Geochemical processes and rare earth element analysis in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reductionas dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE concentrations is evident immediately below the sediment-water interface, which can be related to early diagenetic release of REEs into pore water resulting from the remineralization of particulate organic matter. The highest pore water REE concentrations were measured close to the sediment-water interface at ~2 cm depth. Distinct shale normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shalenormalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.

Chemical and isotopic compositions of basalts and glasses from lavas of the Sierra Leone fault site

According to detailed petrological, geochemical, and isotope-geochemical study, fragments of fresh pillow lavas with chilled glass margins dredged at the Sierra-Leone test site in the axial rift zone of the MAR between 5° and 7°N correspond to MORB tholeiites, which are not primitive mantle melts, but were differentiated in intermediate magmatic (intrusive) chambers. Small-scale geochemical and Sr-Nd isotope heterogeneities were established for the first time in basalts and their glasses. It was shown that some samples have significant nonsystematic differences in the 87Sr/86Sr ratio between basalts and their chilled glasses and less significant difference in e-Nd; higher Sr ratios can be observed both in glasses and basalts of the same lava fragments. No significant correlation is observed between isotope characteristics of samples and their geochemistry; it was also shown that seawater did not affect Sr and Nd isotope compositions of the chilled glasses from the studied pillow lavas. It is suggested that such differences in isotope ratios are related to small-scale heterogeneity of melts owing to incomplete homogenization during their rapid ascent to the surface. Heterogeneity of basaltic melts is explained by their partial contamination by older plutonic rocks (especially gabbroids) of the lower oceanic crust, through which they ascended to the surface of the ocean floor. The wider scatter of the Sr isotopic ratios relative to Nd ones is related to presence of xenocrysts of calcic plagioclase; correspondingly, absence of a Nd mineral carrier in the rocks results in less distinct Nd isotope variations. It was shown that all studied basalts define a single trend along the mantle correlation array in the Sr-Nd isotope diagram. Causes of this phenomenon remain unclear.

Geochemistry of Ninetyeast Ridge basaltic glasses

The Ninetyeast Ridge (NER), a north-south striking, 5,000 km long, 77 to 43 Ma chain of basaltic submarine volcanoes in the eastern Indian Ocean formed as a hotspot track created by rapid northward migration of the Indian Plate over the Kerguelen hotspot. Based on the major and trace element contents of unaltered basaltic glasses from six locations along the NER, we show that the NER was constructed by basaltic magma derived from at least three geochemically distinct mantle sources: (1) a source enriched in highly incompatible elements relative to primitive mantle like the source of the 29-24 Ma flood basalts in the Kerguelen Archipelago; (2) an incompatible element-depleted source similar to the source of Mid-Ocean Ridge Basalt (MORB) erupted along the currently active Southeast Indian Ridge (SEIR); and (3) an incompatible element-depleted source that is compositionally and mineralogically distinct from the source of SEIR MORB. Specifically, this depleted mantle source was garnet-bearing and had higher Y/Dy and Nb/Zr, but lower Zr/Sm, than the SEIR MORB source. We infer that this third source formed as a garnet-bearing residue created during a previous melting event, perhaps an initial partial melting of the mantle hotspot. Subsequently, this residue partially melted over a large pressure range, from slightly over 3 GPa to less than 1 GPa, and to a high extent (~ 30%) thereby creating relatively high SiO2 and FeO contents in some NER basalts relative to SEIR MORB.

Chemical composition of basalts and basaltic glasses from the Sierra Leone Fracture Zone region

Major and trace element (including REE) geochemistry of basalts and chilled basaltic glasses from the MAR axial zone in the vicinity of the Sierra Leone FZ (5-7°10'N) has been studied. Associations of basalts of various compositions with particular ocean-floor geological structural features have been analyzed as well. Three basaltic varieties have been discriminated. Almost ubiquitous are high-Mg basalts (Variety 1) that are derivatives of N-MORB tholeiitic melts and that are produced in the axial zone of spreading. Variety 2 is alkaline basalts widespread on the southwestern flank of the MAR crest zone in the Sierra Leone region, likely generated through deep mantle melting under plume impact. Variety 3 is basalts derivative from T- and P-MORB-like tholeiitic melts and originating through addition of deeper mantle material to depleted upper mantle melts. Magma generation parameters, as calculated from chilled glass compositions, are different for depleted tholeiites (44-55 km, 1320-1370°C) and enriched tholeiites (45-78 km, 1330-1450°C). Mantle plume impact is shown to affect not only tholeiitic basalt compositions but also magma generation conditions in the axial spreading zone, resulting in higher Ti and Na concentrations in melts parental to rift-related basalts occurring near the plume. T- and P-MORBs are also developed near areas where mantle plumes are localized. High-Mg basalts are shown to come in several types with distinctive Ti and Na contents. Nearly every single MAR segment (bounded by sinistral strike slips and the Bogdanov Fracture Zone) is featured by its own basalt type suggesting that it has formed above an asthenospheric diapir with its unique magma generation conditions. These conditions are time variable. Likely causes of temporal and spatial instability of the mantle upwelling beneath this portion of the MAR are singular tectonic processes and plume activity. In sulfide-bearing rift morphostructures (so-called "Ore area'' and the Markov Basin), basalts make up highly evolved suites generated through olivine and plagioclase fractionation, which is suggestive of relatively long-lived magma chambers beneath the sulfide-bearing rift morphostructures. Functioning of these chambers is a combined effect of singular geodynamic regime and plume activity. In these chambers melts undergo deep differentiation leading to progressively increasing concentration of sulfide phase, eventually to be supplied to the hydrothermal plumbing system.

Neodymium isotope ratios of fish debris from late Cretaceous black shales

Neodymium isotopes of fish debris from two sites on Demerara Rise, spanning ~4.5 m.y. of deposition from the early Cenomanian to just before ocean anoxic event 2 (OAE2) (Cenomanian-Turonian transition), suggest a circulation-controlled nutrient trap in intermediate waters of the western tropical North Atlantic that could explain continuous deposition of organic-rich black shales for as many as ~15 m.y. (Cenomanian-early Santonian). Unusually low Nd isotopic data (epsilon-Nd(t) ~-11 to ~-16) on Demerara Rise during the Cenomanian are confirmed, but the shallower site generally exhibits higher and more variable values. A scenario in which southwest-flowing Tethyan and/or North Atlantic waters overrode warm, saline Demerara bottom water explains the isotopic differences between sites and could create a dynamic nutrient trap controlled by circulation patterns in the absence of topographic barriers. Nutrient trapping, in turn, would explain the ~15 m.y. deposition of black shales through positive feedbacks between low oxygen and nutrient-rich bottom waters, efficient phosphate recycling, transport of nutrients to the surface, high productivity, and organic carbon export to the seafloor. This nutrient trap and the correlation seen previously between high Nd and organic carbon isotopic values during OAE2 on Demerara Rise suggest that physical oceanographic changes could be components of OAE2, one of the largest perturbations to the global carbon cycle in the past 150 m.y.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

(Table T1) Nd and Sr isotopic compositions, and Nd and Sm concentrations of glasses from ODP Leg 187 sites

The principal objective of Leg 187 was to locate the Indian/Pacific mantle boundary by sampling and analyzing 8- to 28-Ma seafloor basalts to the north of the Australian Antarctic Discordance (AAD). In this paper we present Sr and Nd isotopic data from basaltic glasses recovered from the 13 sites drilled during Leg 187. Our data show that the boundary region is characterized by a gradual east-west increase in 87Sr/86Sr, with a corresponding decrease in 143Nd/144Nd across a 150-km-wide zone located east and west of the 127°E Fracture Zone. The Sr-Nd isotopic composition of glasses therefore confirms the general conclusions derived by the Leg 187 shipboard scientific party in that the mantle boundary follows a west-pointing, V-shaped depth anomaly that stretches across the ocean floor from the Australian to the Antarctic continental margins. We document that two systematic trends of covariation between 87Sr/86Sr and 143Nd/144Nd can be distinguished, suggesting that the basalts sampled during Leg 187 formed through the interaction of three contrasting source components: (1) a component that lies within the broad spectrum of Indian-type mantle compositions, (2) a boundary component, and (3) a Pacific-type mantle component. The variations in elemental and isotopic compositions indicate that the boundary component represents a distinct mantle region that is associated with the boundary between the Pacific and the Indian mid-ocean-ridge basalt (MORB) sources rather than a dispersed mantle heterogeneity that was preferentially extracted in the boundary region. However, the origin of the boundary component remains an open question. The three components are not randomly intermixed. The Indian and the Pacific mantle sources both interacted with the boundary component, but they seem not to have interacted directly with each other. Large local variability in isotopic compositions of lavas from the mantle boundary region demonstrates that magma extraction processes were unable to homogenize the isotopic contrasts present in the mantle source in this region. Systematic variations in rare earth element (REE) concentrations across the depth anomaly cannot be explained solely by variations in source composition. The observed variations may be explained by an eastward increase and westward decrease in the degree of melting toward the mantle boundary region, compatible with a cooling of the Pacific mantle and a heating of the Indian mantle toward the mantle boundary.