Mineralogy and geochemistry at DSDP Leg 64 Holes

At DSDP Site 477, late Quaternary diatomaceous muds and delta-derived silty-sand turbidites at 2000 meters water depth have been extensively and progressively altered by a deep-seated heat source beneath a sill. Bulk petrologic and microprobe analyses have identified a crudely zoned paragenesis within 260 meters sub-bottom which ranges from unaltered to slightly altered oozes (0-50 m), anhydrite-dolomite claystones (105-125 m), illite-chlorite-pyrite claystones (125-140 m), chlorite-pyrite-calcite-carbonaceous claystones with traces of K-feldspar, albite, epidote (140-190 m), and chlorite-epidote-quartz-albite-pyrrhotite-sphene sandstone (190-260 m). Several petrologic features suggest rapid processes of ocean floor metamorphism: (1) friable and porous textures, (2) abundant relict grains with overgrowths, (3) idiomorphic habits on epidotes, feldspars, and quartz, and (4) a steep gradient in levels of alteration. Many aspects of this hydrothermal assemblage are similar to hydrothermally metamorphosed sandstones of the Cerro Prieto, Mexico, geothermal area.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Geochemistry of tephra from the Taupo Volcanic Zone

The Taupo Volcanic Zone (TVZ), central North Island, New Zealand, is the most frequently active Quaternary rhyolitic system in the world. Silicic tephras recovered from Ocean Drilling Programme Site 1123 (41°47.16'S, 171°29.94'W; 3290 m water depth) in the southwest Pacific Ocean provide a well-dated record of explosive TVZ volcanism since ~1.65 Ma. We present major, minor and trace element data for 70 Quaternary tephra layers from Site 1123 determined by electron probe microanalysis (1314 analyses) and laser ablation inductively coupled plasma mass spectrometry (654 analyses). Trace element data allow for the discrimination of different tephras with similar major element chemistries and the establishment of isochronous tie-lines between three sediment cores (1123A, 1123B and 1123C) recovered from Site 1123. These tephra tie-lines are used to evaluate the stratigraphy and orbitally tuned stable isotope age model of the Site 1123 composite record. Trace element fingerprinting of tephras identifies ~4.5 m and ~7.9 m thick sections of repeated sediments in 1123A (49.0-53.5 mbsf [metres below seafloor]) and 1123C (48.1-56.0 mbsf), respectively. These previously unrecognised repeated sections have resulted in significant errors in the Site 1123 composite stratigraphy and age model for the interval 1.15-1.38 Ma and can explain the poor correspondence between d18O profiles for Site 1123 and Site 849 (equatorial Pacific) during this interval. The revised composite stratigraphy for Site 1123 shows that the 70 tephra layers, when correlated between cores, correspond to ~37-38 individual eruptive events (tephras), 7 of which can be correlated to onshore TVZ deposits. The frequency of large-volume TVZ-derived silicic eruptions, as recorded by the deposition of tephras at Site 1123, has not been uniform through time. Rather it has been typified by short periods (25-50 ka) of intense activity bracketed by longer periods (100-130 ka) of quiescence. The most active period (at least 1 event per 7 ka) occurred between ~1.53 and 1.66 Ma, corresponding to the first ~130 ka of TVZ rhyolitic magmatism. Since 1.2 Ma, ~80% of tephras preserved at Site 1123 and the more proximal Site 1124 were erupted and deposited during glacial periods. This feature may reflect either enhanced atmospheric transport of volcanic ash to these sites (up to 1000 km from source) during glacial conditions or, more speculatively, that these events are triggered by changes in crustal stress accumulation associated with large amplitude sea-level changes. Only 8 of the ~37-38 Site 1123 tephra units (~20%) can be found in all three cores, and 22 tephra units (~60%) are only present in one of the three cores. Whether a tephra is preserved in all three cores does not have any direct relationship to eruptive volume. Instead it is postulated that tephra preservation at Site 1123 is 'patchy' and influenced by the vigorous nature of their deposition to the deep ocean floor as vertical density currents. At this site, at least 5 cores would need to have been drilled within a proximity of 10's to 100's of metres of each other to yield a >99% chance of recovering all the silicic tephras deposited on the ocean surface above it in the past 1.65 Ma.

Petrology of basalts from DSDP Hole 66-487

Basaltic rocks recovered at the Middle America Trench area off Mexico are typical plagioclase-olivine phyric abyssal tholeiites containing less than 0.2 wt.% K2O. Phenocrysts of plagioclase and olivine usually make up the aggregate. Plagioclase phenocrysts are Ca-rich and up to An90. Olivine phenocrysts, which are always attached to plagioclase phenocrysts, are magnesian, Fo88 to Fo89, and contain 0.2 to 0.3 wt. % of NiO. Plagioclase phenocrysts contain numerous glass inclusions with the Mg/Mg+Fe atomic ratio of 0.70 to 0.73, which is distinctly higher than the same ratio of the bulk rock (0.62-0.63). Olivine of Fo88 to Fo89 is equilibrated with the liquid with an Mg/Mg+Fe atomic ratio of about 0.7, assuming the KDMg-Fe between liquid and olivine of 0.3. Small droplets of glass within glass inclusions in plagioclase are more enriched in K2O and volatiles than the host glass. This enrichment may have been caused by the extraction of Al2O3 as plagioclase from the trapped liquid and implies its immiscibility. Aggregates of plagioclase with small amounts of olivine may have been floated from more primitive magma with an Mg/Mg+Fe atomic ratio of about 0.7, judging from the chemical characteristics mentioned above. Flotation must have occurred at relatively high pressure. Large crystals of plagioclase and smaller crystals of olivine are xenocryst rather than phenocryst. Parental magma of Leg 66 basalt was high-MgO olivine tholeiite.

Geochemistry of ash layers from the Bonin Forearc

Many ash-rich layers, varying from a few millimeters to several centimeters thick, were identified in the sedimentary sequences penetrated during Ocean Drilling Program Leg 125 at Sites 782, 784, and 786, located about 400 to 500 km south of Tokyo in the Bonin forearc. The total age range of the ash layers is from Eocene to Pleistocene, although not all sites cover this full span. The ashes consist of vitric, microlite-bearing, and crystal-rich components; the glassy shards are typically highly vesicular, with elongate, flattened bubbles. The dominant crystalline phases are orthopyroxene, clinopyroxene, and plagioclase. The major-element compositions of individual vitric shards collected from selected layers of Holes 782A, 784A, and 786A were determined by electron microprobe analyses; particular care was taken to ensure that the analytical results were not compromised by electron beam damage to the glasses. Compositions range from basalt through andesite and dacite to rhyolite and generally belong to a tholeiitic, low-K suite. There is no indication of any regular secular change during the evolution of the Bonin arc from tholeiitic through calc-alkalic to alkali compositions with time. In Holes 782A and 784A, some high-K rhyolite compositions of late Miocene and Pleistocene age are present. A clear chemical distinction has existed since arc inception between the source(s) of these ashes and the upper mantle source(s) tapped during construction of the igneous basement that formed the forearc.

Geochemistry and petrographic characters at DSDP Leg 58 Holes

Refractive index and chemical composition were determined for glass shards contained in more than 100 tephra layers in DSDP Leg 58 sediment cores collected in the Shikoku Basin, North Philippine Sea. The refractive index is consistent with chemical composition. Refractive index and total iron show a linear relationship. Tephra in Pleistocene and Pliocene sediments is mostly rhyolitic and dacitic (non-alkali), whereas tephra in the Miocene shows wide composition variations in the eastern part of the basin. Basaltic tephra is recognized in Miocene sediments at Sites 443 and 444, but not at Site 442, west of the other two sites. This indicates that the basaltic tephra came from eruption relatively close to those drill sites (perhaps the Kinan Seamounts and the Shichito-Iwo Jima volcanic arc), although the exact source has not been identified.

Geochemistry of ODP Hole 183-1137A basalts

The Kerguelen Plateau and Broken Ridge in the southern Indian Ocean together represent one of the most voluminous large igneous provinces (LIPs) ever emplaced on Earth. A scientific objective of Ocean Drilling Program (ODP) Leg 183 was to constrain the post-melting magma evolution of Kerguelen Plateau magmas. In an effort to better understand this evolution, isotopic and trace element analysis of individual plagioclase crystals hosted within two Kerguelen Plateau basalts recovered from Elan Bank were undertaken. Previous whole-rock studies established that the two host basalts investigated in this study are samples of crustally contaminated (lower group) and relatively uncontaminated (upper group) basalt. Plagioclase phenocrysts from the uncontaminated basalt are dominantly normal zoned and exhibit a 87Sr/86SrI range of 0.704845-0.704985, which overlaps uncontaminated group whole-rock values previously reported. Plagioclase crystals from the contaminated basalt are dominantly reverse zoned and exhibit a 87Sr/86SrI range of 0.705510-0.705735, which all lie within contaminated group whole-rock values previously reported. There are no systematic within crystal core to rim variations in 87Sr/86SrI from either group, with the exception that contaminated group crystal rims have overall less radiogenic 87Sr/86SrI than other zones. These observations indicate that crustal assimilation occurred before the formation of Unit 10 plagioclase phenocrysts, which is supported by parent magma trace element abundance data inverted using carefully calculated partition coefficients. Trace element diffusion modeling indicates that the upper group basalt (Unit 4) experienced a more vigorous eruptive flux than the lower group basalt (Unit 10). We suggest that plagioclase phenocrysts in both the upper and lower group basalts originated from the shallowest section of what was likely a complex magma chamber system. We contend that the magmatic system contained regions of extensive plagioclase-dominated crystal mush. Crustal assimilation was not a significant ongoing process in this portion of the Elan Bank magmatic system. Both basalts exhibit compelling evidence for remobilization and partial resorption of crystalline debris (e.g., reverse zoned crystals, glomerocrysts). We suggest Unit 4 and 10 magmas ascended different sections of the Elan Bank magma system, where the Unit 10 magmas ascended a section of the magma system that penetrated a stranded fragment of continental crust.

Petrology at DSDP Leg 66 Holes

The sandstone petrology of Leg 66 samples provides insights into changes through time in the geology of the source regions along the Guerrero portion of the Middle America continental margin. This in turn constrains possible models of the evolution of the Middle America Trench (e.g., de Czerna, 1971; Malfait and Dinkleman, 1972; Karig, 1974). Primarily medium-grained sands and sandstones, representing the widest variety available of trench/trench slope settings and ages, were analyzed in both light and heavy mineral studies. Standard techniques were used as much as possible in order to compare results from other margins and from ancient rocks.

Geochemistry of Hawaiian volcanics

The "Ko'olau" component of the Hawaiian mantle plume represents an extreme (EM1-type) end member of Hawaiian shield lavas in radiogenic isotope space, and was defined on the basis of the composition of subaerial lavas exposed in the Makapu'u section of Ko'olau Volcano. The 679 m-deep Ko'olau Scientific Drilling Project (KSDP) allows the long-term evolution of Ko'olau Volcano to be reconstructed and the longevity of the "Ko'olau" component in the Hawaiian plume to be tested. Here, we report triple spike Pb isotope and Sr and Nd isotope data on KSDP core samples, and rejuvenation stage Honolulu Volcanics (HV) (together spanning ~2.8 m.y.), and from ~110 Ma basalts from ODP Site 843, thought to be representative of the Pacific lithosphere under Hawai'i. Despite overlapping ranges in Pb isotope ratios, KSDP and HV lavas form two distinct linear arrays in 208Pb/204Pb-206Pb/204Pb isotope space. These arrays intersect at the radiogenic end indicating they share a common component. This "Kalihi" component has more radiogenic Pb, Nd, Hf, but less radiogenic Sr isotope ratios than the "Makapu'u" component. The mixing proportions of these two components in the lavas oscillated through time with a net increase in the "Makapu'u" component upsection. Thus, the "Makapu'u" enriched component is a long-lived feature of the Hawaiian plume, since it is present in the main shield-building stage KSDP lavas. We interpret the changes in mixing proportions of the Makapu'u and Kalihi components as related to changes in both the extent of melting as well as the lithology (eclogite vs. peridotite) of the material melting as the volcano moves away from the plume center. The long-term Nd isotope trend and short-term Pb isotope fluctuations seen in the KSDP record cannot be ascribed to a radial zonation of the Hawaiian plume: rather, they reflect the short length-scale heterogeneities in the Hawaiian mantle plume. Linear Pb isotope regressions through the HV, recent East Pacific Rise MORB and ODP Site 843 datasets are clearly distinct, implying that no simple genetic relationship exists between the HV and the Pacific lithosphere. This observation provides strong evidence against generation of HV as melts derived from the Pacific lithosphere, whether this be recent or old (100 Ma). The depleted component present in the HV is unlike any MORB-type mantle and most likely represents material thermally entrained by the upwelling Hawaiian plume and sampled only during the rejuvenated stage. The "Kalihi" component is predominant in the main shield building stage lavas but is also present in the rejuvenated HV. Thus this material is sampled throughout the evolution of the volcano as it moves from the center (main shield-building stage) to the periphery (rejuvenated stage) of the plume. The presence of a plume-derived material in the rejuvenated stage has significant implications for Hawaiian mantle plume melting models.

Geochemistry of phosphate and glauconites of ODP Leg 128 samples

Glauconites and phosphates have been detected in almost all investigated samples at Sites 798 (uppermost Miocene or lower Pliocene to Pleistocene) and 799 (early middle Miocene to Pleistocene). Autochthonous occurrences appear in very minor quantities (generally below 0.2%) throughout the drilled sequences, whereas allochthonous accumulations are limited to the lower Pliocene or uppermost Miocene sequence at Site 798 (glauconites) and to the upper and middle Miocene sequence at Site 799 (upper and middle Miocene: glauconites; middle Miocene: phosphates). X-ray fluorescence, microprobe, and bulk chemical analyses indicate high variabilities in cations and anions and generally low oxide totals. This is probably related to the substitution of phosphate and fluoride aniors by hydroxide and carbonate anions in phosphates and to the depletion of iron, aluminum, and potassium cations and the enrichment in hydroxide and crystal water in glauconites. Gradients in pore-water contents of dissolved phosphate and fluoride at Sites 798 and 799 suggest a depth of phosphate precipitation between 30 and 50 mbsf, with fluoride as the limiting element for phosphate precipitation at Site 798. Phosphate and fluoride appear to be balanced at Site 799. Crude extrapolations indicate that the Japan-Sea sediments may have taken up approximately 7.2*10**10 g P total/yr during the Neogene and Pleistocene. This amount corresponds to approximately 0.3% of the estimated present-day global transfer of phosphorus into the sediments and suggests that the Japan Sea constitutes an average sink for this element. The two main carriers of phosphorus into the present Japan Sea are the Tshushima and the Liman currents, importing approximately 6.6*10**10 g P and 5.7*10**10 g P per year, respectively. Bulk chemical analyses suggest that at least 36% of P total in the sediments is organically bound phosphorus. This rather high value, which corresponds to the measured Japan-Sea deep-water P organic/P total ratios, probably reflects rapid transport of organic phosphorus into the depth of the Japan Sea.

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.