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.

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.

Aerosols in the Arctic

In this monograph on the basis of materials obtained by the author and his colleagues in Arctic expeditions of 1991-2005 and of published data results of studies effect of aerosols on environmental conditions and marine sedimentation in the Arctic are summarizes. Processes of aeolian transport and transformation of sedimentary material from sources to places of its accumulation in bottom sediments are described. Results of this study can be used to assess current state of ecosystem of Arctic seas and as a background for evaluation of possible human impact on nature during exploration of mineral resources of the Arctic shelf. For oceanographers, geochemists, geoecologists.

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.

Rare earth elements of ROV sample GeoB12338-2 from the Makran accretionary complex

Authigenic carbonates forming at an active methane-seep on the Makran accretionary prism mainly consist of aragonite in the form of microcrystalline, cryptocrystalline, and botryoidal phases. The d13Ccarbonate values are very negative (-49.0 to -44.0 per mill V-PDB), agreeing with microbial methane as dominant carbon source. The d18Ocarbonate values are exclusively positive (+ 3.0 to + 4.5 per mill V-PDB) and indicate precipitation in equilibrium with seawater at bottom water temperatures. The content of rare earth elements and yttrium (REE + Y) determined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and solution ICP-MS varies for each aragonite variety, with early microcrystalline aragonite yielding the highest, cryptocrystalline aragonite intermediate, and later botryoidal aragonite the lowest REE + Y concentrations. Shale-normalised REE + Y patterns of different types of authigenic carbonate reflect distinct pore fluid compositions during precipitation: Microcrystalline aragonite shows high contents of middle rare earth elements (MREE), reflecting REE patterns ascribed to anoxic pore water. Cryptocrystalline aragonite exhibits a seawater-like REE + Y pattern at elevated total REE + Y concentrations, indicating higher concentrations of REEs in pore waters, which were influenced by seawater. Botryoidal aragonite is characterised by seawater-like REE + Y patterns at initial growth stages followed by an increase of light rare earth elements (LREE) with advancing crystal growth, reflecting changing pore fluid composition during precipitation of this cement. Conventional sample preparation involving micro-drilling of carbonate phases and subsequent solution ICP-MS does not allow to recognise such subtle changes in the REE + Y composition of individual carbonate phases. To be able to reconstruct the evolution of pore water composition during early diagenesis, an analytical approach is required that allows to track the changing elemental composition in a paragenetic sequence as well as in individual phases. High-resolution analysis of seep carbonates from the Makran accretionary prism by LA-ICP-MS reveals that pore fluid composition not only evolved in the course of the formation of different phases, but also changed during the precipitation of individual phases.

(Table T1) Geochemical composition of xenoliths and host rocks from ODP Hole 193-1188A and dredge haul MD-138, PACMANUS field

A number of intensely altered, dark xenoliths with palimpsest quench textures were recorded within altered dacitic host rocks at Site 1189 (Roman Ruins, PACMANUS) during Ocean Drilling Program (ODP) Leg 193. Several of these displayed puzzling marginal fringes, apparently of altered plagioclase with variolitic texture, protruding into adjacent host rocks. Despite their alteration, the xenoliths were interpreted as fragments of rapidly chilled, possibly olivine-bearing basalts incorporated into the dacitic magmas either within the crustal plumbing system or during eruption at the seafloor (figures F15, F16, F17, F42, and F43 in Shipboard Scientific Party, 2002, doi:10.2973/odp.proc.ir.193.104.2002). An additional example of formerly spinifex-textured xenolith, the first from Site 1188 (Snowcap) and the first from the upper cristobalite-bearing zone of alteration, has been revealed by postcruise studies. Furthermore, a pristine sample of the parent lithology has been found within a dredge haul (MD-138, Binatang-2000 Cruise of Franklin; 3°43.60'S, 151°40.35'E, 1688 meters below sea level) from the Satanic Mills hydrothermal field at PACMANUS, near ODP Site 1191. The purpose of this report is to document these discoveries and thereby to confirm and build on shipboard interpretations. To my knowledge, similar xenoliths have never before been found in modern island arc or backarc volcanic sequences. Spinifex textures are most common in Archean komatiites, some of which are bimodally associated with calc-alkaline felsic volcanic rocks.

Trace element contents in zircons from oceanic crust

We present newly acquired trace element compositions for more than 300 zircon grains in 36 gabbros formed at the slow-spreading Mid-Atlantic and Southwest Indian Ridges. Rare earth element patterns for zircon from modern oceanic crust completely overlap with those for zircon crystallized in continental granitoids. However, plots of U versus Yb and U/Yb versus Hf or Y discriminate zircons crystallized in oceanic crust from continental zircon, and provide a relatively robust method for distinguishing zircons from these environments. Approximately 80% of the modern ocean crust zircons are distinct from the field defined by more than 1700 continental zircons from Archean and Phanerozoic samples. These discrimination diagrams provide a new tool for fingerprinting ocean crust zircons derived from reservoirs like that of modern mid-ocean ridge basalt (MORB) in both modern and ancient detrital zircon populations. Hadean detrital zircons previously reported from the Acasta Gneiss, Canada, and the Narryer Gneiss terrane, Western Australia, plot in the continental granitoid field, supporting hypotheses that at least some Hadean detrital zircons crystallized in continental crust forming magmas and not from a reservoir like modern MORB.