Chemical and isotope composition of rocks from the Omgon Range, Western Kamchatka coastal area

Hypabyssal rocks of the Omgon Range, Western Kamchatka that intrude Upper Albian-Lower Campanian deposits of the Eurasian continental margin belong to three coeval (62.5-63.0 Ma) associations: (1) ilmenite gabbro-dolerites, (2) titanomagnetite gabbro-dolerites and quartz microdiorites, and (3) porphyritic biotite granites and granite-aplites. Early Paleocene age of ilmenite gabbro-dolerites and biotite granites was confirmed by zircon and apatite fission-track dating. Ilmenite and titanomagnetite gabbro-dolerites were produced by multilevel fractional crystallization of basaltic melts with, respectively, moderate and high Fe-Ti contents and contamination of these melts with rhyolitic melts of different compositions. Moderate- and high-Fe-Ti basaltic melts were derived from mantle spinel peridotite variably depleted and metasomatized by slab-derived fluid prior to melting. The melts were generated at variable depths and different degrees of melting. Biotite granites and granite aplites were produced by combined fractional crystallization of a crustal rhyolitic melt and its contamination with terrigenous rocks of the Omgon Group. The rhyolitic melts were likely derived from metabasaltic rocks of suprasubduction nature. Early Paleocene hypabyssal rocks of the Omgon Range were demonstrated to have been formed in an extensional environment, which dominated in the margin of the Eurasian continent from Late Cretaceous throughout Early Paleocene. Extension in the Western Kamchatka segment preceded the origin of the Western Koryakian-Kamchatka (Kinkil') continental-margin volcanic belt in Eocene time. This research was conducted based on original geological, mineralogical, geochemical, and isotopic (Rb-Sr) data obtained by the authors.

Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.

Late Cretaceous volcaniclastic rocks at DSDP Holes 74-525A and 74-528

Volcaniclastic rocks of Late Cretaceous age occur in four out of five sites (525, 527, 528, 529) drilled on the crest and the northwest flank of the Walvis Ridge during Leg 74. They are mostly interlayered with and overlie basement in the lowermost 10-100 m of the sedimentary section. Rocks from Holes 525A and 528 were studied megascopically and microscopically, by XRD, and XRF chemical analyses of whole-rock major and trace elements were undertaken. The dominant rock of Hole 528 volcaniclastics is a fine-grained (silt to fine sand), mostly matrix-bearing (partly matrix-rich) vitric "tuff," occurring as 5-110 cm thick, partly graded layers, some of which are distinctly bedded. Volcaniclastics of Hole 525A are generally richer in sanidine crystals. Most rocks contain some nonvolcanic clasts, chiefly foraminifers and lesser amounts of shallow-water fossil debris. Scoria shards, clasts of tachylite, and fine-grained basalts as well as chemical analyses suggest a basaltic to intermediate composition for most rocks of Hole 528, whereas volcaniclastics of Hole 525A are more silicic. The occurrence of tachylite and epiclastic, coarse-grained, basaltic clasts throughout the volcaniclastic sequence at Site 528 indicates shallow-water eruptions and perhaps even ocean island volcanism. The minor occurrence in Hole 528 of trachytic? pumice shards with phenocrysts of K-feldspar and the abundance of such shards in rocks from Hole 525A indicate Plinian eruptions characteristic of more mature stages of ocean island evolution. The sedimentary structures of volcaniclastic layers and their occurrence within deep sea calcareous oozes indicate a mass flow origin. Diagenetic alteration of the volcaniclastic rocks is pronounced, and four major stages of glass shard alteration are distinguished. Despite the effects of alteration and small-scale redistribution of elements and the admixture of nonvolcanic components, there were no drastic changes in the chemical composition of the rocks, except for pronounced increases in K and Rb and decreases in Ca and Fe. The basaltic volcaniclastic rocks very much resemble basement basalts in that they are moderately evolved tholeiites derived from an LIL-enriched mantle source with Zr/Nb ratios (Hole 528) of 5 to 6. This, in conjunction with the interbedding of volcaniclastic rocks and basement lavas, indicates contemporaneous seamount or island and basement volcanic activity involving magmas derived from similar sources.

Chemistry of various minerals of altered basalts from ODP Hole 111-504B

Basalts recovered from Hole 504B during ODP Leg 111 are more or less altered, but there is no sign of strong shear stress or widespread penetrative deformation; hence, they retain well their primary (igneous) structures and textures. The effect of alteration is recognized as the partial or total replacement of primary minerals (olivine, clinopyroxene, and plagioclase) by secondary minerals and as the development of secondary minerals in open spaces (e.g., veins, fractures, vugs, or breccia matrix). The secondary minerals include zeolite (laumontite and stilbite), prehnite, chlorite, epidote, Plagioclase (albite and/or oligoclase), amphibole (anthophyllite, cummingtonite, actinolite, and hornblende), sodic augite, sphene, talc, anhydrite, chalcopyrite, pyrite, Fe-Ti oxide, and quartz. Selected secondary minerals from several tens of samples were analyzed by means of an electron-probe microanalyzer; the results are presented along with brief considerations of their compositional features. In terms of the model basaltic system, the following two types of low-variance (three-phase) mineral assemblages were observed: prehnite-epidote-laumontite and prehnite-actinolite-epidote; both include chlorite, albite and/or oligoclase, sphene, and quartz. The mineral parageneses delineated by these low-variance mineral assemblages suggest that the metamorphic grade ranges from the zeolite facies to the prehnite-actinolite facies. The common occurrence of prehnite indicates that greenschist facies conditions were not attained even in the deepest level of Hole 504B, which, in a strict sense, contradicts the previous interpretation that the lower portion of Hole 504B suffered greenschist facies alteration.

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 Qeqertaa xenoliths

This study presents electron microprobe data for dunite xenoliths from a lamprophyre dyke located on the island of Qeqertaa, West Greenland. The minimum age of this dyke is Palaeoproterozoic and it experienced amphibolite facies metamorphism and deformation during that era. The samples consist of nearly 200 xenoliths with a size range of 0.5-8 cm. These dunite xenoliths have olivine Mg#, that range from 80.3 to 94.6 (n = 579) with a mean of 92.6. Orthopyroxene is found in three xenoliths and garnet in five others. The latter suggests the depth of the Qeqertaa xenolith suite to be near the diamond stability-field, which is substantiated by the finding of diamonds in bulk samples of the Qeqertaa dyke. This further indicates the presence of a lithospheric mantle domain dominated by high-Mg# dunite to this depth in Palaeoproterozoic time. Cr-rich spinel, in the 0.1-0.2 mm size range, is found within and between olivine grains in individual xenoliths. These Cr-spinels yield Fe-Mg exchange temperatures of 400-600°C. However, the presence of intermediate spinel compositions spanning the lower temperature solvus suggests that equilibration temperatures were >550°C. Fe3+#, expressed as 100xFe3+/(Fe3++Al+Cr)), is shown to be a useful parameter in order to screen for altered spinel (Fe3+#>10) with disturbed Mg# and Cr#. The screened spinel data (Fe3+#<10) show a distinctly different trend in terms of spinel Cr# versus Mg#, compared to unmetamorphosed xenoliths in Tertiary lavas and dikes from Ubekendt Ejland and Wiedemann Fjord, respectively, also located within the North Atlantic craton. This difference likely reflects amphibolite facies metamorphic resetting of the Qeqertaa xenolith suite by Fe-Mg exchange. Given the similarity of the Qeqertaa xenolith suite with the Ubekendt and Wiedemann suites, in terms of their olivine Mg# and spinel Cr# distribution, high-Mg# dunite is likely to be an important component of the subcontinental lithospheric mantle beneath the North Atlantic craton and appears to have spanned a vertical distance of at least 150 km in this region, even during the Palaeoproterozoic.

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 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 of the gabbroic lithosphere in IODP Holes 304-U1309D and 305-U1309D

IODP Hole U1309D (Atlantis Massif, Mid-Atlantic Ridge 30°N) is the second deepest hole drilled into slow spread gabbroic lithosphere. It comprises 5.4% of olivine-rich troctolites (~ > 70% olivine), possibly the most primitive gabbroic rocks ever drilled at mid-ocean ridges. We present the result of an in situ trace element study carried out on a series of olivine-rich troctolites, and neighbouring troctolites and gabbros, from olivine-rich intervals in Hole U1309D. Olivine-rich troctolites display poikilitic textures; coarse-grained subhedral to medium-grained rounded olivine crystals are included into large undeformed clinopyroxene and plagioclase poikiloblasts. In contrast, gabbros and troctolites have irregularly seriate textures, with highly variable grain sizes, and locally poikilitic clinopyroxene oikocrysts in troctolites. Clinopyroxene is high Mg# augite (Mg# 87 in olivine-rich troctolites to 82 in gabbros), and plagioclase has anorthite contents ranging from 77 in olivine-rich troctolites to 68 in gabbros. Olivine has high forsterite contents (82-88 in olivine-rich troctolites, to 78-83 in gabbros) and is in Mg-Fe equilibrium with clinopyroxene. Clinopyroxene cores and plagioclase are depleted in trace elements (e.g., Ybcpx ~ 5-11 * Chondrite), they are in equilibrium with the same MORB-type melt in all studied rock-types. These compositions are not consistent with the progressively more trace element enriched (evolved) compositions expected from olivine rich primitive products to gabbros in a MORB cumulate sequence. They indicate that clinopyroxene and plagioclase crystallized concurrently, after melts having the same trace element composition, consistent with crystallization in an open system with a buffered magma composition. The slight trace element enrichments and lower Cr contents observed in clinopyroxene rims and interstitial grains results from crystallization of late-stage differentiated melts, probably indicating the closure of the magmatic system. In contrast to clinopyroxene and plagioclase, olivine is not in equilibrium with MORB, but with a highly fractionated depleted melt, similar to that in equilibrium with refractory oceanic peridotites, thus possibly indicating a mantle origin. In addition, textural relationships suggest that olivine was in part assimilated by the basaltic melts after which clinopyroxene and plagioclase crystallized (impregnation). These observations suggest a complex crystallization history in an open system involving impregnation by MORB-type melt(s) of an olivine-rich rock or mush. The documented magmatic processes suggest that olivine-rich troctolites were formed in a zone with large magmatic transfer and accumulation, similar to the mantle-crust transition zone documented in ophiolites and at fast spreading ridges.

Chemical composition of glass inclusions from ODP Holes 157-953C and 157-956B

We report S concentrations and relative proportions of (SO4)2- and S2- in OL- and CPX-hosted glass inclusions and in host glassy lapilli from Miocene basaltic hyaloclastites drilled north and south of Gran Canaria during ODP Leg 157. Compositions of glass inclusions and lapilli resemble those of subaerial Miocene shield basalts on Gran Canaria and comprise mafic to more evolved tholeiitic to alkali basalt and basanite (10.3-3.7 wt.% MgO, 44.5-56.9 wt.% SiO2). Glass inclusions fall into three groups based on their S concentrations: a high-sulfur group (1050 to 5810 ppm S), an intermediate-sulfur group (510 to 1740 ppm S), and a low-sulfur group (<500 ppm S). The most S-rich inclusions have the highest and nearly constant proportion of sulfur dissolved as sulfate determined by electron microprobe measurements of SKa peak shift. Their average S6+/S_total value is 0.75+/-0.09, unusually high for ocean island basalt magmas. The low-sulfur group inclusions have low S6+/S_total ratios (0.08+/-0.05), whereas intermediate sulfur group inclusions show a wide range of S6+/S_total (0.05-0.83). Glassy lapilli and their crystal-hosted glass inclusions with S concentrations of 50 to 1140 ppm S have very similar S6+/S_total ratios of 0.36+/-0.06 implying that sulfur degassing does not affect the proportion of (SO4)2- and S2- in the magma. The oxygen fugacities estimated from S6+/S_total ratios and from Fe3+/Fe2+ ratios in spinel inclusions range from NNO-1.1 to NNO+1.8. The origin of S-rich magmas is unclear. We discuss (1) partial melting of a mantle source at relatively oxidized fO2 conditions, and (2) magma contamination by seawater either directly or through magma interaction with seawater-altered Jurassic oceanic crust. The intermediate sulfur group inclusions represent undegassed or slightly degassed magmas similar to submarine OIB glasses, whereas the low-sulfur group inclusions are likely to have formed from magmas significantly degassed in near-surface reservoirs. Mixing of these degassed magmas with stored volatile-rich ones or volatile-rich magma replenishing the chamber filled by partially degassed magmas may produce hybrid melts with strongly varying S concentrations and S6+/S_total ratios.