Geochemistry and minerals at DSDP Hole 70-504B

In three veins from the lower part of Deep Sea Drilling Project Hole 504B, 298 meters below the top of basement, primary augite is replaced by aegirine-augite. This transformation occurs only in subophitic basalts, at the contact with veins which always include a dark-olive, Mg-rich clay mineral. Talc occurs in one of these veins; it can be regarded either as a vein constituent or as a product of augite alteration. Melanite (Ca,Fe,Ti-rich garnet) appears in only one of these three veins, where a Ca-carbonate is associated with a Mg-rich clay mineral. The occurrence of melanite in Hole 504B could be due to the conjunction of particular conditions: (1) basalt with a subophitic texture, (2) presence of hydrothermal fluids carrying Ca, Fe, Si, Ti, Al, Mg, and Na, (3) rather high temperatures. Possibly the melanite and aegirine-augite formed by deuteric alteration.

Mineral and chemical compositions of hydrothermal ores and sediments from the Menez Gwen Hydrothermal Field, Mid-Atlantic Ridge

Mineralogy and geochemistry of sulfide-bearing rocks and ores discovered within the Menez Gwen Hydrothermal Field are studied. Samples were taken during Cruise 49 of R/V Akademik Mstislav Keldysh of the p.p. Shirshov Institute of Oceanology. Mineral composition of rocks and ores were studied by traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by laser ablation inductively coupled plasma - mass spectrometry (LA-ICP-MS). Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in volcanomictic layered gritstones and/or barite slabs. Mineral composition, zonality and association of trace elements in ore are typical of black smokers formed at the basalt base near the Azores Triple Junction in the MAR. Obtained results make it possible to reconstruct formation history of the Menez Gwen Hydrothermal Field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO2 association) stages.

Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.

Geochemistry of sediments from the Tyrrhenian Sea

At Holes 650A and 651 A, set respectively in the Marsili Basin and the Vavilov Basin, Pleistocene sediments (turbiditic inputs interbedded with essentially hemipelagic sediments) may show layers of mudrocks with moderate to strong induration. Except in the two samples from Hole 651 A, it seems that zeolite crystallization does not play a role in the induration phenomenon. This latter appears to result from in situ clay authigenesis. Secondary K-Fe beidellite or Fe-Mg beidellite form diagenetic growths and bridges between sedimented particles. Turbidites are rich in volcaniclastics (glass, pumices and other volcanogenic elements) but the induration phenomenon appears to be associated essentially with the occurrence of basaltic detritus. It is proposed that clay authigenesis results from low temperature alteration of basaltic fragments issued from Vavilov and probably Marsili seamounts in sediments isolated from seawater by overlying deposits.

Chemistry of basalts of ODP Hole 111-504B

The effect of oxygen fugacity (fO2) on the partition relationship of Mg and Fe between Plagioclase and sillicate liquid was investigated at 1 atm for basaltic samples recovered during ODP Leg 111 from Hole 504B. Samples 111-504B-143R-2 (Piece 8) and 111-504B-169R-1 (Piece 1) have Plagioclase as the liquidus phase. The distribution coefficient of Mg between Plagioclase and melt is constant at about 0.04 against the variation of fO2, whereas that of Fe (total Fe) varies from 0.3 at f(O2) = 0.2 atm to 0.03 at f(o2) = 10**-11.5 at 1200°C. The distribution coefficient of Mg is slightly higher than that calculated from the phenocryst and bulk-rock compositions, suggesting a kinetic disequilibrium effect on the distribution of Mg in Plagioclase. Because Mg, Fe, and Fe3+ have similar diffusion coefficients in silicate melt, the disequilibrium effect is greatly reduced for the exchange reaction of Mg and total Fe between Plagioclase and liquid. The exchange partition coefficient is highly dependent on fo2, with log fo2 ranging from -0.7 to - 11.5 at approximately 1200°C. Using this relationship, the f(O2) of crystallization of the magmas is estimated to be near the one defined by the fayalite-quartz-magnetite assemblage.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and Urich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

Geochemistry of selected Ferrar samples from Northern Victoria Land and George V Land during GANOVEX VIII

Newly sampled basaltic andesites and andesites from the tholeiitic Ferrar Supergroup of northern Victoria Land and George V Land, Antarctica, are attributed to the known low-Ti and high-Ti series. Aside from known sparsely distributed high-Ti extrusives, a high-Ti sill was found in the Alamein Range outside the Rennick Graben. Low-Ti lavas, sills and dikes display wide petrographical, mineral and geochemical variations, reflecting extensive in-situ differentiation. High-Ti rocks from Litell Rocks are homogeneous with respect to mineralogy and geochemistry, minor deviations are shown by the sampled sill. Chilled margins of low-Ti sills, dikes and lava flows exhibit nearly constant bulk-rock chemistry (mg# ~60) within the studied area. Compared to chilled margins from Tasmanian sills, the striking uniformity of the pre-emplacement chemistry of Ferrar magmas over large distances supports the magma transport model of Elliot et al. (1999, doi:10.1016/S0012-821X(99)00023-0). In the area investigated, compositional variations within the low-Ti series, caused by in-situ differentiation, increase towards the Wilson-Bowers Terrane boundary, possibly displaying the asymmetrical distribution of outcrops over this area. Absence of Ferrar occurrences east of the Bowers Terrane remains a matter of palaeo-geodynamic discussion. Besides, the secondary mineralogy of extrusives from Litell Rocks and Monument Nunataks exhibits noticeable differences, which indicates an elevated thermal gradient in the vicinity of Litell Rocks compared to Monument Nunataks during the Cretaceous.

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.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Geochemistry of ODP Hole 135-839B lavas

Four petrographic lava types occur, ranging from aphyric to moderately phyric clinopyroxene-olivine tholeiitic basalts (Unit 1); olivine-clinopyroxene picritic basalts, sparsely to strongly olivine-phyric (Unit 3-type); olivine-clinopyroxene basalts (clinopyroxene dominant) (Unit 4); and moderately to strongly phyric two-pyroxene-plagioclase basaltic andesites (Unit 9-type). The olivine phyric lavas contain forsteritic olivines (extending to Fo92), and very magnesian Cr-rich spinels similar to those occurring in boninitic lavas. The basaltic andesites are mineralogically and petrographically indistinguishable from the modern Tofua Arc basaltic andesites, one notable feature being the highly calcic cores in plagioclase phenocrysts (up to An95). The forsteritic olivines, the Cr-spinels, and the calcic plagioclases are unlikely to have been precipitated in the lava compositions in which they occur, and are thought to have been incorporated from highly primitive melts by way of mixing processes (as advocated by Allan, this volume). Notwithstanding the evidence for mixing, the major element chemistries of the Unit 1- and Unit 9-type lavas are shown to be consistent with the derivation of the Unit 9-type basaltic andesites by means of fractional crystallization, through magmas of similar chemistry to Unit 1. Some trace element discrepancies in the modeling, and the relative volcanic stratigraphy of Site 839, however, preclude a direct liquid line of descent between the actual recovered units. Trace element data as well as TiO2 and Na2O data clearly illustrate the arc-like affinities of the magmas, with strong highfield-strength element depletion and large-ion-lithophile element enrichment. The abundance patterns are very close to those of the Tofua and Kermadec arc magmas, and also Valu Fa. Pb-, Sr-, and Nd-isotopic compositions indicate closest affinities with a "Pacific" MORB source, apparently characteristic of the western, older part of the Lau Basin. A subduction-related isotopic contribution is, however, inferred. The sources of the Site 839 magmas are thus inferred to be similar to, but less depleted geochemically, than those of the modern Tofua Arc magmas. The Site 839 sequence is interpreted as an older remnant of a volcanic construct of the "proto-Tofua arc", originally developed adjacent to the Tonga Ridge. Opening of the eastern Lau Basin, because of southward migrating propagators, has split and isolated the sequence, leaving it stranded within the modern Lau Basin.

Jurassic sedimentation history at DSDP Hole 76-534A

Site 534 reflects a complex interplay of global, basinal, and local influences on sedimentation during the Callovian and Late Jurassic. Rifting and rapid subsidence of the continental margins of the North Atlantic-Tethys seaway occurred during the late Early Jurassic (Sinemurian-Pliensbachian), but rapid spreading between the North American margin (Blake Spur Ridge and magnetic lineation) and the northwest African margin did not commence until the Bathonian or earliest Callovian. Site 534, drilled on marine magnetic anomaly "M-28" of Bryan et al. (1980), was initially about 150 km from either continental margin. The ?middle Callovian basal sediments are dusky red silty marl. Callovian transgression led to active carbonate platforms on the margin, recorded at Site 534 as a rise in the CCD (carbonate compensation depth), then arrival of lime-rich turbidites from the Blake Plateau platform across the Blake Spur Ridge. The host pelagic sediment is greenish black, organic-rich, radiolarian-rich, silty claystone. Hydrothermal activity on the nearby spreading ridge enriched this lower unit in metals. In the Oxfordian, the input of terrestrial silt rapidly diminished; radiolarians or other bioclasts were not preserved. The dark variegated claystone has fine-grained marl and reddish claystone turbidite beds. The late Callovian-Oxfordian Western Tethys has radiolarian chert deposition, marine hiatuses, or organic-rich sediments. The Kimmeridgian and Tithonian had a stable or receding sea level. Near the end of the Jurassic many of the carbonate platforms of the margins were buried beneath prograding fan or alluvial deposits. Carbonate deposition shifted to the deep sea. Site 534 records the deepening of the CCD and ACD (aragonite compensation depth) during the Kimmeridgian and early Tithonian, then a rise of the ACD in the middle Tithonian. Similar trends occurred throughout the Western Tethys-Atlantic. High nannofossil productivity of the seaway led to deposition of very widespread white micritic limestone in the late Tithonian-Berriasian. The underlying sediment had a slower deposition rate of carbonate, therefore its higher clay and associated Fe content produced a red marl. A short sea-level incursion occurred on the Atlantic margins during the Kimmeridgian and is reflected in the Site 534 greenish gray marl unit by numerous turbidite beds of shallow-water carbonates.

Paleoceanography of sediment cores SO202-27-6 and MD01-2416

The glacial-to-Holocene evolution of subarctic Pacific surface water stratification and silicic acid (Si) dynamics is investigated based on new combined diatom oxygen (d18Odiat) and silicon (d30Sidiat) isotope records, along with new biogenic opal, subsurface foraminiferal d18O, alkenone-based sea surface temperature, sea ice, diatom, and core logging data from the NE Pacific. Our results suggest that d18Odiat values are primarily influenced by changes in freshwater discharge from the Cordilleran Ice Sheet (CIS), while corresponding d30Sidiat are primarily influenced by changes in Si supply to surface waters. Our data indicate enhanced glacial to mid Heinrich Stadial 1 (HS1) NE Pacific surface water stratification, generally limiting the Si supply to surface waters. However, we suggest that an increase in Si supply during early HS1, when surface waters were still stratified, is linked to increased North Pacific Intermediate Water formation. The coincidence between fresh surface waters during HS1 and enhanced ice-rafted debris sedimentation in the North Atlantic indicates a close link between CIS and Laurentide Ice Sheet dynamics and a dominant atmospheric control on CIS deglaciation. The Bølling/Allerød (B/A) is characterized by destratification in the subarctic Pacific and an increased supply of saline, Si-rich waters to surface waters. This change toward increased convection occurred prior to the Bølling warming and is likely triggered by a switch to sea ice-free conditions during late HS1. Our results furthermore indicate a decreased efficiency of the biological pump during late HS1 and the B/A (possibly also the Younger Dryas), suggesting that the subarctic Pacific has then been a source region of atmospheric CO2.