Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Geochemistry of Miocene Alborán Basin volcanism

We present new major and trace element and O-Sr-Nd-isotope data for igneous rocks from the western Mediterranean Alborán Sea, collected during the METEOR 51/1 cruise, and for high-grade schists and gneisses from the continental Alborán basement, drilled during the Ocean Drilling Programme (ODP Leg 161, Site 976). The geochemical data allow a detailed examination of crustal and mantle processes involved in the petrogenesis of the lavas and for the first time reveal a zonation of the Miocene Alborán Sea volcanism: (1) a keel-shaped area of LREE-depleted (mainly tholeiitic series) lavas in the central Alborán Sea, generated by high degrees of partial melting of a depleted mantle source and involving hydrous fluids from subducted marine sediments, that is surrounded by (2) a horseshoe-shaped zone with LREE-enriched (mainly calc-alkaline series) lavas subparallel to the arcuate Betic-Gibraltar-Rif mountain belt. We propose that the geochemical zonation of the Miocene Alborán Basin volcanism results from eastward subduction of Tethys oceanic lithosphere coupled with increasing lithospheric thickness between the central Alborán Sea and the continental margins of Iberia and Africa.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Nd and Sr isotopic compositions and isotope dilution trace element concentrations from 7 sediment cores along the southeast Greenland margin

The Nd and Sr isotopic compositions of Quaternary glacial and glacimarine siliciclastic sediments deposited along the margin of southeast Greenland were determined to assess the roles of the Greenland, Iceland, and more distal ice sheets in delivering detritus to this portion of the northern North Atlantic. The isotopic compositions of detritus generated by portions of the southern Greenland Ice Sheet were defined through measurements of till and trough mouth fan sediments. Massive diamicts from the Scoresby Sund trough mouth fan show a restricted range of e-Nd (-11.8 to -16.6) and 87Sr/86Sr (0.7192-0.7246) consistent with their derivation from mixtures of sediments derived from Paleoproterozoic and/or Caledonian basement and Tertiary Greenland basalts. Further south at Kangerlussuaq, till isotopic compositions covary with the underlying basement type, with low e-Nd values in the inner fiord (-18.1) reflecting the erosion of the local Precambrian gneisses, but with higher e-Nd values (-2.3 to 2.5) found where the trough crosses East Greenland Tertiary basalts. Fine-grained (< 63 µm) sediments deposited along the southeast Greenland margin also show regular spatial isotopic variations. Ambient sediments and ice-rafted detritus in the southern Irminger Basin trend towards low e-Nd values (to ~ -28) and 87Sr/86Sr ratios (~ 0.711 to ~ 0.715) and are likely derived from proximal Archean gneisses of SE Greenland. Further north in the northern Irminger and Blosseville Basins, sediments trend toward much higher e-Nd (> -4) and low 87Sr/86Sr (< 0.709) reflecting a component derived from the local Iceland volcanic rocks and/or the East Greenland Tertiary basalts. In all three regions, the locally-derived detritus is intermixed with sediment with an intermediate e-Nd value (~ -10) and 87Sr/86Sr (~ 0.718) that was likely delivered by icebergs emanating from the Eurasian Ice Sheets and not from eastern Greenland. Deposition of glacial sediments from both proximal and distal (Eurasian) sources occurred adjacent to SE Greenland throughout the past 50 Ka, with periodic increases in IRD deposition at various times including those of Heinrich events 1, 2 and 4. These results suggest that at least the southern portions of the Greenland Ice Sheet experienced periodic instabilities during the Last Glacial period.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Rare earth elements of ROV sample GeoB12338-2 from the Makran accretionary complex

Authigenic carbonates forming at an active methane-seep on the Makran accretionary prism mainly consist of aragonite in the form of microcrystalline, cryptocrystalline, and botryoidal phases. The d13Ccarbonate values are very negative (-49.0 to -44.0 per mill V-PDB), agreeing with microbial methane as dominant carbon source. The d18Ocarbonate values are exclusively positive (+ 3.0 to + 4.5 per mill V-PDB) and indicate precipitation in equilibrium with seawater at bottom water temperatures. The content of rare earth elements and yttrium (REE + Y) determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and solution ICP-MS varies for each aragonite variety, with early microcrystalline aragonite yielding the highest, cryptocrystalline aragonite intermediate, and later botryoidal aragonite the lowest REE + Y concentrations. Shale-normalised REE + Y patterns of different types of authigenic carbonate reflect distinct pore fluid compositions during precipitation: Microcrystalline aragonite shows high contents of middle rare earth elements (MREE), reflecting REE patterns ascribed to anoxic pore water. Cryptocrystalline aragonite exhibits a seawater-like REE + Y pattern at elevated total REE + Y concentrations, indicating higher concentrations of REEs in pore waters, which were influenced by seawater. Botryoidal aragonite is characterised by seawater-like REE + Y patterns at initial growth stages followed by an increase of light rare earth elements (LREE) with advancing crystal growth, reflecting changing pore fluid composition during precipitation of this cement. Conventional sample preparation involving micro-drilling of carbonate phases and subsequent solution ICP-MS does not allow to recognise such subtle changes in the REE + Y composition of individual carbonate phases. To be able to reconstruct the evolution of pore water composition during early diagenesis, an analytical approach is required that allows to track the changing elemental composition in a paragenetic sequence as well as in individual phases. High-resolution analysis of seep carbonates from the Makran accretionary prism by LA-ICP-MS reveals that pore fluid composition not only evolved in the course of the formation of different phases, but also changed during the precipitation of individual phases.

Miocene Mediterranean Nd, Sr, C and O isotope composition

Isotopic compositions of marine sediments and fossils have been investigated from northern basins of the Mediterranean to help constrain local oceanographic and climatic changes adjacent to the uplifting Alps. Stable C and O isotope compositions of benthic and planktonic foraminifera from the Umbria-Marche region (UMC) have an offset characteristic for their habitats and the changes in composition mimic global changes, suggesting that the regional conditions of climate and the carbon cycle were controlled by global changes. The radiogenic isotope composition of these fossil assemblages allows recognition of three distinct periods. In the first period, from 25 to 19 Ma, high epsilon-Nd values and low 87Sr/86Sr of sediments and fossils support intense tectonism and volcanism, related to the opening of the western Mediterranean. In the second period, from 19 to 13 Ma the 87Sr/86Sr ratio of Mediterranean (UMC) deviate from the global ocean, which is compatible with rapid uplift of the hinterland and intense influx of Sr from Mesozoic carbonates of the western Apennines. This local control on the seawater was driven by a humid and warm climate and indicates restricted exchange of water with the global ocean. Generally, the epsilon-Nd values of the fossils are very similar to those of Indian Ocean water, with brief periods of a decrease in the epsilon-Nd values coinciding with volcanic events and maybe sea level variation at 15.2 Ma. In the third period, from 13 to 10 Ma the fossils have 87Sr/86Sr similar to those of Miocene seawater while their epsilon-Nd values change considerably with time. This indicates fluctuating influence of the Atlantic versus the Paratethys and/or locally evolved seawater in the Mediterranean driven by global sea level changes. Other investigated localities near the Alps and from the ODP 900 site are compatible with this oceanographic interpretation. However, in the late early Miocene, enhanced local control, reflecting erosion of old crustal silicate rocks near the Alps, results in higher 87Sr/86Sr.

Geochemical composition and atomic formulas of saponites, celadonites and clays from ODP Leg 168 sites

A drilling transect across the sedimented eastern flank of the Juan de Fuca Ridge, conducted during Leg 168 of the Ocean Drilling Program, resulted in the recovery of samples of volcanic basement rocks (pillow basalts, massive basalts, and volcanic glass breccias) that exhibit the effects of low-temperature hydrothermal alteration. Secondary clays are ubiquitous, with Mg-rich and Fe-rich saponite and celadonitic clays commonly accounting for several percent, and up to 10%-20% by volume. Present-day temperatures of the basement sites vary from 15° to 64°C, with the coolest site being about 0.8 Ma, and the warmest site being about 3.5 Ma. Whereas clays are abundant at sites that have been heated to present temperatures of 23°C and higher, the youngest site at 15°C has only a small trace of secondary clay alteration. Alteration increases as temperatures increase and as the volcanic basement ages. The chemical compositions of secondary clays were determined by electron microprobe, and additional trace element data were determined by both conventional nebulization inductively coupled plasma-mass spectroscopy (ICP-MS) and laser-ablation ICP-MS. Trioctahedral saponite and pyrite are characteristic of the interior of altered rock pieces, forming under conditions of low-oxygen fugacity. Dioctahedral celadonite-like clays along with iron oxyhydroxide and Mg-saponite are characteristic of oxidized haloes surrounding the nonoxidized rock interiors. Chemical compositions of the clays are very similar to those determined from other deep-sea basalts altered at low temperature. The variable Mg:Fe of saponite appears to be a systematic function both of the Mg:Fe of the host rock and the oxidation state during water-rock interaction.

Trace element contents in zircons from oceanic crust

We present newly acquired trace element compositions for more than 300 zircon grains in 36 gabbros formed at the slow-spreading Mid-Atlantic and Southwest Indian Ridges. Rare earth element patterns for zircon from modern oceanic crust completely overlap with those for zircon crystallized in continental granitoids. However, plots of U versus Yb and U/Yb versus Hf or Y discriminate zircons crystallized in oceanic crust from continental zircon, and provide a relatively robust method for distinguishing zircons from these environments. Approximately 80% of the modern ocean crust zircons are distinct from the field defined by more than 1700 continental zircons from Archean and Phanerozoic samples. These discrimination diagrams provide a new tool for fingerprinting ocean crust zircons derived from reservoirs like that of modern mid-ocean ridge basalt (MORB) in both modern and ancient detrital zircon populations. Hadean detrital zircons previously reported from the Acasta Gneiss, Canada, and the Narryer Gneiss terrane, Western Australia, plot in the continental granitoid field, supporting hypotheses that at least some Hadean detrital zircons crystallized in continental crust forming magmas and not from a reservoir like modern MORB.

Inorganic geochemical record of ODP Holes 117-722B and 117-724C

High-resolution sampling from late Pleistocene (last 400 k.y.) sediments of Site 722 (upper 16 m) and Site 724 (upper 70 m), and subsequent inorganic geochemical analysis, has defined the history of productivity in the northwest Arabian Sea. Eolian dust input from the Arabian Peninsula and Somalia is characterized by the record of Ti/Al and Cr/Al. This dust record displays strong precessional periodicity (cycles at 25 k.y.) suggesting the Southwest Monsoon and associated winds play a key role in transporting terrigenous material from the land. High biological productivity results in the accumulation of biogenic CaCO3 and opal in the sediments, the latter having an unexpectedly minor contribution to the total mass flux. Due to dilution of the CaCO3 record by the terrigenous component, the record of biological productivity is best exemplified by Ba. Its record, together with that of other metals recording biological association and redox variability (Cu, Ni, Zn, V, U) clearly identifies the interglacial episodes as being more biologically productive. The striking agreement between Ba and the d18O record in planktonic foraminifers suggests that the supply of nutrients during these periods of high productivity is linked to ocean-wide changes in ocean fertility, and not just local upwelling conditions. High levels of phosphate accumulation in interglacial sediments is attributed to both diagenetic phosphorite formation and biogenic skeletal debris. This study provides a detailed record of productivity variation in the northwest Arabian Sea during the late Pleistocene.