(Table 3) Chemical analyses from DSDP Holes 22-214, 22-215 and 22-216 in the Indian Ocean

The basalts and oceanic andesites from the aseismic Ninetyeast Ridge display trachytic, vesicular and amygdaloidal textures suggesting a subaerial volcanic environment. The normative composition of the Ninetyeast Ridge ranges from olivine picriteto nepheline-normative alkaline basalt, suggesting a wide range of differentiation. This is further supported by the fractionation-differentiation trends displayed by transition metal trace elements (Ni, Cr, V and Cu). The Ninetyeast Ridge rocks are enriched in rare earth (RE) and large ion lithophile (LIL) elements and Sr isotopes (0.7043-0.7049), similar to alkali basalts and tholeiites from seamounts and islands, but different from LIL-element-depleted tholeiitic volcanic rocks of the recent seismic mid-Indian oceanic ridge. The constancy of 87Sr/86Sr ratios for basalts and andesites is compatible with a model involving fractional crystallization of mafic magma. The variation of 87Sr/86Sr ratios between 0.97 and 2.79 may possibly be explained in terms of a primordial hot mantle and/or chemically contrasting heterogeneous mantle source layers relatively undepleted in LIL elements at different periods in the geologic past. In general, the Sr isotopic data for rocks from different tectonic environments are consistent with a "zoning-depletion model" with systematically arranged alternate alkali-poor and alkali-rich layers in the mantle beneath the Indian Ocean.

Geochemistry of ODP Leg 135 vitrophyric rhyolite samples

In-situ proton-microprobe analyses are presented for glasses, plagioclases, pyroxenes, olivines, and spinels in eleven samples from Sites 834-836, 839, and 841 (vitrophyric rhyolite), plus a Tongan dacite. Elements analyzed are Mn, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Pb, and Sn (in spinels only). The data are used to calculate two sets of partition coefficients, one set based on the ratio of element in mineral/element in coexisting glass. The second set of coefficients, thought to be more robust, is corrected by application of the Rayleigh fractionation equations, which requires additional use of modal data. Data are presented for phenocryst core-rim phases and microphenocryst-groundmass phases from a few samples. Comparison with published coefficients reveals an overall consistency with those presented here, but with some notable anomalies. Examples are relatively high Zr values for pyroxenes and abnormally low Mn values in olivines and clinopyroxenes from Site 839 lavas. Some anomalies may reflect kinetic effects, but interpretation of the coefficients is complicated, especially in olivines from Sites 836 and 839, by possible crystal-liquid disequilibrium resulting from mixing processes.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

Geochemical composition of the Trincheira Complex in the southwestern Amazon craton, Brazil

We document the first-known Mesoproterozoic ophiolite from the southwestern part of the Amazon craton, corresponding to the Trincheira Complex of Calymmian age, and propose a tectonic model that explains many previously enigmatic features of the Precambrian history of this key craton, and discuss its role in the reconstruction of the Columbia supercontinent. The complex comprises extrusive rocks (fine-grained amphibolites derived from massive and pillowed basalts), mafic-ultramafic intrusive rocks, chert, banded iron formation (BIFs), pelites, psammitic and a smaller proportion of calc-silicate rocks. This sequence was deformed, metasomatized and metamorphosed during the development of the Alto Guaporé Belt, a Mesoproterozoic accretionary orogen. The rocks were deformed by a single tectonic event, which included isoclinal folding and metamorphism of the granulite-amphibolite facies. Layered magmatic structures were preserved in areas of low strain, including amygdaloidal and cumulate structures. Metamorphism was pervasive and reached temperatures of 780-853°C in mafic granulites and 680-720°C in amphibolites under an overall pressure of 6.8 kbar. The geochemical composition of the extrusive and intrusive rocks indicates that all noncumulus mafic-ultramafic rocks are tholeiitic basalts. The mafic-ultramafic rocks display moderately to strongly fractionation of light rare earth elements (LREE), near-flat heavy rare earth elements (HREE) patterns and moderate to strong negative high field strength elements (HFSE) anomalies (especially Nb), a geochemical signature typical of subduction zones. The lowest units of mafic granulites and porphyroblastic amphibolites in the Trincheira ophiolite are similar to the modern mid-ocean ridge basalt (MORB), although they locally display small Ta, Ti and Nb negative anomalies, indicating a small subduction influence. This behavior changes to an island arc tholeiites (IAT) signature in the upper units of fine-grained amphibolites and amphibole rich-amphibolites, characterized by progressive depletion in the incompatible elements and more pronounced negative Ta and Nb anomalies, as well as common Ti and Zr negative anomalies. Tectono-magmatic variation diagrams and chondrite-normalized REE and primitive mantle normalized patterns suggest a back-arc to intra-oceanic island arc tectonic regime for the eruption of these rocks. Therefore, the Trincheira ophiolite appears to have originated in an intraoceanic supra-subduction setting composed of an arc-back-arc system. Accordingly, the Trincheira Complex is a record of oceanic crust relics obducted during the collision of the Amazon craton and the Paraguá block during the Middle Mesoproterozoic. Thus, the recognition of the Trincheira ophiolite and suture significantly changes views on the evolution of the southern margin of the Amazon craton, and how it can influence the global tectonics and the reconstruction of the continents.

(Table 2) Chemical composition of gases in basalts from DSDP Leg 65 Holes

Basalts from different structural provinces in the ocean basins, such as mid-ocean ridges, island arcs, and oceanic plateaus, show marked differences in major and minor element composition stemming from differences in magma source. In addition, there are variations even within individual provinces, based on such processes as crystal fractionation, secondary alteration, and hydrothermal alteration. It is also known that hydrothermal processes can cause changes in the gas composition of submarine basalts. For example, Zolotarev et al. (1978) have established that hydrothermal alteration frequently causes an increase in the CO2 content of basalts. If the homogeneity in composition and concentration of organic gases in oceanic basalts is associated with degassing during epimagmatic alteration, it would be interesting to investigate the relative abundance of gas phases in young basalts from midoceanic ridges. This chapter deals with the distribution of organic gases and CO2 in young basalts recovered on Leg 65 from the Gulf of California. Our aim was to establish the relationship between gas composition and degree of alteration.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.

In-situ Iron isotope measurements and mineral compositions from ODP Hole 206-1256D and IODP Hole 335-U1256D

In-situ Fe isotope measurements have been carried out to estimate the impact of the hydrothermal metamorphic overprint on the Fe isotopic composition of Fe-Ti-oxides and Fe-sulfides of the different lithologies of the drilled rocks from IODP Hole 1256D (eastern equatorial Pacific; 15 Ma crust formed at the East Pacific Rise). Most igneous rocks normally have a very restricted range in their 56Fe/54Fe ratio. In contrast, Fe isotope compositions of hot fluids (> 300 °C) from mid-ocean-ridge spreading centers define a narrow range that is shifted to lower delta 56Fe values by 0.2 per mil - 0.5 per mil as compared to igneous rocks. Therefore, it is expected that mineral phases that contain large amounts of Fe are especially affected by the interaction with a fluid that fractionates Fe isotopes during exsolution/precipitation of those minerals. We have used a femtosecond UV-Laser ablation system to determine mineral 56Fe/54Fe ratios of selected samples with a precision of < 0.1 per mil (2 sigma level) at micrometer-scale. We have found significant variations of the delta 56Fe (IRMM-014) values in the minerals between different samples as well as within samples and mineral grains. The overall observed scale of delta 56Fe (magnetite) in 1256D rocks ranges from - 0.12 to + 0.64 per mil, and of delta 56Fe (ilmenite) from - 0.77 to + 0.01 per mil. Pyrite in the lowermost sheeted dike section is clearly distinguishable from the other investigated lithological units, having positive delta 56Fe values between + 0.29 and + 0.56 per mil, whereas pyrite in the other samples has generally negative delta 56Fe values from - 1.10 to - 0.59 permil. One key observation is that the temperature dependent inter-mineral fractionations of Fe isotopes between magnetite and ilmenite are systematically shifted towards higher values when compared to theoretically expected values, while synthesized, well equilibrated magnetite-ilmenite pairs are compatible with the theoretical predictions. Theoretical considerations including beta-factors of different aqueous Fe-chlorides and Rayleigh-type fractionations in the presence of a hydrous, chlorine-bearing fluid can explain this observation. The disagreement between observed and theoretical equilibrium fractionation, the fact that magnetite, in contrast to ilmenite shows a slight downhole trend in the delta 56Fe values, and the observation of small scale heterogeneities within single mineral grains imply that a general re-equilibration of the magnetite-ilmenite pairs is overprinted by kinetic fractionation effects, caused by the interaction of magnetite/ilmenite with hydrothermal fluids penetrating the upper oceanic crust during cooling, or incomplete re-equilibration at low temperatures. Furthermore, the observation of significant small-scale variations in the 56Fe/54Fe ratios of single minerals in this study highlights the importance of high spatial-resolution-analyses of stable isotope ratios for further investigations.

Glaciological characteristics and carbon dioxide record of ice cores from Antarctica

We report a decadally resolved record of atmospheric CO2 concentration for the last 1000 years, obtained from the West Antarctic Ice Sheet (WAIS) Divide shallow ice core. The most prominent feature of the pre-industrial period is a rapid ~7 ppm decrease of CO2 in a span of ~20-50 years at ~1600 A.D. This observation confirms the timing of an abrupt atmospheric CO2 decrease of ~10 ppm observed for that time period in the Law Dome ice core CO2 records, but the true magnitude of the decrease remains unclear. Atmospheric CO2 variations over the time period 1000-1800 A.D. are statistically correlated with northern hemispheric climate and tropical Indo-Pacific sea surface temperature. However, the exact relationship between CO2 and climate remains elusive due to regional climate variations and/or uneven geographical data density of paleoclimate records. We observe small differences of 0 ~2% (0 ~ 6 ppm) among the high-precision CO2 records from the Law Dome, EPICA Dronning Maud Land and WAIS Divide Antarctic ice cores. However, those records share common trends of CO2 change on centennial to multicentennial time scales, and clearly show that atmospheric CO2 has been increasing above preindustrial levels since ~1850 A.D.

Chemical and isotopic compositions of ocean authigenic carbonates

Oceanic authigenic carbonates are classified according to origin of the carbonate carbon source using a complex methodology that includes methods of sedimentary petrography, mineralogy, isotope geochemistry, and microbiology. Mg-calcite (protodolomite) and aragonite predominate among the authigenic carbonates. All authigenic carbonates are depleted in 13C and enriched in 18O (in PDB system) that indicates biological fractionation of isotopes during carbonate formation. Obtained results show that authigenic carbonate formation is a biogeochemical (microbial) process, which involves carbon from ancient sedimentary rocks, abiogenic methane, and bicarbonate-ion of hydrothermal fluids into the modern carbon cycle.

(Table 2) Chemical composition of quenched glasses from the Mohns and Knipovich Ridges

The aim of this project was a petrogeochemical study of igneous rocks in the areas of the Mohns and Knipovich Ridges, both being the northern extensions of the Mid-Atlantic Ridge (MAR), using data available for quenching glass samples collected during Cruises 36 and 38 of R/V Akademic Mstislav Keldysh and during Cruise 15 of R/V Professor Logachev. Results of igneous rock studying from the Mohns and Knipovich Ridges at the background of evolution of the total North Atlantic Province, which had been identified earlier from tectonic and geophysical data, showed that igneous rocks of the Knipovich Ridge can be ranked as shallow tholeiites, primary melts of which were relatively rich in Na and Si and poor in Fe. This type of magma is characteristic of colder regions of the oceanic lithosphere. Its occurrence in the Knipovich Ridge and its potential propagation up to the Gakkel Ridge suggest that igneous rocks of this region originated under conditions of passive spreading in contrast to the MAR region in vicinity of Iceland and Azores, where substantial contribution of hotter material of a rising plume contributed to formation of the oceanic crust. The North Atlantic Ocean is the youngest province in terms of ocean-floor opening. Geologically and geophysically it is one of well studied regions of the World Ocean. Nevertheless some basic key items of its origin still remain to be clarified. In 1975 Scatler et al. proved specifics of this region manifested in growth of the gravity field, and also in relative height of the ocean floor in the region of 33-70°N, which was associated by them with rise of the hotter mantle, as compared with common regions of the Mid-Atlantic Ridge. Later this view was confirmed by character of magmatism, which differed in depth of generation and by melting degree of the resulting primary magma. Uniqueness of the North Atlantic region was also proved by the fact that this region was marked by extensive geochemical anomalies associated with Azores, Iceland, and Jan Mayen. All of these data allow to consider the northern part of the MAR (north of 33°N) as an united global geotectonic province. The Mohns and Knipovich Ridges located north of Iceland locate at the northern end of this province. This is the least known region. Therefore, new data for ridge areas of 73-77°N are needed for more complete geologic history of the Arctic Basin. The aim of this study was to carry out a complex comparison of magmatism at the Mohns and Knipovich Ridges with magmatism at large segments of the MAR northern province and to reconstruct mechanisms of primary magma formation, as well as conditions of their fractionation. This paper was based on results of studying quenched glasses, which reflect evolution of melt in the course of its formation.

Age determination of sediment core SO75-26KL, Portuguese margin

A benthic isotope record has been measured for core SO75-26KL from the upper Portuguese margin (1099 m water depth) to monitor the response of thermohaline overturn in the North Atlantic during Heinrich events. Evaluating benthic delta18O in TS diagrams in conjunction with equilibrium deltac fractionation implies that advection of Mediterranean outflow water (MOW) to the upper Portuguese margin was significantly reduced during the last glacial (< 15% compared to 30% today). The benthic isotope record along core SO75-26KL therefore primarily monitors variability of glacial North Atlantic conveyor circulation. The 14C-accelerator mass spectrometry ages of 13.54±.07 and 20.46±.12 ka for two ice-rafted detritus (IRD) layers in the upper core section and an interpolated age of 36.1 ka for a third IRD layer deeper in the core are in the range of published 14C ages for Heinrich events H1, H2, and H4. Marked depletion of benthic delta13C by 0.7-1.1 per mil during the Heinrich events suggests reduced thermohaline overturn in the North Atlantic during these events. Close similarity between meltwater patterns (inferred from planktonic delta18O) at Site 609 and ventilation patterns (inferred from benthic delta13C) in core SO75-26KL implies coupling between thermohaline overturn and surface forcing, as is also suggested by ocean circulation models. Benthic delta13C starts to decrease 1.5-2.5 kyr before Heinrich events Hl and H4, fully increased values are reached 1.5-3 kyr after the events, indicating a successive slowdown of thermohaline circulation well before the events and resumption of the conveyor's full strength well after the events. Benthic delta13C changes in the course of the Heinrich events show subtle maxima and minima suggesting oscillatory behavior of thermohaline circulation, a distinct feature of thermohaline instability in numerical models. Inferrred gradual spin-up of thermohaline circulation after Hl and H4 is in contrast to abrupt wanning in the North Atlantic region that is indicated by sudden increases in Greenland ice core delta18O and in marine faunal records from the northern North Atlantic. From this we infer that thermohaline circulation can explain only in part the rapid climatic oscillations seen in glacial sections of the Greenland ice core record.