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.

Mineralogy, and composition of turbidites and background samples at ODP Sites 166-1003 and 166-1007

The lower slope and toe-of-slope sediments of the western flank of the Great Bahama Bank (Sites 1003 and 1007) are characterized by an intercalation of turbidites and periplatform ooze. In general, turbidites form up to 12% of the total mass of the sedimentary column. Based primarily on data from the Bahamas, it has been postulated that steep-sided carbonate platforms shed most of their sediments into the basin during sea-level highstands when the platforms are flooded. This highstand shedding is assumed to be less pronounced along platforms with a ramp-like depositional profile where sediment production is not restricted to sea-level highstand. Miocene to Pliocene sediments recovered in five drill holes during Leg 166 at the western margin of the Great Bahama Bank reveal that turbidite distribution follows a complex pattern that is dependent on several factors such as sedimentation rates, sea-level changes, and slope morphology. To identify the depositional sequences in the cores, the depths of seismic-sequence boundaries were used. The distribution of turbidites within sedimentary sequences varies strongly. Generally, turbidites are clustered at the upper and/or lower portions of the sequences indicating deposition of carbonate turbidites during both highstand and lowstand of sea level. Analyses of the Miocene turbidites show that (1) during high sea level, 60% of all turbidites were deposited at Site 1003 (309 out of 518 turbidites), while during low sea level, two thirds of all turbidites were deposited at Site 1007 (332 out of 486 turbidites); (2) the average thickness of highstand turbidites is 1.5 times higher than the average thickness of lowstand turbidites; and (3) the turbidites display slight differences in composition and sorting. In general, highstand turbidites are less sorted and contain an abundant amount of shallow-water constituents such as green algae, red algae, shallow-water benthic foraminifers (miliolids), and intraclasts. The lowstand turbidites are better sorted and contain abundant planktonic foraminifers and micrite. To complicate matters, highstand and lowstand turbidites seem to be deposited at different locations on the slope. At the lower slope (Site 1003), more turbidites were deposited during highstands, while at the toe of the slope, turbidites were dominantly deposited during sea-level lowstands. The result is a slope section with laterally discontinuous turbidite lenses within periplatform ooze, which is controlled by the interplay of sea-level changes, sediment production, and platform morphology.

Geochemical and mineralogical analyses of clay-rich intervals in ODP Sites 166-1006 and 166-1007

The western flank of the Great Bahama Bank, drilled during ODP Leg 166 at seven sites, represents a prograding carbonate sequence from late Oligocene to Holocene [Eberli et al., Proc. ODP Init. Reports 166 (1997)]. The signatures of the detrital input and of diagenetic alteration are evident in clay enriched intervals from the most distal Sites 1006 and 1007 in the Straits of Florida. Mineralogical and chemical investigations (XRD, TEM, SEM, ICP-MS) run on bulk rocks and on the clay fractions enable the origin and evolution of silicate parageneses to be characterized. Plio-Pleistocene silt and clay interbeds contain detrital clay assemblages comprising chlorite, illite, interstratified illite smectite, smectite, kaolinite and palygorskite. The greater smectite input within late Pliocene units than in Pleistocene oozes may relate either varying source areas or change in paleoclimatic conditions and weathering intensity. The clay intervals from Miocene-upper Oligocene wackestone sections are fairly different, with prevalent smectite in the fine fraction, whose high crystallinity and Mg contents that point towards an authigenic origin. The lower Miocene section, below 1104 mbsf, at depths where compaction features are well developed, is particularly characterized by abundant authigenic Na-K-clinoptilolite filling foraminifer tests. The authigenic smectite and clinoptilolite paragenesis is recorded by the chemical trends, both of the sediment and the interstitial fluid. This diagenetic evolution implies Si- and Mg rich fluids circulating in deeper and older sequences. For lack of any local volcaniclastic input, the genesis of zeolite and the terms of water rock interaction are discussed. The location of the diagenetic front correlates with that of the seismic sequence boundary P2 dated as 23.2 Ma. This correspondence may allow the chronostratigraphic significance of some specific seismic reflections to be reassessed.