Organic geochemistry of late Cenozoic sediments from the eastern subtropical Atlantic

Detailed organic geochemical investigations have been performed on sediment samples from upwelling Site 658 and nonupwelling Sites 657 and 659. The major objective of this study has been the relationship between organic carbon accumulation and paleoclimatic and paleoceanographic conditions in the upwelling area off northwest Africa during late Cenozoic times. The study is based on results from organic carbon, nitrogen, and hydrogen analyses, Rock-Eval pyrolysis, kerogen microscopy, gas chromatography, and gas chromatography/mass spectrometry. In general, nonupwelling Sites 657 and 659 are characterized by low organic carbon values of less than 0.5%. At Site 657, four events of high organic carbon deposition (total organic carbon of 1%-3%) occur and represent turbidites and a slump interval. The upper Pliocene to Pleistocene sediments of upwelling Site 658 display high organic carbon contents of 0.5%-4%, with higher contents concentrated in the upper Pliocene. Accumulation rates of organic carbon vary between 0.1 and 0.5 gC/cm-**2/1000 yr, with maximum values between 3.5 and 3.1 Ma. Short-term cyclic ("Milankovitch-type") variations in organic carbon accumulation suggest climate-controlled mechanisms causing these fluctuations. The quality of organic matter at Site 658 is a mixture of kerogen type II and HI, with a dominance of the marine type. This is indicated by high hydrogen-index values of 200-400 mgHC/gC, low C/N ratios of 5-15, atomic H/C ratios of 1.0-1.5, and high amounts of marine macerals (alginite and liptodetrinite). We have estimated paleoproductivity for Sites 658 and 659 based on the amount of marine organic carbon. At open-marine Site 659, mean paleoproductivity varies between 20 and 50 gC/m**2/yr. At Site 658, mean paleoproductivity reaches high values of 160 to 320 gC/m**2/yr, very similar to those recorded in modern upwelling areas. The changes in productivity off northwest Africa are linked to changes in nutrient supply caused by both upwelling and fluvial input. The change from a dominantly humid climate to one characterized by fluctuations between humid and fully arid climates in northwest Africa occurs between 3.1 and 2.45 Ma.

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.

Organic geochemistry of lower Cretaceous sediments at DSDP Hole 77-535

At Site 535, the four lithologic units of Cretaceous age are controlled by two types of sedimentologic facies: (1) the massive light-colored limestones or marly limestones in which the total organic carbon (TOC) content is low and the organic matter more or less oxidized and (2) laminated dark facies in which the TOC content is higher and associated with a well-preserved organic matter of Type II origin. Very little typical Type III organic matter occurs in the whole series from late Berriasian to Aptian and Cenomanian. Fluctuations from oxidizing to reducing environments of deposition are proposed to account for the variations in properties of the Type II organic matter between the different facies. Dark laminated layers are good but immature potential source rocks: petroleum potential is often higher than 2 kg HC/t of rock.

Lithology and organic geochemistry at DSDP Hole 76-534

The organic facies of Early and middle Cretaceous sediments drilled at DSDP Site 534 is dominated by terrestrially derived plant remains and charcoal. Marine organic matter is mixed with the terrestrial components, but through much of this period was diluted by the terrestrial material. The supply of terrestrial organic matter was high here because of the nearness of the shore and high runoff promoted by a humid temperate coastal climate. Reducing conditions favored preservation of both marine and terrestrial organic matter, the terrestrial materials having reached the site mostly in turbidity currents or in the slow-moving, near-bottom nepheloid layer. An increase in the abundance of terrestrial organic matter occurred when the sea level dropped in the Valanginian and again in the Aptian-Albian, because rivers dumped more terrigenous elastics into the Basin and marine productivity was lower at these times than when sea level was high. A model is proposed to explain the predominance of reducing conditions in the Valanginian-Aptian, of oxidizing conditions in the late Aptian, and of reducing conditions in the Albian-Cenomanian. The model involves influx of oxygen-poor subsurface waters from the Pacific at times of high or rising sea level (Valanginian-Aptian, and Albian- Cenomanian) and restriction of that influx at times of low sea level (late Aptian). In the absence of a supply of oxygenpoor deep water, the bottom waters of the North Atlantic became oxidizing in the late Aptian, probably in response to development of a Mediterranean type of circulation. The influx of nutrients from the Pacific led to an increase in productivity through time, accounting for an increase in the proportion of marine organic matter from the Valanginian into the Aptian and from the Albian to the Cenomanian. Conditions were dominantly oxidizing through the Middle Jurassic into the Berriasian, with temporary exceptions when bottom waters became reducing, as in the Callovian. Mostly terrestrial and some marine organic matter accumulated during the Callovian reducing episode. When Jurassic bottom waters were oxidizing, only terrestrial organic matter was buried in the sediments, in very small amounts.

Phosphorus partition and acumulation rates in sediments of ODP Legs 130 and 138

Understanding phosphorus (P) geochemistry and burial in oceanic sediments is important because of the role of P for modulating oceanic productivity on long timescales. We investigated P geochemistry in seven equatorial Pacific sites over the last 53 Ma, using a sequential extraction technique to elucidate sedimentary P composition and P diagenesis within the sediments. The dominant P-bearing component in these sediments is authigenic P (61-86% of total P), followed in order of relative dominance by iron-bound P (7-17%), organic P (3-12%), adsorbed P (2-9%), and detrital P (0-1%). Clear temporal trends in P component composition exist. Organic P decreases rapidly in younger sediments in the eastern Pacific (the only sites with high sample resolution in the younger intervals), from a mean concentration of 2.3 µmol P/g sediment in the 0-1 Ma interval to 0.4 µmol/g in the 5- 6 Ma interval. Over this same time interval, decreases are also observed for iron-bound P (from 2.1 to 1.1 µmol P/g) and adsorbed P (from 1.5 to 0.7 µmol P/g). These decreases are in contrast to increases in authigenic P (from 6.0-9.6 µmol P/g) and no significant changes in detrital P (0.1 µmol P/g) and total P (12 µmol P/g). These temporal trends in P geochemistry suggest that (1) organic matter, the principal shuttle of P to the seafloor, is regenerated in sediments and releases associated P to interstitial waters, (2) P associated with iron-rich oxyhydroxides is released to interstitial waters upon microbial iron reduction, (3) the decrease in adsorbed P with age and depth probably indicates a similar decrease in interstitial water P concentrations, and (4) carbonate fluorapatite (CFA), or another authigenic P-bearing phase, precipitates due to the release of P from organic matter and iron oxyhydroxides and becomes an increasingly significant P sink with age and depth. The reorganization of P between various sedimentary pools, and its eventual incorporation in CFA, has been recognized in a variety of continental margin environments, but this is the first time these processes have been revealed in deep-sea sediments. Phosphorus accumulation rate data from this study and others indicates that the global pre-anthropogenic input rate of P to the ocean (20x10**10 mol P/yr) is about a factor of four times higher than previously thought, supporting recent suggestions that the residence time of P in the oceans may be as short as 10000-20000 years.

Calcium carbonate, organic carbon, d13C and C/N composition of ODP Sites 186-1150 and 186-1151

Past changes in sea-surface productivity in the Oyashio Current are evaluated on the basis of abundances of biological constituents in sediments from Leg 186 sites. Organic carbon contents at Sites 1150 and 1151 are moderate (0.5 to 1.5 wt%) and have an algal origin as indicated by low C/N ratios (<10) and by carbon isotopic compositions ranging from -23.4 to -21.3. A decreasing trend in organic carbon contents, carbon isotope ratios, and C/N ratios occurs with depth at both sites, probably as a consequence of diagenetic degradation of organic matter. Mass accumulation rates (MARs) determined for organic carbon and carbonates at Sites 1150 and 1151 show an abrupt increase between ~5 and 7 Ma. Similar results have been reported for sites in the Indian Ocean and the Pacific Ocean for the same time interval. As it has been previously suggested, the observed increase in MAR for both carbonate and organic carbon at Leg 186 sites probably resulted from augmented nutrient supply either from continental sources or from a more vigorous ocean circulation.

Mineralogy and pyrolysis at DSDP Hole 62-463

A 15-meter sequence of early Aptian organic-matter-rich sediments, cored at Deep Sea Drilling Project Site 463 (western Mid-Pacific Mountains) has been submitted for detailed mineralogical studies (XRD, SEM) and organiccarbon characterization. Although intense diagenesis has obscured the sedimentary record of depositional conditions, the history has been tentatively reconstructed. Through sustained volcanic activity and alteration processes on the archipelago, large amounts of silica were released into the sea water, resulting in a "bloom" of radiolarians. Hard parts settled in large amounts, yielding a hypersiliceous sediment; amorphous silica was diagenetically transformed into chalcedony, opal-CT and clinoptilolite through dissolution and recrystallization. Oxidization of part of the radiolarian soft parts (1) depleted the sea water in dissolved oxygen, allowing the burial of organic matter, and (2) generated carbon dioxide which led to dissolution of most of the calcareous tests. Moderate depositional depth and a high sedimentation rate are though to have prevailed during this episode. An immature stage of evolution is assigned to the studied organic matter, which is of two origins: autochthonous marine material, and allochthonous humic compounds and plant debris. Rhythmic sedimentation characterizes the distribution of the organic matter; each sequence shows (1) an upward progressive increase in organic-carbon content, and (2) an upward enrichment in marine organic matter.