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.

Calcareous nannofossils in DSDP Leg 87 holes

Drilling at three DSDP drill sites on the western margin of the Pacific Ocean off the coast of Japan yielded thick sequences of hemipelagic muds and clays generally depleted of calcareous nannofossils. Operations at Sites 582 and 583 recovered dominantly Quaternary sediments. The Pliocene/Pleistocene boundary was reached near the bottom of Hole 582B. At both sites, preserved coccolith populations contained generally few to common nannoliths. The effects of reworking were evident throughout most sections at these two sites. Drilling at Site 584 in the Japan Trench recovered Holocene to Miocene sediments. Populations of nannofossils from this site were generally more depleted than those from the two Nankai Trough sites. Reworking within these sections appears to be much less severe than in samples from the more southern sites.

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.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Carbonate and terrigenous content and chemical composition of sediments in the Central Equatorial Pacific

This study addresses changes in the absolute magnitude and spatial geometry of particle flux and export production in a meridional transect across the central equatorial Pacific Ocean's upwelling system during oxygen isotope Stage 11 and Stage 12 and compares these time periods to the current Holocene interglacial system. Temporal and spatial variability in several chemical proxies of export production, and in particular the distributions of Ba, scavenged Al, and P, are studied in a suite of sediment cores gathered along a cross-equator transect at 5°S, 2°S, 0°, 2°N, and 4°N. Because this latitudinal range preserves strong gradients in biogenic particle flux in the modern equatorial Pacific Ocean, we are able to assess variations in the relative magnitude of export production as well as the meridional width of the equatorial system through the late Quaternary glacial/interglacial cycles. During interglacial oxygen isotope Stage 11 the chemical proxies each indicate lower particle flux and export production than during Stage 12. These records are consistent throughout the transect during this time period, but geographic narrowing (during the interglacial) and widening (during the glacial) of the meridional gradient also occurs. Although carbonate concentration varies dramatically through glacial/interglacial cycles at all latitudes studied, the productivity proxies record only minimal glacial/interglacial change at 5°S and 4°N, indicating that the carbonate minima at these latitudes is controlled dominantly by dissolution rather than production. The chemical data indicate that although the spatial geometry of the system during Stages 11 and 12 indicates maximum productivity at the equator during both glacial and interglacial conditions, the absolute magnitude of export production integrated from 5°S to 4°N during Stage 11 was 25-50% less than during Stage 12, and also was 25-50% less than it is now.