Clay mineralogy of ODP Site 188-1165

The Ocean Drilling Program Leg 188 Site 1165 was drilled on the Wild Drift on the Continental Rise off Prydz Bay, East Antarctica to a total depth of 999.1 meters below seafloor (mbsf). It recovered an extensive suite of terrigenous and hemipelagic sediments of early Miocene to Pleistocene age. Of special interest in this study is the sediment column between 0 and 50 mbsf, which consists of a well-preserved section of Pliocene-Pleistocene-age sediments that was sampled at 10-cm intervals. Multiproxy study of this interval could show possible intervals of expansions of the ice-sheet across the continental shelves and express the climatic evolution in Antarctica, particularly during the 'middle' Pliocene warm period (3.15 to 2.85 Ma) which may provide an indication of how the Earth responds to a rise of its surface temperature. According to the existing age model, the upper 50 mbsf stratigraphic sequence of Site 1165 reaches back to ~4.9 Ma. Throughout this interval, the clay-mineral content is characterized by fluctuations of individual clay minerals, particularly smectite and chlorite. The smectite concentration varies mainly between 0% and 30%. Illite fluctuates less between 50% and 80%, and kaolinite varies mainly between 10% and 20%. Chlorite concentrations are mainly 0% to 10%. There is also a noticeable change in magnetic susceptibility at ~34 mbsf that is clearly indicated in the composition of the clay-mineral suite. At this level, smectite decreases and illite, kaolinite and chlorite show some variability. In particular, there is a slight but persistent increase in chlorite. The results from the Plio-Pleistocene transition, with evenly fluctuating smectite and illite contents and the gradually increasing chlorite content, may indicate cooler conditions compared to the mid-Pliocene conditions. Slight increase in illite content and decrease in smectite content towards Pleistocene supports the previous assumption. The results from the mid-Pliocene with the increasing smectite content and decreasing illite content may indicate warmer and possibly interglacial conditions.

Chemical composition of siderites and clay minerals from DSDP Holes 70-506G and 70-507B

As soon as they are emplaced on the sea floor, oceanic basalts go through a low-temperature alteration process which produces black halos concentrical with exposed surfaces and cracks, whereas the grey internal parts of the basaltic pieces apparently remain unaltered. This paper reports for the first time the occurrence of authigenic siderite and ankerite in oceanic basalts and more particularly in the grey internal parts of the latter. Small (8-50 µm) crystals of zoned siderite and ankerite have been observed in ten vesicles of two samples recovered from DSDP Holes 506G and 507B drilled south of the Galápagos Spreading Center (GSC). These Fe-carbonates show a large range of chemical composition (FeCO3 = 47-88%; CaCO3 = 5-40%; MgCO3 = 1-20%; MnCO3 = 0-11%). Most of them are Ca-richer than siderite reported in the literature. The chemical composition of the carbonate clearly reflects the fluctuation of the fluid chemical composition during crystallization. Mn and at least part of the Fe are thought to be hydrothermal in origin, whereas Mg and probably Ca were provided by seawater. It is proposed that siderite and ankerite formed at relatively low temperature (<85°C) and is metastable. The alteration of the GSC basalts seems to have proceeded in two stages: during the first, reducing stage, pyrite precipitated from hydrothermal fluids. A little further in the rock, siderite precipitated from the fluid which had already been modified by the formation of pyrite, and thus in a microenvironment where particular conditions prevailed (high P_CO2, increasing p_S**2- or increasing pH or increasing or decreasing pe). During the second, oxidizing, stage of alteration, a seawater-dominated fluid allowed crystallization of mixtures of Fe-rich smectites and micas, and Fe-hydroxides forming the black halos in the external portion of the basalt pieces and locally oxidizing pyrite and siderite in their innermost part. It is shown in this paper that, even at its earliest stage, and at low temperature, alteration of the upper oceanic crust (lavas) involves fluids enriched in Fe and Mn, interpreted to be of hydrothermal origin.

Sedimentary facies and clay mineralogy of ODP Site 105-646

The grain-size study and analyses of bulk sediment and clay mineral composition of samples collected from the dominant lithologies recovered at ODP Site 646, located on the northern flank of the Eirik Ridge (Labrador Sea), show variations indicating that contour-following currents, linked to Norwegian Sea Overflow Water (NSOW), have controlled sedimentation since the early Pliocene. These currents were influential until the early Pleistocene, despite the onset of major ice-rafting at about 2.5 Ma. A major mineralogical change occurred during the late Miocene: a decrease in the smectite to illite and chlorite ratio and a decrease of the crystallinity of smectites. This change indicates a renewing of the source rocks, which could result from an important hydrological change at this time. This change also is depicted by grain-size data that suggest the bottom current influence should be set earlier than the Pliocene.

Mg/Ca ratios in planktonic foraminifera

The primary Mg/Ca ratio of foraminiferal shells is a potentially valuable paleoproxy for sea surface temperature (SST) reconstructions. However, the reliable extraction of this ratio from sedimentary calcite assumes that we can overcome artifacts related to foraminiferal ecology and partial dissolution, as well as contamination by secondary calcite and clay. The standard batch method for Mg/Ca analysis involves cracking, sonicating, and rinsing the tests to remove clay, followed by chemical cleaning, and finally acid-digestion and single-point measurement. This laborious procedure often results in substantial loss of sample (typically 30-60%). We find that even the earliest steps of this procedure can fractionate Mg from Ca, thus biasing the result toward a more variable and often anomalously low Mg/Ca ratio. Moreover, the more rigorous the cleaning, the more calcite is lost, and the more likely it becomes that any residual clay that has not been removed by physical cleaning will increase the ratio. These potentially significant sources of error can be overcome with a flow-through (FT) sequential leaching method that makes time- and labor-intensive pretreatments unnecessary. When combined with time-resolved analysis (FT-TRA) flow-through, performed with a gradually increasing and highly regulated acid strength, produces continuous records of Mg, Sr, Al, and Ca concentrations in the leachate sorted by dissolution susceptibility of the reacting material. Flow-through separates secondary calcite from less susceptible biogenic calcite and clay, and further resolves the biogenic component into primary and more resistant fractions. FT-TRA reliably separates secondary calcite (which is not representative of original life habitats) from the more resistant biogenic calcite (the desired signal) and clay (a contaminant of high Mg/Ca, which also contains Al), and further resolves the biogenic component into primary and more resistant fractions that may reflect habitat or other changes during ontogeny. We find that the most susceptible fraction of biogenic calcite in surface dwelling foraminifera gives the most accurate value for SST and therefore best represents primary calcite. Sequential dissolution curves can be used to correct the primary Mg/Ca ratio for clay, if necessary. However, the temporal separation of calcite from clay in FT-TRA is so complete that this correction is typically <=2%, even in clay-rich sediments. Unlike hands-on batch methods, that are difficult to reproduce exactly, flow-through lends itself to automation, providing precise replication of treatment for every sample. Our automated flow-through system can process 22 samples, two system blanks, and 48 mixed standards in <12 hours of unattended operation. FT-TRA thus represents a faster, cheaper, and better way to determine Mg/Ca ratios in foraminiferal calcite.