Composition of palygorskite-rich and montmorillonite-rich zeolite-containing sediments from DSDP Sites 164 and 196

Cretaceous, Tertiary, and Quaternary sediments from Deep Sea Drilling Project Sites 164 and 196 (13°12' N, 161°31' W and 30°07' N, 148°34' E, respectively) were analyzed for major chemical elements and mineralogy. Sediments from these sites contain large proportions of authigenic minerals: mainly palygorskite, clinoptilolite and chert in the Cretaceous, and montmorillonite, phillipsite and chert in the Tertiary. The montmorillonite-phillipsite assemblage is thought to be derived from volcanic ash or glass, and the palygorskite-clinoptilolite assemblage is thought to be derived by reaction of biogenic silica with volcanic ash or glass or with montmorillonite and phillipsite. Both assemblages have generally moderate Ti/Al ratios, ranging from 0.026 to 0.047, so most of the palygorskite, clinoptilolite, montmorillonite and phillipsite could not be derived in situ from alteration of basaltic material. Plagioclase compositions suggest that the volcanic precursors were silicic or intermediate, but it is also possible that the sediments have been extensively fractionated by redistribution from nearby seamounts. Available data on other Late Cretaceous sediments in the Pacific were analyzed. Clinoptilolite and chert are present nearly everywhere where palygorskite is abundant; phillipsite is rare where palygorskite is abundant. It is suggested that increased water temperatures during the Cretaceous increased reaction rates and determined the alteration products.

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.

Biomarker and XRD results for the last 3.4 Ma from IODP Site 306-U1313

Various types of abrupt/millennial-scale climate variability such as Dansgaard/Oeschger and Heinrich Events characterized the last glacial period. Over the last decade, a number of studies demonstrated that such millennial-scale climate variability was not limited to the last glacial but inherent to Quaternary climate. Here we review the occurrence and origin of millennial ice-rafting events in the North Atlantic during the late Pliocene and Pleistocene (last 3.4 Ma) with a special focus on North Atlantic Hudson Strait (HS) Heinrich(-like) Events. Besides a clear biomarker signature, we show that Heinrich Layers 5, 4, 2, and 1 in marine sediment cores from across the North Atlantic all bear the organic geochemical fingerprint of the Hudson area. Using this framework and combining previously published results, detailed investigations into the organic and inorganic chemistry of ice-rafted debris (IRD) found across the North Atlantic demonstrate that prior to MIS 16 (~ 650 ka) IRD in the North Atlantic did not originate from the Hudson area of northern Canada. The signature of this early IRD is distinctly different compared to that of HS Heinrich Layers. Rather ice-rafting events during the late Pliocene and early Pleistocene predominantly emanated from the calving of the Greenland and Fennoscandian ice sheets and possibly minor contributions from local ice streams from the North American and British ice sheets. Compared to North Atlantic HS Heinrich Events, these early Pleistocene IRD-events had a limited impact on surface water characteristics in the North Atlantic. North Atlantic HS Heinrich(-like) Events first occurred during MIS 16. At the same time, the dominant frequency in silicate-rich IRD accumulation shifted from the obliquity (41-ka) to a 100-ka frequency across the North Atlantic. Iceberg survivability or a change in iceberg trajectory likely did not control this change in IRD-regime. These results lend further support for the existing hypothesis that an increase in size (thickness) of the Laurentide ice sheet controls the occurrence of North Atlantic HS Heinrich Events, favoring an internal dynamic mechanism for their occurrence.

Dolomite-rich coralline algae in reefs resist dissolution in acidified conditions

Coral reef ecosystems develop best in high-flow environments but their fragile frameworks are also vulnerable to high wave energy. Wave-resistant algal rims, predominantly made up of the crustose coralline algae (CCA) Porolithon onkodes and P. pachydermum, are therefore critical structural elements for the survival of many shallow coral reefs. Concerns are growing about the susceptibility of CCA to ocean acidification because CCA Mg-calcite skeletons are more susceptible to dissolution under low pH conditions than coral aragonite skeletons. However, the recent discovery of dolomite (Mg0.5Ca0.5(CO3)), a stable carbonate, in P. onkodes cells necessitates a reappraisal of the impacts of ocean acidification on these CCA. Here we show, using a dissolution experiment, that dried dolomite-rich CCA have 6-10 times lower rates of dissolution than predominantly Mg-calcite CCA in both high-CO2 (~ 700 ppm) and control (~ 380 ppm) environments, respectively. We reveal this stabilizing mechanism to be a combination of reduced porosity due to dolomite infilling and selective dissolution of other carbonate minerals. Physical break-up proceeds by dissolution of Mg-calcite walls until the dolomitized cell eventually drops out intact. Dolomite-rich CCA frameworks are common in shallow coral reefs globally and our results suggest that it is likely that they will continue to provide protection and stability for coral reef frameworks as CO2 rises.