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.

Geochemical analyses of ODP Leg 135 samples

Statistical analysis of X-ray fluorescence data acquired during Leg 135 indicates that this instrument produces data of comparable precision to good land-based laboratories. We also examined contamination of certain elements caused by crushing during the use of the tungsten carbide apparatus. Although the concentrations of most elements are not altered during crushing, the powders prepared on the ship should not be used in subsequent studies where key elements of the investigation include W, Co, Ta, Pb, and low levels of Nb.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

Chemical composition of bottom sediments from the Baltic Sea

According to geochemical analyses carbonaceous sediments from deep basins of the Baltic Sea containing 3-5% of organic carbon are enriched in some metals such as Cu, Mo, Ni, Pb, Zn, V, and U relative to shallow-water facies of the Bay of Finland. These metals also enrich (relative to background values in clayey rocks) ancient carbonaceous shales, where the average Cu and V contents are slightly higher and that of Mo, Pb, and Zn lower than in deep-sea carbonaceous sediments of the Baltic Sea. In addition, the deep-sea carbonaceous sediments of the Baltic Sea are enriched (but less notably than ancient shales) in Ag, As, Bi, and Cd. These data confirm previous assumptions that carbonaceous sediments accumulating now in seas and oceans can be considered as recent analogs of ancient metalliferous shales.

Physical properties nd chemistry of igneous rocks from the Pigafetta and East Mariana Basins

Physical properties of basalts from Ocean Drilling Program Sites 800 and 801 in the Pigafetta Basin and Site 802 in the East Mariana Basin, including porosity, wet-bulk density, grain density, compressional wave velocity, and thermal conductivity, were measured aboard JOIDES Resolution during Leg 129. The ranges for the properties are large, as typified by the velocity, which varies from 3.46 to 6.59 km/s. Extensively altered basalts immediately above and below a silicified hydrothermal deposit (60-69 m sub-basement depth) at Site 801 display the highest porosity, and lowest bulk density, velocity, and thermal conductivity, whereas the slightly altered rocks from Site 802 and the lowermost part of Site 801 represent the other extreme in physical properties variations. In order to better establish the relationship between physical properties and alteration of the rocks, the compressional wave velocities were compared with results from major and trace elemental analyses and petrographic examination of select samples. For the Leg 129 basalts, velocity displays a generally consistent decrease with increasing K2O, H2O+, loss on ignition, and Rb contents and the value of Fe3+/FeT and decreasing concentrations of SiO2, FeOT, CaO, MgO, and MnO. These trends are consistent with trends documented for the progressive alteration of oceanic crust and indicate that on a laboratory sample scale, basalt alteration is largely responsible for the variation of the physical properties of basalts sampled at Sites 800, 801, and 802.

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.

Chemical and mineral compositions of altered peridotites from ODP Leg 209

Abyssal peridotite from the 15°20'N area of the Mid-Atlantic Ridge show complex geochemical variations among the different sites drilled during ODP Leg 209. Major element compositions indicate variable degrees of melt depletion and refertilization as well as local hydrothermal metasomatism. Strongest evidence for melt-rock interactions are correlated Light Rare Earth Element (LREE) and High Field Strength Element (HFSE) additions at Sites 1270 and 1271. In contrast, hydrothermal alteration at Sites 1274, 1272, and 1268 causes LREE mobility associated with minor HFSE variability, reflecting the low solubility of HFSE in aqueous solutions. Site 1274 contains the least-altered, highly refractory, peridotite with strong depletion in LREE and shows a gradual increase in the intensity of isochemical serpentinization; except for the addition of H2O which causes a mass gain of up to 20 g/100 g. The formation of magnetite is reflected in decreasing Fe(2+)/Fe(3+) ratios. This style of alteration is referred to as rock-dominated serpentinization. In contrast, fluid-dominated serpentinization at Site 1268 is characterized by gains in sulfur and development of U-shaped REE pattern with strong positive Eu anomalies which are also characteristic for hot (350 to 400°C) vent-type fluids discharging from black smoker fields. Serpentinites at Site 1268 were overprinted by talc alteration under static conditions due to interaction with high a_SiO2 fluids causing the development of smooth, LREE enriched patterns with pronounced negative Eu anomalies. These results show that hydrothermal fluid-peridotite and fluid-serpentinite interaction processes are an important factor regarding the budget of exchange processes between the lithosphere and the hydrosphere in slow spreading environments.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.

Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Geochemistry of basaltic rocks from ODP Site 129-801

Middle Jurassic basaltic lavas obtained from Site 801 in the western Pacific Pigafetta Basin represent ocean crust from the oldest segment of the present-day Pacific Ocean. A composite 131 m section shows the basement to be composed of an upper alkalic basalt sequence (about 157 Ma) with ocean island basalt chemical features and a lower tholeiitic basalt sequence (about 167 Ma) with typical normal-type mid-ocean ridge basalt features. The basalt sequences are separated by a quartz-cemented, yellow goethite hydrothermal deposit. Most basalts are altered to some degree and exhibit variable, low-grade smectite-celadonite-pyrite-carbonate-zeolite assemblages developed under a mainly hydrated anoxic environment. Oxidation is very minor, later in development than the hydration assemblages, and largely associated with the hydrothermal deposit. The tholeiitic normal-type mid-ocean ridge basalt has characteristically depleted incompatible element patterns and all compositions are encompassed by recent mid-ocean ridge basalt from the East Pacific Rise. Chemically, the normal-type mid-ocean ridge basalt is divided into a primitive plagioclase-olivine +/- spinel phyric group (Mg* = 72-60) and an evolved (largely) aphyric group of olivine tholeiites (Mg* = 62-40). Both groups form a single comagmatic suite related via open-system fractionation of initial olivine-spinel followed by olivine-plagioclase-clinopyroxene. The alkalic ocean island basalt are largely aphyric and display enriched incompatible element abundances within both relatively primitive olivine-rich basalts and evolved olivine-poor hawaiites related via mafic fractionation. In gross terms, the basement lithostratigraphy is a typical mid-ocean ridge basalt crust, generated at a spreading center, overlain by an off-axis seamount with ocean island basalt chemical characters.

Geochemistry of Central American Volcanic Arc basement samples

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low d18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high d18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

Geochemistry of highly depleted peridotites of the Mid-Atlantic Ridge

During ODP Leg 209, a magma-starved area of the Mid-Atlantic Ridge (MAR) was drilled in the vicinity of the Fifteen-Twenty Fracture Zone (FZ) that offsets one of the slowest portions of the spreading ridge. We present here the results of a bulk rock multi-elemental study of 27 peridotites drilled at Sites 1272 and 1274 (to the south and the north of the FZ, respectively). The peridotites comprise mainly of harzburgites with minor dunites. Clinopyroxene (Cpx), which is interstitial and interpreted as secondary, is observed in Site 1274 peridotites. Sites 1272 and 1274 peridotites have low Al2O3 contents (<1 anhydrous wt.%), high Mg# (>91.5), and bulk rock trace elements compositions mostly below 0.1X primitive mantle (PM). These peridotites, and in particular Site 1272 peridotites, represent the most depleted peridotites yet sampled at a slow spreading ridge. Their compositions indicate high degrees of partial melting and melt extraction. A single open-system melting event (melting plus percolation of melts produced within upwelling mantle) can explain their highly depleted yet linear chondrite-normalized REE patterns, characterized by a steady depletion from HREE to LREE. Late melt-rock reactions and precipitation of Cpx explains the slightly less depleted compositions of Site 1274 peridotites. Hence, the differences in composition between Sites 1272 and 1274 peridotites do not provide evidence for regional variations in the degrees of partial melting from the south to the north of the FZ. The occurrence of highly refractory peridotites in the Fifteen-Twenty area suggests we sampled a more actively convecting mantle than generally supposed below slow spreading centers.

Geochemistry on ferromanganese crusts and nodules from Green Bay, Lake Michigan

The differential solubility of ferromanganese oxides can lead to stratigraphic separation of iron and manganese. Results of chemical analysis of a sequence of ferromanganese nodules overlying iron-rich crusts in northern Green Bay show that selec¬tive ion transport is important in concentrating manganese and associated trace elements near the oxygenated water-sediment interface. Manganese carbonate, which cements ferromanganese nodules, occurs in dark-gray silty sands that are located adjacent to the organic-rich muds of southern Green Bay. These muds contain an average of approximately 3.5 ppm (6x10-5M) interstitial Mn with 2.8 meq/l carbonate alkalinity. Thermodynamic calculation shows that interstitial water approaches equilibrium with MnCO3 in the upper 10 cm of sediment. This carbonate has a composition (Mn73Ca22Fe5)CO3 and has been identified as rhodochrosite.