Calcium isotope ratios from marine barite and carbonate over Paleocene-Eocene Boundary (ODP Sites 1212 and 1221)

Carbonates are invaluable archives of the past, and have been used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales. Such archives are susceptible to diagenetic alteration via dissolution, recrystallization and secondary precipitation, particularly during ocean acidification events when intense dissolution can occur. Despite the importance of diagenesis on proxy fidelity, the effects of diagenesis on the calcium isotopic composition (d44Ca) of carbonates are unclear. Accordingly, bulk carbonate d44Ca was measured at high resolution in two Pacific deep sea sediment cores (ODP Sites 1212 and 1221) with considerably different dissolution histories over the Paleocene-Eocene Thermal Maximum (PETM, ~55 Ma). The d44Ca of marine barite was also measured at the deeper Site 1221, which experienced severe carbonate dissolution during the PETM. Large (~0.8 per mil) variations in bulk carbonate d44Ca occur in the deeper site near the peak carbon isotope excursion, and are correlated with a large drop in carbonate weight percent. Such an effect is seen in neither the 1221 barite record nor the bulk carbonate record at the shallower, less dissolved Site 1212. We contend that ocean chemical changes associated with the abrupt and massive carbon release into the ocean-atmosphere system and subsequent ocean acidification at the PETM affected the bulk carbonate d44Ca record via diagenesis in the sedimentary column. Such changes are considerable, and need to be taken into account when interpreting and modeling Ca isotope data over extreme climatic events associated with ocean chemical evolution.

Chemical composition of zeolites in sandstones at DSDP Sites 445 and 446

Andesitic volcaniclastic sandstones of Middle Eocene age recovered from DSDP Sites 445 and 446, a back-arc basin, contain clinoptilolite, heulandite and analcite as a pore-filling cement. Clinoptilolite and heulandite at Sites 445 and 446 contain different chemical composition from other deep-sea clinoptilolites and heulandites. The dominant cation of both clinoptilolite and heulandite is Na+ ion activity in pore water was greater at the time of their formation. Volcanic glass has acted as a precursor for both clinoptilolite and heulandite at Sites 445 and 446. Biogenic silica is also suggested as a precursor. High Na+ ion activity in pore water also helped to transform clinoptilolite and heulandite to analcite downhole. The necessary Na+ ions for this clinoptilolite, heulandite and analcite at Sites 445 and 446 might have been provided by hydrothermal circulation of seawater through more permeable sandstones deposited during early stages of back-arc basin rifting.

Stable isotopes and XRF data over the Paleocene-Eocene Thermal Maximum from IODP Sites U1403 and U1409

During the Paleocene-Eocene Thermal Maximum (PETM) about 56 million years ago, thousands of petagrams of carbon were released into the atmosphere and ocean in just a few thousand years, followed by a gradual sequestration over approximately 200,000 years. If silicate weathering is one of the key negative feedbacks that removed this carbon, a period of seawater calcium carbonate saturation greater than pre-event levels is expected during the event's recovery phase. In marine sediments, this should be recorded as a temporary deepening of the depth below which no calcite is preserved - the calcite compensation depth (CCD). Previous and new sedimentary records from sites that were above the pre-PETM calcite compensation depth show enhanced carbonate accumulation following the PETM. A new record from an abyssal site in the North Atlantic that lay below the pre-PETM calcite compensation depth shows a period of carbonate preservation beginning about 70,000 years after the onset of the PETM, providing the first direct evidence for an over-deepening of the calcite compensation depth. This record confirms an overshoot in ocean carbonate saturation during the PETM recovery. Simulations with two earth system models support scenarios for the PETM that involve both a large initial carbon release followed by prolonged low-level emissions, consistent with the timing of CCD deepening in our record. Our findings indicate that sequestration of these carbon emissions was most likely the result of both globally enhanced calcite burial above the calcite compensation depth and, at least in the North Atlantic, by a temporary over-deepening of the calcite compensation depth.

Mineral an chemical composition of basalts from DSDP Sites 417 and 418, West Atlantic Ocean

Major element composition ranges of closely associated basalt glass-whole rock pairs from individual small cooling units approach the total known range of basalt glass and whole rock compositions at IPOD sites 417 and 418. The whole rock samples fall into two groups: one is depleted in MgO and distinctly enriched in plagioclase but has lost some olivine and/or pyroxene relative to its corresponding glass; and the other is enriched in MgO and in phenocrysts of olivine and pyroxene as well as plagioclase compared to its corresponding glass. By analogy with observed phenocryst distributions in lava pillows, tubes, and dikes, and with some theoretical studies, we infer that bulk rock compositions are strongly affected by phenocryst redistribution due to gravity settling, flotation, and dynamic sorting after eruption, although specific models are not well constrained by the one-dimensional geometry of drill core. Compositional trends or groupings in whole rock data resulting from such late-stage processes should not be confused with more fundamental compositional effects produced in deep chambers or during partial melting.

Permafrost longterm monitoring sites (Arctic and Antarctic)

About 50 locations ('cold spots') where permafrost (Arctic and Antarctic) in situ monitoring has been taking place for many years or where field stations are currently established (through, for example the Canadian ADAPT program) have been identified. These sites have been proposed to WMO Polar Space Task Group as focus areas for future monitoring by satellite data. Seven monitoring transects spanning different permafrost types have been proposed in addition.

Microbialites and lipid biomarker from coral reefs off the volcanic islands Tahiti and Vanuatu and from the nonvolcanic sites Belize and the Maldives

The occurrence of microbialites in post-glacial coral reefs has been interpreted to reflect an ecosystem response to environmental change. The greater thickness of microbialites in reefs with a volcanic hinterland compared to thinner microbial crusts in reefs with a non-volcanic hinterland led to the suggestion that fertilization of the reefal environment by chemical weathering of volcanic rocks stimulated primary productivity and microbialite formation. Using a molecular and isotopic approach on reef-microbialites from Tahiti (Pacific Ocean), it was recently shown that sulfate-reducing bacteria favored the formation of microbial carbonates. To test if similar mechanisms induced microbialite formation in other reefs as well, the Tahitian microbialites are compared with similar microbialites from coral reefs off Vanuatu (Pacific Ocean), Belize (Caribbean Sea, Atlantic Ocean), and the Maldives (Indian Ocean) in this study. The selected study sites cover a wide range of geological settings, reflecting variable input and composition of detritus. The new lipid biomarker data and stable sulfur isotope results confirm that sulfate-reducing bacteria played an intrinsic role in the precipitation of microbial carbonate at all study sites, irrespective of the geological setting. Abundant biomarkers indicative of sulfate reducers include a variety of terminally-branched and mid chain-branched fatty acids as well as mono-O-alkyl glycerol ethers. Isotope evidence for bacterial sulfate reduction is represented by low d34S values of pyrite (-43 to -42 per mill) enclosed in the microbialites and, compared to seawater sulfate, slightly elevated d34S and d18O values of carbonate-associated sulfate (21.9 to 22.2 per mill and 11.3 to 12.4 per mill, respectively). Microbialite formation took place in anoxic micro-environments, which presumably developed through the fertilization of the reef environment and the resultant accumulation of organic matter including bacterial extracellular polymeric substances (EPS), coral mucus, and marine snow in cavities within the coral framework. ToF-SIMS analysis reveals that the dark layers of laminated microbialites are enriched in carbohydrates, which are common constituents of EPS and coral mucus. These results support the hypothesis that bacterial degradation of EPS and coral mucus within microbial mats favored carbonate precipitation. Because reefal microbialites formed by similar processes in very different geological settings, this comparative study suggests that a volcanic hinterland is not required for microbialite growth. Yet, detrital input derived from the weathering of volcanic rocks appears to be a natural fertilizer, being conductive for the growth of microbial mats, which fosters the development of particularly abundant and thick microbial crusts.

Pollen and spores of sites GeoB8331 and GeoB8323, Namaqualand Mudbelt, Holocene South Africa

To better understand Holocene vegetation and hydrological changes in South Africa, we analyzed pollen and microcharcoal records of two marine sites GeoB8331 and GeoB8323 from the Namaqualand mudbelt offshore the west coast of South Africa covering the last 9900 and 2200 years, respectively. Our data corroborate findings from literature that climate developments apparently contrast between the summer rainfall zone (SRZ) and winter rainfall zone (WRZ) over the last 9900 years, especially during the early and middle Holocene. During the early Holocene (9900-7800 cal.yr BP), a minimum of grass pollen suggests low summer rainfall in the SRZ, and the initial presence of Renosterveld vegetation indicates relatively wet conditions in the WRZ. Towards the middle Holocene (7800-2400 cal. yr BP), a rather moist savanna/grassland rich in grasses suggests higher summer rainfall in the SRZ resulting from increased austral summer insolation and a decline of fynbos vegetation accompanied by an increasing Succulent Karoo vegetation in the WRZ possibly suggests a southward shift of the Southern Hemisphere westerlies. During the last 2200 years, a trend towards higher aridity was observed for the SRZ, while the climate in the WRZ remained relatively stable. The Little Ice Age (ca. 700-200 cal. yr BP) was rather cool in both rainfall zones and drier in the SRZ while wetter in the WRZ.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Cretaceous calcareous nannofossils from Exmouth and Wombat Plateau, Northwest Australia

Three sites drilled during Leg 122, Site 761 on the Wombat Plateau and Sites 762 and 763 on the Exmouth Plateau, provide a composite Cretaceous section ranging in age from Berriasian to Maestrichtian. Together, these sites contain an apparently complete, expanded Aptian-Maestrichtian record. Consistently occurring and moderately well-preserved nannofossil assemblages allow reasonably high biostratigraphic resolution. Our data indicate that traditional middle and Upper Cretaceous nannofossil biozonations are not entirely applicable in this region. In this investigation, we compare in detail the relative ranges of key Cretaceous nannofossil markers in the eastern Indian Ocean and in sections from Europe and North Africa. We have determined which previously used events are applicable, and which additional markers have biostratigraphic utility in this region. Significant differences in Campanian-Maestrichtian assemblages exist between the more northern Site 761 and Sites 762 and 763. Such differences are surprising, considering that these sites are only separated by 3° of latitude. We interpret them as marking a strong thermal gradient over the Exmouth Plateau region. Other results include the recovery of an expanded Albian-Cenomanian sequence containing a mixture of Austral and Tethyan floras, which will enable correlation of biozonations established for these two realms; the recovery of two condensed but apparently complete Cenomanian-Turonian boundary sections; correlation of Upper Cretaceous calcareous nannofossil biostratigraphy with magneto- and foraminifer stratigraphy; and correlation of portions of the Barrow Group equivalents to the Berriasian and Valanginian stages.