Mineralogical composition, copper and d18O at DSDP Site 59-448

Alteration in a submarine remnant volcanic arc should leave an important record of (1) the mineralogy of sea water-volcanic arc rock interaction; (2) the chemistry of solid reaction products; (3) the isotopic characteristics of such reactions (Muehlenbachs and Clayton, 1972; Spooner, Beckinsale, et al , 1977; Spooner, Chapman, et al., 1977); (4) the metallogenesis within such a sequence (Mitchell and Bell, 1973); and (5) the geothermal gradient during the alteration. The volcaniclastic breccias, tuffs, and igneous units of Sites 448 (993 m) and 451 (930.5 m) on the Palau-Kyushu and West Mariana ridges, respectively, are particularly suited for such studies because the thick sequences have remained submarine throughout their history, seemingly unaffected by magmatic or hydrothermal events after cessation of volcanic activity. Also, shipboard observations indicated a change in alteration products with depth. At both sites the igneous units and volcaniclastic rocks were altered to brownish clays and zeolites near the top of the volcanic sequence; to bright blue green clays and zeolites at moderate depths; and to very dark, nearly opaque, forest green clays and zeolites at still greater depths. Native copper occurs both as disseminated pockets in the volcaniclastic breccias and vesicular basalts and as veins in the breccias; native copper is restricted to stratigraphic levels characterized by the absence of sulfides or oxides of copper and iron. Although some native copper is found in vesicles of basalts and may be orthomagmatic, most of it is clearly secondary. Near dikes and sills, higher sulfur fugacity conditions caused the precipitation of iron and copper sulfides with an absence of native copper (Garrels and Christ, 1965). The occurrence of native copper may be an initial stage of Cu metallogenesis that forms porphyry coppers in island arcs (Mitchell and Bell, 1973). This study will address primarily the possibility that hydrothermal sea water interaction with volcanic arc rocks has created the mineralogical and isotopic zonation in Leg 59 cores. Hydrothermal activity can be expected in a rapidly growing island arc and is probably the result of a high geothermal gradient prevalent during arc magmatic activity. The chemical character of the alteration is further discussed by Hajash (1981).

Lithium concentrations and isotope composition of basalt samples from ODP/DSDP Sites from Costa Rica Rift

Ocean Drilling Program (ODP) Hole 504B near the Costa Rica Rift is the deepest hole drilled in the ocean crust, penetrating a volcanic section, a transition zone and a sheeted dike complex. The distribution of Li and its isotopes through this 1.8-km section of oceanic crust reflects the varying conditions of seawater alteration with depth. The upper volcanic rocks, altered at low temperatures, are enriched in Li (5.6-27.3 ppm) and have heavier isotopic compositions (delta7Li=6.6-20.8?) relative to fresh mid-ocean ridge basalt (MORB) due to uptake of seawater Li into alteration clays. The Li content and isotopic compositions of the deeper volcanic rocks are similar to MORB, reflecting restricted seawater circulation in this section. The transition zone is a region of mixing of seawater with upwelling hydrothermal fluids and sulfide mineralization. Li enrichment in this zone is accompanied by relatively light isotopic compositions (-0.8-2.1?) which signify influence of basalt-derived Li during mineralization and alteration. Li decreases with depth to 0.6 ppm in the sheeted dike complex as a result of increasing hydrothermal extraction in the high-temperature reaction zone. Rocks in the dike complex have variable isotopic values that range from -1.7 to 7.9?, depending on the extent of hydrothermal recrystallization and off-axis low-temperature alteration. Hydrothermally altered rocks are isotopically light because 6Li is preferentially retained in greenschist and amphibolite facies minerals. The delta7Li values of the highly altered rocks of the dike complex are complementary to those of high-temperature mid-ocean ridge vent fluids and compatible to equilibrium control by the alteration mineral assemblage. The inventory of Li in basement rocks permits a reevaluation of the role of oceanic crust in the budget of Li in the ocean. On balance, the upper 1.8 km of oceanic crusts remains a sink for oceanic Li. The observations at 504B and an estimated flux from the underlying 0.5 km of gabbro suggest that the global hydrothermal flux is at most 8*10**9 mol/yr, compatible with geophysical thermal models. This work defines the distribution of Li and its isotopes in the upper ocean crust and provides a basis to interpret the contribution of subducted lithosphere to arc magmas and cycling of crustal material in the deep mantle.

Composition of Fe-Mn minerals from island arcs of the West Pacific

This paper presents materials on the chemical and mineralogical composition of Fe-Mn mineralization in island arcs (Kuril, Nampo, Mariana, New Britain, New Hebrides, and Kermadec) in the western part of the Pacific Ocean. The mineralization was proved to be of hydrothermal and/or hydrogenic genesis. The former is produced by hydrothermal Fe and Mn oxi-hydroxides that cement volcanic-terrigenous material in sediments. Some Fe oxyhydroxides can be derived via the halmyrolysis of volcaniclastic material. Crusts of this stage are characterized by fairly low concentrations of trace and rare elements, and their REE composition is inherited from the volcanic-terrigenous material. The minerals of the Mn oxyhydroxides are todorokite and "Ca-birnessite". The Mn/Fe ratio increases away from the discharge sites of the hydrothermal solutions. The hydrogenic Fe-Mn crusts are characterized by high concentrations of trace and minor elements of both the Mn group (Co, Ni, Tl, and Mo) and the Fe group (REE, Y, and Th). The hydrogenic crusts consist of Fe-vernadite and Mn-feroxyhyte. Some of the hydrothermal crusts originally had a hydrothermal genesis. The first data were obtained on crust B30-72-10 from the Macauley Seamount in the Kermadec island arc, which contained anomalously high concentrations of Co (2587 ppm) and other Mn-related trace elements in the absence of hydrogeneous Fe oxyhydroxides.

(Table 5) Quaternary paleoproductivity of organic carbon in oceans based on DSDP cores

By analogy with the present-day ocean, primary productivity of paleoceans can be reconstructed using calculations based on content of organic carbon in sediments and their accumulation rates. Results of calculations based on published data show that primary productivity of organic carbon, mass of phosphorus involved in the process, and content of phosphorus in ocean waters were relatively stable during Cenozoic and Late Mesozoic. Prior to precipitation on the seafloor together with biogenic detritus, dissolved phosphorus could repeatedly be involved in the biogeochemical cycle. Therefore, only less than 0.1% of phosphorus is retained in bottom sediments. Bulk phosphorus accumulation rate in ocean sediments is partly consistent with calculated primary productivity. Some epochs of phosphate accumulation also coincide with maxima of primary productivity and minima of the fossilization coefficient of organic carbon. The latter fact can testify to episodes of acceleration of organic matter mineralization and release of phosphorus from sediments leading to increase in the phosphorus reserve in paleoceans and phosphate accumulation in some places.

Chemical composition of Fe-Mn nodules and crusts from oceans and seas

Fluorine concentrations were determined ionometrically with an error of 0.02% in iron-manganese materials of the ocean. They were: 0.02-0.04% in ocean iron-manganese nodules, with the exception of two specimens (0.08% and 0.20% F); up to 0.02% in iron-manganese nodules of seas; 0.02-1.17% in ore crusts from ocean seamounts; and 0.02% in ore sediments of the Red Sea. Elevated fluorine content of ore crusts is associated with presence of calcium phosphate inclusions in them. Fluorine is not accumulated during iron-manganese nodule mineralization. Its average concentration in the nodules is half that in host deep-sea sediments.

Silicate content in sediment ofthe Santa Monica Basin, California

Seafloor recycling of organic materials in Santa Monica Basin, California was examined through in situ benthic chamber experiments, shipboard whole-core incubations and pore water studies. Mass balance calculations indicate that the data are internally consistent and that the estimated benthic exchange rates compare well with those derived from deep, moored conical sediment traps and hydrographic modeling. Pore water and benthic flux observations indicate that the metabolizable organic matter at the seafloor must be composed of at least two fractions of very different reactivities. While the majority of reactive organic compounds degrade quickly, with a half-life of <=6.5 years, 1/4 of the total metabolizable organic matter appears to react more slowly, with a half-life on the order of 1700 years. Down-core changes in pore water sulfate and titration alkalinity are not explained by stoichiometric models of organic matter diagenesis and suggest that reactions not considered previously must be influencing the pore water concentrations. Measured recycling and burial rates indicate that 43% of the organic carbon reaching the basin seafloor is permanently buried. The results for Santa Monica Basin are compared to those reported for other California Borderland Basins that differ in sedimentation rate and bottom water oxygen content. Organic carbon burial rates for the Borderland Basins are strongly correlated with total organic carbon deposition rate and bulk sedimentation rate. No significant correlation is observed between carbon burial and bottom water oxygen, extent of oxic mineralization and sediment mixing. Thus, for the California Borderlands, it appears that carbon burial rates are primarily controlled by input rates and not by variations in preservation.

Pollen and diatom analysis on varved sediments in Lake Jues (Harz Mountains, Germany)

Studies combining sedimentological and biological evidence to reconstruct Holocene climate beyond the major changes, and especially seasonality, are rare in Europe, and are nearly completely absent in Germany. The present study tries to reconstruct changes of seasonality from evidence of annual algal successions within the framework of well-established pollen zonation and 14C-AMS dates from terrestrial plants. Laminated Holocene sediments in Lake Jues (10°20.70' E, 51°39.30' N, 241 m a.s.l.), located at the SW margin of the Harz Mountains, central Germany, were studied for sediment characteristics, pollen, diatoms and coccal green algae. An age model is based on 21 calibrated AMS radiocarbon dates from terrestrial plants. The sedimentary record covers the entire Holocene period. Trophic status and circulation/stagnation patterns of the lake were inferred from algal assemblages, the subannual structure of varves and the physico-chemical properties of the sediment. During the Holocene, mixing conditions alternated between di-, oligo- and meromictic depending on length and variability of spring and fall periods, and the stability of winter and summer weather. The trophic state was controlled by nutrient input, circulation patterns and the temperature-dependent rates of organic production and mineralization. Climate shifts, mainly in phase with those recorded from other European regions, are inferred from changing limnological conditions and terrestrial vegetation. Significant changes occurred at 11,600 cal. yr. BP (Preboreal warming), between 10,600 and 10,100 cal. yr. BP (Boreal cooling), and between 8,400 and 4,550 cal. yr. BP (warm and dry interval of the Atlantic). Since 4,550 cal. yr. BP the climate became gradually cooler, wetter and more oceanic. This trend was interrupted by warmer and dryer phases between 3,440 and 2,850 cal. yr. BP and, likely, between 2,500 and 2,250 cal. yr. BP.