Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

Geochemistry of glass shards in the volcanic ash layers of the Izu-Bonin Arc

To examine the processes and histories of arc volcanism and of volcanism associated with backarc rifting. 130 samples containing igneous glass shards were taken from the Plioccne-Quatemai^ succession on the rift Hank (Site 788) and the Quaternary fill in the basin fill of the Sumisu Rift (Sites 790 and 791). These samples were subsequently analyzed at the University of Illinois at Chicago and Shizuoka University. The oxides determined by electron probe do not account for the total weight of the material; differences between summed oxides and 100% arise from the water contents, probably augmented by minor losses thai result from alkali vaporization during analysis. Weight losses in colorless glasses are up to 9%; those in brown glasses (dacitcs to basalts) arc no more than 4.5%; shards from the rift-flank (possibly caused by prolonged proximity to ihc scafloor) generally have higher values than those from the rift-basin fill How much of the lost water is magmatic, and how much is hydrated is uncertain; however, although the shards absorb potassium, calcium, and magnesium during hydration in the deep sea, they do so only to a minor extent that does not significantly alter their major element compositions. Therefore, the electron-probe results are useful in evaluating the magmatism recorded by the shards. Pre- and syn-rift Izu-Bonin volcanism were overwhelmingly dominated by rhyolile explosions, demonstrating that island arcs may experience significant silicic volcanism in addition to the extensive basaltic and basaltic andestic activity, documented in many arcs since the 1970s, that occurs in conjunction with the andesitic volcanism formerly thought to be dominant. Andesitic eruptions also occurred before rifting, but the andesitic component in our samples is minor. All the pre- and syn-rift rhyolites and andesites belong to the low-alkali island-arc tholeiitic suite, and contrast markedly with the alkali products of Holocene volcanism on the northernmost Mariana Arc that have been attributed to nascent rifting. The Quaternary dacites and andesites atop the rift flank and in the rift-basin fill are more potassic than those of Pliocene age, as a result of assimilation from the upper arc crust, or from variations in degrees of partial melting of the source magmas, or from metasomatic fluids. All the glass layers from the rift-flank samples belong to low-K arc-tholeiitic suites. Half of those in the Pliocene succession are exclusively rhyolitic: the others contain minor admixtures of dacite and andesite, or andesite and either basaltic andesite or basalt. In Contrast, the Quaternary (syn-rift) volcaniclastics atop the rift-flank lack basalt and basaltic andesite shards. These youngest sediments of the rift flank show close compositional affinities with five thick layers of coarse, rhyolitic pumice deposits in the basin fill, the two oldest more silicic than the younger ones. The coarse layers, and most thin ash layers that occur in hemipelagites below and intercalated between them, are low-K rhyolites and therefore probably came from sources in the arc. However, several thin rhyolitic ash beds in the hemipelagites are abnormally enriched in potassium and must have been provided by more distal sources, most likely to the west in Japan. Remarkably, the Pliocene-Pleistocene geochemistry of the volcanic front does not appear to have been influenced by the syn-rift basaltic volcanism only a few kilometers away. Rare, thin layers of basaltic ash near the bases of the rift-basin successions are not derived from the arc. They deviate strongly from trends that the arc-derived glasses display on oxide-oxide plots, and show close affinities to the basalts empted all over the Sumisu Rift during rifting. These basalts, and the basaltic ashes in the basal rift-basin fill, arc compositionally similar to those erupted from mature backarc basins elsewhere.

Major and trace element geochemistry of ODP Leg 178 holes

Geochemical analyses have been performed on sediment samples collected during Ocean Drilling Program Leg 178 from the continental rise and outer continental shelf of the Antarctic Peninsula. A suite of 21 trace elements was measured by neutron activation analysis in 39 sediment samples, and major element oxides were determined in 67 samples by electron microprobe analyses of fused glass beads. These geochemical data, combined with the X-ray diffraction and X-ray fluorescence data from shipboard analyses, provide a reasonable estimate of the mineral and chemical composition of sediments deposited along the western margin of the Antarctic Peninsula.

Geochemistry of ocean floor and forearc serpentinites

We provide new insights into the geochemistry of serpentinites from mid-ocean ridges (Mid-Atlantic Ridge and Hess Deep), passive margins (Iberia Abyssal Plain and Newfoundland) and fore-arcs (Mariana and Guatemala) based on bulk-rock and in situ mineral major and trace element compositional data collected on drill cores from the Deep Sea Drilling Project and Ocean Drilling Program. These data are important for constraining the serpentinite-hosted trace element inventory of subduction zones. Bulk serpentinites show up to several orders of magnitude enrichments in Cl, B, Sr, U, Sb, Pb, Rb, Cs and Li relative to elements of similar compatibility during mantle melting, which correspond to the highest primitive mantle-normalized B/Nb, B/Th, U/Th, Sb/Ce, Sr/Nd and Li/Y among subducted lithologies of the oceanic lithosphere (serpentinites, sediments and altered igneous oceanic crust). Among the elements showing relative enrichment, Cl and B are by far the most abundant with bulk concentrations mostly above 1000 µg/g and 30 µg/g, respectively. All other trace elements showing relative enrichments are generally present in low concentrations (µg/g level), except Sr in carbonate-bearing serpentinites (thousands of µg/g). In situ data indicate that concentrations of Cl, B, Sr, U, Sb, Rb and Cs are, and that of Li can be, increased by serpentinization. These elements are largely hosted in serpentine (lizardite and chrysotile, but not antigorite). Aragonite precipitation leads to significant enrichments in Sr, U and B, whereas calcite is important only as an Sr host. Commonly observed brucite is trace element-poor. The overall enrichment patterns are comparable among serpentinites from mid-ocean ridges, passive margins and fore-arcs, whereas the extents of enrichments are often specific to the geodynamic setting. Variability in relative trace element enrichments within a specific setting (and locality) can be several orders of magnitude. Mid-ocean ridge serpentinites often show pronounced bulk-rock U enrichment in addition to ubiquitous Cl, B and Sr enrichment. They also exhibit positive Eu anomalies on chondrite-normalized rare earth element plots. Passive margin serpentinites tend to have higher overall incompatible trace element contents than mid-ocean ridge and fore-arc serpentinites and show the highest B enrichment among all the studied serpentinites. Fore-arc serpentinites are characterized by low overall trace element contents and show the lowest Cl, but the highest Rb, Cs and Sr enrichments. Based on our data, subducted dehydrating serpentinites are likely to release fluids with high B/Nb, B/Th, U/Th, Sb/Ce and Sr/Nd, rendering them one of the potential sources of some of the characteristic trace element fingerprints of arc magmas (e.g. high B/Nb, high Sr/Nd, high Sb/Ce). However, although serpentinites are a substantial part of global subduction zone chemical cycling, owing to their low overall trace element contents (except for B and Cl) their geochemical imprint on arc magma sources (apart from addition of H2O, B and Cl) can be masked considerably by the trace element signal from subducted crustal components.

Petrology and relict mineralogy of serpentinites at DSDP Leg 84 Holes

Eleven serpentine samples from DSDP Leg 84 and four serpentinized ultramafic samples from Costa Rica and Guatemala were described and their relict mineral compositions measured by electron microprobe to try to determine the origin of the Leg 84 serpentinites and their relationship to the ultramafic rocks of the onshore ophiolites. The Leg 84 samples comprise more than 90% secondary minerals, principally serpentine, with hematitic and opaque oxides, and minor talc and smectites. Four distinct textural types can be identified according to the distribution of opaque phases and smectite. Remnants of spinel, olivine, orthopyroxene, and clinopyroxene occur variously in the samples; spinal occurs in all the samples. Textural evidence suggests that the serpentinites were originally clinopyroxene-bearing harzburgites. Relict mineral compositions are refractory and relatively uniform: olivine, Fo90.6-90.9; orthopyroxene, En90-91; clinopyroxene, Wo47 En50 Fs3; spinels, Cr/Cr + Al = 0.4-0.6. 567A-29-2, 30-35 cm has slightly more magnesian olivines (Fo92) and orthopyroxene, and more aluminous spinels (Cr/Cr + Al = 0.3). These compositions are similar to those inferred for refractory upper-mantle materials and also fall within the range of compositions for relict minerals in abyssal peridotites. They could be of oceanic origin. The onshore samples include serpentinites, a clinopyroxene-bearing harzburgite, and a clinopyroxenite. They too have magnesium-rich silicate assemblages, but relative to the drilled samples have more iron-rich olivines (Fogo) and more aluminous and sodic pyroxenes; spinels which are clearly relicts are very aluminum-rich (Cr/Cr + Al = 0.1-0.25). These samples are most likely mantle materials, but significantly less depleted. Their relationship to the drilled samples is unclear. Serpentinites were the most common basement materials recovered during Leg 84, and there appears to be a bimodal assemblage (basalt/diabase and serpentine) of igneous rocks sampled from the trench slope. Diapirism of serpentine throughout the trench slope and forearc is suggested as an explanation for this distribution of samples.

Alkenone composition, UK'37 index, and carbon, sulphur, nitrogen and element oxides of ODP Site 186-1151

Ocean Drilling Program (ODP) Site 1151 (Sacks, Suyehiro, Acton, et al., 2000, doi:10.2973/odp.proc.ir.186.2000) is located in an area where the surface water mass is influenced by both the Kuroshio and Oyashio Currents. The site also receives a relatively high flux of detrital materials from riverine input from Honsyu Island and eolian input from Central and East Asia. We analyzed alkenones and alkenoates in the sediments to reconstruct alkenone unsaturation index (Uk'37)-based sea-surface temperature (SST), total organic carbon, and total nitrogen to estimate the terrigenous contribution by the C/N ratio during the last glacial-interglacial cycle. The major elements were also analyzed to examine the variation in terrigenous composition.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Mineralogical and geochemical analyses of serpentines from ODP Hole 125-778A

Thirty-five samples from Hole 778A were prepared for X-ray diffraction (XRD) mineralogical analyses and for chemical analyses of major and trace elements. Most of the selected samples were silt- and sand-sized sedimentary serpentinites or microbreccias except for a soft clast of mafic rock, a hard clast of massive serpentinized peridotite, and a pebble of consolidated, undeformed serpentine microbreccia that contained planktonic foraminifers. Both mineralogical and geochemical analyses allow discrimination of three groups among the analyzed samples. These groups correspond to three stratigraphic intervals present along the drilled section. Group A contains the upper samples (lithologic Unit I). These consist of poorly consolidated serpentine muds carrying hard-rock clasts (serpentinized peridotites, metabasalts). They are characterized by the following mineralogical assemblage: serpentine, Fe-oxides and hydroxides, aragonite, and halite. They exhibit variable SiO2, MgO contents, but are characterized by a SiO2/MgO ratio near 1. CaO content is high in relation to development of aragonite. Al2O3 content is low. Relatively high K2O, Na2O, and Sr contents are present, presumably in relation to interactions with seawater. Group B (30-77 mbsf) contains samples exhibiting very homogeneous chemical and mineralogical compositions. They consist of serpentinite microbreccias exhibiting frequent shear structures. Hard-rock clasts are also present (serpentinized peridotites, metabasalts, one possible chert fragment). The mineralogy of the Group B samples is characterized by the presence of serpentine and authigenic minerals: hydroxycarbonates and hydrogrossular. Calcite and chlorite are also present, but all the samples lack aragonite. Their chemical compositions are remarkably similar to compositions of their parent rocks. Group C contains silt- and sand-sized serpentine and serpentine microbreccias, which are locally rich in red clasts, probably strongly altered (oxidized?) mafic fragments. Intervals having clasts of more diverse origin than those higher in the section were recovered. Clast lithology includes serpentinized peridotites, metabasalts, metavolcaniclastite, meta-olivine gabbro, and amphibolite sandstone. Mineralogy and geochemistry reflect these compositions. Serpentine content of the samples is less than in previous groups. Correlatively, sepiolite, palygorskite, and chlorite-smectite are mineral phases present in the analyzed samples. Accessory igneous minerals (amphiboles, pyroxenes, hematite) also were found. The chemical compositions of most of Group C samples differ from that of massive serpentinized peridotites. The main differences are (1) higher SiO2, CaO, TiO2 and Al2O3 contents, (2) a SiO2/MgO ratio greater than 1, and (3) a negative correlation between Al2O3, and MgO, Cr, and Ni. These characteristics suggest new constraints relative to the flow structure of the flank of Conical Seamount.

Geochemistry at DSDP Leg 73 Holes

In the South Atlantic, at Sites 519 to 523, the dissolution of calcareous oozes ended in the formation of red clays rich in iron and manganese. The early authigenesis of manganese oxides and clays is described in Miocene marly calcareous oozes. The mineralogical and geochemical influences of basaltic basement weathering are shown by the occurrence of palagonite, authigenic clays, and oxides in the basal sediments. The development of red clay facies can be inhibited by local topographic and paleoceanographic changes, as at Site 520.

Major element chemistr yof fallout tephra from ODP Hole 125-782A

New and published analyses of major element oxides (SiO2, TiO2, Al2O3, FeO*, MnO, MgO, CaO, K2O, Na2O and P2O5) from the central Izu Bonin and Mariana arcs (IBM) were compiled in order to investigate the evolution of the IBM in terms of major elements since arc inception at ~49 million years ago. The database comprises ?3500 volcanic glasses of distal tephra fallout and ?500 lava samples, ranging from the Quaternary to mid-Eocene in age. The data were corrected to 4 wt% MgO in order to display the highly resolved temporal trends. These trends show that the IBM major elements have always been "arc-like" and clearly distinct from N-MORB. Significant temporal variations of some major element oxides are apparent. The largest variations are displayed by K4.0. The data support a model wherein the K2O variability is caused by the addition of slab component with strongly differing K2O contents to a fairly depleted subarc mantle; variable extents of melting, or mantle heterogeneity, appear to play a negligible role. The other major element oxides are controlled by the composition and processes of the subarc mantle wedge. The transition from the boninitic and tholeiitic magmatism of the Eocene and Oligocene to the exclusively tholeiitic magmatism of the Neogene IBM is proposed to reflect a change in the composition of the subarc mantle wedge. The early boninitic magmas originate from an ultra-depleted subarc mantle, that is residual to either the melting of E-MORB mantle, or of subcontinental lithospheric mantle. During the Eocene and Oligocene, this residual mantle is gradually replaced by Indian MORB mantle advected from the backarc regions. The Indian MORB mantle is more radiogenic in Nd isotope ratios but also more fertile with respect to major and trace elements. Therefore the Neogene tholeiites have higher Al2O3 and TiO2 contents and lower mg# numbers at given SiO2 content. After the subarc mantle replacement was complete in the late Oligocene or early Miocene, the Neogene IBM entered a "steady state" that is characterized by the continuous advection of Indian MORB mantle from the reararc, which is fluxed by fluids and melt components from slab. The thickness of the IBM crust must have grown with time, but any effects of crustal thickening on the major element chemistry of the IBM magmas appear to be minor relative to the compositional changes that are related to source composition. Therefore next to the processes of melting, the composition of the mantle sources must play a major role in creating substantiative heterogeneities in the major element chemistry of the arc crust.

Chemical analyses and results of sediments from different DSDP Holes from the North Atlantic

Chemical analyses of North Atlantic D.S.D.P. (Deep Sea Drilling Project) sediments indicate that basal sediments generally contain higher concentrations of Fe, Mn, Mg, Pb, and Ni, and similar or lower concentrations of Ti, Al, Cr, Cu, Zn, and Li than the material overlying them. Partition studies on selected samples indicate that the enriched metals in the basal sediments are usually held in a fashion similar to that in basal sediments from the Pacific, other D.S.D.P. sediments, and modern North Atlantic ridge and non-ridge material. Although, on average, chemical differences between basal sediments of varying ages are apparent, normalization of the data indicates that the processes leading to metal enrichment on the crest of the Mid-Atlantic Ridge appear to have been approximately constant in intensity since Cretaceous times. In addition, the bulk composition of detrital sediments also appears to have been relatively constant over the same time period. Paleocene sediments from site 118 are, however, an exception to this rule, there apparently having been an increased detrital influx during this period. The bulk geochemistry, partitioning patterns, and mineralogy of sediments from D.S.D.P. 9A indicates that post-depositional migration of such elements as Mn, Ni, Cu, Zn, and Pb may have occurred. The basement encountered at the base of site 138 is thought to be a basaltic sill, but the overlying basal sediments are geochemically similar to other metalliferous basal sediments from the North Atlantic. These results, as well as those from site 114 where true oceanic basement was encountered, but where there was an estimated 7 m.y. hiatus between basaltic extrusion and basal sediment deposition, indicate that ridge-crest sediments are not necessarily deposited during active volcanism but can be formed after the volcanism has ceased. The predominant processes for metal enrichment in these deposits and those formed in association with other submarine volcanic features is a combination of shallow hydrothermal activity, submarine weathering of basalt, and the formation of ferromanganese oxides which can scavenge metals from seawater. In addition, it seems as though the formation of submarine metalliferous sediments is not restricted to active-ridge areas.