Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Geochemistry and radiogenic isotopes of ODP Hole 157-953C lavas

The Canary Island primitive basaltic magmas are thought to be derived from an HIMU-type upwelling mantle containing isotopically depleted (NMORB)-type component having interacted with an enriched (EM)-type component, the origin of which is still a subject of debate. We studied the relationships between Ni, Mn and Ca concentrations in olivine phenocrysts (85.6-90.0 mol.% Fo, 1,722-3,915 ppm Ni, 1,085-1,552 ppm Mn, 1,222-3,002 ppm Ca) from the most primitive subaerial and ODP Leg 157 high-silica (picritic to olivine basaltic) lavas with their bulk rock Sr-Nd-Pb isotope compositions (87Sr/86Sr = 0.70315-0.70331, 143Nd/144Nd = 0.51288-0.51292, 206Pb/204Pb = 19.55-19.93, 207Pb/204Pb = 15.60-15.63, 208Pb/204Pb = 39.31-39.69). Our data point toward the presence of both a peridotitic and a pyroxenitic component in the magma source. Using the model (Sobolev et al., 2007, Science Vol 316) in which the reaction of Si-rich melts originated during partial melting of eclogite (a high pressure product of subducted oceanic crust) with ambient peridotitic mantle forms olivine-free reaction pyroxenite, we obtain an end member composition for peridotite with 87Sr/86Sr = 0.70337, 143Nd/144Nd = 0.51291, 206Pb/204Pb = 19.36, 207Pb/204Pb = 15.61 and 208Pb/204Pb = 39.07 (EM-type end member), and pyroxenite with 87Sr/86Sr = 0.70309, 143Nd/144Nd = 0.51289, 206Pb/204Pb = 20.03, 207Pb/204Pb = 15.62 and 208Pb/204Pb = 39.84 (HIMU-type end member). Mixing of melts from these end members in proportions ranging from 70% peridotite and 30% pyroxenite to 28% peridotite and 72% pyroxenite derived melt fractions can generate the compositions of the most primitive Gran Canaria shield stage lavas. Combining our results with those from the low-silica rocks from the western Canary Islands (Gurenko et al., 2009, doi:10.1016/j.epsl.2008.11.013), at least four distinct components are required. We propose that they are (1) HIMU-type pyroxenitic component (representing recycled ocean crust of intermediate age) from the plume center, (2) HIMU-type peridotitic component (ancient recycled ocean crust stirred into the ambient mantle) from the plume margin, (3) depleted, MORB-type pyroxenitic component (young recycled oceanic crust) in the upper mantle entrained by the plume, and (4) EM-type peridotitic component from the asthenosphere or lithosphere above the plume center.

Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Microfossils and chemical elements in bottom sediments of the Ashadze-1 Hydrothermal Field (tropical Mid-Atlantic Ridge)

The first thorough analysis of microfossils from ore-bearing sediments of the Ashadze-1 Hydrothermal Field in the Mid-Atlantic Ridge sampled during Cruise 26 of R/V Professor Logachev in 2005 revealed substantial influence of hydrothermal processes on preservation of planktonic calcareous organisms as well as on preservation and composition of benthic foraminifera. From lateral and vertical distribution patterns and secondary alterations of microfossils it is inferred that the main phase of hydrothermal mineralization occurred in Holocene. Heavy metals (Cu, Co, Cr, and Ag) were accumulated by foraminiferal tests and in their enveloping Fe-Mn crusts. Distribution of authigenic minerals replacing foraminiferal tests demonstrates local zoning related to hydrothermal activity. There are three mineral-geochemical zones defined: sulfide zone, zone with elevated Mg content, and zone of Fe-Mn crusts.

Petrology of mafic and ultramafic intrusions from the Portneuf-Mauricie Domain, Grenville Province, Canada

The Portneuf-Mauricie Domain (PMD), located in the south-central part of the Grenville Province, comprises several mafic and ultramafic intrusions hosting Ni-Cu ± platinum-group element (PGE) prospects and a former small mining operation (Lac Édouard mine). These meter- to kilometer-scale, sulfide-bearing intrusions display diverse forms, such as layered and tabular bodies with no particular internal structure, and zoned plutons. They were injected ~ 1.40 Ga into a mature oceanic arc, before and during accretion of the arc to the Laurentian margin. The pressure-temperature conditions of the magmas at the beginning of their emplacement were 3 kbar and 1319-1200 °C (according to the petrologic modeling results from this study). The PMD mineralized intrusions are interpreted to represent former magma chambers or magma conduits in the roots of the oceanic arc. The parent magmas of the mineralized intrusions resulted mainly from the partial melting of a mantle source composed of spinel-bearing lherzolite. Petrologic modeling and the occurrence of primary amphibole in the plutonic rocks indicate that these parent melts were basaltic and hydrous. In addition, fractional crystallization modeling and Mg/Fe ratios suggest that most of the intrusions may have formed from evolved magmas, with Mg# = 60, resulting from the fractionation of more primitive magmas (primary magmas, with Mg# = 68). Petrologic modeling demonstrates that 30% fractional crystallization resulted in the primitive to evolved characteristics of the studied intrusive rocks (as indicated by the crystallization sequences and mineral chemistry). Exceptions are the Réservoir Blanc, Boivin, and Rochette West parent magmas, which may have undergone more extensive fractional crystallization, since these intrusions contain pyroxenes that are more iron rich and have lower Mg numbers than pyroxenes in the other PMD intrusions. The PMD mafic and ultramafic intrusions were intruded into an island arc located offshore from the Laurentian continent. Thus, their presence confirms the existence of a well-developed magmatic network (responsible of the fractionation processes) beneath the Proterozoic arc, which resulted in the wide range of compositions observed in the various plutons.

Geochemistry of Peru margin sediments

This data report tabulates results of chemical analyses of sediments from four sites (680, 682, 685, and 688) drilled during Leg 112 offshore Peru. These sediments were recovered from the forearc basins underlying the Peru upwelling area. They are equivalent in facies and age to the Pisco and Monterey formations, both of which are of considerable economic and geological interest as hydrocarbon source rocks deposited under conditions of coastal upwelling. Sediments recovered from the shelf (Site 680) and slope (Sites 682, 685, and 688) during Leg 112 are unconsolidated and are thermally immature. A lack of consolidation and thermal catagenesis makes these deposits ideal targets for chemical investigation into effects of early diagenesis in organic-carbon-rich siliceous muds.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

AMS 14C ages and isotopic compositions of samples from the Derugin Basin, Sea of Okhotsk

An area of massive barite precipitations was studied at a tectonic horst in 1500 m water depth in the Derugin Basin, Sea of Okhotsk. Seafloor observations and dredge samples showed irregular, block- to column-shaped barite build-ups up to 10 m high which were scattered over the seafloor along an observation track 3.5 km long. High methane concentrations in the water column show that methane expulsion and probably carbonate precipitation is a recently active process. Small fields of chemoautotrophic clams (Calyptogena sp., Acharax sp.) at the seafloor provide additional evidence for active fluid venting. The white to yellow barites show a very porous and often layered internal fabric, and are typically covered by dark-brown Mn-rich sediment; electron microprobe spectroscopy measurements of barite sub-samples show a Ba substitution of up to 10.5 mol% of Sr. Rare idiomorphic pyrite crystals (~1%) in the barite fabric imply the presence of H2S. This was confirmed by clusters of living chemoautotrophic tube worms (1 mm in diameter) found in pores and channels within the barite. Microscopic examination showed that micritic aragonite and Mg-calcite aggregates or crusts are common authigenic precipitations within the barite fabric. Equivalent micritic carbonates and barite carbonate cemented worm tubes were recovered from sediment cores taken in the vicinity of the barite build-up area. Negative d13C values of these carbonates (>-43.5 per mill PDB) indicate methane as major carbon source; d18O values between 4.04 and 5.88 per mill PDB correspond to formation temperatures, which are certainly below 5°C. One core also contained shells of Calyptogena sp. at different core depths with 14C-ages ranging from 20 680 to >49 080 yr. Pore water analyses revealed that fluids also contain high amounts of Ba; they also show decreasing SO4**2- concentrations and a parallel increase of H2S with depth. Additionally, S and O isotope data of barite sulfate (d34S: 21.0-38.6 per mill CDT; d18O: 9.0-17.6 per mill SMOW) strongly point to biological sulfate reduction processes. The isotope ranges of both S and O can be exclusively explained as the result of a mixture of residual sulfate after a biological sulfate reduction and isotopic fractionation with 'normal' seawater sulfate. While massive barite deposits are commonly assumed to be of hydrothermal origin, the assemblage of cheomautotrophic clams, methane-derived carbonates, and non-thermally equilibrated barite sulfate strongly implies that these barites have formed at ambient bottom water temperatures and form the features of a Giant Cold Seep setting that has been active for at least 49 000 yr.

Composition of palagonitized basalts, their alteration products, and palagonitized basaltic glasses

Detailed petrochemical and geochemical studies of two samples of palagonitized basalts collected from depths 3060 and 4800 m have shown that palagonitization of tholeiitic basalt is accompanied by intensive removal of Ca and Mg and some removal of SiO2 from rocks. Appreciable amount of K is added to rocks in this process. Behavior of Fe, Al, Ti, Cr, and Na is inert. Palagonitization of alkalic basalt is accompanied by loss of SiO2, Ca, and Na from rocks. Contents of K and Mg are not changed. Four stages can be discerned in alteration of basalts under deep-sea conditions: syngenetic and diffusional palagonitization, hydrothermal leaching, and underwater weathering. Crusts of Fe-Mn ores are formed through removal of Fe, Mn, Ni, Co, Sn, and Mo from rocks and sorption of Pb, Hg, Yb, La, Bi, W, and Be from sea water.

Radiogenic isotope trace composition of the Labrador Sea

Geological reconstructions and general circulation models suggest that the onset of both Northern Hemisphere glaciation, 2.7 Myr ago, and convection of Labrador Sea Water (LSW) were caused by the closure of the Panama Gateway ~4.5 Myr ago. Time series data that have been obtained from studies of ferromanganese crusts from the northwestern Atlantic suggest that radiogenic isotopes of intermediate ocean residence time (Pb and Nd) can serve as suitable tracers to reconstruct these events. However, it has been unclear until now as to whether the changes that have been observed in isotope composition at this time are the result of increased thermohaline circulation or due to the effects of increased glacial weathering. In this paper we adopt a box model approach to demonstrate that the shifts in radiogenic isotope compositions are unlikely to be due to changes in convection in LSW but can be explained in terms of increases of erosion levels due to the glaciation of Greenland and Canada. Furthermore, we provide experimental evidence for the incongruent release of a labile fraction of strongly radiogenic Pb and nonradiogenic Nd from continental detritus eroding into the Labrador Sea. This can be attributed to the glacial weathering of old continents and accounts for the paradox that one of the areas of the world most deficient in radiogenic Pb should provide such a rich supply of radiogenic Pb to the oceans. An important general conclusion is that the compositions of radiogenic isotopes in seawater are not always a reflection of their continental sources. Perhaps more importantly, the transition from chemical weathering to mechanical erosion is likely to result in significant variations in radiogenic tracers in seawater.