Petrology and geochemistry of basalts from the Vavilov Basin

During ODP Leg 107, two holes were drilled in the basement of Vavilov Basin, a central oceanic area of the Tyrrhenian sea. Hole 655B is located near the Gortani ridge in off-axis position at the western rim of the basin; Hole 651A is located on a basement swell at the axis of the basin. This paper deals with mineral chemistry, major and trace element geochemistry, and petrogenesis of the basalts recovered in the two holes. The mineralogy of the basalts is broadly homogeneous, but all of them have suffered important seawater alteration. Their major-element compositions are similar to both normal-mid-ocean-ridge-basalts (N-MORB) and back-arc-basalts (BAB) except for Na2O contents (BAB-like), and K2O which is somewhat enriched in upper unit of Hole 651 A. Their affinity with N-MORB and BAB is confirmed by using immobile trace elements such as Zr, Y, and Nb. However, basalts from the two sites present contrasting geochemical characteristics on spidergrams using incompatible elements. Hole 655B basalts are homogeneous enriched tholeiites, similar to those from DSDP Hole 373 (located on the opposite side of the basin near the eastern rim), and show affinities with enriched MORB (E-MORB). At Hole 651 A, the two basalt units are chemically distinct. One sample recovered in lower unit is rather similar to those from Hole 655B, but basalts from upper unit display calc-alkaline characteristic evidenced by the increase of light-ion-lithophile-element (LILE)/high-field-strength-element (HFSE) ratio, and appearance of a negative Nb-anomaly, making them comparable with orogenic lavas from the adjacent Eolian arc. The observed chemical compositions of the basalts are consistent with a derivation of the magmas from a N-MORB type source progressively contaminated by LILE-enriched fluids released from dehydration of the bordering subducted plate. Implications for evolution of the Tyrrhenian basin are tentatively proposed taking into consideration geochemical and chronological relationships between basalts from Leg 107 Holes 655B and 651 A, together with data from Leg 42 Site 373 and Vavilov Seamount. These data illustrate back-arc spreading in ensialic basin closely associated with the maturation of the adjacent subduction, followed by the growth of late off-axis central volcano, whereas the active subduction retreats southeastward.

Geochemistry and Nd-Pb isotope ratios of sediments from the Lesser Antilles arc

The Lesser Antilles arc is a particularly interesting island arc because it is presently very active, it is located perpendicular to the South American continent and its chemical and isotopic compositions display a strong north-south gradient. While the presence in the south of a thick pile of sedimentary material coming from the old South American continent has long been suspected to explain the geochemical gradient, previous studies failed to demonstrate unambiguously a direct link between the arc lava compositions and the subducted sediment compositions. Here, we present new Nd, Sm, Th, U and Pb concentrations and Nd-Pb isotopic data for over 60 sediments from three sites located in the fore arc region of the Lesser Antilles arc. New data for DSDP Site 543 drill core located east of Dominica Island complement the data published by White et al. (1985, doi:10.1016/0016-7037(85)90082-1) and confirm their relatively uniform isotopic compositions (i.e., 206Pb/204Pb between 19.13 and 19.53). In contrast, data obtained on DSDP Site 144 located further south, on the edge of the South American Rise and on sediments from Barbados Island are much more variable (206Pb/204Pb ranges from 18.81 to 27.69). The very radiogenic Pb isotopic compositions are found in a 60 m thick black shale unit, which has no age equivalent in the Site 543 drill core. We interpret the peculiar composition of the southern sediments as being due to two factors, (a) the proximity of the South American craton, which contributes coarse grain old detrital material that does not travel far from the continental shelf, and (b) the presence of older sediments including the thick black shale unit formed during Oceanic Anoxic events 2 and 3. The north-south isotopic change known along the Lesser Antilles arc can be explained by the observed geographical changes in the composition of the subducted sediments. About 1% contamination of the mantle wedge by Site 543 sediments explains the composition of the northern islands while up to 10% sediments like those of Site 144 is required in the source of the southern island lavas. The presence of black shales in the subducted pile provides a satisfactory explanation for the very low Delta8/4 values that characterize the Lesser Antilles arc.

Barium in seawater and sediments from the Artic Ocean

As part of ongoing circulation studies in the Arctic, seawater samples for dissolved Ba concentrations were obtained during Sep.-Oct., 1992 at several locations in the Bering Strait, Eastern Chukchi and Southern Beaufort Seas. The results reveal a dynamic rang (10 to 150 nmol/kg) for this element in the Arctic equal to or greater than that in combined Atlantic, Indian and Pacific oceans. Lowest levels are observed in surface waters, with values tending to decrease northwards in the direction of currents generally flowing frorn the Bering Strait along the Alaskan coast. Low surfacc concentrations tend to be accompanied by relatively enriched near bottom levels. On the basis of these spatial distributions, hydrographic observations and a knowledge of its behavior in other marine settings, it appears that Ba can be significantly depleted from surface waters as a result of the highly seasonal biological aclivities over Arctic marginal shelves. Removal at the surface is counteracted to some extent by regeneration at depth or in the sediments and by riverine inputs. The biologically related drawdown is likely to enhance the contrast between 'background' surface Ba levels in the Arctic and waters imprinted by regeneration and/or rivers, These preliminary findings suggest that Ba holds particular promise for tracing river waters and the ventilation of halodine waters hy laterally sinking brines produced during ice formation over the shelves.

Chemical composition of ferromanganese manifestations from the Sea of Okhotsk

New data on microstructures and mineral and chemical compositions of ferromanganese crusts sampled from the western slope of the Kuril Island Arc in the Sea of Okhotsk during cruises of R/V Vulkanolog are discussed. The study of the crusts using analytical electron microscopy methods revealed that their manganese phase is represented by vernadite, Fe-vernadite, todorokite, asbolane, and asbolane-buserite, while iron phase consists of hematite, hydrohematite, ferroxyhite, and magnetite. Lithic mineral assemblage includes apatite, quartz, epidote, and montmorillonite. According to chemical analysis most of the crusts contain significant part of volcanogenic and hydrothermal material. It is evident from elevated values of Mn/Fe and (Mn+Fe)/Ti ratios, low concentrations of some trace elements, and positive Eu anomaly.

U and Th concentrations and isotope ratios of samples from ODP Leg 166

Constraining the history of seawater (234U/238U) is important because this ratio is used to assess the validity of U/Th ages, and because it provides information about the past rate of physical weathering on the continents. This study makes use of U-rich slope sediments from the Bahamas in an attempt to reconstruct seawater (234U/238U) for the last 800 kyr. For the last 360 kyr, U/Th dating of these sediments provides ages and initial (234U/238U) values. Sixty-seven samples, largely from marine highstands, have initial (234U/238U) which scatter somewhat about the modern seawater value (~1.145) but neither this scatter nor the average value increases with age of sample. These data contrast with published coral data and suggest that seawater (234U/238U) has remained within 15? of the modern value for the last 360 kyr. This confirms the rejection of coral U/Th ages where the initial (234U/238U) is significantly different from modern seawater. Data from older highstands, dated with delta18O stratigraphy or by the presence of the Brunhes/Matuyama (B/M) reversal at 780 kyr, allow seawater (234U/238U) to be assessed prior to the range of the 230Th chronometer. Unfortunately, diagenetic scatter in the data between the B/M reversal and 360 kyr is rather large, probably relating to low U concentrations for these samples. But there is no indication of a trend in seawater (234U/238U) with age. High U samples from close to the B/M reversal show less diagenetic scatter and an initial (234U/238U) that averages 1.102. This lower value can be explained by lower seawater (234U/238U) at the time of the B/M reversal, or by progressive loss of 234U from the sediment by alpha-recoil. A simple box model is presented to illustrate the response of seawater (234U/238U) to variations in riverine input, such as might be caused by changes in continental weathering. Comparison of the Bahamas (234U/238U) data with model results indicates that riverine (234U/238U) has not varied by more than 65? for any 100 kyr period during the last 360 kyr. It also indicates that the ratio of physical to chemical weathering on the continents has not been higher than at present for any extended period during the last 800 kyr.

Geochemistry and isotopic ratios of basalts obtained during R/V Akademik Nikolaj Strakhov cruise ANS25

Based on the investigation of samples recovered during Cruise 25 of the R/V ''Akademik Nikolai Strakhov'', the character of magmatism was determined in the flank parts of the rift zone at the 74°05'N and 73°50'N region, where the direction of the rift valley changes from the north-northwest in the Knipovich Ridge to the northeast-trending structures of the Mohns Ridge. It was shown that the tholeiitic magmas of this region shows all the geochemical characteristics of TOR-2, which is typical of the Mohns Ridge and most oceanic rift zones worldwide, and differ from the basalts of the Knipovich Ridge, which are assigned to a shallower type of tholeiitic magmatism (Na-TOR). The persistent depletion of the magmas in terms of lithophile element contents and radiogenic isotope ratios of Sr, Nd, and Pb reflects the conditions of their formation during the ascent of the depleted oceanic mantle, which has occurred without significant complications since the early stages of the formation of the Mohns Ridge.

Geochemistry of sediments from the mid-oceanic Kolbeinsey Ridge

In order to assess recent submarine volcanic contributions to the sediments from the active Kolbeinsey Ridge, surface samples were analyzed chemically. The contribution of major and trace elements studied differ within the study area. A statistical analysis of the geochemical variables using factor analysis and cluster method allows to distinguish possible sample groups. Cluster method identifies three distinct sediment groups located in different areas of sedimentation. Group 1 is characterized by highest contents of Fe2O3, V, Co, Ni, Cu and Zn demonstrating the input of volcaniclastic material. Group 2 comprises high values of CaCO3, CaO and Sr representing biogenic carbonate. Group 3 is characterized by the elements K, Rb, Cs, La and Pb indicating the terrigenous component. The absolute percentage of the volcanic, biogenic and terrigenous components in the bulk sediments was calculated by using a normative sediment method. The highest volcanic component (> 60% on a carbonate free basis) is found on the ridge crest. The biogenic component is highest (10-30%) in the eastern part of the Spar Fracture Zone influenced by the East Iceland Current. Samples from the western and southeastern region of the study area contain more than 90% of terrigenous component which appears to be mainly controlled by input of ice-rafted debris.

Marine osmium isotope record across the Cretaceous-Tertiary boundary

A composite late Maastrichtian (65.5 to 68.5 Ma) marine osmium (Os) isotope record, based on samples from the Southern Ocean (ODP Site 690), the Tropical Pacific Ocean (DSDP Site 577), the South Atlantic (DSDP Site 525) and the paleo-Tethys Ocean demonstrates that subaerially exposed pelagic carbonates can record seawater Os isotope variations with a fidelity comparable to sediments recovered from the seafloor. New results provide robust evidence of a 20% decline in seawater 187Os/188Os over a period of about 200 kyr early in magnetochron C29r well below the Cretaceous-Paleogene Boundary (KPB), confirming previously reported low-resolution data from the South Atlantic Ocean. New results also confirm a second more rapid decline in 187Os/188Os associated with the KPB that is accompanied by a significant increase in Os concentrations. Complementary platinum (Pt) and iridium (Ir) concentration data indicate that the length scale of diagenetic remobilization of platinum group elements from the KPB is less than 1 m and does not obscure the pre-KPB decline in 187Os/188Os. Increases in bulk sediment Ir concentrations and decreases in bulk carbonate content that coincide with the Os isotope shift suggest that carbonate burial flux may have been lower during the initial decline in 187Os/188Os. We speculate that diminished carbonate burial rate may have been the result of ocean acidification caused by Deccan volcanism.

Chemical composition of Ninetyeast Ridge basalts

On Leg 121 of the Ocean Drilling Program, we recovered basaltic rocks from a total of three basement sites in the southern, central, and northern regions of Ninetyeast Ridge. These new sites complement the previous four basement holes drilled during Legs 22 and 26 of the Deep Sea Drilling Project, and confirm the predominantly tholeiitic, light rare earth element-enriched character of the basalts that cap the ridge. The basalts show marked iron enrichment; ferrobasalts occur at Sites 214 and 216 and oceanic andesites at Site 253. All of the basalts recovered during Leg 121 are altered, and range from aphyric olivine tholeiites (Site 756), to strongly plagioclase-phyric basalts (Site 757). Basalts from Site 758, which were clearly erupted in a submarine environment (pillow basalts are present in the section), are sparsely to strongly plagioclase-phyric. The basalts recovered at any one hole are isotopically homogeneous (except for the basalts from Site 758, which show a range of Pb isotopes), and it is possible to relate the magmas at any one site by high-level fractionation processes. However, there are significant variations in isotope ratios and highly incompatible element ratios between sites, which suggest that the mantle source for the ridge basalts was compositionally variable. Such variation, in view of the large volume of magmatic products that form the ridge system, is not surprising. There is not, however, a systematic variation in basalt composition along the ridge. We agree with previous models that relate Ninetyeast Ridge to a mantle plume in the southern Indian Ocean. The tholeiitic, iron-enriched, and voluminous character of the ridge basalts is typical of oceanic islands associated with plumes on or near a mid-ocean ridge (e.g., Iceland, Galapagos Islands, and St. Paul/Amsterdam islands). The absence of recovered alkalic suites is inconsistent with an intraplate setting, such as the Hawaiian Islands or Kerguelen Island. Thus, the major element data, like the gravity data, strongly suggest that the ridge was erupted on or very close to an active spreading center. Isotopically, the most likely plume that created the excess magmatism on the Ridge is the Kerguelen-Heard plume system, but the Ninetyeast Ridge basalts do not represent a simple mixing of the Kerguelen plume and mid-ocean Ninetyeast Ridge basalt mantle.

Geochemistry and mineralogy of interstitial waters and clays in sediments of ODP Leg 180 sites

Oxygen and strontium isotopes and Rb and Ba were determined in interstitial water (IW) collected from Sites 1109, 1115, and 1118 drilled on the Woodlark Rise during Ocean Drilling Program Leg 180. The trace element and mineralogical composition of the clay fraction of sediments isolated from the squeeze cakes corresponding to IW samples from Site 1109 was also determined.

Geochemistry of volcanivlastic sediments of ODP Sites 134-832 and 134-833

Volcaniclastic sediments of North Aoba Basin (Vanuatu) recovered during Ocean Drilling Program (ODP) Leg 134 show a mineralogical and chemical overprint of low grade hydrothermal alteration superimposed on the primary magmatic source compositions. The purpose of this study was to identify authigenic mineral phases incorporated in the volcaniclastic sediments, to distinguish authigenic chemical and mineralogical signals from the original volcaniclastic mineralogical and chemical compositions, and to determine the mechanism of authigenic minerals formation. Mineralogical, micro-chemical and bulk chemical analyses were utilized to identify and characterize authigenic phases and determine the original unaltered ash compositions. 117 volcaniclastic sediment samples from North Aoba Basin Sites 832 and 833 were analyzed. Primary volcaniclastic materials accumulated in North Aoba Basin can be divided into three types. The older basin-filling sequences show three different magmatic trends: high K, calc-alkaline, and low K series. The most recent accumulations are rhyodacitic composition and can be attributed to Santa Maria or Aoba volcanic emissions. Original depositional porosity of volcaniclastic sediments is an important factor in influencing distribution of authigenic phases. Finer-grained units are less altered and retain a bulk mineralogical and chemical composition close to the original pyroclastic rock composition. Coarser grained units (microbreccia and sandstones) are the major hosts of authigenic minerals. At both sites, authigenic minerals (including zeolites, clay minerals, Mg-carbonates, and quartz) exhibit complex zonation with depth that crosses original ash depositional boundaries and stratigraphic limits. The zeolite minerals phillipsite and analcime are ubiquitous throughout the altered intervals. At Site 832, the first zeolite minerals (phillipsite) occur in Pleistocene deposits as shallow as 146 meters below seafloor (mbsf). At Site 833 the first zeolite minerals (analcime) occur in Pleistocene deposits as shallow as 224 mbsf. The assemblage phillipsite + analcime + chabazite appears at 635 mbsf (Site 832) and at 376 mbsf (Site 833). Phillipsite + analcime + chabazite + thomsonite + heulandite are observed between 443 and 732 mbsf at Site 833. Thomsonite is no longer observed below 732 mbsf at Site 833. Heulandite is present to the base of the sections cored. The zeolite assemblages are associated with authigenic clay minerals (nontronite and saponite), calcite, and quartz. Chlorite is noticeable at Site 832 as deep as 851 mbsf. Zeolite zones are present but are less well defined at Site 832. Dolomite and rare magnesite are present below 940 m at Site 832. The coarse-grained authigenic mineral host intervals exhibit geochemical signatures that can be attributed to low grade hydrothermal alteration. The altered intervals show evidence of K2O, CaO, and rare earth elements mobilization. When compared to fine-grained, unaltered units, and to Santa Maria Island volcanics rocks, the altered zones are relatively depleted in rare earth elements, with light rare earth elements-heavy rare earth elements fractionation. Drilling at Site 833 penetrated a sill complex below 840 m. No sill was encountered at Site 832. Complex zonation of zeolite facies, authigenic smectites, carbonates and quartz, and associated geochemical signatures are present at both sites. The mineralogical and chemical alteration overprint is most pronounced in the deeper sections at Site 832. Based on mineralogical and chemical evidence at two locations less than 50 km apart, there is vertical and lateral variation in alteration of the volcaniclastic sediments of North Aoba Basin. The alteration observed may be activated by sill intrusion and associated expulsion of heated fluids into intervals of greater porosity. Such spatial variation in alteration could be attributed to the evolution of the basin axis associated with subduction processes along the New Hebrides Trench.

Chemical and isotopic composition of rocks and minerals at ODP Site 209-1275

This paper reports results of an investigation of a representative collection of samples recovered by deep-sea drilling from the oceanic basement 10 miles west of the rift valley axis in the crest zone of the Mid- Atlantic Ridge at 15°44'N (Sites 1275B and 1275D). Drilling operations were carried out during Leg 209 of the Drilling Vessel JOIDES Resolution within the framework of the Ocean Drilling Program (ODP). The oceanic crust was penetrated to depth of 108.7 m at Site 1275B and 209 m at Site 1275D. We reconstructed the following sequence of magmatic and metamorphic events resulting in the formation of a typical oceanic core complex of slow-spreading ridges: (1) formation of strongly fractionated (enriched in iron and titanium) tholeiitic magmatic melt parental to gabbroids under investigation in a large magma chamber located in a shallow mantle and operating for a long time under steady-state conditions; (2) transfer of the parental magmatic melt of the gabbroids to the base of the oceanic crust, its interaction with host mantle peridotites, and formation of troctolites and plagioclase peridotites; (3) intrusion of enriched trondhjemite melts as veins and dikes in the early formed plutonic complex, contact recrystallization of the gabbro, and development in the peridotite-gabbro complex of enriched geochemical signatures owing to influence of trondhjemite injections; (4) emplacement of dolerite dikes (transformed to diabases); (5) metamorphism of upper epidoteamphibolite facies with participation of marine fluids; and (6) rapid exhumation of the plutonic complex to the seafloor accompanied by greenschist-facies metamorphism. Distribution patterns of Sr and Nd isotopes and strongly incompatible elements in the rocks suggest contributions from two melt sources to the magmatic evolution of the MAR crest at 15°44'N: a depleted reservoir responsible for formation of the gabbros and diabases and an enriched reservoir, from which trondhjemites (granophyres) were derived.

Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.