Germanium contents, Ge/Si ratios, and Sr isotopic composition in deep-sea cherts

Nineteen chert samples from a continuous core of the DSDP (Leg 17, Hole 167) were analysed for Ge; in addition we analysed five samples from other cores. The ages range between Late Jurassic, and Late Eocene. The concentration of Ge changes with age from 0.87 ppm in the oldest samples to 0.23 ppm in the youngest (equivalent to a Ge/Si decrease from 0.00000072 to 0.00000019). The decrease in Ge/Si is well correlated with the 87Sr/86Sr ratio in sea water of the relevant age. The interpretation of this trend may reflect: (a) different levels of Ge/Si in sea water as a result of a different ratio between hydrothermal and riverine input, (b) a diagenetic trend in siliceous sediments, (c) recording (by radiolaria) a transition between a radiolaria dominated ocean (with relatively high Ge/Si ratios in sea water) and diatom domination or (d) a combination of the above.

Barium concentrations und stable isotope ratios of late Paleocene deep-sea sediments

Deep-sea sediment Ba* (Ba/Al2O3(sample) * 15% - Ba(aluminosilicate) records show increasing values synchronous with the evolution of the late Paleocene global d13C maximum, reflecting an increase in marine surface primary production and biogenic barite formation at this time. At two oligotrophic locations, Deep Sea Drilling Project (DSDP) Sites 384 and 527 in the North and South Atlantic, respectively, Ba* increases from 160-360 ppm in the early Paleocene to 1100-3000 ppm during the d13C maximum. At equatorial DSDP Site 577, positioned within or near the high-productivity zone, Ba* increases from ~15,500 ppm in the early Paleocene to ~25,400 ppm in conjunction with late Paleocene maximum d13C values. Linear fitted correlation plots of sediment Ba* content versus surface water d13C in all three regions support barite originating in the euphotic zone. The early to late Paleocene relative increase in Ba* illustrates how burial rates of Corg (relative to Al2O3) accelerated by a factor of ~1.8 and ~6.0 in the eutrophic and oligotrophic areas, respectively. A tentative estimate, weighing our result for the entire ocean, suggests that accumulation rates of organic carbon increased by a factor of 2 during the late Paleocene d13C maximum.

Geochemical analyses of chert nodules and beds from deep-sea sediments (Table 1)

Concentrations of Fe, Mg, Ca, Sr, Mn, Zn, and other heavy metals were analyzed by atomic absorption spectrometry in 27 chert samples from the Pacific deep sea, 17 chert samples from land, and 4 associated sediments from the Pacific Ocean. Among the elements, Fe and Mg concentrations are highly correlatable as are the relationships between Ca and Sr, or between Ca and CO2. The correlation between Fe and Mg is particularly high for Pacific deep-sea flints and cherts, and for cherts of deep-sea origin from outcrops on land. Enrichments in heavy metals were recognized in some deep-sea cherts; volcanogenic cherts are enriched in Fe, a chert nodule containing basaltic fragments is enriched in Zn and Cr, and biogenically enclosed carbonates in flint nodules are enriched in Mn. The correlation of Fe and Mg and their constant ratio [Mg(%)/Fe(%)] of around 0.33 might be characteristic features in the pelagic clays contained in deep-sea flints and cherts, and the concentrations of heavy metals in them would be controlled by the concentrations of Fe-Mg correlated clays. Although the mineralogical nature of the Fe-Mg clay in deep-sea cherts was not clarified by dissolution experiments on opaline minerals in chert, the high concentrations of Fe-montmorillonite and fine-grained olivine or other ferromagnesian silicate minerals in the clay may result in the high correlations between Fe and Mg.

3He/4He and 4He/20Ne ratios in pore water and gas in Pacific deep-sea sediments

We have measured the 3He/3He and 3He/20 Ne ratios of thirty-nine pore water and gas samples in deep-sea sediments collected at twelve sites on the Pacific Ocean bottom during the cruises of Deep Sea Drilling Project Legs 87, 89, 90 and 92. The 3He/4He and 4He/20Ne ratios vary from 0.000000215 to 0.00000165 and from 0.29 to 20, respectively. He in the sample is composed of four components: (1) atmospheric He dissolved in seawater; (2) atmospheric He with mantle-derived He in Pacific bottom water; (3) in situ radiogenic He in the sediment; and (4) crustal He in the basement rock. Assuming that the 20Ne contents are constant with the value of seawater, the depth variations in the 4He/20Ne ratios at five Sites, 583D, 594, 597A, 598A and 504B, may provide useful information on 4He flux at the ocean bottom. The estimated 4He fluxes vary from 2000 to 40000 atoms cm**-2 s**-1 and are one to three orders of magnitude less than those calculated from the excess He in deep ocean water. An overall similarity between the geographical distribution of the 3He/4He ratios and heat flow data is found in the study area, between the East Pacific Rise across the Pacific Ocean and the Japanese Islands. The tendency is well explained by a conventional sea-floor spreading model.

Diagenetic development of deep-sea carbonate sediments from DSDP Holes 30-228, 30-289 and 33-316

Laboratory measurements of ultrasonic velocity (VP, VS) and attenuation (QP**-1, QS**-1) in deep-sea carbonate sequences at DSDP Sites 288, 289 and 316 in the equatorial Pacific were made in conjunction with studies of sediment density, porosity and pore geometry in order to investigate the role of diagenesis in the development of physical properties. Bulk porosity decrease appears to be related more significantly to depth of burial than to age of strata. Both depth of burial and age, however, are important factors controlling the modal pore diameter. In deep-burial diagenesis the modification of pore geometry is influenced by the presence of silica during diagenesis. In carbonate sequences at the three DSDP sites studied, shear wave attenuation anisotropy (QSHH**-1/QSHV**-1) correlates with the shear wave velocity anisotropy. Pore orientation, resulting from overburden pressure and other deep-burial diagenetic processes, is an important factor controlling the increase of VP anisotropy with age and depth of burial. On the basis of observed minor changes in anisotropy values with increasing pressure for some samples, other contributions to VP anisotropy such as grain orientation and bedding lamination cannot be ruled out.

Marine diatoms in deep sea sediments

Long-term evolution is thought to take opportunities that arise as a consequence of mass extinction (as argued, for example, by Gould, 2002) and the following biotic recovery, but there is absolutely no evidence for this being the case. However, our study shows that eutrophication by oceanic mixing also played a part in the enhancement of several evolutionary events amongst marine organisms, and these results could indicate that the rates of oceanic biodiversification may be slowed if upwelling becomes weakened by future global warming. This paper defines three distinct evolutionary events of resting spores of the marine diatom genus Chaetoceros, to reconstruct past upwelling through the analysis of several DSDP, ODP and land-based successions from the North, South and equatorial Pacific as well as the Atlantic Ocean during the past 40 million years. The Atlantic Chaetoceros Explosion (ACE) event occurred across the E/O boundary in the North Atlantic, and is characterized by resting spore diversification that occurred as a consequence of the onset of upwelling following changes in thermohaline circulation through global cooling in the early Oligocene. Pacific Chaetoceros Explosion events-1 and -2 (PACE-1 and PACE-2) are characterized by relatively higher occurrences of iron input following the Himalayan uplift and aridification at 8.5 Ma and ca. 2.5 Ma in the North Pacific region. These events not only enhanced the diversification and increased abundance of primary producers, including that of Chaetoceros, other diatoms and seaweeds, but also stimulated the evolution of zooplankton and larger predators, such as copepods and marine mammals, which ate these phytoplankton and plants. Current thinking suggests new evolutionary niches open up after a mass extinction, but our study finds that eutrophication can also stimulate evolutionary diversification. Moreover, in the opposite fashion, our results show that as thermohaline circulation abates, global warming progresses and the ocean surface becomes warmer, many marine organisms will be affected by the environmental degradation.

Distribution of deep-sea foraminifera in surface sediments east of New Zealand

Paleobathymetric assessments of fossil foraminiferal faunas play a significant role in the analysis of the paleogeographic, sedimentary, and tectonic histories of New Zealand's Neogene marine sedimentary basins. At depths >100 m, these assessments often have large uncertainties. This study, aimed at improving the precision of paleodepth assessments, documents the present-day distribution of deep-sea foraminifera (>63 µm) in 66 samples of seafloor sediment at 90-700 m water depth (outer shelf to mid-abyssal), east of New Zealand. One hundred and thirty-nine of the 465 recorded species of benthic foraminifera are new records for the New Zealand region. Characters of the foraminiferal faunas which appear to provide the most useful information for estimating paleobathymetry are, in decreasing order of reliability: relative abundance of common benthic species; benthic species associations; upper depth limits of key benthic species; and relative abundance of planktic foraminifera. R mode cluster analysis on the quantitative census data of the 58 most abundant species of benthic foraminifera produced six species associations within three higher level clusters: (1) calcareous species most abundant at mid-bathyal to outer shelf depths (<1000 m); (2) calcareous species most abundant at mid-bathyal and greater depths (>600 m); (3) agglutinated species mostly occurring at deep abyssal depths (>3000 m). A detrended correspondence analysis ordination plot exhibits a strong relationship between these species associations and bathymetry. This is manifest in the bathymetric ranges of the relative abundance peaks of many of the common benthic species (e.g., Abditodentrix pseudothalmanni 500-2800 m, Bolivina robusta 200-650 m, Bulimina marginata f. marginata 20-600 m, B. marginata f. aculeata 400-3000 m, Cassidulina norvangi 1000-4500 m, Epistominella exigua 1000-4700 m, and Trifarina angulosa 10-650 m), which should prove useful in paleobathymetric estimates. The upper depth limits of 28 benthic foraminiferal species (e.g., Fursenkoina complanata 200 m, Bulimina truncana 450 m, Melonis affinis 550 m, Eggerella bradyi 750 m, and Cassidulina norvangi 1000 m) have potential to improve the precision of paleobathymetric estimates based initially on the total faunal composition. The planktic percentage of foraminiferal tests increases from outer shelf to upper abyssal depths followed by a rapid decline within the foraminiferal lysocline (below c. 3600 m). A planktic percentage <50% is suggestive of shelf depths, and >50% is suggestive of bathyal or abyssal depths above the CCD. In the abyssal zone there is dramatic taphonomic loss of most agglutinated tests (except some textulariids) at burial depths of 0.1-0.2 m, which negates the potential usefulness of these taxa in paleobathymetric assessments.

Oxygen, hydrogen, and carbon isotopic compositions in deep sea cherts, porcellanites, and coexisting carbonates from DSDP Legs 2, 3, 6, 7, 11, 14, 16, 17, and 20

Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. d18O of chert ranges between 27 and 39%. relative to SMOW, d18O of porcellanite - between 30 and 42%. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases. d18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975; http://www.deepseadrilling.org/32/volume/dsdp32_15.pdf) indicates the possibility of d18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of d18O values, increasing diagenesis being reflected in a lowering of d18O. Drusy quartz has the lowest d18O values. On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts. Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. dD of this water ranges between -78 and -95%. and is not a function of d18O of the cherts (or the temperature of their formation).

Chemical and isotopic compositions of deep-sea carbonate sediments and interstitial waters from DSDP Sites 30-288 and 30-289

Interstitial waters and sediments from DSDP sites 288 and 289 contain information on the chemistry and diagenesis of carbonate in deep-sea sediments and on the role of volcanic matter alteration processes. Sr/Ca ratios are species dependent in unaltered foraminifera from site 289 and atom ratios (0.0012-0.0016) exceed those predicted by distribution coefficent data (~0.0004). During diagenesis Sr/Ca ratios of carbonates decrease and reach the theoretical distribution at a depth which is identical to the depth of Sr isotopic equilibration, where 87Sr/86Sr ratios of interstitial waters and carbonates converge. Mg/Ca ratios in the carbonates do not increase with depth as found in some other DSDP sites, possibly because of diagenetic re-equilibration with interstitial waters showing decreasing Mg(2+)/Ca(2+) ratios with depth due to Ca input and Mg removal by alteration of volcanic matter. Interstitial 18O/16O ratios increase with depth at site 289 to d18O = 0.67? (SMOW), reflecting carbonate recrystallization at elevated temperatures (>/= 20°C), the first recorded evidence of this effect in interstitial waters. Interstitial Sr2+ concentrations reach high levels, up to 1 mM, chiefly because of carbonate recrystallization. However, 87Sr/86Sr ratios decrease from 0.7092 to less than 0.7078, lower than for contemporaneous sea water, showing that there is a volcanic input of strontium at depth. This volcanic component is recorded in the Sr isotopic composition of recrystallized calcites. Isotopic compositions of the unrecrystallized calcites suggests that the rate of increase of the 87Sr/86Sr ratio of sea water with time has been faster since 3 my ago than in the preceding 13 my.

K-Ar dating of altered deep-sea igneous rocks from DSDP Legs 2, 34, and 35

In an attempt to establish criteria for obtaining reliable K-Ar dates, conventional K-Ar studies of several Deep Sea Drilling Project sites were undertaken. K-Ar dates of these rocks may be subject to inaccuracies as the result of sea-water alteration. Inaccuracies may also result from the presence of excess radiogenic 40Ar trapped in rapidly cooled rocks at the time of their formation. The results obtained for DSDP Leg 34 basalts indicate that lowering of K-Ar dates, which is related to potassium addition by weathering, is a major cause of uncertainty in obtaining reliable K-Ar dates for deep-sea rocks. It could not be determined if the potassium addition to the basalts occurred at the time of formation, t_o, or continuously from t_o to the present. Calculations show that sediment cover is not a significant barrier to the diffusion of potassium into the basalt. 40Ar loss contributes, at least in part, to the lowering of the K-Ar date in rocks that have added potassium. The meaning of the K-Ar results obtained for DSDP Legs 35 and 2 basalts could not be unambiguously established. Because of the problems involved, caution must be used in interpreting the meaning of conventional K-Ar dates for deep-sea rocks.