Major and trace element compositions of the Buendnerschiefer samples

The Bündnerschiefer of the Swiss-Italian Alps is a large sedimentary complex deposited on the Piemonte-Liguria and Valais oceans and associated continental margins from the upper Jurassic to Eocene. It is made of a large variety of sequences associated or not with an ophiolitic basement. The Bündnerschiefer makes an accretionary prism that developed syn-tectonically from the onset of alpine subduction, and it records orogenic metamorphism following episodes of HP metamorphism. The Bündnerschiefer shares important similarities with the Otago schists of New Zealand and with the Wepawaug schists of Connecticut, both of which form accretionary prisms and have an orogenic metamorphic imprint. With the aim of testing the hypothesis of mobility of chemical components as a function of metamorphic grade, in this work I present fifty-five bulk chemical analyses of various lithological facies of the Bündnerschiefer collected along the well-studied field gradient of the Lepontine dome of Central Switzerland, in the Prättigau half window of East Switzerland, and in the Tsaté Nappe of Valle d'Aosta (Italy). The dataset includes the concentration of major components, large ion lithophile elements (Rb, Sr, Ba, Cs), high field strength elements (Zr, Ti, Nb, Th, U, Ta, Hf), fluid-mobile light elements (B, Li), volatiles (CO2, S), REEs, and Y, V, Cr, Co, Sn, Pb, Cu, Zn, Tl, Sb, Be, and Au. These data are compared against the compositions of the global marine sediment reservoir, typical crustal reservoirs, and against the previously measured compositions of Otago and Wepawaug schists. Results reveal that, irrespective of their metamorphic evolution, the bulk chemical compositions of orogenic metasediments are characterized by mostly constant compositional ratios (e.g., K2O/Al2O3, Ba/Al2O3, Sr/CaO, etc.), whose values in most cases are undistinguishable from those of actual marine sediments and other crustal reservoirs. For these rocks, only volatile concentrations decrease dramatically as a function of metamorphic temperature, and significant deviations from the reservoir signatures are evident for SiO2, B, and Li. These results are interpreted as an indication of residual enrichment in the sediments, a process taking place during syn-metamorphic dehydration from the onset of metamorphism in a regime of chemical immobility. Residual enrichment increased the absolute concentrations of the chemical components of these rocks, but did not modify significantly their fundamental ratios. This poor compositional modification of the sediments indicates that orogenic metamorphism in general does not promote significant mass transfer from accretionary prisms. In contrast, mass transfer calculations carried out in a shear zone crosscutting the Bündnerschiefer shows that significant mass transfer occurs within these narrow zones, resulting in gains of H2O, SiO2, Al2O3, K2O, Ba, Y, Rb, Cu, V, Tl, Mo, and Ce during deformation and loss of Na2O, CO2, S, Ni, B, U, and Pb from the rock. These components were presumably transported by an aquo-carbonic fluid along the shear zone. These distinct attitudes to mobilize chemical elements from orogenic sediments may have implications for a potentially large number of geochemical processes in active continental margins, from the recycling of chemical components at plate margins to the genesis of hydrothermal ore deposits.

Isotopic composition of igneous rocks from DSDP Site 462

The tholeiitic basalts and microdolerites that comprise the Cretaceous igneous complex in the Nauru Basin in the western equatorial Pacific have moderate ranges in initial 87Sr/86Sr (0.70347 - 0.70356), initial 143Nd/144Nd (0.51278 - 0.51287), and measured 206Pb/204Pb (18.52 - 19.15), 207Pb/204Pb (15.48 - 15.66) and 208Pb/204Pb (38.28 - 38.81). These isotopic ratios overlap with those of both oceanic island basalts (OIB) and South Atlantic and Indian mid-ocean ridge basalts (MORB). However, the petrography, mineralogy, and bulk rock chemistry of the igneous complex are more similar to MORB than to OIB. Also, the rare earth element contents of Nauru Basin igneous rocks are uniformly depleted in light elements (La/Sm(ch) < 1) indicative of a mantle source compositionally similar to that of MORB. These results suggest that the igneous complex is the top of the original ocean crust in the Nauru Basin, and that the notion that the crust must be 15 to 35 m.y. older based on simple extrapolation and identification of the M-sequence magnetic lineations (Larson et al., 1981, doi:10.2973/dsdp.proc.61.1981; Moberly et al., 1985, doi:10.2973/dsdp.proc.81.1984) may be invalid because of a more complicated tectonic setting. The igneous complex most probably was extruded from an ocean ridge system located near the anomalously hot, volcanically active, and isotopically distinct region in the south central Pacific which has been in existence since c. 120 Ma.

Geochemistry of serpentinized peridotites from ODP Holes 207-1272A and 207-1274A

Despite the key importance of altered oceanic mantle as a repository and carrier of light elements (B, Li, and Be) to depth, its inventory of these elements has hardly been explored and quantified. In order to constrain the systematics and budget of these elements we have studied samples of highly serpentinized (>50%) spinel harzburgite drilled at the Mid-Atlantic Ridge (Fifteen-Twenty Fracture zone, ODP Leg 209, Sites 1272A and 1274A). In-situ analysis by secondary ion mass spectrometry reveals that the B, Li and Be contents of mantle minerals (olivine, orthopyroxene, and clinopyroxene) remain unchanged during serpentinization. B and Li abundances largely correspond to those of unaltered mantle minerals whereas Be is close to the detection limit. The Li contents of clinopyroxene are slightly higher (0.44-2.8 µg/g) compared to unaltered mantle clinopyroxene, and olivine and clinopyroxene show an inverse Li partitioning compared to literature data. These findings along with textural observations and major element composition obtained from microprobe analysis suggest reaction of the peridotites with a mafic silicate melt before serpentinization. Serpentine minerals are enriched in B (most values between 10 and 100 µg/g), depleted in Li (most values below 1 µg/g) compared to the primary phases, with considerable variation within and between samples. Be is at the detection limit. Analysis of whole rock samples by prompt gamma activation shows that serpentinization tends to increase B (10.4-65.0 µg/g), H2O and Cl contents and to lower Li contents (0.07-3.37 µg/g) of peridotites, implying that-contrary to alteration of oceanic crust-B is fractionated from Li and that the B and Li inventory should depend essentially on rock-water ratios. Based on our results and on literature data, we calculate the inventory of B and Li contained in the oceanic lithosphere, and its partitioning between crust and mantle as a function of plate characteristics. We model four cases, an ODP Leg 209-type lithosphere with almost no igneous crust, and a Semail-type lithosphere with a thick igneous crust, both at 1 and 75 Ma, respectively. The results show that the Li contents of the oceanic lithosphere are highly variable (17-307 kg in a column of 1 m * 1 m * thickness of the lithosphere (kg/col)). They are controlled by the primary mantle phases and by altered crust, whereas the B contents (25-904 kg/col) depend entirely on serpentinization. In all cases, large quantities of B reside in the uppermost part of the plate and could hence be easily liberated during slab dehydration. The most prominent input of Li into subduction zones is to be expected from Semail-type lithosphere because most of the Li is stored at shallow levels in the plate. Subducting an ODP Leg 209-type lithosphere would mean only very little Li contribution from the slab. Serpentinized mantle thus plays an important role in B recycling in subduction zones, but it is of lesser importance for Li.

Geochemistry of sediments beneath the Tonga-Kermadec arc

The fate of subducted sediment and the extent to which it is dehydrated and/or melted before incorporation into arc lavas has profound implications for the thermo-mechanical nature of the mantle wedge and models for crustal evolution. In order to address these issues, we have undertaken the first measurements of 10Be and light elements in lavas from the Tonga-Kermadec arc and the sediment profile at DSDP site 204 outboard of the trench. The 10Be/9Be ratios in the Tonga lavas are lower than predicted from flux models but can be explained if (a) previously estimated sediment contributions are too high by a factor of 2-10, (b) the top 1-22 m of the incoming sediment is accreted, (c) large amounts of sediment erosion are proposed, or (d) the sediment component takes several Myr longer than the subducting plate to reach the magma source region beneath Tonga. The lavas form negative Th/Be-Li/Be arrays that extend from a depleted mantle source composition to lower Th/Be and Li/Be ratios than that of the bulk sediment. Thus, these arrays are not easily explained by bulk sediment addition and, using partition coefficients derived from experiments on the in-coming sediment, we show that they are also unlikely to result from fluid released during dehydration of the sediment (or altered oceanic crust). However, partial melts of the dehydrated sediment residue formed at ~800 °C during the breakdown of amphibole +/- plagioclase and in the absence of cordierite have significantly lowered Th/Be ratios. The lava arrays can be successfully modelled as 10-15% partial melts of depleted mantle after it has been enriched by the addition of 0.2-2% of these partial melts. Phase relations suggest that this requires that the top of the subducting crust reaches temperatures of ~800 °C by the time it attains ~ 80 km depth which is in excellent agreement with the results of recent numerical models incorporating a temperature-dependent mantle viscosity. Under these conditions the wet basalt solidus is also crossed yet there is no recognisable eclogitic signal in the lavas suggesting that on-going dehydration or strong thermal gradients in the upper part of the subducting plate inhibit partialmelting of the altered oceanic crust.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

Contents of major and noble chemical elements in phosphorites and bottom sediments

Ag and Au are typically concentrated in phosphorites; they genetically related to organic matter of bottom sediments that extract these elements from seawater or interstitial water. Consequently, the phosphorites inherit Ag and Au from host sediments that are not always enriched in them. In contrast to other organic-rich sediments, analyzed sample of recent diatom ooze from the Namibian shelf is not enriched in Ag and Au, although some sediments from this region are enriched in Au. In addition to authigenic Au, allochthonous Au associated with quartz grains and micrograins can also be present in shelf phosphorites. This was observed in oceanic phosphorites of various types. Anomalous Au and Fe contents recorded in one seamount phosphorite sample can be related to extraction of Au and nonferrous metals by ferromanganese hydroxides from seawater. This process can serve as one of major mechanisms of Au supply to ferromanganese crusts on seamounts. Phosphorites and sediments are enriched in Ru simultaneously with U. Author's data show that U content varies from 17 (seamount phosphorite) to 887 ppm (Pleistocene phosphorite nodule from the Namibian shelf). This is probably caused by different types of behavior of light and heavy PGEs in the marine environment.

Geochemistry, trace elements and minerals at DSDP Holes 80-550B and 80-551

The Leg 80 basalts drilled on the Porcupine Abyssal Plain 10 km southwest of Goban Spur (Hole 550B) and on the western edge of Goban Spur (Hole 551), respectively, are typical light-rare-earth-element- (LREE-) depleted oceanic tholeiites. The basalts from the two holes are almost identical; most of their primary geochemical and mineralogical characteristics have been preserved, but they have undergone some low-temperature alteration by seawater, such as enrichment in K, Rb, and Cs and development of secondary potassic minerals of the "brownstone facies." K/Ar dating fail to give realistic emplacement ages; the apparent ages obtained become younger with alteration (causing an increase in K2O). Hole 551 basalts are clearly different from the continental tholeiites emplaced on the margins of oceanizing domains during the prerift and synrift stages.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

Contents and accumulation rates of the rare earth and some other elements in metalliferous sediments from DSDP Hole 92-598

The sediments recovered during DSDP Leg 92 (Site 598) include a complete 16 m.y. record of hydrothermal sedimentation along the western flank of the East Pacific Rise at 19°S. Fifty samples from this sediment column were analyzed to test the hypothesis that the REE composition of the hydrothermal component is primarily acquired via scavenging from seawater. Site 598 provides an ideal sample suite for this purpose: the sediments are lithologically "simple," primarily consisting of a mixture of hydrothermal materials and biogenous carbonates; the composition of the hydrothermal component is essentially constant through space and time; and the sediments have undergone minimal diagenetic alteration. The following observations suggest the above-stated hypothesis is true. The Ce anomaly as well as key indices of light and heavy REE behavior all show that the REE pattern of hydrothermal sediments approaches that of seawater with increasing paleodistance from the rise crest. Moreover, shale-normalized REE patterns are similar to that of seawater, varying only in absolute REE content: the REE content increases with distance from the paleo-rise crest and exhibits a pronounced increase in sediments deposited below the paleolysocline. Based on significant correlative relationships between paleodistance from the rise crest and both the concentration and mass accumulation rates (MARs) of REEs and Fe, we conclude the REEs in the hydrothermal component are derived from the interaction of seawater and Fe in the hydrothermal plume.

Absorption characteristics, major elements and chl a content of samples from Pond 19 at Zackenberg, NE Greenland

1. Shallow arctic lakes and ponds have simple and short food webs, but large uncertainties remain about benthic-pelagic links in these systems. We tested whether organic matter of benthic origin supports zooplankton biomass in a pond in NE Greenland, using stable isotope analysis of carbon and nitrogen in the pond itself and in a 13C-enrichment enclosure experiment. In the latter, we manipulated the carbon isotope signature of benthic algae to enhance its isotopic discrimination from other potential food sources for zooplankton. 2. The cladoceran Daphnia middendorffiana responded to the 13C-enrichment of benthic mats with progressively increasing d13C values, suggesting benthic feeding. Stable isotope analysis also pointed towards a negligible contribution of terrestrial carbon to the diet of D. middendorffiana. This agreed with the apparent dominance of autochthonous dissolved organic matter in the pond revealed by analysis of coloured dissolved organic matter. 3. Daily net production by phytoplankton in the pond (18 mg C/m**2/day) could satisfy only up to half of the calculated minimum energy requirements of D. middendorffiana (35 mg C/m**2/day), whereas benthic primary production alone (145 mg C/m**2/day) was more than sufficient. 4. Our findings highlight benthic primary production as a major dietary source for D. middendorffiana in this system and suggest that benthic organic matter may play a key role in sustaining pelagic secondary production in such nutrient-limited high arctic ponds.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.