Geochemistry at DSDP Leg 92 Holes

The major-element and most of the trace-element data from the different laboratories that contributed to the study of samples recovered during Leg 82 are presented in the following tables. The different basalt groups, identified on the basis of their chemical properties (major and trace elements), were defined from the data available on board the Glomar Challenger as the cruise progressed (see site chapters, all sites, this volume). Most of the data obtained since the end of the cruise and presented in these tables confirm the classification that was proposed by the shipboard party (see site chapters, all sites, this volume). Nevertheless, special mention should be made about Site 564. The shipboard party proposed a single chemical group at this site but noticed significant variations down the hole, mainly in trace-element data. However, the range of variation was small compared to the precision of the measurements. These variations were confirmed by the onshore studies (see papers in Part IV of this volume, especially Brannon's paper, partly devoted to this topic).

(Table 2) Geochemistry and petrograhy of DSDP Leg 82 Holes and MAPCO cruise of Jean Charcot in the Mid-Atlantic Ridge area

The compositions of abyssal glasses obtained on Leg 82 of the awGlomar Challenger and the MAPCO cruise of Jean Charcot have been investigated. Two main compositional groups of Atlantic glasses (A1 and A2) that are separated in space and time were identified. The distribution of these groups in the studied area allowed mapping of the transition zone from A1 to A2 between 30-35°N MAR. We infer that the compositional groups of abyssal glasses of the Atlantic and other oceans reflect the depth of separation of primary melts from the oceanic mantle. Specifically, the primary melt of Group A1 separates from the mantle at a depth of 30-60 km (spinel-peridotite facies) and those for Group A2 from a depth of 15-30 km (plagioclase-peridotite facies). Modifications of dynamic models of the ocean lithosphere are discussed.

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Maceral distribution, stratigraphic position and vitrinite reflectance at DSDP Hole 81-555

Twenty-four sediment samples from late Paleocene to early Eocene were studied for maceral content, vitrinite reflectance, and spectral fluorescence in order to determine some parameters of the origin and diagenetic history of their organic fraction. The sediments had been obtained at Site 555 of DSDP Leg 81 in the northeastern North Atlantic. The bulk of the microscopically visible fraction is made up of humic materials; inertinites follow as a distant second; and liptinites are exceedingly rare. No unequivocal evidence of marine organic matter was found. Humic materials are highly decomposed, showing signs of aerobic (frequency of sclerotinites) as well as anaerobic (abundance of and intimate association with framboidal pyrite) microbial degradation. Vitrinite reflectance values vary between 0.26 and 0.35 Ro and show a slight increase with depth. These values, indicative of a low-rank lignite stage of coalification, contrast somewhat with the sporinite fluorescence spectra, which show the configuration typical for the peat stage. In either case, the evidence for such a low stage of coalification is surprising in view of the depth and age of the sediments.

Organic geochemistry and sedimentology of lower to mid-Cretaceous at DSDP Leg 77 Holes

Analyses of 40 carbonate core samples - 27 from Site 535, 12 from Site 540, and 1 from Site 538A - have confirmed many of the findings of the Shipboard Scientific Party. The samples, all but one Early to mid-Cretaceous in age (Berriasian to Cenomanian), reflect sequences of cyclically anoxic and oxic depositional environments. They are moderately to very dark colored, dominantly planar-parallel, laminated lime mudstones. Most show the effects of intense mechanical compaction. Visual kerogen characteristics and conventional Rock-Eval parameters indicate that these deep basinal carbonates contain varying mixtures of thermally immature kerogen derived from both marine and terrigenous precursors. However, variations in kerogen chemistry are evident upon analysis of the pyrolysis mass spectral data in conjunction with the other geochemical analyses. Particularly diagnostic is the reduction index, Rl, a measure of H2S produced during pyrolysis. Total organic carbon, TOC, ranges from 0.6 to 6.6%, with an overall average of 2.4%. Average TOCs for these fine-grained mudstones are: late Eocene 2.5% (1 sample), Cenomanian 2.2% (6), Albian 2.0% (10), Aptian 1.3% (1), Barremian-Hauterivian 2.8% (11), late Valanginian 4.8% (3), Berriasian-early Valanginian 1.6% (7). Most of the carbonates have source-potential ratings of fair to very good of predominantly oil-prone to mixed kerogen, with only a few gas-prone samples. The ratings correlate well with the inferred depositional environments, i.e., whether oxic or anoxic. Several new organic-geochemical parameters, especially Rl, based on pyrolysis mass spectrometry of powdered whole-rock samples, support this view. Tar from fractures in laminated to bioturbated limestones of Unit IV (late Valanginian) at 535-58-4, 19-20 cm (530 m sub-bottom) appears to be mature, biodegraded, and of migrated rather than on site indigenous origin.

Geochemistry and K-Ar dates of the Mazagan granodiorite at V30-225, VA79-96KD and DSDP Hole 79-544A, off Moroccan coast

Gneissic granodiorite was recovered by drilling at the base of the Mazagan escarpment, 100 km west of the Casablanca, Morocco, at 4000 m water depth. Coarse, predeformative muscovite yielded dates of -515 Ma, fine-grained muscovite of -455 Ma, biotite -360 and 335 Ma, and feldspar -315 Ma. These dates are tentatively correlated with the microscopic results. We assume a minimum age of middle Cambrian for the granodiorite, an Ordovician deformation and mylonitization, and a Late Carboniferous overprint under upper greenschist facies conditions.

Carbonate aggregate mineralogy and stable isotopes at DSDP Site 87-583

Crystalline aggregates composed of calcium carbonate were recovered in the uppermost 50 m of Nankai Trough sediments during DSDP Leg 87A. These aggregates decomposed with time to masses of sandy calcite as determined by X-ray diffraction analysis. Petrographic and scanning electron microscopy revealed textures suggestive of a precursor phrase prior to calcite, and this precursor has been tentatively identified as the mineral ikaite, CaCO3*6H2O. Stable isotope data suggest a large component of terrigenous organic matter as the carbon source, consistent with the appearance of these aggregates in highly reducing pyritic sediments containing abundant plant remains. We propose that these nodules formed in euxinic basins on the upper part of the Trough slope under normal seafloor conditions of pressure and temperature. Calculated temperatures of formation of this phase are not unusually low. The specimens from Site 583 are the first reported occurrences of ikaite in active margin sediments.

Sedimentation in the vicinity of Leg 92 Drill Sites: Studies of site survey cores

Surveys of the areas surrounding the sites drilled on the Leg 92 19°S transect showed that sedimentation at all except the oldest site is dominated by calcium carbonate deposition. The sediments in the area of the oldest site, west of the Austral Fracture Zone, are being deposited beneath the calcium carbonate compensation depth and are dominated by terrigenous and metal-rich hydrogenous and hydrothermal sediments. The noncarbonate sediments in all of the areas east of the Austral Fracture Zone are dominated by hydrothermal sediment similar in composition to that presently being deposited at the East Pacific Rise. Although no biogenic microfossils were present in smear slides of the sediment, geochemical partitioning suggests that a remnant signal of siliceous biogenic deposition may be preserved, especially in gravity core (GC) 8, which was collected from a high heat flow zone near Site 600. The siliceous sediment may also result from the deposition of amorphous hydrothermal silica from the higher concentrations of pore water SiO2 characteristic of the upwelling waters. Sedimentation on the broad plateaus that characterize each area is quite uniform and suggests that sites on these plateaus will be broadly representative of pelagic sedimentation in the area.

Magnetic properties of plutonic rocks at DSDP Leg 82 holes

Ten samples of gabbro and peridotite, with varying degrees of serpentinization, were studied by magnetic techniques and reflected light microscopy. Evidence from these methods suggests that the natural remanent magnetization is primarily of chemical origin. It is generally weak for the gabbros and much stronger for the peridotites. This difference is offset by the fact that the peridotites have generally lower magnetic stability and Koenigsberger ratios. There is a considerable variation in both magnetic parameters and petrology even among closely spaced samples, which suggests that some combination of source heterogeneity and tectonic mixing was involved in the production of these rocks. However, the small number of samples makes this conclusion tentative. There may also have been significant postemplacement alteration involved. All samples show a significant anisotropy of weak field susceptibility that appears to be related to deformation. This anisotropy may be useful in defining petrofabrics.

Chemistry of primary and secondary phases in intraplate basalts and volcaniclastic sediments at DSDP Leg 89 Holes

Electron microprobe data are presented for clinopyroxenes, plagioclases, palagonites, smectites, celadonites, and zeolites in Hole 462A sheet-flow basalts and Site 585 volcaniclastic sediments. Glomerocrystic clinopyroxenes in Hole 462A are predominantly Ti-poor augites with minor fractionation to ferroaugites in rim portions. Quenched plumose clinopyroxenes show considerable variation from Ca-rich to Ca-poor augites, although all are characterized by being Tirich and Cr-poor relative to the glomerocrysts. Two differentiated series of Site 585 pyroxene compositions, calcic augite and diopside-salite, demonstrate the coexistence, in the vitric and lithic clasts, of tholeiitic and alkali basalt types, respectively. Plagioclase compositions in all samples are mainly labradorites, although some zoned Hole 462A glomerocrysts range from An73 to An20 and are characterized by high Mg and Fe contents in the more calcic varieties. The K content of the plagioclases is highest in the more sodic crystals, although the overall higher orthoclase component of Site 585 plagioclases reflects the generally higher bulk-rock K content. The compositions of both secondary smectites and celadonites are similar irrespective of the alteration location (glass, matrix, vesicles, etc.), although brown smectites replacing interstitial glass have marginally higher total Fe contents than pale green and yellow smectites. Analyzed zeolites are mainly phillipsites with variable alkali content, and, together with associated celadonite, represent late-stage alteration repositories for K under mildly oxidizing conditions. The compositions of both early and late secondary minerals are typical of those formed by the submarine alteration of basaltic rocks at low temperatures.

Inorganic and organic geochemistry and sediment descriptions at DSDP Hole 93-603B

About one hundred samples of sediments and rocks recovered in Hole 603B were analyzed for type, abundance, and isotopic composition of organic matter, using a combination of Rock-Eval pyrolysis, C-H-N-S elemental analysis, and isotope-ratio mass spectrometry. Concentrations of major, minor, and trace inorganic elements were determined with a combination of X-ray fluorescence and induction-coupled plasma spectrometry. The oldest strata recovered in Hole 603B (lithologic Unit V) consist of interbedded light-colored limestones and marlstones, and black calcareous claystones of Neocomian age. The inorganic and organic geochemical results suggest a very terrigenous aspect to the black claystones. The organic geochemical results indicate that the limestones and marlstones contain a mixture of highly degraded marine and terrestrial organic matter. Comparison of the Neocomian carbonates at Site 603 with those on the other side of the North Atlantic, off Northwest Africa at Site 367, shows that the organic matter at Site 367 contains more marine organic matter, as indicated by higher pyrolysis hydrogen indices and lighter values of d13C. Comparison of inorganic geochemical results for the carbonate lithologies at Site 603 with those for carbonate lithologies at Site 367 suggests that the Site 603 carbonates may contain clastic material from both North American and African sources. The black claystones at Site 603, on the other hand, probably were derived almost entirely from North American clastic sources. Lithologic Unit IV overlying the Neocomian carbonates, consists of interbedded red, green, and black claystones. The black claystones at Site 603 contain more than ten times the organic carbon concentration of the interbedded green claystones. The average concentration of organic carbon in the black claystones (2.8%), however, is low relative to most mid-Cretaceous black claystones and shales in the Atlantic, particularly those found off Northwest Africa. The geochemical data all suggest that the organic matter in the black claystones is more abundant but generally more degraded than the organic matter in the green claystones, and that it was derived mainly from terrestrial sources and deposited in oxygenated bottom waters. The increased percentage of black claystone beds in the upper Cenomanian section, and the presence of more hydrogen-rich organic matter in this part of the section, probably resulted from the increased production and accumulation of marine organic matter that is represented worldwide near the Cenomanian/Turonian boundary in deep-sea and land sections. A few upper Cenomanian black claystone samples that have hydrogen indices > 150 also contain particularly high concentrations of V and Zn. Most samples of black claystone, however, are not particularly metal-rich compared with other black claystones and shales. Compared with red claystones from lithologic Unit IV, the green and black claystones are enriched in many trace transition elements, especially V, Zn, Cu, Co, and Pb. The main difference between the "carbonaceous" claystones of lithologic Unit IV and "variegated" or "multicolored" claystones of the overlying Upper Cretaceous to lower Tertiary Unit III is the absence of black claystone beds. As observed at several other sites (105 and 386), the multicolored claystones at Site 603 are somewhat enriched in several trace transition elements-especially Cu, Ni, and Cr-relative to most deep-sea clays. The multicolored claystones are not enriched in Fe and Mn, and therefore are not "metalliferous" sediments in the sense of those found at several locations in the eastern Pacific. The source of the slightly elevated concentrations of transition metals in the multicolored claystones probably is upward advection and diffusion of metals from the black claystones of the underlying Hatteras Formation. The red, orange, and green claystone beds of lithologic Unit II (Eocene), like those of Unit III, really represent a continuation of deposition of multicolored claystone that began after the deposition of the Neocomian carbonates. The color of the few black beds that occur within this unit results from high concentrations of manganese oxide rather than high concentrations of organic matter.