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.

Stratigraphic distribution of marine palynomorph species recorded for the Miocene of ODP Hole 105-645E (Table 1)

A total of 145 samples were analyzed for palynology, and all were found to be productive. Residues are dominated by pollen, terrestrial spores, and land plant tissues. Marine palynomorphs occur in all samples, which allowed us to recognize five Miocene dinocyst assemblage zones. Dinocyst assemblages indicate cool-water conditions and suggest a neritic rather than fully oceanic environment, with not only North Atlantic and Norwegian Sea affinities, but also containing both notable protoperidiniacean and possible endemic elements. Dinocyst assemblages indicate an early Miocene age for the bottom of Hole 645E and an age no younger than early late Miocene (Sample 105-645E-24R, CC) near the top of the interval studied. These age assignments provide an estimated initiation of ice rafting in Baffin Bay at between 7.4 and 9.5 Ma. Increased terrigenous influx and apparent disappearance of certain dinocyst taxa occur in the middle to late Miocene and may be related to oceanographic changes or climatic deterioration. Spores and pollen indicate a climate that varied within a temperate regime during the early and middle to early late Miocene, followed by climatic deterioration. Four new dinocyst species are described: Batiacasphaera gemmata, Impletosphaeridium prolatum, Operculodinium vacuolatum, and Selenopemphix brevispinosa. The acritarch genus Cyclopsiella Drugg and Loeblich is emended, and two new combinations have been created: Cyclopsiella granosa (Matsuoka) and Cyclopsiella? laevigata (Chateauneuf). Cyclopsiella granosa (Matsuoka) n. comb. is considered a subjective junior synonym of Cyclopsiella granulata He and Li. Ascostomocystis granulatus Chateauneuf has been provisionally allocated to Cyclopsiella and renamed Cyclopsiella? chateauneufii. Two new acritarch species are described: Cyclopsiella spiculosa and Cymatiosphaera! baffinensis.