Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.     

Species, tissue and gender-related organochlorine bioaccumulation in white-sided dolphins, pilot whales and their common prey in the northwest Atlantic

Organochlorine concentrations were measured in white-sided dolphins, pilot whales, and their prey from the Gulf of Maine and used to identify species, tissue, and gender differences, and trophic transfer trends, in bioaccumulation. Polychlorinated biphenyl concentrations ([PCB]) in dolphin blubber (13 +/- 7.1 micrograms/g fresh wt.) were twice those in pilot whales, but pesticide concentrations (20 +/- 13 micrograms/g fresh) were similar between species. 4,4'-DDE, trans-non-achlor, Cl6(153) and Cl6(138) concentrations were highest. Skin tissues had more recalcitrant organochlorines than the internal organs. Male dolphins bioaccumulated higher concentrations of nonmetabolizable PCBs and hexachlorocyclohexane (HCH) isomers, whereas pilot whales had no gender-related differences in bioaccumulation. Pilot whales, mackerel, and herring had proportionately higher concentrations of DDTs, whereas [PCB] were higher in dolphins and squid. Although these odontocetes feed at the same trophic level and store a similar suite of contaminants, dolphins bioaccumulated higher and potentially hazardous 4,4'-DDE and PCB concentrations from food in their more geographically restricted range.     

The structure,dynamics, and transformation of the estuary lenses in run-off seawater on the shelf of Guinea

Peculiarities of the dynamics and the structure formation in the estuary run-off lenses have been analysed based on field data obtained at the Guinean coast (the central eastern Atlantic Ocean). Attention was paid to the processes of restratification, internal mixing, and exchange in the areas of the frontal zone of the run-off lens and the tidal frontal zone. The stabilization of the front of the estuary run-off lens by means of the periodic washing out of its forepart by tidal upwelling is described. The mechanisms of the energy transformation in the leading part of the lens have been revealed. Effects of run-off and loczalization of transformed waters in the small-scale frontal zones are found. The energy estimations represented will be useful in considering analogous phenomena in other coastal regions.Translated by Mikhail M. Trufanov.     

Composition and quantitative distribution of macrozoobenthos in Amur Bay

The data on the species composition, trophic structure, and distribution of macrozoobenthos in Amur Bay obtained in 2001 are presented. Long-term changes in the benthos are analyzed. In 2001, the total benthos biomass significantly increased, although the parameters of the species richness declined as compared to 1986–1989. In 2001, as well as in the 1970s and 1980s, the benthos trophic structure was characterized by the prevalence of deposit feeders. The entire structure of the benthos is evaluated as an eutrophic one. Eutrophication of the bay is considered to be the most probable cause of the negative changes in the benthic communities of the bay in 2001, as well as 15 years ago.     

Sources and biogeochemical cycling of particulate selenium in the San Francisco Bay estuary

As part of a study of estuarine selenium cycling, we measured the concentration, chemical form (speciation), and distribution of particulate selenium under various river flow conditions in the North San Francisco Bay (from the Golden Gate to the Sacramento and San Joaquin Rivers). We also conducted laboratory studies on the accumulation of selenium by phytoplankton, the critical first step in the transformation of dissolved to particulate selenium. Total particulate selenium concentration in the North SF Bay was relatively constant between high and low flow periods, ranging spatially from 0.05 to 0.35 nmol l⁻¹ and comprising between 5 and 12% of the total water column selenium inventory. Mean concentrations were generally highest in the Carquinez Strait–Suisun Bay region (salinity 0–17) and lowest in Central Bay. However, selenium content of suspended particles varied with river flow, with higher content during low flow (9.76 ± 4.17 nmol g⁻¹; mean ± sd; n = 67) compared to high flow (7.10 ± 4.24 nmol g⁻¹; n = 39). Speciation analyses showed that most particulate selenium is organic selenide (45 ± 27%), with a smaller proportion (typically <30%) of adsorbed selenite + selenate and a varying proportion (35 ± 28%) of elemental selenium. Based on the amount of elemental selenium in the seston (total suspended material), we calculate that resuspension of estuarine sediments could contribute 29–100% of particulate selenium in the water column. While selenium content of SF Bay seston (>0.4 μm) is relatively unenriched compared to phytoplankton (13.6–155 nmol g⁻¹ dry weight) on a mass basis, when normalized to carbon or nitrogen, seston contains a similar selenium concentration to SF Bay sediments or phytoplankton cultures. SF Bay seston is thus comprised of selenium-rich phytoplankton and phyto-detritus, but also inorganic clay mineral particles that effectively “dilute” total particulate selenium. Selenium concentrations in algal cultures (11 species) exposed to 90 nmol l⁻¹ selenite show relatively large differences in selenium accumulation, with the diatoms, chlorophytes and cryptophytes generally having lower selenium cell content (3.8 ± 2.7 × 10⁻⁹ nmol selenium cell⁻¹) compared to the dinoflagellates (193 ± 73 × 10⁻⁹ nmol selenium cell⁻¹). Because phytoplankton are such a rich (but variable) source of selenium, their dynamics could have a profound effect on the particulate selenium inventory in the North SF Bay.     

Methods of fitting the Fisher-Tippett type 1 extreme value distribution

Methods are described for estimating the parameters of the Fisher-Tippet Type 1 extreme value distribution and associated return values from measured extremes, such as maximum wave height. A comparison of these methods, with simulated data, shows that those using Gumbel's plotting position are least satifactory. Maximum likelihood methods give the smallest mean square errors, but the very much simpler method of moments is nearly as good.     

Local buckling strength of ring stiffened cylindrical shells under external pressure

The paper presents a non-linear buckling analysis of ring stiffened cylindrical shells subject to external pressure. The collapse pressure is calculated by assuming failure to occur when the material reaches a plastic stress state defined by the Ilyushin criterion. It is shown in the paper that use of the non-linear theory can reduce the estimated first yield by up to 25% in comparison to the linear buckling analysis used up to now. Comparison of predicted failure loads are in good agreement with the lower bound of test results.