Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.

Abundance of planktic foraminiferal species in sediments at DSDP Sites 10-95, 77-536, and 77-540

Over most of the Gulf of Mexico and Caribbean a hiatus is present between the lower upper Maastrichtian and lowermost Tertiary deposits; sedimentation resumed ~200 ka (upper zone Pla) after the K-T boundary. Current-bedded volcaniclastic sedimentary rocks at Deep Sea Drilling Project (DSDP) Sites 536 and 540, which were previously interpreted as impact-generated megawave deposits of K-T boundary age, are biostratigraphically of pre-K-T boundary age and probably represent turbidite or gravity-How deposits. The top 10 to 20 cm of this deposit at Site 536 contains very rare Micula prinsii, the uppermost Maastrichtian index taxon, as well as low values of Ir (0.6 pbb) and rare Ni-rich spinels. These indicate possible reworking of sediments of K-T boundary age at the hiatus. Absence of continuous sediment accumulation across the K-T boundary in the 16 Gulf of Mexico and Caribbean sections examined prevents their providing evidence of impact-generated megawave deposits in this region. Our study indicates that the most complete trans-K-T stratigraphic records may be found in onshore marine sections of Mexico, Cuba, and Haiti. The stratigraphic records of these areas should be investigated further for evidence of impact deposits.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.

Major, trace element and XRF data for sediments and fish tooth samples, from a shallow marine setting with varying redox conditions (Site U1356, Wilkes Land Margin, E.Antarctica)

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

Depth profiles of pore-water and solid-phase constituents, respiration rates and grain size distribution in sediments of the Clarion-Clipperton Fracture Zone

Manganese nodules of the Clarion-Clipperton Fracture Zone (CCFZ) in the NE Pacific Ocean are highly enriched in Ni, Cu, Co, Mo and rare-earth elements, and thus may be the subject of future mining operations. Elucidating the depositional and biogeochemical processes that contribute to nodule formation, as well as the respective redox environment in both, water column and sediment, supports our ability to locate future nodule deposits and evaluates the potential ecological and environmental effects of future deep-sea mining. For these purposes we evaluated the local hydrodynamics and pore-water geochemistry with respect to the nodule coverage at four sites in the eastern CCFZ. Furthermore, we carried out selective leaching experiments at these sites in order to assess the potential mobility of Mn in the solid phase, and compared them with the spatial variations in sedimentation rates. We found that the oxygen penetration depth is 180 - 300 cm at all four sites, while reduction of Mn and NO3- is only significant below the oxygen penetration depth at sites with small or no nodules on the sediment surface. At the site without nodules, potential microbial respiration rates, determined by incubation experiments using 14C-labelled acetate, are slightly higher than at sites with nodules. Leaching experiments showed that surface sediments covered with big or medium-sized nodules are enriched in mobilizable Mn. Our deep oxygen measurements and pore-water data suggest that hydrogenetic and oxic-diagenetic processes control the present-day nodule growth at these sites, since free manganese from deeper sediments is unable to reach the sediment surface. We propose that the observed strong lateral contrasts in nodule size and abundance are sensitive to sedimentation rates, which in turn, are controlled by small-scale variations in seafloor topography and bottom-water current intensity.

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

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

Chemical and mineral compositions of basalts and volcanic glasses from DSDP Sites 65-483 and 65-485

Major and rare earth element (REE) data for basalts from Holes 483, 483B, and 485A of DSDP Leg 65, East Pacific Rise, mouth of the Gulf of California, support a simple fractional crystallization model for the genesis of rocks from this suite. The petrography and mineral chemistry (presented in detail elsewhere) provide no evidence for magma mixing, but rather a simple multistage cooling process. Based on its lowest TiO2 content (0.88%), FeO*/MgO ratio (0.95 with total Fe as FeO), and Mg# (100 Mg/Mg + Fe" = 70), sample 483-17-2-(78-83) has been selected as the most primitive primary magma of the samples analyzed. This is supported by the REE data which show this sample has the lowest total REE content, a La/Sm_cn (chondrite-normalized) = 0.36, and Eu/Sm_cn = 1.05. Because other samples analyzed have higher SiO2, lower Mg#, and a negative Eu anomaly (Eu/Sm_cn as low as 0.89), they are most likely derivative magmas. Wright-Doherty and trace element modelling support fractional crystallization of 14.1% plagioclase (An88), 6.7% olivine (Fo86), and 4.7% clinopyroxene (Wo41En49Fs10) from 483-17-2-(78-83) to form the least differentiated sample with Mg# = 63. The La/Sm_cn of this derivative magma is almost identical to the parent magma (0.35 to 0.36), but the other samples have higher La/Sm_cn (0.45 to 0.51), more total REE, and lower Mg# (60 to 56). Both Wright-Doherty and trace element modelling indicate that the primary magma chosen cannot produce these more evolved samples. For the major elements, the TiO2 and P2O5 are too low in the calculated versus the observed (1.38 to 1.90; 0.11 to 0.17, respectively, for example). Rayleigh fractionation calculates a lower La/Sm_cn and requires about 60% crystal removal versus 40% for the Wright-Doherty. These more evolved samples must be derived from a parent magma different from the one selected here and, unfortunately, not sampled in this study. A magma formed by a smaller degree of partial melting with slightly more residual clinopyroxene left in the mantle than for sample 483-17-2-(78-83) is required.

Geochemistry of igneous rocks recovered from a transect across the Mariana Trough, arc, fore-arc, and trench, at DSDP Leg 60 Holes and DM17

Major and trace element analyses are presented for 110 samples from the DSDP Leg 60 basement cores drilled along a transect across the Mariana Trough, arc, fore-arc, and Trench at about 18°N. The igneous rocks forming breccias at Site 453 in the west Mariana Trough include plutonic cumulates and basalts with calc-alkaline affinities. Basalts recovered from Sites 454 and 456 in the Mariana Trough include types with compositions similar to normal MORB and types with calc-alkaline affinities within a single hole. At Site 454 the basalts show a complete compositional transition between normal MORB and calc-alkaline basalts. These basalts may be the result of mixing of the two magma types in small sub-crustal magma reservoirs or assimilation of calc-alkaline, arc-derived vitric tuffs by normal MORB magmas during eruption or intrusion. A basaltic andesite clast in the breccia recovered from Site 457 on the active Mariana arc and samples dredged from a seamount in the Mariana arc are calc-alkaline and similar in composition to the basalts recovered from the Mariana Trough and West Mariana Ridge. Primitive island arc tholeiites were recovered from all four sites (Sites 458-461) drilled on the fore-arc and arc-side wall of the trench. These basalts form a coherent compositional group distinct from the Mariana arc, West Mariana arc, and Mariana Trough calc-alkaline lavas, indicating temporal (and perhaps spatial?) chemical variations in the arc magmas erupted along the transect. Much of the 209 meters of basement cored at Site 458 consists of endiopside- and bronzite-bearing, Mg-rich andesites with compositions related to boninites. These andesites have the very low Ti, Zr, Ti/Zr, P, and rare-earthelement contents characteristic of boninites, although they are slightly light-rare-earth-depleted and have lower MgO, Cr, Ni, and higher CaO and Al2O3 contents than those reported for typical boninites. The large variations in chemistry observed in the lavas recovered from this transect suggest that diverse mantle source compositions and complex petrogenetic process are involved in forming crustal rocks at this intra-oceanic active plate margin.

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.

Planktonic foraminiferal abundance and flux in the Porcupine Seabight, Northeast Atlantic

Modern planktonic foraminifera collected with a sediment trap and subfossil assemblages from surface sediments from Galway Mound in the Porcupine Seabight off southwestern Ireland, northeastern Atlantic, were studied to show recent assemblage variations. The sediment trap operated from April to August 2004 and covers the spring bloom and early summer conditions with sampling intervals of 8 days. Eleven different species were recorded. Glorotalia hirsuta, Turborotalita quinqueloba and Globigerinita glutinata appeared predominately in spring. Neogloboquadrina incompta, Globigerina bulloides and Globorotalia inflata were abundant in spring and summer. The highest foraminiferal tests flux occured in June. The faunal composition was similar to subfossil assemblages from surface sediments, but the species proportions were different. This was mainly affected by the subtropical G. hirsuta, which was frequent in 2004 and rare in surface sediment samples and in earlier plankton collections from the southern Porcupine Seabight that were performed during the 1990s. The weight of deposited foraminifera is mainly influenced by spring bloom as indicated by sea-surface chlorophyll-a data. The top three-ranked species, G. hirsuta, N. incompta and G. bulloides contributed 87 % to the foraminiferal carbonate flux at Galway Mound. Foraminiferal carbonate and shell flux as well as the shell size revealed variations, which are related to lunar periodicity. The data infer a lunar pacing of reproduction for the main species as well as for G. glutinata and G. inflata, which was not recorded before.

Geochemistry and petrology of basalts from Celebes Sea

Major-, trace-, and rare-earth element analyses are presented from a suite of basaltic rocks from the basement of the Celebes Sea. The major elements and trace-elements were determined by X-ray fluorescence techniques, and the rare-earth elements were analyzed by instrumental neutron activation analysis. Compositionally the Celebes Sea basalts are very similar to typical normal mid-ocean ridge basalts, such as those described from the Indian Ocean triple junction. Petrogenetic modeling shows that all of the basalts analyzed can be formed by 10% to 20% partial melting of a light rare-earth element-depleted spinel lherzolite followed by fractional crystallization of mixtures of olivine, Plagioclase, and iron oxide. The Celebes Sea is interpreted as a fragment of the basement of the Jurassic Argo abyssal plain trapped during the Eocene to the north of Australia.

Chemical composition of sediments from DSDP Legs 45 and 71

Results of mineralogical and geochemical investigations of post-Middle Jurassic deposits of the Atlantic Ocean are based on materials of the Deep Sea Drilling Project. Comparative characteristics of primary matter for ''black shales'' are given. Exhalative origin of heavy metal accumulation in near-axial sedimentary deeps of the Mid-Atlantic Ridge (23°N) are shown. History of post-Middle Jurassic sedimentation is considered on the base of clay mineral-, clastic component-, trace and rare- chemical element studies.

Geochemistry and petrology of the volcanic rocks from the Sulu Sea

Major-, trace-, and rare-earth element analyses of the basaltic rocks recovered from the basement of the Sulu Sea and of lithic clasts from the pyroclastic unit representing the acoustic basement of the Cagayan Ridge, are presented. The major and trace elements were measured by X-ray fluorescence techniques, and rare-earth elements by instrumental neutron activation analysis. These data show that the Sulu Sea basalts are back-arc tholeiites and the lithic clasts are basalts, basaltic andesites, and andesites typical of volcanic arc suites erupted on continental crust. Petrogenetic modeling is used to show that the Sulu Sea basalts were derived from a heterogeneous mantle, probably representing subcontinental lithosphere, with contributions from a subduction component. The Sulu Sea is interpreted as a back-arc basin formed by rifting of an Oligocene to early Miocene volcanic arc leaving the Cagayan Ridge as a remnant arc. This event occurred during northward subduction of the Celebes Sea basement beneath the Oligocene to early Miocene arc.

Geochemistry and petrogenesis of basalts from DSDP Leg 92 holes

Basalts recovered on DSDP Leg 92 include all the major basalt types so far recovered from the ocean crust of the eastern Pacific. Basalts from Holes 597, 597A, 597B, 597C, and 599B are tholeiites exhibiting all the mineralogical and geochemical characteristics of N-type mid-ocean ridge basalts (MORB). Fragments of ferrobasalts and alkali basalts were also obtained, however, from Holes 60IB and 602B, respectively. Hole 597C, which penetrated 91 m into basement and is the deepest hole so far drilled in fast-spreading crust, yielded basalts that can be divided into three major lithologic units. The lowest unit, Unit III, contains modal olivine and comprises basalts which, at about 8 to 10% MgO, are as basic as any sampled from fast-spreading crust. The middle unit, Unit II, is the most evolved; its basalts are olivine free and contain between 6 and 7.5% MgO. The upper unit, Unit I, is intermediate in composition between Units II and III; it is characterized by both modal olivine and glomerocrysts made up of plagioclase and rare olivine. Unit I is probably a massive flow, whereas Units II and III may be massive flows or sills. The basalts appear to have undergone three stages of alteration ("deuteric," "relatively reducing," and "oxidizing"), the intensity of alteration decreasing markedly downcore. Hole 597B, at 26.4 m of basement penetration the only other "deep" hole, contains just one lithologic unit, which closely resembles Unit I of Hole 597C. Petrogenetic modeling reveals that the three lithologic units in Hole 597C are cogenetic and that they were derived from a depleted mantle source similar to the source of the tholeiites and ferrobasalts sampled in other holes; the alkali basalts are the only rocks derived from enriched mantle. Lavas of Unit III probably lay on the olivine-plagioclase cotectic, whereas the other lavas lay on an olivine-plagioclase-clinopyroxene peritectic. Some 60% of closed-system crystallization is needed to generate the most-evolved from the last-fractionated tholeiite, and a further 50% crystallization (80% overall) is needed to generate the ferrobasalts. Xenocrysts of calcic plagioclase and pseudomorphosed olivine in tholeiites from Hole 597B and Unit I of Hole 597C, and in the ferrobasalts from Hole 601B, provide evidence, however, that some magma mixing may have taken place.