organic geochemical proxies of paleoceanographic paleolimnologic and paleoclimatic processes abstract organic matter constitutes a minor fraction of marine and freshwater sediments yet its important contribution to the sedimentary record can be used to reconstruct marine and continental paleoenvironments the organic matter content of sediments is the residue of past biota the amounts and types of organic matter present in sediments consequently reflect environmental conditions that impacted ecosystems at different past times general sources of the organic matter are inferred from bulk properties such as elemental compositions carbon and nitrogen stable isotope ratios rock eval pyrolysis data and organic petrography details of organic matter origins are refined by analyses of biomarker molecular compositions source changes are proxies for fluctuations in sea level oceanic surface currents and continental climates algal paleoproductivity rates are indicated by organic carbon mass accumulation rates and carbon and nitrogen stable isotopic compositions these parameters record past availability of nutrients and therefore are proxies of surface mixing in the oceans and amount of land runoff to lakes sea surface paleotemperatures are recorded by the number of carbon carbon double bonds in lipid biomarkers produced by marine algae larger proportions of the double bonds are proxies for the cooler surface waters that accompanied periods of global glaciation and intervals of enhanced upwelling the 13c and d values of plant organic matter record past concentrations of carbon dioxide in the atmosphere and changes in delivery of atmospheric moisture respectively diagenesis which causes the concentration and composition of organic matter in sedimentary settings to differ from those of the original biologically synthesized materials can bias organic geochemical paleoenvironmental records the magnitude of this potential source of misinformation must always be considered and evaluated comparison of multiple organic geochemical proxies of past conditions helps to compensate for the effects of diagenetic alterations and thereby to improve interpretations of paleoenvironmental change

sedimentary dynamics of the kimmeridge clay tempests and earthquakes storms are suggested to be an important influence upon the formation of epicontinental black shales controlling both their distribution and facies types a variety of storm produced event beds are described from the kimmeridge clay of dorset these include horizons of graded rip up clasts silt laminae thin graded mud horizons and shell pavements biostratinomy and population dynamics indicate that the pavements represent brief benthic colonization events in a predominantly anaerobic dysaerobic environment differential near surface lithification has also affected the sediments leading to the formation of flow phenomena these include loop structures microfolding and brecciation earthquake induced fissuring also occurs at a number of horizons the kimmeridge clay shows well developed cyclically alternating organic rich shales and mudstones on a decimetre scale a feedback mechanism of storm induced benthic oxygenation and temperature stratified inhibition of storm mixing may account for the abrupt nature of the cyclicity subsidence and sedimentation rate were probably important factors controlling the thickness and organic richness of the sediments whilst the influence of storms was important in controlling the distribution and facies types of these important source rocks the model proposed for the kimmeridge clay may be of general application to many epicontinental black shales in the geological record

diagenetic and catagenetic products of isorenieratene molecular indicators for photic zone anoxia a wide range of novel diagenetic and catagenetic products of the diaromatic carotenoid isorenieratene a pigment of the photosynthetic green sulphur bacteria chlorobiaceae has been identified in a number of sedimentary rocks ranging from ordovician to miocene compound identification is based on nmr mass spectrometry the presence of atropisomers and stable carbon isotopes atropisomers contain an axially chiral centre which in combination with other chiral centres results in two or more diastereomers that can be separated on a normal gc column chlorobiaceae use the reverse tca cycle to fix carbon so that their biomass is enriched in 13c high 13c contents of isorenieratene derivatives therefore support their inferred origins isorenieratene derivatives include c 40 c 33 and c 32 diaryl isoprenoids and short chain aryl isoprenoids with additional aromatic and or s containing rings c 33 and c 32 compounds are diagenetic products of c 33 and c 32 carotenoids formed from isorenieratene during early diagenesis through expulsion of toluene and m xylene respectively cyclisation of the polyene acyclic isoprenoid chain can proceed via an intramolecular diels alder reaction followed by aromatisation of the newly formed ring sulphurisation is also an important process during early diagenesis competing with expulsion and cyclisation sulphur bound isorenieratane is released during progressive diagenesis due to cleavage of relatively weak ss and cs bonds cleavage of c c bonds during aromatisation of newly formed rings and during catagenesis yields short chain compounds the inherent presence of a conjugated double bond system in carotenoids implies that similar diagenetic and catagenetic reactions can occur with all carotenoids chlorobiaceae live at or below the oxic anoxic boundary layer and require both light and h 2s the presence of isorenieratene or its diagenetic and catagenetic products in ancient sedimentary rocks and crude oils is therefore an excellent indication for photic zone anoxia in the depositional environment diagenetic and catagenetic products of isorenieratene are expected to find applications in reconstruction of palaeoenvironments and in oil oil and oil source rock correlation studies their presence in several petroleum source rocks suggests that anoxia is an important environmental parameter for the preservation of organic matter

capturing gypsum rillenkarren morphometry by a 3d photo reconstruction 3d pr technique abstract rillenkarren are small scale straight narrow solution channels that head at the crest of a bare rock slope and are extinguished downslope in this paper the applicability of 3d photo reconstruction technique of the rock surface is proposed for capturing the rillenkarren morphometry on gypsum at first the measurements are used to assess a relationship between the width depth ratio and the depth of the rillenkarren the exponent of this power relationship resulted different from the theoretical value 0 5 confirming that the cross section profiles of a rillenkarren can have a shape different from parabolic the analysis developed for the cross section area the perimeter and the hydraulic radius established that the formation process is able to deep and enlarge the channel the proposed model of the measured longitudinal profiles confirmed that the profile shape can be characterized by a flex point which divide the upstream concave part from the downstream convex one according to previous studies on soil erosion features rills ephemeral gullies and gullies the relationship between the rillenkarren length and its volume was expressed by a power equation the comparison between rillenkarren and soil erosion features allowed to conclude that a single exponent equal to 1 1 can be applied while the coefficient is characteristic of the feature and represents the influence of channel depth and width finally a model of rillenkarren morphometry deduced applying the dimensional analysis and self similarity was applied to the measurements this analysis demonstrated that a single dimensionless relationship is applicable to rillenkarren and rills ephemeral gullies and gullies assessing that a morphometric similarity exists between these different erosion features

geochemistry of oils in the northern viking graben the composition of crude oils in the northern viking graben area reflects the influence of both the type of organic matter and the thermal maturity of jurassic source rocks in the major basin depocenters referred to as the oseberg and troll kitchens forty four oil samples were analyzed and classified primarily based on chemical composition but with recognition of constraints on origins imposed by geographic and stratigraphic locations five groups are recognized 1 snorre oils 2 stratfjord gullfaks oils 3 brent oseberg beta veslefrikk oils 4 oseberg alpha troll oils and 5 agat and blocks 35 8 and 35 11 oils the composition of oils in the first three groups reflects the large relative proportions of marine organic matter and the lower expulsion temperatures characteristic of oils derived from the draupne formation the composition of oils in the last two groups reflects source rocks having more terrestrial organic matter and higher expulsion temperatures the initial phase of hydrocarbon expulsion and migration from the draupne formation in the northern viking graben began about 56 ma in the troll kitchen and about 45 ma in the oseberg kitchen with continued subsidence and heating of jurassic source rocks gases and condensates were expelled beginning about 40 ma in the trollmore kitchen d about 30 ma in the oseberg kitchen this secondary phase of hydrocarbon generation has mixed with and displaced some of the earlier accumulations less

sedimentary nitrogen isotopic ratio as a recorder for surface ocean nitrate utilization in two contrasting regions of the ocean the equatorial pacific and the southern ocean the 15n of core top sediments were strongly related to no3 in surface waters with distance from the equator in the equatorial pacific 15n increased from 7 to 16 as no3 decreased from 8 m to 0 1 m going from 60 to 30 s in the se indian ocean core top 15n increased from 5 to 11 as surface no3 decreased from 25 m to 0 1 m these results are strong evidence that sedimentary 15n in these regions is recording the increasing isotopic enrichment of near surface no3 with its depletion by phytoplankton in the case of the equatorial pacific 15n values for sinking particles collected at 150 m matched well the core top sediment values demonstrating little diagenetic alteration of the near surface generated isotopic signal these equatorial pacific data sets have variations with near surface no3 consistent with rayleigh fractionation kinetics for a fractionation factor u of 2 5 this value is substantially lower than previously found for temperate or polar regions perhaps as a result of differences in phytoplankton species assemblage or growth condition in the southern ocean south of the polar front comparison of 15n values for opal rich sediments south and sinking particles indicates an apparent 5 diagenetic enrichment relative to the surface generated signal that requires further investigation this exception aside our observations show that the surface water relationship of increasing 15n with increasing no3 depletion is generally transmitted to and preserved in the sediments an important requirement for further development and application of this important paleoceanographic tool

interpreting benthic oxygen levels in mudrocks a new approach quantified paleoecology and gamma ray spectrometry have been applied in the analysis of the kimmeridge clay a highly organic rich british jurassic mudrock decreasing benthic oxygen trends are reflected in decreasing species richness and dominance diversity values similarly the degree of fragmentation of the benthos reflects the benthic energy levels and covaries with benthic oxygen the calculation of authigenic uranium values from data gathered by gamma ray spectrometry shows enrichment in more oxygen deficient environments the good correlation between the independently derived paleoecological and authigenic u data indicates the importance of these techniques in environmental analysis of marine petroleum source rocks

bacterial and algal hydrocarbons in sediments from a saline antarctic lake ace lake capillary gas chromatography mass spectrometry c gc ms and iatroscan thin layer chromatography flame ionisation detection tlc fid were used to study hydrocarbon distributions in a sediment core from ace lake a saline meromictic lake in the vestfold hills of antarctica hydrocarbons were abundant in most core sections up to 125 g g dry wt particularly in near surface samples and the distributions were very complex major constituents were identified as phytane 2 6 10 15 19 pentamethyleicosane tetrahydrosqualene a mixture of phytenes cholesta 3 5 diene and fern 7 ene smaller amounts of sterenes and hopenes were also present the predominance of the first 3 acyclic isoprenoids in sediments buried less than 30 cm is consistent with high populations of methanogenic bacteria known to be present phytenes were abundant in all core sections and there was no relationship between their abundance and that of phytane which suggests that they were not derived from methanogenic bacteria phytadienes were minor constituents at all depths studied an unusual feature of some distributions was the high concentrations of fern 7 ene which was the major hydrocarbon in the 20 25 cm core section this alkene was only abundant in sediments which contained high concentrations of methanogen markers suggesting that it may also be indicative of anoxic depositional environments a possible source might be from purple non sulphur bacteria high concentrations of straight chain c29 and c34 alkenes were also found in these sediments but their origin has not been determined major changes in the hydrocarbon distributions with depth indicate that the depositional environment in the lake has altered dramatically since the lake was formed less than 8000 years ago the present condition of permanent anoxic bottom waters probably developed only in the last 1000 years

evidence of recycling of isotopically light co2 aq in stratified black shale basins contrasts between the whitby mudstone and kimmeridge clay formations united kingdom calculation of co 2 aq and p co 2 atm based on proxy temperature and salinity data 18 o and 13 c from belemnite rostra and 13 c toc toc total organic carbon from toarcian marine organic rich shales yields unreasonably large intraformational p co 2 atm variations we postulate that the low 13 c toc values in the shales can instead be explained by episodic release of isotopically light co 2 that had built up below a relatively deep pycnocline halocline the lowest 13 c toc values would thus be associated with mixing and erosion of the pycnocline following extended periods of stable stratification in contrast the studied tithonian oil shales were probably deposited during periods of only slight perturbation of a photic zone chemocline which probably led to only modest release of isotopically light co 2 in addition the higher productivity associated with the nutrient release would have resulted in depletion of the mixed layer co 2 leading to lower fractionation and higher 13 c toc values

stereochemical studies of acyclic isoprenoids xii lipids of methanogenic bacteria and possible contributions to sediments abstract abundant volatile lipids of methanobacterium thermoautotrophicum and methanosarcina barkeri include isoprenoid hydrocarbons c30 and c15 c20 and c25 isoprenoid alcohols m barkeri contains 2 6 10 15 19 pentamethyleicosane whose relative stereochemistry is the same as found in marine sediments indicating that it is a marker of methanogenic activity the c20 c30 and c25 alkenes in m thermoautotrophicum also have a preferred sterochemistry the latter have the 2 6 10 14 18 pentamethyleicosanyl skeleton suggesting that the alkane in marine sediments may derive from methanogens the stereochemistry of squalane in a marine sediment is also compatible with an origin in methanogens in contrast the stereochemistry of pristane in m thermoautotrophicum indicates a fossil fuel contaminant origin suggesting that this and certain other alkanes reported in archaebacteria might also be of contaminant origin there is therefore little evidence at present that the pristane in immature marine sediments originates in methanogens the c15 and c20 saturated alcohols in m thermoautotrophicum have mainly the all r configuration if this is generally true for methanogens the c20 alcohol in the messel shale may originate mainly from methanogens whereas that in the green river shale may originate mainly from photosynthetic organisms

contrasting watermass conditions during deposition of the whitby mudstone lower jurassic and kimmeridge clay upper jurassic formations uk abstract the whitby mudstone formation wmf and kimmeridge clay formation kcf are both jurassic organic rich black shale units containing well preserved marine organic matter despite such gross similarities they exhibit opposite trends in 13 c toc versus wt decarbonated total organic carbon toc r 0 76 for wmf and 0 71 for kcf the 13 c toc versus toc trend also varies geographically within both units only the kcf data exhibit a positive correlation between 13 c toc and 15 n org r 0 76 and the presence of aryl isoprenoids probable indicators of photic zone anoxia maturity differences are insufficient to explain such contrasts bulk and compound specific isotopic variations in the kcf are interpreted largely as a reflection of primary productivity during deposition rather than a dominantly diagenetic signal due to incorporation of sulphurised carbohydrate the contrasts between the formations and the geographic variation in coeval shelf sediments are explained by a model stressing the relative positions and stabilities of the chemocline pycnocline nutricline and euphotic zone and the effect these have on productivity co 2 recycling and bacterial floras

dpy currents in the cusp cleft region a crucial role of southward interplanetary magnetic field geomagnetic variations observed at the meridional chain of stations in greenland during 1982 1992 are utilized for the study of relationships between occurrence of azimuthal currents in the dayside cusp cleft region and changes in the interplanetary magnetic field imf by and bz components events were selected for analysis if 1 the greenland west coast stations were located near magnetic noon 1400 ut and 2 the absolute values of the imf bz were less than by sixteen events were selected under these conditions the analysis shows that intensive azimuthal currents develop in the cusp cleft region in association with the southward imf despite the fact that the imf by component had the same orientation during the few previous hours the direction of these currents westward or eastward is specified by the sign of the by component negative or positive respectively if the imf by is not zero but bz is mainly northward no significant currents are observed in the cusp cleft region at all as a result because magnetic substorms usually follow extended periods of southward bz the dayside cusp cleft magnetic perturbations often precede substorm activity in the midnight sector of the auroral zone this can simply be a connection between the dayside cusp cleft and nighttime auroral electrojets and therefore could be used as the dayside substorm precursors

an isotopic study of biogeochemical relationships between carbonates and organic carbon in the greenhorn formation carbon isotopic compositions of total carbonate inoceramid carbonate micritic carbonate secondary cements total organic carbon and geoporphyrins have been measured in 76 different beds within a 17 m interval of a core through the greenhorn formation an interbedded limestone and calcareous shale unit of cretaceous age cenomanian turonian from the western interior seaway of north america results are considered in terms of variations in the processes of primary production which led to the biosynthesis of the molecular precursors of the geoporphyrins and in secondary processes those mediating the transformation of primary organic material into sedimentary total organic carbon it is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the toc isotopic record and that in these sediments toc is enriched in 13c relative to its primary precursor by 0 6 to 2 8 this enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy variations in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate this correlation is attributed to effects of environmental changes on the marine foodweb these may have included increased atmospheric oxygen associated with the cenomanian turonian oceanic anoxic event the isotopic fractionation associated with fixation of carbon by primary producers is observed to have varied by 1 5 during the interval of deposition it is suggested that this change is due to a variation in the makeup of the community of primary producers and or to a decrease in the atmospheric abundance of co2 during the oceanic anoxic event

photosynthetic fractionation of 13c and concentrations of dissolved co2 in the central equatorial pacific during the last 255 000 years carbon isotopically based estimates of co2 levels have been generated from a record of the photosynthetic fractionation of 13c is equivalent to epsilon p in a central equatorial pacific sediment core that spans the last approximately 255 ka contents of 13c in phytoplanktonic biomass were determined by analysis of c37 alkadienones these compounds are exclusive products of prymnesiophyte algae which at present grow most abundantly at depths of 70 90 m in the central equatorial pacific a record of the isotopic composition of dissolved co2 was constructed from isotopic analyses of the planktonic foraminifera neogloboquadrina dutertrei which calcifies at 70 90 m in the same region values of epsilon p derived by comparison of the organic and inorganic delta values were transformed to yield concentrations of dissolved co2 is equivalent to c e based on a new site specific calibration of the relationship between epsilon p and c e the calibration was based on reassessment of existing epsilon p versus c e data which support a physiologically based model in which epsilon p is inversely related to c e values of pco2 the partial pressure of co2 that would be in equilibrium with the estimated concentrations of dissolved co2 were calculated using henry s law and the temperature determined from the alkenone unsaturation index u k 37 uncertainties in these values arise mainly from uncertainties about the appropriateness particularly over time of the site specific relationship between epsilon p and 1 c e these are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in delta pco2 the ocean atmosphere disequilibrium which appears to have ranged from approximately 110 microatmospheres during glacial intervals ocean atmosphere to approximately 60 microatmospheres during interglacials fluxes of co2 to the atmosphere would thus have been significantly larger during glacial intervals if this were characteristic of large areas of the equatorial pacific then greater glacial sinks for the equatorially evaded co2 must have existed elsewhere statistical analysis of air sea pco2 differences and other parameters revealed significant p 0 01 inverse correlations of delta pco2 with sea surface temperature and with the mass accumulation rate of opal the former suggests response to the strength of upwelling the latter may indicate either drawdown of co2 by siliceous phytoplankton or variation of co2 si oh 4 ratios in upwelling waters

kimmeridge clay sedimentation a new cyclic model abstract the kimmeridgian upper jurassic fine clastic sequences of the boulonnais northern france and dorset southern england represent oxygen controlled environments five facies types with increasingly deteriorating living conditions ranging from normal shelf environments to submarine lifeless desert have been distinguished the widespread occurrence of this facies in the late jurassic north atlantic shelf sea and the palaeogeographic situation require a large scale model to explain the kimmeridge clay sedimentation anoxic conditions are generally explained by one of three models none of which applies directly to the kimmeridge clay a new model derived from the overall palaeogeographic and palaeoclimatic situation is therefore proposed in this model water mass stratification and anoxic bottom conditions refer to a high latitude monsoonal type wind circulation causing a water current and counter current system in the north atlantic shelf sea and the arctic ocean variations in the amount of oxygen in the bottom waters allow recognition of four different cycles with periods ranging from seasonal to 3 107 years they influenced the counter current system and the resulting anoxic conditions

factors controlling 13c contents of sedimentary organic compounds principles and evidence the carbon isotopic composition of any naturally synthesized organic compound depends on 1 the carbon source utilized 2 isotope effects associated with assimilation of carbon by the producing organism 3 isotope effects associated with metabolism and biosynthesis and 4 cellular carbon budgets these factors are reviewed and quantitative considerations summarized particularly with regard to active and passive modes of carbon assimilation by phytoplankton and the existence of discernible regularities in isotope effects associated with lipid biosynthesis it is concluded that n alkyl lipids are in general depleted in 13c by about 1 5 relative to polyisoprenoid lipids produced by the same organism the effects of biological reworking on isotopic compositions of organic carbon are examined and it is suggested that enrichment of 13c in sedimentary organic carbon may result from loss of ch4 from zooplanktonic gut communities isotopic methods for estimation of ancient co2 levels are considered and a hyperbolic form favored for the relationship between concentrations of dissolved co2 and isotopic fractionation

organic geochemical study of the upper kimmeridge clay of the dorset type area abstract results are presented from an organic geochemical investigation of a suite of rock samples taken from the upper kimmeridge clay near kimmeridge dorset all samples contain immature organic matter of marine origin although one horizon the whitestone band contains an additional secondary input of partially biodegraded mature hydrocarbons due to an oil seepage of unknown origin with the exception of increased relative abundances of 4 methylsteroidal hydrocarbons in the more organic rich samples the immature molecular distributions are very similar suggesting a consistent source of organic matter the results are in agreement with the palaeoenvironmental model proposed by tyson et al 1979 for the deposition of the kimmeridge clay where the different lithologies are controlled by a fluctuating oxic anoxic boundary with only the organic poor mudstones being deposited in relatively oxygenated waters

petroleum geochemistry of the kimmeridge clay of onshore southern and eastern england abstract the kimmeridge clay is considered a major oil source rock for the north sea hydrocarbon province the formation is also developed onshore in an organic rich mudstone facies this paper examines the possibility of onshore oil generation from the kimmeridge clay geochemically onshore basin margin sediments contain rich potential source horizons with mainly type l type ll oil prone kerogen but are immature some deeper cleveland basin sediments have reached marginal maturity burial history reconstruction suggests significant formation palaeoburial depths in central areas of the cleveland and wessex basins computed vitrinite isoreflectance contours show the wealden and isle of wight kimmeridge clay to be thermally mature basin modelling suggests an early palaeogene onset of oil generation in parts of the cleveland basin while maximum oil generation could have been reached by the formation base in the isle of wight area during the late cretaceous although basin subsidence ceased in the neogene in the weald and isle of wight where the formation is still deeply buried oil generation probably continued for some time during uplift thus significant quantities of oil could have been generated whether or not this oil is present today however would depend on the correct timing of suitable migration and trap structures

15n 14n variations in cretaceous atlantic sedimentary sequences implication for past changes in marine nitrogen biogeochemistry at two locations in the atlantic ocean dsdp sites 367 and 530 early to middle cretaceous organic carbon rich beds black shales were found to have significantly lower 15n values lower15n 14n ratios than adjacent organic carbon poor beds white limestones or green claystones while these lithologies are of marine origin the black strata in particular have 15n values that are significantly lower than those previously found in the marine sediment record and most contemporary marine nitrogen pools in contrast black organic carbon rich beds at a third site dsdp site 603 contain predominantly terrestrial organic matter and have c and n isotopic compositions similar to organic matter of modern terrestrial origin the recurring15n depletion in the marine derived cretaceous sequences prove that the nitrogen they contain is the end result of an episodic and atypical biogeochemistry existing isotopic and other data indicate that the low15n relative abundance is the consequence of pelagic rather than post depositional processes reduced ocean circulation increased denitrification and hence reduced euphotic zone nitrate availability may have led to cretaceous phytoplankton assemblages that were periodically dominated by n2 fixing blue green algae a possible source of this sediment15n depletion lack of parallel isotopic shifts in cretaceous terrestrially derived nitrogen site 603 argues that the above change in nitrogen cycling during this period did not extend beyond the marine environment

application of an eutrophic lake model to the origin of ancient organic carbon rich sediments in this paper we approach the problem of the origin of organic carbon rich sediments by using an integrated isotopic and organic geochemical study of the annual productivity eutrophication cycle in the water column of lake greifen switzerland and the historical expression of such cycles as found in the sediments the lake greifen water column and sediment studies reveal that 13c carbonate organic matter is correlated with the hydrogen indices hi of kerogens explicable in terms of changing productivity and preservation of the organic matter and the co2 budget of the water body the lake model implies that if high productivity in co2 limited surface waters high nutrient co2 ratio was controlling the preservation of organic matter a correlation between decreasing 13c carbonate organic matter and increasing hi values may be observed in contrast if low to moderate productivity in co2 unlimited surface waters low nutrient co2 ratio where bottom water anoxia promotes the preservation of organic matter a correlation between increasing 13c carbonate organic matter and increasing hi values may be observed application of this model to two well known jurassic sequences gave a correlation of increasing hi values with decreasing 13c carbonate organic matter for the kimmeridge clay formation united kingdom and increasing hi values with increasing 13c carbonate organic matter for the early toarcian shales france this suggests that the controlling factor of the former deposit was high primary bioproductivity and of the latter deposit anoxic bottom water conditions

stable carbon isotopes of amorphous kerogens from phanerozoic sedimentary rocks amorphous kerogens from phanerozoic sedimentary rocks may be divided into two groups on the basis of their 13c values h amorphous kerogens have isotopic values in the range of 24 to 20 per mil and l amorphous kerogens have isotopic values in the range of 35 to 26 per mil the occurrence of amorphous kerogens in the intermediate isotopic range from one rock unit in the data set suggests a weak continuum may exist between these two groups phytoplankton and to a lesser extent zooplankton and bacteria are considered to be the precursors for both kerogen types a plausible explanation for this dichotomy may be found in the source of co2 utilized by phytoplankton which is considered to be controlled by environmental factors h amorphous kerogens are expected to occur in silled basins that are overlain by expansive well circulated deep 500 m water where the prevailing source of carbon in the photic zone is atmospheric derived co2 conversely l amorphous kerogens are expected to occur in restricted basins that are overlain by stratified shallow 200 m water where the prevailing source of carbon in the photic zone may be organic derived co2

application of pyrolysate carbon isotope and biomarker technology to organofacies definition and oil correlation problems in north sea basins abstract detailed sampling of apparently homogeneous potential source rock intervals frequently indicates unsuspected variations in organic facies which may or may not be reflected in the wireline logs carbon isotope analyses of pyrolysates provide a useful technique in these investigations which are essential for valid oil to source correlations in the jurassic of a north sea viking graben well the rich source shales at the top of the draupne formation are significantly depleted in 13 c and correlate with the oils from this area thus suggesting that this interval has acted as the primary source of the viking graben crudes a quite different pattern is evident in a well from the central graben and the data not only explain why the oils of the greater ekofisk area are relatively enriched in 13 c but also demonstrate that the variations within these oils are facies controlled pyrolysate carbon isotopes provide an excellent correlation between the middle devonian upper caithness flagstones of the inner moray firth and the beatrice crude oil this correlation is supported by the biomarker data and there is no need to appeal to a contribution from either an upper or middle jurassic source to achieve a match with the beatrice oil

chlorobiaceae in palaeozoic seas revealed by biological markers isotopes and geology biomarker hydrocarbons in oils and sediments have considerable potential for assessing the nature of biological processes in the past but only a few can be uniquely related to particular organisms reef hosted oils in the silurian of the michigan basin canada and the devonian of western canada have high abundances of 1 alkyl 2 3 6 trimethylbenzenes their precise structures suggest that they are diagenetic products of aromatic carotenoids of the green sulphur bacteria individual components are enriched in 13c by 7 8 relative to the saturated hydrocarbons of the same oil an isotopic anomaly of this magnitude and direction correlates with a component of photosynthetic carbon assimilation by the reductive tricarboxylic acid cycle these results together with data on palaeoenvironments provide compelling evidence for the existence in ancient restricted seas of microbial communities containing chlorobiaceae organisms with distinctive biochemistry which leave morphologically identifiable remains

aryl isoprenoids and diaromatic carotenoids in paleozoic source rocks and oils from the western canada and williston basins abstract aryl isoprenoids in the range c13 c31 have been identified in source rock bitumens and oils from several paleozoic age petroleum systems in the western canada and williston basins the principal compounds possess the 2 alkyl 1 3 4 trimethyl substitution pattern characteristic of diaromatic carotenoids found in the chlorobiaceae family of photosynthetic sulfur bacteria two c40 perhydrodiaromatic carotenoids which are structurally related to the presumed precursors of the aryl isoprenoids have also been identified in oils and source rock bitumens of the duvernay late devonian petroleum system pyrolysis gas chromatograms of kerogens isolated from several paleozoic source rocks show an unusual abundance of 1 2 3 4 tetramethylbenzene it is proposed that this compound arises from cleavage of diaromatic carotenoid moieties which have been incorporated into the kerogen structure with increasing maturation concentrations of the aryl isoprenoids in duvernay source rock bitumens increase to a point whereas the c40 perhydrodiaromatic carotenoids decrease steadily previous studies have suggested that aryl isoprenoids may be indicators of enhanced salinity environments this is not supported by the present work which shows high concentrations in source rocks associated with presumed normal marine salinities there is however a general association with intervals of condensed clastic or mixed clastic carbonate sedimentation within carbonate depositional systems from the association found and from parallels to modern habitats of photosynthetic bacteria it can be inferred that these biomarkers indicate prolific bacterial growth in a stratified water column at and below the oxic anoxic boundary layer in sub tropical to tropical marine environments

black shales and carbon isotopes in pelagic sediments from the tethyan lower jurassic detailed sampling and analysis of jurassic pelagic limestones and marls from italy hungary and switzerland have enabled construction of an isotope stratigraphy across the pliensbachian toarcian boundary with resolution to the zonal level the oxygen isotope record is unremarkable the carbon isotopes however show two positive excursions one relatively minor during the pliensbachian margaritatus zone subnodosus subzone the other more major during the toarcian early falciferum zone where a maximum 13c value of 4 52 pdb is attained these intervals are known to be favoured periods of organic rich sedimentation in diverse parts of the globe and the isotopic excursions are interpreted as a response to abnormally high rates of storage of organic carbon in the sedimentary record a comparable phenomenon has been documented from the cenomanian turonian boundary in the cretaceous where it has been referred to the influence of an oceanic anoxic event some italian sections spanning this lower jurassic interval contain organic rich shales in the falciferum zone the isotopic signatures from their included locally manganiferous carbonate betray a considerable diagenetic overprint and they cannot therefore be incorporated in a composite isotopic curve carbon isotopes from the organic carbon itself are extremely negative falling to 33 pdb and in one section examined in detail correlate with the calcium carbonate content of the shales they may reflect a partial change to a non calcified planktonic biota during deposition of this lime poor interval possibly responding to upwelling and increased fertility of near surface waters the onset of upwelling may have been as early as spinatum tenuicostatum zone time that is at the pliensbachian toarcian boundary

control of the preservation of organic matter by productivity and sulphate reduction in kimmeridgian shales from dorset uk abstract the kimmeridgian shales of dorset uk have a very wide range of total organic carbon toc content and hydrogen index hi these cyclic changes of organic carbon accumulation are usually interpreted in terms of biomass changes induced by variations in productivity the influence of such variations on the intensity of sulphate reduction and consequently on the preservation of organic carbon were studied the pyrite content does not reflect the full extent of sulphate reduction for sediments with a toc content greater than 10 when easily reducible iron is no longer available h 2 s is preferentially fixed as organic compounds in algal bodies a sulphate reduction index sri initial c org residual c org was calculated for each sediment on the basis of the sulphate reduction reaction stoichiometry and a drastic change in sulphate reduction intensity was seen for toc contents of about 10 above this value the sri is low and decreases with increasing toc content the sediments are rich in organic carbon composed of well laminated stacked algal bodies and were probably deposited at an oxygen depleted water sediment interface in this instance the quality and the amount of organic matter buried depends directly on the organic fluxes towards the redox interface it is assumed that the high relative input of organic matter which can be metabolized exceeds the availability of sulphate in the pore waters so that part of it escapes sulphate reduction and is probably degraded by other processes methanogenesis for toc contents less than 10 the sri is higher and variable the sediments show traces of burrowing and the depositional conditions are thought to be dysaerobic it is proposed that under such conditions bioturbation brings both sulphate and reducible iron into the sediment and that sulphate reduction mainly expressed by the presence of pyrite consumes all the available organic matter which can be metabolized the strong variability in the intensity of sulphate reduction depends on various parameters such as the genetic type of planktonic organic matter the method of transportation to the sediment and possibly the earlier oxic degradation during transportation

sulphidic mediterranean surface waters during pliocene sapropel formation sapropels organic matter rich layers are common in neogene sediments of the eastern mediterranean sea the formation of these layers has been attributed to climate related increases in organic matter production1 2 3 and increased organic matter preservation due to oxygen depletion in more stagnant bottom waters2 3 here we report that eastern mediterranean pliocene sapropels4 contain molecular fossils of a compound isorenieratene known to be synthesized by photosynthetic green sulphur bacteria suggesting that sulphidic euxinic and therefore anoxic conditions prevailed in the photic zone of the water column these sapropels also have a high trace metal content which is probably due to the efficient scavenging of these metals by precipitating sulphides in a euxinic water column the abundance and sulphur isotope composition of pyrite are consistent with iron sulphide formation in the water column we conclude that basin wide water column euxinia occurred over substantial periods during pliocene sapropel formation in the eastern mediterranean sea and that the ultimate degradation of the increased organic matter production was strongly influential in generating and sustaining the euxinic conditions