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.     

Chronology and evolution of the northern Iceland Plateau

New aeromagnetic data, K-Ar age determinations of dredged marine igneous rocks, as well as other geophysical evidence have shed light on the chronology, nature and evolution of the northern Iceland Plateau. Correspondence between seismic refraction profiles taken on the Jan Mayen Ridge and westward through Jan Mayen Island, suppressed aeromagnetic anomalies, earthquake surface wave studies, and ages of dredged igneous rocks suggest these strata may form an extended region of thickened crust, possibly of Caledonian age, extending westward toward the Kolbeinsey Ridge and northwest to the south wall of the Jan Mayen Fracture Zone.     

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     

Relationships between Campi Flegrei and Mt. Somma volcanism: evidence from melt inclusions in clinopyroxene phenocrysts from volcanic breccia xenoliths

Summary We present compositions of reheated melt inclusions in clinopyroxene phenocrysts from three mafic xenoliths in Breccia Museo, Campi Flegrei, Italy. Melt inclusion compositions are remarkably different from the compositions of known contemporary Campi Flegrei lavas, being significantly enriched in K₂O and depleted in Na₂O. Some differences are also evident in FeO^* (total Fe as FeO) and TiO₂ contents. The clinopyroxene phenocrysts could not have crystallised from Campi Flegrei magmas. We suggest that they originated from a volcanic system genetically very similar to, and possibly linked with, the >14 ka volcanic system of Mt. Somma, another Campanian volcano ∼ 30 km east from Campi Flegrei, from which Vesuvius subsequently developed. This result indicates a close relationship (or link) between the two volcanic systems which have until now been considered separate. We speculate that the link was established prior to eruption of the Neapolitan Yellow Tuff (NYT) (∼ 12 ka). The xenoliths were derived from a volcanic system older than the host breccias themselves. We suggest that this older volcanism had close similarities with the volcanism of the older products of Mt. Somma (∼25 ka). Received March 20, 2000; accepted November 2, 2000