The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

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.     

The production of biogenic silica in the Weddell and Scotia Seas

During the EPOS leg 2 cruise (European Polarstern Study, November 1988–January 1989), the production rate of biogenic silica in the euphotic zone was measured by the ³⁰Si method at stations in the Scotia and Weddell Seas.The highest integrated production rates were observed in the Scotia Sea (range: 11.2–20.6 mmol Si m⁻² day⁻¹), the marginal ice zone of the Weddell Sea exhibiting somewhat lower values (range: 6.0–20.0 mmol Si m⁻²day⁻¹).Our results demonstrate that as far as biogenic silica production is concerned the marginal ice zone of the Weddell Sea is considerably less productive than that of the Ross Sea. Our results also indicate that the water of the Antarctic Circumpolar Current (ACC) could be more productive in late spring and early summer than at the beginning of spring. Possible reasons for the differences among the three subsystems (Ross Sea, Weddell Sea and ACC) are discussed.     

JGOFS studies in the equatorial Pacific

This special issue is the third and final volume containing results from the JGOFS Process Study in the equatorial Pacific. Most of the Study in the equational Pacific. Most of the contributions evolved either from the US JGOFS workshop in 1994 on the equatorial Pacific in Scottsdale, AZ or from the NATO Advanced Research Workshop on the Carbon Cycle of the Equatorial Pacific in 1995 in Noumea, New Caledonia.     

The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.     

Variability in concentration of suspensates in an estuarine environment

Three data sets of suspensate concentrations, collected under different sampling plans, were analyzed to develop a minimal sampling period, consistent with a predetermined precision. Individual samples collected during any part of a given day were within ±50% of the daily average. In the main channel of the estuary, a monthly sampling scheme closely approximated a weekly pattern; however, seasonal sampling was unsatisfactory. Outside the main channel, weekly, monthly, and seasonal sampling patterns did not differ greatly. Variability in suspensate concentrations must be considered when calculating sediment flux in estuarine and coastal waters.     

Spectral-temporal structure of variations in the atmospheric total ozone in central Eurasia

The results of long-term (1980–2003) systematic measurements of the total ozone content at the Issyk Kul station (42.6° N, 77.0° E; 1650 m above sea level) are presented. The statistical characteristics and spectral structure of variations in the total ozone and the main tendencies of its temporal variability are determined. It is found that the total ozone content decreased in 1980–2003 at an average rate of (?1.29±0.08) DU/yr. The results of Fourier and wavelet analyses have shown that only oscillations with periods of 12, 27–29, and 102–105 months are rather stable and can be represented as harmonic oscillations. Oscillations with periods shorter than six months have the character of periodically arising pulsations. Among these, oscillations with periods of 27–29 and 34–37 days can be distinguished. It is noted that the spectral-temporal structure of variations in the total ozone content obtained from ground-based measurements at the Issyk Kul station is in good agreement with the corresponding structure obtained from TOMS satellite measurements.