Stable isotope record, carbonate and organic carbon content of the Miocene section of IODP Site 321-U1337

The Miocene Climatic Optimum (~17-14.7 Ma) represents one of several major interruptions in the long-term cooling trend of the past 50 million years. To date, the processes driving high-amplitude climate variability and sustaining global warmth during this remarkable interval remain highly enigmatic. We present high-resolution benthic foraminiferal and bulk carbonate stable isotope records in an exceptional, continuous, carbonate-rich sedimentary archive (Integrated Ocean Drilling Program Site U1337, eastern equatorial Pacific Ocean), which offer a new view of climate evolution over the onset of the Climatic Optimum. A sharp decline in d18O and d13C at ~16.9 Ma, contemporaneous with a massive increase in carbonate dissolution, demonstrates that abrupt warming was coupled to an intense perturbation of the carbon cycle. The rapid recovery in d13C at ~16.7 Ma, ~200 k.y. after the beginning of the MCO, marks the onset of the first carbon isotope maximum within the long-lasting "Monterey Excursion". These results lend support to the notion that atmospheric pCO2 variations drove profound changes in the global carbon reservoir through the Climatic Optimum, implying a delicate balance between changing CO2 fluxes, rates of silicate weathering and global carbon sequestration. Comparison with a high-resolution d13C record spanning the onset of the Cretaceous Oceanic Anoxic Event 1a (~120 Ma ago) reveals common forcing factors and climatic responses, providing a long-term perspective to understand climate-carbon cycle feedbacks during warmer periods of Earth's climate with markedly different atmospheric CO2 concentrations.

Mineralogy of ODP Hole 117-722B (Appendix)

Bulk mineralogy of the terrigenous fraction of 99 samples from ODP Site 722 on the Owen Ridge, western Arabian Sea, has been determined by x-ray diffraction, using an internal standard method. The sampling interval, approximately 4.3 k.y., provides a detailed mineralogic record for the past 500 k.y. Previous studies have identified important modern continental sediment sources and the mineral assemblages presently derived from each. These studies have also demonstrated that most of this material is supplied by southwest and northwest winds during the summer monsoon. A variety of marine and terrestrial records and general circulation model (GCM) simulations have indicated the importance of monsoonal circulation during the Pleistocene and Holocene and have demonstrated increased aridity during glacial times and increased humidity during inter glacials. The mineralogic data generated here were used to investigate variations in source area weathering conditions during these environmental changes. Terrigenous minerals present include smectite, illite, palygorskite, kaolinite, chlorite, quartz, plagioclase feldspar, and dolomite. This mineralogy is consistent with the compositions of source areas presently supplying sediment to the Arabian Sea. An R-mode factor analysis has identified four mineral assemblages present throughout the past 500 k.y.: quartz/chlorite/dolomite (Factor 1), kaolinite/plagioclase/illite (Factor 2), smectite (Factor 3), and palygorskite/dolomite (Factor 4). Chlorite, illite, and palygorskite are extremely susceptible to chemical weathering, and a spectral comparison of these factors with the eolian mass accumulation rate (MAR) record from Hole 722B (an index of dust source area aridity) indicates that Factors 1, 2, and 4 are directly related to changes in aridity. Because of these characteristics, Factors 1,2, and 4 are interpreted to originate from arid source regions. Factor 3 is interpreted to record more humid source conditions. Time-series of scores for the four factors are dominated by short-term (10-100 k.y.) variability, and do not correlate well to glacial/interglacial fluctuations in the time domain. These characteristics suggest that local climatic shifts were complex, and that equilibrium weathering assemblages did not develop immediately after climatic change. Spectral analysis of factor scores identifies peaks at or near the primary Milankovitch frequencies for all factors. Factor 1 (quartz/chlorite/dolomite), Factor 2 (kaolinite/plagioclase/illite), and Factor 4 (illite/palygorskite) are coherent and in phase with the MAR record over the 23, 41, and 100 k.y. bands, respectively. The reasons for coherency at single Milankovitch frequencies are not known, but may include differences in the susceptibilities of minerals to varying time scales of weathering and/or preferential development of suitable continental source environments by climatic changes at the various Milankovitch frequencies.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Sedimentological and paleomagnetic investigations on two gravity cores and ODP sites 113-690 and 693 off Kapp Norvegia, Antarctic continental margin

Oligocene to Quaternary sediments were recovered from the Antarctic continental margin in the eastern Weddell Sea during ODP Leg 113 and Polarstern expedition ANT-VI. Clay mineral composition and grain size distribution patterns are useful for distinguishing sediments that have been transported by ocean currents from those that were ice-rafted. This, in turn, has assisted in providing insights about the changing late Paleogene to Neogene sedimentary environment as the cryosphere developed in Antarctica. During the middle Oligocene, increasing glacial conditions on the continent are indicated by the presence of glauconite sands, that are interpreted to have formed on the shelf and then transported down the continental slope by advancing glaciers or as a result of sea-level lowering. The dominance of illite and a relatively high content of chlorite suggest predominantly physical weathering conditions on the continent. The high content of biogenic opal from the late Miocene to the late Pliocene resulted from increased upwelling processes at the continental margin due to increased wind strength related to global cooling. Partial melting of the ice-sheet occurred during an early Pliocene climate optimum as is shown by an increasing supply of predominantly current-derived sediment with a low mean grain size and peak values of smectite. Primary productivity decreased at ~ 3 Ma due to the development of a permanent sea-ice cover close to the continent. Late Pleistocene sediments are characterized by planktonic foraminifers and biogenic opal, concentrated in distinct horizons reflecting climatic cycles. Isotopic analysis of AT. pachyderma produced a stratigraphy which resulted in a calculated sedimentation rate of 1 cm/k.y. during the Pleistocene. Primary productivity was highest during the last three interglacial maxima and decreased during glacial episodes as a result of increasing sea-ice coverage.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Chemistry of interstitial water of samples from DSDP Leg 38

Interstitial waters recovered during Leg 38 show large changes in major ion composition and also in oxygen isotope composition. Increases in Ca[++] and Sr[++] and decreases in K[+], Mg[++], and O18/O16 are interpreted in terms of extensive diagenesis of terrigenous, volcanic, or basaltic igneous materials in the sediments and underlying basalts. Slight, but well-established increases in chlorinity with depth indicate that these postulated weathering reactions involve uptake of water to a measurable extent. Interstitial waters from sites drilled on the Inner Voring Plateau suggest the infusion of fresh waters by aquifers from the mainland of Norway.

Chemical composition of the chalcophanite rich surface of an encrusted rock ashore Lake Macquarie, Australia

Mineralogical interest in the nature of manganese oxide particulates in natural marine water (Suess, 1979), natural lake water (Klaveness, 1977), and simulated lake water (Giovanoli, 1980), prompted a search for such particulates in a large New South Wales coastal lake. The investigated waters did show the existence of manganese oxide replacement phenomena in fragmentary sedimentary rocks near the south margin of Lake Macquarie. The black crusts of manganese oxide discovered on rocks close to the waterline have revealed a three layers structure. Layer A (0-35 micron), adjacent to the rock, is composed essentially of kaolinite of weathering origin, together with low levels of manganese oxide without detectable Zn. Layer B (35-80 micron) follows as a manganese oxide layer containing admixed kaolinite and low amounts of Zn. Layer C (80-130 micron) is the closest to the surface and is made of Chalcophanite containing 10-15% of ZnO.

(Table 1) 87Sr/86Sr and Sr/Ca ratios in foraminiferal calcite from DSDP Holes 3-21 and 39-357

The 87Sr/86Sr ratio of ancient seawater, as recorded in marine carbonates, is an important tracer of long-term variations in ocean chemistry (Burke et al., 1982, doi:10.1130/0091-7613(1982)10<516:VOSSTP>2.0.CO;2; Peterman et al., 1970, doi:10.1016/0016-7037(70)90154-7; Dasch and Biscaye, 1971, doi:10.1016/0012-821X(71)90164-6; Veizer and Compston, 1974, doi:10.1016/0016-7037(74)90099-4; Brass, 1976, doi:10.1016/0016-7037(76)90025-9). However, the Sr isotope balance of the oceans has been difficult to constrain; consequently, attempts to evaluate the temporal 87Sr/86Sr changes have been largely qualitative. To constrain the causes of these variations we have measured 87Sr/86Sr ratios in carefully cleaned unrecrystallized foraminifera from DSDP sites 21 and 357. The data presented here have been quantitatively modelled taking advantage of recent advances in understanding of the Sr geochemical cycle. They suggest that whereas hydrothermal fluxes and carbonate recycling are of major importance in defining the marine 87Sr/86Sr ratio, the major control over its variations through the Cenozoic has been changes in the isotope composition of Sr derived from the weathering of silicate rocks.

Nd and Sr isotope record of ODP Sites 121-756 and 122-762 sediments

We have analyzed the Nd isotopic composition of both ancient seawater and detrital material from long sequences of carbonated oozes of the South Indian Ocean which are ODP Site 756 (Ninety East Ridge (-30°S), 1518 m water depth) and ODP Site 762 (Northwest Australian margin, 1360 m water depth). The measurements indicate that the epsilon-Nd changes in Indian seawater over the last 35 Ma result from changes in the oceanic circulation, large volcanic and continental weathering Nd inputs. This highlights the diverse nature of those controls and their interconnections in a small area of the ocean. These new records combined with those previously obtained at the equatorial ODP Sites 757 and 707 in the Indian Ocean (Gourlan et al., 2008, doi:10.1016/j.epsl.2007.11.054) established that the distribution of intermediate seawater epsilon-Nd was uniform over most of the Indian Ocean from 35 Ma to 10 Ma within a geographical area extending from 40°S to the equator and from -60°E to 120°E. However, the epsilon-Nd value of Indian Ocean seawater which kept an almost constant value (at about -7 to -8) from 35 to 15 Ma rose by 3 epsilon-Nd units from 15 to 10 Ma. This sharp increase has been caused by a radiogenic Nd enrichment of the water mass originating from the Pacific flowing through the Indonesian Passage. Using a two end-members model we calculated that the Nd transported to the Indian Ocean through the Indonesian Pathway was 1.7 times larger at 10 Ma than at 15 Ma. The Nd isotopic composition of ancient seawater and that of the sediment detrital component appear to be strongly correlated for some specific events. A first evidence occurs between 20 and 15 Ma with two positive spikes recorded in both epsilon-Nd signals that are clearly induced by a volcanic crisis of, most likely, the St. Paul hot-spot. A second evidence is the very large epsilon-Nd decrease recorded at ODP Sites 756 and 762 during the past 10 Ma which has never been previously observed. The synchronism between the epsilon-Nd decrease in seawater from 10 to 5 Ma and evidences of desertification in the western part of the nearly Australian continent suggests enhanced weathering inputs in this ocean from this continent as a result of climatic changes.

Mineralogy, geochemistry, isotopic ratios and foraminifer occurrence in ODP Hole 183-1139A

Mixed terrigenous-pelagic sediments from the Oligocene-lower Miocene interval of Hole 1139A accumulated on the flank of an eroded alkalic volcano, Skiff Bank. In this study, I explore relationships among sediment fluxes, especially of organic carbon and the clay mineral by-products of silicate weathering, and lithologic, tectonic, climatic, and biologic forcing factors. Benthic foraminifers indicate that Skiff Bank had subsided to lower bathyal depths (1000-2000 m) by the Oligocene. Two prominent maxima in noncarbonate concentration at 28 and 22 Ma correspond to peaks in the terrigenous flux; also, high noncarbonate concentrations are associated with larger grain sizes (silt) and higher opal concentrations. These and higher-frequency variations of noncarbonate concentration were probably controlled by glacioeustatic/climatic changes, with higher noncarbonate concentrations caused by increased erosion during glacial lowstands. Around 27 Ma, benthic foraminiferal d18O values decreased 0.7 per mil as the noncarbonate concentration decreased after the 28-Ma maximum. A paucity of clay-sized sediment and clay minerals suggests that physical erosion, by waves and/or ice, predominated under weathering-limited conditions. Low organic carbon concentrations (~0.13 wt%) also suggest a harsh environment and/or poor preservation in coarse (>2 µm) sediments that were extensively bioturbated below the oxygen minimum zone.