Composition of bentonite-, smectite-rich- and ash beds from DSDP Leg 19 holes

Late Cenozoic ash deposits cored in Deep Sea Drilling Project Leg 19 in the far northwest Pacific and in the Bering Sea have altered to bentonite beds. Some bentonite layers were subsequently replaced by carbonate beds. A significant part of the Neogene volcanic history of land areas adjacent to the far north Pacific is represented by these diagenetic deposits. Bentonite beds are composed of authigenic smectite and minor amounts of clinoptilolite. Authigenic smectite has fewer illite layers than detrital smectite. Opal-A and opal-CT, abundant in Bering Sea sediment, are not found in ash or bentonite layers. The percentage of smectite in the total clay-mineral assemblage of ash beds is greater than that for adjacent terrigenous sediment, but the total amount of clay minerals in ash sequences is less than in surrounding deposits. Morphology of the 17-Å peak of smectite found in ash may represent newly formed, poorly crystalline smectite. Smectite becomes better crystallized as bentonite layers form. The percentage of smectite of the total clay-mineral assemblage in bentonite beds is greater than that in surrounding sediment, and, in contrast to ash beds, the total amount of clay minerals (mostly smectite) in bentonite layers is greater than in adjacent terrigenous sediment. Apparently, silica is not mobilized when volcanic ash layers transform to bentonite beds. Saponite-nontronite varieties of smectite and high Fe/Al and Ti/Al ratios distinguish bentonite beds derived from basaltic parent material from those beds formed from more silicic volcanic ash. These silicic ash beds produce bentonite composed mostly of montmorillonite. The basal sediment section at site 192 is rich with bentonite beds. Smectite in the upper part of this section (Eocene) was formed by low-temperature diagenesis of volcanic debris of intermediate or more silicic composition derived from arc or Pacific volcanoes. In contrast, smectite from the lowest 10 to 20 m of the sedimentary section (Cretaceous) is formed from either low-temperature or hydrothermal alteration of the underlying basaltic basement and associated pyroclastic debris. This near-basement smectite contains Mg and K acquired from sea water and Si, Al, Fe, Ti, and Mn released from the volcanic material.

Ash layers, hyaloclastite, and alteration of basaltic glass at DSDP Leg 65 Holes

Three types of tephra deposits were recovered on Leg 65 of the Deep Sea Drilling Project (DSDP) from three drill sites at the mouth of the Gulf of California: (1) a series of white ash layers at Sites 483, 484, and 485; (2) a layer of plagioclase- phyric sideromelane shards at Site 483; and (3) an indurated, cross-bedded hyaloclastite in Hole 483B. The ash layers in (1) are composed of colorless, fresh rhyolitic glass shards with minor dacitic and rare basaltic shards. These are thought to be derived from explosive volcanoes on the Mexican mainland. Most of the shards in (2) are fresh, but some show marginal to complete alteration to palagonite. The composition of the glass is that of a MORB-type tholeiite, low in Fe and moderately high in Ti, and possibly erupted from off-axis seamounts. Basaltic glass shards occurring in silt about 45 meters above the basement at Site 484 A in the Tamayo Fracture Zone show a distinctly alkalic composition similar to that of the single basement basalt specimen drilled at this site. The hyaloclastite in (3) is made up chiefly of angular sideromelane shards altered to smectite and zeolites (mainly phillipsite) and minor admixtures of terrigenous silt. A very high K and Ba content indicates significant uptake of at least these elements from seawater. Nevertheless, the unusual chemical composition of the underlying massive basalt flow is believed to be reflected in that of the hyaloclastite. This is a powerful argument for interpreting the massive basalt as a surface flow rather than an intrusion. Glass alteration is different in the glassy margins of flows than in thicker glassy pillow rinds. Also, it appears to proceed faster in coarse- than fine-grained sediments.

(Table 1) Chemical composition and bulk densities of dolerites from ODP Hole 504B lower dikes

Chemical interactions between seawater and the oceanic crust have been widely investigated during recent years. However, most of these studies concern the uppermost volcanic part of the crust. The contribution of the underlying sheeted dike complex to the global budget of the oceans is inferred solely from some ophiolite studies and from the 500-m high-level dike section of DSDP/ODP 504B which was drilled in 1981. Hole 504B is the only place where a continuous and long (1260 m) section in the sheeted dike complex has been cored, and it is now regarded as a reference section for the upper oceanic crust. Many petrological and chemical data from these dolerites are available, including the relative proportions of veins, extensively altered adjacent rocks, and less altered 'host-rocks'. For these three reasons, considering the entire dike section penetrated by Hole 504B is a unique chance to study chemical fluxes related to hydrothermal alteration of this part of the oceanic crust. The calculation of any chemical flux implies knowledge of the chemical composition of the fresh precursor (protolith). Previously, mean compositions of glasses (=P1a) or basalts from the Hole 504B volcanics have been used as protoliths. In this paper, we calculate and discuss the use of various protoliths based on dolerites from Hole 504B. We show that the most adequate and realistic protolith is the mean of individual protoliths that we calculated from the acquisition, by automatic mode, of about 1000 microprobe analyses in each thin-section of dolerite from the Hole 504B lower dikes. Consequently, PFm is further used to calculate chemical fluxes in the dike section of Hole 504B. The chemical compositions of the host-rocks adjacent to alteration halos tend to converge to that of PFm with depth, except for Fe2O3t and TiO2. Because the volume percent of alteration halos increases with depth, the total fluxes related to these halos increase with depth. This explains why the mean flux (host-rocks+halos+veins) of the upper dikes is roughly similar to the mean flux of the lower dikes. During the alteration of the entire Hole 504B dike section, the dolerites gained relatively large quantities of Fe2O3t (+4.0 g/100 cm**3) and released much SiO2 (-6.8 g/100 cm**3), CaO (-5.8 g/100 cm**3), and TiO2 (1.6 g/100 cm**3), and minor Al2O3 (-0.7 g/100 cm**3) and MgO (-0.7 g/100 cm**3). We show the importance of the choice of the protolith in the calculation of chemical budget, particularly for elements showing low flux values. In Hole 504B, the Mg uptake by the volcanics during low temperature alteration added to the Mg release by the dikes gives a net flux of -0.07x10**14 g/year. We propose that part of the Mg uptake by the oceanic crust, which is necessary to compensate the rivers input (-1.33x10**14 g/year), occurs in the underlying gabbros and/or in sections which are altered such as Trinity and Troodos ophiolites. Compared with ophiolites, fluxes calculated for elements other than Mg for the entire crust are generally similar (in tendency, if not in absolute value) to that we obtained from Hole 504B.

Elemental and stable isotopic composition of fine fraction samples of ODP Site 115-709 (Table 1)

Stable isotopic and minor element compositions were measured on the fine fraction of pelagic carbonate sediments from Ocean Drilling Program Site 709 in the central Indian Ocean. This section ranges in age from 47 Ma to the present. The observed compositional variations are the result of either paleoceanographic changes (past oceanic chemical or temperature variations) or diagenetic changes. The CaCO3 record is little affected by diagenesis. From previous work, carbonate content is known to be determined by the interplay of biological productivity, water column dissolution, and dilution. The carbon isotopic record is generally similar to previously published curves. A good correlation was observed between sea-level high stands and high 13C/12C ratios. This supports Shackleton's hypothesis that as the proportion of organic carbon buried in marine sediments becomes larger, oceanic-dissolved inorganic carbon becomes isotopically heavier. This proportion appears to be higher when sea level is higher and organic carbon is buried in more extensive shallow-shelf sediments. The strontium content and oxygen isotopic composition of carbonate sediments are much more affected by burial diagenesis. Low strontium concentrations are invariably associated with high values of d18O, probably indicating zones of greater carbonate recrystallization. Nevertheless, there is an inverse correlation between strontium concentration and sea level that is thought to be a result of high-strontium aragonitic sedimentation on shallow banks and shelves during high stands. Iron and manganese concentrations and, to a lesser extent, magnesium and strontium concentrations and carbon isotopic ratios are affected by early diagenetic reactions. These reactions are best observed in a slumped interval of sediments that occurs between 13.0 and 17.5 Ma. As a result of microbial reduction of manganese and iron oxides and dissolved sulfate, it is hypothesized that small amounts of mixed-metal carbonate cements are precipitated. These have low carbon isotopic ratios and high concentrations of metals.

Mineralogy at DSDP Site 82-558 and Hole 82-563

Downhole bulk-sample and clay-mineral analytical results for Sites 558 and 563 are presented in this chapter. These results show a Tertiary climatic and hydrologic evolution similar to that at other DSDP drill sites in the northeastern Atlantic Ocean (Sites 398, 403-406, 548-550, 552-555). The sediments recovered at both sites are primarily calcareous and chalky oozes characterized by >90% carbonate and minor quartz and plagioclase feldspar. Clay minerals smectite, kaolinite, illite, and chlorite are present throughout the cores; upsection, illite increases at the expense of smectite. The clay mineralogy suggests climatic cooling and increased ocean circulation during the Miocene. Intervals rich in very fine grained (<2 µm) quartz suggest times of increased eolian input. This could have resulted from development, during Oligocene and late Miocene time, of an arid, desertlike sediment provenance that lasted until the present day.

(Table S1) Stable carbon and oxygen isotopes and Mg/Ca ratios of planktonic foraminifera from ODP Hole 198-1209B

The Paleocene-Eocene Thermal Maximum (PETM) has been attributed to a rapid rise in greenhouse gas levels. If so, warming should have occurred at all latitudes, although amplified toward the poles. Existing records reveal an increase in high-latitude sea surface temperatures (SSTs) (8° to 10°C) and in bottom water temperatures (4° to 5°C). To date, however, the character of the tropical SST response during this event remains unconstrained. Here we address this deficiency by using paired oxygen isotope and minor element (magnesium/calcium) ratios of planktonic foraminifera from a tropical Pacific core to estimate changes in SST. Using mixed-layer foraminifera, we found that the combined proxies imply a 4° to 5°C rise in Pacific SST during the PETM. These results would necessitate a rise in atmospheric pCO2 to levels three to four times as high as those estimated for the late Paleocene.

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(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.

Mineralogy, geochemistry and elemental ratios of ODP Core 171B-1049C-8X

Inorganic geochemistry and mineralogy of Core 171B-1049C-8X, containing a Cretaceous/Tertiary boundary section, was investigated by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The ages of samples analyzed stretched from the latest Maastrichtian into the Danian. XRD measurements were made using the peak height method. A reduction in low-magnesium calcite and an increase in quartz were found above the spherule layer. Substantial amounts of dolomite were noted just above the spherule layer. XRF analyses were performed using the RHSMALL program to measure the abundance of major and minor elements. Replicate analyses for each technique were performed to assess the precision of the results. The section above the spherule bed was found to be characterized by peaks in many elements, including Si, Al, Fe, and Mg, as well as the following elemental ratios: Fe/Al, Ni/Al, Zr/Rb, and Rb/Sr'. Above the spherule bed, there were significant reductions in Ca, Sr/Ca, Ti/Al, K/Al, Rb/Al, Cr/Al, Ba/Al, biogenic Ba, and excess P.