Diagenetic alteration of organic matter in DSDP Leg 57 Holes

I analyzed Leg 57 sediments organogeochemically and spectroscopically. Organic carbon and extractable organic matter prevail from the Pliocene to the Miocene. Humic acids occur widely from the Pleistocene to the lower Miocene and one portion of the Oligocene. The absence of humic acids in Oligocene and Cretaceous samples suggests that humic acids had changed to kerogen. Visible spectroscopic data reveal that humic acids in this study have a low degree of condensed aromatic-ring system, which is a feature of anaerobic conditions during deposition, and that chlorophyll derivatives that had at first combined with humic acids moved to the solvent- soluble fraction during diagenesis. The elemental compositions of humic acids show high H/C and O/C ratios, which seem appropriate to a stage before transformation to kerogen. The relation between the linewidths and g-values on the electron spin resonance data indicates that the free radicals in humic acids are quite different from those in kerogen. The low spin concentrations of kerogen and the yields of humic acids up to the lower Miocene demonstrate that organic matter in these sediments is immature. The foregoing indicate the necessity to isolate humic acids even in ancient rocks in the study of kerogen.

Physical properties and minerals of Leg 65 Holes basalts

Velocities and densities of submarine basalts obtained during Leg 65 are distinguished by their relatively high values (about 6.3 km/s and 2.9 g/cm/**3, respectively). This is consistent with their low degree of alteration. The range of velocities covered by these samples correlates well with porosity, and a comparison with in situ velocities from refraction data suggests maximum porosities ih the upper 100 meters of the crust of about 10%.

Magnetic properties of ODP Hole 109-670A

Magnetic fabrics of serpentinized peridotites are related to anisomorphic magnetite formed during serpentinization. In the less serpentinized facies they are, however, mainly mimetic of the high temperature deformation prior to serpentinization. In more serpentinized peridotites, the magnetic fabrics, related to magnetite veins which are more developed in this case, are superimposed on mimetic fabrics. Remanent properties, hysteresis loop parameters, and Curie temperatures were measured. Natural remanent magnetizations (NRM) have crystallization remanent magnetic (CRM) origin. Measured magnetic parameters suggest that pseudo-single domain (PSD) grains of magnetite are present in samples with low degree of serpentinization. The samples with high degree of serpentinization contain mainly multi-domain (MD) magnetite grains.

Geochemistry of Walvis Ridge basalts

The proposed origins for the Enriched Mantle I component are many and various and some require an arbitrary addition of an exotic component, be it pure sediment or an enriched melt from the subcontinental lithosphere. With Pitcairn, Walvis Ridge is the 'type-locality' for the Enriched Mantle I (EMI) component. We analyzed basalts from DSDP Site 525A, Site 527 and Site 528 on the Walvis Ridge with the aim to constrain the history of its source. The isotopic compositions we measured for the three sites overlap with the values obtained by Richardson et al. (1982a) and extend towards less radiogenic Sr and more radiogenic Pb and Nd isotopic compositions. We used our new trace element and radiogenic isotope (Hf, Nd, Pb and Sr) characterization in combination with the literature data to produce the simplest possible model that satisfies the trace element and isotopic constraints. Although the elevated 207Pb/204Pb with respect to 206Pb/204Pb predicts an ancient origin for EMI, none of the proposed origins had modeled it as such. The data is consistent with the EMI composition being formed by the addition of a melt to a mantle with bulk Earth-like composition followed by melt extraction of a low degree melt. The timing of these two events is such that the metasomatism has to have taken place prior to 4 Ga and the subsequent melt removal before 3.5 Ga. This confirms the expectation of an ancient character for the EMI component. The Walvis Ridge data shows two distinct two component mixing trends: one formed by the less enriched Site 527 and Site 528 basalts and one formed by the Site 525A basalts. The two trends have the EMI endmember in common. The less depleted end of the Site 527-Site 528 basalts is FOZO-like and can be explained by the addition of a recycled component (basaltic oceanic crust plus sediment). This recycled component was altered during subduction. The sense and magnitude of the chemical fractionation resulting from the subduction alteration are in agreement with dehydration experiments on basalts and sediment. Compared to other EMI like basalts the Walvis Ridge basalts have flatter REE patterns and show less fractionation between large ion lithophile and heavy REE elements. Using the isotopic compositions as constrains for the parent-daughter ratios we were able to model the trace element patterns of the basalts as melting between 5 and 10% for Site 525A and between 10 and 15% for the depleted end of the Site 528-Site 527 array. In all cases a significant portion of melting takes place in the garnet stability field.

14C ages, grain size distribution and foraminifer abundance of sediments from the Barents Sea shelf

The origin of friable sediments blanketing the Barents Sea shelf is considered. It is shown that their characteristic seismoacoustic record patterns reflect low degree of diagenetic transformations and indicates continuous sedimentation. According to traditional views, this single sedimentary complex also includes diamicton, and the section is interpreted as a three-unit structure: diamicton, which is considered a till; the overlying friable sediments accumulated under different conditions of deglaciation in glaciomarine settings; and the postglacial marine sediments. It is demonstrated that such views are inconsistent with geomorphologic features (datings by physical methods included) indicating a prolonged hiatus that separates epochs of the diamicton accumulation and formation of friable sediments. The analysis revealed that the composition, vertical succession, and lateral distribution of different lithological types of friable sediments are related to the regular spatiotemporal replacements of different facies settings in the transgressing Arctic sea rather than by the glacial process. This inference is confirmed by the composition of foraminiferal assemblages.

Strontium isotope geochemistry of ODP Leg 113 sites

The concentration of dissolved Sr and the distribution of 87Sr/86Sr isotope ratios in Leg 113 interstitial waters may be interpreted in terms of mixing of Sr from four different reservoirs: indigenous seawater, marine carbonate minerals, and basaltic and siliceous detrital material. The input to the pore water from these reservoirs is determined by the reactivity of the reservoir rather than its size. The presence of strontium derived from siliceous detrital material is unequivocally demonstrated in the pore waters of the hemipelagic deposits, and is also significant in the calcareous Maud Rise sediments due to the unusually low degree of carbonate recrystallization. Also, alteration of basic volcanic material is important at several sites.

Organic chemistry of sediments of the Peru margin

Organic-carbon-rich anoxic sediments from the continental shelf (Site 680) and the lower continental slope (Site 688) off Peru were studied to determine factors controlling the accumulation of reduced sulfur. High concentrations of organic matter in diatomaceous muds, its thermal immaturity, and the presence of abundant hydrogen-containing organic compounds lead to the conclusion that organic matter is not limiting for reduced sulfur formation. Rather, high degrees of iron pyritization at Site 680 limit pyrite accumulation in sediments from this shelf site. The low degree of iron pyritization and nearly complete reduction of dissolved sulfate at Site 688 suggest that a lack of interstitial sulfate is limiting pyrite formation there. Although factors that limit the formation of sedimentary iron sulfide are different at each site, the resulting average reduced-sulfur concentrations are remarkably similar (0.85 wt.% at Site 680 and 0.86 wt.% at Site 688). Carbon to sulfur (C/S) ratios are higher in samples containing in excess of 3 wt.% organic carbon than the average of 2.8 in normal marine sediments and have been primarily influenced by variations in organic matter concentrations.

Paleomagnetism of basalts from ODP Hole 109-648A

Paleomagnetic parameters of 55 basalt samples from Hole 648B on the Mid-Atlantic Ridge were studied. Negative NRM inclinations were found for 10 samples between 10 and 25 m sub-bottom depth. Several hypotheses related to this phenomenon are discussed. NRM intensities, susceptibilities, median destructive fields, and Koenigsberger ratios are slightly different for pillow and massive basalts. One can suggest from measured parameters that magnetic carriers for massive and pillow basalts are PSD titanomagnetite grains more or less close to PSD-MD threshold size with a low degree of alteration.

Composition of organic matter from black shales drilled in the Cape Verde Basin in DSDP Hole 41-367

Results of geochemical studies of organic matter in black shales from the Cape Verde Basin are reported. Based on these results, in combination with data of petrographic analysis, conclusions are made about sapropelic nature of their organic matter and low degree of its coalification. It corresponds to the proto-catagenetic substage of sedimentary rocks. Black shales of the Cape Verde Basin are classified as potential oil source strata.

Ar and U-Th-Pb age determinations for minerals from ODP Holes of ODP Legs 173 and 210

We report U-Pb and 39Ar-40Ar measurements on plutonic rocks recovered from the Ocean Drilling Program (ODP) Legs 173 and 210. Drilling revealed continental crust (Sites 1067 and 1069) and exhumed mantle (Sites 1070 and 1068) along the Iberia margin and exhumed mantle (Site 1277) on the conjugate Newfoundland margin. Our data record a complex igneous and thermal history related to the transition from rifting to seafloor spreading. The results show that the rift-to-drift transition is marked by a stuttering start of MORB-type magmatic activity. Subsequent to initial alkaline magmatism, localized mid-oceanic ridge basalts (MORB) magmatism was again replaced by basin-wide alkaline events, caused by a low degree of decompression melting due to tectonic delocalization of deformation. Such "off-axis" magmatism might be a common process in (ultra-) slow oceanic spreading systems, where "magmatic" and "tectonic" spreading varies in both space and time.

Alkenone data of sediment traps off Cape Blanc, NW Africa

We analysed long-chain alkenones in sinking particles and surface sediments from the filamentous upwelling region off Cape Blanc, NW Africa, to evaluate the transfer of surface water signals into the geological record. Our study is based on time-series sediment trap records from 730 m (1990-1991) to 2195-3562 m depth (1988-1991). Alkenone fluxes showed considerable interannual variations and no consistent seasonality. The average flux of C37 and C38 alkenones to the deep traps was 1.9 µg/m**2/d from March 1988 to October 1990 and sevenfold higher in the subsequent year. Alkenone fluxes to the shallower traps were on average twice as high and showed similar temporal variations. The alkenone unsaturation indices UK'37, UK38Me and UK38Et closely mirrored the seasonal variations in sea-surface temperature (weekly Reynolds SST). Time lags of 10-48 days between the SST and unsaturation maxima suggest particle sinking rates of about 80 and 280 m/d for the periods of low and high alkenone fluxes, respectively. The average flux-weighted UK'37 temperature for the 4-year time series of the deeper traps was 22.1°C, in perfect agreement with the mean weekly SST for the same period. This and the comparison with seasonal temperature variations in the upper 100 m of the water column suggests that UK'37 records principally the yearly average of the mixed-layer temperature in this region. A comparison between the average annual alkenone fluxes to the lower traps (2400 µg/m**2/yr) and into the underlying sediments (4 µg/m**2/yr) suggests that only about 0.2% of the alkenones reaching the deep ocean became preserved in the sediments. The flux-weighted alkenone concentrations also decreased considerably, from 2466 µg/gC in the water column to 62 µg/gC in the surface sediments. Such a low degree of alkenone preservation is typical for slowly accumulating oxygenated sediments. Despite these dramatic diagenetic alkenone losses, the UK'37 ratio was not affected. The average UK'37 value of the sediments (0.796±0.010 or 22.3±0.3°C) was identical within error limits to the 4-year average of the lower traps. The unsaturation indices for C38 alkenones and the ratio between C37 and C38 alkenones also revealed a high degree of stability. Our results do not support the hypothesis that UK'37 is biased towards higher values during oxic diagenesis.

High-pressure experiments on a natural olivine gabbro from ODP Hole 176-735B

We have conducted high-pressure experiments on a natural oceanic gabbro composition (Gb108). Our aim was to test recent proposals that Sr-enrichment in rare primitive melt inclusions from Mauna Loa, Hawaii, may have resulted from melting of garnet pyroxenite formed in the magma source regions by reaction of peridotite with siliceous, Sr-enriched partial melts of eclogite of gabbroic composition. Gb108 is a natural, Sr-enriched olivine gabbro, which has a strong positive Sr anomaly superimposed on an overall depleted incompatible trace element pattern, reflecting its origin as a plagioclase-rich cumulate. At high pressures it crystallises as a coesite eclogite assemblage, with the solidus between 1,300 and 1,350°C at 3.5 GPa and 1,450 and 1,500°C at 4.5 GPa. Clinopyroxenes contain 4-9% Ca-eskolaite component, which varies systematically with pressure and temperature. Garnets are almandine and grossular-rich. Low degree partial melts are highly siliceous in composition, resembling dacites. Coesite is eliminated between 50 and 100°C above the solidus. The whole-rock Sr-enrichment is primarily hosted by clinopyroxene. This phase dominates the mode (>75 wt%) at all investigated PT conditions, and is the major contributor to partial melts of this eclogite composition. Hence the partial melts have trace element patterns sub-parallel to those of clinopyroxene with ~10* greater overall abundances and with strong positive Sr anomalies. Recent studies of primitive Hawaiian volcanics have suggested the incorporation into their source regions of eclogite, formerly gabbroic material recycled through the mantle at subduction zones. The models suggest that formerly gabbroic material, present as eclogite in the Hawaiian plume, partially melted earlier than surrounding peridotite (i.e. at higher pressure) because of the lower solidus temperature of eclogite compared with peridotite. This produced highly siliceous melts which reacted with surrounding peridotite producing hybrid pyroxene + garnet lithologies. The Sr-enriched nature of the formerly plagioclase-rich gabbro was present in the siliceous partial melts, as demonstrated by these experiments, and was transferred to the reactive pyroxenite. These in turn partially melted, producing Sr-enriched picritic liquids which mixed with normal picritic partial melts of peridotite before eruption. On rare occasions these mixed, relatively Sr-rich melts were trapped as melt inclusions in primitive olivine phenocrysts.Yaxley-Sobolev

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Hole 69-504B and 70-504B

About 150 basalt samples from Hole 504B, near the Costa Rica Rift were analyzed for sulfur content and sulfur-isotope composition. The basement in Hole 504B can be divided into an upper part, which has oxidative alteration (274.5-550 m below sea floor), and a lower part, which has nonoxidative alteration (550-835 m below sea floor) (the interval from 540 to 585 meters actually is transitional). This division is reflected in both the sulfur content and the sulfurisotope composition. Oxidative alteration of basalts by sea water at low temperatures has resulted in a depletion in sulfur in the upper part of the hole (mostly less than 600 ppm S) as compared to fresh sulfur-saturated oceanic tholeiites (900-1200 ppm S). High amounts of sulfur in the lower part of the hole are a result of precipitation of secondary pyrite under non-oxidative or weakly oxidative conditions from solutions which dissolved igneous sulfides. The average sulfur-isotope composition of the primary igneous sulfides is d34S = -0.01 per mil, which is close to the assumed mantle sulfur composition (d34S = 0 per mil. Pyrite and sulfate sulfur extracted together in a separate preparation step (as "pyrite-sulfate" sulfur) indicate addition of sea-water sulfate to the upper part of the basalts. The d34S of secondary pyrite isolated by hand-picking varies between -8.0 and +5.8 per mil; the "pyrite-sulfate" sulfur (d34S = -4.8 to +10.5 per mil), as well as that of the isolated pyrite, may have originated in the precipitation of pyrite from solutions containing sulfur from the dissolution of igneous sulfides, but addition of sulfur transported by hydrothermal solutions cannot be excluded.

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Holes 69-504B and 70-504B

Whole-rock basalt samples from the upper half of Deep Sea Drilling Project Hole 504B have oxygen-isotope compositions typical of mid-ocean-ridge basalts which have experienced a moderate degree of low-temperature alteration by sea water. By contrast, d18O values in the lower half of the hole correspond to basalts which have experienced almost no detectable oxygen-isotope alteration. These observations suggest that the overall water/rock ratio was lower in the lower half of the drilled crust. A correlation between d18O values and 87Sr/86Sr ratios suggests that the water/rock ratio, rather than temperature variation, was the main factor determining basalt d18O values. Hydrogen-isotope data appear to be consistent with a low water/rock ratio in the lower part of the crust.