Rare earth and trace elements in igneous and metamorphic minerals of oceanic gabbros from the Mid-Atlantic Ridge

SIMS analyses have been carried out on clinopyroxenes, plagioclases and amphiboles of six gabbroic samples from Holes 921-924 of the Ocean Drilling Program Leg 153 sited in the MARK area of the Mid-Atlantic Ridge at the ridge-transform intersection, to investigate the rare earth, trace and volatile element distribution in the lower ocean crust during igneous crystallization and higher grade metamorphic conditions. The metagabbros underwent granulite to subgreenschist facies conditions through three main tectono-metamorphic phases: (1) ductile regime (750 < T < 1000 °C and P = 0.3 GPa); (2) transitional regime (600 < T < 700 °C and P = 0.2 GPa); (3) brittle regime (350 < T < 600 °C and P < 0.2 GPa). Igneous clinopyroxenes show Cl-chondrite normalized patterns depleted in LREE, and nearly flat for HREE. The rare earth and trace element distributions in igneous clinopyroxenes and plagioclases indicate that these minerals act as REE reservoirs, and comprise the main contribution to the overall rock content. The abundances in igneous minerals reflect the degree of fractionation of the parent liquids. In metamorphic clinopyroxenes recrystallized in anhydrous assemblages, the REE and trace elements patterns mimic those of the primary ones. Conversely, clinopyroxerie re-equilibrated in amphibolebearing assemblages shows a significant increase in REE, Ti, Zr, Y and V, a negative Eu anomaly, and slight decreases in Sr and Ba. An overall increase of REE and some trace elements is evident in hydrous assemblages, with preferential partitioning in the amphibole. It shows high Ti (18196-22844 ppm), LREE depleted patterns and LaN/SmN = 0.10-0.33, LaN/YbN = 0.10-0.30. Amphiboles from granoblastic assemblages show homogeneous patterns with no or a positive anomaly for TiN and negative anomalies for SrN and ZrN. Volatiles in amphibole are low, with Cl/F < 1; H2O% is significantly lower than the stoichiometric ratio (1.33-1.53%). The composition of the clinopyroxene and amphibole recrystallized in low-strain domains records evidence of incomplete re-equilibration, and element diffusion and partitioning is in part controlled by the textural site. The possible origins of the fluids involved in the metamorphic recrystallization are discussed: (1) remobilization from igneous amphibole; (2) exsolution from evolved melts; (3) introduction of seawater-derived fluids modified in rock-dominated systems; (4) injection of highly evolved hydrous melts during the metamorphic process.

Geochemistry and isotopic ratios of basalts from ODP Leg 163 sites

Voluminous, subaerial magmatism resulted in the formation of extensive seaward-dipping reflector sequences (SDRS) along the Paleogene Southeast Greenland rifted margin. Drilling during Leg 163 recovered basalts from the SDRS at 66ºN (Site 988) and 63ºN (Sites 989 and 990). The basalt from Site 988 is light rare-earth-element (REE) enriched (La(n)/Yb(n) = 3.4), with epsilon-Nd(t=60) = 5.3, 87Sr/86Sr = 0.7034, and 206Pb/204Pb = 17.98. It is similar to tholeiites recovered from the Irminger Basin during Leg 49 and to light-REE-enriched tholeiites from Iceland. Drilling at Site 989, the innermost of the sites on the 63ºN transect, was proposed to extend recovery of the earliest part of the SDRS initiated during Leg 152. These basalts are, however, younger than those from Site 917 and are compositionally similar to basalts from the more seaward Sites 990 and 915. Many of the basalts from Sites 989 and 990 show evidence of contamination by continental crust (e.g., epsilon-Nd(t=60) extends down to -3.7, 206Pb/204Pb extends down to 15.1). We suggest that the contaminant is a mixture of Archean granulite and amphibolite and that the most contaminated basalts have assimilated ~5% of crust. Uncontaminated basalts are isotopically similar to basalts from Site 918, on the main body of the SDRS, and are light-REE depleted. Consistent with previous models of the development of this margin, we show that at the time of formation of the basalts from Sites 989 and 990 (1) melting was at relatively shallow levels in a fully-fledged rift zone; (2) fragments of continental crust were present in the lithosphere above the zones of melt generation; and (3) the sublithospheric mantle was dominated by a depleted Icelandic plume component.

(Table 1) Results from XRD analysis as well as sediment type and selected results from ring shear experiments

The location of the seaward tip of a subduction thrust controls material transfer at convergent plate margins, and hence global mass balances. At approximately half of those margins, the material of the subducting plate is completely underthrust so that no accretion or even subduction erosion takes place. Along the remaining margins, material is scraped off the subducting plate and added to the upper plate by frontal accretion. We here examine the physical properties of subducting sediments off Costa Rica and Nankai, type examples for an erosional and an accretionary margin, to investigate which parameters control the level where the frontal thrust cuts into the incoming sediment pile. A series of rotary-shear experiments to measure the frictional strength of the various lithologies entering the two subduction zones were carried out. Results include the following findings: (1) At Costa Rica, clay-rich strata at the top of the incoming succession have the lowest strength (µres = 0.19) while underlying calcareous ooze, chalk and diatomite are strong (up to µres = 0.43; µpeak = 0.56). Hence the entire sediment package is underthrust. (2) Off Japan, clay-rich deposits within the lower Shikoku Basin inventory are weakest (µres = 0.13-0.19) and favour the frontal proto-thrust to migrate into one particular horizon between sandy, competent turbidites below and ash-bearing mud above. (3) Taking in situ data and earlier geotechnical testing into account, it is suggested that mineralogical composition rather than pore-pressure defines the position of the frontal thrust, which locates in the weakest, clay mineral-rich (up to 85 wt.%) materials. (4) Smectite, the dominant clay mineral phase at either margin, shows rate strengthening and stable sliding in the frontal 50 km of the subduction thrust (0.0001-0.1 mm/s, 0.5-25 MPa effective normal stress). (5) Progressive illitization of smectite cannot explain seismogenesis, because illite-rich samples also show velocity strengthening at the conditions tested.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

Chlorine concentrations and stable isotope ratios in Izu Bonin tephra

d37Cl values were determined for Izu Bonin arc magmas erupted 0-44 Ma in order to better understand the time-dependent processing of volatiles in subduction zones. Pristine ash-sized particles (glass, pumice, scoria, and rock fragments) were handpicked from tephra drilled at ODP Site 782. d37Cl values for these particles span a large range from -2.1 to +1.7 per mil (error = ± 0.3 per mil) vs. SMOC (Standard Mean Ocean Chloride, defined as 0 per mil). The temporal data extend the previously reported range of d37Cl values of -2.6 to 0.4 per mil (bulk ash) and -5.4 to -0.1 per mil (volcanic gases) from the Quaternary Izu Bonin-Mariana volcanic front to more positive values. Overall, the temporal data indicate a time-progressive evolution, from isotopically negative Eocene and Oligocene magmas (-0.7 ± 1.1 per mil, n = 10) to Neogene magmas that have higher ?37Cl values on average (+0.3 ± 1.1 per mil; n = 13). The increase is due to the emergence of positive d37Cl values in the Neogene, while minimum d37Cl values are similar through time. The range in d37Cl values cannot be attributed to fractionation during melt formation and differentiation, and must reflect the diversity of Cl present in the arc magma sources. Cl clearly derives from the slab (> 96% Cl in arc magmas), but d37Cl values do not correlate with isotope tracers (e.g. 207Pb/204Pb and 87Sr/86Sr) that are indicative of the flux from subducting sedimentary and igneous crust. Given the steady, high Cl flux since at least 42 Ma, the temporal variability of d37Cl values is best explained by a flux from subducting isotopically positive and negative serpentinite formed in the ocean basins that mingles with and possibly overprints the isotopically negative flux from sediment and igneous crust at arc front depths. The change in the d37Cl values before and after backarc spreading may reflect either a tectonically induced change in the mechanism of serpentinite formation on the oceanic plate, or possibly the integration of isotopically positive wedge serpentinite as arc fluid source during the Neogene. Our study suggests that serpentinites are important fluid sources at arc front depth, and implies the return of isotopically positive and negative Cl from the Earth surface to the mantle.