Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.     

Spatio-temporal variability of small copepods (especially Oithona plumifera) in shallow nearshore waters off the south coast of South Africa

Although small copepods are one of the main dietary sources for many commercially important fish, their role in the pelagic trophic dynamics has traditionally been underestimated due to the methodology commonly used in plankton sampling. Temporal variation in abundance of adults and nauplii of small copepods (particularly Oithona plumifera) in nearshore waters on the south coast of South Africa was investigated fortnightly over 14 months at site (km) and location (100 m) scales. Sampling was within <500 m of the shore, where depth was ca. 10 m, using vertical hauls of an 80-μm mesh plankton net from 1 m above the seabed to the surface. Twenty-seven adult copepod taxa were recorded, but Oithona spp. was consistently the most abundant. Taxon richness was 7–19 on each sampling occasion. There was strong temporal variation (Oithona varied between 0 and 2300 m⁻³), but much of this was short-term variability (e.g. between consecutive sampling sessions), with no seasonality or other long-term discernable patterns. There were periods of consistently low numbers, but very high numbers often followed samples with low abundances. Nor was there spatial structure at the location scale, though numbers differed between sites. Despite considerable variability at the location scale within sites, Kenton consistently showed higher densities than High Rocks. Separate analyses, with Bonferroni adjustment, showed that this difference was significant on eight out of 21 occasions for Oithona, six for other pelagic copepods and three for nauplii. This suggests that hydrodynamics favour aggregation of plankton at Kenton. A high degree of short-term variability, with a tendency for aggregation of small zooplankton at certain sites has implications for both pelagic processes and food-web links between the benthic and pelagic environments.     

Evaluation of long-term extreme response statistics of jack-up platforms

This paper is concerned with the models appropriate for the dynamic assessment of jack-ups, concentrating particularly on the long-term response due to random ocean waves and on work-hardening plasticity models used for spud-can response. A methodology for scaling of short-term statistics, calculated using a Constrained NewWave technique, is shown in a numerical experiment for an example jack-up and central North Sea location. The difference in long-term extreme response statistics due to various footing assumptions is emphasised. Results for two environmental load conditions are described (one excluding and one including wind and current effects) and the role of sea-state severity in the variation of short-term extreme response statistics is also highlighted.     

Cloning of a chub metallothionein cDNA and development of competitive RT-PCR of chub metallothionein mRNA as a potential biomarker of heavy metal exposure

Metallothionein has been assayed in a range of aquatic animal tissues as an indicator of metal exposure. We sequenced chub (Leuciscus cephalus) metallothionein cDNA which showed over 90% homology to common carp, goldfish and stone loach and 77% homology to rainbow trout sequences for metallothionein. We then used the extended primer method to develop an accurate quantitative competitive RT-PCR assay for metallothionein mRNA. RT-PCR was used to measure metallothionein mRNA in feral chub from a range of field sites, with different levels of heavy metal pollution, in the West Midlands, UK. Measurements were complemented by analysis of liver and gill metallothionein protein by capillary electrophoresis. There was no significant difference in the metallothionein protein levels between fish of different rivers and there was no evidence of elevation of mRNA at the sites of highest metal exposure. The level of metal exposure (e.g. zinc, nickel and cadmium each ranging between 15 and 28 microg/l ) at the pH (7.5-8.5) of these rivers appears insufficient to elevate hepatic or gill metallothionein in chub. A lack of elevation of hepatic metallothionein mRNA in chub exposed to zinc, copper and manganese for 24 h and 10 days in the laboratory also suggests a non-responsiveness of this species.     

Distributions of dissolved and particulate biogenic thiols in the subartic Pacific Ocean

Dissolved and particulate concentrations of the biogenic thiols cysteine (Cys), arginine–cysteine (Arg–Cys), glutamine–cysteine (Gln–Cys), γ-glutamate–cysteine (γ-Glu–Cys) and glutathione (GSH) were measured in the subartic Pacific Ocean in the summer of 2003 using high performance liquid chromatography (HPLC) with precolumn derivatization as reported in previous work. In this study, a preconcentration protocol for the derivatized thiols was utilized to extend detection limits of dissolved thiols to picomolar levels. The measured concentrations of particulate and dissolved thiols were uncoupled, with distinctive depth profiles and large differences in the particulate to dissolved ratios between individual compounds. Glutathione was the most abundant particulate thiol whereas the most abundant dissolved thiol was γ-Glu–Cys, with concentrations as high as 15 nM. Given the relatively small pool of intracellular γ-Glu–Cys and the very low dissolved concentrations of GSH, we hypothesize that glutathione released from cells is rapidly converted to the potentially degradation resistant γ-Glu–Cys outside the cell. The relatively high concentrations of other dissolved thiols compared to particulate concentrations implies both biological exudation and slow degradation rates. Some thiols appear to vary with changes in nutrient availability but this effect is difficult to decouple from changes in community structure inferred from pigment analyses. Dissolved thiol concentrations also exceed typical metal concentrations in the subartic Pacific, supporting previous arguments that they may be important in metal speciation.     

Nature of the connection between the Northern and Southern Zechstein Basins across the Mid North Sea High

The seismic expression of a salt-filled channel which cuts across the Mid North Sea High in Quadrant 37 is described, with features interpreted as being produced by salt-edge dissolution forming both eastern and western margins of the channel. The apparent half-graben nature of the channel is shown to be only superficial, and due to complex faulting associated with, but not defining, its western margin. The shallower faulting here is a Mesozoic to early Tertiary growth fault related to local dissolution of Zechstein salt. The dissolution effect appears in turn to have been localized by the presence of a deeper fault that was already downthrown to the east in Zechstein times, when it seems to have limited the eastward progradation of Zechstein shelf carbonates and anhydrites, and had probably ceased to move significantly before the onset of the Late Cimmerian erosional phase. The origin of this arcuate fault is tentatively ascribed to subsidence around a granite batholith. Zechstein salt originally spread some distance to the east and west of the channel; it was dissolved from the edges inwards, mainly before the Late Cretaceous, giving rise to a thicker Mesozoic sequence on parts of the flanks of the channel than in the middle. Besides providing an interesting structural case history, the features described have implications regarding Zechstein sedimentation, reservoir potential, the tectonic history of the North Sea, and the nature of the Mid North Sea High itself.     

Fishers' responses to management measures and their socio-economic effects

This session presented a wide range of papers on cooperativeresearch, design of alternative gears and fishing strategies,and new analyses to support management. The contributed papersreflected a real desire to explore different approaches andstrategies to fishery management. It is apparent that fishery policy has had a mixed record ofsuccess and failure at best. In most regions of the world, manystocks are still being overfished or have been severely overfishedin the past. Although rebuilding programmes for overfished stockshave been developed, nationally as well as internationally,only a few have been successful, many others are works in progressand, in too many cases, rebuilding     

Variability of hydrodynamic load predictions for a tension leg platform

A survey of diffraction/radiation analyses has been performed on behalf of the International Ship and Offshore Structures Congress, Committee I.2. This paper presents the results from the survey, including data from 17 organisations plotted in a common format. The variability of the computed hydrodynamic loads and responses is discussed, and it is concluded that there is a degree of uncertainty in results predicted on the basis of commonly used idealisations. Even in long period waves the variability between the computed results is considerable. To obtain reliable results at the shorter periods associated with heave, pitch and roll resonances of a deep water TLP, much finer meshes than those used by most of the participating organisations would be required.