Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Geochemistry of the volcanic basement of ODP Hole 134-831B

The basement of Bougainville Guyot drilled at Site 831 consists of andesitic hyalobreccias derived from a submarine arc volcano. The volcanic sequence has been dated by K/Ar at approximately 37 Ma. The 121 m of andesitic hyalobreccias drilled in Hole 831B have been divided into five subunits of two types: one appears to be primary, and the other contains evidence of reworking and a subaerial clastic input. Variations are attributed to fluctuations in water depth. The distinctive hyalobreccias consist of andesitic blebs with chilled margins and peripheral fractures set in a chaotic greenish matrix that is mainly altered glass, with crystals similar to those in the blebs or clasts. Their formation is attributed to violent reaction of andesitic magma discharged into seawater, in perhaps the submarine equivalent of fire-fountaining. There was limited reworking by currents and debris flows on the flanks of the submarine volcano. The andesite shows no significant compositional variation in phenocryst phases throughout the drilled sequence and contains phenocrysts of plagioclase (An88-43), clinopyroxene (Ca44Mg46Fe10-Ca41Mg40Fe19), orthopyroxene (Ca4Mg79Fe17-Ca3Mg58Fe39), and titanomagnetite. There is a systematic change in volcanic composition with height in the section, from more mafic andesites at the base, to overlying more acid andesites, and strong evidence exists that magma mixing may have played a significant role in the genesis of these lavas. The andesites have affinities with the low-K arc tholeiite series. Trace element and isotopic systematics for these rocks indicate very minor involvement of a LILE- and 87Sr-enriched slab-derived fluid in their petrogenesis. This accords with the previous suggestion that Bougainville Guyot forms part of an Eocene proto-island arc developed along the southern side of the d'Entrecasteaux Zone, above a southward-dipping subduction zone.

Mineralogy and diagenesis of slope sediments at DSDP Leg 84 holes

The distribution and composition of minerals in the silt and clay fraction of the fine-grained slope sediments were examined. Special interest was focused on diagenesis. The results are listed as follows. (1) Smectite, andesitic Plagioclase, quartz, and low-Mg calcite are the main mineral components of the sediment. Authigenic dolomite was observed in the weathering zones of serpentinites, together with aragonite, as well as in clayey silt. (2) The mineralogy and geochemistry of the sediments is analogous to that of the andesitic rocks of Costa Rica and Guatemala. (3) Unstable components like volcanic glass, amphiboles, and pyroxenes show increasing etching with depth. (4) The diagenetic alteration of opal-A skeletons from etching pits and replacement by opal-CT to replacement by chalcedony as a final stage corresponds to the typical opal diagenesis. (5) Clinoptilolite is the stable zeolite mineral according to mineral stability fields; its neoformation is well documented. (6) The early diagenesis of smectites is shown by an increase of crystallinity with depth. Only the smectites in the oldest sediments (Oligocene and early Eocene) contain nonexpanding illite layers.

Major oxides, trace elements and rare earth elements of selected basalt samples at DSDP Hole 83-504B

DSDP Hole 504B is the deepest section drilled into oceanic basement, penetrating through a 571.5-m lava pile and a 209-m transition zone of lavas and dikes into 295 m of a sheeted dike complex. To define the basement composition 194 samples of least altered basalts, representing all lithologic units, were analyzed for their major and 26 trace elements. As is evident from the alteration-sensitive indicators H2O+, CO2, S, K, Mn, Zn, Cu, and the iron oxidation ratio, all rocks recovered are chemically altered to some extent. Downhole variation in these parameters enables us to distinguish five depth-related alteration zones that closely correlate with changes in alteration mineralogy. Alteration in the uppermost basement portion is characterized by pronounced K-uptake, sulfur loss, and iron oxidation and clearly demonstrates low-temperature seawater interaction. A very spectacular type of alteration is confined to the depth range from 910 to 1059 m below seafloor (BSF). Rocks from this basement portion exhibit the lowest iron oxidation, the highest H2O+ contents, and a considerable enrichment in Mn, S, Zn, and Cu. At the top of this zone a stockwork-like sulfide mineralization occurs. The chemical data suggest that this basement portion was at one time within a hydrothermal upflow zone. The steep gradient in alteration chemistry above this zone and the ore precipitation are interpreted as the result of mixing of the upflowing hydrothermal fluids with lower-temperature solutions circulating in the lava pile. Despite the chemical alteration the primary composition and variation of the rocks can be reliably established. All data demonstrate that the pillow lavas and the dikes are remarkably uniform and display almost the same range of variation. A general characteristic of the rocks that classify as olivine tholeiites is their high MgO contents (up to 10.5 wt.%) and their low K abundances (-200 ppm). According to their mg-values, which range from 0.60 to 0.74, most basalts appear to have undergone some high-level crystal fractionation. Despite the overall similarity in composition, there are two major basalt groups that have significantly different abundances and ratios of incompatible elements at similar mg-values. The majority of the basalts from the pillow lava and dike sections are chemically closely related, and most probably represent differentiation products of a common parental magma. They are low in Na2O, TiO2, and P2O5, and very low in the more hygromagmaphile elements. Interdigitated with this basalt group is a very rarely occurring basalt that is higher in Na2O, TiO2, P2O5, much less depleted in hygromagmaphile elements, and similar to normal mid-ocean ridge basalt (MORB). The latter is restricted to Lithologic Units 5 and 36 of the pillow lava section and Lithologic Unit 83 of the dike section. The two basalt groups cannot be related by differentiation processes but have to be regarded as products of two different parental magmas. The compositional uniformity of the majority of the basalts suggests that the magma chamber beneath the Costa Rica Rift reached nearly steady-state conditions. However, the presence of lavas and dikes that crystallized from a different parental magma requires the existence of a separate conduit-magma chamber system for these melts. Occasionally mixing between the two magma types appears to have occurred. The chemical characteristics of the two magma types imply some heterogeneity in the mantle source underlying the Costa Rica Rift. The predominant magma type represents an extremely depleted source, whereas the rare magma type presumably originated from regions of less depleted mantle material (relict or affected by metasomatism).

Geochemistry of basalts fropm DSDP Leg 65 basalts

Samples of basalt collected on Leg 65 near 22°N on the East Pacific Rise all display the depleted light rare-earth pattern of "normal" oceanic crust. Consequently the La/Ta ratio is close to 18, as opposed to the value of 9 associated with the flat or enriched patterns found along parts of the Mid-Atlantic Ridge and the Emperor Seamount chain. The Leg 65 samples are chemically similar to those from the CYAMEX area at 21 °N and to the Leg 54 samples from 9°N, suggesting homogeneity of the upper mantle under the northern part of the East Pacific Rise over a minimum distance of about 1500 km. The geochemistry of the rocks and their field relationships with respect to depth and distance from the axis of the Rise show no pattern of distribution linked to the degree of fractional crystallization and thus cast doubt on any possible model involving large, long-lived magma chambers at the axis of the Rise.

Mineralogy and chemical composition of ODP Sites 129-800 and 129-801

Sites 800 and 801 in the Pigafetta Basin allow the sedimentary history over the oldest remaining Pacific oceanic crust to be established. Six major deposition stages and events are defined by the main lithologic units from both sites. Mineralogical and chemical investigations were run on a large set of samples from these units. The data enable the evolution of the sediments and their depositional environments to be characterized in relation to the paleolatitudinal motion of the sites. The upper part of the basaltic crust at Site 801 displays a complex hydrothermal and alteration evolution expressed particularly by an ochre siliceous deposit comparable to that found in the Cyprus ophiolite. The oldest sedimentary cover at Site 801 was formed during the Callovian-Bathonian (stage 1) with red basal siliceous and metalliferous sediments similar to those found in supraophiolite sequences, and formed near an active ridge axis in an open ocean. Biosiliceous sedimentation prevailed throughout the Oxfordian to Campanian, with rare incursions of calcareous input during the middle Cretaceous (stages 2, 4, and 5). The biosiliceous sedimentation was drastically interrupted during the Aptian-Albian by thick volcaniclastic turbidite deposits (stage 3). The volcanogenic phases are pervasively altered and the successive secondary mineral parageneses (with smectites, celadonite, clinoptilolite, phillipsite, analcime, calcite, and quartz) define a "mineral stratigraphy" within these deposits. From this mineral stratigraphy, a similar lithologic layer is defined at the top of the Site 800 turbidite unit and the bottom of the Site 801 turbidite unit. Then, the two sites appear to have been located at the same distal distance from a volcanic source (hotspot). They crossed this locality, at about 10°S, at different times (latest Aptian for Site 800, middle Albian for Site 801). The Cretaceous siliceous sedimentation stopped during the late Campanian and was followed by deposition of Cenozoic pelagic red clay (stage 6). This deep-sea facies, which formed below the carbonate compensation depth, contains variable zeolite authigenesis in relation to the age of deposition, and records the global middle Cenozoic hiatus events. At the surface, the red clay from this part of the Pacific shows a greater detrital component than its equivalents from the central Pacific deep basins.

Chemical and isotopic compositions of sediments from DSDP Hole 21-204

The highly depleted intra-oceanic Tonga-Kermadec island arc forms an endmember of arc systems and a unique location in which to isolate the effects of the slab flux. High precision TIMS uranium, thorium, strontium, neodymium, and lead isotopes, along with complete major and trace element data, have been obtained on an extensive sample set comprising fifty-eight lavas along the arc as well as nineteen samples of the subducting sediments at DSDP site 204 just to the east of the Tonga-Kermadec trench. Ca/Ti and Al/Ti ratios extend from values appropriate to an N-MORB source in the southern Kermadecs to very high ratios in Tonga interpreted to reflect increasing degrees of depletion of the mantle wedge due to backarc basalt extraction. The isotope data emphasize the need for four components in the petrogenesis of the lavas: (1) the mantle wedge; (2) a component with elevated 207Pb/204Pb towards which the Kermadec and southern Tongan lavas extend; (3) a component characterised by high 206Pb/204Pb, Ta/Nd, and low 143Nd/144Nd observed only in the northernmost Tongan islands of Tafahi and Niuatoputapu; (4) a fluid component characterised by strong enrichments of Rb, Ba, U, K, Ph, and Sr, relative to Th, Zr, and the REE and producing large 238U excesses ((230Th/238U) = 0.8-0.5) in the more depleted lavas. The mantle wedge (Component 1) is isotopically similar to the source of the Lau BABB. Component 2 is average pelagic sediment on the downgoing Pacific plate as observed at DSDP sites 595/596 and in the upper sections of the sediment pile at DSDP site 204. Mass balance calculations indicate that less than 0.5% is recycled into the arc lavas; essentially all the subducted sediment is returned to the upper mantle (~0.03 km**3/yr). Exceptionally low concentrations of Ta and Nb relative to Th and the LREE requires that this sediment component is added as a partial melt which was in equilibrium with residual rutile or ilmenite. Component 3 is identified as volcaniclastics from the Louisville Ridge which comprise the lower 44 m of the sediment section intersected at DSDP site 204. These volcaniclastics are spatially restricted to the vicinity of the Louisville Ridge and provide a unique sediment tracer which can be used to show that it takes 4 Myr from the time of subduction to its first appearance in the arc lava signature. Component 4, the fluid contribution to the lava source is inferred to contribute ~1 ppm Rb, 10 ppm Ba, 0.02 ppm U, 600 ppm K, 0.2 ppm Ph, and 30 ppm Sr. It has 87Sr/86Sr = 0.7035 and 206Pb/204Pb = 18.5 and thus it is inferred to have been derived from dehydration of the subducting altered oceanic crust. U-Th isotope disequilibria reflect the time since fluid release from the subducting slab and a reference line through the lowest (230Th/232Th) lavas constrains this to be 30000-50000 yr. The U-Th and Th-Ra isotope systematics are decoupled, and it is suggested that Th-Ra isotope disequilibria record the time since partial melting and thus indicate rapid channelled magma ascent. Olivine gabbro xenoliths from Raoul are interpreted as cumulates to their host lavas with which they form zero age U-Th isochrons indicating that minimal time was spent in magma chambers. The subduction signature is not observed in lavas from the backarc island of Niuafo'ou. These were derived from partial melting of fertile peridotite at 130-160 km depth with melt rates around 0.0002 kg/m**3/yr.

Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.

Geochemistry at DSDP Leg 62 Holes

A total of 191 samples was collected for inorganic geochemical analyses from DSDP Holes 463, 464, 465, 465A, and 466. These samples were collected with two main goals. First, at least one sample was collected from each core, whenever possible, to document the general geochemical variability within lithologic units. Unfortunately, several lithologic units were inadequately sampled because of poor recovery, mostly due to the presence of chert. The least-sampled units are Units III in Hole 464 and Units IB and II in Hole 466. The second goal was to look for geochemical differences between contrasting lithologies within main lithologic units, particularly between cyclic interbeds of red and green limestone in Lithologic Unit II, Hole 463, and between olive, laminated limestone and gray, massive limestone in Lithologic Unit II, Hole 465A.

Mineralogy and geochemistry of Miocene tuff from ODP Hole 129-802A

Drilling at Ocean Drilling Program Site 802 in the central Mariana Basin, northwest Pacific Ocean, revealed an unexpected 222-m-thick sequence of well-cemented tuff of Miocene age. The deposits are unusual in that their source is presumably an unmapped seamount and they exhibit several peculiar petrological and mineralogical features. The well-developed secondary mineral sequence which includes analcime is rare in such relatively young, unburied deposits, in an area where there is little other evidence of hydrothermal activity. The massive tuff section also contains abundant fissure veins made of a rare silicate carbonate sulfate hydroxide hydrate of calcium, called thaumasite, which has not before been described in deep submarine deposits. The smectite-zeolite-thaumasite paragenesis coincides with the presence of chloride and calcium-enriched interstitial waters. The diagenetic evolution of the deposit appears to have been largely controlled by the depositional mode. The discharges of disaggregated and rejuvenated volcaniclasts seem to have been abrupt and repeated. The Miocene tuff at Site 802 thus provides new insights on the interactions between basaltic glass, biogenic phases, and seawater, in a specific deep-sea environment.

Petrology and geochemistry of silicified upper Miocene chalk at DSDP Site 69-504

Chert, Porcellanite, and other silicified rocks formed in response to high heat flow in the lower 50 meters of 275 meters of sediments at Deep Sea Drilling Project Site 504, Costa Rica Rift. Chert and Porcellanite partly or completely replaced upper Miocene chalk and limestone. Silicified rock occurs as nodules, laminae, stringers, and casts of burrows, and consists of quartz and opal-CT in varying amounts, associated with secondary calcite. The secondary silica was derived from dissolution of opal-A (biogenic silica), mostly diatom frustules and radiolarian tests. Temperature data obtained at the site indicate that transformation of opal-A to opal-CT began at about 50°C, and transformation from opal-CT to quartz at about 55°C. Quartz is most abundant close to basement basalts. These silica transformations occurred over the past 1 m.y., and took place so rapidly that there was incomplete ordering of opal-CT before transformation to quartz; opal-CT formed initially with an uncommonly wide d spacing. Quartz shows poor crystallinity. Chemical data show that the extensively silicified rocks consist of over 96% SiO2; in these rocks, minor and trace elements decreased greatly, except for boron, which increased. Low Al2O3 and TiO2 contents in all studied rocks preclude the presence of significant volcanic or terrigenous detritus. Mn content increases with depth, perhaps reflecting contributions from basalts or hydrothermal solutions. Comparisons with cherts from oceanic plateaus in the central Pacific point to a more purely biogenic host sediment for the Costa Rica Rift cherts, more rapid precipitation of quartz, and formation nearer a spreading center. Despite being closer to continental sources of ash and terrigenous detritus, Costa Rica Rift cherts have lower Al2O3, Fe2O3, and Mn concentrations.