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.

Seawater carbonate chemistry and net dissolution rate for experiment of Shiraho reef

Acidification of the oceans by increasing anthropogenic CO2 emissions will cause a decrease in biogenic calcification and an increase in carbonate dissolution. Previous studies have suggested that carbonate dissolution will occur in polar regions and in the deep sea where saturation state with respect to carbonate minerals (Omega) will be <1 by 2100. Recent reports demonstrate nocturnal carbonate dissolution of reefs, despite a Omega a (aragonite saturation state) value of >1. This is probably related to the dissolution of reef carbonate (Mg-calcite), which is more soluble than aragonite. However, the threshold of Omega for the dissolution of natural sediments has not been clearly determined. We designed an experimental dissolution system with conditions mimicking those of a natural coral reef, and measured the dissolution rates of aragonite in corals, and of Mg-calcite excreted by other marine organisms, under conditions of Omega a > 1, with controlled seawater pCO2. The experimental data show that dissolution of bulk carbonate sediments sampled from a coral reef occurs at Omega a values of 3.7 to 3.8. Mg-calcite derived from foraminifera and coralline algae dissolves at Omega a values between 3.0 and 3.2, and coralline aragonite starts to dissolve when Omega a = 1.0. We show that nocturnal carbonate dissolution of coral reefs occurs mainly by the dissolution of foraminiferans and coralline algae in reef sediments.

Seawater carbonate chemistry, growth rate and morphology of Calcidiscus leptoporus (RCC1135) during experiments, 2011

The coccolithophore Calcidiscus leptoporus (strain RCC1135) was grown in dilute batch culture at CO2 levels ranging from ~200 to ~1600 µatm. Increasing CO2 concentration led to an increased percentage of malformed coccoliths and eventually (at ~1500 µatm CO2) to aggregation of cells. Carbonate chemistry of natural seawater was manipulated in three ways: first, addition of acid; second, addition of a HCO3/CO3 solution; and third, addition of both acid and HCO3/CO3 solution. The data set allowed the disentangling of putative effects of the different parameters of the carbonate system. It is concluded that CO2 is the parameter of the carbonate system which causes both aberrant coccolithogenesis and aggregation of cells.

Stable isotope record, opal accumulation rate and geochemistry of middle Miocene sediments of IODP Site 321-U1338

During the middle Miocene, Earth's climate transitioned from a relatively warm phase (Miocene climatic optimum) into a colder mode with re-establishment of permanent ice sheets on Antarctica, thus marking a fundamental step in Cenozoic cooling. Carbon sequestration and atmospheric CO2 drawdown through increased terrestrial and/or marine productivity have been proposed as the main drivers of this fundamental transition. We integrate high-resolution (1-3 k.y.) benthic stable isotope data with XRF-scanner derived biogenic silica and carbonate accumulation estimates in an exceptionally well-preserved sedimentary archive, recovered at Integrated Ocean Drilling Program Site U1338, to reconstruct eastern equatorial Pacific productivity variations and to investigate temporal linkages between high- and low-latitude climate change over the interval 16-13 Ma. Our records show that the climatic optimum (16.8-14.7 Ma) was characterized by high amplitude climate variations, marked by intense perturbations of the carbon cycle. Episodes of peak warmth at (southern hemisphere) insolation maxima coincided with transient shoaling of the carbonate compensation depth and enhanced carbonate dissolution in the deep ocean. A switch to obliquity-paced climate variability after 14.7 Ma concurred with a general improvement in carbonate preservation and the onset of stepwise global cooling, culminating with extensive ice growth over Antarctica at ~13.8 Ma. We find that two massive increases in opal accumulation at ~14.0 and ~13.8 Ma occurred just before and during the final and most prominent cooling step, supporting the hypothesis that enhanced siliceous productivity in the eastern equatorial Pacific contributed to CO2 drawdown.

Geochemistry, lithology, and bulk density of Cricket Flat paleosol samples

The high-resolution marine isotope climate record indicates pronounced global cooling during the Langhian (16-13.8 Ma), beginning with the warm middle Miocene climatic optimum and ending with significant Antarctic ice sheet expansion and the transition to "icehouse" conditions. Terrestrial paleoclimate data from this interval is sparse and sometimes conflicting. In particular, there are gaps in the terrestrial record in the Pacific Northwest during the late Langhian and early Serravallian between about 14.5 and 12.5 Ma. New terrestrial paleoclimate data from this time and region could reconcile these conflicting records. Paleosols are particularly useful for reconstructing paleoenvironment because the rate and style of pedogenesis is primarily a function of surface environmental conditions; however, complete and well-preserved paleosols are uncommon. Most soils form in erosive environments that are not preserved, or in environments such as floodplains that accumulate in small increments; the resulting cumulic soils are usually thin, weakly developed, and subject to diagenetic overprinting from subsequent soils. The paleosol at Cricket Flat in northeastern Oregon is an unusually complete and well-preserved paleosol from a middle Miocene volcanic sequence in the Powder River Volcanic Field. An olivine basalt flow buried the paleosol at approximately 13.8 ± 0.6 Ma, based on three 40Ar/39Ar dates on the basalt. We described the Cricket Flat paleosol and used its physical and chemical profile and micromorphology to assess pedogenesis. The Cricket Flat paleosol is an Ultisol-like paleosol, chemically consistent with a high degree of weathering. Temperature and rainfall proxies suggest that Cricket Flat received 1120 ± 180 mm precipitation y-1 and experienced a mean annual temperature of 14.5 ± 2.1 °C during the formation of the paleosol, significantly warmer and wetter than today. This suggests slower cooling after the middle Miocene climatic optimum than is seen in the existing paleosol record.