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.     

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.     

Acoustic reflectors in the surface layers of deep sea sediments

Using ultrasonic scanning it is possible to display the position of an acoustic discontinuity within a sediment core and the amplitude of the reflected signal which results from it. From these results it has been possible to examine the effect of variations in the geotechnical properties on the reflection of compressional waves at normal incidence within the core at a frequency of 100 kHz. The occurrence of acoustic reflectors in the surface layers of North Atlantic sediments has also been examined.Two ultrasonic scanning systems for the non-destructive testing of marine sediment cores have been developed. The performance of the two systems has been evaluated using the results from measurements made on a suite of marine sediment cores from the North Atlantic in conjunction with X-ray scanning and geological analysis of the same cores.     

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.     

Chlorinated hydrocarbons in seawater: Analytical method and levels in the northeastern Pacific

A method is described for analyzing nanogram quantities of chlorinated hydrocarbons from 1-1 samples of seawater. Seawater samples are pumped through a copper column containing a mixture by weight of 5% activated carbon powder, 10% MgO and 85% refined diatomaceous earth. The chlorinated hydrocarbons in the seawater are adsorbed or trapped on the column and subsequently eluted with 30% benzene in acetone (v/v) for analysis by gas-liquid chromatography.This procedure was used to analyze chlorinated hydrocarbon levels in samples collected off the southern California coast. We suggest that anthropogenic chlorinated hydrocarbons can be used for the investigation of large-scale ocean currents and mixing processes.