(Table 1) Chemical composition and bulk densities of dolerites from ODP Hole 504B lower dikes

Chemical interactions between seawater and the oceanic crust have been widely investigated during recent years. However, most of these studies concern the uppermost volcanic part of the crust. The contribution of the underlying sheeted dike complex to the global budget of the oceans is inferred solely from some ophiolite studies and from the 500-m high-level dike section of DSDP/ODP 504B which was drilled in 1981. Hole 504B is the only place where a continuous and long (1260 m) section in the sheeted dike complex has been cored, and it is now regarded as a reference section for the upper oceanic crust. Many petrological and chemical data from these dolerites are available, including the relative proportions of veins, extensively altered adjacent rocks, and less altered 'host-rocks'. For these three reasons, considering the entire dike section penetrated by Hole 504B is a unique chance to study chemical fluxes related to hydrothermal alteration of this part of the oceanic crust. The calculation of any chemical flux implies knowledge of the chemical composition of the fresh precursor (protolith). Previously, mean compositions of glasses (=P1a) or basalts from the Hole 504B volcanics have been used as protoliths. In this paper, we calculate and discuss the use of various protoliths based on dolerites from Hole 504B. We show that the most adequate and realistic protolith is the mean of individual protoliths that we calculated from the acquisition, by automatic mode, of about 1000 microprobe analyses in each thin-section of dolerite from the Hole 504B lower dikes. Consequently, PFm is further used to calculate chemical fluxes in the dike section of Hole 504B. The chemical compositions of the host-rocks adjacent to alteration halos tend to converge to that of PFm with depth, except for Fe2O3t and TiO2. Because the volume percent of alteration halos increases with depth, the total fluxes related to these halos increase with depth. This explains why the mean flux (host-rocks+halos+veins) of the upper dikes is roughly similar to the mean flux of the lower dikes. During the alteration of the entire Hole 504B dike section, the dolerites gained relatively large quantities of Fe2O3t (+4.0 g/100 cm**3) and released much SiO2 (-6.8 g/100 cm**3), CaO (-5.8 g/100 cm**3), and TiO2 (1.6 g/100 cm**3), and minor Al2O3 (-0.7 g/100 cm**3) and MgO (-0.7 g/100 cm**3). We show the importance of the choice of the protolith in the calculation of chemical budget, particularly for elements showing low flux values. In Hole 504B, the Mg uptake by the volcanics during low temperature alteration added to the Mg release by the dikes gives a net flux of -0.07x10**14 g/year. We propose that part of the Mg uptake by the oceanic crust, which is necessary to compensate the rivers input (-1.33x10**14 g/year), occurs in the underlying gabbros and/or in sections which are altered such as Trinity and Troodos ophiolites. Compared with ophiolites, fluxes calculated for elements other than Mg for the entire crust are generally similar (in tendency, if not in absolute value) to that we obtained from Hole 504B.

Magnetic properties and oxide petrography of ODP Hole 111-504B

Magnetic properties measurements were performed on 47 samples drilled during Leg 111 of the Ocean Drilling Program and oxide petrography was studied in 32 samples taken at depths throughout the sheeted dike complex in Hole 504B. Integration of these data with results from previous DSDP legs shows that while natural remanent magnetization is constant with depth, magnetic susceptibility increases and median demagnetizing field and the Q ratio decrease with depth in the section. These trends appear to be a result of an increase in deuteric oxidation and a decrease in hydrothermal alteration of primary titanomagnetite with depth. A distinct change in stable magnetic inclination occurs between the extrusive basalts and the sheeted dikes and may be a result of tectonic rotation of the upper extrusive basalts.

Geochemistry of DSDP Hole 83-504B minerals

Leg 83 of the Deep Sea Drilling Project has deepened Hole 504B to over 1 km into basement, 1350 m below the seafloor (BSF). The hole previously extended through 274.5 m of sediment and 561.5 m of pillow basalts altered at low temperature (< 100°C), to 836 m BSF. Leg 83 drilling penetrated an additional 10 m of pillows, a 209-m transition zone, and 295 m into a sheeted dike complex. Leg 83 basalts (836-1350 m BSF) generally contain superimposed greenschist and zeolite-facies mineral parageneses. Alteration of pillows and dikes from 836 to 898 m BSF occurred under reducing conditions at low water/rock ratios, and at temperatures probably greater than 100°C. Evolution of fluid composition resulted in the formation of (1) clay minerals, followed by (2) zeolites, anhydrite, and calcite. Alteration of basalts in the transition zone and dike sections (898-1350 m BSF) occurred in three basic stages, defined by the opening of fractures and the formation of characteristic secondary minerals. (1) Chlorite, actinolite, pyrite, albite, sphene, and minor quartz formed in veins and host basalts from partially reacted seawater (Mg-bearing, locally metal-and Si-enriched) at temperatures of at least 200-250°C. (2) Quartz, epidote, and sulfides formed in veins at temperatures of up to 380°C, from more evolved (Mg-depleted, metal-, Si-, and 18O-enriched) fluids. (3) The last stage is characterized by zeolite formation: (a) analcite and stilbite formed locally, possibly at temperatures less than 200°C followed by (b) formation of laumontite, heulàndite, scolecite, calcite, and prehnite from solutions depleted in Mg and enriched in Ca and 18O, at temperatures of up to 250°C. The presence of small amounts of anhydrite locally may be due to ingress of relatively unaltered seawater into the system during Stage 3. Alteration was controlled by the permeability of the crust and is characterized by generally incomplete recrystallization and replacement reactions among secondary minerals. Secondary mineralogy in the host basalts is strongly controlled by primary mineralogy. The alteration of Leg 83 basalts can be interpreted in terms of an evolving hydrothermal system, with (a) changes in solution composition because of reaction of seawater fluids with basalts at high temperatures; (b) variations in permeability caused by several stages of sealing and reopening of cracks; and (c) a general cooling of the system, caused either by the cooling of a magma chamber beneath the spreading center and/or the movement of the crust away from the heat source. The relationship of the high-temperature alteration in the transition zone and dike sections to the low-temperature alteration in the overlying pillow section remains uncertain.

Distribution of Au and Pd in basalts and diabases in DSDP/ODP Hole 504B

Au contents have been determined in 77 samples of basalts and sheeted diabase dikes. Pd has been evaluated in 39 of the samples. The mean amount of Au is 3 parts per billion (ppb), fluctuating from 0.4 to 10 ppb. Au contents appear to be independent in type and intensity of alteration as well as with depth sub-bottom, although in the lower part of Hole 504B, 1900-2000 mbsf, Au contents are markedly decreased (mean: 1.1 ppb) and show a distinct correlation with a decrease in Zn contents. Pd contents vary from 2 to 360 ppb (mean: 37 ppb) Pd is higher in basalts (53.7 ppb) and lower in diabase dikes (30 ppb), especially in moderately or strongly altered ones (12.5 ppb).

40Ar/39Ar analysis for incremental heating experiments at DSDP Holes 77-537 and 77-538A

Drilling penetrated pre-Mesozoic crystalline basement beneath abbreviated sedimentary sequences overlying fault blocks in the southeastern Gulf of Mexico. At Hole 538A, located on Catoche Knoll, a foliated, regional metamorphic association of variably mylonitic felsic gneisses and interlayered amphibolite is intruded by post-tectonic diabase dikes. Hornblende from the amphibolite displays internally discordant 40Ar/39Ar age spectra, suggesting initial post-metamorphic cooling at about 500 Ma followed by a mild thermal disturbance at about 200 Ma. Biotite from the gneiss yields a plateau age of 348 Ma, which is interpreted to result from incorporation of extraneous argon components when the biotite system was opened during the about 200 Ma thermal overprint. A whole-rich diabase sample from Hole 538A records a crystallization age of 190.4 ± 3.4 Ma. A lower grade phyllitic metasedimentary sequence was penetrated at Hole 537, drilled about 30 km northwest of Catoche Knoll. Whole-rock phyllite samples display internally discordant 40Ar/39Ar age spectra, but plateau segments clearly document an early Paleozoic metamorphism at about 500 Ma. The age and lithologic character of the basement terrane penetrated at Holes 537 and 538A suggest that the drilled fault blocks are underlain by attenuated fragments of continental crust of "Pan-African" affinity. This supports pre-Mesozoic tectonic reconstructions that locate Yucatan in the present Gulf recess during the amalgamation of Pangea.

Geochemistry of igneous rock samples of ODP Site 125-786

A morphologically complex igneous basement was penetrated at Leg 125 Site 786 beneath approximately 100 m of Eocene-Pleistocene sediments at 31°52.45 'N, 141°13.59'E in a 3082-m water depth. The site is located on the forearc basement high (FBH) of the Izu-Bonin (Ogasawara) Arc. In the broadest terms, the sequence in Hole 786B consists of a basal sheeted dike complex, heavily mineralized in places, with overlying pillow lavas giving way to a complex and repeated sequence of interlayered volcanic breccias and lava flows with some thin sedimentary intervals. The sequence has been further cut by dikes or sills, particularly of high-Ca and intermediate-Ca boninite, and is locally strongly sheared by faulting. The whole basement has been covered with middle Eocene-early Pleistocene sediments. A monomict breccia forms the shallowest portion of Hole 786B and a polymict breccia having Mn-oxide-rich clast coatings and matrix forms the deepest part of Hole 786A (-100-160 mbsf). The basement is tectonized in some places, and a mineralized stockwork is present in the deepest part of Hole 786B. A wide variety of rock types form this basement, ranging from mafic to silicic in character and including high-, intermediate-, and low-Ca boninites, intermediate- and low-Ca bronzite andesites, andesite, dacite, and rhyolite groups. Intragroup and intergroup relationships are complicated in detail, and several different upper mantle source(s) probably were involved. A significant role for orthopyroxene-clinopyroxene-plagioclase fractionation is indicated in the mafic-intermediate groups, and the most probable complementary cumulates should be noritic gabbros. Many overall similarities but some subtle differences are noted between the igneous basement at Site 786 and the subaerial outcrops of the FBH to the south in the type boninite locality of Chichijima. Both suites were derived by hydrous melting of a relatively shallow, refractory (harzburgitic) upper mantle source. These Bonin forearc basement rocks are similar in many respects to those of Eocene-Oligocene age now forming the forearc of the Marianas at Leg 60 Site 458 and on Guam. In sharp distinction, the geochemistry of the Eocene-Pleistocene ash sequences overlying the Bonin FBH must have been derived from a very different upper mantle source, implying considerable across-strike differences in sub-arc mantle composition.

B, d11B, K and d18O data for altered oceanic crust at DSDP Sites 417/418

Samples of drilled oceanic crust, from DSDP Holes 417A, 417D and 418A and ODP Hole 735B, and oceanic crust from the Oman and Cyprus ophiolites, were analyzed for B contents and d11B. Composite samples from DSDP Holes 417A, 417D and 418A were used to represent the upper 550 m of altered oceanic crustal Layer 2A. Whole-rock samples from the Troodos ophiolite, Cyprus, and the Oman ophiolite were selected to represent crustal Layer 2B dikes. Composite samples from ODP Hole 735B were used to represent crustal Layer 3. The B content of the DSDP composites ranges from 7.2 ppm to 104 ppm and correlates with both d1818O and K, showing that it is a good indicator of the extent of low temperature alteration. The d11B of the DSDP composites varies between -2.5? and 5.4?. The B content of the samples from the Troodos ophiolite ranges from 2.4 ppm to 8.1 ppm; d11B varies from -0.9? to 7.8?. The B content of the Oman ophiolite samples ranges from 5.0 ppm to 11.1 ppm; d11B varies from -1.6? to 16.9?. The B content of the samples from ODP Hole 735B ranges from 1.1 ppm to 7.1 ppm; d11B varies from -4.3? to 24.9?. The general pattern displayed by these samples is one of greatest (and most variable) B enrichment at the top of the crust and least enrichment at the bottom of the section. All of these samples are enriched compared to unaltered MORB, which is believed to have a B content of approximately 0.5 ppm. The d11B values of deeper samples, from Layers 2B and 3, are more variable and generally higher than those from Layer 2A. Boron contents and d11B are not correlated. The data from the DSDP Site 417/418 composites indicate that the d11B of fluid circulating in the upper crust changes only slightly during alteration, increasing by an average of 5.1? with an accompanying decrease in B concentration of 7%. Low temperature alteration appears to be a water-dominated process resulting in minor modification of circulating seawater. A minimum water-rock ratio of 400 is calculated for these samples, implying a minimum low-temperature seawater flux through the upper oceanic crust of 3.4?10**14 l/y. The average B content of altered oceanic crust, as represented by these samples, is 5.2+/-1.7 ppm and the average d11B is 3.4+/-1.1?. This average isotopic composition is measurably different from the apparent average of oceanic sediments, supporting the idea that d11B could be useful for identifying the source(s) of B in island arcs.

Chemical and strontium isotopic compositions of interstitial waters from sediments of ODP Site 135-841

The depth variations in the major chemical components dissolved in interstitial waters from the Tonga margin (ODP Site 841) are much more pronounced than those usually observed in deep-sea sediments. The extensive alteration of volcanic Miocene sediments to secondary minerals such as analcime, clays, and thaumasite forms a CaCl2-rich brine. The brine results from a high exchange of Ca to Na, K, and Mg and an increase in Cl concentrations due to removal of H2O from the fluid during the authigenesis of hydrous minerals. The formation of thaumasite could have partly controlled the concentration of dissolved SO4, HCO3, and Ca in the Miocene sediments. The strontium isotopic signature of the interstitial water suggests that alteration of the volcanic Miocene sediments occurred a long time after sedimentation. A transient diffusion model indicates that molecular diffusion was not prevented by lithologic barriers and that the formation of secondary minerals in the Miocene sediment occurred over a short period of time (e.g.,dikes into the Miocene sediments.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

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).

Chemical and isotopic composition of rocks and minerals at ODP Site 209-1275

This paper reports results of an investigation of a representative collection of samples recovered by deep-sea drilling from the oceanic basement 10 miles west of the rift valley axis in the crest zone of the Mid- Atlantic Ridge at 15°44'N (Sites 1275B and 1275D). Drilling operations were carried out during Leg 209 of the Drilling Vessel JOIDES Resolution within the framework of the Ocean Drilling Program (ODP). The oceanic crust was penetrated to depth of 108.7 m at Site 1275B and 209 m at Site 1275D. We reconstructed the following sequence of magmatic and metamorphic events resulting in the formation of a typical oceanic core complex of slow-spreading ridges: (1) formation of strongly fractionated (enriched in iron and titanium) tholeiitic magmatic melt parental to gabbroids under investigation in a large magma chamber located in a shallow mantle and operating for a long time under steady-state conditions; (2) transfer of the parental magmatic melt of the gabbroids to the base of the oceanic crust, its interaction with host mantle peridotites, and formation of troctolites and plagioclase peridotites; (3) intrusion of enriched trondhjemite melts as veins and dikes in the early formed plutonic complex, contact recrystallization of the gabbro, and development in the peridotite-gabbro complex of enriched geochemical signatures owing to influence of trondhjemite injections; (4) emplacement of dolerite dikes (transformed to diabases); (5) metamorphism of upper epidoteamphibolite facies with participation of marine fluids; and (6) rapid exhumation of the plutonic complex to the seafloor accompanied by greenschist-facies metamorphism. Distribution patterns of Sr and Nd isotopes and strongly incompatible elements in the rocks suggest contributions from two melt sources to the magmatic evolution of the MAR crest at 15°44'N: a depleted reservoir responsible for formation of the gabbros and diabases and an enriched reservoir, from which trondhjemites (granophyres) were derived.