Chemical composition and sulfur-isotope ratios in DSDP Legs 69-and 70

As part of the geochemical-petrological study of basalts recovered from DSDP Hole 504B (Leg 70) on the southern flank of the Costa Rica Rift, we investigated specially the relationships between the distribution and isotopic composition of sulfur of scattered and vein sulfides on the one hand, and the observed pattern and processes of secondary alterations on the other. The following groups of observations are essential: (1) variations in the contents and isotopic composition of sulfur of different forms of sulfides are clearly interrelated and are observed solely in porous horizons established on the basis of detailed geophysical experiments; (2) the enrichment of sulfides in the light sulfur isotope decreases from the upper to the lower horizons, and within horizons in the direction of the less-altered rock; (3) the increase of d34S values of scattered sulfides in individual permeable zones parallels a decrease in the degree of iron oxidation in the contents of crystallization water, and in the concentrations of Mg, K, and Li in the rock.

Major, trace and rare earth elements and minerals at DSDP Legs 69-70 Holes

We obtained major and trace element data on 113 samples from basalts drilled during DSDP Legs 69 and 70 in the Costa Rica Rift area. The majority have major and trace element characteristics typical of ocean-ridge tholeiities. Most of the basalts are relatively MgO rich (MgO > 8 wt.%) and have Mg values (MgO/MgO + 0.85FeO x 100) of about 53, characteristics that clearly indicate that the various magmas underwent only a small amount of crystal fractionation before being erupted onto the seafloor. According to their normative mineralogies, the rocks are olivine tholeiites. A few samples plot close to the diopside-hypersthene join of the projected basalt tetrahedron. Except for basalts from two thin intervals in Hole 504B, which differ significantly from all the other basalts of the hole, practically no chemical downhole variation could be established. In the two exceptional intervals, both TiO2 and P2O5 contents are markedly enriched among the major oxides. The trace elements in these intervals are distinguished by relatively high contents of magmatophile elements and have flat to enriched chondrite-normalized distribution patterns of light rare earth elements (LREE). Most of the rocks outside these intervals are strongly depleted in large-ionlithophile (LIL) elements and LREE. We offer no satisfactory hypothesis for the origin of these basalts at this time. They might have originated within pockets of mantle materials that were more primitive than the LIL-element-depleted magmas that were the source of the other basalts. A significant change with depth in the type of alteration occurs in the 561 meters of basalt cored in Hole 504B. According to the behavior of such alteration-sensitive species as K2O, H2O-, CO2, S, Tl, and the iron oxidation ratio, the alteration is oxidative in the upper part and nonoxidative or even reducing in the lower part. The oxidative alteration may have resulted from low temperature basalt/seawater interaction, whereas hydrothermal solutions may be responsible for the nonoxidative alteration.

d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

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.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

(Table 1) Physical properties of basalts from DSDP Legs 69 and 70

Physical properties of basalts from Deep Sea Drilling Project Sites 504 and 505, south of the Costa Rica Rift, including wet-bulk density, water content, sonic velocity, and thermal conductivity, were measured on board D/V Glomar Challenger during Legs 69 and 70. The mean wet-bulk density is 2.90±0.06 g/cm**3, porosity 5.0±2.2%, sonic velocity 5.75±0.30 km/s, and thermal conductivity 1.67±0.09 W/m°K. Basalts from this young ocean crust (5.9 m.y.) have relatively low porosity and consequently high density and sonic velocity, as compared to average DSDP basalts. Some systematic trends in depth variation of physical properties were found: down to Core 40 in Hole 504B, grain densities were lower than those deeper in the hole, whereas porosity in the upper section was higher. This can be attributed either to differences in the flow type or in the nature of alteration of basalts at the different levels in the hole.

(Table 1) Compressional-wave and shear-wave velocities and elastic constants from DSDP Legs 69 and 70

Shear-wave and compressional-wave velocities of 26 basalt samples collected at Site 504 during Deep Sea Drilling Project Legs 69 and 70 were measured at elevated confining pressures. The young basalts have higher velocities than average DSDP basalts, because of their lack of alteration. Measurements of sample porosity are combined with laboratory and in situ velocity measurements to yield estimates of total crustal porosity: 13% at the top of Layer 2, and very low porosity below a depth of 2.0 km.

Geochemistry of minerals at DSDP Hole 70-504B

Hole 504B, drilled into the 5.9 Ma crust of the southern flank of the Costa Rica Rift, tapped a hydrothermal system in its conductive stage. Three alteration zones were encountered along the 561.5 meters of basement drilled. The upper alteration zone, 274.5 to 584.5 meters below the seafloor (BSF), is characterized by the presence of color zonation in which red halos are located between dark gray inner rock portions and dark gray outer bands. The red halos are characterized by an abundance of iddingsite, and they have higher K2O contents and Fe3+/FeT ratios, but lower SiO2 contents, than the adjacent dark gray inner zones. The dark gray outer bands are characterized by the presence of celadonite-nontronite. Saponite is omnipresent in these three alteration bands. Phillipsite is the only zeolite that occurs in the upper alteration zone. The upper alteration zone is interpreted as being the result of low-temperature alteration, with large amounts of cold oxygenated seawater percolating through the upper ocean crust. In the upper alteration zone, the formation of red halos was both preceded and followed by formation of dark gray outer bands. Then followed formation of dark gray cores. The lower alteration zone (584.5-835.5 m BSF) is characterized by the absence of color zonation, the downward-increasing abundance of pyrite and saponite, and the presence of quartz, talc, and calcite. The chemical changes (downhole MgO enrichment and concomitant CaO depletion) observed in the basalts of the lower alteration zone are thought to result from reactions of oceanic basalts with evolved seawater (i.e., solutions derived from seawater that has already reacted with ocean crust), which is thus depleted in oxygen, potassium, and radiogenic strontium. This alteration process, which was responsible for saponite formation in both the upper and lower alteration zones, was rock dominated, and it took place under suboxic to anoxic conditions during a second stage of alteration. Reaction temperatures could have progressively increased with depth. There is also a zeolitic zone that essentially coincides with the lower part of the upper alteration zone (between 528.5 and 563 m BSF). The host rock adjacent to veins of zeolite exhibits a greenish discoloration due to the intensive replacement of the igneous minerals. The replacement minerals result in significant increases in the bulk rock K2O, MgO, CaO, CO2, and H2O+ contents. The solutions circulating along the newly opened fissures had high Ca activity, and minerals probably precipitated in these fissures at 60°C or 110°C. These hydrothermal solutions circulated later than those responsible for the formation of the minerals that characterize the upper and lower alteration zones.

Geochemistry and minerals at DSDP Hole 70-504B

In three veins from the lower part of Deep Sea Drilling Project Hole 504B, 298 meters below the top of basement, primary augite is replaced by aegirine-augite. This transformation occurs only in subophitic basalts, at the contact with veins which always include a dark-olive, Mg-rich clay mineral. Talc occurs in one of these veins; it can be regarded either as a vein constituent or as a product of augite alteration. Melanite (Ca,Fe,Ti-rich garnet) appears in only one of these three veins, where a Ca-carbonate is associated with a Mg-rich clay mineral. The occurrence of melanite in Hole 504B could be due to the conjunction of particular conditions: (1) basalt with a subophitic texture, (2) presence of hydrothermal fluids carrying Ca, Fe, Si, Ti, Al, Mg, and Na, (3) rather high temperatures. Possibly the melanite and aegirine-augite formed by deuteric alteration.

Secondary minerals and geochemistry at DSDP Legs 68 and 69

Basalt samples recovered during DSDP Legs 68, 69, and 70 from a 550-meter-thick section in two holes near the Costa Rica Rift (Holes 501 and 504B) were found to contain the following secondary minerals: trioctahedral and dioctahedral smectite, chlorite, mixed-layer clays, talc, hematite, pyrite, foujasite, phillipsite, analcime, natrolite, thomsonite, gyrolite, aragonite, calcite, anhydrite, chalcocite, Fe-hydrosilicate, okenite, apophyllite, actinolite, cristobalite, quartz, and magnesite. A less positive identification of bismutite was made. A mineral rich in Mn and minerals with strong reflections at 12.9 Å and 3.20 Å remain unidentified. Trioctahedral smectite replaces glass and olivine in the basalt groundmass. The other secondary minerals occur in veins. The distribution of the secondary minerals in the basalt section shows both hydrothermal and oxidizing-nonoxidizing zonation. Most of the secondary minerals formed under alkaline, nonoxidizing conditions at temperatures up to 120° C. An acidic regime probably existed in the lowest portion of basalt. Oxidative diagenesis followed nonoxidative diagenesis in the upper part of the section. Oxidative diagenesis is characterized by the absence of celadonite, rare occurrences of dioctahedral smectite, and widespread hematite and phillipsite.

(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.