Petrology and isotope characteristics of basalts from ODP Hole 111-504B

Petrography and isotope geochemical characteristics of H, O, S, Sr, and Nd have been described for basalts recovered from Hole 504B during Leg 111 of the Ocean Drilling Program. The petrographic and chemical features of the recovered basalts are similar to those obtained previously (DSDP Legs 69, 70, and 83); they can be divided into phyric (plagioclase-rich) and aphyric (Plagioclase- and clinopyroxene-rich) basalts and show low abundances of TiO2, Na2O, K2O, and Sr. This indicates that the basalts belong to Group D, comprising the majority of the upper section of the Hole 504B. The diopside-rich nature of the clinopyroxene phenocrysts and Ca-rich nature of the Plagioclase phenocrysts are also consistent with the preceding statement. The Sr and Nd isotope systematics (average 87Sr/86Sr = 0.70267 ± 0.00007 and average 143Nd/144Nd = 0.513157 ± 0.000041) indicate that the magma sources are isotopically heterogeneous, although the analyzed samples represent only the lowermost 200-m section of Hole 504B. The rocks were subjected to moderate hydrothermal alteration throughout the section recovered during Leg 111. Alteration is limited to interstices, microfractures, and grain boundaries of the primary minerals, forming chlorite, actinolite, talc, smectite, quartz, sphene, and pyrite. In harmony with the moderate alteration, the following alteration-sensitive parameters show rather limited ranges of variation: H2O = 1.1 ±0.2 wt%, dD = - 38 per mil ± 4 per mil, d180 = 5.4 per mil ± 0.3 per mil, total S = 562 ± 181 ppm, and d34S = 0.8 per mil ± 0.3 per mil. Based on these data, it was estimated that the hydrothermal fluids had dD and d180 values only slightly higher than those of seawater, the water/rock ratios were as low as 0.02-0.2, and the temperature of alteration was 300°-400°C. Sulfur exists predominantly as pyrite and in minor quantities as chalcopyrite. No primary monosulfide was detected. This and the d34S values of pyrite (d34S = 0.8 per mil) suggest that primary pyrrhotite was almost completely oxidized to pyrite by reaction with hydrothermal fluids containing very little sulfate.

Sulfur concentrations and isotope ratios in sediments from Kiel Bay, western Baltic Sea

The isotope-ratios of sulfur-components in several sedimentologically different cores of recent marine sediments from Kiel Bay (Baltic Sea) were investigated. In addition, quantitative determinations were made on total sulfur, sulfate, sulfide, chloride, organic carbon, iron and watercontent in the sediment or in the pore-water solution. The investigations gave the following results: 1. The sulfur in the sediment (about 0.3 -2 % of the dry sample) was for the most part introduced into the sediment after sedimentation. This confirms the results of Kaplan et al. (1963, doi:10.1016/0016-7037(63)90074-7). The yield of Sulfur from organic material is very small (in our samples about 5-10% of the total sulfur in the sediment). 2. The sulfur bound in the sediment is taken from the sulfate of the interstitial water. During normal sedimentation, the exchange of sulfate by diffusion significant for changes in the sulfur-content goes down to a sediment depth of 4-6 cm. In this way the sulfate consumed by reduction and formation of sulfide or pyrite is mostly replaced. The uppermost layer of the sediment is an partly open system for the sulfur. The diagenesis of the sulfur is allochemical. 3. The isotope-values of the sediment-sulfur are largely influenced by the sulfur coming into the sediment by diffusion and being bound by bacteriological reduction. Due to the prevailing reduction of 32S and reverse-diffusion of sulfate into the open sea-water, an 32S enrichment takes place in the uppermost layer of the sediment. delta34S-values in the sediment range between -15 and -35 ? while seawater-sulfate has +20 ?. No relationship could be established between sedimentological or chemical changes and isotope-ratios. In the cores, successive sandy and clayly layers showed no change in the delta-values. The sedimentation rate, however, seems to influence isotope-ratios. In one core with low sedimentationrates the delta34S-values varied between -29 and -33 ?, while cores with higher sedimentationrates showed values between -17 and -24 ?. 4. As sediment depth increases, the pore-water sulfate shows decreasing concentrations (in a depth of 30-40 cm we found between 20 and 70 % of the seawater-values), and increasing delta 34S-values (in one case reaching more than +60 ?). The concentration of sulfide in the pore-water increases with sediment-depth (reaching 80 mg S/l in one case). The (delta34S-values of the pore-water-sulfide in all cores show increases paralleling the sulfate sulfur, with a nearly constant delta-distance of 50-60 ? in all cores. This seems to confirm the genetic relationship between the two components.

Sulphur chemistry of the ODP Site 206-1256 volcanic section

Sulfide mineralogy and the contents and isotope compositions of sulfur were analyzed in a complete oceanic volcanic section from IODP Hole 1256D in the eastern Pacific, in order to investigate the role of microbes and their effect on the sulfur budget in altered upper oceanic crust. Basalts in the 800 m thick volcanic section are affected by a pervasive low-temperature background alteration and have mean sulfur contents of 530 ppm, reflecting loss of sulfur relative to fresh glass through degassing during eruption and alteration by seawater. Alteration halos along fractures average 155 ppm sulfur and are more oxidized, have high SO4/Sum S ratios (0.43), and lost sulfur through oxidation by seawater compared to host rocks. Although sulfur was lost locally, sulfur was subsequently gained through fixation of seawater-derived sulfur in secondary pyrite and marcasite in veins and in concentrations at the boundary between alteration halos and host rocks. Negative d34S[sulfide-S] values (down to -30 per mil) and low temperatures of alteration (down to ~40 °C) point to microbial reduction of seawater sulfate as the process resulting in local additions of sulfide-S. Mass balance calculations indicate that 15-20% of the sulfur in the volcanic section is microbially derived, with the bulk altered volcanic section containing 940 ppm S, and with d34S shifted to -6.0 per mil from the mantle value (0 per mil). The bulk volcanic section may have gained or lost sulfur overall. The annual flux of microbial sulfur into oceanic basement based on Hole 1256D is 3-4 * 10**10 mol S/yr, within an order of magnitude of the riverine sulfate source and the sedimentary pyrite sink. Results indicate a flux of bacterially derived sulfur that is fixed in upper ocean basement of 7-8 * 10**-8 mol/cm**-2/yr1 over 15 m.y. This is comparable to that in open ocean sediment sites, but is one to two orders of magnitude less than for ocean margin sediments. The global annual subduction of sulfur in altered oceanic basalt lavas based on Hole 1256D is 1.5-2.0 * 10**11 mol/yr, comparable to the subduction of sulfide in sediments, and could contribute to sediment-like sulfur isotope heterogeneities in the mantle.

Sulfur in bottom sediments and intersitial waters of the Gulf of California

The book is devoted to study of diagenetic changes of organic matter and mineral part of sediments and interstitial waters of the Pacific Ocean due to physical-chemical and microbiological processes. Microbiological studies deal with different groups of bacteria. Regularities of quantitative distribution and the role of microorganisms in geochemical processes are under consideration. Geochemical studies highlight redox processes of the early stages of sediment diagenesis, alterations of interstitial waters, regularities of variations in chemical composition of iron-manganese nodules.