Concentration of hydrogen sulfide in waters of the Black Sea in the layer of its coexistence with oxygen

About 100 parallel determinations of hydrogen sulfide by the volumetric and photometric methods were made in the layer of coexistence of oxygen with hydrogen sulfide (C layer). Thiosulfates were determined simultaneously. Regardless of locations of the stations, determinations by two methods coincided for the entire range of depths of occurrence of the C layer upper boundary. Within the C layer hydrogen sulfide readings obtained by these two independent methods agreed; thiosulfates were not found by direct measurements. Difference in the readings appears at the lower boundary of the C layer and below it, accompanied by appearance of thiosulfates. It is therefore concluded that it is correct to determine the upper boundary of the C layer by the iodometric method and to use concentration of hydrogen sulfide obtained by this method in the C layer to calculate rate of chemical oxidation of hydrogen sulfide in quasistationary processes.

Iodine speciation at time series station DYFAMED

Iodine speciation analysis was carried out upon seawater samples collected in July 1993 at the DYFAMED station (43 °25?N, 7 °52?E) located in the northwestern Mediterranean Sea. Dissolved iodate and iodide were directly determined by differential pulse polarography and cathodic stripping square wave voltammetry, respectively, and organically bound iodine was estimated by wet-chemical oxidation with sodium hypochlorite. Iodate is the predominant species ranging from 416 nM in surface waters to 480 nM in bottom waters. Iodide is present in significant concentrations up to 60 nM in surface waters, undetectable between 500 and 1000 m depth and present in very low but measurable concentrations (about 6 nM) in deep waters. The vertical profile of total free iodine demonstrates observable removal from surface waters, slight enrichment at about 200 m depth and constant there below. Up to 40 nM of organically bound iodine has been estimated between 20 to 30 m. Factorial analysis of different iodine species with biologically relevant parameters provided strong evidence for iodine biophilic features.

Carbon and nitrogen content of marine pore waters

We have developed sampling methods and an analytical system to determine the concentration of dissolved organic C (DOC) in marine pore waters. Our analytical approach is a modification of recently developed high-temperature, Pt-catalyzed oxidation methods; it uses Chromatographic trapping of the DOC-derived CO2 followed by reduction to CH4 and flame ionization detection. Sampling experiments with nearshore sediments indicate that pore-water separation by whole-core squeezing causes artificially elevated DOC concentrations, while pore-water recovery by sectioning and centrifugation does not appear to introduce DOC artifacts. Results from a set of northwestern Atlantic continental slope cores suggest that net DOC production accounts for >50% of the organic C that is recycled at the sediment-water interface.

Chemical and isotopic compositions of ocean authigenic carbonates

Oceanic authigenic carbonates are classified according to origin of the carbonate carbon source using a complex methodology that includes methods of sedimentary petrography, mineralogy, isotope geochemistry, and microbiology. Mg-calcite (protodolomite) and aragonite predominate among the authigenic carbonates. All authigenic carbonates are depleted in 13C and enriched in 18O (in PDB system) that indicates biological fractionation of isotopes during carbonate formation. Obtained results show that authigenic carbonate formation is a biogeochemical (microbial) process, which involves carbon from ancient sedimentary rocks, abiogenic methane, and bicarbonate-ion of hydrothermal fluids into the modern carbon cycle.

Planktological-chemical observation during the International Indian Ocean Expedition (IIOE) with RV "Meteor" in 1964/65

The present volume contains the planktological data collected during the expedition of the "Meteor" to the Indian Ocean in 1964/65. It was the main objective of the expedition to study the up- and downwelling conditioned along the western and eastern coasts of the Arabian Sea by the northeastern monsoon. It is from these areas that the greater part of the data here presented was obtained. A few values from the Red Sea have been added. As the title "Planktological-Chemical Data" implies, it was chiefly with the help of chemical methods that the planktological investigations, with the exception of the particle size analysis and phytoplankton counting conducted optically, were carried out. These investigations were above all devoted to a quantitative survey of particulate matter and plankton, the latter being sampled by water-bottle and net. The zooplankton hauls were taken with the Indian Ocean Standard Net according to the international guidelines laid down for the expedition. As a rule, double catches were made at every station, one sample being intended for laboratory analysis at the Indian Ocean Biological Centre in Ernakulam, South India, and the other for the Institut für Meereskunde in Kiel. In addition to determining the standing stock, the production rate of phytoplankton was measured by the 14C method. These experiments were mainly conducted during the latter half of the expedition. The planktological studies primarily covered the euphotic zone, extending into the underlying water layers up to a depth of 600 m. The investigations were above all directed towards ascertaining the quantity of organic substance, formed by primary production, in its relation to environmental conditions and determining whether or not organic substance is actively transported from the surface into the deeper layers by the periodically migration organisms of the deep scattering layers. Depending on the station time available, a few samples could now and then be taken from deeper layers. The present volume of planktological-chemical data addresses itself to all those concerned processing the extensive material collected during the International Indian Ocean Expedition. As a readily accessible work of reference, it hopes to serve as an aid in the evaluation and interpretation of the expedition results. The complementary ecological data such as temperature, salinity, and oxygen content as well as the figures obtained on abundance and distribution in depth of the nutrients essential for primary production may be found in the volume of physical-chemical data published in Series A of the "Meteor"-Forschungsergebnisse No. 2, 1966 (Dietrich et al., 1966).

Chemical composition of manganese nodules and a ferromanganese crust using different methods

In the 1960s and 1970s, the Kennecott Corporation conducted a number of activities in the evaluation of manganese nodule deposits as well as in their possible hydrometallurgy.

Chemical composition of nodules from two locations in the Pacific Ocean using different methods

Manganese nodules recovered in the Pacific Ocean by the U. S. Bureau of Mines and by DeepSea Ventures Ltd. are studied for their chemical composition using X microprobe and X-ray fluorescence methods.

Description and chemical and mineral composition of iron oxide samples from two Finnish lakes

Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

Chemical composition of interstitial waters from sediments of brine-bearing deeps of the Red Sea

Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).

Chemical composition of hydrothermal sulfide minerals from the Rainbow, Logachev-1, and Logachev-2 hydrothermal fields

Composition of ore minerals in MAR sulflde occurrences related to ultramaflc rocks was studied using methods of mineragraphy, electron microscopy, microprobe analysis, and X-ray analysis. Objects are located at various levels of maturity of sulflde mounds owing to differences in age, duration and degree of activity of the following hydrothermal systems: generally inactive Logatchev-1 field (up to 66.5 ka old), inactive Logatchev-2 field (3.9 ka), and generally active Rainbow field (up to 23 ka). Relative to MAR submarine ore occurrences in the basalt substrate, mineralization in the hydrothermal fields mentioned above is characterized by high contents of Au, Cd, Co, and Ni, along with presence of accessory minerals of Co and Ni. The studied mounds differ in quantitative ratios of major minerals and structural-textural features of ores that suggest their transformation. Ores in the Logatchev-1 field are characterized by the highest Cu content and development of a wide range of multistage contrast exsolution structures of isocubanite and bornite. In the Logatchev-2 field, sphalerite-chalcopyrite and gold-arsenic exsolution structures are present, but isocubanite exsolution structures are less diverse and contrast. The Rainbow field is marked by presence of homogenous isocubanite and the subordinate development of exsolution structures. The authors have identified four new phases in the Cu-Fe-S system. Phases X and Y (close to chalcopyrite and isocubanite, respectively) make up lamellae among isocubanite exsolution products in the Logatchev-1 and Logatchev-2 fields. Phase Y includes homogenous zones in zonal chimneys of the Rainbow field. Phases A and B formed in the orange bornite domain at low-temperature alteration of chalcopyrite in the Logatchev-1 field. Mineral assemblages of the Cu-S system are most abundant and diverse in the Logatchev-1 field, but their development is minimal in the Logatchev-2 field where mainly Cu-poor sulfides of the geerite-covellite series have been identified. Specific features of mineral assemblages mentioned above reflect the maturity grade of sulfide mounds and can serve as indicators of maturity.

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.

Chemical and isotopic compositions of rocks and minerals from the Palenyi Island, Por'ya Guba (Bay), White Sea

Hypersthene-garnet-sillimanite-quartz enclaves were studied in orthopyroxene-plagioclase and orthopyroxene-clinopyroxene crystalline schists and gneisses from shear zones exposed in the Palenyi Island within the Early Proterozoic Belomorian Mobile Belt. Qualitative analysis of mineral assemblages indicates that these rocks were metamorphosed to the granulite facies (approximately 900°C and 10-11 kbar). Oxygen isotopic composition was determined in rock-forming minerals composing zones of the enclaves of various mineral and chemical composition. Closure temperatures of the isotopic systems obtained by methods of oxygen isotopic thermometry are close to values obtained with mineralogical geothermometers (garnet-orthopyroxene and garnet-biotite) and correspond to the high-temperature granulite facies (860-900°C). Identified systematic variations in d18O values were determined in the same minerals from zones of different mineral composition. Inasmuch as these zones are practically in contact with one another, these variations in d18O cannot be explained by primary isotopic heterogeneity of the protolith. Model calculations of the extent and trend of d18O variations in minerals suggest that fluid-rock interaction at various integral fluid/rock ratios in discrete zones was the only mechanism that could generate the zoning. This demonstrates that focused fluid flux could occur in lower crustal shear zones. Preservation of high-temperature isotopic equilibria of minerals testifies that the episode of fluid activity at the peak of metamorphism was very brief.