Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

Higher plant vegetation changes during Pliocene sapropel formation

The δ¹³C values of higher plant wax C_27–33 n-alkanes were determined in three, time-equivalent Pliocene (2.943 Ma) sapropels and homogeneous calcareous ooze from three different sites forming an east-west transect in the eastern Mediterranean Basin in order to study the composition of the vegetation on the continents surrounding the Mediterranean Sea. A two-end member mixing model transformed the measured δ¹³C values into the contribution of C₄ plants to the terrestrial vegetation. These calculations indicated a high C₄ plant contribution (i.e. 40–50%) in the periods just before and just after sapropel formation. During sapropel deposition the C₄ plant contribution increased by up to 20% at all sites. This is interpreted to record the increased overall plant coverage of the Mediterranean borderlands resulting from the change in formerly barren desert areas into C₄ grass-dominated savannahs as a response to the wetter climate during sapropel deposition. Enhanced accumulation rates (ARs) of long-chain n-alkanes (C_27–33) and n-alkan-1-ols (C_26–30) towards the middle of the sapropel in concert with a decrease in the Ti/Al ratio confirm an increased delivery of terrigenous organic matter at all sites. These biomarkers were probably predominantly fluvially transported to the Mediterranean Sea, not only by the Nile but by fossil wadi river systems on the northern African continent.     

Evaluation of on-line pyrolysis two-dimensional gas chromatography time-of-flight mass spectrometry (Py-GC × GC-ToFMS) on whole sediments from a Mediterranean sapropel sequence

Analysis of the molecular composition of the organic matter (OM) from whole sediment samples can avoid analytical bias that might result from isolation of components from the sediment matrix, but has its own analytical challenges. We evaluated the use of GC × GC-ToFMS to analyze the pyrolysis products of six whole sediment samples obtained from above, within and below a 1 million year old OM-rich Mediterranean sapropel layer. We found differences in pyrolysis products <n-C₂₂ between the OM-rich sapropel samples and the OM-poor background marls. The presence of alkyl pyrroles, probably derived from chlorophyll, in pyrolysates of the sapropels but not in those of the marls suggests that higher marine productivity and greater OM preservation accompanied deposition of the sapropels. Detection of tetramethyl benzenes considered to be pyrolysis products of isorenieratene in the sapropel samples is evidence that nitrogen-fixing green sulfur bacteria contributed to the high productivity. Greater abundances of shorter chain aliphatic hydrocarbons, pyrroles, furans and alkyl aromatics in the pyrolysates of sapropel samples relative to the marls confirm better preservation of marine OM in the sapropels. In addition, the presence of greater amounts of thiophenes in the sapropels than in the marls is consistent with the existence of euxinic conditions during sapropel deposition. The combination of whole sediment pyrolysis and GC × GC-ToFMS is promising, but the procedure requires careful selection of its multiple analytical variables, particularly the pyrolysis temperature and the operational features of the GC columns.     

Sea-land oxygen isotopic relationships from planktonic foraminifera and speleothems in the Eastern Mediterranean region and their implication for paleorainfall during interglacial intervals

The oxygen and carbon stable isotope compositions of cave speleothems provide a powerful method for understanding continental climate change. Here, we examine the question of the regionality of this isotopic record and its linkage with the marine isotopic record in the Eastern Mediterranean (EM) region. The study presents a new, accurately dated 250-kyr δ¹⁸O and δ¹³C record determined from speleothems of the Peqiin Cave, Northern Israel. Its comparison with the continuous 185-kyr isotopic record of the Soreq Cave speleothems from Central Israel reveals striking similarities. Thus, a strong regional climatic signal, brought about by variations in temperature and rainfall amount, is reflected in both cave records. Low δ¹⁸O minima in the Peqiin profile for the last 250- to 185-kyr period (interglacial marine isotopic stage 7) match the timing of sapropels 9 to 7 and are indicative of high rainfall in the EM region at these times. The combined Soreq and Peqiin δ¹⁸O record for the last 250 kyr excellently matches the published Globigerinoides ruber (G. ruber) marine δ¹⁸O record for the EM Sea, with the isotopic compositional difference Δ_{G.ruber-speleothems} remaining relatively constant at −5.6 ± 0.7‰, thus establishing for the first time a robust, exploitable link between the land and the marine isotopic records. The correspondence of low δ¹⁸O speleothem values and high cave water stands with low G. ruber δ¹⁸O values during interglacial sapropel events indicates that these periods were characterized by enhanced rainfall in the EM land and sea regions. By use of sea surface temperatures derived from alkenone data as a proxy for land temperatures at the Soreq Cave, we calculate the paleorainfall δ¹⁸O values and its amounts. Maximum rainfall and lowest temperature conditions occurred at the beginning of the sapropel events and were followed by decrease in rainfall and increase in temperatures, leading to arid conditions. The record for the last 7000 yr shows a trend toward increasing aridity and agrees well with climatic and archeological data from North Africa and the Middle East.     

Biogeochemical specifics of sapropel formation in Cisbaikalian undrained lakes (exemplified by Lake Ochki)

The biogeochemistry of organic lacustrine sediments (sapropels) has been poorly studied in Siberia. In this paper we show the specifics of sapropel formation caused by low pH and mineralization of water by the example of Lake Ochki in Cisbaikalia. The main sources of organic matter are zoo- and phytoplankton, which concentrate mostly basic chemical elements and also some alkaline, alkali-earth, and chalcophile elements and move them to the sediment. The calculated enrichment factors (EF) have shown that the lake plankton is strongly enriched with phosphorus and chalcophile elements. The calculations have also revealed a great contribution of the plankton to the elemental composition of sapropel (Me_bio, %): P (-100), Cd (57), Br (45), Hg (40), Se and Na (30), Zn (23), K (21), and Ca (15). Elements are rather uniformly distributed throughout the 3.2 m thick sapropel layer. Lithophile elements (Al, Sc, Ti, Y, Zr, Nb) and LREE are mostly from a terrigenous source. The high contents of mobile elements (Cd, Sb, Sn, Pb, Zn) in the upper part of sapropel are probably due to anthropogenic factors. The high Cu and Zn contents in some sapropel layers are probably related to the inflow of deep-level groundwaters, and the elevated contents of Hg, Cd, and Sb might have been caused by forest fires.     

The use of sapropels as amendments in radiocaesium and radiostrontium contaminated soils

Two issues are addressed in this paper: the solid/liquid distribution behaviour of radiocaesium (¹³⁷Cs and ¹³⁴Cs) and radiostrontium (⁹⁰Sr) in sapropels, and the potential effectiveness of sapropels as amendments to remediate soils contaminated with these radionuclides. It is shown that the solid/liquid partitioning of radiocaesium and radiostrontium in sapropels is governed by the same processes as in soils. Experimental K_D values measured in a representative solution vary between 300 and 5000 dm³ kg⁻¹ for radiocaesium and between 15 and 50 dm kg⁻¹ for radiostrontium. These K_D values can be interpreted quantitatively on the basis of the main factors which govern the solid/liquid partitioning of these radionuclides.This quantitative approach also allows predictions to be made on the potential effectiveness of sapropel amendments in contaminated soils. These predictions agree very well with experimental results from simple laboratory experiments aimed at investigating the amendment effect. Addition of 1–4 wt.% doses of 2 sapropel samples with different radiocaesium retention characteristics had no significant effect on the radiocaesium distribution coefficient in sandy soils. It is therefore expected that the addition of such sapropels will not result in a decrease of the radiocaesium soil-to-plant transfer, at least not from the point of view of the increase of the radiocaesium retention in the amended soil. Addition of 1–4 wt.% doses of a high CEC sapropel to low CEC sandy soils increased the radiostrontium distribution coefficient up to 3.5 times. It can thus be expected that addition of such high CEC sapropel will increase the radiostrontium retention in the amended soil, and thus decrease the radiostrontium soil-to-plant transfer.     

Sources of neutral lipids in a temperate intertidal sediment

The compositions of sterol, alcohol and ketone fractions from an oxic intertidal surface sediment from Corner Inlet. Victoria, Australia, have been examined by capillary gas chromatographymass spectrometry and related to the lipids of diatoms cultured from the sediment and to lipids of the sea-grass Zostera muelleri. Of the more than thirty sterols in the sediment most appear to derive from diatoms, including the major sterol 24-methylcholesta-5.22E-dien-3β-ol. Small amounts of 24-ethylcholesterol probably derive from Zostera, with a minor diatom contribution. 5α-stanols, both fully saturated and with a side-chain double bond, represented ca. 14% of the total sterols: a significant proportion of these are probably derived from marine invertebrates. These organisms also contribute C₂₆ sterols. most of the cholesterol and possibly small amounts of Δ-sterols. The data suggest that in situ biohydrogenation of stenols was not a major process in sterol transformation in the surface oxic sediment. Alcohols ranged from C₁₂ to C₃₀ and showed an unusual abundance of unsaturated components with Δ⁹-16:1 being the major constituent. The long-chain alcohols probably originate largely from Zostera but the shorter-chain. C₁₂-C₂₀. alcohols are at least partly derived from wax esters of unknown origin. Diatoms do not contribute significant amounts of alcohols. Ketones were not major constituents of the sediment and consisted mainly of 6.10.14-trimethylpentadecan-2-one and a series of n-alkan-2-ones ranging from C₁₆ to C₃₃. The latter showed a similar distribution to that of the n-alkanes but the correspondence was not sufficient to substantiate a product-precursor relationship. Very long-chain C₃- C₃₉ unsaturated methyl and ethyl ketones, which may originate from the marine unicellular alga Emiliania huxleyi. were present in low concentration.     

Environmental significance of mid- to late Holocene sapropels in Old Man Lake,Coorong coastal plain,South Australia: An isotopic,biomarker and palaeoecological perspective

The Holocene successions of numerous shallow lakes located along the Coorong coastal plain in South Australia attest to the impact of rising sea level and changing climate on their depositional environment. Old Man Lake is one of the smallest perennial alkaline lakes in the region. Its succession comprises a basal lagoonal sand rich in humic organic matter (OM) overlain by a 3.7 m thick upward shoaling lacustrine mudstone. The latter features three discrete sapropel units deposited between 3270 and 4910 cal yr BP, a time of increasing aridity throughout southeastern Australia. A core taken from the lake’s eastern margin yielded sedimentological, mineralogical, geochronological and micropaleontological data. Coring at five other sites across the lake provided sections of the humic and sapropelic facies (n = 20) for total organic carbon and Rock–Eval analysis; isotopic characterization of their micritic carbonate (δ¹³C_carb, δ¹⁸O_carb) and co-existing OM (δ¹³C_org); and GC–MS and GC–irMS analysis of their free aliphatic hydrocarbons. For each ‘sapropel event’ high productivity of diatoms and green algae was the principal driver of the accumulation and preservation of OM in such high concentrations. The precursor algal blooms were likely triggered by the influx of fresh water following winter rainfall. The combination of kerogen hydrogen index and δ¹³C_carb–δ¹³C_org, previously employed to track secular changes in algal productivity and organic preservation, proved useful in identifying synchronous geographic differences in these processes across the lake. Highly branched isoprenoids (HBI: C_25:1 ≫ C_20:0) are prominent components of the aliphatic hydrocarbons in the sapropels, confirming the significant contribution of diatoms to their OM. The C isotopic signatures of the principal C_25:1 HBI isomer and the co-occurring C₂₃–C₃₁ odd carbon numbered n-alkanes further document the non-uniformity of biomass preservation within and between the three sapropel units. The evidence from this study suggests that seasonal algal blooms and meromixis, although not necessarily an anoxic hypoliminion, were required for sapropel formation in the Holocene lakes of the Coorong region. Higher resolution sampling, dating and comparative analysis (microfossil, biomarker and isotopic) of these sapropels is required to clarify their potential significance as palaeoclimate proxies.     

Late Quaternary sapropel sediments in the eastern Mediterranean Sea: Faunal variations and chronology

Distinctive planktonic foraminiferal assemblages which characterize particular late Quaternary sapropel layers in deep basin sediments from the eastern Mediterranean Sea have been identified using cluster analysis. Three distinct clusters allow for identification and intercore correlation of the nine sapropels deposited during the last 250,000 yr. Cluster 1, representing sapropel layers S1 and S9, exhibits low abundances of Neogloboquadrina dutertrei and high abundances of Globigerinoides ruber; Cluster 2, which groups S3, S5, and S7, contains high abundances of G. ruber, N. dutertrei, and Globigerina bulloides, and Cluster 3, which includes samples from S4, S6, and S8, is marked by extremely abundant N. dutertrei and G. bulloides, and rare G. ruber. Analysis of sedimentation rates in 14 cores reveals the following approximate ages for the sapropel layers: S2 = 52,000 yr B.P.; S3 = 81,000–78,000 yr B.P.; S4 = 100,000–98,000 yr B.P.; and S5 = 125,000–116,000 yr B.P. As previously suggested, sedimentation rates on the Mediterranean Ridge were determined to be relatively constant during the last 127,000 yr. In contrast, basin sedimentation rates have fluctuated markedly from lower rates during interglacial stage 5 to higher rates during the last glacial episode. These glacial/interglacial differences are most pronounced in the northern Ionian Basin, because of increased terrigenous sediment deposition during glacial episodes. Unusually high biogenic sedimentation rates occurred in an arc south of Crete during the deposition of sapropel S5, probably due to higher productivity in this region.     

Geochemistry of Diagenesis of Organogenic Sediments: An Example of Small Lakes in Southern West Siberia and Western Baikal Area

Organogenic sediments (sapropels) in lakes are characterized by a reduced type of diagenesis, during which organic compounds are decomposed, the chemical composition of the pore waters is modified, and authigenic minerals (first of all, pyrite) are formed. Pyrolysis data indicate that organic matter undergoes radical transformatons already in the uppermost sapropel layers, and the composition of this organic matter is principally different from the composition of the organic matter of the its producers. The sapropels contain kerogen, whose macromolecular structure starts to develop during the very early stages of diagenesis, in the horizon of unconsolidated sediment (0–5 cm). The main role in the diagenetic transformations of organic matter in sediments is played by various physiological groups of microorganisms, first of all, heterotrophic, which amonifying, and sulfate-reducing bacteria. SO₄^2? and Fe²⁺ concentrations in the pore waters of the sediments are determined to decrease (because of bacterial sulfate reduction), while concentrations of reduced Fe and S species (pyrite) in the solid phase of the sediment, conversely, increase. Comparative analysis shows that, unlike sapropels in lakes in the Baikal area, sapropels in southern West Siberia are affected by more active sulfate reduction, which can depend on both the composition of the organic matter and the SO₄^2? concentration in the pore waters.     

Combined organic and inorganic geochemical reconstruction of paleodepositional conditions of a Pliocene sapropel from the eastern Mediterranean Sea

Layers of organic-carbon-rich sapropels in the sediment record of the Mediterranean Sea give evidence of repetitive changes in regional Plio-Pleistocene climate. Results from biomarker molecule and major and trace element analyses of closely spaced samples are used to reconstruct the conditions leading to deposition of a Pliocene sapropel at Ocean Drilling Program (ODP) Site 969 on the Mediterranean Ridge. Organic carbon concentrations increase from 0.2% outside the sapropel and peak to more than 30% within it. Major and trace elemental composition and biomarker-derived parameters indicate elevated productivity, depletion of water-column dissolved-oxygen content, and changes in sediment provenance in response to climatic changes. Budgets of rhenium, thallium, and other trace metals indicate that deep-water exchange between the Mediterranean subbasins and the Atlantic Ocean was not completely interrupted during sapropel formation. Enrichment factors of redox-sensitive and sulfide-forming trace metals as well as the presence of isorenieratene derivatives and high stanol/sterol ratios point to an extended zone of anoxic water masses. Depth profiles of biomarker compositions (sterols, long-chain alkenones, alkandiols and -ketols, fatty acids) indicate great floral diversity during deposition of a single sapropel and highlight the sensitive response of the marine community to variable environmental conditions. Changes in water mass circulation and eolian transport can be reconstructed by use of both lithogenic elements and average chain lengths of n-alkanes (ACL index).     

Restricted utility of δC of bulk organic matter as a record of paleovegetation in some loess-paleosol sequences in the Chinese Loess Plateau

Molecular stratigraphic analyses using gas chromatograph-mass spectrometry have been performed in the upper section (S₀, L₁, S₁) of the Yuanbo loess-paleosol sequences in northwest China, with a record extending from the last interglaciation through the present interglaciation. The CPI (Carbon Preference Index) values of both n-alkanols and n-alkan-2-ones display variations between loess deposits and paleosols, showing a correlation with the magnetic susceptibility record, an indicator of the East Asian summer monsoon. The observed variations in the indexes in relation to changes in lithology/paleoclimate are proposed to result from microbial degradation of higher plant lipids in the paleosols. The CPI values of n-alkanes, n-alkanols, and n-alkan-2-ones are negatively correlated with δ¹³C of bulk organic matter. The correlations suggest that the observed glacial-interglacial variations of δ¹³C data in the loess stratigraphy reflect the relative importance of the contribution of paleovegetation compared with microorganisms (including both the degradation and the addition of organic matter) and allochthonous loess/soil parent materials. It is thus necessary to evaluate the contributions of the latter two before the paleovegetation can be reconstructed based on the δ¹³C analysis of bulk organic matter in some loess-paleosol sequences of the Chinese Loess Plateau.     

Controls on the age of vascular plant biomarkers in Black Sea sediments

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated.Here we show compound-specific radiocarbon (¹⁴C) ages of terrigenous biomarkers and bulk ¹⁴C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. ¹⁴C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C₂₉₊₃₁ alkanes and n-C₂₈₊₃₀ fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C₂₉₊₃₁ alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C₂₉₊₃₁ alkanes show contributions from petrogenic sources, n-C₂₈₊₃₀ fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C₂₈ and n-C₃₀ fatty acids appear clearly much less influenced by autochthonous sources than n-C₂₄ and n-C₂₆ fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.     

Sterols of a contemporary lacustrine sediment

C₂₆, C₂₇, C₂₈ and C₂₉ sterols, including Δ⁵-, Δ²²- and Δ^5,22-sterols and both 5α- and 5β-stanols, have been identified in the contemporary lacustrine sediment of Rostherne mere (Cheshire, England). Amounts of total sterols decrease from ca. 400 ppm extracted sediment dry weight for the 0–7 cm sediment section to ca. 40 ppm for the corresponding 18–30 cm section. 5α-stanols are of far greater abundance than the 5α-stanol isomers. The carbon number distributions of unsaturated and saturated sterols and the increase in stanol: Δ⁵-sterol ratio with sediment depth provide indirect evidence for the operation of a sterol hydrogenation process. C₂₉ sterols preponderate at lower sediment depths, suggesting a predominantly higher plant input, whereas C²⁷ sterols are more abundant in the surface sediment.     

Relations between the Chemical Composition of Organic Matter in Lacustrine Ecosystems and the Genesis of Their Sapropel

The paper presents data on sapropels from ten lacustrine systems at the Barabinsk and Kulunda plains in Novosibirsk region. The sapropels are classified according to the type of the biological contribution to their origin and the content of organic matter. The sapropel of lakes Kachkulnya and Barchin, which are rich in organic matter and differ by the type of their origin (macrophytogenic and planktonogenic), were studied in much detail with the application of the following techniques: X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), and elemental (CHNSO) analysis. Groups of organic compounds contained in the organic matter were determined by successive extraction, and the monosaccharide composition was studied by high-performance liquid chromatography (HPLC). The organic matter of sapropel with different type of boilogical contribution was discovered to differ in elemental (CHNSO) composition, group of organics, and the monosaccharide compositions. Our results led us to conclude that the genesis of sapropel significnalty imprints the composition of its organic matter.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

Petroleum geochemistry of the Potwar Basin, Pakistan: 1. Oil-oil correlation using biomarkers, δC and δD

Geochemical characterisation of 18 crude oils from the Potwar Basin (Upper Indus), Pakistan is carried out in this study. Their relative thermal maturities, environment of deposition, source of organic matter (OM) and the extent of biodegradation based on the hydrocarbon (HC) distributions are investigated. A detailed oil-oil correlation of the area is established. Gas chromatography-mass spectrometry (GC-MS) analyses and bulk stable carbon and hydrogen isotopic compositions of saturated and aromatic HC fractions reveals three compositional groups of oils. Most of the oils from the basin are typically generated from shallow marine source rocks. However, group A contains terrigenous OM deposited under highly oxic/fluvio-deltaic conditions reflected by high pristane/phytane (Pr/Ph), C₃₀ diahopane/C₂₉Ts, diahopane/hopane and diasterane/sterane ratios and low dibenzothiophene (DBT)/phenanthrene (P) ratios. The abundance of C₁₉-tricyclic and C₂₄-tetracyclic terpanes are consistent with a predominant terrigenous OM source for group A. Saturated HC biomarker parameters from the rest of the oils show a predominant marine origin, however groups B and C are clearly separated by bulk δ¹³C and δD and the distributions of the saturated HC fractions supporting variations in source and environment of deposition of their respective source rocks. Moreover, various saturated HC biomarker ratios such as steranes/hopanes, diasteranes/steranes, C₂₃-tricyclic/C₃₀ hopane, C₂₈-tricyclic/C₃₀ hopane, total tricyclic terpanes/hopanes and C₃₁(R + S)/C₃₀ hopane show that two different groups are present. These biomarker ratios show that group B oils are generated from clastic-rich source rocks deposited under more suboxic depositional environments compared to group C oils. Group C oils show a relatively higher input of algal mixed with terrigenous OM, supported by the abundance of extended tricyclic terpanes (up to C₄₁₊) and steranes.Biomarker thermal maturity parameters mostly reached to their equilibrium values indicating that the source rocks for Potwar Basin oils must have reached the early to peak oil generation window, while aromatic HC parameters suggest up to late oil window thermal maturity. The extent of biodegradation of the Potwar Basin oils is determined using various saturated HC parameters and variations in bulk properties such as API gravity. Groups A and C oils are not biodegraded and show mature HC profiles, while some of the oils from group B show minor levels of biodegradation consistent with high Pr/n-C₁₇, Ph/n-C₁₈ and low API gravities.     

Climatic variability during the last 90 ka of the southern and northern Levantine Basin as evident from marine records and speleothems

The influence of the northern Atlantic and tropical monsoonal systems, as recorded by the River Nile, on the climate variability of the southeastern Mediterranean was studied in two cores taken by the R/V Marion Dufresne: one core taken SE of Cyprus representing the northern Levantine Basin (core 9501, 980 m water depth) and the other located ˜380 km further south, represents the southeastern Levantine Basin in an area influenced by the River Nile plume (core 9509, 884 m water depth). The study was performed at relatively high resolution using several proxies: δ¹⁸O of Globigerinoides ruber, sediment characteristics and index colour parameters in core sections representing the last 86 ka. A low-resolution alkenone sea surface temperature record was also measured. The time frame in both cores was mostly constrained by ‘wiggle’ matching with the nearby well-dated δ¹⁸O and δ¹³C record of the Soreq Cave, which is mainly influenced by the eastern Mediterranean water vapor. The sedimentary record of the southern core is strongly influenced by the River Nile contribution throughout the last 86 ka, as evidenced by the higher sedimentation rates compared with the northern core (20 cm/ka vs. 5 cm/ka), continuously darker sediment colour, and higher TOC values (0.6–0.9 vs. 0.25 wt% not including sapropels). During sapropels S1 and S3, present in both cores, the influence of the River Nile became more widespread, reaching as far as Cyprus. Yet, the influence of the River Nile remained stronger in the south, as evident by the higher TOC values in the southern core throughout the entire 90 ka period and the longer duration of S1 in the southern core. An anomalous low δ¹⁸O interval that is not recorded in western Mediterranean occurred between 58 and 49 ka in the Levantine Basin and is more developed in the northern core. This period correlates with D-O interstadial 14 and maximum northern hemisphere insolation during the lastglacial cycle, suggesting that the warming mainly impacted the northern Levant.The Eastern Mediterranean Sea and land area was considerably warmer than the western Mediterranean throughout the LGM – Holocene transition, and the δ¹⁸O_{G. ruber} drop of 4.5‰ is significantly greater than the 3‰ shift found for the western Mediterranean δ¹⁸O_{G. bulloides}, both differences reflecting an increased continental effect from the western to eastern Mediterranean. Comparison between the marine and the land δ¹⁸O records suggests that the origin of rain over the land is composed of mixed signal from the southern and northern Levantine Basin. The study of Δδ¹⁸O_sea–land variations demonstrates that various factors have influenced the sea–land relationship during the last 90 ka. The ‘amount effect’ has an important influence on rainfall δ¹⁸O during interglacial periods (particularly sapropel periods), whereas during glacial periods, increased land distances and elevation differences arising from decrease in sea level may have brought about decrease in δ¹⁸O of rainfall due to Rayleigh distillation processes. These influences were superimposed on those of sea surface water δ¹⁸O changes brought about by continental ice melting, and the strong effects felt in the southern Levantine Basin of the high River Nile input during periods of enhanced monsoonal activity.     

Sterols in interstitial waters of marine sediments

In order to attempt to elucidate the nature of biogeochemical processes occurring at the water-sediment interface, sterols have been analysed in near bottom sea and interstitial waters collected in the eastern and western intertropical Atlantic ocean. Free and esterified sterol concentrations range from 0.2 to 82 μg l^?1 and are much higher than those found in overlying sea water, which range from 0.2 to 1.7 μg l^?1 for the dissolved fraction and from 0.01 to 0.07 μg l^?1 for the particulate fraction. Cholest-5-en-3β-ol and 24-ethylcholest-5-en-3β-ol are the dominant sterols in sea and interstitial waters. The variability encountered for the relative importance of minor sterols such as 24-methylcholesta-5,24(28)-dien-3β-ol and stanols, 5α-cholest-22(E)-en-3β-ol, 5α-cholestan-3β-ol and 24-ethyl-5α-cholestan-3β-ol in interstitial water and their variation with depth is discussed in terms of diversity of inputs and bacterial activity. For sediments cored off the Mauritanian coast, a productive area characterized by an intense upwelling, the chemical signatures observed in interstitial water through stanol/stenol ratios occur at levels of very high heterotrophic aerobic bacterial biomass estimations. The study of the sterol composition of interstitial water could constitute a valuable tool in appreciating the intensity of chemical and biological processes occurring in the first few metres of recent marine sediments.     

Enhanced regeneration of phosphorus during formation of the most recent eastern Mediterranean sapropel (S1)

Phosphorus regeneration and burial fluxes during and after formation of the most recent sapropel S1 were determined for two deep-basin, low-sedimentation sites in the eastern Mediterranean Sea. Organic C/P ratios and burial fluxes indicate enhanced regeneration of P relative to C during deposition of sapropel S1. This is largely due to the enhanced release of P from organic matter during sulfate reduction. Release of P from Fe-bound P also increased, but this was only a relatively minor source of dissolved P. Pore-water HPO₄²⁻ concentrations remained too low for carbonate fluorapatite formation. An increased burial of biogenic Ca-P (i.e., fish debris) was observed for one site. Estimated benthic fluxes of P during sapropel formation were elevated relative to the present day (∼900 to 2800 vs. ∼70 to 120 μmol m⁻² yr⁻¹). The present-day sedimentary P cycle in the deep-basin sediments is characterized by two major zones of reaction: (1) the zone near the sediment-water interface where substantial release of HPO₄²⁻ from organic matter takes place, and (2) the oxidation front at the top of the S1 where upward-diffusing HPO₄²⁻ from below the sapropel is sorbed to Fe-oxides. The efficiency of aerobic organisms in retaining P is reflected in the low organic C/P ratios in the oxidized part of the sapropel. Burial efficiencies for reactive P were significantly lower during S1 times compared with the present day (∼7 to 15% vs. 64 to 77%). Budget calculations for the eastern Mediterranean Sea demonstrate that the weakening of the antiestuarine circulation and the enhanced regeneration of P both contributed to a significant increase in deep-water HPO₄²⁻ concentrations during sapropel S1 times. Provided that sufficient vertical mixing occurred, enhanced regeneration of P at the seafloor may have played a key role in maintaining increased productivity during sapropel S1 formation.