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.

Radiocarbon ages and diatom abundance in cores GA306-BC4 and GA306-GC4 obtained during Galathea 3 cruise, West Greenland

Diatom assemblages from Holsteinsborg Dyb on the West Greenland shelf were analysed with high temporal resolution for the last 1200 years. A high degree of consistency between changes in frequency of selected diatom species and instrumental data from the same area during the last 70 years confirms the reliability of diatoms (particularly sea-ice species and warm-water species) for the study of palaeoceanographic changes in this area. A general cooling trend with some fluctuations is marked by an increase in sea-ice species throughout the last 1200 years. A relatively warm period with increased influence of Atlantic water masses of the Irminger Current (IC) is found at AD 750-1330, although with some oceanographic variability after AD 1000. A pronounced oceanographic shift occurred at AD 1330, corresponding in time to the transition from the so-called 'Medieval Warm Period' (MWP) to the 'Little Ice Age' (LIA). The LIA cold episode is characterized by three intervals with particularly cold sea-surface conditions at AD 1330-1350, AD 1400-1575 and AD 1660-1710 as a result of variable influence of Polar waters in the area. During the last 70 years, two relatively warm periods and one cold period (the early 1960s to mid-1990s) are indicated by changes in the diatom components. Our study demonstrates that sedimentary records on the West Greenland shelf provide valuable palaeoenvironment data that confirm a linkage between local and large-scale North Atlantic oceanographic and atmospheric oscillations.