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.     

Arsenic incorporation in a salt marsh ecosystem

Replicate portions of a Delaware salt marsh were enclosed in cylindrical microcosms and exposed to elevated levels of inorganic arsenic (arsenate). All biotic and abiotic components in dosed cylinders rapidly incorporated arsenic. Spartina blades showed the greatest arsenic enrichment, with dosed plants incorporating arsenic concentrations an order of magnitude higher than controls. Spartina detritus and sediments also exhibited greatly elevated arsenic concentrations. Virtually all of the arsenic was incorporated into plant tissue or strongly sorbed to cell surfaces. Thus, elevated arsenic concentrations in estuarine waters will be reflected in living and non-living components of a salt marsh ecosystem, implying that increased arsenic will be available to organisms within the marsh ecosystem.     

Kinetic studies of lead(II) uptake by the seagrass Zostera muelleri in water by radiotracing,atomic absorption spectrometry and electrochemical techniques

Evidence was found that uptake of lead from seawater in both model and natural systems by the leaves of the seagrass Zostera muelleri does occur for live, dead and scraped leaves at all the lead concentrations tested. Positive uptake of lead was measured using the three analytical techniques of radio-tracer, differential pulse anodic stripping voltammetry and atomic absorption spectrometry; similar uptake profiles were obtained for each technique. Profiles always showed an initial rapid uptake phase followed by a gradual transition to a plateau phase at which an approximate equilibrium between lead attached to seagrass and free ionic lead in seawater was reached. The presence of active lead uptake processes was indicated in experiments which attempted to remove lead from leaves by a chelating agent.     

Four-element CODAR beam forming

An HF radar called the Coastal Ocean Dynamics Applications Radar (CODAR) is presently being used in several forms to measure ocean surface parameters. The original version was developed by the National Oceanic and Atmospheric Administration (NOAA) and utilizes a four-element receive array. The array consists of four equally spaced elements arranged on a circle with a radius of 0.2151 wavelengths (at 25.4 MHz). It was designed to measure ocean currents using a direction-finding technique based on an extension to a simple two-element interferometer. The problem of determining the bearing of a radiating source can be readily shown to be equivalent to that incurred in spectral estimation. In an attempt to improve upon the processing of existing data, modern nonlinear spectral estimation techniques are applied in a beam-forming bearing estimation procedure and compared against several direction-finding algorithms. Enhancement of bearing estimators via analysis of the eigenstructure of a spatial correlation matrix is included. Antenna response patterns are calculated and used to investigate properties of direction-finding algorithms. Simulated data are used for a comparison of direction finding and beam forming. The asymmetrical bias of each method is investigated to determine its effect on the error in estimating the angle of arrival of a radar target.     

A note on turbulent perturbations of salinity in a partially mixed estuary

Measurements of salinity perturbations in a partially mixed estuary have been used to evaluate the usefulness of an inductive salinometer and to determine some of the characteristics of the salinity perturbations. The salinometer performed satisfactorily under most conditions. Although internal wave like effects were present, the turbulence fluctuations were dominant. The salinity fluctuations and the turbulent fluxes $\text{sw}$ and $\text{su}$ were found to behave in a manner similar to the density fluctuations in a thermally stratified atmospheric boundary layer and a laboratory open channel flow. A quadrant analysis suggested that the contribution of each quadrant to the turbulent flux changed with Ri. The turbulence parameters ν and c_γ were found to decrease and increase respectively as Ri increases.     

Weathering process at the natural fission reactor of Bangombé

 The uranium deposits in the basin of Franceville (Gabon) host the only natural fission reactors known in the world. Unique geological conditions favoured a natural fission reaction 2 Ga ago. This was detected by anomalous isotopic compositions of uranium and rare earth elements (REE), which are produced by the fission reaction. In total, 16 reactor zones were found. Most of them are mined out. The reactor zone of Bangombé, is only 10–11 m below the surface. This site has been influenced by surface weathering processes. Six drill cores have been sampled at the site of the reactor zone of Bangombé during the course of the study and only one drill core (BAX 08) hit the core of the reactor. From these data and previous drilling campaigns, the reactor size is estimated to be 10 cm thick, 2–3 m wide and 4–6 m long. The migration of fission products can be traced by the anomalous isotope ratios of REE because of the fission process. The ¹⁴⁹Sm/¹⁴⁷Sm ratio close to the reactor zone is only 0.28 (normal: 0.92) because of the intense neutron capture of ¹⁴⁹Sm and subsequent transmutation, whereas ¹⁴⁷Sm is enriched by the fission reaction. Similar changes in isotopic patterns are detectable on other REE. The isotope ratios of Sm and Nd of whole rock and fracture samples surrounding the reactor indicate that fission-genic REE migrated only a few decimetres above and mainly below the reactor zone. Organic matter (bitumen) seems to act as a trap for fission-genic REE. Additional REE-patterns show less intense weathering with increasing depth in the log profile and support a simple weathering model. Received: 26 November 1999 · Accepted: 2 May 2000