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.     

MAXIPOL: a balloon-borne experiment for measuring the polarization anisotropy of the cosmic microwave background radiation

We discuss MAXIPOL, a bolometric balloon-borne experiment designed to measure the E-mode polarization anisotropy of the cosmic microwave background radiation (CMB) on angular scales of 10^′ to 2°. MAXIPOL is the first CMB experiment to collect data with a polarimeter that utilizes a rotating half-wave plate and fixed wire-grid polarizer. We present the instrument design, elaborate on the polarimeter strategy and show the instrument performance during flight with some time domain data. Our primary dataset was collected during a 26 h turnaround flight that was launched from the National Scientific Ballooning Facility in Ft. Sumner, New Mexico in May 2003. During this flight five regions of the sky were mapped. Data analysis is in progress.     

Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

Hydrothermal Metalliferous Sediments and Waters Off the Lesser Antilles

Considerable metal enrichments have been found in hydrothermal fluids and metalliferous sediments off the central Lesser Antilles Volcanic Arc. The elements variably enriched in the fluids as a result of the hydrothermal activity are Fe, Mn, As, Si, B, Li and in the sediments, Fe, P, Mo, As, Sb, Hg, Cu and Pb. Variations in the concentrations of these elements in both fluids and sediments along the arc result from a number of factors, the most important of which is the stage that each island's volcano has reached in its eruptive cycle. Although hydrothermal mineralization on the sea floor off the islands is only low grade, phase separation in the hydrothermal fluids at depth could be leading to higher grade stockwork mineralization below the vent fields or the discharge of metal rich brines on the lower flanks of the volcanic islands.     

Animal-sediment relations in shallow water benthic communities

Ninety benthic samples were used to study animal-sediment relations in Tomales Bay, California. While most of the benthic species studied were found more often in a particular type of substrate, individuals of such species were occasionally found in other substrates. There is a striking tendency for species occurring outside of their characteristic environment to be associated with the most diverse assemblages of the foreign substrate. Species low in the order of succession are those species that are found more frequently on other substrates. These phenomena are explained in terms of environmental stability. The concepts involved suggest a means of predicting the sequence of faunal changes following the alteration of the substrate.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

Molecular simulations of metal adsorption to bacterial surfaces

The atomic-scale interactions that occur between cations and the metal-binding cell wall components common to many gram-positive bacteria were investigated using molecular simulations techniques. We examined the adsorption of Cd and Pb onto peptidoglycan and teichoic acid components of the bacterial cell wall using classical energy force field methods. Within the framework of molecular mechanics and the Cerius² modeling software, we used energy minimization, conformational analysis, and molecular dynamics to examine the different components of the cell wall and to determine relative binding energies and structural configurations of the cell wall components, both with and without the metals present. Electronic structure calculations of representative metal-organic complexes validate the more practical classical methods required in simulating the large number of atoms associated with the cell wall components. The classical force field simulations were conducted in both gas phase and solvated periodic cells. Force field-based simulation techniques can adequately describe the interactions of Cd with the cell wall, defining both metal ion coordinations and binding distances. However, the classical force field approach is inconsistent in describing the observed Pb-cell wall interactions due to possible limitations in the force field parameters, the propensity for Pb to form hydroxides at circumneutral pH, or the dominance of other adsorption mechanisms.     

A rooftop tuned mass damper frame

This article documents the analytical study and feasibility of placing a tuned mass damper in the form of a limber rooftop moment frame atop relatively stiff structures to reduce seismic acceleration response. Six existing structures were analytically studied using a suite of time history and response spectra records. The analyses indicate that adding mass in conjunction with a limber frame results in an increase in the fundamental period of each structure. The fundamental period increase generally results in a decrease in seismic acceleration response for the same time history and response spectra records. Owing to the limber nature of the rooftop frames, non‐linear analysis methods were required to evaluate the stability of the rooftop tuned mass damper frame. The results indicate the addition of a rooftop tuned mass damper frame reduces the seismic acceleration response for most cases although acceleration response can increase if the rooftop frame is not tuned to accommodate the specific structure's dynamic behaviour and localized soil conditions. Appropriate design of the rooftop tuned mass damper frame can result in decreased seismic acceleration response. This translates to safer structures if used as a retrofit measure or a more economical design if used for new construction. Copyright © 2003 John Wiley & Sons, Ltd.     

Natural Gradient Tracer Test to Evaluate Natural Attenuation of MTBE Under Anaerobic Conditions

A natural gradient tracer test using perdeuterated MTBE was conducted in an anaerobic aquifer to determine the relative importance of dispersion and degradation in reducing MTBE concentrations in ground water. Preliminary ground water chemistry and hydraulic conductivity data were used to place the tracer within an existing dissolved MTBE plume at Port Hueneme, California. Following one year of transport, the tracer plume was characterized in detail.
Longitudinal dispersion was identified as the dominant mechanism for lowering the perdeuterated MTBE concentrations. The method of moments was used to determine the longitudinal and lateral dispersion coefficients (0.85 m²/day and 0.08 m²/day, respectively). A mass-balance analysis, carried out after one year of transport, accounted for 110% of the injected mass and indicated that no significant mass loss occurred. The plume structure created by zones of higher and lower hydraulic conductivity at the site was complex, consisting of several localized areas of high tracer concentration in a lower concentration plume. This is important because the aquifer has generally been characterized as exhibiting fairly minor heterogeneity. In addition, the tracer plume followed a curved flowpath that deviated from the more macroscopic direction of ground water flow inferred from local ground water elevation measurements and the behavior of the existing plume. Understanding the mass balance, plume structure, curvature of the tracer plume, and consequently natural attenuation behavior required the detailed sampling approach employed in this study. These data imply that a detailed understanding of site hydrogeology and an extensive sampling network may be critical for the correct interpretation of monitored natural attenuation of MTBE.