Chemical and Sr isotopic compositions of 3 step leachates and residues of bulk samples, zeolites, and smectites from Lower Miocene sediments at ODP Site 166-1007

Massive clinoptilolite authigenesis was observed at about 1105 meters below sea floor (mbsf) in lower Miocene wellcompacted carbonate periplatform sediments from the Great Bahama Bank [Ocean Drilling Program, ODP Leg 166, Site 1007]. The diagenetic assemblage comprises abundant zeolite crystallized within foraminifer tests and sedimentary matrix, as well as Mg smectites. In carbonate-rich deposits, the formation of the zeolite requires a supply of silica. Thus, the objective of the study is to determine the origin of the silica supply, its diagenetic evolution, and consequently the related implications on interpretation of the sedimentary record, in terms of local or global paleoceanographic change. For lack of evidence for any volcaniclastic input or traces of Si-enriched deep fluids circulation, an in situ biogenic source of silica is validated by isotopic data and chemical modeling for the formation of such secondary minerals in shallow-water carbonate sequences. Geochemical and strontium isotopic data clearly establish the marine signature of the diagenetic zeolite, as well as its contemporaneous formation with the carbonate deposition (Sr model ages of 19.6-23.2 Ma). The test of saturation for the pore fluids specifies the equilibrium state of the present mineralogical assemblage. Seawater-rock modeling specifies that clinoptilolite precipitates from the dissolution of biogenic silica, which reacts with clay minerals. The amount of silica (opal-A) involved in the reaction has to be significant enough, at least 10 wt.%, to account for the observed content of clinoptilolite occurring at the most zeolite-rich level. Modeling also shows that the observed amount of clinoptilolite (~19%) reflects an in situ and short-term reaction due to the high reactivity of primary biogenic silica (opal-A) until its complete depletion. The episodic occurrence of these well-lithified zeolite-rich levels is consistent with the occurrence of seismic reflectors, particularly the P2 seismic sequence boundary located at 1115 mbsf depth and dated as 23.2 Ma. The age range of most zeolitic sedimentary levels (biostratigraphic ages of 21.5-22 Ma) correlates well with that of the early Miocene glaciation Mi-1 and Mi-1a global events. Thus, the clinoptilolite occurrence in the shallow carbonate platform environment far from volcanogenic supply, or in other sensitive marine areas, is potentially a significant new proxy for paleoproductivity and oceanic global events, such as the Miocene events, which are usually recognized in deep-sea pelagic sediments and high latitude deposits.

Sedimentologic and magnetic data of sediment cores on the western slope of the Mid-Atlantic Ridge

The relative paleointensity (RPI) method assumes that the intensity of post depositional remanent magnetization (PDRM) depends exclusively on the magnetic field strength and the concentration of the magnetic carriers. Sedimentary remanence is regarded as an equilibrium state between aligning geomagnetic and randomizing interparticle forces. Just how strong these mechanical and electrostatic forces are, depends on many petrophysical factors related to mineralogy, particle size and shape of the matrix constituents. We therefore test the hypothesis that variations in sediment lithology modulate RPI records. For 90 selected Late Quaternary sediment samples from the subtropical and subantarctic South Atlantic Ocean a combined paleomagnetic and sedimentological dataset was established. Misleading alterations of the magnetic mineral fraction were detected by a routine Fe/kappa test (Funk, J., von Dobeneck, T., Reitz, A., 2004. Integrated rock magnetic and geochemical quantification of redoxomorphic iron mineral diagenesis in Late Quaternary sediments from the Equatorial Atlantic. In: Wefer, G., Mulitza, S., Ratmeyer, V. (Eds.), The South Atlantic in the Late Quaternary: reconstruction of material budgets and current systems. Springer-Verlag, Berlin/Heidelberg/New York/Tokyo, pp. 239-262). Samples with any indication of suboxic magnetite dissolution were excluded from the dataset. The parameters under study include carbonate, opal and terrigenous content, grain size distribution and clay mineral composition. Their bi- and multivariate correlations with the RPI signal were statistically investigated using standard techniques and criteria. While several of the parameters did not yield significant results, clay grain size and chlorite correlate weakly and opal, illite and kaolinite correlate moderately to the NRM/ARM signal used here as a RPI measure. The most influential single sedimentological factor is the kaolinite/illite ratio with a Pearson's coefficient of 0.51 and 99.9% significance. A three-member regression model suggests that matrix effects can make up over 50% of the observed RPI dynamics.

Seawater carbonate chemistry and Bathymodiolus brevior shell variables near Eifuku volcano, Japan, 2009

Increasing atmospheric carbon dioxide levels are causing ocean acidification, compromising the ability of some marine organisms to build and maintain support structures as the equilibrium state of inorganic carbon moves away from calcium carbonate. Few marine organisms tolerate conditions where ocean pH falls significantly below today's value of about 8.1 and aragonite and calcite saturation values below 1. Here we report dense clusters of the vent mussel B. brevior in natural conditions of pH values between 5.36 and 7.29 on northwest Eifuku volcano, Mariana arc, where liquid carbon dioxide and hydrogen sulphide emerge in a hydrothermal setting. We find that both shell thickness and daily growth increments in shells from northwest Eifuku are only about half those recorded from mussels living in water with pH>7.8. Low pH may therefore also be implicated in metabolic impairment. We identify four-decade-old mussels, but suggest that the mussels can survive for so long only if their protective shell covering remains intact: crabs that could expose the underlying calcium carbonate to dissolution are absent from this setting. The mussels' ability to precipitate shells in such low-pH conditions is remarkable. Nevertheless, the vulnerability of molluscs to predators is likely to increase in a future ocean with low pH.