fast and accurate estimates of bottom albedos, along with other parameters such as in-water remote sensing reflectance. The real-time ocean bottom optical topographer, ROBOT, reveals high-resolution 3-dimentional bottom topography for target identification. Field data and results from recent Coastal Benthic Optical Properties field campaign, 1999 and 2000, are presented. Advantages and limitations of these vehicles and applications of modular sensor packages are compared and discussed.     

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.     

Sedimentary and faunal events revealed by a revised correlation of post‐glacial Hirnantian (Late Ordovician) strata in the Welsh Basin,UK

The discovery of a previously unrecognized unconformity and of new faunas in the type Llandovery area underpins a revised correlation of Hirnantian strata in mid Wales. This has revealed the sedimentary and faunal events which affected the Lower Palaeozoic Welsh Basin during the global rise in sea level that followed the end‐Ordovician glacial maximum and has allowed their interpretation in the context of local and global influences. In peri‐basinal shelfal settings the onset of post‐glacial deepening is recorded by an unfossiliferous, transgressive shoreface sequence (Cwm Clyd Sandstone and Garth House formations) which rests unconformably on Rawtheyan rocks, deformed during an episode of pre‐Hirnantian tectonism. In the deep water facies of the basin centre, this same sequence boundary is now recognized as the contact between fine‐grained, re‐sedimented mudstones and an underlying regressive sequence of turbidite sandstones and conglomerates; it is at a level lower than previously cited and calls into question the established lithostratigraphy. In younger Hirnantian strata, graptolites associated with the newly recognized Ystradwalter Member (Chwefri Formation) demonstrate that this distal shelf unit correlates with the persculptus graptolite‐bearing Mottled Mudstone Member of the basinal succession. Together these members record an important macrofaunal recolonization of the Welsh Basin and mark a key event in the post‐glacial transgression. Further deepening saw the establishment of a stratified water column and the imposition of anoxic bottom water conditions across the basin floor. These post‐glacial Hirnantian events are consistent with the re‐establishment of connections between a silled Welsh Basin and the open Iapetus Ocean. However, a comparison with other areas suggests that each event records a separate deepening episode within a pulsed glacio‐eustatic transgression, while also reflecting changes in post‐glacial climate and patterns of oceanic circulation and associated biotic flux. British Geological Survey © NERC 2009. All rights reserved.