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.     

Late-Quaternary supply of terrigenous organic matter to the Congo deep-sea fan (ODP site 1075): implications for equatorial African paleoclimate

Late-Quaternary sections (about 1 Ma) from the Congo deep-sea fan (ODP Leg 175, site 1075) were used to reconstruct the terrigenous organic matter supply to the easternmost equatorial Atlantic Ocean. Variations in quantity and quality of the riverine organic matter reflect the interaction between the paleoclimatic development within the continental catchment area and the paleoceanographic conditions in the Congo river plume. To characterize the delivery of organic matter from terrigenous and marine sources, we used elemental and bulk carbon isotopic analyses, Rock-Eval pyrolysis, lignin chemistry, and organic petrology. High-amplitude fluctuations occurring about every 15-25 ka reveal a mainly precessional control on organic sedimentation. Results from Rock-Eval pyrolysis indicate a mixed kerogen type III/II, as would be anticipated in front of a major river. Fluctuations in T_max from Rock-Eval pyrolysis demonstrate pronounced cyclic changes in the delivery of low- and high-mature organic matter. Contribution of the low-mature organic fraction was strongest during warm climates supporting enhanced marine production offshore of the Congo. Organic petrological observations confirm the existence of abundant terrigenous plant tissues, both non-oxidized (vitrinite) and oxidized (inertinite). Charcoal-like organic matter (fusinite) is attributed to periods of increased bush fires in the continental hinterland, and implies more arid climatic conditions. Results from ratios of specific phenolic lignin components suggest that terrigenous organic matter in Late-Quaternary sections of site 1075 mainly derives from non-woody angiosperm tissue, i.e., grasses and leaves. Correlation between the amount of specific lignin phenols and the bulk '¹³C_org signature fosters the conclusion that an appreciable amount of the terrigenous organic fraction derives from C4 plant matter. This may cause an underestimation of the terrigenous proportion of bulk organic matter when assessments are based on bulk carbon isotopic signatures alone.     

Trace metals and hydrocarbons in sediments from the Southampton water region,with particular reference to the influence of oil refinery effluent

The concentrations of a number of trace metals (Co, Ni, Cu, Zn, Ag, Cd and Hg) have been determined in sediments from cores collected in the Southampton Water region. Measurements of total hydrocarbons were also made on several of the cores. Markedly elevated concentrations of copper, up to 362 μg/g dry wt, were found in sediments which were collected close to the discharge points of oil refinery outfalls and which also showed concentrations of total hydrocarbons considerably greater than the background levels for the estuary. The results of selective chemical extractions showed that much of the copper was present in the non-lattice fraction of the sediment. Although the concentrations of Co, Ni, Zn and Cd were significantly correlated with those of copper in the core showing the highest concentrations of this element, these metals were not enhanced in comparison with the levels found in several other parts of the estuary. Variations in concentrations of metals in sediments throughout the estuary were not correlated with differences in organic carbon content.     

Alboran Sea late cenozoic tectonic and stratigraphic evolution

Analysis of airgun seismic profiles from the Alboran Sea reveals a complex morphostructure with margins, basins, and structural highs. North of the Alboran Ridge, south-facing margins have a passive style of evolution, with thick progradational sequences of post-Messinian deposits, whereas north-facing margins are tectonized along structural highs with reduced sediment cover. Basins are extensional features developed since the Early Miocene by mechanisms of tectonic escape and pull-apart, under generalized northwest-southeast to north-south compression. Depositional sequences in this semi-land-locked sea were controlled by the local tectonism and influenced by global sea-level oscillations.     

Histopathological biomarkers in estuarine fish species for the assessment of biological effects of contaminants

The increasing emphasis on the assessment and monitoring of estuarine ecosystems has highlighted the need to deploy appropriate biological indices for these locations. Fish diseases and histopathology, with a broad range of causes, are increasingly being used as indicators of environmental stress since they provide a definite biological end-point of historical exposure. This study reports on the histopathological alterations observed in selected organs and tissues of three species of estuarine fish (Platichthys flesus, Pomatoschistus minutus and Zoarces viviparus), captured from four British estuaries (the Tyne, Tees, Mersey and Alde), differently impacted by contaminants, including PAHs. A biannual sampling regime was used to identify the important seasonal variations that occur in terms of the observed biological effects. Inflammatory lesions and hepatocellular fibrillar inclusions attained their highest prevalence in P. flesus captured from the Tyne, Tees and Mersey. The presence of pre-neoplastic and neoplastic toxicopathic lesions was highest in P. flesus captured from these sites, when compared to fish from the Aide reference site. In particular, the prevalence of hepatic foci of cellular alteration (up to 43.3%) and hepatocellular adenoma (up to 10%) were highest in P. flesus captured from the Mersey estuary. Intersex (ovotestis) was only recorded in male P.flesus captured from the Mersey estuary (up to 8.3%) and from male Z. viviparous captured from the Tyne estuary (25%). Pathologies associated with the gill and the kidney were also most prevalent in fish captured from the Tyne, Tees and Mersey estuaries. This study has successfully applied histopathology to an estuarine monitoring program, both for the recording of toxicopathic lesions in the liver and other organs, and for the detection of the endpoint of endocrine disruption, intersex. As such, it provides a powerful integrative tool for the assessment of biological effects of contaminants in these environments.     

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.     

Physical and anthropogenic effects on observed long-term nutrient changes in the Irish Sea

The trend in Irish Sea nutrient concentrations over the last four decades has been considered to reflect changes in anthropogenic loading. Comparison of a long-term database for the Menai Strait, North Wales, with an established historic data set for the Cypris station, Isle of Man, indicates that climate also has a significant influence on observations of nutrient concentrations. Data are presented detailing long-term shifts in nitrate, phosphate and silicate measurements since the 1960s at these two fixed sampling sites in the Irish Sea. Broad systematic changes observed in all three nutrients over the decades show a rise from the 1960s through to the 1980s, followed generally by an overall decline in the 1990s. Decadal-scale salinity changes occur in the opposite sense to nutrient changes. Anthropogenic inputs from freshwater cannot fully account for observed nutrient trends, neither is there evidence for shifts in nutrient concentrations in oceanic waters over the past four decades. Climatically forced movement in the geographical position of the freshwater/seawater mixing zone over a decadal time scale could, however, give rise to the observed shifts in nutrient concentration and salinity. This cannot alter nutrient concentration and salinity per se, but causes the measurements taken at fixed sampling sites to fluctuate inversely over this time scale. It is concluded that there is complex interplay between anthropogenic loading and climate affecting the distribution of nutrients in the Irish Sea.     

Dynamics and control of a towed underwater vehicle system, part I: model development

Autonomous vehicles are being developed to replace the conventional, manned surface vehicles that tow mine hunting towed platforms. While a wide body of work exists that describes numerical models of towed systems, they usually include relatively simple models of the towed bodies and neglect the dynamics of the towing vehicle. For systems in which the mass of the towing vehicle is comparable to that of the towed vehicle, it becomes important to consider the dynamics of both vehicles. In this work, we describe the development of a numerical model that accurately captures the dynamics of these new mine hunting systems. We use a lumped mass approximation for the towcable and couple this model to non-linear numerical models of an autonomous surface vehicle and an actively controlled towfish. Within the dynamics models of the two vehicles, we include non-linear controllers to allow accurate maneuvering of the towed system.