Mineralogy and geochemistry of sulfide minerals and bulk rocks from ODP Hole 176-735B

Ocean Drilling Program (ODP) Leg 176 built upon the work of ODP Leg 118 wherein the 500-m section that was sampled represented the most complete recovery of an intact portion of lower oceanic crust ever described. During Leg 176, we deepened Hole 735B to >1500 m below seafloor in an environment where gabbroic rocks have been tectonically exposed at the Southwest Indian Ridge. This new expedition extended the remarkable recovery (>85%) that allowed unprecedented investigations into the nature of the lower oceanic crust as a result of Leg 118. Sulfide mineral and bulk rock compositions were determined from samples in the 1000-m section of oceanic gabbros recovered during Leg 176. The sulfide assemblage of pyrrhotite, chalcopyrite, pentlandite, and troilite is present throughout this section, as it is throughout the 500-m gabbroic section above that was sampled during Leg 118. Troilite is commonly present as lamellae, and the only interval where troilite was not observed is from the uppermost 150 m of the section sampled during Leg 118, which is intensely metamorphosed. The common presence of troilite indicates that much of the sulfide assemblage from Hole 735B precipitated from a magmatic system and subsequently underwent low-temperature reequilibration. Evaluation of geochemical trends in bulk rock and sulfides indicates that the combined effects of olivine accumulation in troctolites and high pentlandite to pyrrhotite ratios account for the sporadic bulk rock compositions high in Ni. Bulk rock and sulfide mineral geochemical indicators that are spatially coincident with structural and physical properties anomalies indicate a heretofore unrecognized lithologic unit boundary in this section. Platinum-group element (PGE) compositions were also determined for 36 samples from throughout the section that were recovered during Leg 176. Whereas most samples had low (<0.4 ppb) PGE concentrations, rare samples had elevated PGE values, but no unique common trend between these samples is evident.

Composition and alteration of volcanic rocks of ODP Hole 119-738C

During ODP Leg 119 one basement hole was drilled at Site 738, on the Southern Kerguelen Plateau. The 38.2 m of basement rocks drilled comprises three basaltic aa-lava flows with basal and top breccias, overlain by Turanian marine carbonates. Site 738 basalts probably erupted near a fracture zone, and were emplaced during the plateau-forming stage of Kerguelen Plateau evolution under quiet, subaerial to shallow water conditions. The basalts are T-MORB, chemically resembling Mesozoic continental flood basalts of the southern hemisphere. Two slightly different magma batches are distinguished by Fe, Ti, Al, Zr, and REE concentrations. Prior to eruption, the magmas had undergone significant olivine and some clinopyroxene fractionation. Incompatible and immobile trace element concentrations and ratios point to a veined upper mantle source, where a refractory mineral assemblage retains Nb, Ta, and the HREE. The basaltic melts derived from this regionally veined, enriched upper mantle have high LREE, and especially Ba and Th concentrations and bear the DUPAL isotopic signature gained from deep- seated, recycled, old oceanic(?) crust. A saponite-celadonite secondary mineral assemblage confines the alteration temperature to <170°C. Alteration is accompanied by net gains of H2O, CO2, K2O, and Rb, higher oxidation, minor Na2O, SiO2 gains, and losses of V and CaO. Released Ca, together with Ca from seawater, precipitated as calcite in veins and vesicles, plumbed the circulation system and terminated the rock/open seawater interaction.

Geochemistry and isotopic ratios of samples from the Tiger gabbroic complex, Northern Victoria Land, Antarctica

Subduction related mafic/ultramafic complexes marking the suture between the Wilson Terrane and the Bowers Terrane in northern Victoria Land (Antarctica) are well-suited for evaluating the magmatic and structural evolu- tion at the Palaeo-Pacific continental margin of Gondwana. One of these intru- sions is the "Tiger Gabbro Complex" (TGC), which is located at the southern end of the island-arc type Bowers Terrane. The TGC is an early Palaeozoic island-arc related layered igneous complex characterized by extraordinarly fresh sequences of ultramafic, mafic and evolved lithologies and extensive development of high-temperature high-strain zones. The goal of the present study is to establish the kinematic, petrogenetic and temporal development of the TGC in order to evaluate the magmatic and structural evolution of the deep crustal roots of this Cambrian-aged island-arc. Fieldwork during GANOVEX X was carried out to provide insight into: (i) the spatial relations between the different igneous lithologies of the TGC, (ii) the nature of the contact between the TGC and Bowers Terrane, and (iii) the high-temperature shear zones exposed in parts of the TGC. Here, we report the results of detailed field and petrological observations combined with new geochronological data. Based on these new data, we tentatively propose a petrogenetic-kinematic model for the TGC, which involves a two-phase evolution during the Ross orogeny. These phases can be summarized as: (i) an early phase (maximum age c. 530 Ma) involving tectono-magmatic processes that were active at the deep crustal level represented by the TGC within the Bowers island arc and within a general NE-SW directed contractional regime and (ii) a late phase (maximum age c. 490 Ma) attributed to the late Ross orogenic intrusion of the TGC into the higher-crustal metasedimentary country rocks of the Bowers Terrane under NE-SW directed horizontal maximum stress and subsequent cooling.

Geochemistry at DSDP Leg 82 Holes

The nine holes (556-564) drilled during DSDP Leg 82 in a region west and southwest of the Azores Platform (Fig. 1) exhibit a wide variety of chemical compositions that indicate a complex petrogenetic history involving crystal fractionation, magma mixing, complex melting, and mantle heterogeneity. The major element chemistry of each hole except Hole 557 is typical of mid-ocean ridge basalts (MORBs), whereas the trace element and rare earth element (REE) abundances and ratios are more variable, and show that both depleted Type I and enriched Type II basalts have been erupted in the region. Hole 556 (30-34 Ma), located near a flow line through the Azores Triple Junction, contains typically depleted basalts, whereas Hole 557 (18 Ma), located near the same flow line but closer to the Azores Platform, is a highly enriched FeTi basalt, indicating that the Azores hot-spot anomaly has existed in its present configuration for at least 18 Ma, but less than 30-34 Ma. Hole 558 (34-37 Ma), located near a flow line through the FAMOUS and Leg 37 sites, includes both Type I and II basalts. Although the differences in Zr/Nb and light REE/heavy REE ratios imply different mantle sources, the (La/Ce)ch (>1) and Nd isotopic ratios are almost the same, suggesting that the complex melting and pervasive, small-scale mantle heterogeneity may account for the variations in trace element and REE ratios observed in Hole 558 (and FAMOUS sites). Farther south, Hole 559 (34-37 Ma), contains enriched Type II basalts, whereas Hole 561 (14-17 Ma), located further east near the same flow line, contains Type I and II basalts. In this case, the (La/Ce)ch and Nd isotopic ratios are different, indicating two distinct mantle sources. Again, the existence along the same flow line of two holes exhibiting such different chemistry suggests that mantle heterogeneity may exist on a more pervasive and transient smaller scale. (Hole 560 was not sampled for this study because the single basalt clast recovered was used for shipboard analysis.) All of the remaining three holes (562, 563, 564), located along a flow line about 100 km south of the Hayes Fracture Zone (33°N), contain only depleted Type I basalts. The contrast in chemical compositions suggests that the Hayes Fracture Zone may act as a "domain" boundary between an area of fairly homogeneous, depleted Type I basalts to the south (Holes 562-564) and a region of complex, highly variable basalts to the north near the Azores hot-spot anomaly (Holes 556-561).

Geochemistry of basalts from ODP Hole 113-690C

Basalts from Maud Rise, Weddell Sea, are vesicular and olivine-phyric. Major, trace, and rare earth element concentrations are similar to those of alkali basalts from ocean islands and seamounts. The rocks are low in MgO, Cr, Ni, and Sc, and high in TiO2, K2O, P2O5, Zr, and LREE contents. The abundance of "primary" biotite and apatite in the matrix indicates the melting of a hydrous mantle. Prevalence of olivine and absence of plagioclase in the rocks suggests that the volatile in the melt was an H2O-CO2 mixture, where H2O was <0.5. Mantle derived xenocrysts in the basalt include corroded orthopyroxene, chromite, apatite, and olivine. Olivine (Fo90) is too magnesian to be in equilibrium with the basalts, as they contain only 5-6 wt% MgO. Based on the presence of mantle xenocrysts, the high concentration of incompatible elements, the spatial and chemical affinity with other ocean island basalts from the area, and the relative age of the basalt (overlain by late Campanian sediments), it is suggested that Maud Rise was probably generated by hot-spot activity, possible during a ridge crest jump prior to 84 Ma (anomaly 34 time). Iddingsite, a complex intergrowth of montmorillonite and goethite, is the major alteration product of second generation olivine. It is suggested that iddingsite crystallized at low temperatures (<200°C) from an oxidized fluid during deuteric alteration. Vesicles are commonly filled by zeolites which have been replaced by K-feldspars.

Geochemical analysis of minerals from sediment core CRP-2 in the Ross Sea, Antarctica

Distribution patterns, petrography, whole-rock and mineral chemistry, and shape and fabric data are described for the most representative basement lithologies occurring as clasts (granule to bolder grain-size class) from the 625 m deep CRP-2/2A drillcore. A major change in the distribution pattern of the clast types occurs at c. 310 mbsf., with granitoid-dominated clasts above and mainly dolerite clasts below; moreover, compositional and modal data suggest a further division into seven main detrital assemblages or petrofacies. In spite of this variability, most granitoid pebbles consist of either pink or grey biotite±hornblende monzogranites. Other less common and ubiquitous lithologies include biotite syenogranite, biotite-hornblende granodiorite, tonalite, monzogranitic porphyries (very common below 310 mbsf), microgranite, and subordinately, monzogabbro, Ca-silicate rocks, biotite-clinozoisite schist and biotite orthogneiss (restricted to the pre-Pliocene strata). The ubiquitous occurrence of biotite±hornblende monzogranite pebbles in both the Quaternary-Pliocene and Miocene-Oligocene sections, apparently reflects the dominance of these lithologies in the onshore basement, and particularly in the Cambro-Ordovician Granite Harbour Igneous Complex which forms the most extensive outcrop in southern Victoria Land. The petrographical features of the other CRP-2/2A pebble lithologies are consistent with a supply dominantly from areas of the Transantarctic Mountains facing the CRP-2/2A site, and they thus provide further evidence of a local provenance for the supply of basement clasts to the CRP-2/2A sedimentary strata.

Analysis of the iron oxide assemblages in the ANDRILL AND-1B drill core, Ross Sea, Antarctica

The AND-1B drill core recovered a 13.57 million year Miocene through Pleistocene record from beneath the McMurdo Ice Shelf in Antarctica (77.9°S, 167.1°E). Varying sedimentary facies in the 1285 m core indicate glacial-interglacial cyclicity with the proximity of ice at the site ranging from grounding of ice in 917 m of water to ice free marine conditions. Broader interpretation of climatic conditions of the wider Ross Sea Embayment is deduced from provenance studies. Here we present an analysis of the iron oxide assemblages in the AND-1B core and interpret their variability with respect to wider paleoclimatic conditions. The core is naturally divided into an upper and lower succession by an expanded 170 m thick volcanic interval between 590 and 760 m. Above 590 m the Plio-Pleistocene glacial cycles are diatom rich and below 760 m late Miocene glacial cycles are terrigenous. Electron microscopy and rock magnetic parameters confirm the subdivision with biogenic silica diluting the terrigenous input (fine pseudo-single domain and stable single domain titanomagnetite from the McMurdo Volcanic Group with a variety of textures and compositions) above 590 m. Below 760 m, the Miocene section consists of coarse-grained ilmenite and multidomain magnetite derived from Transantarctic Mountain lithologies. This may reflect ice flow patterns and the absence of McMurdo Volcanic Group volcanic centers or indicate that volcanic centers had not yet grown to a significant size. The combined rock magnetic and electron microscopy signatures of magnetic minerals serve as provenance tracers in both ice proximal and distal sedimentary units, aiding in the study of ice sheet extent and dynamics, and the identification of ice rafted debris sources and dispersal patterns in the Ross Sea sector of Antarctica.

Chemical composition of sediments from DSDP Site 223, Indian Ocean

Detailed major- and trace-element chemistry is presented for 41 sediment samples from DSDP Site-223 borehole cores. A marked change in chemical (and mineralogical) character is shown at the end of the Early Miocene Epoch which relates to tectonic events and associated changes in sedimentary regime. Enrichment in the contents of such elements as Mg, Cr and Ni compared with average values for fine-grained sediments occurs throughout the sequence and is particularly marked in the upper group of samples. A basic-ultrabasic provenance is suggested - the Oman ophiolites. Leaching with combined acid-reducing agent indicated typical lithogenous-character ordering for the elements and emphasised the enrichment of Mg, Cr, Ni (and Li, Cu, Zn, Pb, Fe and Ti) over values for near-shore muds and terrigenous material. Factor analysis on the bulk chemical data identifies the main lithogenous and biogenous components, subdividing the latter. It separates the upper and lower group of chemically dissimilar sediments and delineates a Mn-hydroxide phase. It also shows the essentially independent roles of Na, Ba and P.

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

(Table 1) Chemical composition of volcanic rocks from the Mariisky sequence and extrusive vent rocks of the Mary Cape, Schmidt Peninsula (North Sakhalin)

Early Cretaceous volcanic rocks of the Mariisky sequence and Early Cenozoic extrusive-vent rocks of the Mary Cape are exposed at the most northwest of the Schmidt Peninsula, North Sakhalin. In chemical composition, all the rocks are subdivided into four groups. Three groups include volcanic rocks of the Mariisky sequence, which consists, from bottom to top, of calc-alkaline rocks, transitional calc-alkaline-tholeiite rocks, and incompatible element-depleted tholeiites. These rocks show subduction geochemical signatures and are considered as a fragment of the Moneron-Samarga island arc system. Trace-element modeling indicates their derivation through successive melting of a garnet-bearing mantle and garnet-free shallower mantle sources containing amphibole; pyroxene; and, possibly, spinel. The mixed subduction and intra-plate characteristics of the extrusive vent rocks of the Mary Cape attest to their formation in a transform continental margin setting.