Source Characterization of Sedimentary Organic Matter in a Tropical Estuary, Southwest Coast of India: A Biomarker Approach

The source, fate and diagentic pathway of sedimentary organic matter in estuaries are difficult to delineate due to the complexity of organic matter sources, intensive physical mixing and biological processes. A combination of bulk organic matter techniques and molecular biomarkers are found to be successful in explaining organic matter dynamics in estuaries. The basic requirement for these multi-proxy approaches are (i) sources have significantly differing characteristics, (ii) there are a sufficient number of tracers to delineate all sources and (iii) organic matter degradation and processing have little, similar or predictable effects on end member characteristics. Although there have been abundant researches that have attempted to tackle difficulties related to the source and fate of organic matter in estuarine systems, our understanding remains limited or rather inconsistent regarding the Indian estuaries. Cochin estuary is the largest among many extensive estuarine systems along the southwest coast of India. It supports as much biological productivity and diversity as tropical rain forests. In this study, we have used a combination of bulk geochemical parameters and different group of molecular biomarkers to define organic matter sources and thereby identifying various biogeochemical processes acting along the salinity gradient of the Cochin estuary

Assessment of heavy metals' bonding with various sedimentary phases in Shefa-Rud river (Guilan Province)

In the present investigation, bulk and chemical partitioning of elements in the Shefa-Rud riverbed sediments are studied. Higher concentrations of elemental concentrations have been observed in estuarine zone when compared with riverine sediments (except for Al, Fe, Pb and Mn). Manganese is mobilized under anoxic conditions prevailing in the Caspian Sea. Lithogenous materials are greatly diluted in the estuarine zone by various pollutants present in the Caspian Sea. Organic metallic bonds are not significantly present in the area of study. Geological units of the area of study have resulted in the lower concentrations of elemental concentrations of riverbed sediments when compared with published values for mean crust and world sediments ones. Though, cluster analysis has clearly shown the importance of alumina-silicates in controlling the distribution of Fe and Mn in riverbed sediments but it could not depict controlling mechanism for other studied elements. Geochemical Index (Igeo) and Enrichment Factor (EF) values are indicative of a clean environment throughout the river course. These values are in a well agreement with results of chemical partitioning data. Quantification of EF values is not logically possible and therefore Igeo values can be used more effectively.

Survey of past, present pollutants via sediment cores analysis in the coastal trend of Caspian Sea

This is especially well supported by down core variation Zn concentration. As Caspian Sea water intrudes into the Bay, it may be concluded that some part of pollution has sea origin. The geochemical index (Igeo) was reformulated for the area of study using chemical partitioning as well as Pb-210 results. The newly developed geochemical index is indicative of low to medium pollution intensity in the Bay of Gorgan. Thus, any additional pollution into the area of study may leave adverse effects on the aquatic ecology of Bay of Gorgan. Further, lithogenous and non-lithogenous inputs of metals into the Bay were assessed. For this purpose and through chemical partitioning, association of metals with different sedimentary phases was determined. The overall results show that about 114th total metal concentration have been added into the Bay of Gorgan through human activities.

Geochemical variations in Solimões formation sediments (Acre basin, Western Amazonia)

SUMMARYMajor mineral, major element and minor element compositions are documented for a suite of drill core sediment samples representing a ~350m profile through the Solimões Formation sediments (Western Amazonia). Major element compositions are quantified using a chemical index of alteration (CIA) in order to asses the degree of weathering. Significant variations in CIA values throughout the profile, as well as abrupt changes between overlying, suggest that during the generation and deposition of thes sediments there were rapid changes in the ambient tectonic setting.

Geochemical Variability of the Rapakivi Itu Province, State of São Paulo, SE Brazil

This paper describes the chemical variability of the Late Precambrian Itu Rapakivi Province (IRP), State of São Paulo, SE Brazil, based on 187 selected analyses from the Itu, São Francisco, Sorocaba, Campina do Veado and Sguario/ Correa granites. The IRP has an almost uniform petrographic character conferred by the overall dominance of subalkaline biotite granites. Monzogranites (adamellites), granodiorites, quartz syenites, quartz monzonites are rare to very rare rock types and tonalites and quartz diorites are almost restricted to enclaves. Typical chemical features are the high FeO*/MgO ratio, a clustering of the K2O values between 4.5 and 6.0 wt.% and K2O/Na2O ratios which define the IRP as mildly potassic although more potassic rocks also occur. The overal Peacock Alkalinity Index is 54 defining the Province as alkali-calcic. In the Shand diagram the data cluster near the metaluminous/peraluminous boundary. Relationships between Nb, Rb and Y stress the within plate character of the IRP and the relationships between Rb, Ba and Sr reveal the importance of feldspar fractionation in magma evolution. The data also show an interbody and an intrabody chemical variability due to the variation in the composition of the crustal magma protoliths, as assigned by K/Rb relations. The presence of several magmatic cycles which built up the major intrusions reflects a magma ascent from collecting chambers successively drained and recharged, a feature in agreement with the clear link between the bodies and long lived, successively reactivated, transcurrent faults. Most of the chemical features of the IRP correspond to those of the classical Finnish rapakivi granites.

Geochemical and radioactivity characterization of rocks from the Rio Preto (Go) Project

The Rio Preto Project, developed by the extinct Brazilian nuclear state company, Nuclebrás, during the late 70s and early 80s, consisted of basic geological mapping and radiometric characterization by aerogeophysical gamma-ray spectrometry, without channel discrimination, of a surface area of 650 km2 located to the west of the Chapada dos Veadeiros National Park on the northeastern of Goiás State, Brazil, including the confluence area of Claro and Preto Rivers. Additionally, the natural radioelements U, Th and 40K were determined by gamma-ray spectrometry in 300 rock samples from cores of the Rio Preto Project area. The tests were conducted at LABIDRO-Isotopes and Hydrochemistry Laboratory of the Departament of Petrology and Metallogeny (DPM) of the Institute of Geosciences and Exact Sciences, UNESP, in Rio Claro, SP, Brazil. This paper reports the results of petrographic characterization and chemical analyses of major oxides (SiO2, TiO2, Al2O3, Fe2O3, MgO, MnO, K2O, Na2O, CaO and P2O5) for all samples used to determine the natural radioelements present in the region. The organic matter content results obtained by colorimetry are also reported for selected cores of different lithotypes in order to investigate the possible relationship between graphite and the radioelements uranium and thorium. Finally, uranium content and 234U/238U activity ratio data for selected samples of schists and gneisses of the Lower Member of the Ticunzal Formation suggest the influence of weathering processes in the area. © 2012 Sociedade Brasileira de Geofísica.

Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen

The Effingen Member is a low-permeability rock unit of Oxfordian age (ca. 160 Ma) that occurs across northern Switzerland. It comprises sandy calcareous marls and (argillaceous) limestones. This report describes the hydrogeochemistry, mineralogy and supporting physical properties of the Effingen Member in three boreholes in the Jura-Südfuss area: Oftringen, Gösgen and Küttigen, where it is 220–240 m thick. The top of the Effingen Member is at 420, 66 and 32 m depths at the three sites. Core materials are available from Oftringen and Gösgen, whereas information from Küttigen is limited to cuttings, in-situ hydrogeological testing and geophysical logging. Hydrogeological boundaries of the Effingen Member vary between locations. Ground-water flows were identified during drilling at the top (Geissberg Member), but not at the base, of the Effingen Member at Oftringen, at the base (Hauptrogenstein Formation) of the Effingen Member at Gösgen, and in a limestone layer (Gerstenhübel unit) within the Effingen Member at Küttigen. The marls and limestones of the Effingen Member have carbonate contents of 46–91 wt.-% and clay-mineral contents of 5–37 wt.-%. Pyrite contents are up to 1.6 wt.-%, but no sulphate minerals were detected by routine analyses. Clay minerals are predominantly mixed-layer illite-smectite, illite and kaolinite, with sporadic traces of chlorite and smectite. Veins filled with calcite ± celestite occur through the Effingen Member at Oftringen but not at Gösgen or Küttigen. They formed at 50–70 ºC from externally derived fluids, probably of Miocene age. Water contents are 0.7–4.2 wt.-%, corresponding to a water-loss porosity range of 1.9–10.8 vol.-%. Specific surface areas, measured by the BET method, are 2–30 m2/g, correlating with clay-mineral contents. Water activity has been measured and yielded surprisingly low values down to 0.8. These cannot be explained by pore-water salinity alone and include other effects, such as changes in the fabric due to stress release or partial saturation. Observed variations in measurements are not fully understood. Cation exchange capacity (CEC) and exchangeable cation populations have been studied by the Ni-en method. CEC, derived from the consumption of the index cation Ni, is 9–99 meq/kgrock at a solid:liquid ratio of 1, correlating with the clay-mineral content. Cation concentrations in Ni-en extract solutions are in the order Na+≥Ca2+>Mg2+>K+>Sr2+. However, the analytical results from the Ni-en extractions have additional contributions from cations originating from pore water and from mineral dissolution reactions that occurred during extraction, and it was not possible to reliably quantify these contributions. Therefore, in-situ cation populations and selectivity coefficients could not be derived. A suite of methods have been used for characterising the chemical compositions of pore waters in the Effingen Member. Advective displacement was used on one sample from each Oftringen and Gösgen and is the only method that produces results that approach complete hydrochemical compositions. Aqueous extraction was used on core samples from these two boreholes and gives data only for Cl- and, in some cases, Br-. Out-diffusion was used on core samples from Oftringen and similarly gives data for Cl- and Br- only. For both aqueous extraction and out-diffusion, reaction of the experimental water with rock affected concentrations of cations, SO42 and alkalinity in experimental solutions. Another method, centrifugation, failed to extract pore water. Stable isotope ratios (δ18O and δ2H) of pore waters in core samples from Oftringen were analysed by the diffusive exchange method and helium contents of pore water in Oftringen samples were extracted for mass spectrometric analysis by quantitative outgassing of preserved core samples. Several lines of evidence indicate that drillcore samples might not have been fully saturated when opened and subsampled in the laboratory. These include comparisons of water-loss porosities with physical porosities, water-activity measurements, and high contents of dissolved gas as inferred from ground-water samples. There is no clear proof of partial saturation and it is unclear whether this might represent in-situ conditions or is due to exsolution of gas due to the pressure release since drilling. Partial saturation would have no impact on the recalculation of pore-water compositions from aqueous extraction experiments using water-loss porosity data. The largest uncertainty in the pore-water Cl- concentrations recalculated from aqueous extraction and out-diffusion experiments is the magnitude of the anion-accessible fraction of water-loss porosity. General experience of clay-mineral rich formations suggests that the anion-accessible porosity fraction is very often about 0.5 and generally in a range of 0.3 to 0.6 and tends to be inversely correlated with clay-mineral contents. Comparisons of the Cl- concentration in pore water obtained by advective displacement with that recalculated from aqueous extraction of an adjacent core sample suggests a fraction of 0.27 for an Oftringen sample, whereas the same procedure for a Gösgen sample suggests a value of 0.64. The former value for anion-accessible porosity fraction is presumed to be unrepresentative given the local mineralogical heterogeneity at that depth. Through-diffusion experiments with HTO and 36Cl- suggest that the anion-accessible porosity fraction in the Effingen Member at Oftringen and Gösgen is around 0.5. This value is proposed as a typical average for rocks of the Effingen Member, bearing in mind that it varies on a local scale in response to the heterogeneity of lithology and pore-space architecture. The substantial uncertainties associated with the approaches to estimating anion-accessible porosity propagate into the calculated values of in-situ pore-water Cl- concentrations. On the basis of aqueous extraction experiments, and using an anion-accessible porosity fraction of 0.5, Cl- concentrations in the Effingen Member at Oftringen reach a maximum of about 14 g/L in the centre. Cl- decreases upwards and downwards from that, forming a curved depth profile. Cl- contents in the Effingen Member at Gösgen increase with depth from about 3.5 g/L to about 14 g/L at the base of the cored profile (which corresponds to the centre of the formation). Out-diffusion experiments were carried out on four samples from Oftringen, distributed through the Effingen Member. Recalculated Cl- concentrations are similar to those from aqueous extraction for 3 out of the 4 samples, and somewhat lower for one sample. Concentrations of other components, i.e. Na+, K+, Ca2+, Mg2+, Sr2+, SO42- and HCO3- cannot be obtained from the aqueous extraction and out-diffusion experimental data because of mineral dissolution and cation exchange reactions during the experiments. Pore-water pH also is not constrained by those extraction experiments. The only experimental approach to obtain complete pore-water compositions for samples from Oftringen and Gösgen is advective displacement of pore water. The sample from Oftringen used for this experiment is from 445 m depth in the upper part of the Effingen Member and gave eluate with 16.5 g/L Cl- whereas aqueous extraction from a nearby sample indicated about 9 g/L Cl-. The sample from Gösgen used for advective displacement is from 123 m depth in the centre of the Effingen Member sequence and gave eluate with about 9 g/L Cl- whereas aqueous extraction gave 11.5 g/L Cl-. In both cases the pore waters have Na-(Ca)-Cl compositions and SO42- concentrations of about 1.1 g/L. The Gösgen sample has a Br/Cl ratio similar to that of sea water, whereas this ratio is lower for the Oftringen sample. Taking account of uncertainties in the applied experimental approaches, it is reasonable to place an upper limit of ca. 20 g/L on Cl- concentration for pore water in the Effingen Member in this area. There are major discrepancies between pore-water SO42- concentrations inferred from aqueous extraction or out-diffusion experiments and those obtained from advective displacement in both the Oftringen and Gösgen cases. A general conclusion is that all or at least part of the discrepancies are attributable to perturbation of the sulphur system and enhancement of SO42- by sulphate mineral dissolution and possibly minor pyrite oxidation during aqueous extraction and out-diffusion. Therefore, data for SO42- calculated from those pore-water sampling methods are considered not to be representative of in-situ conditions. A reference pore-water composition was defined for the Effingen Member in the Jura Südfuss area. It represents the probable upper limits of Cl- contents and corresponding anion and cation concentrations that are reasonably constrained by experimental data. Except for Cl- and possibly Na+ concentrations, this composition is poorly constrained especially with respect to SO42- and Ca2+ concentrations, and pH and alkalinity. Stable isotope compositions, δ18O and δ2H, of pore waters in the Effingen Member at Oftringen plot to the right of the meteoric water line, suggesting that 18O has been enriched by water-rock exchange, which indicates that the pore waters have a long residence time. A long residence time of pore water is supported by the level of dissolved 4He that has accumulated in pore water of the Effingen Member at Oftringen. This is comparable with, or slightly higher than, the amounts of 4He in the Opalinus Clay at Benken. Ground waters were sampled from flowing zones intersected by boreholes at the three locations. The general interpretation is that pore waters and ground-water solutes may have similar origins in Mesozoic and Cenozoic brackish-marine formations waters, but ground-water solutes have been diluted rather more than pore waters by ingress of Tertiary and Quaternary meteoric waters. The available hydrochemical data for pore waters from the Effingen Member at these three locations in the Jura-Südfuss area suggest that the geochemical system evolved slowly over geological periods of time, in which diffusion was an important mechanism of solute transport. The irregularity of Cl- and δ18O profiles and spatial variability of advective ground-water flows in the Malm-Dogger system suggests that palaeohydrogeological and hydrochemical responses to changing tectonic and surface environmental conditions were complex.

Geochemical and palynological results of IODP Hole 302-M0004A from Lomonosov Ridge, Arctic Ocean

Several episodes of abrupt and transient warming, each lasting between 50,000 and 200,000 years, punctuated the long-term warming during the Late Palaeocene and Early Eocene (58 to 51 Myr ago) epochs**1,2. These hyperthermal events, such as the Eocene Thermal Maximum 2 (ETM2) that took place about 53.5 Myr ago**2, are associated with rapid increases in atmospheric CO2 content. However, the impacts of most events are documented only locally**3,4. Here we show, on the basis of estimates from the TEX86' proxy, that sea surface temperatures rose by 3-5 °C in the Arctic Ocean during the ETM2. Dinoflagellate fossils demonstrate a concomitant freshening and eutrophication of surface waters, which resulted in euxinia in the photic zone. The presence of palm pollen implies**5 that coldest month mean temperatures over the Arctic land masses were no less than 8 °C, in contradiction of model simulations that suggest hyperthermal winter temperatures were below freezing**6. In light of our reconstructed temperature and hydrologic trends, we conclude that the temperature and hydrographic responses to abruptly increased atmospheric CO2 concentrations were similar for the ETM2 and the better-described Palaeocene-Eocene Thermal Maximum**7,8, 55.5 Myr ago.

Geochemical and nannofossil analyses of Cenomanian/Turonian sediments of DSDP Hole 75-530A

One of the key objectives of Deep Sea Drilling Project (DSDP) Leg 75 was to shed light on the underlying causes of Cretaceous oceanic anoxia in the South Atlantic by addressing two major hypotheses: productivity productivity-driven anoxia vs. enhanced ocean stratification leading to preservation of organic matter and black shale deposition. Here we present a detailed geochemical dataset from sediments deposited during the Cenomanian/Turonian (C/T) transition and the global oceanic anoxic event 2 (OAE 2) at DSDP Site 530A, located off-shore Namibia (southeast Angola Basin, north of Walvis Ridge). To characterise the succession of alternating black and green shales at this site and to reconstruct the evolution of their paleoenvironmental setting, we have combined data derived from investigations on bulk organic matter, biomarkers and the inorganic fraction. The location of the C/T boundary itself is biostratigraphically not well constrained due to the carbonate-poor (but organic matter-rich) facies of these sediments. The bulk d13Corg record and compound-specific d13C data, in combination with published as well as new biostratigraphic data, enabled us to locate more precisely the C/T boundary at DSDP Site 530A. The compound-specific d13C record is the first of this kind reported from C/T black shales in the South Atlantic. It is employed for paleoenvironmental reconstructions and chemostratigraphic correlation to other C/T sections in order to discuss the paleoceanographic aspects and implications of the observations at DSDP Site 530A in a broader context, e.g., with regard to the potential trigger mechanisms of OAE 2, global changes in black shale deposition and climate. On a stratigraphic level, an approximation and monitoring of the syndepositional degree of oxygen depletion within the sediments/bottom waters in comparison to the upper water column is achieved by comparing normalised concentrations of redox-sensitive trace elements with the abundance of highly source specific molecular compounds. These biomarkers are derived from photoautotrophic and simultaneously anoxygenic green sulphur bacteria (Chlorobiacea) and are interpreted as paleoindicators for events of photic zone euxinia. In contrast to a number of other OAE 2 sections that are characterised by continuous black shale sequences, DSDP Site 530A represents a highly dynamic setting where newly deposited black shales were repeatedly exposed to conditions of subtle bottom water re-oxidation, presumably leading to their progressive alteration into green shales. The frequent alternation between both facies and the related anoxic to slight oxygenated conditions can be best explained by variations in vertical extent of an oxygen minimum zone in response to changes in a highly productive western continental margin setting driven by upwelling.

Geochemical parameters of sediments and water of the Black Sea, data of Cruise 8 of R/V Vityaz-2

The book presents results of comprehensive geological investigations carried out during Cruise 8 of R/V "Vityaz-2" to the western part of the Black Sea in 1984. Systematic studies in the Black Sea during about hundred years have not weakened interest in the sea. Lithological and geochemical studies of sediments in estuarine areas of the Danube and the Kyzyl-Irmak rivers, as well as in adjacent parts of the deep sea and some other areas were the main aims of the cruise. Data on morphological structures of river fans, lithologic and chemical compositions of sediments in the fans and their areal distribution, forms of occurrence of chemical elements, role of organic matter and gases in sedimentation and diagenesis are given and discussed in the book.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.

Organic geochemical character of selected cores at DSDP Hole 75-530A

The Albian/Cenomanian strata in Hole 530A are organically richer than are the post-Cenomanian strata. Organic matter is thermally immature and appears to be of dominantly marine origin with either variable levels of oxidation or variable amounts of terrestrial input. Geochemical data alone cannot establish whether the black shales present in Hole 530A represent deposition within a stagnant basin or within an expanded oxygen-minimum layer

Geochemical characterization of black shales from the Tarfaya Basin

Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen-rich organic matter (Type I-II kerogen) which qualifies these laminated black shale sequences as excellent oil-prone source rocks. Low Tmax values obtained from Rock-Eval pyrolysis (404-425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short-chain n-alkanes (C16-C22) and long-chain (C25-C35) n-alkanes with no obvious odd-over-even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC-MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur-containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level-driven fluctuations in the palaeoenvironment during sedimentation.

Organic geochemical character and hydrocarbon source potential of selected black shales at DSDP Hole 93-603B

LECO analysis, pyrolysis assay, and bitumen and elemental analysis were used to characterize the organic matter of 23 black shale samples from Deep Sea Drilling Project Leg 93, Hole 603B, located in the western North Atlantic. The organic matter is dominantly gas-prone and/or refractory. Two cores within the Turonian and Cenomanian, however, contained significant quantities of well-preserved, hydrogen-enriched, organic matter. This material is thermally immature and represents a potential oil-prone source rock. These sediments do not appear to have been deposited within a stagnant, euxinic ocean as would be consistent with an "oceanic anoxic event." Their organic geochemical and sedimentary character is more consistent with deposition by turbidity currents originating on the continental shelf and slope.