Geochemical composition of surface snow, ice and debris from glaciers in Norway, Nepal and New Zealand

Alpine glacier samples were collected in four contrasting regions to measure supraglacial dust and debris geochemical composition. A total of 70 surface glacier ice, snow and debris samples were collected in 2009 and 2010 in Svalbard, Norway, Nepal and New Zealand. Trace elemental abundances in snow and ice samples were measured via inductively coupled plasma mass spectrometry (ICP-MS). Supraglacial debris mineral, bulk oxide and trace element composition were determined via X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF). A total of 45 elements and 10 oxide compound abundances are reported. The uniform data collection procedure, analytical measurement methods and geochemical comparison techniques are used to evaluate supraglacial dust and debris composition variability in the contrasting glacier study regions. Elemental abundances revealed sea salt aerosol and metal enrichment in Svalbard, low levels of crustal dust and marine influences to southern Norway, high crustal dust and anthropogenic enrichment in the Khumbu Himalayas, and sulfur and metals attributed to quiescent degassing and volcanic activity in northern New Zealand. Rare earth element and Al/Ti elemental ratios demonstrated distinct provenance of particulates in each study region. Ca/S elemental ratio data showed seasonal denudation in Svalbard and Norway. Ablation season atmospheric particulate transport trajectories were mapped in each of the study regions and suggest provenance pathways. The in situ data presented provides first order glacier surface geochemical variability as measured from four diverse alpine glacier regions. This geochemical surface glacier data is relevant to glaciologic ablation rate understanding as well as satellite atmospheric and land-surface mapping techniques currently in development.

Lithogeochemical and isotope (Rb-Sr, Sm-Nd, Pb-Pb whole rock and Lu-Hf zircon) composition of samples from the Shackleton Range, East Antarctica

Three distinct, spatially separated crustal terranes have been recognised in the Shackleton Range, East Antarctica: the Southern, Eastern and Northern Terranes. Mafic gneisses from the Southern Terrane provide geochemical evidence for a within-plate, probably back-arc origin of their protoliths. A plume-distal ridge origin in an incipient ocean basin is the favoured interpretation for the emplacement site of these rocks at c. 1850 Ma, which, together with a few ocean island basalts, were subsequently incorporated into an accretionary continental arc/supra-subduction zone tectonic setting. Magmatic underplating resulted in partial melting of the lower crust, which caused high-temperature granulite-facies metamorphism in the Southern Terrane at c. 1710-1680 Ma. Mafic and felsic gneisses there are characterised by isotopically depleted, positive Nd and Hf initials and model ages between 2100 and 2000 Ma. They may be explained as juvenile additions to the crust towards the end of the Palaeoproterozoic. These juvenile rocks occur in a narrow, c. 150 km long E-W trending belt, inferred to trace a suture that is associated with a large Palaeoproterozoic accretionary orogenic system. The Southern Terrane contains many features that are similar to the Australo-Antarctic Mawson Continent and may be its furthermost extension into East Antarctica. The Eastern Terrane is characterised by metagranitoids that formed in a continental volcanic arc setting during a late Mesoproterozoic orogeny at c. 1060 Ma. Subsequently, the rocks experienced high-temperature metamorphism during Pan-African collisional tectonics at 600 Ma. Isotopically depleted zircon grains yielded Hf model ages of 1600-1400 Ma, which are identical to Nd model ages obtained from juvenile metagranitoids. Most likely, these rocks trace the suture related to the amalgamation of the Indo-Antarctic and West Gondwana continental blocks at ~600 Ma. The Eastern Terrane is interpreted as the southernmost extension of the Pan-African Mozambique/Maud Belt in East Antarctica and, based on Hf isotope data, may also represent a link to the Ellsworth-Whitmore Mountains block in West Antarctica and the Namaqua-Natal Province of southern Africa. Geochemical evidence indicates that the majority of the protoliths of the mafic gneisses in the Northern Terrane formed as oceanic island basalts in a within-plate setting. Subsequently the rocks were incorporated into a subduction zone environment and, finally, accreted to a continental margin during Pan-African collisional tectonics. Felsic gneisses there provide evidence for a within-plate and volcanic arc/collisional origin. Emplacement of granitoids occurred at c. 530 Ma and high-temperature, high-pressure metamorphism took place at 510-500 Ma. Enriched Hf and Nd initials and Palaeoproterozoic model ages for most samples indicate that no juvenile material was added to the crust of the Northern Terrane during the Pan-African Orogeny but recycling of older crust or mixing of crustal components of different age must have occurred. Isotopically depleted mafic gneisses, which are spatially associated with eclogite-facies pyroxenites, yielded late Mesoproterozoic Nd model ages. These rocks occur in a narrow, at least 100 km long, E-W trending belt that separates alkaline ocean island metabasalts and within-plate metagranitoids from volcanic arc metabasalts and volcanic arc/syn-collisional metagranitoids in the Northern Terrane. This belt is interpreted to trace the late Neoproterozoic/early Cambrian Pan-African collisional suture between the Australo-Antarctic and the combined Indo-Antarctic/West Gondwana continental blocks that formed during the final amalgamation of Gondwana.

Geochemistry of DSDP Leg 65 basalts

Leg 65 of the Deep Sea Drilling Project successfully recovered basalts from four sites in the mouth of the Gulf of California, thus completing a transect begun during Leg 64 from the continental margin of Baja California to the east side of the East Pacific Rise (EPR). Sixty-three whole-rock samples from Sites 482, 483, and 485 have been analyzed by X-ray fluorescence techniques, and a further eleven samples by instrumental neutron-activation techniques, in order to assess magma variability within and between sites. Although the major element compositions and absolute hygromagmatophile (HYG) element abundances are quite variable, all of the basalts are subalkaline tholeiites exhibiting strong more-HYG element (e.g., Rb, La, Nb, Ta) depletion (LaN/YbN ~ 0.4; Nb/Zr ~ 0.02; Ba/Zr ~ 0.23; Th/Hf ~ 0.05). These ratios, together with La/Ta ratios of 20 and Th/Ta ratios of 1.25, demonstrate that the Leg 65 basalts resemble the depleted "N-type" ocean ridge basalts recovered from the Mid-Atlantic Ridge (MAR) at 22 °N and other sections of the EPR. Zr/Ti, Zr/Y, and La/Yb ratios increase with increasing fractionation. It is clear that the basalts recovered from Sites 482, 483, and 485 were all derived from a compositionally similar source and that the compositional differences observed between lithological units can be explained by varying degrees of open system fractional crystallization (magma mixing) in subridge magma chambers. The basaltic rocks recovered from Site 474 near the margin of Baja California, and Sites 477, 478, and 481 in the Guaymas Basin, all drilled during Leg 64, have consistently higher Th/Hf, La/Sm, Zr/Ti, and Zr/Y ratios and higher absolute Sr contents than the Leg 65 basalts. While some of these variations may be explained by different conditions of partial melting, it is considered more likely that the mantle source underlying the Guaymas Basin is chemically distinct from that feeding the EPR at the mouth of the Gulf. These source variations probably reflect the complex tectonic setting of the Gulf of California, the magmas formed at the inception of spreading and in the central part of the Gulf containing a minor but significant component of sub-continental (calc-alkaline) material.

Geochemical composition and atomic formulas of saponites, celadonites and carbonates from ODP Leg 168 sites

With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Geochemistry at DSDP Leg 60

Eocene to Pleistocene volcanogenic sediments from the Mariana Trough and the Mariana arc-trench system have been studied by X-ray diffraction, X-ray fluorescence, and atomic absorption, and with a scanning electron microscope with an X-ray-energy-dispersive attachment. The mineralogical composition of the volcaniclastic sediments (tuffs) is the same as that of the other associated sediments (mudstones). Diagenetic alterations are significant and seem to result from two processes. The first (low-temperature alteration) develops with age and depth; it consists of the genesis of pure smectite, coupled with zeolites (phillipsite, clinoptilolite). The second is limited to sediments immediately overlying basalts and to the altered basalts themselves. It consists of the massive development of palygorskite, and seems to be linked with hydrothermal activity in the igneous basement.

Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Chemical composition of basalts and basaltic glasses from the Sierra Leone Fracture Zone region

Major and trace element (including REE) geochemistry of basalts and chilled basaltic glasses from the MAR axial zone in the vicinity of the Sierra Leone FZ (5-7°10'N) has been studied. Associations of basalts of various compositions with particular ocean-floor geological structural features have been analyzed as well. Three basaltic varieties have been discriminated. Almost ubiquitous are high-Mg basalts (Variety 1) that are derivatives of N-MORB tholeiitic melts and that are produced in the axial zone of spreading. Variety 2 is alkaline basalts widespread on the southwestern flank of the MAR crest zone in the Sierra Leone region, likely generated through deep mantle melting under plume impact. Variety 3 is basalts derivative from T- and P-MORB-like tholeiitic melts and originating through addition of deeper mantle material to depleted upper mantle melts. Magma generation parameters, as calculated from chilled glass compositions, are different for depleted tholeiites (44-55 km, 1320-1370°C) and enriched tholeiites (45-78 km, 1330-1450°C). Mantle plume impact is shown to affect not only tholeiitic basalt compositions but also magma generation conditions in the axial spreading zone, resulting in higher Ti and Na concentrations in melts parental to rift-related basalts occurring near the plume. T- and P-MORBs are also developed near areas where mantle plumes are localized. High-Mg basalts are shown to come in several types with distinctive Ti and Na contents. Nearly every single MAR segment (bounded by sinistral strike slips and the Bogdanov Fracture Zone) is featured by its own basalt type suggesting that it has formed above an asthenospheric diapir with its unique magma generation conditions. These conditions are time variable. Likely causes of temporal and spatial instability of the mantle upwelling beneath this portion of the MAR are singular tectonic processes and plume activity. In sulfide-bearing rift morphostructures (so-called "Ore area'' and the Markov Basin), basalts make up highly evolved suites generated through olivine and plagioclase fractionation, which is suggestive of relatively long-lived magma chambers beneath the sulfide-bearing rift morphostructures. Functioning of these chambers is a combined effect of singular geodynamic regime and plume activity. In these chambers melts undergo deep differentiation leading to progressively increasing concentration of sulfide phase, eventually to be supplied to the hydrothermal plumbing system.

Chemical composition of rocks and minerals from the Karymsky volcanic center, Eastern Kamchatka

The powerful eruption in the Akademii Nauk caldera on January 2, 1996 marked a new activity phase of the Karymsky volcano and became a noticeable event in the history of modern volcanism in Kamchatka. The paper reports data obtained by studying more than 200 glassy melt inclusions in phenocrysts of olivine (Fo82-72), plagioclase (An92-73), and clinopyroxene (Mg# 83-70) in basalts of the 1996 eruption. The data were used to estimate composition of the parental melt and physicochemical parameters of the magma evolution. According to our data, the parental melt corresponded to low magnesium, high aluminum basalt (SiO2 = 50.2%, MgO = 5.6%, Al2O3 = 17%) of the mildly potassium type (K2O = 0.56%) and contained much dissolved volatile components (H2O = 2.8%, S = 0.17%, and Cl = 0.11%). Melt inclusions in the minerals are similar in chemical composition, a fact testifying that the minerals crystallized simultaneously with one another. Their crystallization started at pressure ~1.5 kbar, proceeded within a narrow temperature range of 1040+/-20°C, and continued until near-surface pressure ~100 bar was reached. Degree of crystallization of the parental melt during its eruption was close to 55%. Massive crystallization was triggered by H2O degassing under pressure <1 kbar. Magma degassing in an open system resulted in escape of 82% H2O, 93% S, and 24% Cl (of their initial contents in the parental melt) to the fluid phase. Release of volatile compounds to the atmosphere during the eruption that lasted for 18 h was estimated as 1.7x10**6 t H2O, 1.4x10**5 t S, and 1.5x10**4 t Cl. Concentrations of most incompatible trace elements in the melt inclusions are close to those in the rocks and to the expected fractional differentiation trend. Melt inclusions in plagioclase were found to be selectively enriched in Li. The Li-enriched plagioclase with melt inclusions thought to originate from cumulate layers in the feeding system beneath Karymsky volcano, in which plagioclase interacted with Li-rich melts/brines and was subsequently entrapped and entrained by the magma during the 1996 eruption.

Chemistry of various minerals of altered basalts from ODP Hole 111-504B

Basalts recovered from Hole 504B during ODP Leg 111 are more or less altered, but there is no sign of strong shear stress or widespread penetrative deformation; hence, they retain well their primary (igneous) structures and textures. The effect of alteration is recognized as the partial or total replacement of primary minerals (olivine, clinopyroxene, and plagioclase) by secondary minerals and as the development of secondary minerals in open spaces (e.g., veins, fractures, vugs, or breccia matrix). The secondary minerals include zeolite (laumontite and stilbite), prehnite, chlorite, epidote, Plagioclase (albite and/or oligoclase), amphibole (anthophyllite, cummingtonite, actinolite, and hornblende), sodic augite, sphene, talc, anhydrite, chalcopyrite, pyrite, Fe-Ti oxide, and quartz. Selected secondary minerals from several tens of samples were analyzed by means of an electron-probe microanalyzer; the results are presented along with brief considerations of their compositional features. In terms of the model basaltic system, the following two types of low-variance (three-phase) mineral assemblages were observed: prehnite-epidote-laumontite and prehnite-actinolite-epidote; both include chlorite, albite and/or oligoclase, sphene, and quartz. The mineral parageneses delineated by these low-variance mineral assemblages suggest that the metamorphic grade ranges from the zeolite facies to the prehnite-actinolite facies. The common occurrence of prehnite indicates that greenschist facies conditions were not attained even in the deepest level of Hole 504B, which, in a strict sense, contradicts the previous interpretation that the lower portion of Hole 504B suffered greenschist facies alteration.

Geochemistry of minerals at DSDP Hole 70-504B

Hole 504B, drilled into the 5.9 Ma crust of the southern flank of the Costa Rica Rift, tapped a hydrothermal system in its conductive stage. Three alteration zones were encountered along the 561.5 meters of basement drilled. The upper alteration zone, 274.5 to 584.5 meters below the seafloor (BSF), is characterized by the presence of color zonation in which red halos are located between dark gray inner rock portions and dark gray outer bands. The red halos are characterized by an abundance of iddingsite, and they have higher K2O contents and Fe3+/FeT ratios, but lower SiO2 contents, than the adjacent dark gray inner zones. The dark gray outer bands are characterized by the presence of celadonite-nontronite. Saponite is omnipresent in these three alteration bands. Phillipsite is the only zeolite that occurs in the upper alteration zone. The upper alteration zone is interpreted as being the result of low-temperature alteration, with large amounts of cold oxygenated seawater percolating through the upper ocean crust. In the upper alteration zone, the formation of red halos was both preceded and followed by formation of dark gray outer bands. Then followed formation of dark gray cores. The lower alteration zone (584.5-835.5 m BSF) is characterized by the absence of color zonation, the downward-increasing abundance of pyrite and saponite, and the presence of quartz, talc, and calcite. The chemical changes (downhole MgO enrichment and concomitant CaO depletion) observed in the basalts of the lower alteration zone are thought to result from reactions of oceanic basalts with evolved seawater (i.e., solutions derived from seawater that has already reacted with ocean crust), which is thus depleted in oxygen, potassium, and radiogenic strontium. This alteration process, which was responsible for saponite formation in both the upper and lower alteration zones, was rock dominated, and it took place under suboxic to anoxic conditions during a second stage of alteration. Reaction temperatures could have progressively increased with depth. There is also a zeolitic zone that essentially coincides with the lower part of the upper alteration zone (between 528.5 and 563 m BSF). The host rock adjacent to veins of zeolite exhibits a greenish discoloration due to the intensive replacement of the igneous minerals. The replacement minerals result in significant increases in the bulk rock K2O, MgO, CaO, CO2, and H2O+ contents. The solutions circulating along the newly opened fissures had high Ca activity, and minerals probably precipitated in these fissures at 60°C or 110°C. These hydrothermal solutions circulated later than those responsible for the formation of the minerals that characterize the upper and lower alteration zones.

Biological, physical and chemical characteristics of water and sediment samples from the Volga River delta, northern Caspian

Based on the data of synchronous observations of hydrophysical and biogeochemical parameters in the near-mouth and shallow-water areas of the northern Caspian in 2000-2001, the scale of spatiotemporal variability in the following characteristics of the water-bottom system was estimated (1) flow velocity and direction within vortex structures formed by the combined effect of wind, discharge current, and the presence of higher aquatic plants; (2) dependence of the spatial distribution of the content and composition of suspended particulate matter on the hydrodynamic regime of waters and development of phytoplankton; (3) variations in the grain-size, petrographic, mineralogical, and chemical compositions of the upper layer of bottom sediments at several sites in the northern Caspian related to the particular local combination of dominant natural processes; and (4) limits of variability in the group composition of humus compounds in bottom sediments. The acquired data are helpful in estimating the geochemical consequences of a sea level rise and during the planning of preventive environmental protection measures in view of future oil and gas recovery in this region.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.