Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

H, O, Sr, and Nd isotope ratios and water, Rb, Sr, Sm, and Nd content of ODP Hole 116-717C and 116-718C samples (Table 2)

Mineralogical and H, O, Sr, and Nd isotope compositions have been analyzed on a set of representative samples from the 17-m.y. section in ODP Leg 116 Holes 717C and 718C. Based on the mineralogical composition of the fraction <2 µm together with the lithogenic-biogenic composition of the fraction >63 µm, the whole section can be subdivided into three major periods of sedimentation. Between 17.1 and 6 m.y., and between 0.8 m.y. to present, the sediments are characterized by sandy and silty turbiditic inputs with a high proportion of minerals derived from a gneissic source without alteration. In the fraction <2 µm, illite and chlorite are dominant over smectite and kaolinite. The granulometric fraction >63 µm contains quartz, muscovite, biotite, chlorite, and feldspars. The 6-to 0.8-m.y. period is represented by an alternation of sandy/silty horizons, muds, and calcareous muds rich in smectite, and kaolinite (50% to 85% of the fraction <2 µm) and bioclastic material. The presence of smectite and kaolinite, as well as the 18O/16O and the 87Sr/86Sr ratios of the fraction <2 µm, imply an evolution in a soil environment and exchanges with meteoric ground water. The ranges of isotopic compositions are limited throughout the section: d18O quartz = 11.7 to 13.3 per mil, 87Sr/86Sr = 0.733 to 0.760 and epsilon-Nd (0) = -17.4 to -13.8. These values are within those of the High Himalaya Crystalline series, and they are considered to reflect this source region. The data imply that, since 17 Ma, this formation has supplied the major part of the eroded material.

(Table 1) Elemental abundances in DSDP Core 86-577B-1

An Ir anomaly of 61 ng/cm**2 was found in Deep Sea Drilling Project Hole 577B at the same stratigraphic level as the Cretaceous/Tertiary boundary defined by nannoplankton. This close correspondence supports the asteroid-impact theory for the Cretaceous/Tertiary boundary extinctions.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Element analyses and isotope composition of basalts from the West Valley segment, Juan de Fuca Ridge, northeast Pacific

The 50 km-long West Valley segment of the northern Juan de Fuca Ridge is a young, extension-dominated spreading centre, with volcanic activity concentrated in its southern half. A suite of basalts dredged from the West Valley floor, the adjacent Heck Seamount chain, and a small near-axis cone here named Southwest Seamount, includes a spectrum of geochemical compositions ranging from highly depleted normal (N-) MORB to enriched (E-) MORB. Heck Seamount lavas have chondrite-normalized La/Sm en -0.3, 87Sr/86Sr = 0.70235 - 0.70242, and 206Pb/204Pb = 18.22 - 18.44, requiring a source which is highly depleted in trace elements both at the time of melt generation and over geologic time. The E-MORB from Southwest Seamount have La/Sm en -1.8, 87Sr/86Sr = 0.70245 - 0.70260, and 206Pb/204Pb = 18.73 - 19.15, indicating a more enriched source. Basalts from the West Valley floor have chemical compositions intermediate between these two end-members. As a group, West Valley basalts from a two-component mixing array in element-element and element-isotope plots which is best explained by magma mixing. Evidence for crustal-level magma mixing in some basalts includes mineral-melt chemical and isotopic disequilibrium, but mixing of melts at depth (within the mantle) may also occur. The mantle beneath the northern Juan de Fuca Ridge is modelled as a plum-pudding, with "plums" of enriched, amphibole-bearing peridotite floating in a depleted matrix (DM). Low degrees of melting preferentially melt the "plums", initially removing only the amphibole component and producing alkaline to transitional E-MORB. Higher degrees of melting tap both the "plums" and the depleted matrix to yield N-MORB. The subtly different isotopic compositions of the E-MORBs compared to the N-MORBs require that any enriched component in the upper mantle was derived from a depleted source. If the enriched component crystallized from fluids with a DM source, the "plums" could evolve to their more evolved isotopic composition after a period of 1.5-2.0 Ga. Alternatively, the enriched component could have formed recently from fluids with a lessdepleted source than DM, such as subducted oceanic crust. A third possibility is that enriched material might be dispersed as "plums" throughout the upper mantle, transported from depth by mantle plumes.

Natural oxides, elements and remanent magnetization intensities and directions at DSDP Hole 93-603B

Dark green spherules occur in the lower part of a turbidite in Section 603B-22-3, at the 70 cm level. In all probability these spherules originally consisted of massive glass, but now appear to have become completely altered into smectite. The presence of numerous microscopic fissures in the spherules probably mediated in the alteration process. Judging by the presence of similar spherules at the Cretaceous/Tertiary (K/T) boundary in DSDP Hole 390B, the green spherules are thought to represent diagenetically altered impact ejecta from one large or several smaller extraterrestrial objects at the end of the Cretaceous. The presence of anomalously high concentrations of Ni, Co, and As higher up in the turbidite are in agreement with an expected enrichment of these elements in the K/T boundary clay. However, precise Ir analyses are necessary in order to confirm this.

Geochemistry of ODP Leg 125 peridotites

Ocean Drilling Program Leg 125 recovered serpentined harzburgites and dunites from a total of jive sites on the crests and flanks of two serpen finite seamounts, Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc. These are some of the first extant forearc peridotites reported in the literature and they provide a window into oceanic, supra-subduction zone (SSZ) mantle processes. Harzbutrgites from both seamounts are very refractory with low modal clinopyroxene (<4%), chrome-rich spinels (cx-number = 0.40-0.80), very low incompatible element contents, and (with the exception of amphibole-bearing samples) U-shaped rare earth element (REE) profiles with positive Eu anomalies. Both sets of peridotites have olivine-spinel equilibration temperatures that are low compared with abyssal peridotites, possibly because of water-assisted diffusional equilibration in the SSZ environment However, other features indicate that the harzburgites from the two seamounts have very different origins. Harzburgites from Conical Seamount are characterized by calculated oxygen fugacities between FMQ (fayalite- magnetite- quartz) - 1.1 (log units) and FMQ + 0.4 which overlap those of mid-ocean ridge basalt (MORB) peridotites. Dunites from Conical Seamotmt contain small amounts of clinopyroxene, orthopyroxene and amphibole and are light REE (LREE) enriched. Moreover; they are considerably more oxidized than the harzburgites to which they are spatially related, with calculated oxygen fugacities of FMQ -0.2 toFMQ + 1.2. Using textural and geochemical evidence, we interpret these harzburgites as residual MORB mantle (from 15 to 20 % fractional melting) which has subsequently been modified by interaction with boninitic melt ivithin the mantle wedge, and these dunites as zones of focusing of this melt in which pyroxene has preferentially been dissolved from the harzbutgite protolith. In contrast, harzburgites from Torishima Forearc Seamount give calculated oxygen fugacities between FMQ + 0.8 and FMQ + l.6, similar to those calculated for other subduction-zone related peridotites and similar to those calculated for the dunites (FMQ + 1.2 to FMQ + 1.8) from the same seamount. In this case, we interpret both the harzburgites and dunites as linked to mantle melting (20-25 % fractional melting) in a supra-subduction zone environment The results thus indicate that the forearc is underlain by at least two types of mantle lithosphere, one being trapped or accreted oceanic lithosphere, the other being lithosphere formed by subduction-related melting. They also demonstrate that both types of mantle lithosphere may have undergone extensive interaction with subduction-derived magmas.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.