Dissolution rate spectra data of calcite single crystal and micrite material

The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Critical insight is available from analysis of the relationship between the reaction rate and its distribution over the mineral surface. This analysis recognizes the fundamental variance of the rate. The resulting anisotropic rate distributions are completely obscured by the common practice of surface area normalization. In a simple experiment using a single crystal and its polycrystalline counterpart, we demonstrate the sensitivity of dissolution rate to grain size, results that undermine the use of "classical" rate constants. Comparison of selected published crystal surface step retreat velocities (Jordan and Rammensee, 1998) as well as large single crystal dissolution data (Busenberg and Plummer, 1986) provide further evidence of this fundamental variability. Our key finding highlights the unsubstantiated use of a single-valued "mean" rate or rate constant as a function of environmental conditions. Reactivity predictions and long-term reservoir stability calculations based on laboratory measurements are thus not directly applicable to natural settings without a probabilistic approach. Such a probabilistic approach must incorporate both the variation of surface energy as a general range (intrinsic variation) as well as constraints to this variation owing to the heterogeneity of complex material (e.g., density of domain borders). We suggest the introduction of surface energy spectra (or the resulting rate spectra) containing information about the probability of existing rate ranges and the critical modes of surface energy.

Ocean acidification decreases the light-use efficiency in an Antarctic diatom under dynamic but not constant light, link to supplementary data

There is increasing evidence that different light intensities strongly modulate the effects of ocean acidification (OA) on marine phytoplankton. The aim of the present study was to investigate interactive effects of OA and dynamic light, mimicking natural mixing regimes. The Antarctic diatom Chaetoceros debilis was grown under two pCO2 (390 and 1000 latm) and light conditions (constant and dynamic), the latter yielding the same integrated irradiance over the day. To characterize interactive effects between treatments, growth, elemental composition, primary production and photophysiology were investigated. Dynamic light reduced growth and strongly altered the effects of OA on primary production, being unaffected by elevated pCO2 under constant light, yet significantly reduced under dynamic light. Interactive effects between OA and light were also observed for Chl production and particulate organic carbon (POC) quotas. Response patterns can be explained by changes in the cellular energetic balance. While the energy transfer efficiency from photochemistry to biomass production (Phi_e,C) was not affected by OA under constant light, it was drastically reduced under dynamic light. Contrasting responses under different light conditions need to be considered when making predictions regarding a more stratified and acidified future ocean.

Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.

Radionuclide analyses, and sedimentation and accumulation rates of sediment core PS2319-1

There is increasing evidence indicating that syndepositional redistribution of sediment on the seafloor by bottom currents is common and can significantly affect sediment mass accumulation rates. Notwithstanding its common incidence, this process (generally referred to as sediment focusing) is often difficult to recognize. If redistribution is near synchronous to deposition, the stratigraphy of the sediment is not disturbed and sediment focusing can easily be overlooked. Ignoring it, however, can lead to serious misinterpretations of sedimentary fluxes, particularly when past changes in export flux from the overlying water are inferred. In many instances, this problem can be resolved, at least for sediments deposited during the late Quaternary, by normalizing to the flux of 230Th scavenged from seawater, which is nearly constant and equivalent to the known rate of production of 230Th from the decay of dissolved 234U. We review the principle, advantages and limitations of this method. Notwithstanding its limitations, it is clear that 230Th normalization does provide a means of achieving more accurate interpretations of sedimentary fluxes and eliminates the risk of serious misinterpretations of sediment mass accumulation rates.

Grain size effects on excess Thorium-230 of sediment cores from the Southern Ocean and the South East Atlantic

Excess Thorium-230 (230Thxs) as a constant flux tracer is an essential tool for paleoceanographic studies, but its limitations for flux normalization are still a matter of debate. In regions of rapid sediment accumulation, it has been an open question if 230Thxs-normalized fluxes are biased by particle sorting effects during sediment redistribution. In order to study the sorting effect of sediment transport on 230Thxs, we analyzed the specific activity of 230Thxs in different particle size classes of carbonate-rich sediments from the South East Atlantic, and of opal-rich sediments from the Atlantic sector of the Southern Ocean. At both sites, we compare the 230Thxs distribution in neighboring high vs. low accumulation settings. Two grain-size fractionation methods are explored. We find that the 230Thxs distribution is strongly grain size dependent, and 50-90% of the total 230Thxs inventory is concentrated in fine material smaller than 10 µm, which is preferentially deposited at the high accumulation sites. This leads to an overestimation of the focusing factor Psi, and consequently to an underestimation of the vertical flux rate at such sites. The distribution of authigenic uranium indicates that fine organic-rich material has also been re-deposited from lateral sources. If the particle sorting effect is considered in the flux calculations, it reduces the estimated extent of sediment focusing. In order to assess the maximum effect of particle sorting on Psi, we present an extreme scenario, in which we assume a lateral sediment supply of only fine material (< 10 µm). In this case, the focusing factor of the opal-rich core would be reduced from Psi = 5.9 to Psi = 3.2. In a more likely scenario, allowing silt-sized material to be transported, Psi is reduced from 5.9 to 5.0 if particle sorting is taken into consideration. The bias introduced by particle sorting is most important for strongly focused sediments. Comparing 230Thxs-normalized mass fluxes biased by sorting effects with uncorrected mass fluxes, we suggest that 230Thxs-normalization is still a valid tool to correct for lateral sediment redistribution. However, differences in focusing factors between core locations have to be evaluated carefully, taking the grain size distributions into consideration.