Chemistry of igneous rocks from, the Celebes Sea basement

Major and trace elements, mineral chemistry, and Sr-Nd isotope ratios are reported for representative igneous rocks of Ocean Drilling Program Sites 767 and 770. The basaltic basement underlying middle Eocene radiolarianbearing red clays was reached at 786.7 mbsf and about 421 mbsf at Sites 767 and 770, respectively. At Site 770 the basement was drilled for about 106 m. Eight basaltic units were identified on the basis of mineralogical, petrographical, and geochemical data. They mainly consist of pillow lavas and pillow breccias (Units A, B, D, and H), intercalated with massive amygdaloidal lavas (Units Cl and C2) or relatively thin massive flows (Unit E). Two dolerite sills were also recognized (Units F and G). All the rocks studied show the effect of low-temperature seafloor alteration, causing almost total replacement of olivine and glass. Calcite, clays, and Fe-hydroxides are the most abundant secondary phases. Chemical mobilization due to the alteration processes has been evaluated by comparing elements that are widely considered mobile during halmyrolysis (such as low-field strength elements) with those insensitive to seafloor alteration (such as Nb). In general, MgO is removed and P2O5 occasionally enriched during the alteration of pillow lavas. Ti, Cs, Li, Rb, and K, which are the most sensitive indicators of rock/seawater interaction, are generally enriched. The most crystalline samples appear the least affected by chemical changes. Plagioclase and olivine are continuously present as phenocrysts, and clinopyroxene is confined in the groundmass. Textural and mineralogical features as well as crystallization sequences of Site 770 rocks are, in all, analogous to typical mid-ocean-ridge basalts (MORBs). Relatively high content of compatible trace elements, such as Ni and Cr, indicate that these rocks represent nearly primitive or weakly fractionated MORBs. All the studied rocks are geochemically within the spectrum of normal MORB compositional variation. Their Sr/Nd isotopic ratios plot on the mantle array (87Sr/87Sr 0.70324-0.70348 with 143Nd/144Nd 0.51298-0.51291) outside the field of Atlantic and Pacific MORBs. However, Sr and Nd isotopes are typical of both Indian Ocean MORBs and of some back-arc basalts, such as those of Lau Basin. The mantle source of Celebes basement basalts does not show a detectable influence of a subduction-related component. The geochemical and isotopic data so far obtained on the Celebes basement rocks do not allow a clear discrimination between mid-ocean ridge and back-arc settings.

Feldspar Pb-isotope ratios for earliest Pleistocene sediments of the sub-polar North Atlantic Ocean

Relatively little is known in detail about the locations of the early Pleistocene ice-sheets responsible for ice-rafted debris (IRD) inputs to the sub-polar North Atlantic Ocean during intensification of northern hemisphere glaciation (iNHG). To shed new light on this problem, we present the first combined in-depth analysis of IRD flux and geochemical provenance of individual sand-sized IRD deposited in the sub-polar North Atlantic Ocean during the earliest large amplitude Pleistocene glacial, marine isotope stage (MIS) 100 (~2.52 Ma), arguably the key glacial during iNHG. IRD provenance is assessed using laser ablation lead (Pb) isotope analyses of single feldspar grains. We find that the Pb-isotope composition (206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb) of individual ice-rafted (>150 µm) feldspars deposited at DSDP Site 611A, ODP Site 981 and IODP Site U1308 during MIS 100 records a shift from predominantly Archaean-aged circum-North Atlantic Ocean continental sources during early glacial ice-rafting events to dominantly Palaeozoic and Proterozoic-aged sources during full glacial conditions. The distribution of feldspars in Pb-Pb space for full glacial MIS 100 more closely resembles that documented for feldspars deposited at the centre of the last glacial IRD belt (at IODP/DSDP Site U1308/609) during ambient (non-Heinrich-event) ice-rafting episodes of MIS 2 (~23.8 ka) than that documented for MIS 5d (~106 ka). Comparison of our early Pleistocene and last glacial cycle datasets suggests that MIS 100 was characterised by abundant iceberg calving from large ice-sheets on multiple continents in the high northern latitudes (not just on Greenland).

Geochemistry and petrology of ODP Site 136-843 basalts

About 13 m of Cretaceous, tholeiitic basalt, ranging from normal (N-MORB) to transitional (T-MORB) mid-ocean-ridge basalts, was recovered at Ocean Drilling Program Site 843 west of the island of Hawaii. These moderately fractionated, aphyric lavas are probably representative of the oceanic basement on which the Hawaiian Islands were built. Whole-rock samples from parts of the cores exhibiting only slight, low-temperature, seawater alteration were analyzed for major element, trace element, and isotopic composition. The basalts are characterized by enrichment in the high field strength elements relative to N-MORB, by a distinct positive Eu anomaly, and by Ba/Nb and La/Nb ratios that are much lower than those of other crustal or mantle-derived rocks, but their isotope ratios are similar to those of present-day N-MORB from the East Pacific Rise. Hole 843A lavas are isotopically indistinguishable from Hole 843B lavas and are probably derived from the same source at a lower degree of partial melting, as indicated by lower Y/Nb and Zr/Nb ratios and by higher concentrations of light and middle rare earth elements and other incompatible elements relative to Hole 843B lavas. Petrographic and trace-element evidence indicates that the Eu anomaly was the result of neither plagioclase assimilation nor seawater alteration. The Eu anomaly and the enrichments in Ta, Nb, and possibly U and K relative to N-MORB apparently are characteristic of the mantle source. Age-corrected Nd and Sr isotopic ratios indicate that the source for the lavas recovered at ODP Site 843 was similar to the source for Southeast Pacific MORB. An enriched component within the Cretaceous mantle source of these basalts is suggested by their initial 208Pb/204Pb-206Pb/204Pb and epsilon-Nd-206Pb/204Pb ratios. The Sr-Pb isotopic trend of Hawaiian post-shield and post-erosional lavas cannot be explained by assimilation of oceanic crust with the isotopic composition of the Site 843 basalts.

Beryllium, thorium and protactinium isotope ratios in sediments from the Galapagos microplate

Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Sedimentology and geochemistry of Oxygen Isotope Stage 3 and Holocene sediments from Laguna Potrok Aike, Patagonia

Seismic reflection studies in the maar lake Laguna Potrok Aike (51°58? S, 70°23? W) revealed an erosional unconformity associated with a sub-aquatic lake-level terrace at a water depth of 30m. Radiocarbon-dated, multi-proxy sediment studies of a piston core from this location indicate that the sediment below this discontinuity has an age of 45kyr BP (Oxygen Isotope Stage 3), and was deposited during an interval of high lake level. In comparison to the Holocene section, geochemical indicators of this older part of the record either point towards a different sediment source or to a different transport mechanism for Oxygen Isotope Stage 3 sediments. Holocene sedimentation started again before 6790cal. yr BP, providing a sediment record of hydrological variability until the present. Geochemical and isotopic data indicate a fluctuating lake level until 5310cal. yr BP. During the late Holocene the lake level shows a receding tendency. Nevertheless, the lake level did not drop below the 30m terrace to create another unconformity. The geochemical characterization of volcanic ashes reveals evidence for previously unknown explosive activity of the Reclús and Mt. Burney volcanoes during Oxygen Isotope Stage 3.

Pb isotopes in Cenozoic sediments of ODP Site 177-1090

Nd and Pb isotopic compositions extracted from bulk deep sea sediments have been shown to be robust proxies for deep water circulation as well as weathering provenance and intensity over geologically young time scales. In this study we evaluated ten deep sea samples from Ocean Drilling Program (ODP) site 1090 ranging in age from mid Eocene to early-Miocene to test whether Pb isotopic compositions extracted from geologically older sediments record reliable seawater isotopic ratios and to evaluate the source of the extracted Pb. The sequential extraction protocol used in this study is similar to protocols reported for previous studies and produces acetic acid, hydroxylamine hydrochloride (HH) and residue fractions. Each extracted fraction was analyzed for Pb isotopes, rare earth elements (REEs), and a suite of major elements. Similar 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios are recorded from the acetic acid and HH fractions for ~70-80% of the samples, suggesting that either the acetic acid dissolves Fe-Mn oxides or multiple phases are recording the same seawater isotopic value. Several indirect tests, such as Al mass balance, comparison of Sr isotopes in HH extracts to contemporaneous seawater Sr isotopes, and comparison of Nd isotopic compositions in HH extracts to published fossil fish teeth values, provide evidence that Pb isotopic compositions measured in our bulk HH extracts record bottom water values. The relationship between Pb, Mn and Ca concentrations in HH fractions indicates that Fe-Mn oxides and a Mn-bearing carbonate are the dominant phases contributing seawater Pb. Comparison of REE patterns derived from the HH fraction and total digestions of Fe-Mn nodule standards reveals that the trivalent REEs exhibit patterns consistent with the parent archive, but Ce can be fractionated during extraction. Ratios of REEs also produce unique fields for each fraction and can be used to test the purity of the seawater signal of the extraction protocol. Finally, an initial evaluation of Pb isotopic compositions in fossil fish indicates that this archive is not suitable for bottom water Pb isotope studies.

Stable isotope record of sediment core MD98-2177

We present a reconstruction of El Niño Southern Oscillation (ENSO) variability spanning the Medieval Climate Anomaly (MCA, A.D. 800-1300) and the Little Ice Age (LIA, A.D. 1500-1850). Changes in ENSO are estimated by comparing the spread and symmetry of d18O values of individual specimens of the thermocline-dwelling planktonic foraminifer Pulleniatina obliquiloculata extracted from discrete time horizons of a sediment core collected in the Sulawesi Sea, at the edge of the western tropical Pacific warm pool. The spread of individual d18O values is interpreted to be a measure of the strength of both phases of ENSO while the symmetry of the d18O distributions is used to evaluate the relative strength/frequency of El Niño and La Niña events. In contrast to previous studies, we use robust and resistant statistics to quantify the spread and symmetry of the d18O distributions; an approach motivated by the relatively small sample size and the presence of outliers. Furthermore, we use a pseudo-proxy approach to investigate the effects of the different paleo-environmental factors on the statistics of the d18O distributions, which could bias the paleo-ENSO reconstruction. We find no systematic difference in the magnitude/strength of ENSO during the Northern Hemisphere MCA or LIA. However, our results suggest that ENSO during the MCA was skewed toward stronger/more frequent La Niña than El Niño, an observation consistent with the medieval megadroughts documented from sites in western North America.

Major-oxides and trace-elements at DSDP Hole 78-543A

Four chemically distinct basalts were cored in 44 m of basement penetration at Deep Sea Drilling Project Site 543, in Upper Cretaceous crust just seaward of the deformation front of the Barbados Ridge and north of the Tiburon Rise. All four types are moderately fractionated abyssal tholeiites. The four types have different magnetic inclinations, all of reversed polarity, suggesting eruption at different times which recorded secular variation of the earth's magnetic field. Extensive replacement of Plagioclase by K-feldspar has occurred at the top of the basalts, giving analyses with K2O contents up to 5 %. The earliest stages of alteration were dominantly oxidative, resulting in fractures lined with celadonite and dioctahedral smectite, and pervasive replacement of olivine and most intersertal glass with iron hydroxides and green clay minerals. Latef, non-oxidative alteration resulted in formation of olive-green clays and pyrite veins in a portion of the rocks. Basalts affected by this alteration actually lost K2O (to abundances lower than in adjacent fresh basalt glasses), and gained MgO (to abundances higher than in the glasses). Finally, fractures and interpillow voids were lined with calcite, sealing in much fresh glass. Oxygen-isotope measurements on the calcite indicate that this occurred at 12 to 25C. Either altering fluids were warm or the basalts had become buried with a considerable thickness of sediments, such that temperatures increased until a conductive thermal gradient was established, when the veining occurred.

Chemical and isotopic compositions of rocks, ores, and hydrothermal minerals from the Rainbow and Logachev-2 hydrothermal fields

The aim of this paper is to analyze and compare mineralogy and geochemistry of copper-zinc sulfide ores from the Logachev-2 and Rainbow hydrothermal fields of the Mid-Atlantic Ridge (MAR) confined to serpentinite protrusions. It was found that Zn(Fe) and Cu, Fe(Zn) sulfides had been deposited in black smokers pipes almost simultaneously from intermittently flowing, nonequilibrium H2S-low solutions of different temperatures. Pb isotope composition confirmed that the deep oceanic crust had been a source of lead. The ores from the Rainbow field are 20-fold higher in Co than ores restricted to basalts and show a high ratio of Co/Ni=46. The ores from the Rainbow field are enriched in 34S isotope (aver. d34S=10 per mil) because of constant flow of cold sea water into the subsurface zone of the hydrothermal system. Ores from the Logachev-2 field are 8 times higher in gold compared to other MAR regions. Sulfide ores from the Rainbow and Logachev-2 fields have no analogues among MAR ore occurrences in terms of enrichment in valuable components (Zn, Cd, Co, and Au).

Geochemistry, isotopic ratios and mineral composition of samples from ODP Leg 163 sites

Thirty-five samples from the drill core of the three Leg 163 sites (Sites 988, 989, and 990) off the southeast coast of Greenland were analyzed for 27 major, minor, and trace elements by X-ray fluorescence (XRF) and for 25 trace elements, including 14 rare-earth elements (REEs), by an inductively coupled plasma source mass spectrometer (ICP/MS). Sr- and Nd-isotope data are reported for seven samples and oxygen-isotope data are reported for 19 plagioclase separates. In addition, a reconnaissance survey of the composition of the main mineral phases, plagioclase, pyroxene, and oxides was determined on an electron microprobe to provide the basic information required for petrogenetic modeling. Olivine pseudomorphs are present in many of the samples, but in no case was an olivine grain found that was fresh enough to give a reliable analysis. The chemical and isotopic data recorded here were determined to provide a comparison with the larger data sets acquired by the Edinburgh, Copenhagen, and Leicester laboratories from both Legs 152 and 163 drill cores. This will permit a detailed comparison of the North Atlantic flood basalt province as a whole with the better known Columbia River, Deccan, and Karoo continental flood basalt provinces, for which substantial chemical data sets are already available at Washington State University.

Isotope characterisation of Villars Cave stalagmites

We present a new mid-latitude speleothem record of millennial-scale climatic variability during OIS3 from the Villars Cave that, combined with former published contemporaneous samples from the same cave, gives a coherent image of the climate variability in SW-France between ~55 ka and ~30 ka. The 0.82 m long stalagmite Vil-stm27 was dated with 26 TIMS U-Th analyses and its growth curve displays variations that are linked with the stable isotopes, both controlled by the climatic conditions. It consists in a higher resolved replicate of the previously published Vil-stm9 and Vil-stm14 stalagmites where Dansgaard-Oeschger (DO) events have been observed. The good consistency between these three stalagmites and the comparison with other palaoeclimatic reconstructions, especially high resolution pollen records (ODP 976 from the Alboran Sea, Monticchio Lake record from southern Italy) and the nearby MD04-2845 Atlantic Ocean record, permits to draw a specific climatic pattern in SW-France during the OIS3 and to see regional differences between these sites. Main features of this period are: 1) warm events corresponding to Greenland Interstadials (GIS) that are characterized by low speleothem d13C, high temperate pollen percentages, warm temperatures and high humidity; among these events, GIS#12 is the most pronounced one at Villars characterized by an abrupt onset at ~46.6 ka and a duration of about 2.5 ka. The other well individualized warm event coincides with GIS#8 which is however much less pronounced and occurred during a cooler period as shown by a lower growth rate and a higher d13C; 2) cold events corresponding to Greenland Stadials (GS) that are clearly characterized by high speleothem d13C, low temperate pollen abundance, low temperature and enhanced dryness, particularly well expressed during GS coinciding with Heinrich events H5 and H4. The main feature of the Villars record is a general cooling trend between the DO#12 event ~45.5 ka and the synchronous stop of the three stalagmites at ~30 ka ±1, with a first well marked climatic threshold at ~41 ka after which the growth rate and the diameter of all stalagmites slows down significantly. This climatic evolution differs from that shown at southern Mediterranean sites where this trend is not observed. The ~30 ka age marks the second climatic threshold after which low temperatures and low rainfalls prevent speleothem growth in the Villars area until the Lateglacial warming that occurred at ~16.5 ± 0.5 ka. This 15 ka long hiatus, as the older Villars growth hiatus that occurred between 67.4 and 61 ka, are linked to low sea levels, reduced ocean circulation and a southward shift of the Polar Front that likely provoked local permafrost formation. These cold periods coincide with both low summer 65°N insolation, low atmospheric CO2 concentration and large ice sheets development (especially the Fennoscandian).