Geochemistry of Miocene "blue tuff" samples

Distinctive, massive to stratified, pale blue volcaniclastics, initially referred to as the "blue tuff," were encountered at all four sites drilled during ODP Leg 127 in the Japan Sea. Detailed vertical sequence analysis, plagioclase chemistry, plagioclase 87Sr/86Sr isotopic composition, and 40Ar/39Ar age dating indicate that thick sequences of the blue tuff are not genetically related. Blue tuffs at Hole 794B were apparently deposited by density flows at ambient temperature. Deposition was penecontemporaneous with a large submarine phreatomagmatic eruption at 14.9 Ma in bathyal or deeper water depths. The blue tuffs at this location comprise mostly reworked hydroclastic glass shards and lesser amounts of plagioclase crystals. Pyrogenic plagioclase has an average An mole% of 18±3. Comparison of blue tuff plagioclase compositions with the composition of plagioclase from acoustic basement at Site 794 suggests that these rocks are not genetically related. As such, the extrapolation of sediment accumulation rate data in conjunction with this more precise age for the blue tuff corroborates previous minimum age estimates of 16.2 Ma for acoustic basement at Site 794. Blue tuffs at Hole 796B were probably deposited at ambient temperatures by downslope slumping and density flow of reworked pyrogenic debris. This debris includes abundant bubble wall glass shards and plagioclase crystals, with variable admixture of volcanic lithic and intrabasinal fragments. Pyrogenic fragments were produced by subaerial or shallow submarine, magmatic eruptions dated at 7.6 Ma. Blue tuffs contain a heterogeneous mixture of unrelated fragments including a mixed population of plagioclase crystals. The average An mole% of the predominant, probable comagmatic, plagioclase population is 30±4. The two sequences of blue tuff studied are distinct in age, mineral composition, and the eruptive origin of pyroclastic fragments. Preliminary 87Sr/86Sr isotopic compositions of plagioclase, however, indicates that blue tuffs at both locations are the product of typical, subduction-related island arc magmatism. Based on the results of this study, there is no justification for stratigraphic correlation of widespread, Miocene, blue to blue-gray bentonitic tuff and tuffaceous sandstones nor the interpretation that these strata are indicative of regional, explosive submarine volcanism genetically related to rifting and formation of the Japan Sea. Rather, these reworked pyroclastic strata of intermediate composition were deposited over a protracted 6-8 m.y. period in association with widespread, subduction-related submarine to subaerial volcanism in the Japan Sea backarc basin.

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.

(Table 1) Geochemical and geothermometry data from fibrous calcite vein fills in the Dabashan Fold Belt, China

Fibrous calcite veins with organic inclusions have been widely considered as indicators of oil and gas generation and migration under overpressure. Abundant fibrous calcite veins containing organic-bearing inclusions occur in faulted Lower Paleozoic through Triassic hydrocarbon source rocks in the Dabashan Foreland Belt (DBF). d13CPDB and d18OPDB values of the fibrous calcite range from - 4.8 to -1.9 to per mil and - 12.8 to - 8.4 per mil respectively, which is lighter than that of associated carbonate host rocks ranging from - 1.7 to + 3.1 per mil and - 8.7 to - 4.5 per mil. A linear relationship between d13CPDB and d18OPDB indicates that the calcite veins were precipitated from a mixture of basinal and surface fluids. The fibrous calcite contains a variety of inclusions, such as solid bitumen, methane bearing all-liquid inclusions, and vapor-liquid aqueous inclusions. Homogenization temperatures of aqueous inclusions range from 140 to 196° with an average of 179°. Salinities of aqueous inclusions average 9.7 wt% NaCl. Independent temperatures from bitumen reflectance and inclusion phase relationships of aqueous and methane inclusions were used to determine fluid pressures. Results indicate high pressures, elevated above typical lithostatic confining pressure, from 150 to 200 MPa. The elevated salinity and high temperature and pressure conditions of the fibrous calcite veins argue against an origin solely from burial overpressure resulting from clay transformation and dehydration reactions. Instead fluid inclusion P-T data and geochemistry results and regional geology indicate abnormally high pressures during fluid migration. These findings indicate that tectonic stress generated fracture and fault fluid pathways and caused migration of organic bearing fluids from the DBF during the Yanshan orogeny.