Strontium isotopic composition and chronology of sediments from DSDP Site 90-588

We report 261 strontium isotopic analyses of well-preserved planktonic foraminifers from three Deep Sea Drilling Project Sites (519, 588, and 607). These samples cover the period from 24 Ma to present with an average of approximately one sample per 100 ka. The combination of high sample density and uniformity of analytical procedures has produced a well-defined record of changes in the 87Sr/86Sr of seawater during the Neogene. The record can be viewed as a series of essentially linear segments with slopes ranging from as high as 0.00006/m.y. to as low as 0/m.y. The times associated with major inflections in the curve do not appear to correspond to simple geologic phenomena such as eustatic cycles, but are probably controlled by a combination of tectonic and climatic factors that influenced the abundance and isotopic composition of terrestrial strontium input to the oceans. The strontium isotopic data are consistent with a progressive increase in the chemical weathering rates of the continents during the Neogene, probably related to repeated glaciations, increased exposure of continents by lowered sea level, and increased continental relief resulting from high rates of tectonic uplift.

Ba/Ca ratios in Neogloboquadrina pachyderma of sedimet core 94B17

Down-core samples of the planktonic foraminifer Neogloboquadrina pachyderma sinistral from the Mendeleyev Ridge in the western Arctic Ocean have been analyzed for Ba/Ca and d18O. The apparent distribution coefficient for N. pachyderma sin. is estimated at DBa = 0.22 ± 0.02. A meltwater event is identified at around 11.8 14C kyr BP and is coincident with elevated Ba/Ca ratios. The barium enrichment is believed to be the result of enhanced weathering and erosion following glaciation. Additionally, barium may have desorbed from shelf sediments as sea level rose. Changes in Ba/Ca correlate with the retreat of the Laurentide Ice Sheet and the evolution of the Mackenzie River drainage basin. Therefore maximum Ba/Ca in Arctic surface waters at 11.8 ka may be indicative of an increase in the export of freshwater from the Arctic to the North Atlantic, potentially contributing to the onset of the Younger Dryas. This work suggests that Ba/Ca in planktonic foraminifera may be a useful indicator of the timing and processes associated with deglaciation.

X-ray fluorescence scanning of discrete samples on the Schwalbenberg II loess-paleosol sequence, raw data, magnetic susceptibility, organic carbon and U-ratio as grainsize index

The Schwalbenberg II loess-paleosol sequence (LPS) denotes a key site for Marine Isotope Stage (MIS 3) in Western Europe owing to eight succeeding cambisols, which primarily constitute the Ahrgau Subformation. Therefore, this LPS qualifies as a test candidate for the potential of temporal high-resolution geochemical data obtained X-ray fluorescence (XRF) scanning of discrete samplesproviding a fast and non-destructive tool for determining the element composition. The geochemical data is first contextualized to existing proxy data such as magnetic susceptibility (MS) and organic carbon (Corg) and then aggregated to element log ratios characteristic for weathering intensity [LOG (Ca/Sr), LOG (Rb/Sr), LOG (Ba/Sr), LOG (Rb/K)] and dust provenance [LOG (Ti/Zr), LOG (Ti/Al), LOG (Si/Al)]. Generally, an interpretation of rock magnetic particles is challenged in western Europe, where not only magnetic enhancement but also depletion plays a role. Our data indicates leaching and top-soil erosion induced MS depletion at the Schwalbenberg II LPS. Besides weathering, LOG (Ca/Sr) is susceptible for secondary calcification. Thus, also LOG (Rb/Sr) and LOG (Ba/Sr) are shown to be influenced by calcification dynamics. Consequently, LOG (Rb/K) seems to be the most suitable weathering index identifying the Sinzig Soils S1 and S2 as the most pronounced paleosols for this site. Sinzig Soil S3 is enclosed by gelic gleysols and in contrast to S1 and S2 only initially weathered pointing to colder climate conditions. Also the Remagen Soils are characterized by subtle to moderate positive excursions in the weathering indices. Comparing the Schwalbenberg II LPS with the nearby Eifel Lake Sediment Archive (ELSA) and other more distant German, Austrian and Czech LPS while discussing time and climate as limiting factors for pedogenesis, we suggest that the lithologically determined paleosols are in-situ soil formations. The provenance indices document a Zr-enrichment at the transition from the Ahrgau to the Hesbaye Subformation. This is explained by a conceptual model incorporating multiple sediment recycling and sorting effects in eolian and fluvial domains.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Chemical composition of the red bed layer in DSDP Hole 38-336

Clay minerals were studied in samples from the Eocene red bed layer of DSDP Hole 336. It is shown that composition and distribution of clay minerals have zoning, which is usually typical for the terrestrial crust of chemical weathering of basic rocks.

Mineral quantification of a Jordan Cretaceous outcrop (Section GM3, Ghawr Al Mazar, Ghor al Mazrar)

Cyclic fluctuations in global sea level during epochs of warm greenhouse climate have remained enigmatic, because absence or subordinate presence of polar ice during these periods precludes an explanation by glacio-eustatic forcing. An alternative concept suggests that the water-bearing potential of groundwater aquifers is equal to that of ice caps and that changes in the dynamic balance of aquifer charge versus discharge, as a function of the temperature-related intensity of the hydrological cycle, may have driven eustasy during warm climates. However, this idea has long been neglected for two reasons: 1) the large storage potential of subsurface aquifers was confused with the much smaller capacity of rivers and lakes and 2) empirical data were missing that document past variations in the hydrological cycle in relation to eustasy. In the present study we present the first empirical evidence for changes in precipitation, continental weathering intensity and evaporation that correlate with astronomically (long obliquity) forced sea-level cycles during the warmest period of the Cretaceous (Cenomanian-Turonian). We compare sequence-stratigraphic data with changes in the terrigenous mineral assemblage in a low-latitude marine sedimentary sequence from the equatorial humid belt at the South-Tethyan margin (Levant carbonate platform, Jordan), thereby avoiding uncertainties from land-ocean correlations. Our data indicate covariance between cycles in weathering and sea level: predominantly chemical weathering under wet climate conditions is reflected by dominance of weathering products (clays) in deposits that represent sea-level fall (aquifer charge > discharge). Conversely, preservation of weathering-sensitive minerals (feldspars, epidote and pyroxenes) in transgressive sediments reflects decreased continental weathering due to dryer climate (aquifer discharge > charge). Based on our results we suggest that aquifer-eustasy represents a viable alternative to glacio-eustasy as a driver of cyclic 3rd-order sea-level fluctuations during the middle Cretaceous greenhouse climate, and it may have been a pervasive process throughout Earth history.

Lead isotopes inthe Eastern Equatorial Pacific

The influence of atmospheric dust on climate and biogeochemical cycles in the oceans is well understood but poorly quantified. Glacial atmospheric dust loads were generally greater than those during the Holocene, as shown, for example, by the covariation of dust fluxes in the Equatorial Pacific and Antarctic ice cores. Nevertheless, it remains unclear whether these increases in dust flux were associated with changes in sources of dust, which would in turn suggest variations in wind patterns, climate or paleo-environment. Such questions can be answered using radiogenic isotope tracers of dust provenance. Here, we present a 160-kyr high-precision lead isotope time-series of dust input to the Eastern Equatorial Pacific (EEP) from core ODP Leg 138, Site 849 (0°11.59' N, 110°31.18' W). The Pb isotope record, combined with Nd isotope data, rules out contributions from Northern Hemisphere dust sources, north of the Intertropical Convergence Zone, such as Asia or North Africa/Sahara; similarly, eolian sources in Australia, Central America, the Northern Andes and Patagonia appear insignificant based upon the radiogenic isotope data. Fluctuations in Pb isotope ratios throughout the last 160 kyr show, instead, that South America remained the prevailing source of dusts to the EEP. There are two distinct South American Pb isotope end-members, constrained to be located in the south Central Volcanic Zone (CVZ, 22° S - 27.5° S) and the South Volcanic Zone (SVZ, 33° S - 43° S), with the former most likely originating in the Atacama Desert. Dust availability in the SVZ appears to be related to the weathering of volcanic deposits and the development of ash-derived Andosols, and influenced by local factors that might include vegetation cover. Variations in the dust fluxes from the two sources are in phase with both the dust flux and temperature records from Antarctican ice cores. We show that the forcing of dust provenance over time in the EEP overall is influenced by high-southerly-latitude climate conditions, leading to changes in the latitudinal position and strength of the South Westerlies as well as the coastal winds that blow northward along the Chilean margin. The net result is a modulation of dust emission from the Atacama Desert and the SVZ via a northward migration of the South Westerlies during cold periods and southward retreat during glacial terminations.

Clay mineralogy of the Cenozoic Pagodroma Group, East Antarctica

The Cenozoic Pagodroma Group in the northern Prince Charles Mountains, East Antarctica, is a glaciomarine succession of fjordal character, comprising four uplifted formations of different ages. The composition of the <2 µm fraction of sediments of the Pagodroma Group was analysed in order to help identify source areas, past weathering conditions and glacial regimes. Both clay and non-clay minerals have been quantified. The assemblage of the upper Oligocene to lower Miocene Mount Johnston Formation is characterised by the dominance of illite and intermediate concentrations of chlorite. Similar to that assemblage is the clay mineral suite of the middle Miocene Fisher Bench Formation, where illite and chlorite together account for 95% of the clay minerals. The middle to upper Miocene Battye Glacier Formation is the only formation with significant and persistent smectite concentrations, although illite is still dominant. The kaolinite concentration is also high and is even higher than that of chlorite. The clay fraction of the upper Pliocene to lower Pleistocene Bardin Bluffs Formation is characterised by maximum kaolinite concentrations and relatively low illite and chlorite concentrations. The bulk of the clay fraction in each formation can be explained by the physical weathering and erosion of a nearby source under glacial conditions. In the case of Mount Johnston Formation and Fisher Bench Formation this source may be situated in the metavolcanic and gneissic rocks of Fisher Massif. The sediments of the Bardin Bluffs Formation indicate a local source within the Amery Oasis, where Proterozoic granitoid rocks and gneisses, and Permo-Triassic fluvial rocks of the Amery Group are exposed. These results suggest a strong local imprint on the glacial sediments as northwards flowing ice eroded the bedrock in these areas. The origin of the clay fraction of the Battye Glacier Formation is a matter of debate. The smectite and kaolinite content most easily can be explained by erosion of sources largely hidden beneath the ice upstream. Less likely, these clay minerals reflect climatic conditions that were much warmer and wetter than today, facilitating chemical weathering.

Mineralogy of southern Kerguelen Plateau sediments

Kaolinite, goethite, minor hematite, and gibbsite were found in fluvial upper Lower Cretaceous basal sediment from the Southern Kerguelen Plateau, Sites 748 and 750, 55°S latitude. This mineral assemblage, derived from the weathering of basalt, indicates near-tropical weathering conditions with high orographic rainfall, at least 100 cm per year. The climate deteriorated by the Turonian or Coniacian, as indicated by the decline in kaolinite content of this sediment. The Upper Cretaceous sediment at Site 748 consists of 200 m of millimeter-laminated, sparsely fossiliferous, wood-bearing glauconitic siltstone and clay stone with siderite concretions deposited on a shelf below wave base. Some graded and cross beds indicate that storms swept over the shelf and reworked the sediment. Overlying this unit is 300 m of intermittently partly silicified, bryozoan-inoceramid-echinoderm-rich glauconitic packstones, grainstones, and wackestones. The dominant clay mineral in both units is identical to the mineral composition of the glauconite pellets: randomly interstratified smectite-mica. The clay fraction has a higher percent of expandable layers than the mineral of the glauconite pellets, and the clay of the underlying subunit has a higher percentage of expandable layers than the clay of the carbonate subunit. Potassium levels mirror these mineral variations, with higher K levels in minerals that have a lower percentage of expandable layers. The decrease in expandability of the mineral in the upper subunit is attributed to diagenesis, the result of higher porosity.

Clay mineralogy of Cape Roberts sediment cores

The clay mineral assemblages of the ca. 1600 m thick Cenozoic sedimentary succession recovered at the CRP-1, CRP-2/2A and CRP-3 drill sites off Cape Roberts on the McMurdo Sound shelf, Antarctica, were analysed in order to reconstruct the palaeoclimate and the glacial history of this part of Antarctica. The sequence can be subdivided into seven clay mineral units that reflect the transition from humid to subpolar and polar conditions. Unit I (35-33.6 Ma) is characterised by an almost monomineralic assemblage consisting of well crystalline, authigenic smectite, and therefore does not allow a palaeoclimatic reconstruction. Unit II (33.6-33.1 Ma) has also a monomineralic clay mineral composition. However, the assemblage consists of variably crystallized smectite that, at least in part, is of detrital origin and indicates chemical weathering under a humid climate. The main source area for the clays was in the Transantarctic Mountains. Minor amounts of illite and chlorite appear for the first time in Unit III (33.1-31 Ma) and suggest subordinate physical weathering. The sediments of Unit IV (31-30.5 Ma) have strongly variable smectite and illite concentrations indicating an alternation of chemical weathering periods and physical weathering periods. Unit V (30.5-24.2 Ma) shows a further shift towards physical weathering. Unit VI (24.2-18.5 Ma) indicates strong physical weathering under a cold climate with persistent and intense illite formation. Unit VII (18.5 Ma to present) documents an additional input of smectite derived from the McMurdo Volcanic Group in the south.

Biostratigraphy and Sr isotopic composition of sediments from DSDP Legs 12, 14, 15, 17, 20-22, and 30

We present the data used to construct the Cenozoic and Cretaceous portion of the Phanerozoic curve of seawater 87Sr/86Sr that had been given in summary form by W.H. Burke co-workers. All Cenozoic samples (128) and 22 Cretaceous samples are foram-nannofossil oozes and limestones from DSDP cores distributed among 13 sites in the Atlantic, Pacific and Indian Oceans, and the Caribbean Sea. Non-DSDP Cretaceous samples (126) include limestone, anhydrite and phosphate samples from North America, Europe and Asia. Determination of the 87Sr/86Sr value of seawater at particular times in the past is based on comparison of ratios derived from coeval marine samples from widely separated geographic areas. These samples are characterized by a wide variety of diagenetic and burial histories. The large size and cosmopolitan nature of the data set decreases the likelihood that, among coeval data, systematic error has been introduced by a similar pattern of diagenetic alteration of the ratios. There is good clustering of data points throughout the Cenozoic and Cretaceous curve. The consistency of data is illustrated by Cenozoic and Cretaceous data plots that include a separate symbol for each DSDP site and non-DSDP sample location. More than 98% of the data points are enclosed by upper and lower lines that define a narrow band. For any given time, the correct seawater ratio probably lies within this band. A line drawn within the band represents our estimate of the actual seawater ratio as a function of time. The general configuration of the Cenozoic and Cretaceous curve appears to be strongly influenced by the history of plate interactions and sea-floor spreading. Specific rises and falls in the 87Sr/86Sr of seawater, however, may be caused by a variety of factors such as variation in lithologic composition of the crust exposed to weathering, configuration and topographic relief of continents, volcanic activity, rate of sea-floor spreading, extent of continental inundation by epeiric seas, and variations in both climate and paleooceanographic conditions. Many or all of these factors are probably related to global tectonic processes, yet their combined effect on the temporal variation of seawater 87Sr/86Sr can complicate a direct platetectonic interpretation for portions of the seawater curve.

Secondary mineral assemblages in a volcanic sequence of ODP Hole 104-642E

Mineralogical and geochemical analyses of alteration products from upper and lower volcanic series recovered during ODP Leg 104 reveal variations both in composition and order of crystallization of clay minerals vesicles and voids filling and replacing glass. These results provide information about successive alteration stages of rocks and interlayered volcaniclastic sediments. The first stage, related to initial basalt-seawater interaction, is characterized by development of Fe-smectites, especially Fe-rich saponite. A second stage of intermittently superimposed subaerial weathering is marked by iron-oxides-halloysite-kaolinite formation. The third episode, interpreted as hydrothermal on the basis of O-isotopic data, is defined by postburial coprecipitation of Fe-poor, Mg-rich saponite and celadonite. A distinct final and pervasive hydrothermal stage, occurring mainly in the lower series and dominated by Al-smectites-zeolites assemblage, indicates changes toward a more reducing alteration environment.