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.     

The distribution of total and electrochemically available copper in the northwestern atlantic ocean

Copper in a series of samples from the northwestern Atlantic has been determined by anodic stripping voltammetry (ASV) and atomic absorption spectrometry after preconcentration by cobalt—APDC coprecipitation. Samples from a transect across the continental shelf directly off the New York Bight showed a linear relationship between total copper and salinity (31–34‰) and less than 5% of the total copper was detectable by ASV. A slope water station showed less than 9% of the total copper to be ASV detectable in the upper 780m, below which the ASV detectable copper increased to 70% at 3000 m. The Sargasso Sea profiles showed less than 7% ASV detectable copper in the upper 150 m; the fraction of the total copper detected by ASV increased to about 80% of the total copper at greater depths. The reduced availability of copper to the ASV measurement in coastal waters and open ocean surface waters appears to be related to recent contact with waters where biological productivity occurs.     

Preservation of enzymic activity in marine plankton by low-temperature freezing

The measurement of enzymic activity in plankton communities is useful in the study of marine ecosystems. Such measurements can lead to a clearer understanding of the biological transformations in plankton communities at a particular time. However, the assays are somewhat time-consuming. To facilitate analysis of large numbers of samples, we have developed a method of quick-freezing of whole cells and of cell-free extracts of the diatom, Skeletonema costatum, followed by storage at ?60°C for up to one week. No loss in either the electron transport system (ETS) or the glutamate dehydrogenase (GDH) activity occurs. Similar conditions of storage can be used for the preservation of ETS activity in the marine copepod Calanus pacificus. Also, no measurable loss in either the GDH or the ETS activity is detectable after the quick-frozen whole cells of S. costatum have been kept frozen for over a year.     

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.