The origin of refractory minerals in comet 81P/Wild 2

Refractory Ti-bearing minerals in the calcium-, aluminum-rich inclusion (CAI) Inti, recovered from the comet 81P/Wild 2 sample, were examined using analytical (scanning) transmission electron microscopy (STEM) methods including imaging, nanodiffraction, energy-dispersive spectroscopy (EDX) and electron energy loss spectroscopy (EELS). Inti fassaite (Ca(Mg,Ti,Al)(Si,Al)₂O₆) was found to have a Ti³⁺/Ti⁴⁺ ratio of 2.0 ± 0.2, consistent with fassaite in other solar system CAIs. The oxygen fugacity (logf_O2) of formation estimated from this ratio, assuming equilibration among phases at 1509 K, is −19.4 ± 1.3. This value is near the canonical solar nebula value (−18.1 ± 0.3) and in close agreement with that reported for fassaite-bearing Allende CAIs (−19.8 ± 0.9) by other researchers using the same assumptions. Nanocrystals of osbornite (Ti(V)N), 2–40 nm in diameter, are embedded as inclusions within gehlenite, spinel and diopside in Inti. Vanadium is heterogeneously distributed within some osbornite crystals. Compositions range from pure TiN to Ti_0.36V_0.64N. The possible presence of oxide and carbide in solid solution with the osbornite was evaluated. The osbornite may contain O, but C is not present at detectable levels. The presence of osbornite, likely a refractory early condensate, together with the other refractory minerals in Inti, indicates that the parent comet contains solids that condensed closer to the proto-sun than the distance at which the parent comet itself accreted. The estimated oxygen fugacity and the reported isotopic and chemical compositions are consistent with Inti originating in the inner solar system like other meteoritic CAIs. These results provide insight for evaluating the validity of models of radial mass transport dynamics in the early solar system. The oxidation environments inferred for the Inti mineral assemblage are inconsistent with an X-wind formation scenario. In contrast, radial mixing models that allow accretion of components from different heliocentric distances can satisfy the observations from the cometary CAI Inti.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Epistemological possibilities and imperatives of complexity research: a reply to Reitsma

Reitsma (A response to ‘simplifying complexity’. Geoforum 34 (1) (2003) 13), in response to the article ‘Simplifying Complexity’ (Manson, S.M., Simplifying complexity: a review of complexity theory. Geoforum 32 (3) (2001) 405), highlights a number of interesting and important aspects of complexity theory that invite further discussion. In particular, there are three areas of complexity research that are open to deeper exploration: (1) the width and breadth of ‘complexity’ defined as a scientific endeavor; (2) the role of theory relative to practice and their relationship with pattern and process in complex systems; and (3) the need for greater discussion and exploration in order to define the conceptual bounds of complexity theory.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

The distribution of radiogenic heat production as a function of depth in the Sierra Nevada Batholith, California

Geochemical analyses and geobarometric determinations have been combined to create a depth vs. radiogenic heat production database for the Sierra Nevada batholith, California. This database shows that mean heat production values first increase, then decrease, with increasing depth. Heat production is 2 μW/m³ within the 3-km-thick volcanic pile at the top of the batholith, below which it increases to an average value of 3.5 μW/m³ at 5.5 km depth, then decreases to 0.5–1 μW/m³ at 15 km depth and remains at these values through the entire crust below 15 km. Below the crust, from depths of 40–125 km, the batholith's root and mantle wedge that coevolved beneath the batholith appears to have an average radiogenic heat production rate of 0.14 μW/m³. This is higher than the rates from most published xenolith studies, but reasonable given the presence of crustal components in the arc root assemblages. The pattern of radiogenic heat production interpreted from the depth vs. heat production database is not consistent with the downward-decreasing exponential distribution predicted from modeling of surface heat flow data. The interpreted distribution predicts a reasonable range of geothermal gradients and shows that essentially all of the present day surface heat flow from the Sierra Nevada could be generated within the 35 km thick crust. This requires a very low heat flux from the mantle, which is consistent with a model of cessation of Sierran magmatism during Laramide flat-slab subduction, followed by conductive cooling of the upper mantle for 70 m.y. The heat production variation with depth is principally due to large variations in uranium and thorium concentration; potassium is less variable in concentration within the Sierran crust, and produces relatively little of the heat in high heat production rocks. Because silica content is relatively constant through the upper 30 km of the Sierran batholith, while U, Th, and K concentrations are highly variable, radiogenic heat production does not vary directly with silica content.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

<Emphasis Type="Italic">Deepwater Horizon</Emphasis> Oil Spill Impacts on Salt Marsh Fiddler Crabs (<Emphasis Type="Italic">Uca</Emphasis> spp.)

The Deepwater Horizon oil spill was the largest marine oil spill in US waters to date and one of the largest worldwide. Impacts of this spill on salt marsh vegetation have been well documented, although impacts on marsh macroinvertebrates have received less attention. To examine impacts of the oil spill on an important marsh invertebrate and ecosystem engineer, we conducted a meta-analysis on fiddler crabs (Uca spp.) using published sources and newly available Natural Resources Damage Assessment (NRDA) and Gulf of Mexico Research Initiative (GoMRI) data. Fiddler crabs influence marsh ecosystem structure and function through their burrowing and feeding activities and are key prey for a number of marsh and estuarine predators. We tested the hypothesis that the spill affected fiddler crab burrow density (crab abundance), burrow diameter (crab size), and crab species composition. Averaged across multiple studies, sites, and years, our synthesis revealed a negative effect of oiling on all three metrics. Burrow densities were reduced by 39 % in oiled sites, with impacts and incomplete recovery observed over 2010–2014. Burrow diameters were reduced from 2010 to 2011, but appeared to have recovered by 2012. Fiddler crab species composition was altered through at least 2013 and only returned to reference conditions where marsh vegetation recovered, via restoration planting in one case. Given the spatial and temporal extent of data analyzed, this synthesis provides compelling evidence that the Deepwater Horizon spill suppressed populations of fiddler crabs in oiled marshes, likely affecting other ecosystem attributes, including marsh productivity, marsh soil characteristics, and associated predators.     

A numerical simulation of residual circulation in Tampa Bay. Part I: Low-frequency temporal variations

The residual (time-average) salinity and circulation in a numerical ocean model of the Tampa Bay estuary are shown to experience significant temporal variation under realistic forcing conditions. A version of the Estuarine Coastal Ocean Model developed for Tampa Bay with 70 by 100 horizontal grid points and 11 sigma levels is examined for the years 2001–2003. Model output variables are averaged over the entire time of the simulation to generate long-term residual fields. The residual axial current is found to be dominated by the buoyancy-driven baroclinic circulation with an outflow (southwestward) at the surface and to the sides of the shipping channel, and an inflow (northeastward) usually occurring subsurface within or above the shipping channel. Averages over 30 d are used to examine variations in the residual fields. During the simulation the average surface salinity near the head of Tampa Bay varies with the freshwater inflow, from 12‰ to 33%. At the bay mouth salinity varies from 30%. to 36%.. A localized measure of the baroclinic circulation in the shipping channel indicates the residual circulation can vary strongly, attaining a magnitude triple the long-term mean value. The baroclinic circulation can be disrupted, going to near zero or even reversing, when the buoyancy-driven flow is weak and the surface winds are to the northeast. Three time periods, representing different environmental conditions, are chosen to examine these results in detail. A scaling argument indicates the relative strength of buoyancy versus wind as ΔρgH²(LC _Dω²)⁻¹, where δρ is head-to-mouth density difference across the bay,g is gravitational acceleration,H is depth,L is bay length,C _D is the surface wind drag coefficient, andw is wind speed. Tampa Bay is usually in the buoyancy dominated regime. The importance of winds in the weak-buoyancy case is demonstrated in an additional simulation without wind stress.     

Boundary-layer parameterizations for applied dispersion modeling over urban areas

Many applied dispersion models require the knowledge of boundary-layer parameters such as sensible heat flux,Q _H , friction velocity,u _*, and turbulent energy components, _w and _v . Formulas are suggested for calculating these parameters over a wide variety of types of ground surfaces, based on simple observations of wind speed near the ground and fractional cloud cover, and specification of constants such as roughness length, albedo, and soil moisture availability. Observations ofu _*,Q _H , _w , and _v during field experiments in St. Louis and Indianapolis are used to test the formulas for urban sites. Relative errors of about ±20% in the predictions are seen to occur whenu _*,Q _H , _w , and _v are large. However, when these quantities are small (e.g.,u _* < 0.2 m/s), the errors in the predictions are as large as the mean value of the quantity itself.In addition, it is concluded from studies of available field data and theories that the magnitude of _w is not well-known at elevations above about 100m during the late afternoon and night. Some simple parameterizations for _w . are suggested that are consistent with the observed steady decrease in ground-level concentration in the afternoon and the sudden increase in concentration that can occur a few hours after sunset due to wind shears associated with a low-level jet, for continuous plumes emitted from moderate to tall stacks.