Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Comparison of the LEW88516 and ALHA77005 martian meteorites: Similar but distinct

Abstract By mineral and bulk compositions, the Lewis Cliff (LEW) 88516 meteorite is quite similar to the ALHA77005 martian meteorite. These two meteorites are not paired because their mineral compositions are distinct, they were found 500 km apart in ice fields with different sources for meteorites, and their terrestrial residence ages are different. Minerals in LEW88516 include: olivine, pyroxenes (low- and high-Ca), and maskelynite (after plagioclase); and the minor minerals chromite, whitlockite, ilmenite, and pyrrhotite. Mineral grains in LEW88516 range up to a few mm. Texturally, the meteorite is complex, with regions of olivine and chromite poikilitically enclosed in pyroxene, regions of interstitial basaltic texture, and glass-rich (shock) veinlets. Olivine compositions range from Fo₆₄ to Fo₇₀, (avg. Fo₆₇), more ferroan and with more variation than in ALHA77005 (Fo₆₉ to Fo₇₃). Pyroxene compositions fall between En₇₇Wo₄ and En₆₅Wo₁₅ and in clusters near En₆₃Wo₉ and En₅₃Wo₃₃, on average more magnesian and with more variation than in ALHA77005. Shock features in LEW88516 range from weak deformation through complete melting. Bulk chemical analyses by modal recombination of electron microprobe analyses, instrumental neutron activation, and radiochemical neutron activation confirm that LEW88516 is more closely related to ALHA77005 than to other known martian meteorites. Key element abundance ratios are typical of martian meteorites, as is its non-chondritic rare earth pattern. Differences between the chemical compositions of LEW88516 and ALHA77005 are consistent with slight differences in the proportions of their constituent minerals and not from fundamental petrogenetic differences. Noble gas abundances in LEW88516, like those in ALHA77005, show modest excesses of ⁴⁰Ar and ¹²⁹Xe from trapped (shock-implanted) gas. As with other ALHA77005 and the shergottite martian meteorites (except EETA79001), noble gas isotope abundances in LEW88516 are consistent with exposure to cosmic rays for 2.5–3 Ma. The absence of substantial effects of shielding from cosmic rays suggest LEW88516 spent this time as an object no larger than a few cm in diameter.     

Water level variations in the Neuse and Pamlico Estuaries,North Carolina due to local and remote forcing

Water level time series records from the Neuse and Pamlico River Estuaries were statistically compared to local and distant wind field data, water level records within the Pamlico Sound and also coastal ocean sites to determine the relative contribution of each time series to water levels in the Neuse and Pamlico Estuaries. The objectives of this study were to examine these time series data using various statistical methods (i.e. autoregressive, empirical orthogonal function analysis (EOF), exploratory data analysis (EDA)) to determine short- and long-time-scale variability, and to develop predictive statistical models that can be used to estimate past water level fluctuations in both the Neuse Estuary (NE) and Pamlico Estuary (PE). Short- and long-time-scale similarities were observed in all time series of estuarine, Pamlico Sound and subtidal coastal ocean water level and wind component data, due to events (nor'easters, fronts and tropical systems) and seasonality. Empirical orthogonal function analyses revealed a strong coastal ocean and wind field contribution to water level in the NE and PE. Approximately 95% of the variation was captured in the first two EOF components for water level data from the NE, sound and coastal ocean, and 70% for the PE, sound and coastal ocean. Spectral density plots revealed strong diurnal signals in both wind and water level data, and a strong cross correlation and coherency between the NE water level and the North/South wind component. There was good agreement between data and predictions using autoregressive statistical models for the NE (R² = 0.92) and PE (R² = 0.76). These methods also revealed significant autoregressive lags for the NE (days 1 and 3) and for the PE (days 1, 2 and 3). Significant departures from predictions are attributed to local meteorological and hydrological events. The autoregressive techniques showed significant predictive improvement over ordinary least squares methods. The results are considered within the context of providing long time-scale hindcast data for the two estuaries, and the importance of these data for multidisciplinary researchers and managers.     

Relationship between the velocity ellipsoids of galactic-disk stars and their ages and metallicities

The dependences of the velocity ellipsoids of F-G stars of the thin disk of the Galaxy on their ages and metallicities are analyzed based on the new version of the Geneva-Copenhagen Catalog. The age dependences of the major, middle, and minor axes of the ellipsoids, and also of the dispersion of the total residual velocity, obey power laws with indices 0.25, 0.29, 0.32, and 0.27 (with uncertainties ±0.02). Due to the presence of thick-disk objects, the analogous indices for all nearby stars are about a factor of 1.5 larger. Attempts to explain such values are usually based on modeling relaxation processes in the Galactic disk. Elimination of stars in the most numerous moving groups from the sample slightly reduces the corresponding indices (0.22, 0.26, 0.27, and 0.24). Limiting the sample to stars within 60 pc of the Sun, so that the sample can be considered to be complete, leaves both the velocity ellipsoids and their age dependences virtually unchanged. With increasing age, the velocity ellipsoid increases in size and becomes appreciablymore spherical, turns toward the direction of the Galactic center, and loses angular momentum. The shape of the velocity ellipsoid remains far from equilibrium. With increasing metallicity, the velocity ellipsoid for stars of mixed age increases in size, displays a weak tendency to become more spherical, and turns toward the direction of the Galactic center (with these changes occurring substantially more rapidly in the transition through the metallicity [Fe/H]≈−0.25). Thus, the ellipsoid changes similarly to the way it does with age; however, with decreasing metallicity, the rotational velocity about the Galactic center monotonically increases, rather than decreases (!). Moreover, the power-law indices for the age dependences of the axes depend on the metallicity, and display a maximum near [Fe/H] ≈−0.1. The age dependences of all the velocity-ellipsoid parameters for stars with equal metallicity are roughly the same. It is proposed that the appearance of a metallicity dependence of the velocity ellipsoids for thin-disk stars, recorded from the close to the Sun, is most likely due to the radial migration of stars.     

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Martian water vapor: Mars Express PFS/LW observations

We present the seasonal and geographical variations of the martian water vapor monitored from the Planetary Fourier Spectrometer Long Wavelength Channel aboard the Mars Express spacecraft. Our dataset covers one martian year (end of Mars Year 26, Mars Year 27), but the seasonal coverage is far from complete. The seasonal and latitudinal behavior of the water vapor is globally consistent with previous datasets, Viking Orbiter Mars Atmospheric Water Detectors (MAWD) and Mars Global Surveyor Thermal Emission Spectrometer (MGS/TES), and with simultaneous results obtained from other Mars Express instruments, OMEGA and SPICAM. However, our absolute water columns are lower and higher by a factor of 1.5 than the values obtained by TES and SPICAM, respectively. In particular, we retrieve a Northern midsummer maximum of 60 pr-μm, lower than the 100-pr-μm observed by TES. The geographical distribution of water exhibits two local maxima at low latitudes, located over Tharsis and Arabia. Global Climate Model (GCM) simulations suggest that these local enhancements are controlled by atmospheric dynamics. During Northern spring, we observe a bulge of water vapor over the seasonal polar cap edge, consistent with the northward transport of water from the retreating seasonal cap to the permanent polar cap. In terms of vertical distribution, we find that the water volume mixing ratio over the large volcanos remains constant with the surface altitude within a factor of two. However, on the whole dataset we find that the water column, normalized to a fixed pressure, is anti-correlated with the surface pressure, indicating a vertical distribution intermediate between control by atmospheric saturation and confinement to a surface layer. This anti-correlation is not reproduced by GCM simulations of the water cycle, which do not include exchange between atmospheric and subsurface water. This situation suggests a possible role for regolith-atmosphere exchange in the martian water cycle.     

Computing the Sensitivity Kernels for 2.5-D Seismic Waveform Inversion in Heterogeneous,Anisotropic Media

2.5-D modeling and inversion techniques are much closer to reality than the simple and traditional 2-D seismic wave modeling and inversion. The sensitivity kernels required in full waveform seismic tomographic inversion are the Fréchet derivatives of the displacement vector with respect to the independent anisotropic model parameters of the subsurface. They give the sensitivity of the seismograms to changes in the model parameters. This paper applies two methods, called ‘the perturbation method’ and ‘the matrix method’, to derive the sensitivity kernels for 2.5-D seismic waveform inversion. We show that the two methods yield the same explicit expressions for the Fréchet derivatives using a constant-block model parameterization, and are available for both the line-source (2-D) and the point-source (2.5-D) cases. The method involves two Green’s function vectors and their gradients, as well as the derivatives of the elastic modulus tensor with respect to the independent model parameters. The two Green’s function vectors are the responses of the displacement vector to the two directed unit vectors located at the source and geophone positions, respectively; they can be generally obtained by numerical methods. The gradients of the Green’s function vectors may be approximated in the same manner as the differential computations in the forward modeling. The derivatives of the elastic modulus tensor with respect to the independent model parameters can be obtained analytically, dependent on the class of medium anisotropy. Explicit expressions are given for two special cases—isotropic and tilted transversely isotropic (TTI) media. Numerical examples are given for the latter case, which involves five independent elastic moduli (or Thomsen parameters) plus one angle defining the symmetry axis.