A 220 ka palaeoenvironmental reconstruction of the Fuentillejo maar lake record (Central Spain) using biomarker analysis

The sedimentary record of the volcanic lake known as the Fuentillejo maar (central Spain) offers the opportunity to determine the palaeoenvironmental evolution of the central-southern part of the Iberian Peninsula during the Middle and Upper Pleistocene. A total of 439 samples from the upper 88 m of a ca. 142 m long core (spanning the last ca. 355 ka) were examined. The interval corresponds to the last 220 ka of the record. High n-alkane CPI values and the presence of sulfur revealed that little diagenetic signal attenuation or modification had occurred. A number of n-alkane-based indices (e.g. predominant n-alkane, ACL, Paq and TAR_HC ratios, and the proportion of C₂₇, C₂₉ and C₃₁ n-alkanes with respect to the summed C₂₇ + C₂₉ + C₃₁) alkanes, showed changing conditions in the organic matter input to the maar lake over time, with episodes involving a major input of terrestrial vegetation, alternating with others in which algae or a mixed input of terrestrial plants, aquatic macrophytes and algae occurred. The proportions of C₂₇, C₂₉ and C₃₁ were useful for reconstructing the palaeoenvironmental evolution of the basin as they allowed assignment of several dry intervals during which grasses developed, while during humid phases trees expanded at the expense of grasses.In general, we found good correspondence between these episodes and the climatic cycles observed in δ¹⁸O records from ices cores in Greenland and Antarctica, as well as from marine cores. Thus, we conclude that global palaeoclimatological changes were recorded in the maar record. Likewise, Heinrich Events appeared to be reflected in the n-alkane indices. This was confirmed by single spectral analysis and cross spectral analysis with the insolation curve on 21 July at a latitude of 65°N. The approach revealed that the cycles interpreted in the Fuentillejo record (103, 41, 23 and 19 ka) showed evidence of orbital influence related to the astronomical cycles of the eccentricity variation in the Earth’s orbit, the Earth’s obliquity oscillation, and the precession variation (Milankovitch theory).     

Improved understanding of the petroleum systems of the Niger Delta Basin,Nigeria

Biomarker and n-alkane compound specific stable carbon isotope analyses (CSIA) were carried out on 58 crude oil samples from shallow water and deepwater fields of the Niger Delta in order to predict the depositional environment and organic matter characteristics of their potential source rocks. Using a source organofacies prediction approach from oil geochemistry, the presence in the western deepwater oils relatively abundant C₂₇ steranes, C₃₀ 24-n-propyl cholestane, low oleanane index, relatively low pr/ph ratios, gammacerane, and positive to nearly flat C₁₂–C₃₀ n-alkane compound specific stable carbon isotope profiles, suggests that the source facies that expelled these oils contain significant marine derived organic matter deposited under sub-oxic and stratified water column conditions. This contrasts with the terrigenous organic matter dominated source rocks accepted for shallow water Niger Delta oils. Oils in the shallow water accumulations can be separated into terrigenous and mixed marine-terrigenous families. The terrigenous family indicates expulsion from source rock(s) containing overwhelmingly higher plant source organic matter (average oleanane index = 0.48, high C₂₉ steranes) as well as having negative sloping n-alkane isotope profiles. Oxic source depositional conditions (pr/ph > 2.5) and non-stratified conditions (absence to low gammacerane content) are inferred for the terrigenous family. The mixed marine-terrigenous family has biomarker properties that are a combination of the deepwater and terrigenous shallow water oils. Bitumen extracts of the sub-delta Late Cretaceous Araromi Formation shale in the Dahomey Basin are comparable both molecularly and isotopically to the studied western deepwater oil set, but with an over all poor geochemical correlation. This poor geochemical match between Araromi shale and the western deepwater oils does not downgrade the potential of sub-delta Cretaceous source rock contribution to the regional oil charge in the deepwater Niger Delta.     

n-Alkane evidence for the onset of wetter conditions in the Sierra Nevada,California (USA) at the mid-late Holocene transition, ~ 3.0 ka

n-Alkane biomarker distributions in sediments from Swamp Lake (SL), in the central Sierra Nevada of California (USA), provide evidence for an increase in mean lake level ~ 3000 yr ago, in conjunction with widespread climatic change inferred from marine and continental records in the eastern North Pacific region. Length distributions of n-alkane chains in modern plants growing at SL were determined and compared to sedimentary distributions in a core spanning the last 13 ka. As a group, submerged and floating aquatic plants contained high proportions of short chain lengths (< nC₂₅) compared to emergent, riparian and upland terrestrial species, for which chain lengths > nC₂₇ were dominant. Changes in the sedimentary n-alkane distribution over time were driven by variable inputs from plant sources in response to changing lake level, sedimentation and plant community composition. A shift toward shorter chain lengths (nC_21, nC₂₃) occurred between 3.1 and 2.9 ka and is best explained by an increase in the abundance of aquatic plants and the availability of shallow-water habitat in response to rising lake level. The late Holocene expansion of SL following a dry mid-Holocene is consistent with previous evidence for increased effective moisture and the onset of wetter conditions in the Sierra Nevada between 4.0 and 3.0 ka.     

Biomarker evidence for Botryococcus and a methane cycle in the Eocene Huadian oil shale,NE China

The saturated and unsaturated hydrocarbons of two samples (HD-19 and HD-21) from the same section of the Middle Eocene lacustrine Huadian oil shale in NE China were identified and shown to be mainly from algal and bacterial sources. Comparison of the two samples provided an opportunity to explore the contribution from telalginite to the hydrocarbon profiles. Cells identified from microscopy as Botryococcus in the telalginite of HD-21 were confirmed as belonging to the L race of B. braunii from the presence of monoaromatic lycopane derivatives and small amounts of several lycopadienes. Lycopane was abundant and was probably derived from biohydrogenation of lycopadienes and related lipids on the basis of δ¹³C values. Hopane distributions showed a dominance of those with the biological 17β,21β-stereochemistry, as expected for an immature shale, with low amounts of 17β,21α-hopanes (moretanes) and 17α,21β-hopanes. Two hopenes were also abundant and assigned as C₂₉ and C₃₀ neohop-13(18)-enes, which occurred together with the C₂₉ and C₃₀ hop-17(21)-enes. These had depleted carbon isotope values (−43.7‰ to −50.8‰), indicative of production by methane oxidizing bacteria (methanotrophs). The high proportion of hopanoids with carbon numbers < C₃₂ indicates extensive post-depositional diagenetic alteration of bacteriohopanepolyols as well as a direct input of C₃₀ hopanoids. The data clearly indicate that there was active utilization of methane in this lacustrine depositional setting, but isoprenoid hydrocarbon biomarkers for methanogens, such as pentamethylicosane (PMI) and squalane, were in surprisingly low abundance. It is possible that these bacterial contributions were present as polar lipids. The origins of an unusual C₃₈ isoprenoid alkane assigned as bipristane are uncertain, but may be from methanogens. Steranes and sterenes were relatively minor components, but abundant diasterenes and 4-methyldiasterenes were present, reflecting significant conversion of the original lipid composition by way of clay-catalysed diagenesis. The biomarker data suggest that the bottom waters in the original depositional environment had low O₂ content, but the sediments were probably neither sulfidic nor strongly reducing. The high content of organic matter in the shale likely reflects both high (but fluctuating) productivity due to eutrophic conditions in the overlying water and good preservation in the sediments.     

Occurrence and composition of solid bitumens from the Bulonggoer Devonian paleo-oil reservoir,North Xinjiang,China

The Bulonggoer paleo-oil reservoir (BPR) on the northwest Junggar Basin is the first Devonian paleo-oil reservoir discovered in North Xinjiang, China. Solid bitumens occur within sandstone pores and as veins filling fractures. Samples of both types were analyzed using stable carbon isotope and reflectance measurements, as well as molecular biomarker parameters.The extremely positive δ¹³C values and biomarker indicators of depositional environment/lithology, such as pristane/phytane (Pr/Ph), C₂₉/C₃₀ hopane, diasteranes/regular steranes and dibenzothiophene/phenanthrene ratios, indicate a siliciclastic source for the BPR and their deposition in a highly reducing hypersaline environment. The presence of long chain n-alkanes and abundant tetracyclic diterpanes, C₂₀–C₂₁ tricyclic terpanes and perylene are indicators of higher plant organic matter input. Moreover, the bimodal distribution of C₂₇ > C₂₈ < C₂₉ regular steranes and abundant methyltriaromatic steroids also support a contribution of microalgae as well as higher plants organic matter. The similar molecular composition and thermal maturity parameters indicate that the reservoir and veined solid bitumens were altered from a common paleo-petroleum, which originated from peak oil window matured source rocks.All solid bitumens from the BPR are characterized by relatively low bitumen reflectance values (Rb% < 0.7), suggesting that they were generated from low temperature processes rather than oil thermal cracking. Comparatively, the Rb% values for veined bitumens are higher than reservoir bitumens, indicating that the veined bitumens occurred earlier and experienced higher thermal conditions.     

Thermal degradation of rye and maize straw: Lipid pattern changes as a function of temperature

Future climatic conditions may coincide with an increased potential for wildfires in grassland and forest ecosystems, whereby charred biomass would be incorporated into soils. Molecular changes in biomass upon charring have been frequently analysed with a focus on black carbon. Aliphatic and aromatic hydrocarbons, known to be liberated during incomplete combustion of biomass have been preferentially analysed in soot particles, whereas determinations of these compounds in charred biomass residues are scarce. We discuss the influence of increasing charring temperature on the aliphatic and aromatic hydrocarbon composition of crop grass combustion residues. Straw from rye, representing C₃ grasses and maize, representing C₄ grasses, was charred in the presence of limited oxygen at 300, 400 and 500 °C. Typical n-alkane distribution patterns with a strong predominance of long chain odd-numbered n-alkanes maximising at C₃₁ were observed in raw straw. Upon combustion at 300 °C aliphatic hydrocarbons in char were dominated by sterenes, whereas at 400 °C sterenes disappeared and medium chain length n-alkanes, maximising around n-C₂₀, with a balanced odd/even distribution were present. At a charring temperature of 500 °C n-alkane chain length shifted to short chain homologues, maximising at C₁₈ with a pronounced predominance of even homologues. Even numbered, short chain n-alkanes in soils may thus serve as a marker for residues of charred biomass. Aromatic hydrocarbons indicate an onset of aromatization of biomass already at 300 °C, followed by severe aromatization upon incomplete combustion at 400–500 °C. The diagnostic composition of aliphatic and aromatic hydrocarbons from charred biomass affords potential for identifying residues from burned vegetation in recent and fossil soils and sediments.     

Precise indices based on n-alkane distribution for quantifying sources of sedimentary organic matter in coastal systems

Precise indices based on n-alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n-alkane signatures: seagrass (Zostera sp.) produced mainly n-C₁₇, n-C₁₉, n-C₂₁, n-C₂₃ and n-C₂₅ alkanes, algae (Rhodophyta, Chlorophyta) produced n-C₁₅ and n-C₁₇ and the terrigenous input [Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n-C₂₅, n-C₂₇, n-C₂₉, n-C₃₁ and n-C₃₃. From the above and literature n-alkane fingerprints, we developed a set of indices (n-alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n-alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C₂₇ + C₂₉ + C₃₁/C₁₅ + C₁₇ + C₁₉; terrestrial to aquatic ratio) and the P_aq (C₂₃ + C₂₅/C₂₃ + C₂₅ + C₂₉ + C₃₁; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n-alkanes for quantifying the source composition of SOM in complex coastal systems.     

Calibrating n-alkane Sphagnum proxies in sub-Arctic Scandinavia

Moss covered, high latitude wetlands hold large amounts of terrestrial organic matter (OM), which may be vulnerable to expected climate warming. Molecular analysis of fluvially transported material from these regions can distinguish between different sources of terrestrial OM. Sphagnum moss may represent one of the major sources. This study aimed to quantitatively establish a molecular proxy for identifying Sphagnum-derived OM from high latitude peatlands in the sub-Arctic coastal ocean. We collected and analyzed Sphagnum species throughout northern Sweden and Finland. Results show that the C₂₅/(C₂₅ + C₂₉) n-alkane ratio is most suitable for terrestrial OM source apportionment in these coastal regions since, compared to other n-alkane Sphagnum proxies, it shows (i) the least variation between species, (ii) the most constant values for different latitudinal regimes and (iii) the largest dynamic range to the higher plant end member in two-source mixing models. Application of the proxy to surface sediments and suspended particulate matter in the sub-Arctic northern Baltic Sea shows that 68–103% of the terrestrial OM fraction is derived from Sphagnum-rich peatland. We recommend that future studies on terrestrial OM fluxes into (sub-)Arctic regions should apply the C₂₅/(C₂₅ + C₂₉) proxy to improve insight into the contribution of Sphagnum-derived terrestrial OM from climate-vulnerable, high latitude wetlands.     

Acyclic isoprenoid biomarkers and evolution of biosynthetic pathways in green microalgae of the genus Botryococcus

Acyclic isoprenoids were among the earliest lipids on Earth and today > 30,000 isoprenoid-derived compounds are known, testifying to the remarkable diversification in isoprenoid biosynthetic pathways over time. Many of the isoprenoids have proven to be useful biomarkers in geochemical studies and evidence from sedimentary studies has the potential to provide a timeline for the evolution of different types of isoprenoid biosynthesis. A single green microalgal species termed Botryococcus braunii has been recognised as a major contributor of organic matter to sediments as old as the Precambrian. Modern studies of the taxonomy of B. braunii using molecular biology techniques have shown that the major clades identified from 18S rRNA gene sequences correspond to races A, B, L and S, which are defined on the basis of their hydrocarbon composition. The biosynthetic pathways by which C₃₀–C₃₇ botryococcenes are produced by the B race have now been shown to be due to a duplication of the squalene synthase gene, followed by subsequent changes to the genes, such that one pathway leads to the production of the C₃₀ botryococcene and the other to squalene. Both products are then methylated to produce botryococcenes and methylated squalenes having higher carbon numbers. The mode of biosynthesis of lycopadiene in race L is unclear, but may involve coupling of two C₂₀ phytyl diphosphates. From an examination of the geological record of botryococcenes and lycopadiene it seems likely that these pathways probably evolved early in the Eocene (ca. 55 Ma) and thus are more recently evolved than the genes for highly branched isoprenoid (HBI) alkenes first produced by diatoms about 92 Ma ago. Botryococcane produced from botryococcenes and a monoaromatic hydrocarbon produced from lycopadiene-related lipids, presumably under anoxic conditions, show promise as age diagnostic biomarkers. In view of these results, it seems likely that the Botryococcus species recorded in sediments predating the Eocene lacked the ability to produce botryococcenes or lycopadiene, but nonetheless still contained polymeric non-isoprenoid alkyl chains in the form of an algaenan which on preservation gave rise to a multitude of organic rich rocks.     

Characterization of organic matter and depositional environment of Tertiary mudstones from the Sylhet Basin,Bangladesh

The Sylhet Basin of Bangladesh is a sub-basin of the Bengal Basin. It contains a very thick (up to 22 km) Tertiary stratigraphic succession consisting mainly of sandstones and mudstones. The Sylhet succession is divided into the Jaintia (Paleocene–late Eocene), Barail (late Eocene–early Miocene), Surma (middle–late Miocene), Tipam (late Miocene–Pliocene) and Dupitila Groups (Pliocene–Pleistocene), in ascending order. The origin of the organic matter (OM) and paleoenvironment of deposition have been evaluated on the basis of C, N, S elemental analysis, Rock-Eval pyrolysis and gas chromatography–mass spectrometry (GC–MS) analysis of 60 mudstone samples collected from drill core and surface outcrops. Total organic carbon (TOC) content ranges from 0.11% to 1.56%. Sulfur content is low in most samples. TOC content in the Sylhet succession varies systematically with sedimentation rate, with low TOC caused by clastic dilution produced by high sedimentation rates arising from rapid uplift and erosion of the Himalaya.The OM in the succession is characterized by systematic variations in pristane/phytane (Pr/Ph), oleanane/C₃₀ hopane, n-C₂₉/n-C₁₉ alkane, Tm/Ts [17α(H)-22,29,30-trisnorhopane/18α(H)-22,29,30-trisnorhopane] and sterane C₂₉/(C₂₇ + C₂₈ + C₂₉) ratios during the middle Eocene to Pleistocene. Based on biomarker proxies, the depositional environment of the Sylhet succession can be divided into three phases. In the first (middle Eocene to early Miocene), deposition occurred completely in seawater-dominated oxic conditions, with abundant input of terrestrial higher plants, including angiosperms. The second phase (middle to late Miocene) consisted of mainly freshwater anoxic conditions along with a small seawater influence according to eustasic sea level change, with diluted OM derived from phytoplankton and a lesser influence from terrestrial higher plants. Oxygen-poor freshwater conditions prevailed in the third phase (post-late Miocene). Planktonic OM was relatively abundant in this stage, while a high angiosperm influx prevailed at times. T_max values of ca. 450 °C, vitrinite reflectance (R_o) of ca. 0.66% and methylphenanthrene index (MPI 3) of ca. 1 indicate the OM to be mature. The lower part (middle Eocene to early Miocene) of the succession with moderate TOC content and predominantly terrestrial OM could have generated some condensates and oils in and around the study area.     

Geochemical characteristics of Tertiary saline lacustrine oils in the Western Qaidam Basin,northwest China

Based on the systematic analyses of light hydrocarbon, saturate, aromatic fractions and C isotopes of over 40 oil samples along with related Tertiary source rocks collected from the western Qaidam basin, the geochemical characteristics of the Tertiary saline lacustrine oils in this region was investigated. The oils are characterized by bimodal n-alkane distributions with odd-to-even (C₁₁–C₁₇) and even-to-odd (C₁₈–C₂₈) predominance, low Pr/Ph (mostly lower than 0.6), high concentration of gammacerane, C₃₅ hopane and methylated MTTCs, reflecting the high salinity and anoxic setting typical of a saline lacustrine depositional environment. Mango’s K₁ values in the saline oils are highly variable (0.99–1.63), and could be associated with the facies-dependent parameters such as Pr/Ph and gammacerane indexes. Compared with other Tertiary oils, the studied Tertiary saline oils are marked by enhanced C₂₈ sterane abundance (30% or more of C₂₇–C₂₉ homologues), possibly derived from halophilic algae. It is noted that the geochemical parameters of the oils in various oilfields exhibit regular spatial changes, which are consistent with the depositional phase variations of the source rocks. The oils have uncommon heavy C isotopic ratios (−24‰ to −26‰) and a flat shape of the individual n-alkane isotope profile, and show isotopic characteristics similar to marine organic matter. The appearance of oleanane and high 24/(24 + 27)-norcholestane ratios (0.57–0.87) in the saline oils and source rocks confirm a Tertiary organic source.     

Distribution and significance of novel low molecular weight sterenes in an immature evaporitic sediment from the Jinxian Sag,North China

An unusual series of C₂₂–C₂₇ monounsaturated sterenes and C₂₄–C₃₀ tetracyclic terpanes (17,21-secohopanes) were detected in relatively high concentrations in an immature evaporitic marl sediment of the Jinxian Sag, Bohai Bay Basin, North China. The site of unsaturation in these novel sterenes is assigned tentatively to the D ring on the basis of mass spectral interpretation, which also distinguishes them from reported unsaturated sterenes. Other hydrocarbon biomarker or stable isotope characteristics are indicative of microbial (e.g. methyl hopanes), phytoplankton or higher plant (depleted δ¹³C values of isoprenoids and hopanes) inputs and an anoxic carbonate depositional environment (hexacyclic hopanes; tetracyclic terpanes). The hydrocarbon composition showed no obvious biodegradation and the relatively high concentration of unsaturated terpenoids (e.g. gammacerene) and low values of other established maturity parameters (T_s/T_m = 0.23; R_o = 0.44%; T_max = 417 °C), are consistent with sediments of low maturity. The novel, low molecular weight sterenes and the tetracyclic terpanes may be early diagenetic products of microbial sources in a carbonate environment.     

Pregnanes as molecular indicators for depositional environments of sediments and petroleum source rocks

Steroids with unconventional side chains have increasingly been applied as diagnostic markers for geological source and age assessments. However, one of the most distinctive characteristics, the abnormal abundance of pregnane and homopregnane in ancient sediments and petroleum, remains unresolved. Higher pregnane and homopregnane, as well as C₂₃–C₂₆ 20-n-alkylpregnanes, relative to the regular steranes were observed in samples collected from different petroleum basins in China. These included Precambrian marine carbonate-derived petroleum (NW Sichuan Basin), Lower Paleozoic marine marl derived crude oils (Tarim Basin), and Eocene hypersaline lacustrine carbonate source rocks and associated petroleum (Bohai Bay Basin). However, all of the samples have many common biomarker characteristics, such as pristane/phytane ratios < 1, low amounts of diasteranes and high C₂₉/C₃₀ hopane (∼0.6–1), C₃₅/C₃₄ hopane (mostly ⩾ 1) and dibenzothiophene/phenanthrene (DBT/PHEN, mostly 0.5–1) ratios revealing a contribution from anoxic carbonate/marl source rocks deposited in restricted, clastic-starved settings. We suggest that 5α,l4β,l7β-pregnane and homopregnane, as well as their higher C₂₃–C₂₆ homologues, are geological products derived from steroids bound to the kerogen by a sulfurized side chain. Carbon or carbonate minerals are considered to be natural catalysts for this cracking reaction via preferential cleavage of the bond between C-20 and C-22. Similar distributions occur in the short chain analogues of 4-methylsterane, triaromatic steroid and methyltriaromatic steroid hydrocarbons, providing circumstantial evidence for this proposal. The ratio of pregnane and homopregnane to the total regular steranes and the ratio of C₂₇ diasteranes to cholestanes can be sensitive indicators of sedimentary environments and facies. In general, high diasteranes and low pregnanes (with homologues) indicate an oxic water column or significant input of terrigenous organic matter in clay rich source rocks and some organic lean carbonate rocks. Low diasteranes with high pregnanes implies restricted, sulfur rich conditions, typical of anoxic carbonate source rocks. Furthermore, the two ratios may be useful to assess the variation of mineralogy and openness of source rock depositional settings.     

Radiocarbon analysis of halophilic microbial lipids from an Australian salt lake

Assigning accurate dates to hypersaline sediments opens important terrestrial records of local and regional paleoecologies and paleoclimatology. However, as of yet no conventional method of dating hypersaline systems has been widely adopted. Biomarker, mineralogical, and radiocarbon analyses of sediments and organic extracts from a shallow (13 cm) core from a hypersaline playa, Lake Tyrrell, southeastern Australia, produce a coherent age-depth curve beginning with modern microbial mats and extending to ~ 7500 cal yr BP. These analyses are furthermore used to identify and constrain the timing of the most recent change in hydrological regime at Lake Tyrrell, a shift from a clay deposit to the precipitation of evaporitic sands occurring at some time between ~ 4500 and 7000 yr. These analyses show the potential for widespread dating of hypersaline systems integrating the biomarker approach, reinforce the value of the radiocarbon content of biomarkers in understanding the flow of carbon in modern ecologies, and validate the temporal dimension of data provided by biomarkers when dating late Quaternary sediments.     

Elemental and organic geochemistry of Gondwana sediments from the Krishna–Godavari Basin,India

Elemental and organic geochemical studies have been carried out on the Gondwana sediments, collected from the outcrops of Permian and Jurassic–Cretaceous rocks in the Krishna–Godavari basin on the eastern coast of India, to understand their paleo and depositional environment and its implications for hydrocarbon generation in the basin. Amongst the studied formations, the Raghavapuram, Gollapalli and Tirupati form a dominant Cretaceous Petroleum System in the west of the basin. Raghavapuram shales and its stratigraphic equivalents are the source rock and Gollapalli and Tirupati sandstones form the reservoirs, along with basaltic Razole formation as the caprock. Major element systematics and X-ray diffraction study of the sandstones indicate them to be variably enriched with SiO₂ relative to Al₂O₃ and CaO, which is associated, inherently with the deposition and diagenesis of the Gondwana sediments. Post-Archean Average Shale normalized rare earth elements in shales show enrichment in most of the samples due to the increasing clay mineral and organic matter assemblage. A negative europium and cerium anomaly is exhibited by the REE's in majority of rocks. Composed primarily of quartz grains and silica cement, the Gollapalli and Tirupati sandstones have characteristics of high quality reservoirs. The shales show a significant increase in the concentration of redox sensitive trace elements, Ni, V, Cr, Ba and Zn. The total organic carbon content of the shales ranges between 0.1 and 0.5 wt%. Programmed pyrolysis of selected samples show the Tmax values to range between 352–497 °C and that of hydrogen index to be between 57–460 mgHC/gTOC. The organic matter is characterized by, mainly, gas prone Type III kerogen. The n-alkane composition is dominated by n-C₁₁–C₁₈ and acyclic isoprenoid, phytane. The aromatic fraction shows the presence of naphthalene, anthracene, phenanthrene, chrysene and their derivatives, resulting largely from the diagenetic alteration of precursor terpenoids. The organic geochemical proxies indicate the input of organic matter from near-shore terrestrial sources and its deposition in strongly reducing, low oxygen conditions. The organic matter richness and maturity derived from a favorable depositional setting has its bearing upon the Gondwana sediments globally, and also provides promising exploration opportunities, particularly in the Raghavapuram sequence of the KG basin.     

Organic geochemical characteristics and oil generating potential of the Upper Jurassic Safer shale sediments in the Marib-Shabowah Basin,western Yemen

The organic rich Safer shales exposed in the north-central part of onshore Marib-Shabowah Basin are evaluated and their depositional environments are interpreted. Total organic carbon contents (TOC) of the shales range from 1.02–16.8 wt%, and yield hydrogen index (HI) values ranging from 130 to 820 mg HC/g TOC, consistent with mainly Type II with minor contributions from Type I and mixed Types II–III kerogens. The Safer shale samples have vitrinite reflectance values in the range of 0.5–1.0 R_o%, indicating early mature to peak mature stage for oil generation. T_max values range from 429–438 °C, which are in reasonably good agreement with vitrinite reflectance data. Kerogen microscopy shows that the Safer shales are characterized by high amounts of organic matter, consisting predominantly of yellow fluorescing amorphous organic matter and alginite of marine origin. This is supported by their high content of hydrogen rich Type II and I oil-prone kerogen.The biomarker distributions of the Upper Jurassic Safer extracts are characterized by dominant low to medium molecular weight compounds (n-C₁₄ to n-C₂₀), low Pr/Ph ratio (<1.0), high phytane/n-C₁₈ ratios (0.82–2.68), and predominant regular sterane C₂₇. All biomarker parameters clearly indicate that the organic matter was derived from marine algal inputs and deposited under anoxic (reducing) conditions. Hypersaline conditions also prevailed during deposition of these sediments, as indicated by the presence of gammacerane.     

Evidence for euphotic zone anoxia during the deposition of Aptian source rocks based on aryl isoprenoids in petroleum,Sergipe–Alagoas Basin,northeastern Brazil

Four crude oil samples from the Sergipe–Alagoas Basin, northeastern Brazil, were analyzed using full scan gas chromatography–quadrupole mass spectrometry (GC–qMS) for biomarkers, in order to correlate them using aromatic carotenoids thereby enhancing knowledge about the depositional environment of their source rocks. The geochemical parameters derived from saturated fractions of the oils show evidence of little or no biodegradation and similar thermal maturation (Ts/(Ts + Tm) for terpanes, C₂₉ αββ/(αββ + ααα), C₂₇, and C₂₉ 20S/(20S + 20R) for steranes). Low pristane/phytane ratios and the abundance of gammacerane and β-carotane are indicative of an anoxic and saline depositional environment for the source rocks. Moreover, we identified a large range of diagenetic and catagenetic products of the aromatic carotenoid isorenieratene, including C₄₀, C₃₃, and C₃₂ diaryl isoprenoids and aryl isoprenoid derivatives with short side chains and/or additional rings. These results indicate anoxia in the photic zone during the deposition of the source rocks.     

Biomarkers of novel ecosystem development in boreal forest soils

Novel ecosystem development is occurring within the western boreal forest of Canada due to land reclamation following oil sand surface mining. Sphagnum peat is the primary organic amendment used to reconstruct soil in these novel ecosystems. We hypothesised that ecosystem recovery would be indicated by an increasing similarity in the biomolecular characteristics of novel soil organic matter (SOM) derived from peat to those of natural boreal ecosystems. We evaluated the use of the homologous series of long chain (⩾ C₂₁) n-alkanes with odd/even predominance to monitor the re-establishment of boreal forest on these anthropogenic soils. The lipids were extracted from dominant vegetation inputs and SOM from a series of natural and novel ecosystem reference plots. Twice the concentration of n-alkanes was extracted from natural than from novel ecosystem SOM (p < 0.01). We observed unique n-alkane signatures for the source vegetation, e.g. peat material was dominated by C₃₁, and aspen (Populus tremuloides Michx.) leaves by C₂₅. The n-alkane distribution differed between the two systems (p < 0.001) and reflected the dominant vegetation input, i.e. peat or tree species. Our results indicate that further research is required to clarify the influence of vegetation or disturbance on the signature of n-alkanes in SOM; however, the use of n-alkanes as biomarkers of novel ecosystem development is a promising application.     

Organic matter distribution in the modern sediments of the Pearl River Estuary

We determined biomarker concentrations and distributions for surface sediments from 54 sites in the Pearl River Estuary, China. We focus on a suite of four biomarker-based indicators for relative terrestrial to marine organic matter (OM) source: the branched-isoprenoid tetraether (BIT) index, the ratio of high/low molecular weight n-alcohols [(ΣC_26–34/(ΣC₁₆₊₁₈ + ΣC_26–34)], an analogous ratio for n-fatty acids and the ΣC₂₉-steroids/(ΣC₂₉-steroids + brassicasterol) ratio. All four exhibit the same terrestrial to marine transition seen in previous bulk δ¹³C studies, but with an abrupt decrease in the relative terrestrial contribution across the delta front to pro-delta transition. Concentrations of terrestrially-derived biomarkers show no systematic decrease across the transition. Instead, the decrease in the proportion of terrestrial OM is due to a decrease in the sedimentation rate and associated terrestrial OM burial across the delta toe. This suggests that diagenetic controls on the fate of terrestrial OM, such as increased biodegradation where sedimentation rate is low, are subordinate to sedimentological processes. Biomarker-derived temperature values are cooler than expected for the lower Pearl River catchment, suggesting that the dominant component of the terrestrial OM is derived from the cooler upland regions of the catchment. The dominance of input from more distal terrain with greater topographic relief is evidence for the importance of geomorphological control on terrigenous OM transport. Collectively, the results demonstrate the importance of sedimentological processes in the supply, deposition and transport of terrestrial OM.     

Organic geochemistry and depositional environment of the Aptian bituminous limestone in the Kale Gümüşhane area (NE-Turkey): An example of lacustrine deposits on the platform carbonate sequence

The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average T_max value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The T_max values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C₂₆–C₃₀) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C₂₉ is the dominant sterane, with C₂₉ > C₂₇ > C₂₈. The bituminous limestone samples have low C₂₂/C₂₁ ratios, high C₂₄/C₂₃ tricyclic terpane ratios and very low C₃₁R/C₃₀ hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.