Holocene and late glacial palaeoceanography and palaeolimnology of the Black Sea: Changing sediment provenance and basin hydrography over the past 20,000 years

The elemental geochemistry of Late Pleistocene and Holocene sediments of the Black Sea, recovered in box cores from the basin margins and a 5-m gravity core from the central abyssal region of the basin, identifies two terrigenous sediment sources over the last 20 kyrs. One source region includes Anatolia and the southern Caucasus; the second region is the area drained by rivers entering the Black Sea from Eastern Europe. Alkali metal:Al and heavy:light rare-earth element ratios reveal that the relative contribution of the two sources shifted abruptly every few thousand years during the late glacial and early Holocene lacustrine phase of the basin. The shifts in source were coeval with changes in the lake level as determined from the distribution of quartz and the heavy mineral-hosted trace elements Ti and Zr.The geochemistry of the abyssal sediments further recorded a sequence of changes to the geochemistry of the water column following the lacustrine phase, when high salinity Mediterranean water entered the basin beginning 9.3 kyrs BP. Bottom water that had been oxic throughout the lake phase became anoxic at approximately 8.4 kyrs BP, as recorded by the accumulation from the water column of several redox-sensitive trace metals (Mo, Re, U). The accumulation of organic carbon and several trace nutrients (Cd, Cu, Ni, Zn) increased sharply ca. 0.4 kyrs later, at 8.0 kyrs BP, reflecting an increase of primary productivity. Its increase was coeval with a shift in the dinoflagellate ecology from stenohaline to euryhaline assemblages. During this profound environmental change from the lacustrine to the marine phase, the accumulation rate of the lithogenous sediment fraction decreased as much as 10-fold in response to the rise of the water level in the basin from a low stand ca. 9.3 ka to its current level.     

An autonomous instrument for time series analysis of TCO2 from oceanographic moorings

The design and testing of a robotic analyzer for autonomous TCO₂ measurement from oceanographic moorings is described. The analyzer employs a conductimetric method of TCO₂ measurement wherein CO₂ from an acidified sample diffuses across a semi-permeable membrane into a NaOH solution decreasing the conductivity of the base. The instrument is capable of ～850 analyses over a period of at least six months. It is designed to operate to depths of at least 1000 m. TCO₂ calibration is based on in situ standardization throughout a deployment.We report both laboratory and in situ tests of the analyzer. In the laboratory automated analyses over a period of 38 days at temperatures ranging from 8° to 25 °C yielded a TCO₂ accuracy and precision of ±2.7 μmol/kg. In situ tests were conducted at the WHOI dock with a deployment of 8 weeks at in situ temperatures of 5°–13 °C. The accuracy and precision of TCO₂ analyses over the deployment period, based on in situ calibration, was ±3.6 μmol/kg.Laboratory tests of reagent and standard solution stability are also reported. Standards, based on Certified Reference Material were followed for periods of up to 2 years. In all cases TCO₂ increased. Drift of the standards was the equivalent of ～1 to 3 μmol/kg per 6 months. The conductivity indicator solution was found to be stable for at least 2 months.     

Fatty acid uptake by marine sediment particles

The uptake of oleic acid by various size-fractions of a marine sediment suggests that the finer-grained particles are mainly responsible for fatty acid uptake.     

4D technology: where are we,and where are we going?

4D reservoir monitoring is now becoming established as a normal part of business in some companies, in some regions such as the North Sea, and for some applications, such as thermally enhanced oil recovery. Some spectacular technical successes have been reported, mostly in monitoring water floods. We are beginning to understand how to acquire and process surveys to achieve good results. There is still, however, much to improve in how we use 4D technology to capture its potential value in field management and still some way to go in the tool itself, to make it faster, cheaper and more sensitive to small production effects.     

Siliceous microfossil record of late Holocene oceanography and climate along the west coast of Vancouver Island, British Columbia (Canada)

Diatoms, silicoflagellates, and biogenic silica (BSi) were analyzed from two piston cores recovered from Effingham Inlet, British Columbia. Relatively productive marine conditions from 4850 to 4000 cal yr BP were followed by a transition to the modern ocean-climate regime marked by a decreased siliceous microfossil production since 2800 cal yr BP. This change in the northeast Pacific climate was characterized by an apparent cooling associated with higher rainfall and lower light levels. The reduced abundance of most spring-summer bloom diatom taxa (Skeletonema-Thalassiosira-Chaetoceros) was coupled with a decreased abundance of diatoms normally associated with incursions of offshore water into coastal inlets. This pattern reflected a weaker summer upwelling along Vancouver Island associated with the insolation-related increase in the strength of the Aleutian Low and a weakened North Pacific High. After ca. 2800 cal yr BP, diatom assemblages also indicated more frequent periods of relatively low spring-summer surface water salinity and a disruption of the typical bloom sequence, indicative of increased climatic variability. A period of warmer and drier climate conditions and possibly increased coastal upwelling offshore occurred ca. 1450-1050 cal yr BP. The most recent 500 yr are marked by reduced diatom production and the appearance of three distinct diatom biomarkers in the stratigraphic record (Rhizosolenia setigera ca. AD 1940; Minidiscus chilensis ca. AD 1860; Thalassionema nitzschioides morphotype A, ca. AD 1550). The oceanographic changes recorded in Effingham Inlet are correlative with other marine and terrestrial paleoenvironmental records in the northeast Pacific Ocean.     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

X-ray photoelectron spectroscopic study of ferromanganese nodules: Chemical speciation for selected transition metals

Analysis of manganese nodules, with emphasis on speciation of transition metal components, has been carried out using x-ray photoelectron spectroscopy. In nodules containing predominantly δ-MnO₂, Co(III) was identified from an examination of XPS photopeak structural features. In a nodule composed of todorokite, Cu(II) and Ni(II) were detected in oxide environments, but the quantity of cobalt was insufficient to be studied in detail.     

A study of the geochemistry of suspended particulate matter in coastal waters

The concentrations of Si, Al, Ti, Fe, K, Ca, Mg, P and Mn, before and after chemical leaching, in particulate matter from waters off the west coast of Scotland have been measured in vertical profiles at two seasons. The distribution of Si and Ca are shown partly to reflect temporal changes in biological production in different waters. The distributions of Al, Ti, Fe, K and Mg have been used to distinguish different sources and types of suspended alumino-silicates, and to trace probable circulation patterns in the water mass.While Si and Ti contents of the particulate matter are unaffected by mild chemical leaching, large amounts of other elements, notably Mg, K and Al, can be removed by this treatment. Presumably, these losses indicate preferential release of these elements from octahedral and interlayer sites in clay mineral lattices.The distribution of particulate P covaries with non-silicate Fe in the surface waters, while in bottom waters, high concentrations of particulate Fe and Mn are associated. The relationship of Fe and P is considered to be due to the presence of particulate ferriphosphates derived from runoff. The particulate Mn and Fe in deep waters is produced by the precipitation of dissolved metals released from bottom sediments by diagenesis.     

Settling fluxes in Saanich and Jervis Inlets, British Columbia, Canada: sources and seasonal patterns

We conducted a multi-year sediment-trap experiment in Saanich and Jervis Inlets, British Columbia, Canada. Moorings with traps positioned at three depths were placed near the mouth and toward the head of each fjord, and deployments were monthly. We present fluxes of total mass, biogenic silica (BSi), particulate organic carbon (POC) and aluminium (Al), as well as the δ¹³C signal of the POC, and we compare the sediment-trap fluxes to primary-production measurements made during the experiment.Diatomaceous silica and aluminosilicates were the primary components of the settling flux, while organic matter from marine (largely diatoms) and terrestrial sources was occasionally a significant portion of the sinking material. Fluxes of BSi and POC were highest in the spring and summer, tracing maxima in local primary production. These fluxes decreased, increased or remained constant with depth due to water-column remineralisation and variability in processes that cause fluxes to increase with depth. Al fluxes followed local precipitation and river runoff at the landward stations, and with remarkable faithfulness in Saanich Inlet. Near the mouths, there was little seasonality in Al flux, and the increases of flux with depth reveal sedimentary plumes at each fjord’s sill. Tidal and deepwater-renewal components of the plumes are evident, and the plume in Saanich Inlet was particularly intense. Fluxes of Al to deep sediment traps associated with renewal flows were also observed toward the head of each fjord.Marine δ¹³C endmembers are estimated from relationships between δ¹³C and BSi concentrations, and measures of soil δ¹³C from each fjord were available. These endmembers are used with the δ¹³C record to quantify marine and terrigenous contributions to the POC flux. Marine POC composed 54-72% of the total POC caught by shallow sediment traps in spring and summer, and 36-54% in fall and winter. Primary production and sediment-trap fluxes are used to estimate annually averaged export ratios (shallow-trap flux:autotrophic assimilation) for marine POC and Si. POC export ratios (0.092-0.14) were low for these productive waters, but they compare with other results based on sediment-trap fluxes from coastal waters where terrigenous OC has been subtracted. Export ratios of Si were calculated using an estimated Si:C assimilation ratio and, therefore, are susceptible to error, but the high results (>0.8) suggest that BSi was exported more efficiently than POC. The possibility that POC was preferentially lost after interception by sediment traps is also considered. Primary production and settling fluxes were higher in Saanich Inlet than in Jervis Inlet, while export ratios of OC and Si were similar in both fjords, away from the nepheloid layer near the sill of Saanich Inlet.