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 fate of dumped sediments monitored by a high-resolution multibeam echosounder system,Weser Estuary,German Bight

With the development of high-resolution multibeam echosounder systems (MBES) for surveying shallow-water areas a new tool is available to monitor rapid changes in seabed morphology as, e.g., caused by the dumping of dredge spoil in coastal waters. In this study, four data sets of repeated bathymetric surveys with a MBES were processed and analyzed. The data were collected in a 1.94-km² dumping site in the outer Weser Estuary (German Bight). Between June and December 1998, 2.6 million m³ of dredged sediment were deposited there. The bathymetric maps generated in the course of this study reveal features such as subaqueous dunes, scour holes, and mounds of dumped dredge spoil. The mean water depth decreased by about 1 m during the dumping period. Furthermore, difference grids showing changes in sediment volume allowed a calculation of the sediment budget for the monitored area. After a time period of only 5 months, 0.5 million m³ of the originally dumped 2.6 million m³ of dredge spoil had already been removed from the dumping site.     

Diet shifts of Caribbean grunts (Haemulidae) and snappers (Lutjanidae) and the relation with nursery-to-coral reef migrations

The spatial size distribution of grunts and snappers have previously indicated the separation of juveniles in nursery habitats from the adults on the coral reef. This implies life cycle migrations from nursery habitats (such as seagrass beds and mangroves) to the coral reef. If diet shifts are related to such migrations, then the diets of these fish must change before or around the fish size at which such migrations take place. A wide size range of juveniles of two grunt species (Haemulon sciurus and Haemulon flavolineatum) and of two snapper species (Lutjanus apodus and Ocyurus chrysurus) were caught in seagrass beds and mangroves, and their gut contents identified and quantified. Regression analysis between fish size and dietary importance of small crustaceans showed a negative relationship in all four species. Positive relations were found for H. sciurus, L. apodus and O. chrysurus between fish length and the dietary importance of decapods, and for L. apodusand O. chrysurus between fish length and prey fish importance. Critical changes in the fish diets with fish size were examined by application of a Canonical Correspondence Analysis (CCA). The CCA yielded three clusters of size-classes of fishes with similar diets, and application of a Mantel test showed that each of these clusters had significantly different diets, and that each cluster diet was significantly specialised. The size at which a fish species ‘switched’ from one cluster to another was compared with size-at-maturity data and with the typical size at which these species migrate from the nursery habitats to the coral reef. H. sciurus and H. flavolineatum may be prompted to migrate from the nursery habitats to coral reef habitats because of dietary changes, or because of the development of the gonads. For L. apodus and O. chrysurus, a dietary changeover forms a more likely explanation for nursery-to-reef migrations than does sexual maturation because these species reach maturity at sizes much larger than the maximum size of individuals found in nursery habitats. Although other factors may theoretically initiate or promote the migration patterns, the results of this study indicate that ontogenetic dietary changes may crucially influence the nursery-to-coral reef migrations of these reef fish species.     

Distribution of trace and major elements in sediment and pore waters of the Lena Delta and Laptev Sea

Sediment cores collected during the SPASIBA expedition in 1991 were analysed for their trace- and major element concentrations. Leachable (0.1 N HCl) as well as residual concentrations were determined. Fe and Mn were measured in the interstitial waters to characterize redox conditions. Lateral distribution patterns of solid phase Cu, Cd, Ni, Pb and Zn show a small increase in concentration from the Lena Delta in seaward direction. In general concentrations of these metals are very low and similar to natural background values. With some exceptions, solid phase profiles with depth of all investigated elements do not show strong variations. No enrichment of Pb and Zn in surface layers was found. Remobilization processes and transport of particles enriched in Mn are responsible for Mn accumulation in a particular area. Pore-water concentrations of dissolved Mn in the latter sediments are very high (> 700 μM) and suggest strong Mn reduction directly below the sediment-water interface. In contrast to Mn, the depth profiles of Cd show a surface layer with lower concentrations and an increase deeper down the sediment. The C/N ratio in the sediment decreases from 13 in the Lena mouth to 9 in the more marine part of the Laptev Sea. Surface sediments in the Laptev Sea are very uniform and homogeneous and show only small concentration gradients.     

Prolonged Magmatic and Tectonic Development of the Caribbean Igneous Province Revealed by a Diving Submersible Survey

Using the diving submersible survey NAUTICA we investigated the central part of the Caribbean large igneous province (CLIP) to observe and sample internal portions of this proposed oceanic plateau. Most of the samples are gabbroic and doleritic rocks; basalts are scarce. Radiometric dating by ⁴⁰Ar/³⁹Ar incremental heating experiments indicate that the intrusive rocks are Campanian in age (81–75 Ma). In some places these intrusive rocks underlie older Santonian (85–83 Ma) extrusive basaltic rocks, suggesting that the Campanian rocks represent a sill injection and an underplating episode. Results of the diving program supplemented by information from ODP and DSDP drilling sites document a 20 m.y. period (94–75 Ma) of igneous activity in the submerged portion of the Caribbean large igneous province (CLIP). In the northern part of the Beata Ridge late Campanian and/or post Campanian uplift is documented by prominent Maastrichtian (71–65 Ma) erosion and the establishment of a Paleocene-middle Eocene (65–49 Ma) carbonate platform. During and after the uplift an extensional period is indicated by seismic images and the subsidence (3 km depth) of the carbonate platform. Paleocene ages (55–56 Ma) determined on some volcanic samples are attributed to localised decompression mantle melting that accompanied the extension. We document a prolonged period of magmatic and tectonic events that do not fit with the current models of short-lived plateau formation during mantle plume initiation but shares many similarities with the constructional histories of other oceanic large igneous provinces.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Genetic Relationships Among One Non-Endemic and Two Endemic Mediterranean Triplefin Blennies (Pisces, Blennioidei)

Abstract. Three triplefin blennies occur sympatrically in the Mediterranean Sea; Tripterygion tripteronotus and T. melanurus are endemic, whereas T. delaisi is also found in the Eastern Atlantic. Although very similar in morphology, ecology and behaviour, some striking differences exist among reproductive strategies. Several authors proposed hypotheses on the evolution of these species. In order to enhance insight into the genetic structure of this genus, an enzyme electrophoretic survey was performed. Samples of 40 to 45 specimens of each species were collected near Calvi (Corsica, France). Twenty-four enzyme loci were analysed, of which 17 appeared polymorphic. T. delaisi showed a high level of average observed heterozygosity (H_o) of 0.140, as opposed to very low levels of 0.009 and 0.021 in T. tripteronotus and T. melanurus , respectively. Nei's genetic distance was 0.21 between T. delaisi and T. tripteronotus , 0.35 between T. delaisi and T. melanurus and 0.45 between T. tripteronotus and T. melanurus . We hypothesise that divergence of these species started before the Pleistocene and that the endemic species survived the Pleistocene glaciations in refugia within the Mediterranean. The possibility that T. tripteronotus and T. delaisi diverged through sympatric speciation is discussed.