Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Geochemistry of ODP Site 135-834 basalts

New major, trace element, and isotope data (Pb, Sr, and Nd) reveal an impressive compositional variation in the basalts recovered from Site 834. Major element compositions span almost the entire range observed in basalts from the modern axial systems of the Lau Basin, and variations are consistent with low-pressure fractionation of a mid-ocean-ridge-basalt (MORB)-like parent, in which plagioclase crystallization has been somewhat suppressed. Trace element compositions deviate from MORB in all but one unit (Unit 7) and show enrichments in large-ion-lithophile elements (LILEs) relative to high-field-strength elements (HFSEs) more typically associated with island-arc magmas. The Pb-isotope ratios define linear trends that extend from the field of Pacific MORB to highly radiogenic values similar to those observed in rocks from the northernmost islands of the Tofua Arc. The Sr-isotope compositions also show significant variation, and these too project from radiogenic values back into the field for Pacific MORB. The variations in key trace element and isotopic features are consistent with magma mixing between two relatively mafic melts: one represented by Pacific MORB, and the other by a magma similar to those erupted on 'Eua when it was part of the original Tongan arc, or perhaps members of the Lau Volcanic Group (LVG). Based on our model, the most radiogenic compositions (Units 2 and 8) represent approximately 50:50 mixtures of these MORB and arc end-members. Magma mixing requires that both components are simultaneously available, and implies that melts have not shown a compositional progression from arc-like to MORB-like with extension at this locality. Rather, it is apparent that essentially pristine MORB can erupt as one of the earliest products of backarc initiation. Indeed, repetition of isotopic and trace element signatures with depth suggests that eruptions have been triggered by periodic injections of fresh MORB melts into the source regions of these magmas. The slow and almost amagmatic extension of the original arc complex envisaged to explain the observed chemistry is also consistent with the horst-and-graben topography of the western side of the Lau Basin. Given the similarities between basalts erupted at the modern Lau Basin spreading centers and MORB from the Indian Ocean, the overwhelming evidence for involvement of mantle similar to Pacific MORB in the petrogenesis of basalts from Site 834 is a new and important observation. It indicates that the original arc was underlain by asthenospheric material derived from the Pacific mantle convection cell, and that this has somehow been replaced by Indian Ocean MORB during the last ~5.5 Ma.

Geochemistry of basaltic rocks from ODP Site 129-801

Middle Jurassic basaltic lavas obtained from Site 801 in the western Pacific Pigafetta Basin represent ocean crust from the oldest segment of the present-day Pacific Ocean. A composite 131 m section shows the basement to be composed of an upper alkalic basalt sequence (about 157 Ma) with ocean island basalt chemical features and a lower tholeiitic basalt sequence (about 167 Ma) with typical normal-type mid-ocean ridge basalt features. The basalt sequences are separated by a quartz-cemented, yellow goethite hydrothermal deposit. Most basalts are altered to some degree and exhibit variable, low-grade smectite-celadonite-pyrite-carbonate-zeolite assemblages developed under a mainly hydrated anoxic environment. Oxidation is very minor, later in development than the hydration assemblages, and largely associated with the hydrothermal deposit. The tholeiitic normal-type mid-ocean ridge basalt has characteristically depleted incompatible element patterns and all compositions are encompassed by recent mid-ocean ridge basalt from the East Pacific Rise. Chemically, the normal-type mid-ocean ridge basalt is divided into a primitive plagioclase-olivine +/- spinel phyric group (Mg* = 72-60) and an evolved (largely) aphyric group of olivine tholeiites (Mg* = 62-40). Both groups form a single comagmatic suite related via open-system fractionation of initial olivine-spinel followed by olivine-plagioclase-clinopyroxene. The alkalic ocean island basalt are largely aphyric and display enriched incompatible element abundances within both relatively primitive olivine-rich basalts and evolved olivine-poor hawaiites related via mafic fractionation. In gross terms, the basement lithostratigraphy is a typical mid-ocean ridge basalt crust, generated at a spreading center, overlain by an off-axis seamount with ocean island basalt chemical characters.

Geochemistry of last glacial sediments of Isla de los Estados, southeastern Tierra del Fuego

The island of Isla de los Estados is situated at 54.5°S, 64°W, east of Argentinian Tierra del Fuego, and is located in a sensitive geographic position in relation to the zonal circulation between Antarctica and South America. Its terrestrial records of the last deglaciation, recording atmospheric conditions but within an oceanic setting, can help to clarify changes of regional circulation patterns, both atmospheric and marine. Here, we present geochemical analyses from 16-10 ka cal BP of a peat core from Lago Galvarne Bog at the northern coast of the island, and a lake sediment core from Laguna Cascada 3 km further south. The data comprise TC, TN, loss on ignition analyses and continuous XRF scanning on both cores as well as age-depth modeling based on AMS-14C dating. Deglaciation and onset of peat formation in the coastal areas began before 16 ka cal BP followed by a rapid glacial retreat and the start of lacustrine sedimentation further inland. Data suggest initially windy conditions with permafrost succeeded by gradually warmer and wetter conditions until ca 14.5 ka cal BP. The warming trend slows down until ca 13.5 ka cal BP, followed by arid conditions culminating around 12.8 ka cal BP. Our data suggest fairly warm conditions and the establishment of denser peat and forest vegetation ca 10.6 ka cal BP, contemporaneous with the onset of the Antarctic thermal optimum. This indicates large-scale shifts in the placement of zonal flow and the Westerlies at the beginning of the Holocene.

Geochemistry of Central American Volcanic Arc basement samples

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low d18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high d18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

Geochemical composition and radiocarbon ages of cores from Lago Fugnano, Tierra del Fuego

Recent advances in the chronology and the palaeoclimatic understanding of Antarctic ice core records point towards a larger heterogeneity of latitudinal climate fluctuations than previously thought. Thus, realistic palaeoclimate reconstructions rely in the development of a tight array of well-constrained records with a dense latitudinal coverage. Climatic records from southernmost South America are critical cornerstones to link these Antarctic palaeoclimatic archives with their South American counterparts. At 54° S on the Island of Tierra del Fuego, Lago Fagnano is located in one of the most substantially and extensively glaciated regions of southernmost South America during the Late Pleistocene. This elongated lake is the largest (~110km long) and non-ice covered lake at high southern latitudes. A multi-proxy study of selected cores allows the characterisation of a Holocene sedimentary record. Detailed petrophysical, sedimentological and geochemical studies of a complete lacustrine laminated sequence reveal variations in major and trace elements, as well as organic content, suggesting high variability in environmental conditions. Comparison of these results with other regional records allows the identification of major known late Holocene climatic intervals and the proposal for a time for the onset of the Southern Westerlies in Tierra del Fuego. These results improve our understanding of the forcing mechanisms behind climate change in southernmost Patagonia.

Geochemistry of Indian Ocean tephra and Afro-Arabian lavas

Widespread silicic pyroclastic eruptions of the Oligocene Afro-Arabian flood volcanic province (ignimbrites and airfall tuffs) produced up to 20% of the total flood volcanic stratigraphy (>6*10**4 km**3). Volumes of individual ignimbrites and tuffs exposed on land range from ~150 to >2000 km**3 and eight major units (15-100 m thick) were erupted in <2 Myr, placing these amongst the largest-magnitude silicic pyroclastic eruptions on Earth. They are compositionally distinctive time-stratigraphic markers which were deposited as co-ignimbrite ashfall deposits on a near-global scale around the time of the Oi2 cooling anomaly at ~30 Ma. Two ignimbrites from the lower part of the flood volcanic succession in Yemen have been correlated to: (a) the conjugate rifted margin of Ethiopia (>500 km distant); and (b) to two deep sea ash layers sampled by ODP Leg 115 in the Indian Ocean ~2700 km to the southeast. This correlation is based on whole rock analyses of silicic units for isotope ratios (Pb, Nd) and rare earth element compositions, in conjunction with novel in situ Pb isotope laser ablation multicollector inductively coupled plasma mass spectroscopy analysis of groundmass and glass shards. Compositional diversity preserved on the scale of individual ash shards in these deep sea tephra layers record chemical heterogeneity present in the silicic magma chambers that is not evident in the welded on-land deposits. Ages of the ash layers can be established by correlation to precisely dated on-land ignimbrites, and current evidence suggests that while these eruptions may have exacerbated already changing climatic conditions, they both marginally post-date the Oi2 global cooling anomaly.

Geochemistry of highly depleted peridotites of the Mid-Atlantic Ridge

During ODP Leg 209, a magma-starved area of the Mid-Atlantic Ridge (MAR) was drilled in the vicinity of the Fifteen-Twenty Fracture Zone (FZ) that offsets one of the slowest portions of the spreading ridge. We present here the results of a bulk rock multi-elemental study of 27 peridotites drilled at Sites 1272 and 1274 (to the south and the north of the FZ, respectively). The peridotites comprise mainly of harzburgites with minor dunites. Clinopyroxene (Cpx), which is interstitial and interpreted as secondary, is observed in Site 1274 peridotites. Sites 1272 and 1274 peridotites have low Al2O3 contents (<1 anhydrous wt.%), high Mg# (>91.5), and bulk rock trace elements compositions mostly below 0.1X primitive mantle (PM). These peridotites, and in particular Site 1272 peridotites, represent the most depleted peridotites yet sampled at a slow spreading ridge. Their compositions indicate high degrees of partial melting and melt extraction. A single open-system melting event (melting plus percolation of melts produced within upwelling mantle) can explain their highly depleted yet linear chondrite-normalized REE patterns, characterized by a steady depletion from HREE to LREE. Late melt-rock reactions and precipitation of Cpx explains the slightly less depleted compositions of Site 1274 peridotites. Hence, the differences in composition between Sites 1272 and 1274 peridotites do not provide evidence for regional variations in the degrees of partial melting from the south to the north of the FZ. The occurrence of highly refractory peridotites in the Fifteen-Twenty area suggests we sampled a more actively convecting mantle than generally supposed below slow spreading centers.

Geochemistry of the gabbroic lithosphere in IODP Holes 304-U1309D and 305-U1309D

IODP Hole U1309D (Atlantis Massif, Mid-Atlantic Ridge 30°N) is the second deepest hole drilled into slow spread gabbroic lithosphere. It comprises 5.4% of olivine-rich troctolites (~ > 70% olivine), possibly the most primitive gabbroic rocks ever drilled at mid-ocean ridges. We present the result of an in situ trace element study carried out on a series of olivine-rich troctolites, and neighbouring troctolites and gabbros, from olivine-rich intervals in Hole U1309D. Olivine-rich troctolites display poikilitic textures; coarse-grained subhedral to medium-grained rounded olivine crystals are included into large undeformed clinopyroxene and plagioclase poikiloblasts. In contrast, gabbros and troctolites have irregularly seriate textures, with highly variable grain sizes, and locally poikilitic clinopyroxene oikocrysts in troctolites. Clinopyroxene is high Mg# augite (Mg# 87 in olivine-rich troctolites to 82 in gabbros), and plagioclase has anorthite contents ranging from 77 in olivine-rich troctolites to 68 in gabbros. Olivine has high forsterite contents (82-88 in olivine-rich troctolites, to 78-83 in gabbros) and is in Mg-Fe equilibrium with clinopyroxene. Clinopyroxene cores and plagioclase are depleted in trace elements (e.g., Ybcpx ~ 5-11 * Chondrite), they are in equilibrium with the same MORB-type melt in all studied rock-types. These compositions are not consistent with the progressively more trace element enriched (evolved) compositions expected from olivine rich primitive products to gabbros in a MORB cumulate sequence. They indicate that clinopyroxene and plagioclase crystallized concurrently, after melts having the same trace element composition, consistent with crystallization in an open system with a buffered magma composition. The slight trace element enrichments and lower Cr contents observed in clinopyroxene rims and interstitial grains results from crystallization of late-stage differentiated melts, probably indicating the closure of the magmatic system. In contrast to clinopyroxene and plagioclase, olivine is not in equilibrium with MORB, but with a highly fractionated depleted melt, similar to that in equilibrium with refractory oceanic peridotites, thus possibly indicating a mantle origin. In addition, textural relationships suggest that olivine was in part assimilated by the basaltic melts after which clinopyroxene and plagioclase crystallized (impregnation). These observations suggest a complex crystallization history in an open system involving impregnation by MORB-type melt(s) of an olivine-rich rock or mush. The documented magmatic processes suggest that olivine-rich troctolites were formed in a zone with large magmatic transfer and accumulation, similar to the mantle-crust transition zone documented in ophiolites and at fast spreading ridges.

Elements and mineralogical compostions from different sediment cores off the southern China Sea

The mineralogy, major and trace elements, and neodymium and strontium isotopes of surface sediments in the South China Sea (SCS) are documented with the aim of investigating their applicability in provenance tracing. The results indicate that mineralogical compositions alone do not clearly identify the sources for the bulk sediments in the SCS. The Nd isotopic compositions of the SCS sediments show a clear zonal distribution. The most negative epsilon-Neodymium values were obtained for sediments from offshore South China (-13.0 to -10.7), while those from offshore Indochina are slightly more positive (-10.7 to -9.4). The Nd isotopic compositions of the sediments from offshore Borneo are even higher, with epsilon-Neodymium ranging from -8.8 to -7.0, and the sediments offshore from the southern Philippine Arc have the most positive epsilon-Neodymium values, from -3.7 to +5.3. This zonal distribution in epsilon-Neodymium is in good agreement with the Nd isotopic compositions of the sediments supplied by river systems that drain into the corresponding regions, indicating that Nd isotopic compositions are an adequate proxy for provenance tracing of SCS sediments. Sr isotopic compositions, in contrast, can only be used to identify the sediments from offshore South China and offshore from the southern Philippine Arc, as the 87Sr/86Sr ratios of sediments from other regions overlapped. Similar zonal distributions are also apparent in a La-Th-Sc discrimination diagram. Sediments fromthewestmargin of the SCS, such as those fromBeibuwan Bay, offshore fromHainan Island, offshore from Indochina, and from the Sunda Shelf plot in the same field, while those offshore from the northeastern SCS, offshore from Borneo, and offshore from the southern Philippine Arc plot in distinct fields. Thus, the La-Th-Sc discrimination diagram, coupledwith Nd isotopes, can be used to trace the provenance of SCS sediments. Using this method, we re-assessed the provenance changes of sediments at Ocean Drilling Program (ODP) Site 1148 since the late Oligocene. The results indicate that sediments deposited after 23.8 Ma (above 455 mcd: meters composite depth) were supplied mainly from the eastern South China Block, with a negligible contribution from the interior of the South China Block. Sediments deposited before 26 Ma (beneath 477 mcd) were supplied mainly from the North Palawan Continental Terrane, which may retain the geochemical characteristics of the materials covered on the late Mesozoic granitoids along the coastal South China. For that the North Palawan Continental Terrane is presently located within the southern Philippine Arc but was located close to ODP Site 1148 in the late Oligocene. The weathering products of volcanic material associated with the extension of the SCS ocean crust also contributed to these sediments. The rapid change in sediment source at 26-23.8 Ma probably resulted from a sudden cessation of sediment supply from the North Palawan Continental Terrane. Wesuggest that the North Palawan Continental Terrane drifted southwards alongwith the extension of the SCS ocean crust during that time, and when the basin was large enough, the supply of sediment from the south to ODP Site 1148 at the north slope may have ceased.

Strontium isotope ratios of fish teeth from ODP sites in the central North Pacific

Strontium isotopic compositions of ichthyoliths (microscopic fish remains) in deep-sea clays recovered from the North Pacific Ocean (ODP holes 885A, 886B, and 886C) are used to provide stratigraphic age control within these otherwise undatable sediments. Age control within the deep-sea clays is crucial for determining changes in sedimentation rates, and for calculating fluxes of chemical and mineral components to the sediments. The Sr isotopic ages are in excellent agreement with independent age datums from above (diatom ooze), below (basalt basement) and within (Cretaceous-Tertiary boundary) the clay deposit. The 87Sr/86Sr ratios of fish teeth from the top of the pelagic clay unit (0.7089891), indicate an Late Miocene age (5.8 Ma), as do radiolarian and diatom biostratigraphic ages in the overlying diatom ooze. The 87Sr/86Sr ratio (0.707887) is consistent with a Cretaceous-Tertiary boundary age, as identified by anomalously high iridium, shocked quartz, and sperules in Hole 886C. The 87Sr/86Sr ratios of pretreated fish teeth from the base of the clay unit are similar to Late Cretaceous seawater (0.707779-0.7075191), consistent with radiometric ages from the underlying basalt of 81 Ma. Calculation of sedimentation rates based on Sr isotopic ages from Hole 886C indicate an average sedimentation rate of 17.7 m/Myr in Unit II (diatom ooze), 0.55 m/Myr in Unit IIIa (pelagic clay), and 0.68 m/Myr in Unit IIIb (distal hydrothermal precipitates). The Sr isotopic ages indicate a period of greatly reduced sedimentation (or possible hiatus) between about 35 and 65 Ma (Eocene-Paleocene), with a linear sedimentation rate of only 0.04 m/Myr The calculated sedimentation rates are generally inversely proportional to cobalt accumulation rates and ichthyolith abundances. However, discrepancies between Sr isotope ages and cobalt accumulation ages of l0-15 Myr are evident, particularly in the middle of the clay unit IIIa (Oligocene-Paleocene).