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.

(Table 3) Oxygen isotope ratios of benthic foraminifera from DSDP Hole 80-548

Presently, the intermediate depths of the North Atlantic Ocean are occupied by a great lens of warm, saline water whose source is the Mediterranean Sea. This water flows both westward and northward, finally entering the Norwegian Sea where it may contribute to the formation of North Atlantic Deep Water. The Late Neogene history of Mediterranean Outflow in the Atlantic can be monitored at DSDP-IPOD Site 548 on the continental slope Southwest of Ireland using benthic Foraminifera oxygen isotope values. Isotopic data from 154 samples indicate that Mediterranean water was absent from the mid-depth North Atlantic from 3.4 to 3.2 Ma ago. However, at about 2.9 Ma ago the isotopic values at Site 548 diverge from those recorded from the deep North Atlantic and they can be interpreted to indicate the appearance of a new water mass, possibly Mediterranean water, in the North Atlantic water column. This appearance may be related to climatic changes that occurred around the Mediterranean Basin at about 2.9 Ma ago. The analysis of 189 samples for grain-size distributions shows that a significant increase in the silt-size fraction occurs at the same level that isotopic analysis indicates a change in bottom waters at Site 548. The grainsize data support the hypothesis that mid-depth water-mass changes occurred at about 2.9 Ma ago.