Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM

The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 10¹⁹ and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.     

Plastic buckling of ring-stiffened conical shells under external hydrostatic pressure

The paper describes experimental tests carried out on three ring-stiffened cones that were tested to destruction under external hydrostatic pressure. The cones were carefully machined from EN1A Steel. All three cones failed by plastic non-symmetric bifurcation buckling in a mode commonly known as general instability. In this mode the entire ring-shell combination buckles bodily.The paper also provides a design chart using the results obtained from these three vessels, together with the results of six other vessels obtained from other tests. The design chart allows the possibility of obtaining a plastic knock down factor, so that the theoretical buckling pressures, based on elastic theory, can be divided by the plastic knockdown factor, to give the predicted buckling pressure. This method can also be used for the design of full-scale vessels.     

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.     

Geomorphological evidence for upslope canyon-forming processes on the northern KwaZulu-Natal shelf,SW Indian Ocean,South Africa

A geomorphological and statistical analysis of slope canyons from the northern KwaZulu-Natal continental margin is documented and compared with submarine canyons from the Atlantic margin of the USA. The northern KwaZulu-Natal margin is characterized by increasing upslope relief, concave slope-gradient profiles and features related to upslope growth of the canyon forms. Discounting slope-gradient profile, this morphology is strikingly similar to canyon systems of the New Jersey slope. Several phases of canyon incision indicate that downslope erosion is also an important factor in the evolution of the northern KwaZulu-Natal canyon systems. Despite the strong similarities between the northern KwaZulu-Natal and New Jersey slope-canyon systems, key differences are evident: (1) the concavity of the northern KwaZulu-Natal slope, contrasting with the ∼linear New Jersey slope; (2) the relative isolation of the northern KwaZulu-Natal canyons, rather than the dense clustering of the New Jersey canyons; and (3) the absence of strongly shelf-breaching canyons along the northern KwaZulu-Natal margin. In comparison with the New Jersey margin, we surmise a more youthful stage of canyon evolution, a result of either the canyons themselves being younger or the formative processes being less active. Less complicated patterns of erosion resulting from reduced sediment availability have developed in northern KwaZulu-Natal. The reduction in slope concavity on the New Jersey margin may be the result of grading of the upper slope by intensive headward erosion, a process more subdued—or less evident—on the KwaZulu-Natal margin.     

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     

An evaluation of metal bioaccessibility in estuarine sediments using the commercially available protein, bovine serum albumin

The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L^− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment.     

Can turbidity caused by Corophium volutator (Pallas) activity be used to assess sediment toxicity rapidly?

The standard toxicity test organism, Corophium volutator, exhibits a behavioural response to contaminated sediments that causes increased turbidity of overlying water. We quantify the effects of this response to an estuarine sediment spiked with copper and hydrocarbon contaminated sediments from an oil installation in the North Sea. Turbidity measured 24 h after the start of a toxicity test shows a strong relationship with contaminant concentrations and with mortality after 10 days. Turbidity measurements can therefore give a rapid indication of sediment toxicity, permitting a reduction in storage time of sediments to be used in dilution series and toxicity identification evaluation (TIE) tests, reducing the likelihood of contaminants degrading prior to testing.     

Primary production in the eastern tropical Pacific: A review

The eastern tropical Pacific includes 28 million km² of ocean between 23.5°N and S and Central/South America and 140°W, and contains the eastern and equatorial branches of the north and South Pacific subtropical gyres plus two equatorial and two coastal countercurrents. Spatial patterns of primary production are in general determined by supply of macronutrients (nitrate, phosphate) from below the thermocline. Where the thermocline is shallow and intersects the lighted euphotic zone, biological production is enhanced. In the eastern tropical Pacific thermocline depth is controlled by three interrelated processes: a basin-scale east/west thermocline tilt, a basin-scale thermocline shoaling at the gyre margins, and local wind-driven upwelling. These processes regulate supply of nutrient-rich subsurface waters to the euphotic zone, and on their basis we have divided the eastern tropical Pacific into seven main regions. Primary production and its physical and chemical controls are described for each.Enhanced rates of macronutrient supply maintains levels of primary production in the eastern tropical Pacific above those of the oligotrophic subtropical gyres to the north and south. On the other hand lack of the micronutrient iron limits phytoplankton growth (and nitrogen fixation) over large portions of the open-ocean eastern tropical Pacific, depressing rates of primary production and resulting in the so-called high nitrate-low chlorophyll condition. Very high rates of primary production can occur in those coastal areas where both macronutrients and iron are supplied in abundance to surface waters. In these eutrophic coastal areas large phytoplankton cells dominate; conversely, in the open-ocean small cells are dominant. In a ‘shadow zone’ between the subtropical gyres with limited subsurface ventilation, enough production sinks and decays to produce anoxic and denitrified waters which spread beneath very large parts of the eastern tropical Pacific.Seasonal cycles are weak over much of the open-ocean eastern tropical Pacific, although several eutrophic coastal areas do exhibit substantial seasonality. The ENSO fluctuation, however, is an exceedingly important source of interannual variability in this region. El Niño in general results in a depressed thermocline and thus reduced rates of macronutrient supply and primary production. The multi-decadal PDO is likely also an important source of variability, with the ‘El Viejo’ phase of the PDO resulting in warmer and lower nutrient and productivity conditions similar to El Niño.On average the eastern tropical Pacific is moderately productive and, relative to Pacific and global means, its productivity and area are roughly equivalent. For example, it occupies about 18% of the Pacific Ocean by area and accounts for 22–23% of its productivity. Similarly, it occupies about 9% of the global ocean and accounts for 10% of its productivity. While representative, these average values obscure very substantial spatial and temporal variability that characterizes the dynamics of this tropical ocean.