Nitrate dynamics in a rural headwater catchment: measurements and modelling

This study was designed to improve our understanding of, and mechanistically simulate, nitrate (NO₃) dynamics in a steep 9.8 ha rural headwater catchment, including its production in soil and delivery to a stream via surface and subsurface processes. A two‐dimensional modelling approach was evaluated for (1) integrating these processes at a hillslope scale annually and within storms, (2) estimating denitrification, and (3) running virtual experiments to generate insights and hypotheses about using trees in streamside management zones (SMZs) to mitigate NO₃ delivery to streams. Total flow was mathematically separated into quick‐ and slow‐flow components; the latter was routed through the HYDRUS software with a nitrogen module designed for constructed wetlands. Flow was monitored for two years. High surface‐soil NO₃ concentrations started to be delivered to the stream via preferential subsurface flow within two days of the storm commencing. Groundwater NO₃‐N concentrations decreased from 1.0 to less than 0.1 mg l^?1 from up‐slope to down‐slope water tables, respectively, which was attributed to denitrification. Measurements were consistent with the flushing of NO₃ mainly laterally from surface soil during and following each storm. The model accurately accounted for NO₃ turnover, leading to the hypotheses that denitrification was a minor flux (<3 kg N ha^?1) compared to uptake (98^?127 kg N ha^?1), and that SMZ trees would reduce denitrification if they lowered the water table. This research provides an example of the measurement and modelling of NO₃ dynamics at a small‐catchment scale with high spatial and temporal resolution. Copyright © 2013 John Wiley & Sons, Ltd.     

Barium uptake into the shells of the common mussel (Mytilus edulis) and the potential for estuarine paleo-chemistry reconstruction

In this study we test if calcite shells of the common mussel, Mytilus edulis, contain barium in proportion to the water in which they grew. Similar to all bivalves analyzed to date, the [Ba/Ca]_shell profiles are characterized by a relatively flat background [Ba/Ca]_shell, interrupted by sharp [Ba/Ca]_shell peaks. Previous studies have focused on these [Ba/Ca]_shell peaks, but not on the background [Ba/Ca]_shell. We show that in both laboratory and field experiments, there is a direct relationship between the background [Ba/Ca]_shell and [Ba/Ca]_water in M. edulis shells. The laboratory and field data provided background Ba/Ca partition coefficients (D_Ba) of 0.10 ± 0.02 and 0.071 ± 0.001, respectively. This range is slightly higher than the D_Ba previously determined for inorganic calcite, and slightly lower than foraminiferal calcite. These data suggest that M. edulis shells can be used as an indicator of [Ba/Ca]_water, and therefore, fossil or archaeological M. edulis shells could be used to extend knowledge of estuarine dissolved Ba throughputs back in time. Moreover, considering the inverse relationship between [Ba/Ca]_water and salinity, background [Ba/Ca]_shell data could be used as an estuary specific indicator of salinity. The cause of the [Ba/Ca]_shell peaks is more confusing, both the laboratory and field experiments indicate that they cannot be used as a direct proxy of [Ba/Ca]_water or phytoplankton production, but may possibly be caused by barite ingestion.     

Coalification in Carboniferous sediments from the Lötschberg base tunnel

Vitrinite reflectance (Rr), proximate analysis and carbon isotope composition (δ¹³C) have been used to characterise coal samples from two zones of Late Carboniferous sediments (Gastern and Ferden) in the Aar massif where they are penetrated by the Lötschberg base tunnel (constructed between 1999 and 2005). Samples are characterised by variable ash yields (21.7–93.9%; dry basis); those with ash yields of less than ~50% and with volatile matter content (V;dry ash-free basis) within the limits 2 < V% ≤ 8 are anthracite. Values of Rr range from 3.89% to 5.17% and indicate coalification to the rank of anthracite and meta-anthracite in both Gastern and Ferden Carboniferous zones. Samples of anthracite and shale from the Gastern Carboniferous exhibit a relatively small range in δ¹³C values (–24.52‰ to –23.38‰; mean: –23.86‰) and are lighter than anthracite samples from the Ferden Carboniferous (mean: –22.20‰). The degree of coalification in the Gastern and Ferden Carboniferous zones primarily depends on the maximum rock temperature (T) attained as a result of burial heating. Vitrinite reflectance based estimates of T range from ~290° –360 °C. For a proposed palaeogeothemal gradient of 25 ° C/km at the time of maximum coalification the required overburden is attributable to relatively thin autochtonous Mesozoic/Cenozoic sedimentary cover of the Aar massif and Gastern granite and deep tectonic burial beneath advancing Helvetic, Ultrahelvetic and Prealpine (Penninic) nappes in Early Oligocene to Miocene.     

Bias in estimating fractal dimension with the rescaled-range (R/S) technique

Fractal geostatistics are being applied to subsurface geological data as a way of predicting the spatial distribution of hydrocarbon reservoir properties. The fractal dimension is the controlling parameter in stochastic methods to produce random fields of porosity and permeability. Rescaled range (R/S)analysis has become a popular way of estimating the fractal dimension, via determination of the Hurst exponent (H). A systematic investigation has been undertaken of the bias to be expected due to a range of factors commonly inherent in borehole data, particularly downhole wireline logs. The results are integrated with a review of previous work in this area. Small datasets. overlapping samples, drift and nonstationariry of means can produce a very large bias, and convergence of estimates of H around 0.85–0.90 regardless of original fractal dimension. Nonstationarity can also account for H>1, which has been reported in the literature but which is theoretically impossible for fractal time series. These results call into question the validity of fractal stochastic models built using fractal dimensions estimated with the R/Smethod.     

CSCO_3 CYCLES IN SALAWUSU RIVER BASINSINCE 150KA B.P.

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A first look at the effects of ionospheric signal bending on a globally processed GPS network

This study provides a first attempt at quantifying potential signal bending effects on the GPS reference frame, coordinates and zenith tropospheric delays (ZTDs). To do this, we homogeneously reanalysed data from a global network of GPS sites spanning 14 years (1995.0–2009.0). Satellite, Earth orientation, tropospheric and ground station coordinate parameters were all estimated. We tested the effect of geometric bending and dTEC bending corrections, which were modelled at the observation level based, in part, on parameters from the International Reference Ionosphere 2007 model. Combined, the two bending corrections appear to have a minimal effect on site coordinates and ZTDs except for low latitude sites. Considering five days (DOY 301–305, 28 October–1 November 2001) near ionospheric maximum in detail, they affect mean ZTDs by up to ~1.7 mm at low latitudes, reducing to negligible levels at high latitudes. Examining the effect on coordinates in terms of power-spectra revealed the difference to be almost entirely white noise, with noise amplitude ranging from 0.3 mm (high latitudes) to 2.4 mm (low latitudes). The limited effect on station coordinates is probably due to the similarity in the elevation dependence of the bending term with that of tropospheric mapping functions. The smoothed z-translation from the GPS reference frame to ITRF2005 changes by less than 2 mm, though the effect combines positively with that from the second order ionospheric refractive index term. We conclude that, at the present time, and for most practical purposes, the geometric and dTEC bending corrections are probably negligible at current GPS/reference frame precisions.     

PALEOMAGIA: A PHP/MYSQL database of the Precambrian paleomagnetic data

Most paleomagnetic applications require a precise, rationally organized and up-todate catalogue or database of paleomagnetic results worldwide. These include reconstructions of continents, calculations of the Apparent Polar Wander Paths (APWPs) or paleolatitude drift curves, testing the Geocentric Axial Dipole (GAD) model, studies of geomagnetic paleosecular variation or reversal asymmetries, comparison of coeval results obtained from different types of rocks, estimation of inclination shallowing in sedimentary rocks and understanding the delay in remanence acquisition caused by slow cooling in large intrusions. For this purpose, various databases, such as the Global Paleomagnetic Database (GPMDB), and the Magnetics Information Consortium Database (MagIC) have been generated. This paper presents a new relational database (PALEOMAGIA) where 3278 entries of Precambrian data have been split geographically, sorted according to age and rock types and ranked using a revised version of the Van der Voo grading scheme. The latest geochronologic information is included wherever available. Significant effort has been put to the retrieval and archiving of data published in the last decade, which are virtually nonexistent in GPMDB. Here we present the database and its browser-based user interface from a scientific and a technical point of view.     

Ar/Ar thermochronology of the Kampa Dome, southern Tibet: Implications for tectonic evolution of the North Himalayan gneiss domes

Structural and thermochronological studies of the Kampa Dome provide constraints on timing and mechanisms of gneiss dome formation in southern Tibet. The core of Kampa Dome contains the Kampa Granite, a Cambrian orthogneiss that was deformed under high temperature (sub-solidus) conditions during Himalayan orogenesis. The Kampa Granite is intruded by syn-tectonic leucogranite dikes and sills of probable Oligocene to Miocene age. Overlying Paleozoic to Mesozoic metasedimentary rocks decrease in peak metamorphic grade from kyanite + staurolite grade at the base of the sequence to unmetamorphosed at the top. The Kampa Shear Zone traverses the Kampa Granite — metasediment contact and contains evidence for high-temperature to low-temperature ductile deformation and brittle faulting. The shear zone is interpreted to represent an exhumed portion of the South Tibetan Detachment System. Biotite and muscovite ⁴⁰Ar/³⁹Ar thermochronology from the metasedimentary sequence yields disturbed spectra with 14.22 ± 0.18 to 15.54 ± 0.39 Ma cooling ages and concordant spectra with 14.64 ± 0.15 to 14.68 ± 0.07 Ma cooling ages. Petrographic investigations suggest disturbed samples are associated with excess argon, intracrystalline deformation, mineral and fluid inclusions and/or chloritization that led to variations in argon systematics. We conclude that the entire metasedimentary sequence cooled rapidly through mica closure temperatures at  14.6 Ma. The Kampa Granite yields the youngest biotite ⁴⁰Ar/³⁹Ar ages of  13.7 Ma immediately below the granite–metasediment contact. We suggest that this age variation reflects either varying mica closure temperatures, re-heating of the Kampa Granite biotites above closure temperatures between 14.6 Ma and 13.7 Ma, or juxtaposition of rocks with different thermal histories. Our data do not corroborate the “inverse” mica cooling gradient observed in adjacent North Himalayan gneiss domes. Instead, we infer that mica cooling occurred in response to exhumation and conduction related to top-to-north normal faulting in the overlying sequence, top-to-south thrusting at depth, and coeval surface denudation.     

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ⁶⁵Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ⁶⁵Cu_{solution-solid} = δ⁶⁵Cu_solution − δ⁶⁵Cu_solid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to −0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ⁶⁵Cu_{solution-solid} ranging from ∼+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ⁶⁵Cu of natural waters and soils is probably considerable.     

Annual,Seasonal, and Regional Variability in Diet of Atlantic Croaker (<Emphasis Type="Italic">Micropogonias undulatus)</Emphasis> in Chesapeake Bay

Atlantic croaker is one of the most abundant demersal fish in Chesapeake Bay. Until recently, when substantial declines in abundance have occurred, high biomass supported elevated fisheries landings. Therefore, study of the diet of Atlantic croaker is important to understand its own dynamics and its role in the Chesapeake Bay ecosystem. Patterns in the diet of croaker varied annually, seasonally, and spatially, but were not strongly correlated with any measured environmental variables. Although the majority of the diet of croaker consisted of polychaetes and other benthic items, about 20% of the croaker diet by weight consisted of anchovy and other fishes. Croaker consumption of anchovy is likely a result of crepuscular feeding that has not been captured in previous studies that sampled during the day and with bottom trawls. Thus, croaker influences both the benthic and pelagic components of the Chesapeake Bay food web and incorporating such diel patterns in diet may increase the reliability of fishery ecosystem models.