Miocene dissolution facies and microfacies at Northwest Atlantic Deep Sea Drilling Project Site 93-603

Depth fluctuations of the lysocline and calcite compensation depth (CCD) through time were investigated at Deep Sea Drilling Project Site 603, Leg 93. The CCD fell during the middle Miocene at the onset of the Western Boundary Undercurrent, correlated with seismic Horizon X. Subsequently deposited units show fluctuations of the dissolution curve. Major changes in dissolution facies correspond with lithologic boundaries.

(Table 7) Representative electron microprobe analyses for natroalunite and larger FeOx spheroids of experiment ADSU6

Acid-sulfate alteration of basalt by SO2-bearing volcanic vapors has been proposed as one possible origin for sulfate-rich deposits on Mars. To better define mineralogical signatures of acid-sulfate alteration, laboratory experiments were performed to investigate alteration pathways and geochemical processes during reaction of basalt with sulfuric acid. Pyroclastic cinders composed of phenocrysts including plagioclase, olivine, and augite embedded in glass were reacted with sulfuric acid at 145 °C for up to 137 days at a range of fluid : rock ratios. During the experiments, the phenocrysts reacted rapidly to form secondary products, while the glass was unreactive. Major products included amorphous silica, anhydrite, and Fe-rich natroalunite, along with minor iron oxides/oxyhydroxides (probably hematite) and trace levels of other sulfates. At the lowest fluid : rock ratio, hexahydrite and an unidentified Fe-silicate phase also occurred as major products. Reaction-path models indicated that formation of the products required both slow dissolution of glass and kinetic inhibitions to precipitation of a number of minerals including phyllosilicates and other aluminosilicates as well as Al- and Fe-oxides/oxyhydroxides. Similar models performed for Martian basalt compositions predict that the initial stages of acid-sulfate alteration of pyroclastic deposits on Mars should result in formation of amorphous silica, anhydrite, Fe-bearing natroalunite, and kieserite, along with relict basaltic glass. In addition, analysis of the experimental products indicates that Fe-bearing natroalunite produces a Mössbauer spectrum closely resembling that of jarosite, suggesting that it should be considered an alternative to the component in sulfate-rich bedrocks at Meridiani Planum that has previously been identified as jarosite.

Foraminiferal abundance, carbonat concentration and dissolution index of sediment core W9903B-51GC

In order to investigate the paleoceanographic record of dissolution of calcium carbonate (CaCO3) in the central equatorial Pacific Ocean, we have studied the relationship between three indices of foraminiferal dissolution and the concentration and accumulation of CaCO3, opal, and Corg in Core WEC8803B-GC51 (1.3°N, 133.6°W; 4410 m). This core spans the past 413 kyr of deposition and moved in and out of the lysoclinal transition zone during glacial-interglacial cycles of CaCO3 production and dissolution. The record of dissolution intensity provided by foraminiferal fragmentation, the proportion of benthic foraminifera, and the foraminiferal dissolution index consistently indicates that the past corrosion of pelagic CaCO3 in the central equatorial Pacific does not vary with the observed sedimentary concentration of CaCO3. Although there is a weak low-frequency variation (~100 kyr) in dissolution intensity, it is unrelated to sedimentary CaCO3 concentration. There are many shorter-lived episodes where high CaCO3 concentration is coincident with poor foraminiferal preservation, and where, conversely, low CaCO3 concentration is coincident with superb foraminiferal preservation. Spectral analyses indicate that dissolution maxima consistently lagged glacial maxima (manifest by the SPECMAP delta18O stack) in the 100-kyr orbital band. Additionally, there is no relationship between dissolution and the accumulation of biogenic opal or Corg or between dissolution and the burial ratio of Corg/CINorg (calculated from Corg and CaCO3). Because previous studies of this core strongly suggest that surface water productivity varied closely with CaCO3 accumulation, both the mechanistic decoupling of carbonate dissolution from CaCO3 concentration (and from biogenic accumulation) and the substantial phase shift between dissolution and global glacial periodicity effectively obscure any simple link between export production, CaCO3 concentration, and dissolution of sedimentary CaCO3.

Fragmentation and dissolution of benthic foraminifera in Kiel Bight, Baltic Sea, Germany

Early diagenetic ultrastructural alterations of benthic foraminifers of the genera Elphidium and Ophthalmina from the shallow water sediments of the Kiel Bight were investigated by scanning electron microscopy. Pure solution patterns were deduced from supplementary experiments.//Several carbonate destroying processes can be specified by ultrastructural patterns of the shell surfaces. Based on these patterns three zones are established, each showing different mechanisms of shell fragmentation: 1) zone of abrasion, 2) zone of disintegration, 3) zone of corrosion. This zonation depends on the water depth and is caused primarily by water agitation and by under saturation of the bottom water with respect to carbonate.

(Table 2) Dissolution rate of sediments at DSDP Site 70-506

Dissolution rates of calcareous ooze were measured for samples from Deep Sea Drilling Project (DSDP) Site 506, which is in the area of the Galapagos Spreading Center. Using the free-drift method, measurements were carried out at 25 °C and atmospheric pressure. No significant difference in dissolution rates was found among the samples from three holes. However, in the present samples, the concentration of carbonate ion in seawater that is in equilibrium with calcite is 20 to 30% greater than is the case with synthetic calcite. That is, the dissolution rate of calcite under nearequilibrium conditions is greater than that of either synthetic calcite or sediments from the central Pacific (Morse, 1978). These results are consistent with field evidence indicating that the calcium carbonate compensation depth in the Galapagos region is shallower than in most other Pacific regions (Berger et al., 1976).

Geochemistry of pore water and sediments offshore Nicaragua and Costa Rica

Four volcanic ash-bearing marine sediment cores and one ash-free reference core were examined during research cruise RV Meteor 54/2 offshore Nicaragua and Costa Rica to investigate the chemical composition of pore waters related to volcanic ash alteration. Sediments were composed of terrigenous matter derived from the adjacent continent and contained several distinct ash layers. Biogenic opal and carbonate were only minor components. The terrigenous fraction was mainly composed of smectite and other clay minerals while the pore water composition was strongly affected by the anaerobic degradation of particulate organic matter via microbial sulphate reduction. The alteration of volcanic matter showed only a minor effect on major element concentrations in pore waters. This is in contrast to prior studies based on long sediment cores taken during the DSDP, where deep sediments always showed distinct signs of volcanic ash alteration. The missing signal of ash alteration is probably caused by low reaction rates and the high background concentration of major dissolved ions in the seawater-derived pore fluids. Dissolved silica concentrations were, however, significantly enriched in ash-bearing cores and showed no relation to the low but variable contents of biogenic opal. Hence, the data suggest that silica concentrations were enhanced by ash dissolution. Thus, the dissolved silica profile measured in one of the sediment cores was used to derive the in-situ dissolution rate of volcanic glass particles in marine sediments. A non-steady state model was run over a period of 43 kyr applying a constant pH of 7.30 and a dissolved Al concentration of 0.05 ?M. The kinetic constant (AA) was varied systematically to fit the model to the measured dissolved silica-depth profile. The best fit to the data was obtained applying AA = 1.3 * 10**-U9 mol of Si/cm**2/ s. This in-situ rate of ash dissolution at the seafloor is three orders of magnitude smaller than the rate of ash dissolution determined in previous laboratory experiments. Our results therefore imply that field investigations are necessary to accurately predict natural dissolution rates of volcanic glasses in marine sediments.

Seawater carbonate chemistry and dissolution rates by boring microflora during ex situ experiments with dead corals (Porites lobata), 2009

Eight-month-old blocks of the coral Porites lobata colonized by natural Hawaiian euendolithic and epilithic communities were experimentally exposed to two different aqueous pCO2 treatments, 400 ppmv and 750 ppmv, for 3 months. The chlorophyte Ostreobium quekettii dominated communities at the start and at the end of the experiment (65-90%). There were no significant differences in the relative abundance of euendolithic species, nor were there any differences in bioeroded area at the surface of blocks (27%) between pCO2 treatments. The depth of penetration of filaments of O. quekettii was, however, significantly higher under 750 ppmv (1.4 mm) than under 400 ppmv (1 mm). Consequently, rates of carbonate dissolution measured under elevated pCO2 were 48% higher than under ambient pCO2 (0.46 kg CaCO3 dissolved m2/a versus 0.31 kg /m2/a). Thus, biogenic dissolution of carbonates by euendoliths in coral reefs may be a dominant mechanism of carbonate dissolution in a more acidic ocean.

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.

Dolomite-rich coralline algae in reefs resist dissolution in acidified conditions

Coral reef ecosystems develop best in high-flow environments but their fragile frameworks are also vulnerable to high wave energy. Wave-resistant algal rims, predominantly made up of the crustose coralline algae (CCA) Porolithon onkodes and P. pachydermum, are therefore critical structural elements for the survival of many shallow coral reefs. Concerns are growing about the susceptibility of CCA to ocean acidification because CCA Mg-calcite skeletons are more susceptible to dissolution under low pH conditions than coral aragonite skeletons. However, the recent discovery of dolomite (Mg0.5Ca0.5(CO3)), a stable carbonate, in P. onkodes cells necessitates a reappraisal of the impacts of ocean acidification on these CCA. Here we show, using a dissolution experiment, that dried dolomite-rich CCA have 6-10 times lower rates of dissolution than predominantly Mg-calcite CCA in both high-CO2 (~ 700 ppm) and control (~ 380 ppm) environments, respectively. We reveal this stabilizing mechanism to be a combination of reduced porosity due to dolomite infilling and selective dissolution of other carbonate minerals. Physical break-up proceeds by dissolution of Mg-calcite walls until the dolomitized cell eventually drops out intact. Dolomite-rich CCA frameworks are common in shallow coral reefs globally and our results suggest that it is likely that they will continue to provide protection and stability for coral reef frameworks as CO2 rises.

Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.

Seawater carbonate chemistry, survival rate, shell mass growth, shell dissolution and locomotory speed of Limacina retroversa in a laboratory experiment

Anthropogenic carbon dioxide emissions induce ocean acidification, thereby reducing carbonate ion concentration, which may affect the ability of calcifying organisms to build shells. Pteropods, the main planktonic producers of aragonite in the worlds' oceans, may be particularly vulnerable to changes in sea water chemistry. The negative effects are expected to be most severe at high-latitudes, where natural carbonate ion concentrations are low. In this study we investigated the combined effects of ocean acidification and freshening on Limacina retroversa, the dominant pteropod in sub polar areas. Living L. retroversa, collected in Northern Norwegian Sea, were exposed to four different pH values ranging from the pre-industrial level to the forecasted end of century ocean acidification scenario. Since over the past half-century the Norwegian Sea has experienced a progressive freshening with time, each pH level was combined with a salinity gradient in two factorial, randomized experiments investigating shell degradation, swimming behavior and survival. In addition, to investigate shell degradation without any physiologic influence, one perturbation experiments using only shells of dead pteropods was performed. Lower pH reduced shell mass whereas shell dissolution increased with pCO2. Interestingly, shells of dead organisms had a higher degree of dissolution than shells of living individuals. Mortality of Limacina retroversa was strongly affected only when both pH and salinity reduced simultaneously. The combined effects of lower salinity and lower pH also affected negatively the ability of pteropods to swim upwards. Results suggest that the energy cost of maintaining ion balance and avoiding sinking (in low salinity scenario) combined with the extra energy cost necessary to counteract shell dissolution (in high pCO2 scenario), exceed the available energy budget of this organism causing the pteropods to change swimming behavior and begin to collapse. Since L. retroversa play an important role in the transport of carbonates to the deep oceans these findings have significant implications for the mechanisms influencing the inorganic carbon cycle in the sub-polar area.