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.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Geochemistry at DSDP Holes 85-573B and 85-574C

Eocene-Oligocene metalliferous sediments and associated lithologies from the central equatorial Pacific are described in detail. Geochemical analyses of 54 sediment and 2 basalt samples are presented for 34 elements. Detailed stratigraphic and statistical analyses of these data, combined with mineralogic studies, indicate the presence of volcanic glass and seven main mineral phases: biogenic calcite and opal, Fe smectite, goethite, dMnO2, carbonate fluorapatite, and barite. Fe smectite formed by reactions between Fe oxyhydroxides and biogenic opal, causing the dissolution of calcite and the precipitation of barite. Diagenesis was oxic. Sediments have rare earth element distributions similar to those in seawater. The metal content of the sediments is related to competition between the supply rates of hydrothermal and biogenic particles, but has been enhanced by early diagenetic processes. Eocene-Oligocene metalliferous sediments compare closely to those currently being deposited in the Bauer Basin and on the flanks of the East Pacific Rise. There is, however, no evidence that they were deposited in close proximity to an active hydrothermal system.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.