Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Whole-rock geochemistry of amphibolites and metagabbros from ODP Holes 173-1067A and 173-1068A

The Leg 173 Site 1067 and 1068 amphibolites and metagabbros from the west Iberia margin exhibit variable whole-rock compositions from primitive to more evolved (Mg numbers = 49-71) that are generally incompatible trace and rare earth element enriched (light rare earth element [LREE] = 11-89 x chondrite). The Site 1067 amphibolites are compositionally similar to the basalts reported at Site 899 from this same region, based on trace and rare earth element contents. The Site 1068 amphibolites and metagabbros are similar to the Site 899 diabases but are more LREE enriched. However, the Sites 1067 and 1068 amphibolites and metagabbros are not compositionally similar to the Site 900 metagabbros, which are from the same structural high as the Leg 173 samples. The Leg 173 protoliths may be represented by basalts, diabases, and/or fine-grained gabbros that formed from incompatible trace element-enriched liquids.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Geochemistry of Miocene Alborán Basin volcanism

We present new major and trace element and O-Sr-Nd-isotope data for igneous rocks from the western Mediterranean Alborán Sea, collected during the METEOR 51/1 cruise, and for high-grade schists and gneisses from the continental Alborán basement, drilled during the Ocean Drilling Programme (ODP Leg 161, Site 976). The geochemical data allow a detailed examination of crustal and mantle processes involved in the petrogenesis of the lavas and for the first time reveal a zonation of the Miocene Alborán Sea volcanism: (1) a keel-shaped area of LREE-depleted (mainly tholeiitic series) lavas in the central Alborán Sea, generated by high degrees of partial melting of a depleted mantle source and involving hydrous fluids from subducted marine sediments, that is surrounded by (2) a horseshoe-shaped zone with LREE-enriched (mainly calc-alkaline series) lavas subparallel to the arcuate Betic-Gibraltar-Rif mountain belt. We propose that the geochemical zonation of the Miocene Alborán Basin volcanism results from eastward subduction of Tethys oceanic lithosphere coupled with increasing lithospheric thickness between the central Alborán Sea and the continental margins of Iberia and Africa.

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.

Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

Major components and major and trace elements from ODP Site 175-1085

We have analyzed 33 Pliocene bulk sediment samples from Ocean Drilling Program Site 1085 in the Cape Basin, located offshore of western Africa in the Angola-Benguela Current system, for 17 major and trace elements, and interpreted their associations and temporal variations in the context of an allied data set of CaCO3, opal, and Corg. We base our interpretations on elemental ratios, accumulation rates, inter-element correlations, and several multi-element statistical techniques. On the basis of qualitative assessment of downhole changes in the distributions of P and Ba, utilized as proxies of export production, we conclude that highs in bulk and biogenic accumulation that occur at 3.2 Ma, 3.0 Ma, 2.4 Ma, and 2.25 Ma were caused by increases in export production as well as terrigenous flux, and record a greater sequestering of organic matter during these time periods. Studies of refractory elements and other indicator proxies (SiO2, Al2O3, TiO2, Fe2O3, MgO, V, Cr, Sr, and Zr) strongly suggest that the terrigenous component of the bulk sediment is composed of two compositional end-members, one being 'basaltic' in composition and the other similar to an 'average shale'. The basaltic end-member comprises approximately 10-15% of the total bulk sediment and its presence is consistent with the local geology of source material in the drainage basin of the nearby Orange River. The increase in bulk accumulation at 2.4 Ma appears to reflect a greater relative increase in basaltic input than the relative increase in shale-type input. Although studies such as this cannot precisely identify the transport mechanisms of the different terrigenous components, these results are most consistent with variations in sea level (and associated changes in shelf geometry and fluvial input) being responsible for the changing depositional conditions along the Angolan Margin during this time period.

Petrology of basalts from DSDP Hole 83-504B

Basalts from Hole 504B, Leg 83, exhibit remarkable uniformity in major and trace element composition throughout the 1075.5 m of basement drilled. The majority of the basalts, Group D', have unusual compositions relative to normal (Type I) mid-ocean ridge basalts (MORB). These basalts have relatively high mg values (0.60-0.70) and CaO abundances (11.7-13.7%; Ca/Al = 0.78-0.89), but exhibit a marked depletion in compatible trace elements (Cr and Ni); moderately incompatible trace elements (Zr, Y, Ti, etc.); and highly incompatible trace elements (Nb, LREE, etc.). Petrographic and compositional data indicate that most of these basalts are evolved, having fractionated significant amounts of plagioclase, olivine, and clinopyroxene. Melting experiments on similar basalt compositions from the upper portion of Hole 504B (Leg 70; Autio and Rhodes, 1983) indicate that the basalts are co-saturated with olivine and plagioclase and often clinopyroxene on the 1-atm. liquidus. Two rarely occurring groups, M' and T, are compositionally distinct from Group D' basalts. Group T is strongly depleted in all magmaphile elements except the highly incompatible ones (Nb, La, etc.), while Group M' has moderate concentrations of both moderately and highly incompatible trace elements and is similar to Type I MORB. Groups M' and T cannot be related to Group D' nor to each other by crystal fractionation, crystal accumulation, or magma mixing. The large differences in magmaphile element ratios (Zr/Nb, La/Yb) among these three chemical groups may be accounted for by complex melting models and/or local heterogeneity of the mantle beneath the Costa Rica Ridge. Xenocrysts and xenoliths of plagioclase and clinopyroxene similar in texture and mineral composition to crystals in coarse-grained basalts from the lower portion of the hole are common in Hole 504B basalts. These suggest that addition of solid components either from conduit or magma chamber walls has occurred and may be a common source of disequilibrium crystals in these basalts. However, mixing of plagioclase-laden depleted melts (similar to the Costa Rica Ridge Zone basalts) with normal MORB magmas could provide an alternate source for some refractory plagioclase crystals found out of equilibrium in many phyric MORB. The uniformity of major element compositions in Hole 504B basalts affords an ideal situation for investigating the effects of alteration on some major and trace elements in oceanic basalts. Alteration observed in whole-rock samples records primarily two events - a high-temperature and a low-temperature phase. High-temperature phases include: chlorite, talc, albite, actinolite, sphene, quartz, and pyrite. The low-temperature phases include smectite (saponite), epistilbite or laumontite, and minor calcite. Laumontite may actually straddle the gap between the low- and high-temperature mineral assemblages. Alteration is restricted primarily to partial replacement of primary phases. Metamorphic grade, in general, increases from the top to the bottom of Hole 504B (Legs 69, 70, and 83) as seen in the change from a smectiteto- chlorite-dominated secondary mineral assemblage. However, a systematic progression for the interval recovered during Leg 83 is not apparent. Rather, the extent of alteration appears to be a function of the initial texture and fracture density. Variations in whole-rock major and trace element concentrations cannot be attributed convincingly to any differences in alteration observed. Compositional characteristics of the secondary minerals indicated that extensive remobilization of elements has not occurred; local redistribution is suggested in most cases. Thus, the major and trace element signature of these basalts remains effectively the same as the original composition prior to alteration.

Solid phase analysis of sediment core GeoB9309-1 from the Zambezi (or Mozambique) deep-sea fan

The Zambezi deep-sea fan, the largest of its kind along the east African continental margin, is poorly studied to date, despite its potential to record marine and terrestrial climate signals in the southwest Indian Ocean. Therefore, gravity core GeoB 9309-1, retrieved from 1219 m water depth, was investigated for various geophysical (magnetic susceptibility, porosity, colour reflectance) and geochemical (pore water and sediment geochemistry, Fe and P speciation) properties. Onboard and onshore data documented a sulphate/methane transition (SMT) zone at ~ 450-530 cm sediment depth, where the simultaneous consumption of pore water sulphate and methane liberates hydrogen sulphide and bi-carbonate into the pore space. This leads to characteristic changes in the sediment and pore water chemistry, as the reduction of primary Fe (oxyhydr)oxides, the precipitation of Fe sulphides, and the mobilization of Fe (oxyhydr)oxide-bound P. These chemical processes also lead to a marked decrease in magnetic susceptibility. Below the SMT, we find a reduction of porosity, possibly due to pore space cementation by authigenic minerals. Formation of the observed geochemical, magnetic and mineralogical patterns requires a fixation of the SMT at this distinct sediment depth for a considerable time-which we calculated to be ~ 10 000 years assuming steady-state conditions-following a period of rapid upward migration towards this interval. We postulate that the worldwide sea-level rise at the last glacial/interglacial transition (~ 10 000 years B.P.) most probably caused the fixation of the SMT at its present position, through drastically reduced sediment delivery to the deep-sea fan. In addition, we report an internal redistribution of P occurring around the SMT, closely linked to the (de)coupling of sedimentary Fe and P, and leaving a characteristic pattern in the solid P record. By phosphate re-adsorption onto Fe (oxyhydr)oxides above, and formation of authigenic P minerals (e.g. vivianite) below the SMT, deep-sea fan deposits may potentially act as long-term sinks for P.

Benthic oxygen isotopes, Zr/Al and grain size fractions over the Miocene-Pliocene boundary in the Gulf of Cadiz

During the latest Messinian, hemipelagic sediments exhibiting precession-induced climate variability were deposited. These are overlain by Pliocene sediments deposited at a much higher sedimentation rate, with much higher and more variable XRF-scanning Zr/Al ratios than the underlying sediment, and that show evidence of winnowing, particle sorting and increasing grain size, which we interpret to be related to the increasing flow of MOW. Pliocene sedimentary cyclicity is clearly visible in both the benthic d18O record and the Zr/Al data and is probably also precessionally controlled. On the basis of these results, we conclude that contouritic sedimentation, associated with weak Mediterranean-Atlantic exchange, began in the Gulf of Cadiz virtually at or shortly after the Miocene-Pliocene boundary, with two contouritic bigradational sandy-beds within the fourth precession cycle after the Miocene-Pliocene boundary.

Major and trace elements and interelement ratios at DSDP Leg 81 Holes

Fifty-two samples of basalt from the four holes drilled on the Leg 81 transect across the Rockall margin were analyzed by X-ray fluorescence for Rb, Sr, Y, Zr, and Nb. On the basis of these results 13 samples were chosen for major and supplementary trace-element analysis. The results show no progressive change in the character of the volcanism, from Hole 555 in the continental domain through Holes 552 and 553A in the dipping reflector sequence to Hole 554A on the outer high. Two distinct magma types are present, apparently reflecting heterogeneity of the underlying mantle, but both types are present in both Holes 553A and 555, while Hole 552 and Hole 554 are each composed of a single type. Both magma types have a clear ocean-floor basalt signature when examined by discrimination diagrams, as does the basalt from Deep Sea Drilling Project Site 112, which formed at the same time as the Leg 81 basalts slightly farther south along the spreading center. In contrast, the basalts of East Greenland, formed at the same time, are more enriched in incompatible elements and have a within-plate geochemical signature, as is found in some basalts of Iceland today. Clearly the present distinction in geochemistry between the basalts of Iceland and those erupting well south on the Reykjanes Ridge was already established when continental splitting took place.

Mineral and chemical compositions of clay sediments from the Pacific Ocean, DSDP data

Mineral and chemical compositions, as well as conditions of formation of clay sediments in major structural elements of the Pacific Ocean floor with different ages are under consideration in the monograph. Depending on evolution of the region two ways of clay sediment formation are identified: terrigenous and authigenic. It is shown that terrigenous clay sediments predominate in marginal parts of the Pacific Ocean. Authigenic mineral formation occurring in the basal part of the sedimentary cover primarily results from removal of material from underlying basalts. This material is released during secondary alteration of the basalts due to their interaction with sea water, as well as with deep solutions.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

Geochemistry of the Kimmeridge Clay Formation, Dorset Coast

The Kimmeridge Clay Formation (KCF) and its equivalents worldwide represent one of the most prolonged periods of organic carbon accumulation of the Mesozoic. In this study, we use the molybdenum (Mo) stable isotope system in conjunction with a range of trace metal paleoredox proxies to assess how seawater redox varied both locally and globally during the deposition of the KCF. Facies with lower organic carbon contents (TOC 1-7 wt %) were deposited under mildly reducing (suboxic) conditions, while organic-rich facies (TOC >7 wt %) accumulated under more strongly reducing (anoxic or euxinic) local conditions. Trace metal abundances are closely linked to TOC content, suggesting that the intensity of reducing conditions varied repeatedly during the deposition of the KCF and may have been related to orbitally controlled climate changes. Long-term variations in d98/95Mo are associated with the formation of organic-rich intervals and are related to third-order fluctuations in relative sea level. Differences in the mean d98/95Mo composition of the organic-rich intervals suggest that the global distribution of reducing conditions was more extensive during the deposition of the Pectinatites wheatleyensis and lower Pectinatites hudlestoni zones than during the deposition of the upper Pectinatites hudlestoni and Pectinatites pectinatus zones. The global extent of reducing conditions during the Kimmerigidan was greater than today but was less widespread than during the Toarcian (Early Jurassic) oceanic anoxic event. This study also demonstrates that the Mo isotope system in Jurassic seawater responded to changes in redox conditions in a manner consistent with its behavior in present-day sedimentary environments.