Accumulation and composition of terrigenous material on Ceara rise over the past 55 Ma

Ceara Rise, located east the Amazon River mouth, is covered with a thick blanket of pelagic carbonate and hemipelagic terrigenous sediment. The terrigenous component has been extracted from 57 bulk sediment samples at Ocean Drilling Program (ODP) Sites 925 and 929 on Ceara Rise to obtain a Cenozoic record of riverine discharge from northern South America. From the early Eocene to early Miocene (55-20 Ma), terrigenous accumulation was dominated by moderate amounts of generally large-grained, gray to green sediment especially depleted in elements that are enriched in post-Archaean shale (e.g. Cs, Th, Yb). However, pulsed inputs of relatively small-grained, gray to green terrigenous sediment less depleted in the above elements occurred in the late Eocene and Oligocene. The accumulation of terrigenous sediment decreased significantly until 16.5 Ma. In the middle Miocene (16.5-13 Ma), terrigenous accumulation was dominated by small amounts of small-grained, tan sediment notably depleted in Na and heavy rare earth elements. The accumulation rate of terrigenous sediment increased markedly from the latest Miocene (10 Ma) to the present day, a change characterized by deposition of gray-green sediment enriched in elements that are enriched in post-Archaean shale. Observed changes in terrigenous sediment at Ceara Rise record tectonism and erosion in northern South America. The Brazil and Guyana shields supplied sediment to the eastern South American margin until the middle Miocene (20-16.5 Ma) when a period of thrusting, shortening and uplift changed the source region, probably first to highly weathered and proximal Phanerozoic sediments. By the late Miocene (9 Ma), there was a transcontinental connection between the Andes and eastern South America. Weathering products derived from the Andes have increasingly dominated terrigenous deposition at Ceara Rise since the Late Miocene and especially since the late Pliocene.

Composition of native Cu, Cu isotope and mineral analysis from different samples of ODP and DSDP

Ocean drilling has revealed that, although a minor mineral phase, native Cu ubiquitously occurs in the oceanic crust. Cu isotope systematics for native Cu from a set of occurrences from volcanic basement and sediment cover of the oceanic crust drilled at several sites in the Pacific, Atlantic and Indian oceans constrains the sources of Cu and processes that produced Cu**0. We propose that both hydrothermally-released Cu and seawater were the sources of Cu at these sites. Phase stability diagrams suggest that Cu**0 precipitation is favored only under strictly anoxic, but not sulfidic conditions at circum-neutral pH even at low temperature. In the basaltic basement, dissolution of primary igneous and potentially hydrothermal Cu-sulfides leads to Cu**0 precipitation along veins. The restricted Cu-isotope variations (delta 65Cu = 0.02-0.19 per mil) similar to host volcanic rocks suggest that Cu**0 precipitation occurred under conditions where Cu+-species were dominant, precluding Cu redox fractionation. In contrast, the Cu-isotope variations observed in the Cu**0 from sedimentary layers yield larger Cu-isotope fractionation (delta 65Cu = 0.41-0.95 per mil) suggesting that Cu**0 precipitation involved redox processes during the diagenesis, with potentially seawater as the primary Cu source. We interpret that native Cu precipitation in the basaltic basement is a result of low temperature (20°-65 °C) hydrothermal processes under anoxic, but not H2S-rich conditions. Consistent with positive delta 65Cu signatures, the sediment cover receives major Cu contribution from hydrogenous (i.e., seawater) sources, although hydrothermal contribution from plume fallout cannot be entirely discarded. In this case, disseminated hydrogenous and/or hydrothermal Cu might be diagenetically remobilized and reprecipitated as Cu**0 in reducing microenvironment.