Chemical composition in phosphate materials from the ocean floor

Content, distribution patterns, and speciation of Cl in phosphorites and bone phosphate from the ocean floor, as well as in a set of samples from the land are studied. Total Cl content varies from 0.05 to 4.25% in phosphorites and from 2.48 to 2.75% in recent phosphate-bearing sediments. Recent phosphorites are enriched in Cl relative to ancient ones. Bound Cl content (not extractable by washing), which increases with lithification, varies from 0.17 to 0.60% in ocean and land phosphorites and from 0.02% to 1.30% in bone phosphate. Na content in most samples is higher relative to Na of NaCl due to its incorporation into the crystal lattice of apatite. However, the opposite relationship is observed in some samples indicating partial Cl incorporation into the anion complex of phosphate. Behavior of Cl in phosphorites from the present-day ocean floor is controlled by early diagenetic processes, whereas the role of weathering, catagenesis, and hydrogeological factors may be crucial for phosphorites on continents.

Composition of phosphorites from continental margins, seamounts, and islands

Behavior of molybdenum and manganese is studied in phosphorite samples from shelves, seamounts, and islands of the ocean. In shelf phosphorites molybdenum and manganese contents are 2-128 and 12-1915 ppm, respectively, while the Mo/Mn ratio varies from 0.004 to 4.5. Phosphorites from ocean seamounts impregnated with ferromanganese oxyhydroxides contain 0.84-14.5 ppm Mo and 0.1-17% Mn. The Mo/Mn ratio varies within 0.0008-0.004. Phosphate bearing ferromanganese crusts overlying seamount phosphorites contain 54-798 ppm Mo and 10-20% Mn; the Mo/Mn ratio varies within 0.002-0.005. Corresponding values for most island phosphorites are 0.44-11.2 ppm, 27-287 ppm, and 0.008-0.20. Phosphorites from reduced environment are characterized by relative enrichment in Mo and depletion in Mn, whereas the Mo/Mn ratio reaches maximum values. The ratio decreases with transition to suboxic and oxic conditions. Molybdenum content in recent shelf sediments is commonly higher than that in authigenic phosphorites from these sediments. Recent phosphorite nodules from the Namibian shelf become depleted in Mo and Mn during their lithification, but Pliocene-Pleistocene nodules of similar composition and origin from the same region are enriched in Mo and characterized by variable Mn content. Higher Mo contents in phosphate bearing ferromanganese crusts result from coprecipitation of Mo and Mn from seawater. Unweathered phosphorites on continents and phosphorites from ocean shelves are largely enriched in Mo with the Mo/Mn ratio varying from 0.01 to 1.0. This is an evidence of their formation in reduced conditions.

(Table 1) Calcite, siderite, and stable isotopes d13C and d18O at DSDP Hole 93-603B

Diagenesis of the fine-grained, feldspathic sandstones in the Lower Cretaceous submarine fan complex cored in DSDP Hole 603B can be considered to have occurred in three stages: (1) replacement of matrix and framework grains by pyrite, siderite, phillipsite (?), and particularly by ferroan calcite; (2) dissolution of ferroan calcite and feldspars to produce secondary macroporosity; and (3) development of sparse feldspar and quartz overgrowths, and authigenic modification of remnant matrix. Only ferroan calcite is a volumetrically important diagenetic mineral phase (up to 50 vol.%). Matrix in thin sandstone turbidite deposits has been extensively replaced by ferroan calcite. Carbon stable isotope data suggest that organic diagenesis had only a minor influence on calcite precipitation. Oxygen stable isotope data indicate that the minimum average calcite precipitation temperature was 40° C. Preliminary calculations show that steadystate diffusion of Ca+ + from the dissolution of nannoplankton skeletal material in the interbedded pelagic marls to the associated sandstones is a feasible transport mechanism. A thick sandstone unit from 1234-1263 m sub-bottom is extensively replaced by calcite near the upper and lower contacts. Farther into the sand body away from the contacts, the sandstone has good secondary porosity resulting from the dissolution of ferroan calcite that partially replaced matrix and framework grains. The central portion of the thick sand appears to be a channel with high-energy clean sand. We believe that the channel provided a conduit for focused flow of diagenetic compactional fluids responsible for dissolution. Focused flow may be the result of the earlier lithification of the pelagic limestones and thin-bedded sandstones which, then formed vertical permeability barriers. Calcite dissolution has occurred and may still be occurring at temperatures less than 65°C.

(Table 1) Age of sediments with anomalously high Hg concentrations in core BDP-98, Lake Baikal

Mercury distribution was examined in the sediments of Lake Baikal that were sampled within the scope of the Baikal Drilling International Project in 1996-1999. The Hg concentrations in the ancient sediments are close to those in the modern sediments with the exception of a few peak values, whose ages coincide with those of active volcanism in adjacent areas. Mercury was demonstrated to be contained in the sediments in the adsorbed Hg0 mode, predominantly in relation with organic matter. When the organic matter of the bottom sediments is decomposed in the course of lithification, Hg is retained in the sediments adsorbed on the residual organic matter, and the concentration of this element corresponds to its initial content in the bottom sediments during their accumulation. Mercury concentrations in lithologically distinct bottom sediments of Lake Baikal and its sediments as a whole depend on the climate. Sediments that were formed during warm periods of time contain more Hg than those produced during cold periods or glaciation. Periodical variations in the Hg concentrations in the bottom sediments of Lake Baikal reflect the variations in the contents of this element in the Earth's atmosphere in the Late Cenozoic, which were, in turn, controlled by the climatic variations on the planet and, thus, can be used for detailed reconstructions of variations in the average global temperature near the planet's surface.

Lithology and approximate sub-bottom depths and ages of the transition of soft to firm ooze and of firm ooze to chalk at DSDP Leg 89 and 90 Sites

Leg 90 recovered approximately 3705 m of core at eight sites lying at middle bathyal depths (1000-2200 m) (Sites 587 to 594) in a traverse from subtropical to subantarctic latitudes in the southwest Pacific region, chiefly on Lord Howe Rise in the Tasman Sea. This chapter summarizes some preliminary lithostratigraphic results of the leg and includes data from Site 586, drilled during DSDP Leg 89 on the Ontong-Java Plateau that forms the northern equatorial point of the latitudinal traverse. The lithofacies consist almost exclusively of continuous sections of very pure (>95% CaCO3) pelagic calcareous sediment, typically foraminifer-bearing nannofossil ooze (or chalk) and nannofossil ooze (or chalk), which is mainly of Neogene age but extends back into the Eocene at Sites 588, 592, and 593. Only at Site 594 off southeastern New Zealand is there local development of hemipelagic sediments and several late Neogene unconformities. Increased contents of foraminifers in Leg 90 sediments, notably in the Quaternary interval, correspond to periods of enhanced winnowing by bottom currents. Significant changes in the rates of sediment accumulation and in the character and intensity of sediment bioturbation within and between sites probably reflect changes in calcareous biogenic productivity as a result of fundamental paleoceanographic events in the region during the Neogene. Burial lithification is expressed by a decrease in sediment porosity from about 70 to 45% with depth. Concomitantly, microfossil preservation slowly deteriorates as a result of selective dissolution or recrystallization of some skeletons and the progressive appearance of secondary calcite overgrowths, first about discoasters and sphenoliths, and ultimately on portions of coccoliths. The ooze/chalk transition occurs at about 270 m sub-bottom depth at each of the northern sites (Sites 586 to 592) but is delayed until about twice this depth at the two southern sites (Sites 593 and 594). A possible explanation for this difference between geographic areas is the paucity of discoasters and sphenoliths at the southern sites; these nannofossil elements provide ideal nucleation sites for calcite overgrowths. Toward the bottom of some holes, dissolution seams and flasers appear in recrystallized chalks. The very minor terrigenous fraction of the sediment consists of silt- through clay-sized quartz, feldspar, mica, and clay minerals (smectite, illite, kaolinite, and chlorite), supplied as eolian dust from the Australian continent and by wind and ocean currents from erosion on South Island, New Zealand. Changes in the mass accumulation rates of terrigenous sediment and in clay mineral assemblages through time are related to various external controls, such as the continued northward drift of the Indo-Australian Plate, the development of Antarctic ice sheets, the increased desertification of the Australian continent after 14 m.y. ago, and the progressive increase in tectonic relief of New Zealand through the late Cenozoic. Disseminated glass shards and (altered) tephra layers occur in Leg 90 cores. They were derived from major silicic eruptions in North Island, New Zealand, and from basic to intermediate explosive volcanism along the Melanesian island chains. The tephrostratigraphic record suggests episodes of increased volcanicity in the southwest Pacific centered near 17, 13, 10, 5 and 1 m.y. ago, especially in the middle and early late Miocene. In addition, submarine basaltic volcanism was widespread in the southeast Tasman Sea around the Eocene/Oligocene boundary, possibly related to the propagation of the Southeast Indian Ridge through western New Zealand as a continental rift system.

(Table 3) Reduced inorganic sulphur, d34S and nickel content of ODP Leg 165 sites

Leg 165 of the Ocean Drilling Program afforded a unique opportunity to investigate organic and inorganic geochemistry across a wide gradient of sediment compositions and corresponding chemical pathways. The solid fractions at Sites 998, 999, 1000, and 1001 reveal varying proportions of reactive carbonate species, a labile volcanic ash fraction occurring in discrete layers and as a dispersed component, and detrital fluxes that derive from continental weathering. The relative proportions and reactivities of these end-members strongly dictate the character of the diagenetic profiles observed during the pore-water work of Leg 165. In addition, alteration of the well-characterized basaltic basement at Site 1001 has provided a strong signal that is reflected in many of the dissolved components. The relative effects of basement alteration and diagenesis within the sediment column are discussed in terms of downcore relationships for dissolved calcium and magnesium. With the exception of Site 1002 in the Cariaco Basin, the sediments encountered during Leg 165 were uniformly deficient in organic carbon (typically <0.1 wt%). Consequently, rates of organic oxidation were generally low and dominated by suboxic pathways with subordinate levels of bacterial sulfate reduction and methanogenesis. The low rates of organic remineralization are supported by modeled rates of sulfate reduction. Site 1000 provided an exception to the generally low levels of microbially mediated redox cycling. At this site the sediment is slightly more enriched in organic phases, and externally derived thermogenic hydrocarbons appear to aid in driving enhanced levels of redox diagenesis at great depths below the seafloor. The entrapment of these volatiles corresponds with a permeability seal defined by a pronounced Miocene minimum in calcium carbonate concentration recognized throughout the basin and with a dramatic downcore increase in the magnitude of limestone lithification. The latter has been tentatively linked to increases in alkalinity associated with microbial oxidation of organic matter and gaseous hydrocarbons. Recognition and quantification of previously unconstrained large volumes and frequencies of Eocene and Miocene silicic volcanic ash within the Caribbean Basin is one of the major findings of Leg 165. High frequencies of volcanic ash layers manifest as varied but often dominant controls on pore-water chemistry. Sulfur isotope results are presented that speak to secondary metal and sulfur enrichments observed in ash layers sampled during Leg 165. Ultimately, a better mechanistic understanding of these processes and the extent to which they have varied spatially and temporally may bear on the global mass balances for a range of major and minor dissolved components of seawater.

(Figure 2) Stratigraphic distribution of Schizosphaerella in DSDP Hole 79-547B

The Jurassic (hemi)pelagic continental margin deposits drilled at Hole 547B, off the Moroccan coast, reveal striking Tethyan affinity. Analogies concern not only types and gross vertical evolution of facies, but also composition and textures of the fine sediment and the pattern of diagenetic alteration. In this context, the occurrence of the nanno-organism Schizosphaerella Deflandre and Dangeard (sometimes as a conspicuous portion of the fine-grained carbonate fraction) is of particular interest. Schizosphaerella, an incertae sedis taxon, has been widely recorded as a sediment contributor from Tethyan Jurassic deeper-water carbonate facies exposed on land. Because of its extremely long range (Hettangian to early Kimmeridgian), the genus Schizosphaerella (two species currently described, S. punctulata Deflandre and Dangeard and S. astrea Moshkovitz) is obviously not of great biostratigraphic interest. However, it is of interest in sedimentology and petrology. Specifically, Schizosphaerella was often the only component of the initial fine-grained fraction of a sediment that was able to resist diagenetic obliteration. However, alteration of the original skeletal structure did occur to various degrees. Crystal habit and mineralogy of the fundamental skeletal elements, as well as their mode of mutual arrangement in the test wall with the implied high initial porosity of the skeleton (60-70%), appear to be responsible for this outstanding resistance. Moreover, the ability to concentrate within and, in the case of the species S. punctulata, around the skeleton, large amounts of diagenetic calcite also contributed to the resistance. In both species of Schizosphaerella, occlusion of the original skeletal void space during diagenesis appears to have proceeded in an analogous manner, with an initial slight uniform syntaxial enlargement of the basic lamellar skeletal crystallites followed, upon mutual impingement, by uneven accretion of overgrowth cement in the remaining skeletal voids. However, distinctive fabrics are evident according to the different primary test wall architecture. In S. punctulata, intraskeletal cementation is usually followed by the growth of a radially structured crust of bladed to fibrous calcite around the valves. These crusts are interpreted as a product of aggrading neomorphism, associated with mineralogic stabilization of the original, presumably polyphase, sediment. Data from Hole 547B, along with inferences, drawn from the fabric relationships, suggest that the crusts formed and (inferentially) mineralogic stabilization occurred at a relatively early time in the diagenetic history in the shallow burial realm. An enhanced rate of lithification at relatively shallow burial depths and thus the chance for neomorphism to significantly influence the textural evolution of the buried sediment may be related to a lower Mg/Ca concentration ratio in the oceanic system and, hence, in marine pore waters in pre-Late Jurassic times.

Chemical composition of samples from DSDP Holes 16-163 and 17-164

Considerable postsedimentational alteration of fine dispersed minerals in Cretaceous sedimentary sequences was found in three deep-sea drillholes (163, 164, 169). Original Fe-montmorillonites formed from basalts were converted during lithification to mixed-layer montmorillonite-hydromicas and then to pure hydromicas (celadonites). An assumption that the minerals were originally of authigenic-diagenetic composition is based on a broad spectrum of other diagenetic minerals present: silica group from opal A to opal CT and quartz, clinoptilolite and palygorskite. In addition, quartz-hydromica ratio is strikingly atypical of aeolian transport.