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.     

Star formation, massive stars, and super star clusters in nearby galaxies

The Square Kilometer Array (SKA) will enable studies of star formation in nearby galaxies with a level of detail never before possible outside of the Milky Way. Because the earliest stages of stellar evolution are often inaccessible at optical and near-infrared wavelengths, high spatial resolution radio observations are necessary to explore extragalactic star formation. The SKA will have the sensitivity to detect individual ultracompact HII regions out to the distance of nearly 50 Mpc, allowing us to study their spatial distributions, morphologies, and populations statistics in a wide range of environments. Radio observations of Wolf-Rayet stars outside of the Milky Way will also be possible for the first time, greatly expanding the range of conditions in which their mass loss rates can be determined from free-free emission. On a vastly larger scale, natal of super star clusters will be accessible to the SKA out to redshifts of nearly z 0.1. The unprecedented sensitivity of radio observations with the SKA will also place tight constraints on the star formation rates as low as 1M yr⁻¹ in galaxies out to a redshift of z 1 by directly measuring the thermal radio flux density without assumptions about a galaxy’s magnetic field strength, cosmic ray production rate, or extinction.     

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.     

Longevity of fluorine-bearing tremolite on Venus

There is a general belief that hydrous minerals cannot exist on Venus under current surface conditions. This view was challenged when Johnson and Fegley (2000, Icarus 146, 301-306) showed that tremolite (Ca₂Mg₅Si₈O₂₂(OH)₂), a hydrous mineral, is stable against thermal decomposition at current Venus surface temperatures, e.g., 50% decomposition in 4 Ga at 740 K. To further explore hydrous mineral thermal stability on Venus, we experimentally determined the thermal decomposition kinetics of fluorine-bearing tremolite. Fluor-tremolite is thermodynamically more stable than OH-tremolite and should decompose more slowly. However how much slower was unknown. We measured the decomposition rate of fluorine-bearing tremolite and show that its decomposition is several times to greater than ten times slower than that of OH-tremolite. We also show that F-bearing tremolite is depleted in fluorine after decomposition and that fluorine is lost as a volatile species such as HF gas. If tremolite ever formed on Venus, it would probably also contain fluorine. The exceptional stability of F-bearing tremolite strengthens our conclusions that if hydrous minerals ever formed on Venus, they could still be there today.     

The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

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.     

Coulometric total carbon dioxide analysis for marine studies: maximizing the performance of an automated gas extraction system and coulometric detector

A global survey of the distribution of dissolved CO₂ taking advantage of sampling opportunities provided by the World Ocean Circulation Experiment: World Hydrographic Program (WOCE-WHP) is being carried out through 1995. Goals include the measurement of oceanic inorganic carbon transport and the development of a data base from which future fossil-fuel CO₂ build-up can be monitored. The analytical method selected for total carbon dioxide (C_T) is gas extraction of acidified seawater with coulometric titration of the acid formed by the resultant carbon dioxide and monoethanolamine. To combine high accuracy and precision (± 1.5 μmol/kg for C_T ≥ 2000 μmol/kg) with a high rate of analysis, we have modified an automated single-parameter system. Following prototype development between 1987 and 1990, an instrument emerged with the acronym Somma standing for single-operator multiparameter metabolic analyzer. Improved functional and operating procedures have integrated electronic calibration, CO₂ gas calibration, and sample analysis with automated pressure, temperature, and conductivity (salinity) sensing into a single convenient transportable package.     

Abundance of the introduced seastar, Asterias amurensis, and spatial variability in soft sediment assemblages in SE Tasmania: Clear correlations but complex interpretation

The northern Pacific seastar, Asterias amurensis, was first collected in southeast Tasmania in 1986. Mistaken for the endemic asteroid Uniophora granifera, its true identity was not realised until 1992. It is now a conspicuous predator in soft sediment habitats in this region, and is considered a major threat to native assemblages and commercial species. We examined the structure of soft sediment assemblages at different spatial scales in southeast Tasmania, and correlated spatial variation in community composition with seastar abundances. We found that the structure of soft sediment assemblages is highly variable at a range of spatial scales from metres to tens of kilometres. Clear differences in the composition of assemblages and abundances of major taxa were detected between areas with and without seastars and between areas with low and high seastar densities. However, the nature of these patterns suggests that they are more likely due to differences in sediment characteristics than due to impacts of the seastar. Thus, spatial differences in soft sediment assemblages might have been erroneously attributed to seastars without detailed information on important physical factors such as sediment characteristics. A second survey, using larger sampling units (1 m²) but across a more limited spatial extent, targeted bivalves and heart urchins that were identified as important prey of the seastar in observations of feeding and in experimental studies. Large-scale patterns of abundance and size structure were consistent with seastar effects anticipated from small-scale experimental and feeding studies for some, but not all, species. While the field survey ultimately provided evidence about the presence or absence of seastar impacts at large-scales, the identification of key ecological variables in experimental and feeding studies proved crucial to both the design and interpretation of patterns observed in the large-scale surveys. Overall, this work highlighted the necessity to consider multiple lines of evidence rather than relying on a single ‘inferential’ test, in the absence of pre-impact data.     

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.