Coulometric TCO2 analyses for marine studies; an introduction

Progress in the introduction of coulometry for the analysis of total carbon dioxide (TCO₂) in marine waters is described. An extractor—stripper removes CO₂ that is measured coulometrically by the quantity of electricity (coulombs) used to electrogenerate OH^? ions for the titration of the acid formed by the reaction of CO₂ and ethanolamine. The equivalence point is detected photometrically with thymolphthalein as the indicator, and Faraday's Law relates coulombs to equivalents of titrant generated and CO₂ determined so that there are no standard curves needed or titrants to standardize or store. Accuracy was determined by adding gelatin capsules containing 100–1500 μg C of pure CaCO₃ into the stripper, and accuracies of better than ± 1 μg C were achieved. The best precision for natural seawater (± 1 standard error) of ± 0.5 μmol l^?1 was found for 17 samples of Bermuda coastal waters having a mean TCO₂ of 2007.2 μmol l^?1 (0.05% CV). Sources of error and precautions are discussed. This method, which has been used successfully at sea, can be used to study a variety of marine phenomena involving TCO₂.     

Massless scalar field in Robertson-Walker space-time

Recently, exact spatially-homogeneous solutions have been found for a conformally invariant massless scalar fieldS(t) coupled to a Robertson-Walker geometry. We investigate extending these solutions to inhomogeneous scalar fieldsS(t, x ^l ). For an isotropic scalar fieldS(t, r) we find a solution satisfying three of the five field equations. If we use REDUCE, we show that the remaining equations forceS=S(t).     

Characterization of soil's structural crust by spectral reflectance in the SWIR region (1.2–2.5 μm)

Structural crust is a thin layer formed on the soil surface after a rainstorm. The crust is the result of a physical segregation and rearrangement of soil particles in a way that affects some of the soil properties, such as infiltration, runoff and soil erosion. In practice, there is no rapid, in situ method for monitoring, assessing and mapping crust intensity and quality. In this study, a controlled spectral investigation of the structural crust across the NIR–SWIR spectral region was conducted on three selected Israeli soils, to study the potential of reflectance radiation to detect structural crust in soils. Two major factors served as the driving forces for this study: (1) there is no valid method for in situ assessment of the crust's characteristics in the agriculture field, and (2) the crust might bias thematic remote sensing of soils, because the thin layer of crust blocks photon–matter interaction, which represents the relevant soil body. Through the use of a laboratory rainfall simulator and a sensitive spectrometer, it was revealed that for three selected soils, significant spectral differences occurred between the crust and its bulk soil. The spectral information was found to be related to changes in particle size distribution and texture at the surface of the soil. This conclusion was based on indications of absorption of OH in clay lattice, OH in adsorbed water and CO₃ in carbonates. It was concluded that the structural crust is a phenomenon that should not be ignored by remote-sensing users. In fact, in the field of agriculture, the spectral properties of crust can be used as tools for estimating the crust's intensity.     

About Darcy's law in non-Galilean frame

This paper is aimed towards investigating the filtration law of an incompressible viscous Newtonian fluid through a rigid non-inertial porous medium (e.g. a porous medium placed in a centrifuge basket). The filtration law is obtained by upscaling the flow equations at the pore scale. The upscaling technique is the homogenization method of multiple scale expansions which rigorously gives the macroscopic behaviour and the effective properties without any prerequisite on the form of the macroscopic equations. The derived filtration law is similar to Darcy's law, but the tensor of permeability presents the following remarkable properties: it depends upon the angular velocity of the porous matrix, it verifies Hall–Onsager's relationship and it is a non-symmetric tensor. We thus deduce that, under rotation, an isotropic porous medium leads to a non-isotropic effective permeability. In this paper, we present the results of numerical simulations of the flow through rotating porous media. This allows us to highlight the deviations of the flow due to Coriolis effects at both the microscopic scale (i.e. the pore scale), and the macroscopic scale (i.e. the sample scale). The above results confirm that for an isotropic medium, phenomenological laws already proposed in the literature fails at reproducing three-dimensional Coriolis effects in all types of pores geometry. We show that Coriolis effects may lead to significant variations of the permeability measured during centrifuge tests when the inverse Ekman number Ek⁻¹ is 𝒪(1). These variations are estimated to be less than 5% if Ek⁻¹<0.2, which is the case of classical geotechnical centrifuge tests. We finally conclude by showing that available experimental data from tests carried out in centrifuges are not sufficient to determining the effective tensor of permeability of rotating porous media. Copyright © 2004 John Wiley & Sons, Ltd.     

A stepwise method for determining the number of component distributions in a mixture

This paper considers the problem of estimatingm, the number of components in a finite mixture of distributions from a parametric family. A step-up procedure using the bootstrap method is proposed. Some properties of the procedure are illustrated with simulation studies. An example of the method, applied to orientation of beach clasts, is given.     

A time series analysis of sound propagation in a strongly multipathshallow water environment with an adiabatic normal mode approach

Measured time series were generated by small omnidirectional explosive sources in a shallow water area. A bottom-mounted hydrophone recorded sound signals that propagated over a sloping bottom. The time series in the 250-500 Hz band were analyzed with a broad-band adiabatic normal mode approach. The measured waveforms contain numerous bottom interacting multipaths that are complicated by the subbottom structure that contains high-velocity layers near the water-sediment interface. Several of the details of the geoacoustic structure and the depth of the water column at the receiver are inferred from comparisons of the measured data to simulated time series. The sensitivity of broad-band matched-field ambiguity surfaces in the range-depth plane for a single receiver to selected waveguide parameters is examined. A consistent analysis is made where the simulated time series are compared to the measured time series along with the single-receiver matched-field localization solutions for ranges out to 5 km. In this range interval, it was found that the peak cross-correlation between the measured and simulated time series varied between 0.84 and 0.69. The difference between the GPS range and the range obtained from the matched-field solution varied from 0 to 63 m. The geoacoustic structure obtained in the analysis consists of an 8-m low-velocity sediment layer over an 8-m high-velocity layer followed by a higher velocity, infinite half-space     

Evolution of 2:1 layered silicates in low-grade metamorphosed Liassic shales of Central Switzerland

White mica from the Liassic black shales and slates in Central Switzerland was analysed by transmission electron microscopy (TEM) and electron microprobe to determine its textural and compositional evolution during very low-grade prograde metamorphism. Samples were studied from the diagenetic zone, anchizone and epizone (T ≈100°–450 °C). Phyllosilicate minerals analysed include illite/smectite (I/S), phengite, muscovite, brammallite, paragonite, margarite and glauconite. Textural evolution primarily is towards larger, more defect-free grains with compositions that approach those of their respective end-members. The smectite-to-illite transformation reduced the amounts of the exchange components SiK_?1Al_?1, MgSiAl_?2, and Fe³⁺Al_?1. These trends continue to a lesser degree in the anchizone and epizone. Correlations between the proportion of smectite in I/S and the composition of I/S indicate that smectite layers may contain a high layer charge. Illite in I/S bears a compositional resemblance to macrocrystalline phengite in some samples, but is different in others. Paragonite first appears in the upper diagenetic zone or lower anchizone as an interlayer-deficient brammallite, and it may be mixed with muscovite on the nanometre scale. Owing to the small calculated structure factor for paragonite-muscovite superstructures, conventional X-ray powder diffraction cannot distinguish between mixed-layer structures and a homogeneous compositionally intermediate solid solutions. However, indirect TEM evidence shows that irregularly shaped domains of Na- and K-rich mica exist below 10 nm. Subsequent coarsening of domains at higher grades produced discrete paragonite grains at the margins of muscovite crystals or in laths parallel to the basal plane of the host muscovite. Margarite appears in the epizone and follows a textural evolution similar to paragonite in that mixtures of margarite, paragonite, and muscovite may initially occur on the nanometre scale. However, no evidence of interlayer-poor margarite has been found.     

Depositional and post‐depositional history of warm stage deposits at Knocknacran,Co. Monaghan,Ireland: implications for preservation of Irish last interglacial deposits

Organic‐rich deposits, uncovered during overburden removal from mantled gypsum karst at Knocknacran opencast gypsum mine, Co. Monaghan, are the best candidate to date for a last interglacial record in Ireland. The two till and organic‐rich deposits (preserved at different quarry elevations) were emplaced on to a Tertiary dolerite surface during high‐energy flood events and subsequently folded and faulted by movement towards sinkholes in underlying gypsum. Uranium–thorium disequilibrium dating suggests that the organic‐rich deposits in the upper section were hydrologically isolated at ca. 41 ka and those in the lower section at ca. 86 ka. Interpretation of the pollen content, although tentative because of the depositional and post‐depositional history of the material, suggests that the organic material originated in a warm stage possibly warmer than the post‐Eemian interstadials. The unusual setting of preservation may indicate that in situ, last interglacial deposits have generally been removed by erosion in Ireland. Copyright © 2004 John Wiley & Sons, Ltd.     

On salinity regimes and the vertical structure of residual flows in narrow tidal estuaries

An examination is made of the circulation in narrow estuaries subject to a predominant tidal forcing. Velocity structures are derived separately for residual flow components associated with (a) river flow, (b) wind stress, (c) a well-mixed longitudinal density gradient and (d) a fully stratified saline wedge. Dimensionless parameters are introduced to indicate the magnitude of each component and these parameters are evaluated for 9 major estuaries, thereby revealing their sensitivity to each component.For a channel of constant breadth and depth, formulae are deduced for the length of saline intrusion, L. Comparisons with observed data show that such formulae may be used with confidence to predict changes in L arising from variations in river flow, tidal range or channel depths.The level of stratification is shown to be related to a product of two parameters, one associated with velocity structure and a second involving the square of the ‘flow ratio’ $\text{u}\text{u}\text{?}$ (i.e. residual velocity/amplitude of the tidal velocity). This relationship provides a simple classification system for estuarine stratification which can be used to indicate the sensitivity of any particular estuary to changing conditions.