Sea-level rise impacts on longitudinal salinity for a low-gradient estuarine system

Climatic Change - Salinity response to sea-level rise is evaluated for a low-gradient, tidally active estuary, the lower St. Johns River, Florida. A high-resolution numerical model is forced by...     

Space-time interaction amongst clusters of mining induced seismicity

Elementary cluster analysis of induced seismicity in a South African gold mine has shown that there is a clear interaction amongst the clusters; and that the level of the interaction is a function of the distance. The clusering algorithm used is an adaptation of the single-link cluster analysis which considers both three-dimensional space and time. A high level of interaction between the clusters is demonstrated from the cross-correlation analysis of seismic activity rates and radiated energy. A distinct decrease in the value of correlation coefficients was detectable as distance increased. This was somewhat surprising, considering the simplicity of the technique used. Since no attempt is made to study the physical mechanisms of interaction, these results are very preliminary, but interesting from an observational point of view.     

The use of acidimetric titration as a novel approach to study particulate trace metal speciation and mobility: Application to sediments of the Scheldt estuary

The study of trace metal speciation has benefited from a great deal of interest leading to the development and the diversification of sequential extraction schemes (SES), which triggered the need for harmonization by the standard, measurements and testing programme (SM & T). However, some uncertainties still persist in the application of the harmonized 3-step protocol, because of the difficulty in conceptualizing a technique that can be applied to environmental samples irrespective of their nature. The alternative method proposed in this study is based on the solubility of the sample components progressively dissolved during the course of an acidimetric titration by 1 mol L⁻¹ HCl. The major HCl-reactive mineralogical components are identified using mass balance calculation of H⁺ consumed by their dissolution together with the amount of major elements released into solution. The speciation of minor and trace elements is investigated by comparing their titrations to those of the major elements. This approach is much simpler than SES because it uses simple non-selective H⁺ at room temperature instead of a complex experimental design of so-called specific reagents. The different mineral components of the solid are no longer operationally defined and the problem of selectivity is irrelevant to the titration approach. The method was applied to several sediment samples from the Scheldt estuary and the particulate phase was further examined by Scanning Electron Microprobe and X-ray Diffraction techniques. The nearly complete consumption of H⁺ in the suspension is balanced by the total dissolution of carbonates and Fe-oxyhydroxides. In contrast to the speciation inferred from the Tessier SES, the acidimetric titration has demonstrated that the carbonate phase does not significantly contain trace metals with the exceptions of 40% of the Mn and 30% of the Co. In contrast, the Fe-oxyhydroxides seem to play a major role and account for 70% of Pb and 20% of Cr, in addition to 60% of P and additional amounts of 20% Co and 40% Mn. 70% of the Cu also occur in the oxyhydroxide phase, more likely coprecipitated with gibbsite. 90% of the Cd and 85% of Zn can be attributed to the Acid Volatile Sulfide (AVS) phase as evidenced from S titration. The acidimetric titration method not only provides information on the speciation of trace metals but also allows the quantification of their reactivity and mobility, if one considers that the titration roughly mimics pH changes that may occur as a result of chemical disequilibrium in the environment. The results demonstrate the potential of the acidimetric titration as an alternative to SES protocols in geochemical and environmental regulation studies. This method is applicable to a wide variety of environmental materials with little or minor adjustments.     

Chemical signature of intermediate water masses along western Portuguese margin

Although the circulation of intermediate water masses in the eastern North Atlantic remains poorly defined, the presence of fresher intermediate waters, the Sub-Artic (SAIW) and the Antarctic Intermediate Water (AAIW), as well the saline intermediate Mediterranean Water (MW), has been tracked using biogeochemical properties. Here we assess the hydrographic and chemical structures of intermediate waters along the western Portuguese margin by examining the vertical distributions and property-property plots of chemical tracers (oxygen and nutrients). AAIW was traced by low oxygen and high nutrients, while SAIW was recognized by low nutrients. The Mediterranean Water (MW) undercurrent is shown to spread towards the eastern flank of Gorringe bank. Concurrently, the fresher waters gained salt by direct incorporation of MW, while this water was enriched in nutrients on its way northward and westward owing, to a great extent, to the entrainment of an AAIW branch. The distributions of nutrients and apparent oxygen utilization are discussed in terms of regional ocean circulation. Our analysis suggests a circulation pattern of the various intermediate waters along the western Portuguese margin: MW extends all over the area, but its presence is more pronounced around cape St. Vincent; SAIW apparently moves southward, reaching the Gorringe bank region, and AAIW flows northward along the coast and around the bank.     

Experimental determination of carbon isotope fractionation between CaCO3 and graphite

Carbon isotopic exchange between graphite and three polymorphs of CaCO₃ was investigated at temperatures of 600-1400 °C and at pressures from 1.4 to 2.3 GPa. Fractionation factors at all temperatures were determined by the partial exchange treatment of Northrop and Clayton (1966).Graphite starting material for the majority of the experiments was milled in water for 20-25 h, producing aggregates of nanosheets. The sheets range in width from 50 to 1000 nm and in thickness from 20 to 30 nm, and they retain hexagonal symmetry.Isotopic exchange appears to be the sum of surface exchange and interior exchange. At 1100-1400 °C, interior exchange exceeded surface exchange, probably by a combination of grain growth, as determined by increase in crystallite size, recrystallization, as observed in FESEM images, and diffusion. In some runs at 1200 and 1400 °C with an isotopic contrast between the initial graphite and calcite of close to 50‰, equilibrium fractionation was actually overstepped due to a kinetic effect. A weighted regression of fractionation factors from the high-temperature runs yields the line of equilibrium interior exchange:

     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Impact of Earth radiation pressure on GPS position estimates

GPS satellite orbits available from the International GNSS Service (IGS) show a consistent radial bias of up to several cm and a particular pattern in the Satellite Laser Ranging (SLR) residuals, which are suggested to be related to radiation pressure mismodeling. In addition, orbit-related frequencies were identified in geodetic time series such as apparent geocenter motion and station displacements derived from GPS tracking data. A potential solution to these discrepancies is the inclusion of Earth radiation pressure (visible and infrared) modeling in the orbit determination process. This is currently not yet considered by all analysis centers contributing to the IGS final orbits. The acceleration, accounting for Earth radiation and satellite models, is introduced in this paper in the computation of a global GPS network (around 200 IGS sites) adopting the analysis strategies from the Center for Orbit Determination in Europe (CODE). Two solutions covering 9 years (2000–2008) with and without Earth radiation pressure were computed and form the basis for this study. In previous studies, it has been shown that Earth radiation pressure has a non-negligible effect on the GPS orbits, mainly in the radial component. In this paper, the effect on the along-track and cross-track components is studied in more detail. Also in this paper, it is shown that Earth radiation pressure leads to a change in the estimates of GPS ground station positions, which is systematic over large regions of the Earth. This observed “deformation” of the Earth is towards North–South and with large scale patterns that repeat six times per GPS draconitic year (350 days), reaching a magnitude of up to 1 mm. The impact of Earth radiation pressure on the geocenter and length of day estimates was also investigated, but the effect is found to be less significant as compared to the orbits and position estimates.