Geochemistry of ODP Hole 183-1137A basalts

The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.

Geochemistry of oceanic crust of the North Atlantic

87Sr/a6Sr ratios, Sr, K, Rb and Cs contents and the petrology of basalts and secondary phases recovered from deep basement drilling at DSDP Sites 332B, 417A, 417D and 418A show that the oceanic crust alters in four distinct stages characterized by formation of palagonite, smectite and calcite (Stages I, II and III, respectively). Stage IV represents the final compaction of the crust, including a dehydration of the crust without major chemical changes. Isotopic age determinations by Hart and Staudigel (1978, doi:10.1029/GL005i012p01009) and Richardson et al. (doi:10.1029/JB085iB12p07195), show that, at least for Atlantic-type crustal regimes, Stage I and II last for a maximum of 3 m.y., and Stage III lasts beyond Stage I and II, but is probably completed in significantly less than 10 m.y. Stage IV is long-lived and may still be active at 100 m.y. Stages I and II, the phase of halmyrolysis, include geochemically significant interactions between seawater and basalt for the upper 500 m of layer II and involve volumes of seawater containing a large basaltic component. Stage III solutions show evidence of less seawater-basalt interaction, at least to depths of 500 m; calcites deposited from these solutions have Sr isotopic ratios close to seawater values; but also have very low Sr/Ca ratios indicating a large basalt Ca component in the solutions. Smectite formation is the result of the interaction of seawater and basalt. The initial 87Sr/a6Sr ratios of smectites represent the Sr isotopic composition of the solution when the smectite is being formed. Thereafter, alkalies may be continuously added to interlayer positions in the smectite in order of decreasing hydration energy (Cs is more enriched than Rb, Rb more than K). The later-formed carbonates have very low alkali concentrations, and 87Sr/86Sr ratios identical to contemporaneous seawater. Therefore, since the alkali concentrations in a whole rock sample are affected by different alteration processes, the alkali concentrations alone are not reliable indicators of the degree of alteration.

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The ultramafic-hosted Logatchev hydrothermal field (LHF) is characterized by vent fluids, which are enriched in dissolved hydrogen and methane compared with fluids from basalt-hosted systems. Thick sediment layers in LHF are partly covered by characteristic white mats. In this study, these sediments were investigated in order to determine biogeochemical processes and key organisms relevant for primary production. Temperature profiling at two mat-covered sites showed a conductive heating of the sediments. Elemental sulfur was detected in the overlying mat and metal-sulfides in the upper sediment layer. Microprofiles revealed an intensive hydrogen sulfide flux from deeper sediment layers. Fluorescence in situ hybridization showed that filamentous and vibrioid, Arcobacter-related Epsilonproteobacteria dominated the overlying mats. This is in contrast to sulfidic sediments in basalt-hosted fields where mats of similar appearance are composed of large sulfur-oxidizing Gammaproteobacteria. Epsilonproteobacteria (7- 21%) and Deltaproteobacteria (20-21%) were highly abundant in the surface sediment layer. The physiology of the closest cultivated relatives, revealed by comparative 16S rRNA sequence analysis, was characterized by the capability to metabolize sulfur com- ponents. High sulfate reduction rates as well as sulfide depleted in 34S further confirmed the importance of the biogeochemical sulfur cycle. In contrast, methane was found to be of minor relevance for microbial life in mat-covered surface sediments. Our data indicate that in conductively heated surface sediments microbial sulfur cycling is the driving force for bacterial biomass production although ultramafic- hosted systems are characterized by fluids with high levels of dissolved methane and hydrogen.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

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.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Chronology and petrology of sediment cor DAPC2

Evidence from paleoclimatic archives suggests that Earth's climate experienced rapid temperature changes associated with pronounced interhemispheric asymmetry during the last glacial period. Explanations for these climate excursions have converged on nonlinear interactions between ice sheets and the ocean's thermohaline circulation, but the driving mechanism remains to be identified. Here we use multidecadal marine records of faunal, oxygen isotope, and sediment proxies from the northeast Atlantic proximal to the western margins of the last glacial British Ice Sheet (BIS) to document the coupling between ice sheet dynamics, ocean circulation, and insolation changes. The core data reveal successions of short-lived (80-100 years), high-amplitude ice-rafted debris (IRD) events that were initiated up to 2000 years before the deposition of detrital carbonate during Heinrich events (HE) 1 and 2. Progressive disintegration of the BIS 19-16 kyr before present (B.P.) occurred in response to abrupt ocean-climate warmings that impinged on the northeast Atlantic during the early deglaciation. Peak IRD deposition recurs at 180-220 year intervals plausibly involving repeated breakup of glacial tidewater margins and fringing marine ice shelves. The early deglaciation culminated in a major meltwater pulse at ~16.3 kyr B.P. followed by another discharge associated with HE1 some 300 years after. We conclude that temperature changes related to external forcing and marine heat transport caused a rapid response of the BIS and possibly other margins of the Eurasian Ice Sheet. Massive but short-lived meltwater surges influenced the Atlantic meridional overturning circulation thereby contributing to North Atlantic climate variability and bipolar climatic asymmetry.

Geochemical composition and crystallization conditions of melts from the Mid Atlantic Ridge near Ascension Island (7-11°S)

Phase equilibria simulations were performed on naturally quenched basaltic glasses to determine crystallization conditions prior to eruption of magmas at the Mid-Atlantic Ridge (MAR) east of Ascension Island (7°11°S).The results indicate that midocean ridge basalt (MORB) magmas beneath different segments of the MAR have crystallized over a wide range of pressures (100-900MPa). However, each segment seems to have a specific crystallization history. Nearly isobaric crystallization conditions (100-300MPa) were obtained for the geochemically enriched MORB magmas of the central segments, whereas normal (N)-MORB magmas of the bounding segments are characterized by polybaric crystallization conditions (200-900MPa). In addition, our results demonstrate close to anhydrous crystallization conditions of N-MORBs, whereas geochemically enriched MORBs were successfully modeled in the presence of 0.4-1wt% H2O in the parental melts.These estimates are in agreement with direct (Fourier transform IR) measurements of H2O abundances in basaltic glasses and melt inclusions for selected samples. Water contents determined in the parental melts are in the range 0.04-0.09 and 0.30-0.55 wt% H2O for depleted and enriched MORBs, respectively. Our results are in general agreement (within ±200MPa) with previous approaches used to evaluate pressure estimates in MORB. However, the determination of pre-eruptive conditions of MORBs, including temperature and water content in addition to pressure, requires the improvement of magma crystallization models to simulate liquid lines of descent in the presence of small amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation

40Ar-39Ar dating of rocks drilled at sites 60-458 and 60-459

40Ar-39Ar dating of a high-MgO bronzite andesite from near the top of basement drilled at Site 458 shows the characteristic symptoms of artificially disturbed samples - i.e., an inverse staircase-type age spectrum, approximate linearity on an isochron plot, and concordance between total fusion age and isochron age. From conclusions based on other artificially disturbed samples (Ozima et al., 1979), we suggest that the reference isochron age (33.6 Ma) approximates the age of the sample. A basalt from deeper in Hole 458 gives an isochron age of 19.1 ± 0.2 Ma, which is slightly younger than the plateau age of 21.4 ± 1.0 Ma. Both ages are, however, considerably younger than the age of fossils in the overlying sediments (30 - 34 Ma). The age discrepancy may be explained if the 40Ar-39Ar age represents the age of secondary minerals, which formed later. No useful age data were obtained from a basalt sample recovered from Hole 459B.

Benthic foraminifera and stable isotope composition in Paleocene-Eocene sediments

In the late Paleocene to early Eocene, deep sea benthic foraminifera suffered their only global extinction of the last 75 million years and diversity decreased worldwide by 30-50% in a few thousand years. At Maud Rise (Weddell Sea, Antarctica; Sites 689 and 690, palaeodepths 1100 m and 1900 m) and Walvis Ridge (Southeastern Atlantic, Sites 525 and 527, palaeodepths 1600 m and 3400 m) post-extinction faunas were low-diversity and high-dominance, but the dominant species differed by geographical location. At Maud Rise, post-extinction faunas were dominated by small, biserial and triserial species, while the large, thick-walled, long-lived deep sea species Nuttallides truempyi was absent. At Walvis Ridge, by contrast, they were dominated by long-lived species such as N. truempyi, with common to abundant small abyssaminid species. The faunal dominance patterns at the two locations thus suggest different post-extinction seafloor environments: increased flux of organic matter and possibly decreased oxygen levels at Maud Rise, decreased flux at Walvis Ridge. The species-richness remained very low for about 50 000 years, then gradually increased. The extinction was synchronous with a large, negative, short-term excursion of carbon and oxygen isotopes in planktonic and benthic foraminifera and bulk carbonate. The isotope excursions reached peak negative values in a few thousand years and values returned to pre-excursion levels in about 50 000 years. The carbon isotope excursion was about -2 per mil for benthic foraminifera at Walvis Ridge and Maud Rise, and about -4 per mil for planktonic foraminifera at Maud Rise. At the latter sites vertical gradients thus decreased, possibly at least partially as a result of upwelling. The oxygen isotope excursion was about -1.5 per mil for benthic foraminifera at Walvis Ridge and Maud Rise, -1 per mil for planktonic foraminifera at Maud Rise. The rapid oxygen isotope excursion at a time when polar ice-sheets were absent or insignificant can be explained by an increase in temperature by 4-6°C of high latitude surface waters and deep waters world wide. The deep ocean temperature increase could have been caused by warming of surface waters at high latitudes and continued formation of the deep waters at these locations, or by a switch from dominant formation of deep waters at high latitudes to formation at lower latitudes. Benthic foraminiferal post-extinction biogeographical patterns favour the latter explanation. The short-term carbon isotope excursion occurred in deep and surface waters, and in soil concretions and mammal teeth in the continental record. It is associated with increased CaC03-dissolution over a wide depth range in the oceans, suggesting that a rapid transfer of isotopically light carbon from lithosphere or biosphere into the ocean-atmosphere system may have been involved. The rapidity of the initiation of the excursion (a few thousand years) and its short duration (50 000 years) suggest that such a transfer was probably not caused by changes in the ratio of organic carbon to carbonate deposition or erosion. Transfer of carbon from the terrestrial biosphere was probably not the cause, because it would require a much larger biosphere destruction than at the end of the Cretaceous, in conflict with the fossil record. It is difficult to explain the large shift by rapid emission into the atmosphere of volcanogenic CO2, although huge subaerial plateau basalt eruptions occurred at the time in the northern Atlantic. Probably a complex combination of processes and feedback was involved, including volcanogenic emission of CO2, changing circulation patterns, changing productivity in the oceans and possibly on land, and changes in the relative size of the oceanic and atmospheric carbon reservoirs.

(Table 2) Geochemistry of K-feldspars and associated plagioclase phenocrysts and rims at DSDP Legs 69, 52, 51 and 19

Basalts from some holes of the Deep Sea Drilling Project contain secondary K-feldspar which forms pseudomorphs after calcic (>76% An) Plagioclase cores, whereas Plagioclase of rims and microlites (68-74% An) remains unaltered. In basalts of Hole 504B two such grains with relics of Plagioclase in the central parts of phenocysts were recovered. The composition of the Plagioclase rims and of non-replaced phenocrysts is An79-81; the composition of relics is An83. The An and Ab contents of the K-feldspar is higher than in K-feldspar from altered basalt in Hole 418A in the Atlantic Ocean near the Bermuda Rise. Replacement of plagioclases by K-feldspar evidently is caused by oxygen-rich nearbottom sea water penetrating into basalts. The temperature interval of K-feldspathization is probably in the range 30 to 80°C, more-calcic Plagioclase being replaced by K-feldspar at higher temperatures.

Calcareous nannofossils in ODP Hole 131-808C

ODP Leg 131 recovered nannofossil-bearing sediments from Site 808 in the Nankai Trough, western Pacific Ocean. Three holes were examined for nannofossils, 808A, 808B, and 808C. A total of 22 nannofossil events were recognized, of which 10 are used as zonal markers. The sediments recovered from Hole 808A (0-111.4 mbsf) contain Pleistocene nannofossil assemblages that are mostly well preserved. All samples from this hole were assigned to nannofossil Zone NN21. The nannofossil assemblages observed in Hole 808B (111.0-358.8 mbsf) are poorly to well preserved and were all assigned to the Pleistocene. The NN21/NN20 Boundary is placed at 230.7 ± 4.4 mbsf. Hole 808C was cored from 298.5 to 1327 mbsf and basalt was reached at 1289.9 mbsf. The sediments recovered range in age from the upper part of Zone NN20 of the Pleistocene to Zone NN5 of the middle Miocene and contain poorly to well-preserved nannofossil assemblages. The Pliocene/Pleistocene Boundary, marked by the FO Gephyrocapsa caribbeanica, was placed at 776.3 ±1.6 mbsf, and the Miocene/Pliocene Boundary is tentatively placed at 955.9 ±1.5 mbsf. The lowermost sediments above basement as well as a sediment sample intercalated between basalt flows are assigned to Zone NN5, with an age of approximately 15 Ma. Age estimates provided by nannofossils show that the sedimentation rate in the trench-fill deposits of the Nankai Trough was very high, 800-1350 m/m.y (0-0.46 Ma), whereas in the Shikoku Basin deposits (> 0.46 Ma), the sedimentation rate was much lower (24-200 m/m.y). These age estimates also provide an extrapolated age of approximately 15 Ma for the basaltic basement at Site 808.

Analyses of Manganese nodules off Izu Island

Manganese nodules have been found by the author in the shallow waters of the Hyotan-se bank west of Shikime-jima, an island of the Izu archipelago in the Sea of Japan. The slopes around the bank are steep and rocks are exposed; gravels and coarse material cover the broad and flat plain on its top; andesite and basalt, which are very common in the bedrock, are found mingled with liparite gravels together with a number of manganese concretions from the bank.