Geochemistry and petrology of ODP Leg 121 basalts

Basement lavas from Sites 756, 757, and 758 on Ninetyeast Ridge are tholeiitic basalts. Lavas from Sites 756 and 757 appear to be subaerial eruptives, but the lowermost flows from Hole 758A are pillow lavas. In contrast to the compositional variation during the waning stages of Hawaiian volcanism, no alkalic lavas have been recovered from Ninetyeast Ridge and highly evolved lavas were recovered from only one of seven drill sites (DSDP Site 214). All lavas from Site 758 have relatively high MgO contents (8-10 wt%), and they are less evolved than lavas from Sites 756 and 757. Although abundances of alkali metals in these Ninetyeast Ridge basalts were significantly modified by postmagmatic alteration, abundances of other elements reflect magmatic processes. At Site 757 most of the lavas are Plagioclase cumulates, but lava compositions require two compositionally distinct, AhCb-rich parental magmas, perhaps segregated at relatively low mantle pressures. In addition, at both Sites 756 and 758 more than one compositionally distinct parental magma is required. The compositions of these Ninetyeast Ridge lavas, especially those from Site 758, require a source component with a depleted composition; specifically, the abundance ratios Th/Ta, Th/La, Ba/Nb, Ba/La, and La/Ce in these lavas are generally less than the ratios inferred for primitive mantle. Lavas from Ninetyeast Ridge and the Kerguelen Archipelago have very different chondrite-normalized REE patterns, with lower light REE/heavy REE (LREE/HREE) ratios in lavas from Ninetyeast Ridge. However, lavas from Sites 757 and 758 have Pb isotope ratios that overlap with the field defined by lavas from the Kerguelen Archipelago (Weis and Frey, this volume). Therefore, these Ninetyeast Ridge lavas contain more of a component that is relatively depleted in LREE and other highly incompatible elements, but have similar amounts of the component that controls radiogenic Pb isotopes. A model involving mixing between components related to a depleted source and an enriched plume source has been proposed for the oldest Kerguelen Archipelago basalts and Ninetyeast Ridge lavas. Although the incompatible element characteristics of the Ninetyeast Ridge lavas are intermediate between depleted MORB and Kerguelen Archipelago basalts, these data are not consistent with a simple two-component mixing process. A more complex model is required.

Geochemistry of minerals from lavas of ODP Leg 135 holes

We use Nomarski differential interference contrast imaging to reveal the wealth of complex detail in plagioclase zoning for selected samples from Sites 834, 839, and 841. All sites contain some plagioclase with the very complex internal core zoning, convolute zoning, or very fine-scale euhedral oscillatory zoning of the sort generally considered typical of island-arc volcanic rocks. Plagioclase with contrasted zoning styles may coexist within a single lithologic unit or even within a single thin section. Especially notable is the presence of scattered plagioclase phenocrysts with complex zoning throughout Unit 7 in Hole 834B, which in other respects is relatively uniform in composition and appears to have had little or no differential sorting of crystals and liquid. Although our study is by no means comprehensive, it is sufficient to indicate that magmatic conditions have been variable during crystallization of these rocks, and mixing or at least minor contamination may be required to explain some of the relations observed. By analogy with experimental studies, it is possible that variations in water content, either over time or within different parts of a chamber or conduit system, have contributed to the observed contrasts in zoning.

Geochemistry of Fe-Mn crusts in sediments of the Central Indian Ridge

Layered Fe-Mn crusts from the off-axis region of the first segment of the Central Indian Ridge north of the Rodrigues Triple Junction were studied geochemically and mineralogically. Vernadite (delta-MnO2) is the main mineral oxide phase. 230Thxs and Co concentrations suggest high growth rates of up to 29 mm/Myr and a maximum age of the basal crust layer of 1 Ma. Whereas most of the major and minor elements show concentrations which are typical of hydrogenetic formation, Co, Pb, Ni and Ti concentrations are strikingly lower. Concentrations and distribution of the strictly trivalent rare-earths and yttrium (REY) are typical of hydrogenetic ferromanganese oxide precipitates, but in marked contrast, the crusts are characterized by negative CeSN (shale normalized) anomalies and (Ce/Pr)SN ratios less than unity. Profiles through the crusts reveal only minor variations of the REY distribution and (Ce/Pr)SN ratios range from 0.45 to 0.68 (compared to ratios of up to 2 for typical hydrogenetic crusts from the Central Indian Basin). The apparent bulk partition coefficients between the crusts and seawater suggest that for the strictly trivalent REY the adsorption-desorption equilibrium has been reached. Positive Ce anomalies in the partition coefficient patterns reveal preferential uptake of Ce, but to a lesser extent than in normal hydrogenetic crusts. A new parameter (excess Ce, Cexs) to quantify the degree of decoupling of Ce from REY(III) is established on the basis of partition coefficients. Cexs/Cebulk ratios suggest that the CIR crusts formed by precipitation of Fe-Mn oxides from a hydrothermal plume and that in hydrothermal plumes and normal seawater the enrichment of Ce results from the same oxidative sorption process. The growth rates, calculated with 230Thxs data as well as with the Co formula, are inversely related to Cexs.

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Geochemistry at DSDP Leg 82 Holes

DSDP Leg 82 drilled nine sites to the southwest of the Azores Islands on the west flank of the Mid-Atlantic Ridge (MAR) in an attempt to determine the temporal and spatial evolution of the Azores "hot-spot" activity. The chemistry of the basalts recovered during Leg 82 is extremely varied: in Holes 558 and 561, both enriched (E-type: CeN/YbN = 1.5 to 2.7; Zr/Nb = 4.5 to 9.6) and depleted (or normal-N-type: CeN/YbN = 0.6 to 0.8; Zr/Nb > 20) mid-ocean ridge basalts (MORB) occur as intercalated lava flows. To the north of the Hayes Fracture Zone, there is little apparent systematic relationship between basalt chemistry and geographic position. However, to the south of the Hayes Fracture Zone, the chemical character of the basalts (N-type MORB) is more uniform. The coexistence of both E-type and N-type MORB in one hole may be explicable in terms of either complex melting/ fractionation processes during basalt genesis or chemically heterogeneous mantle sources. Significant variation in the ratios of strongly incompatible trace elements (e.g., La/Ta; Th/Ta) in the basalts of Holes 558 and 561 are not easily explicable by processes such as dynamic partial melting or open system crystal fractionation. Rather, the trace element data require that the basalts are ultimately derived from at least two chemically distinct mantle sources. The results from Leg 82 are equivocal in terms of the evolution of the Azores "hot spot," but would appear not to be compatible with a simple model of E-type MORB magmatism associated with upwelling mantle "blobs." Models that invoke a locally chemically heterogeneous mantle are best able to account for the small-scale variation in basalt chemistry.

Geochemistry of oceanic crust of the Cocos Plate

New geochemical data from the Cocos Plate constrain the composition of the input into the Central American subduction zone and demonstrate the extent of influence of the Galápagos Hotspot on the Cocos Plate. Samples include sediments and basalts from Ocean Drilling Program (ODP) Site 1256 outboard of Nicaragua, gabbroic sills from ODP Sites 1039 and 1040, tholeiitic glasses from the Fisher Ridge off northwest Costa Rica, and basalts from the Galápagos Hotspot Track outboard of Central Costa Rica. Site 1256 basalts range from normal to enriched MORB in incompatible elements and have Pb and Nd isotopic compositions within the East Pacific Rise MORB field. The sediments have similar 206Pb/204Pb and only slightly more radiogenic 207Pb/204Pb and 208Pb/204Pb isotope ratios than the basalts. Altered samples from the subducting Galápagos Hotspot Track have similar Nd and Pb isotopic compositions to fresh Galápagos samples but have significantly higher Sr isotopic composition, indicating that the subduction input will have a distinct geochemical signature from Galápagos-type mantle material that may be present in the wedge beneath Costa Rica. Gabbroic sills from Sites 1039 and 1040 in East Pacific Rise (EPR) crust show evidence for influence of the Galápagos Hotspot ?100 km beyond the morphological hotspot track.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

Physico-chemical parameters of sediment core PG1972-1 (09-Tik-03) from a Tundra Lake, Northeastern Siberia

Thermokarst lakes in the Siberian Arctic contain sediment archives that can be used for paleoenvironmental inference. Until now, however, there has been no study from the inner Lena River Delta with a focus on diatoms. The objective of this study was to investigate how the diatom community in a thermokarst lake responded to past limnogeological changes and what specific factors drove variations in the diatom assemblage. We analysed fossil diatom species, organic content, grain-size distribution and elemental composition in a sediment core retrieved in 2009 from a shallow thermokarst lake in the Arga Complex, western Lena River Delta. The core contains a 3,000-year record of sediment accumulation. Shifts in the predominantly benthic and epiphytic diatom species composition parallel changes in sediment characteristics. Paleoenvironmental and limnogeological development, inferred from multiple biological and sedimentological variables, are discussed in the context of four diatom zones, and indicate a strong relation between changes in the diatom assemblage and thermokarst processes. We conclude that limnogeological and thermokarst processes such as lake drainage, rather than direct climate forcing, were the main factors that altered the aquatic ecosystem by influencing, for example, habitat availability, hydrochemistry, and water level.

Dissolved iron and Fe(II) in an iron induced Southern Ocean phytoplankton bloom measured during TANGAROA cruise SOIREE

During the 13 day Southern Ocean Iron RE-lease Experiment (SOIREE), dissolved iron concentrations decreased rapidly following each of three iron-enrichments, but remained high (>1 nM, up to 80% as FeII) after the fourth and final enrichment on day 8. The former trend was mainly due to dilution (spreading of iron-fertilized waters) and particle scavenging. The latter may only be explained by a joint production-maintenance mechanism; photoreduction is the only candidate process able to produce sufficiently high FeII, but as such levels persisted overnight (8 hr dark period) -ten times the half-life for this species- a maintenance mechanism (complexation of FeII) is required, and is supported by evidence of increased ligand concentrations on day 12. The source of these ligands and their affinity for FeII is not known. This retention of iron probably permitted the longevity of this bloom raising fundamental questions about iron cycling in HNLC (High Nitrate Low Chlorophyll) Polar waters.

Geochemistry and trace elements at DSDP Hole 78-543A

The upper part of the basaltic substratum of the Atlantic abyssal plain, approaching subduction beneath the Barbados Ridge and thus presumably beneath the Lesser Antilles island arc, is made of typical LREE-depleted oceanic tholeiites. Mineralogical (microprobe) and geochemical (X-ray fluorescence, neutron activation analyses) data are given for 12 samples from the bottom of Hole 543A, which is 3.5 km seaward of the deformation front of the Barbados Ridge complex. These basalts are overlain by a Quaternary to Maestrichtian-Campanian sedimentary sequence. Most of the basalts are relatively fresh (in spite of the alteration of olivine and development of some celadonite, clays, and chlorite in their groundmass), and their mineralogical and geochemical compositions are similar to those of LREE-depleted recent basalts from the Mid-Atlantic Ridge. The most altered samples occur at the top of the basaltic sequence, and show trends of enrichment in alkali metals typical of altered oceanic tholeiites.

Geochemistry of basalts from ODP Hole 113-690C

Basalts from Maud Rise, Weddell Sea, are vesicular and olivine-phyric. Major, trace, and rare earth element concentrations are similar to those of alkali basalts from ocean islands and seamounts. The rocks are low in MgO, Cr, Ni, and Sc, and high in TiO2, K2O, P2O5, Zr, and LREE contents. The abundance of "primary" biotite and apatite in the matrix indicates the melting of a hydrous mantle. Prevalence of olivine and absence of plagioclase in the rocks suggests that the volatile in the melt was an H2O-CO2 mixture, where H2O was <0.5. Mantle derived xenocrysts in the basalt include corroded orthopyroxene, chromite, apatite, and olivine. Olivine (Fo90) is too magnesian to be in equilibrium with the basalts, as they contain only 5-6 wt% MgO. Based on the presence of mantle xenocrysts, the high concentration of incompatible elements, the spatial and chemical affinity with other ocean island basalts from the area, and the relative age of the basalt (overlain by late Campanian sediments), it is suggested that Maud Rise was probably generated by hot-spot activity, possible during a ridge crest jump prior to 84 Ma (anomaly 34 time). Iddingsite, a complex intergrowth of montmorillonite and goethite, is the major alteration product of second generation olivine. It is suggested that iddingsite crystallized at low temperatures (<200°C) from an oxidized fluid during deuteric alteration. Vesicles are commonly filled by zeolites which have been replaced by K-feldspars.