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.     

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.     

Wintertime rates of net primary production and nitrate and ammonium uptake in the southern Benguela upwelling system

The elevated levels of primary productivity associated with eastern boundary currents are driven by nutrient- rich waters upwelled from depth, such that these regions are typically characterised by high rates of nitrate-fuelled phytoplankton growth. Production studies from the southern Benguela upwelling system (SBUS) tend to be biased towards the summer upwelling season, yet winter data are required to compute annual budgets and understand seasonal variability. Net primary production (NPP) and nitrate and ammonium uptake were measured concurrently at six stations in the SBUS in early winter. While euphotic zone NPP was highest at the stations nearest to the coast and declined with distance from the shore, a greater proportion was potentially exportable from open-ocean surface waters, as indicated by the higher specific nitrate uptake rates and f-ratios (ratio of nitrate uptake to total nitrogen consumption) at the stations located off the continental shelf. Near the coast, phytoplankton growth was predominantly supported by ammonium despite the high ambient nitrate concentrations. Along with ammonium concentrations as high as 3.6 µmol l^–1, this strongly suggests that nitrate uptake in the inshore SBUS, and by extension carbon drawdown, is inhibited by ammonium, at least in winter, although this has also been hypothesised for the summer.     

An intercomparison of seawater filtration procedures

Filtration systems, used for the preparation of coastal seawater samples for trace analysis, have been intercompared to determine the extent of contamination arising during the filtration process. The results show that all the systems intercompared are able to provide uncontaminated filtrates for copper, nickel, cobalt and manganese and, with two exceptions, for cadmium and iron, at levels that would be encountered in uncontaminated coastal waters.     

Dissolved copper,zinc and cadmium in the Southern Bight of the North Sea

Concentrations of dissolved copper, zinc and cadmium have been measured in the Dutch and Belgian coastal and offshore regions of the Southern Bight (North Sea), with the aim to compare levels in the central, most saline part of the Bight with those in the coastal region that is under the influence of the rivers Rhine and Scheldt, as well as with those in open ocean surface waters.     

安徽铜陵凤凰山夕卡岩型铜矿床中辉钼矿Re-Os同位素年龄及其地质意义

铜陵矿集区是我国长江中下游Cu-Au-Fe-Mo成矿带中最重要的有色金属基地之一,凤凰山矿床是铜陵矿集区的重要组成部分,为一个典型的夕卡岩型铜矿床。本文利用Re-Os同位素定年方法对凤凰山铜矿床进行了成矿时代测定,获得了辉钼矿的Re-Os同位素模式年龄范围为139.1±2.4～142.0±2.2Ma,等时线年龄为141.1±1.4Ma,与矿区内石英二长闪长岩和花岗闪长岩SHRIMP锆石U-Pb年龄(144.2±2.3Ma)相吻合,也与铜陵地区其他矿田的成矿时代基本一致,可能为岩石圈减薄事件的成矿响应。     

Variability in the speciation of iron in the northern North Sea

Variations in the speciation of iron in the northern North Sea were investigated in an area covering at least two different water masses and an algal bloom, using a combination of techniques. Catalytic cathodic stripping voltammetry was used to measure the concentrations of reactive iron (Fe_R) and total iron (Fe_T) in unfiltered samples, while dissolved iron (Fe_D) was measured by GFAAS after extraction of filtered sea water. Fe_R was defined by the amount of iron that complexed with 20 μM 1-nitroso-2-napthol (NN) at pH 6.9. Fe_T was determined after UV-digestion at pH 2.4. Concentrations of natural organic iron complexing ligands and values for conditional stability constants, were determined in unfiltered samples by titration. Mean concentrations of 1.3 nM for Fe_R, 10.0 nM for Fe_T and 1.7 nM for Fe_D were obtained for the area sampled. Fe_R concentrations increased towards the south of the area investigated, as a result of the increased influence of continental run off. Fe_R concentrations were found to be enhanced below the nutricline (below 40 m) as a result of the remineralisation of organic material. Enhanced levels of Fe_T were observed in some surface samples and in samples collected below 30 m at stations in the south of the area studied, thought to be a result of high concentrations of biogenic particulate material and the resuspended sediments respectively. Fe_D concentrations varied between values similar to those of Fe_T in samples from the north of the area to values similar to those of Fe_R in the south. The bloom was thought to have influenced the distribution of both Fe_R and Fe_T, but less evidence was observed for any influence on Fe_R and Fe_D. The concentration of organic complexing ligands, which could possibly include a contribution from adsorption sites on particulate material, increased slightly in the bloom area and in North Sea waters. Iron was found to be fully (99.9%) complexed by the organic complexing ligands at a pH of 6.9 and largely complexed (82–96%) at pH 8. The ligands were almost saturated with iron suggesting that the ligand concentration could limit the concentration of iron occurring as dissolved species.     

Responses of marine phytoplankton in iron enrichment experiments in the northern North Sea and northeast Atlantic Ocean

Short-term iron enrichment experiments were carried out with samples collected in areas with different phytoplankton activity in the northern North Sea and northeast Atlantic Ocean in the summer of 1993. The research area was dominated by high numbers of pico-phytoplankton, up to 70,000 ml⁻¹. Maximum chlorophyll a concentrations varied from about 1.0 μg l⁻¹ in a high-reflectance zone (caused by loose coccoliths, remnants from a bloom of Emiliania huxleyi) and about 3.5 μg l⁻¹ in a zone in which the phytoplankton were growing, to about 0.5 μg l⁻¹ in the northeast Atlantic Ocean. From the high-reflectance zone to the northeast Atlantic Ocean, nitrate concentrations increased from 0.5 μM to 6.0 μM. Concentrations of reactive iron in surface water showed an opposite trend and decreased from about 2.6 nM in the high-reflectance zone to <1.0 nM in the northeast Atlantic Ocean. In the research area, no signs of true iron deficiency were found, but iron enrichments in the high-reflectance zone, numerically dominated by Synechococcus sp., resulted in increased nitrate uptake. Ammonium uptake was hardly affected. Strong support for the effect of Fe on cell physiology is given by the increase in the f-ratio. Net growth rates of the phytoplankton (changes in cell numbers over 24 h) were almost unchanged. Phytoplankton collected from the northeast Atlantic Ocean, did not show changes in the nitrogen metabolism upon addition of iron. Net growth rates in these incubations were low or negative, with only slightly higher values with additional iron.     

Dissolved aluminium in the Weddell-Scotia Confluence and effect of Al on the dissolution kinetics of biogenic silica

In the Scotia and Weddell Seas the concentration of dissolved Al was 1–1.5 nM in ice-free surface waters, up to 3 nM in ice-covered waters and about 2.6 nM in bottom waters. The solubility and the dissolution rate of diatomaceous silica, obtained from net samples and from incubations in the presence or absence of dissolved Al, were inversely related to solid-phase Al/Si ratios. At in situ temperatures, dissolution rates for Antarctic diatoms are higher than those for diatoms from temperate regions. Effects on distribution patterns of silicic acid in the Weddell Sea are discussed.     

Bioaccumulation and biomarkers in the sea star Asterias rubens (Echinodermata: Asteroidea): a North Sea field study

During two North Sea field trips in March 1995 and September 1996 sea stars, Asterias rubens, were collected at various stations along pollution gradients in order to study the relation between biochemical markers and levels of accumulated contaminants. Biomarkers measured were: cytochrome P450 level, benzo[a]pyrene hydroxylase (BPH) activity, acetylcholinesterase (AChE) activity and DNA integrity. Accumulation levels of heavy metals, polychlorinated biphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons (PAHs) in the pyloric caeca of sea stars indicate different pollution gradients, influenced by rivers in The Netherlands, UK and Germany. For some contaminants, especially PAHs, relatively high levels were found in the central part of the North Sea (Dogger Bank). On the basis of multivariate statistics, stations near the mouth of the Elbe and the Rhine/Meuse were shown to have different patterns of biomarker responses. Sea stars from stations in coastal zones showed relatively high levels of cytochrome P450 and 'P418', another haemoprotein that is present in most marine invertebrates. The station nearest to the Elbe Estuary showed the lowest BPH and AChE activity. DNA integrity was lower especially in stations near the Dutch coast and in a station near the Tees/Tyne estuaries. Using these biomarkers as early warning signals of exposure and/or adverse effects, this type of monitoring can be used also in the future to study the spatial and temporal trends in the quality of coastal waters.