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.     

Preliminary observations of oxygen and carbon dioxide of the wintertime Bering Sea marginal ice zone

Wintertime oxygen and pH profiles across the marginal ice zone of the central and southeastern Bering Sea shelf are analyzed and compared with summer data. During the winter, at water depths shallower than 75 m, the water column is homogeneous and near freezing. Between the 75- and 200-m isobaths the structure is essentially two-layered, a cool and fresh upper layer overlying a warmer, more saline bottom layer. The oxygen concentration in the surface mixed layer is higher than the summer values, but the degree of saturation is lower because of the lower temperature in winter. The oxygen degree of saturation in the bottom mixed layer on the shelf in winter are higher than in the surface water in winter and the bottom water in summer.In summer the oxygen and carbon dioxide data show extreme variability governed primarily by biological processes. Winter oxygen and pH data, however, do not scatter as much as the summer data and indicate conservative mixing of several sub-surface water masses. The surface water is undersaturated in both oxygen and carbon dioxide and seems to absorb oxygen, but little carbon dioxide, from the atmosphere.Two stations were occupied in the Aleutian Basin. The homogeneous surface layer has the same oxygen and pH values as in the minimum temperature layer observed in the summer by other investigators at the same location. The result substantiates the hypothesis of early investigators that the summer minimum temperature layer is the remnant local winter water. All winter surface waters sampled are undersaturated with respect to oxygen, suggesting that the input of oxygen through the air-sea exchange does not keep up with the rate of upwelling and cooling, which reduces the degree of oxygen saturation. Surface carbon dioxide is also undersaturated because of cooling. The maximum temperature layer at these two Aleutian Basin stations is warmer, fresher, and contains more oxygen, but less carbon dioxide, than in the summer, suggesting advective input of some nonlocal seawater.     

Upwelling and river runoff as sources of dissolved nitrous oxide to the Alsea estuary,Oregon

Surface waters of Alsea Bay, an unpolluted estuary on the Oregon coast, were analysed for nitrous oxide, nitrate and nitrite on a weekly or biweekly basis during the summer of 1979. The estuary was found to be a variable source of N₂O to the atmosphere. Large and rapid increases in the concentrations of N₂O, NO₃^?, and NO₂^? occurred at the beginning of the sampling period and are attributed to the influx of nutrient-rich upwelling water into the estuary with the tide. The subsequent decline in concentrations of nitrate, nitrite and nitrous oxide over the remainder of the summer is attributed to a decrease in upwelling intensity, a decline in nitrification rates and to assimilatory nitrate reduction. Measurements of nitrous oxide at six stations along the Alsea River were also made in September and October before and after the onset of the rainy season. Samples taken after flood conditions were established were systematically 50% higher than pre-flood samples. The data suggest that soil runoff results in elevated concentrations of N₂O in rivers.     

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.