Organic geochemistry of sediments of the Gulf of California

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material. The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter. Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (d13C) values of kerogens decrease by 1-1.5 per mil near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.

Organic facies variations in the Mesozoic South Atlantic DSDP Holes

Visual kerogen and total organic carbon determinations indicate that there are two periods of organic enrichment events in the Mesozoic sediments of the South Atlantic. The first period, from the Late Jurassic through the late Aptian, is recorded in sediments from the Falkland Plateau, the Cape Basin, and the Angola Basin. Apparently, salinity stratification in the restricted basin, coupled with rising sea level, led to bottom water anoxia and organic enrichment. The second event, from the late Albian to the Santonian period, is recorded in sediments from the Angola Basin and the Sao Paulo Plateau. It appears to have been caused by development of an anoxic oxygen minimum zone at midwater depths. Organic matter sedimentation in the Mesozoic South Atlantic is controlled by geologic, climatic, eustatic, and Oceanographic factors.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

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.

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.

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.

Organic- and carbonate-carbon values and extract data for DSDP Holes 63-467 and 63-471

Quantity, type, and maturity of the organic matter of middle Miocene to Quaternary sediments from the eastern North Pacific (Deep Sea Drilling Project Leg 63) were determined. Hydrocarbons and fatty acids in lipid extracts were analyzed by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Kerogens were investigated by Rock-Eval pyrolysis and microscopy, and vitrinite reflectance values were determined. At Site 467, in the San Miguel Gap of the outer California Continental Borderland, organic carbon contents range from 1.46% to 5.40%. Normalized to organic carbon, total extracts increase from about 10 to 36 mg/g Corg with depth. The organic matter is a mixture of both marine and terrestrial origin, with the marine organic matter representing a high proportion in some of the samples. Steroid hydrocarbons - sterenes and steradienes in the upper part of the section and steranes in the deepest sample - are the most abundant compounds in the nonaromatic hydrocarbon fractions. Perylene, alkylated thiophenes, and aromatic steroid hydrocarbons dominate in the aromatic hydrocarbon fractions of the shallower samples; increasing maturation is indicated by a more petroleumlike aromatic hydrocarbon distribution. Microscopy revealed a high amount of liptinitic organic matter and confirmed the maturation trend as observed from analysis of the extracts. The vitrinite reflectance may be extrapolated to a bottom-hole value of nearly 0.5% Ro. The liquid hydrocarbon potential of the sediments at higher maturity levels is rated to be good to excellent. At Site 471, off Baja California, organic carbon values are between 0.70% and 1.12%. Extract values increase with depth, as at Site 467. The investigation of the soluble and insoluble organic matter, despite some compositional similarities, consistently revealed a more terrigenous influx compared with Site 467. Thus the potential for liquid hydrocarbon generation is lower, the organic matter being more gas-prone. The deepest sample analyzed indicates the onset of hydrocarbon generation. At this site, frequent sand intercalations offer pathways for migration and possibly reservoir formation.

Carbonate, organic carbon and nitrogen, bitumen and rock-eval pyrolysis at DSDP Leg 79 Holes

The lipids and kerogens of 15 sediment samples from Site 547 (ranging from Pleistocene to Early Jurassic/Triassic) and 4 from Site 545 (Cretaceous) have been analyzed. A strong terrestrial contribution of organic matter was found, and significant autochthonous inputs were also present, especially at Site 545. Both strongly reduced and highly oxidized sediments have been found in the Cenozoic and Jurassic samples of Site 547. On the contrary, all the Cretaceous sections of Sites 547 and 545 are anoxic. Sediments from anoxic paleoenvironments are immature and have a high content of sterenes, diasterenes, steradienes, hopenes, and ßß hopanes. Samples from oxic paleoenvironments are mainly mature and their content of hopenes and steriod structures is below the detection level. Nevertheless, their hopane distributions have the immature ßß homologs as the predominant molecular markers. For Site 545 the most abundant molecular markers are ring A monoaromatic steranes, and their presence is attributed to microbial and chemical transformations during early diagenesis.

Salinity and concentrations of organic carbon in bays of the White Sea

Organic carbon in bays of the White Sea was studied for the first time in 1987. Bays of various types in the Kandalaksha Gulf and the Onega Gulf were investigated. Concentration of C_org ranged from 3.5 to 9 mg/l. The highest weighted-mean concentration of C_org occurred in shallow bays of the Onega Gulf (Suma Bay - 6.17 mg/l, Kolezhma Bay - 5.25 mg/1); slightly lower levels occurred in the Soroka Bay (4.85 mg/l) and Kem' Bay (4.78 mg/l). The lowest concentrations were in deep bays of the Kandalaksha Gulf (Chupa Bay - 4.35 mg/l, Velikaya Salma Bay - 4.10 mg/l). As a rule C_org concentration decreases with depth in deep-water bays (but increases slightly in the thermocline layer). The key factor governing organic matter concentration in the bays of the Onega Gulf with river runoff is allochthonous terrigenous organic matter, as indicated by negative correlation of C_org with salinity (R=-0.83+/-0.07, p=0.96) and nonsignificant correlation with primary production.

Organic compounds at DSDP Hole 90-593

Corg and Norg contents in the acid insoluble mineral fraction were studied in sediments of Site 593. Both decrease systematically from Recent to early Miocene over 425 m of carbonate facies. C/N ratios (7-11) are typically marine and indicate that residual organic matter, bound to clay minerals, was originally scavenged from the marine habitat rather than being of terrigenous origin. Variations of Corg and Norg are almost entirely controlled by rates of sedimentation, which gradually increase from Recent to early Miocene. Preliminary results of carbohydrate distribution indicate that epigenetic and diagenetic processes alter both the concentrations and the ratios of individual monomers with depth. Total carbohydrate concentrations in the samples diminish from 91 µg/g sediment at 18 m sub-bottom depth to 49 µg/g at 335 m. In contrast, sugars in the acid insoluble residue increase with depth, suggesting release of structural polysaccharides and their subsequent association with clay minerals. Ratios of arabinose to fucose, which are about 6:1 in Recent carbonaceous sediments intercepted by sediment traps, vary from 1:1 in the youngest sample to 1:2.5 in the oldest.

Organic geochemical studies of DSDP Leg 64 Holes

Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.