A reevaluation of the oceanic uranium budget for the Holocene

We present a new assessment of the pre-anthropogenic U budget for the Holocene ocean. We find that the gross input of U to the ocean lies in the range 53±17 Mmol/year, where the dominant source is river runoff (42.0±14.5 Mmol/year) and the direct discharge of groundwater could represent a significant additional input (9.3±8.7 Mmol/year). The soluble U flux associated with the aeolian input of crustal dust is minor (1.8±1.1 Mmol/year), falling well within the errors associated with the riverine flux. Removal of U to the organic rich sediments of salt marshes and mangrove swamps during river–sea mixing may significantly modify the riverine flux, such that the net U input is reduced to 42±18 Mmol/year. Evaluation of the U isotope budget demonstrates that the limits we have established on the U input flux are reasonable and suggests that direct groundwater discharge may play a significant role in maintaining the oceanic excess of ²³⁴U. The total sink of U from the ocean lies in the range 48±14 Mmol/year. We find that three major processes control the magnitude of this flux: (1) removal to oxygen-depleted sediments (26.9±12.2 Mmol/year); (2) incorporation into biogenic carbonate (13.3±5.6 Mmol/year); and (3) crustal sequestration during hydrothermal alteration and seafloor weathering (5.7±3.3 Mmol/year). The removal of U to opaline silica (0.6±0.3 Mmol/year) and hydrogenous phases (1.4±0.8 Mmol/year) is minimal, falling well within the errors associated with the other sinks. That the input and output fluxes balance within the calculated errors implies that U may be in steady state in the Holocene ocean. In this case, the input and output fluxes lie in the range 34–60 Mmol/year, giving an oceanic U residence time of 3.2–5.6×10⁵ years. However, given the large uncertainties, a significant imbalance between the Holocene input and output fluxes cannot be ruled out. The constancy of the ancient seawater U concentration implies that the U budget is in steady state over the time period of a glacial–interglacial climate cycle (10⁵ year). A Holocene flux imbalance must, therefore, be offset by an opposing flux imbalance during glacial periods or at the interglacial–glacial transition. We suggest that the storage of U in the coastal zone and shallow water carbonates during interglacial periods and the release of that U at or following the interglacial–glacial transition could be sufficient to affect the short-term stability of the U budget. Providing tighter constraints on U fluxes in the Holocene ocean is a prerequisite to understanding the U budget on the time scale of a glacial–interglacial climate cycle and using this element as a valuable palaeoceanographic proxy.     

Origin and significance of 13-hydroxychlorophyll derivatives in sediments

The authenticity of hydroxychlorophyll derivatives in sediments has been verified by subjecting pure chlorophyll preparations to the extraction method used for sediments. Model studies of chlorophyll autoxidation reveal hydroxychlorophyll as the major product formed in the presence of hydrogen peroxide. Its stability to further oxidation implies that hydroxychlorophyll derivatives are not precursors of aetioporphyrins and are more likely to produce cycloalkanoporphyrins via the processes of diagenesis. The occurrence of 13²-hydroxyphaeophytin a throughout a sediment core from Loch Ness confirms it to be a widespread chlorophyll oxidation product formed during early diagenesis. Profiles of hydroxychlorophyll derivatives in a sediment core from an Antarctic lake demonstrate their potential for use as markers of oxidation processes in palaeoenvironmental assessment.     

Molecular fossils as a tool for tracking Holocene sea-level change in the Loch of Stenness,Orkney

Sediments deposited in the Loch of Stenness (Orkney Islands, Scotland) during the Holocene transgression, previously dated to between ~5939–5612 bp , were analysed for molecular fossils – lipids and chlorophyll pigments from primary producers – that complement conventional microfossil and lithological approaches for studying past sea-level change. While microfossil and lithological studies identified a transgression between 102 and 81 cm core depth, key molecular fossils fluctuate in occurrence and concentration between 118 and 85 cm, suggesting an earlier start to the transgression. Terrestrial lipid concentrations decreased and algal-derived, short-chain, n-alkanoic acid concentrations increased at 118 cm, indicating a disruption of the freshwater lake conditions associated with the early stages of the marine transgression. The lipid and pigment analyses provided information that complements and extends that from microfossil analysis, presenting a more complete record of Holocene sea-level changes and local vegetation changes in the Loch of Stenness. The isostatic stability of Stenness during the Holocene points towards other factors to explain the transgression, such as regional factors and/or melting of the Antarctic ice sheet (which occurred up to 3 ka).     

Field measurement and associated controlling factors for ground water seepage in a piedmont impoundment

Knowledge of groundwater seepage to and from lakes can be an important component of scientific investigations involving water and geochemical budgets. Measurements of groundwater seepage at Lake Anna, a man-made lake in central Virginia, show that inflow to the lake occurs even under dry summer conditions. Seepage rates were found to be correlated with the elevation of the near-shore water table, which responded rapidly to rainfall events in the fractured rock terrane in which Lake Anna is located. Seepage rates did not decline uniformly with distance offshore. This result contrasts with those for lakes underlain by relatively homogeneous porous media where measurements generally confirm the prediction that seepage rates drop off exponentially with distance from shore. The along shore variability of seepage rates in Lake Anna was related to a topographic index that is used to describe drainage from hillslopes. This suggests that seepage in impoundments such as Lake Anna may be strongly controlled by drainage pathways that pre-date the lake.     

THERMOLUMINESCENCE AND THE TERRESTRIAL AGE OF METEORITES

The use of thermoluminescence (TL) to determine the terrestrial age of meteorites is investigated. It is found that meteorites can be divided into two groups. One group, in which members lose their low temperature TL rather rapidly (the “low retentivity” group), may be dated up to about 100 years after fall, although with little accuracy. The other (the “high” group) is more retentive, and may still be dated several hundred years after fall. A meteorite of unknown date of fall may be assigned to the high or low group by laboratory determination of the rate of decay of the low temperature TL. Weathering coats the grains with limonite and lowers the intensity of the TL. The percentage reduction is constant for various intensities, but the peak height ratio is changed. Therefore, for weathered specimens, a method which examines the decrease in the intensity of a single peak is preferred to one which depends upon peak height ratios: this is made possible by artificially irradiating the meteorites. The following terrestrial ages for finds were obtained: Plainview 225–300 years; Dimmitt 280–330 years; Calliham 350–400 years. Bluff, Etter, Potter, Shields and Wellman (c) proved to be too old to be dated by our methods (≥ 500 years). None of the low group finds available to us proved to be young enough to be dated precisely. Terrestrial ages indicate an extremely low efficiency of recovery (≤ 1%) for meteorites that are not seen to fall. Artificially irradiating the meteorites also revealed the fact that 9 of our 19 meteorites were saturated with respect to thermoluminescence when they entered the atmosphere, and therefore that a technique based on this phenomenon would not be applicable to such specimens to obtain their cosmic ray exposure age.     

Assessing the suitability of OSPAR EcoQOs for eutrophication vs ICES criteria for England and Wales

This paper provides a preliminary evaluation of the suitability of OSPAR Ecological Quality objectives for eutrophication for coastal and offshore waters of England and Wales on the basis of ICES criteria. In principle, EcoQOs are easy to understand, but responses to nutrient enrichment are complex. Few studies provide unequivocal evidence of links between inputs and response. Monitoring is generally feasible and in place, but needs to be improved. The best EcoQO is winter nutrient concentrations. Chlorophyll concentrations are a good indicator in environments susceptible to nutrient enrichment. The EcoQO for zoobenthos/fish kills potentially meets all criteria for a good indicator; EcoQOs for phytoplankton indicator species, oxygen concentrations and zoobenthos changes do not. Greater emphasis needs to be placed on seasonal effects of nutrient inputs and phytoplankton response, natural susceptibility of different water bodies, differences between coastal and offshore environments, and developing longer time series of data.