Stable organic carbon isotope record and total organic carbon content from the Cenomanian-Turonian boundary

Ocean Drilling Program (ODP) Leg 207 recovered expanded sections of organic-carbon-rich laminated shales on Demerara Rise (western tropical Atlantic). High-resolution organic carbon isotope and total organic carbon (TOC) records are presented, which span the Cenomanian-Turonian boundary interval (CTBI), including the Oceanic Anoxic Event (OAE) 2, from four sites oriented along a NW striking depth transect. These records represent the first high-resolution carbon isotope records across OAE 2 from the South American margin of the tropical Atlantic. Due to the scarcity of age significant fossils, the main purpose of this study was to develop a detailed carbon isotope stratigraphy in order to correlate the CTBI across the depth transect and to tie this to biostratigraphically well-defined sections in the Western Interior Basin (Pueblo, USA), boreal shelf seas (Eastbourne, England), and western Tethys (Oued Mellegue, Tunisia). All four sections studied document a 6 per mil increase of d13Corg values at the base of the CTBI, which is followed by an interval of elevated d13Corg values and a subsequent decrease. Our results supply an important stratigraphic base for subsequent paleoceanographic studies on Late Cenomanian to Early Turonian sediments from Demerara Rise and elsewhere.

Geochemistry of basalts of the Indian Ocean

Indian Ocean crust formed at Sites 765 and 766 is geochemically comparable to that presently forming in the Red Sea. In both cases, we interpret the crust as reflecting high degrees of mantle melting that are associated with an enhanced thermal gradient below recently rifted continental lithosphere. Asthenospheric melts formed in this environment are rich in CaO and FeO, poor in Na2O and Al2O3, and characterized by depleted rare earth element (REE) profiles ([La/Sm]n approximately 0.5-0.6). Both the Red Sea basalts and the basalts at Sites 765 and 766 are distinct from those erupted at the present Mid-Indian Ocean Ridge. The isotope characteristics of the Site 765 basalts define a geochemical signature similar to that of the present-day Mid-Indian Ocean Ridge basalts (MIORB). The Indian Ocean mantle domain is distinct from that of the Atlantic and Pacific oceans, and this distinction has persisted since Jurassic time, when the Site 765 oceanic crust was formed.

Geochemistry of karst headwaters

This study investigated CO2 degassing and related carbon isotope fractionation effects in the Wiesent River that drains a catchment in the karst terrain of the Fraconian Alb, Southern Germany. The river was investigated by physico-chemical and stable isotope analyses of water and dissolved inorganic carbon during all seasons in 2010 along 65 km long downstream transects between source and mouth. This data set contains the results of field and solute parameters (temperature, conductivity, pH, total alkalinity, total CO2, and pCO2) and stable isotope analyses (d2H-H2O, d18O-H2O, d13C-DIC) for the Wiesent River and major tributaries.

Geochemistry on core 202-1240A

The modern Eastern Equatorial Pacific (EEP) Ocean is a large oceanic source of carbon to the atmosphere1. Primary productivity over large areas of the EEP is limited by silicic acid and iron availability, and because of this constraint the organic carbon export to the deep ocean is unable to compensate for the outgassing of carbon dioxide that occurs through upwelling of deep waters. It has been suggested that the delivery of dust-borne iron to the glacial ocean could have increased primary productivity and enhanced deep-sea carbon export in this region, lowering atmospheric carbon dioxide concentrations during glacial periods. Such a role for the EEP is supported by higher organic carbon burial rates documented in underlying glacial sediments but lower opal accumulation rates cast doubts on the importance of the EEP as an oceanic region for significant glacial carbon dioxide drawdown. Here we present a new silicon isotope record that suggests the paradoxical decline in opal accumulation rate in the glacial EEP results from a decrease in the silicon to carbon uptake ratio of diatoms under conditions of increased iron availability from enhanced dust input. Consequently, our study supports the idea of an invigorated biological pump in this region during the last glacial period that could have contributed to glacial carbon dioxide drawdown. Additionally, using evidence from silicon and nitrogen isotope changes, we infer that, in contrast to the modern situation, the biological productivity in this region is not constrained by the availability of iron, silicon and nitrogen during the glacial period. We hypothesize that an invigorated biological carbon dioxide pump constrained perhaps only by phosphorus limitation was a more common occurrence in low-latitude areas of the glacial ocean.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Geochemistry of ODP Hole 135-839B lavas

Four petrographic lava types occur, ranging from aphyric to moderately phyric clinopyroxene-olivine tholeiitic basalts (Unit 1); olivine-clinopyroxene picritic basalts, sparsely to strongly olivine-phyric (Unit 3-type); olivine-clinopyroxene basalts (clinopyroxene dominant) (Unit 4); and moderately to strongly phyric two-pyroxene-plagioclase basaltic andesites (Unit 9-type). The olivine phyric lavas contain forsteritic olivines (extending to Fo92), and very magnesian Cr-rich spinels similar to those occurring in boninitic lavas. The basaltic andesites are mineralogically and petrographically indistinguishable from the modern Tofua Arc basaltic andesites, one notable feature being the highly calcic cores in plagioclase phenocrysts (up to An95). The forsteritic olivines, the Cr-spinels, and the calcic plagioclases are unlikely to have been precipitated in the lava compositions in which they occur, and are thought to have been incorporated from highly primitive melts by way of mixing processes (as advocated by Allan, this volume). Notwithstanding the evidence for mixing, the major element chemistries of the Unit 1- and Unit 9-type lavas are shown to be consistent with the derivation of the Unit 9-type basaltic andesites by means of fractional crystallization, through magmas of similar chemistry to Unit 1. Some trace element discrepancies in the modeling, and the relative volcanic stratigraphy of Site 839, however, preclude a direct liquid line of descent between the actual recovered units. Trace element data as well as TiO2 and Na2O data clearly illustrate the arc-like affinities of the magmas, with strong highfield-strength element depletion and large-ion-lithophile element enrichment. The abundance patterns are very close to those of the Tofua and Kermadec arc magmas, and also Valu Fa. Pb-, Sr-, and Nd-isotopic compositions indicate closest affinities with a "Pacific" MORB source, apparently characteristic of the western, older part of the Lau Basin. A subduction-related isotopic contribution is, however, inferred. The sources of the Site 839 magmas are thus inferred to be similar to, but less depleted geochemically, than those of the modern Tofua Arc magmas. The Site 839 sequence is interpreted as an older remnant of a volcanic construct of the "proto-Tofua arc", originally developed adjacent to the Tonga Ridge. Opening of the eastern Lau Basin, because of southward migrating propagators, has split and isolated the sequence, leaving it stranded within the modern Lau Basin.

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 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.

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 Early Cretaceous basaltic rocks from ODP Sites 123-765 and 123-766

The Early Cretaceous basaltic rocks obtained from Sites 765 and 766 in the eastern Indian Ocean floor were mostly iron-rich normal mid-ocean ridge basalts (N-MORB), which were derived from a depleted mantle source having strongly light rare earth element (LREE)-depleted rare-earth patterns and a high titanium/zirconium (Ti/Zr) ratio. Basaltic rocks in the upper part of the Site 765 basement section include megacrysts and gabbroic fragments of widely varying mineral chemistry. These megacrysts range from An90 plagioclase, including highly magnesian basaltic glass coexisting with augite of Mg# (= 100 Mg/[Fe+Mg]) at 85, to An50 plagioclase coexisting with hypersthene. This varying mineralogy of megacrysts and gabbroic fragments indicates that a considerable degree of fractional crystallization took place in the magma chamber. The unusual negative correlation between incompatible elements (e.g., TiO2) and FeO*/MgO observed among Site 765 basement basalts and fresh volcanic glasses suggest source-mantle heterogeneity in terms of FeO*/MgO. Strontium isotope ratios (87Sr/86Sr) of the basaltic rocks from both sites are between 0.7027 and 0.7033 and are comparable to those of mid-Indian Ocean ridge basalts (MIORB). The basalt pebbles encountered in the sedimentary section may have been transported from the basement highs nearer the Australian continent and include basaltic compositions ranging from primitive N-MORBs to evolved enriched (E)-MORBs. Their mantle source was not as depleted as that of the basement basalts. These rocks may be the products of earlier volcanism that took place during the rifting of the Australian continent.

Organic geochemistry records from two Palaeocene-Eocene Thermal Maximum sections in Denmark

Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.