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.

X-ray fluorescence data (calcium and iron), bulk organic d13C, and dinoflagellate cysts of ODP Hole 189-1172D

The 'Paleocene/Eocene Thermal Maximum' or PETM (~55 Ma) was associated with dramatic warming of the oceans and atmosphere, pronounced changes in ocean circulation and chemistry, and upheaval of the global carbon cycle. Many relatively complete PETM sequences have by now been reported from around the world, but most are from ancient low- to midlatitude sites. ODP Leg 189 in the Tasman Sea recovered sediments from this critical phase in Earth history at Sites 1171 and 1172, potentially representing the southernmost PETM successions ever encountered (at ~70° to 65° S paleolatitude). Downhole and core logging data, in combination with dinoflagellate cyst biostratigraphy, magneto-stratigraphy, and stable isotope geochemistry indicate that the sequences at both sites were deposited in a high accumulation-rate, organic rich, marginal marine setting. Furthermore, Site 1172 indeed contains a fairly complete P-E transition, whereas at Site 1171, only the lowermost Eocene is recovered. However, at Site 1172, the typical PETM-indicative acme of the dinocyst Apectodinium was not recorded. We conclude that unfortunately, the critical latest Paleocene and PETM intervals are missing at Site 1172. We relate the missing section to a sea level driven hiatus and/or condensed section and recovery problems. Nevertheless, our integrated records provide a first-ever portrait of the trend toward, and aftermath of, the PETM in a marginal marine, southern high-latitude setting.

Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

Description and iron and manganese content of ferromanganese nodules from Oneida Lake, NY

Ferromanganese nodules in the deep-sea and in freshwater lakes usually accrete layers rich in manganese oxides alternating with layers rich in iron oxides. The mechanism producing these alternating layers is unknown; indeed, the mechanism producing the nodules themselves is unknown. In Oneida Lake, New York, precipitants from the lake water and the surfaces of nodules at the sediment-water interface are enriched in Mn, whereas nodules buried in lake sediments have surface layers enriched in Fe. It is hypothesized here, using field and laboratory evidence, that reduction and mobilization of Mn from the nodule surface during periods of anoxic sediment cover produce the high Fe layers observed in the nodules.

Whole rock and Cr-rich spinel geochemistry of ODP Legs 152 and 163 and DSDP Hole 38-338 samples

Coring during Ocean Drilling Program and Deep Sea Drilling Project Legs 163, 152, 104, 81, and 38 recovered sequences of altered basalt from North Atlantic seaward-dipping reflector sequences (SDRS) erupted during the initial rifting of Greenland from northern Europe and likely associated with excessive mantle temperatures caused by an impacting mantle plume head. Cr-rich spinel is found abundantly as inclusions and groundmass crystals within the olivine-rich lavas of Hole 917A (Leg 152) cored into the Southeast Greenland SDRS, but only rarely as inclusions within plagioclase in the lavas of the Vøring Plateau SDRS, and it is absent from other cored SDRS lavas from the Rockall Plateau and Southeast Greenland. Eruptive melt compositions determined from inferred, thermodynamically-defined, spinel-melt exchange equilibria indicate that the most primitive melts represented by Hole 917A basalts have Mg/(Mg + Fe2+) at least as high as 0.70 and approach near-primary mantle melt compositions. In contrast, Cr-rich spinels from Hole 338 (Leg 38) lavas on the Vøring Plateau SDRS give evidence for melt with Mg/(Mg + Fe2+) only as high as 0.64. This study underlines that primitive melts similar to those from Hole 917A comprise only a small fraction of the eruptive North Atlantic SDRS melts, and that most SDRS basalts were, in fact, too evolved to have precipitated Cr-rich spinel, with true melt Mg/(Mg + Fe2+) likely below 0.60. The evolved nature of the SDRS basalts implies large amounts of fractionation at the base of the crust or deep within it, consistent with seismic results that indicate an abnormally thick Layer 3 underlying the SDRS.

Composition of bentonite-, smectite-rich- and ash beds from DSDP Leg 19 holes

Late Cenozoic ash deposits cored in Deep Sea Drilling Project Leg 19 in the far northwest Pacific and in the Bering Sea have altered to bentonite beds. Some bentonite layers were subsequently replaced by carbonate beds. A significant part of the Neogene volcanic history of land areas adjacent to the far north Pacific is represented by these diagenetic deposits. Bentonite beds are composed of authigenic smectite and minor amounts of clinoptilolite. Authigenic smectite has fewer illite layers than detrital smectite. Opal-A and opal-CT, abundant in Bering Sea sediment, are not found in ash or bentonite layers. The percentage of smectite in the total clay-mineral assemblage of ash beds is greater than that for adjacent terrigenous sediment, but the total amount of clay minerals in ash sequences is less than in surrounding deposits. Morphology of the 17-Å peak of smectite found in ash may represent newly formed, poorly crystalline smectite. Smectite becomes better crystallized as bentonite layers form. The percentage of smectite of the total clay-mineral assemblage in bentonite beds is greater than that in surrounding sediment, and, in contrast to ash beds, the total amount of clay minerals (mostly smectite) in bentonite layers is greater than in adjacent terrigenous sediment. Apparently, silica is not mobilized when volcanic ash layers transform to bentonite beds. Saponite-nontronite varieties of smectite and high Fe/Al and Ti/Al ratios distinguish bentonite beds derived from basaltic parent material from those beds formed from more silicic volcanic ash. These silicic ash beds produce bentonite composed mostly of montmorillonite. The basal sediment section at site 192 is rich with bentonite beds. Smectite in the upper part of this section (Eocene) was formed by low-temperature diagenesis of volcanic debris of intermediate or more silicic composition derived from arc or Pacific volcanoes. In contrast, smectite from the lowest 10 to 20 m of the sedimentary section (Cretaceous) is formed from either low-temperature or hydrothermal alteration of the underlying basaltic basement and associated pyroclastic debris. This near-basement smectite contains Mg and K acquired from sea water and Si, Al, Fe, Ti, and Mn released from the volcanic material.