Description: Sorption of trace metals by suspended particulate matter (SPM) in estuarine systems has important implications for the fate of dissolved metals in these waters. This paper describes the development of a single extraction procedure for SPM-associated trace metals, using a ligand competition approach with EDTA as the added complexing ligand. The use of EDTA allows the determination of available particulate trace metals using well defined constraints with respect to the competition for trace metals between EDTA and the particles. Incubation experiments showed that equilibrium times between EDTA and particulate material of 72h were required to reach equilibrium for most of the metals studied (Cu, Zn, Mn, Ni, Co, Al, Fe, Pb and Mg). Optimum conditions included a 0.05M EDTA concentration and the use of an extractant: particulate matter ratio of 200:1 (v:w). Kinetic calculations on data from the incubation experiments were used to calculate the apparent stability constants (K(MeS)) for the metal-particulate matter interaction and indicated values ranging from 10-2.1 for K(MgS) to 10-13.5 for K(CuS). Copyright (C) 1999 Elsevier Science B.V.

Description: 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.

Description: Eight techniques for cleaning particulate material and epibionts from the tissue of Fucus vesiculosus were tested on seaweed collected from a metal-contaminated estuary in the southwest of England. When assessed by scanning electron microscopy, only one was found to have efficiently removed the particulate material on the tissue. This technique consisted of applying a 1:9 ethanol:seawater mixture to the surface of the thallus, and scraping with a PTFE spatula. Analysis of Cu, As, Fe, Mn, and Zn content in the tissues cleaned by this technique showed that, in this case, only Fe concentrations decreased significantly when compared to tissue cleaned by rinsing in seawater only. The study is the first to systematically assess cleaning techniques for marine macroalgae and illustrates the need for standard methods for the sampling and analysis of seaweed tissue

Description: 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 (FeR) and total iron (FeT) in unfiltered samples, while dissolved iron (FeD) was measured by GFAAS after extraction of filtered sea water. FeR was defined by the amount of iron that complexed with 20 μM 1-nitroso-2-napthol (NN) at pH 6.9. FeT 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 FeR, 10.0 nM for FeT and 1.7 nM for FeD were obtained for the area sampled. FeR concentrations increased towards the south of the area investigated, as a result of the increased influence of continental run off. FeR concentrations were found to be enhanced below the nutricline (below ∼40 m) as a result of the remineralisation of organic material. Enhanced levels of FeT 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. FeD concentrations varied between values similar to those of FeT in samples from the north of the area to values similar to those of FeR in the south. The bloom was thought to have influenced the distribution of both FeR and FeT, but less evidence was observed for any influence on FeR and FeD. 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.

Description: Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe-R) in the absence and presence of 2 mu M Dp, Fe-R being defined as that which was complexed by 20 mu M NN at pH 6.9 in the presence of 1.8 mM H2O2 and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe-R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe-R, iron(III) and iron(II), respectively, using a 60 s deposition time. The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe-R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.

Description: Exposure of Fucus spiralis germlings to precise copper concentrations (0 to 844 nM Cu2+) in chemically defined medium demonstrated a relationship between urltrastructural changes and growth retardation with increasing copper concentration. Electron-translucent vesicles, present in ova, which normally disappear after fertilization, accumulated in germlings exposed to Cu2+ above 10.6 nM, suggesting that copper may inhibit a metabolic pathway involved in cell wall formation which is initiated by fertilization No membrane damage was observed during the exposure period. During a post-exposure period in copper-free medium, recovery occurred (rhizoid extension, apical hair formation) in germlings previously exposed to concentrations below 106 nM Cu2+ and electron-translucent vesicles became granular and disappeared. It is proposed that the electron-translucent vesicles contain a cell wall precursor and that copper inhibits its incorporation into the cell wall, preventing growth and development of the zygote.

Description: The growth of Fucus vesiculosus L, germlings in chemically defined culture media containing a range of Cu concentrations (20-1000 nM) was monitored simultaneously with measurement of the Cu speciation in the media by competitive equilibrium-adsorptive cathodic stripping voltammetry, Fucus vesiculosus germlings were found to exude Cu-complexing Ligands with conditional stability constants of the order of 1.6 x 10(11), Ligand concentrations increased with increasing total dissolved Cu concentrations (Cu-T) until a concentration of 500-800 neq Cu.L-1 was reached. Concentrations of the ligand exceeded Cu-T in treatments containing 20 and 100 nM Cu-T were similar to Cu-T in the 500-nM Cu treatment, but were less than Cu-T in the 1000-nM treatment. Therefore, [Cu2+] were calculated to be at concentrations of 10(-11) - 10(-10) M in the 20- and 100-nM treatments, 10(-9) M in the 500-nM treatment, and 10(-7) M in the 1000-nM treatment, Growth rates were lowest at Cu2+ concentration 〉 10(-9). These results are discussed within the context of the potential roles for exuded copper-complexing ligands