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

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

The occurrence and distribution of phenylphenanthrenes,phenylanthracenes and binaphthyls in Palaeozoic to Cenozoic shales from China

The distributions of phenylphenanthrenes, phenylanthracenes and binaphthyls in sediment extracts have been investigated in a set of lacustrine shales from the Eocene Shahejie Formation (well SG 1) in the western Depression of Liaohe Basin, East China. All isomers of these phenyl substituted polycyclic aromatic hydrocarbons (PAHs) have been identified in the m/z 254 mass chromatograms by comparison of the mass spectra and standard retention indices with those published elsewhere. The 2,2′-binaphtyl/1,2′-binaphthyl ratio values show a linear increase with increasing maturity, and have a good correlation with T_max (°C). Therefore, they can be used as an effective maturity indictor for source rocks in this study. In the main phase of the oil generation window, the 3-phenylphenanthrene and 2-phenylphenanthrene prevail over other isomers, and some thermodynamically unstable isomers including all phenylanthracenes, 4-phenylphenanthrene and 1,1′-binaphthyl are present at very low concentrations or below the detection limit in the m/z 254 mass chromatograms. The absolute concentrations of individual phenylphenanthrene and binaphthyl isomers were obtained by comparison of the peak areas with that of internal standard phenanthrene-d10. All isomers are present at low concentrations at low maturity stages and then show an abrupt increase at a depth of ≈3100 m, corresponding to the onset of the intensive C₁₅₊ hydrocarbon generation. The Phenylphenanthrene Ratio (2- + 3-PhP)/[(2- + 3-PhP) + (4- + 1- + 9-PhP)] shows a reverse change with increasing maturity at the low maturity stage. It displays a drastic increase at a depth of ≈3100 m and then remains at a nearly constant value. This study can expand the understanding of the formation and distribution of phenyl substituted PAHs in sedimentary organic matter deposited in various environments.     

An experimental study of the mechanism of the replacement of magnetite by pyrite up to 300 °C

We present the results of an experimental study into the sulfidation of magnetite to form pyrite/marcasite under hydrothermal conditions (90-300 °C, vapor saturated pressures), a process associated with gold deposition in a number of ore deposits. The formation of pyrite/marcasite was studied as a function of reaction time, temperature, pH, sulfide concentration, solid-weight-to-fluid-volume ratio, and geometric surface area of magnetite in polytetrafluoroethylene-lined autoclaves (PTFE) and a titanium and stainless steel flow-through cell. Marcasite was formed only at pH_21°C <4 and was the dominant Fe disulfide at pH_21°C 1.11, while pyrite predominated at pH_21°C >2 and formed even under basic conditions (up to pH_21°C 12-13). Marcasite formation was favored at higher temperatures. Fine-grained pyrrhotite formed in the initial stage of the reaction together with pyrite in some experiments with large surface area of magnetite (grain size <125 μm). This pyrrhotite eventually gave way to pyrite. The transformation rate of magnetite to Fe disulfide increased with decreasing pH (at 120 °C; pH_120°C 0.96-4.42), and that rate of the transformation increased from 120 to 190 °C.Scanning electron microscope (SEM) imaging revealed that micro-pores (0.1-5 μm scale) existed at the reaction front between the parent magnetite and the product pyrite, and that the pyrite and/or marcasite were euhedral at pH_21°C <4 and anhedral at higher pH. The newly formed pyrite was micro-porous (0.1-5 μm); this micro-porosity facilitates fluid transport to the reaction interface between magnetite and pyrite, thus promoting the replacement reaction. The pyrite precipitated onto the parent magnetite was polycrystalline and did not preserve the crystallographic orientation of the magnetite. The pyrite precipitation was also observed on the PTFE liner, which is consistent with pyrite crystallizing from solution. The mechanism of the reaction is that of a dissolution-reprecipitation reaction with the precipitation of pyrite being the rate-limiting step relative to magnetite dissolution under mildly acidic conditions (e.g., pH_155°C 4.42).The experimental results are in good agreement with sulfide phase assemblage and textures reported from sulfidized Banded Iron Formations: pyrite, marcasite and pyrrhotite have been found to exist or co-exist in different sulfidized Banded Iron Formations, and the microtextures show no evidence of sub-μm-scale pseudomorphism of magnetite by pyrite.     

How depositional conditions control input, composition, and degradation of organic matter in sediments from the Chilean coastal upwelling region

In a comprehensive study, we compared depositional conditions, organic matter (OM) composition, and organic carbon turnover in sediments from two different depositional systems along the Chilean continental margin: at ∼23° S off Antofagasta and at ∼36° S off Concepción. Both sites lie within the Chilean coastal upwelling system and have an extended oxygen minimum zone in the water column. However, the northern site (23° S) borders the Atacama Desert, while the southern site (36° S) has a humid hinterland. Eight surface sediment cores (up to 30 cm long) from water depths of 126-1350 m were investigated for excess ²¹⁰Pb (²¹⁰Pb_xs) activity, total organic and total inorganic carbon concentrations (TOC and TIC, respectively), C/N-ratios, organic carbon isotopic compositions (δ¹³C), chlorin concentrations, Chlorin Indices (CI), and sulfate reduction rates (SRR). Sediment accumulation rates obtained from ²¹⁰Pb-analysis were similar in both regions (0.04-0.15 cm yr⁻¹ at 23° S, 0.10-0.19 cm yr⁻¹ at 36° S), although total ²¹⁰Pb_xs fluxes indicated that the vertical particle flux was higher at 36° S than at 23° S. We propose that sediment focusing in isolated deposition centers led to high sediment accumulation rates at 23° S. Furthermore, there were no indications for sediment mixing at 23° S, while bioturbation was intense at 36° S. δ¹³C-values (−24.5‰ to −20.1‰ vs. VPDB) and C/N-ratios (molar, 8.6-12.8) were characteristic of a predominantly marine origin of the sedimentary OM in both investigated areas. The extent of OM alteration in the water column was partly reflected in the surface sediments as chlorin concentrations decreased and C/N-ratios and CI increased with increasing water depth of the sampling site. SRR were lower at 23° S (areal SRR 0.12-0.60 mmol m⁻² d⁻¹) than at 36° S (areal SRR 0.82-1.18 mmol m⁻² d⁻¹), which was partly due to the greater water depth of most of the sediments investigated in the northern region and consistent with a lower quality of the sedimentary OM at 23° S. Reaction rate constants for TOC degradation that were obtained from measured SRR (k_SRR; 0.0004-0.0022 yr⁻¹) showed a good correspondence to k_TOC that were derived from the depth profiles of TOC (0.0003-0.0014 yr⁻¹). Both, k_SRR and k_TOC, reflect differences in OM composition. At 36° S they were related to the degradation state of bulk OM (represented by C/N-ratios), whereas near 23° S they were related to the freshness of a small fraction of labile OM (represented by CI). Our study shows that although rates of organic carbon accumulation were similar in both investigated sites, the extent and kinetics of organic carbon degradation were closely linked to differing depositional conditions.     

Determination of thermal maturity and organic matter type by principal components analysis of the distributions of polycyclic aromatic compounds

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on the basis of theoretical considerations and empirical observations. The PAC maturity parameters, unlike those derived from saturated biomarker stereoisomers, are typically effective across the entire oil generation window. To compensate for the effects of OM type on the maturity parameters, they were combined using principal components analysis. The resulting first principal component was in good agreement with independent indicators of maturity. The relative distributions of C₀–C₃ alkylphenanthrenes, dibenzothiophene, methyldibenzothiophenes and methyldibenzofurans were evaluated by a separate principal components analysis. The results permitted an independent grouping of the samples by OM type and suggested additional, simple molecular ratios that allow graphical recognition of OM type, including the ratio of dibenzothiophenes to dibenzofurans and a ratio using C₂-alkylphenanthrene isomers.     

Preservation of hydrocarbons and biomarkers in oil trapped inside fluid inclusions for >2 billion years

Oil-bearing fluid inclusions occur in a ca. 2.45 Ga fluvial metaconglomerate of the Matinenda Formation at Elliot Lake, Canada. The oil, most likely derived from the conformably overlying deltaic McKim Formation, was trapped in quartz and feldspar during diagenesis and early metamorphism of the host rock, probably before ca. 2.2 Ga. Molecular geochemical analyses of the oil reveal a wide range of compounds, including CH₄, CO₂, n-alkanes, isoprenoids, monomethylalkanes, aromatic hydrocarbons, low molecular weight cyclic hydrocarbons, and trace amounts of complex multi-ring biomarkers. Maturity ratios show that the oil was generated in the oil window, with no evidence of extensive thermal cracking. This is remarkable, given that the oils were exposed to upper prehnite-pumpellyite facies metamorphism (280-350 °C) either during migration or after entrapment. The fluid inclusions are closed systems, with high fluid pressures, and contain no clays or other minerals or metals that might catalyse oil-to-gas cracking. These three attributes may all contribute to the thermal stability of the included oil and enable survival of biomarkers and molecular ratios over billions of years. The biomarker geochemistry of the oil in the Matinenda Formation fluid inclusions enables inferences about the organisms that contributed to the organic matter deposited in the Palaeoproterozoic source rocks from which the analysed oil was generated and expelled. The presence of biomarkers produced by cyanobacteria and eukaryotes that are derived from and trapped in rocks deposited before ca. 2.2 Ga is consistent with an earlier evolution of oxygenic photosynthesis and suggests that some aquatic settings had become sufficiently oxygenated for sterol biosynthesis by this time. The extraction of biomarker molecules from Palaeoproterozoic oil-bearing fluid inclusions thus establishes a new method, using low detection limits and system blank levels, to trace evolution through Earth’s early history that avoids the potential contamination problems affecting shale-hosted hydrocarbons.     

Changes in the composition of organic matter from prodeltaic sediments after a large flood event (Po River, Italy)

The Po River (Italy) experienced a 100-year flood in October 2000. Surface sediments (0-1 cm) from cross-shelf transects were collected in the Po prodelta area (Adriatic Sea) in December 2000, in order to describe the distribution of organic matter (OM) along the main sediment dispersal system immediately after the flood event. Stations were subsequently reoccupied in October 2001 and April 2002. This sampling program provided a special opportunity to characterize the initial surficial flood deposit and the evolution of its associated OM over the course of 2 years. CuO oxidation, elemental, δ¹³C, Δ¹⁴C, and grain-size analyses were carried out to characterize the source, age, and spatial variability of sedimentary OM. Statistical analysis (PERMANOVA) was then applied to investigate temporal changes in different portions of the Po prodelta area. Isotopic and biomarker data suggest that the sedimentary OM in the flood deposit was initially dominated by aged (Δ¹⁴C_Dec-00 = −298.7 ± 56.3‰), lignin-poor OM (Λ_Dec-00 = 1.96 ± 0.33 mg/100 mg OC), adsorbed on the fine material (clay_Dec-00 = 72.1 ± 4.8%) delivered by the flood. In the 2 years following the flood, post-depositional processes significantly increased the content of lignin (Λ_Oct-01 = 2.19 ± 0.51 mg/100 mg OC; Λ_Apr-02 = 2.61 ± 0.63 mg/100 mg OC); and coarse material (silt and sand), while decreasing the contributions from aged OC (Δ¹⁴C_Oct-01 = −255.7 ± 32.8‰; Δ¹⁴C_Apr-02 = −213.2 ± 30.4‰) and fine fraction (clay_Oct-01 = 54.8 ± 9.5%; clay_Apr-02 = 44.6 ± 13.3%). The major changes were observed in the northern and central portions of the prodelta.     

LA-MC-ICPMS Pb-Pb dating of rutile from slowly cooled granulites: Confirmation of the high closure temperature for Pb diffusion in rutile

Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The ²⁰⁷Pb-²⁰⁶Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (T_c) for Pb diffusion in rutile that is less than the T_c of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the T_c for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher T_c than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current T_c estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.     

Thermal evolution of n- and iso-alkanes in oils. Part 1: Pyrolysis model for a mixture of 78 alkanes (C1-C32) including 13,206 free radical reactions

A mechanistic model consisting of 13,206 lumped free radical reactions has been developed to describe the thermal evolution of a mixture of 78 alkanes: all n-alkanes from C₁ to C₃₂ and 46 branched alkane model compounds from C₄ to C₃₂. The mixture was meant to represent the major part of the saturated fraction of petroleum. The rate constants used are available from the literature. The lumping together procedure is described and the model validated on the basis of several experimental results from the literature and relating to pure alkanes. The model is also compared to the saturated fraction obtained from pyrolysis of Elgin oil at 372 °C for up to 1000 h. The cracking global activation energy of n-C₁₅ as well as iso-C₁₅ is close to 69 kcal/mol in the range 200-350 °C. The implications of the model for geological reservoirs will be discussed in a following paper.     

Organic geochemical characteristics of crude oils from the Masila Basin, eastern Yemen

The Masila Basin is an important hydrocarbon province in Yemen, but the origin of hydrocarbons and their generation history are not fully understood. In this regard, 10 crude oils from different petroleum reservoir sections in the Masila Basin were characterized by a variety of biomarker and non-biomarker parameters using GC, GC-MS and stable carbon isotope techniques. Oils from the Masila Basin display pristane/phytane (Pr/Ph) ratios ranging from 1.7 to 2.0, low sulfur content, high C₃₅ homohopane index, relatively high C₂₇ sterane concentrations and relatively high tricyclic terpanes suggesting a marine clay source rock that was deposited in mildly anoxic to suboxic conditions with dominantly algal organic matter. C₂₉ 20S/(20S + 20R) steranes and ββ/(ββ + αα) sterane ratios indicate that the Masila oils have reached peak oil window maturity. Another related feature of these oils is the absence of 18α (H)-oleanane, which suggests a source age older than Cretaceous. The carbon isotope compositions are similar to those of the potential source rocks, which range from −25.4‰ to −28.3‰, indicating a marine environment. The new data presented in this paper suggest that the Masila oils constitute one oil family and that the oil originated from the Upper Jurassic Madbi source rock in the basin.     

Geochemical features and origin of natural gas in heavy oil area of the Western Slope,Songliao Basin,China

The Western Slope of the Songliao Basin is rich in heavy oil resources (>70 × 10⁸ bbl), around which there are shallow gas reservoirs (∼1.0 × 10¹² m³). The gas is dominated by methane with a dryness over 0.99, and the non-hydrocarbon component being overwelmingly nitrogen. Carbon isotope composition of methane and its homologs is depleted in ¹³C, with δ¹³C₁ values being in the range of −55‰ to −75‰, δ¹³C₂ being in the range of −40‰ to −53‰ and δ¹³C₃ being in the range of −30‰ to −42‰, respectively. These values differ significantly from those solution gases source in the Daqing oilfield. This study concludes that heavy oils along the Western Slope were derived from mature source rocks in the Qijia-Gulong Depression, that were biodegraded. The low reservoir temperature (30–50 °C) and low salinity of formation water with neutral to alkaline pH (NaHCO₃) appeared ideal for microbial activity and thus biodegradation. Natural gas along the Western Slope appears mainly to have originated from biodegradation and the formation of heavy oil. This origin is suggested by the heavy δ¹³C of CO₂ (−18.78‰ to 0.95‰) which suggests that the methane was produced via fermentation as the terminal decomposition stage of the oil.     

Late Quaternary environmental change of Yellow River Basin: An organic geochemical record in Bohai Sea (North China)

Bulk geochemical characterization (total organic carbon, grain size distribution, carbon isotope composition) and molecular biomarkers (lignin phenols, straight chain aliphatic hydrocarbons, glycerol dialkyl glycerol tetraethers) were analyzed for a 21 m core from the Bohai Sea (North China), spanning ca 21 ka BP. These paleo-proxies presented remarkable differences between the late glacial period and the Holocene, reflecting continental and coastal environments, respectively. Two peat layers were deposited during the period of ca 9000-8460 yr BP. Thereafter the core site has been consistently covered by seawater until recent reclamation of land from the sea. The occurrence of a total organic carbon maximum from ca 6000-3800 yr BP was attributed to delivery of organic carbon enriched sediments via the Yellow River, consistent with increased vegetation density and higher development of soil under warm and humid mid-Holocene climate conditions. The distributions of lignin phenol compositions and C₃₁/C₂₉n-alkane ratio suggested the largest expansion of woody plants between ca 5300 and 4000 yr BP, corresponding to the extremely favorable climatic conditions. Since ca 3800 yr BP, an abrupt increase in the C₃₁/C₂₉n-alkane ratio suggested higher abundance of grasses, consistent with a drying climate trend after the mid-Holocene. Since our coastal sediments close to the Yellow River outflow contain catchment-integrated environmental signals of the river basin, molecular proxies demonstrate that the variability of vegetation distributions in the Holocene is a widespread phenomenon in those areas adjacent to Yellow River Basin.     

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C₁₅₊ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen.     

A new method for synthesizing fluid inclusions in fused silica capillaries containing organic and inorganic material

Considerable advances in our understanding of physicochemical properties of geological fluids and their roles in many geological processes have been achieved by the use of synthetic fluid inclusions. We have developed a new method to synthesize fluid inclusions containing organic and inorganic material in fused silica capillary tubing. We have used both round (0.3 mm OD and 0.05 or 0.1 mm ID) and square cross-section tubing (0.3 × 0.3 mm with 0.05 × 0.05 mm or 0.1 × 0.1 mm cavities). For microthermometric measurements in a USGS-type heating-cooling stage, sample capsules must be less than 25 mm in length. The square-sectioned capsules have the advantage of providing images without optical distortion. However, the maximum internal pressure (P; about 100 MPa at 22 °C) and temperature (T; about 500 °C) maintained by the square-sectioned capsules are less than those held by the round-sectioned capsules (about 300 MPa at room T, and T up to 650 °C).The fused silica capsules can be applied to a wide range of problems of interest in fluid inclusion and hydrothermal research, such as creating standards for the calibration of thermocouples in heating-cooling stages and frequency shifts in Raman spectrometers. The fused silica capsules can also be used as containers for hydrothermal reactions, especially for organic samples, including individual hydrocarbons, crude oils, and gases, such as cracking of C₁₈H₃₈ between 350 and 400 °C, isotopic exchanges between C₁₈H₃₈ and D₂O and between C₁₉D₄₀ and H₂O at similar temperatures. Results of these types of studies provide information on the kinetics of oil cracking and the changes of oil composition under thermal stress.When compared with synthesis of fluid inclusions formed by healing fractures in quartz or other minerals or by overgrowth of quartz at elevated P-T conditions, the new fused-silica method has the following advantages: (1) it is simple; (2) fluid inclusions without the presence of water can be formed; (3) synthesized inclusions are large and uniform, and they are able to tolerate high internal P; (4) it is suitable for the study of organic material; and (5) redox control is possible due to high permeability of the fused silica to hydrogen.     

Biogeochemistry of mineral-organic associations across a long-term mineralogical soil gradient (0.3-4100 kyr), Hawaiian Islands

Organic matter (OM) in mineral-organic associations (MOAs) represents a large fraction of carbon in terrestrial ecosystems which is considered stable against biodegradation. To assess the role of MOAs in carbon cycling, there is a need to better understand (i) the time-dependent biogeochemical evolution of MOAs in soil, (ii) the effect of the mineral composition on the physico-chemical properties of attached OM, and (iii) the resulting consequences for the stabilization of OM. We studied the development of MOAs across a mineralogical soil gradient (0.3-4100 kyr) at the Hawaiian Islands that derived from basaltic tephra under comparable climatic and hydrological regimes. Mineral-organic associations were characterized using biomarker analyses of OM with chemolytic methods (lignin phenols, non-cellulosic carbohydrates) and wet chemical extractions, surface area/porosity measurements (N₂ at 77 K and CO₂ at 273 K), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results show that in the initial weathering stage (0.3 kyr), MOAs are mainly composed of primary, low-surface area minerals (olivine, pyroxene, feldspar) with small amounts of attached OM and lignin phenols but a large contribution of microbial-derived carbohydrates. As high-surface area, poorly crystalline (PC) minerals increase in abundance during the second weathering stage (20-400 kyr), the content of mineral-associated OM increased sharply, up to 290 mg C/g MOA, with lignin phenols being favored over carbohydrates in the association with minerals. In the third and final weathering stage (1400-4100 kyr), metastable PC phases transformed into well crystalline secondary Fe and Al (hydr)oxides and kaolin minerals that were associated with less OM overall, and depleted in both lignin and carbohydrate as a fraction of total OM. XPS, the N₂ pore volume data and OM-mineral volumetric ratios suggest that, in contrast to the endmember sites where OM accumulated at the surfaces of larger mineral grains, topsoil MOAs of the 20-400-kyr sites are composed of a homogeneous admixture of small-sized PC minerals and OM, which originated from both adsorption and precipitation processes. The chemical composition of OM in surface-horizon MOAs, however, was largely controlled by the uniform source vegetation irrespective of the substrate age whereas in subsoil horizons, aromatic and carboxylic C correlated positively with oxalate-extractable Al and Si and CuCl₂-extractable Al concentrations representing PC aluminosilicates and Al-organic complexes (r² > 0.85). Additionally, XPS depth profiles suggest a zonal structure of sorbed OM with aromatic carbons being enriched in the proximity of mineral surfaces and amide carbons (peptides/proteins) being located in outer regions of MOAs. Albeit the mineralogical and compositional changes of OM, the rigidity of mineral-associated OM as analyzed by DSC changed little over time. A significantly reduced side chain mobility of sorbed OM was, however, observed in subsoil MOAs, which likely arose from stronger mineral-organic bindings. In conclusion, our study shows that the properties of soil MOAs change substantially over time with different mineral assemblages favoring the association of different types of OM, which is further accentuated by a vertical gradient of OM composition on mineral surfaces. Factors supporting the stabilization of sorbed OM were (i) the surface area and reactivity of minerals (primary or secondary crystalline minerals versus PC secondary minerals), (ii) the association of OM with micropores of PC minerals (via ‘sterically’ enhanced adsorption), (iii) the effective embedding of OM in ‘well mixed’ arrays with PC minerals and monomeric/polymeric metal species, (iv) the inherent stability of acidic aromatic OM components, and (iv) an impaired segmental mobility of sorbed OM, which might increase its stability against desorption and microbial utilization.     

Late Quaternary glaciation and equilibrium-line altitudes of the Mayan Ice Cap, Guatemala, Central America

The Sierra los Cuchumatanes (3837 m), Guatemala, supported a plateau ice cap and valley glaciers around Montaña San Juan (3784 m) that totaled ∼ 43 km² in area during the last local glacial maximum. Former ice limits are defined by sharp-crested lateral and terminal moraines that extend to elevations of ∼ 3450 m along the ice cap margin, and to ca. 3000-3300 m for the valley glaciers. Equilibrium-line altitudes (ELAs) estimated using the area-altitude balance ratio method for the maximum late Quaternary glaciation reached as low as 3470 m for the valley glaciers and 3670 m for the Mayan Ice Cap. Relative to the modern altitude of the 0°C isotherm of ∼ 4840 m, we determined ELA depressions of 1110-1436 m. If interpreted in terms of a depression of the freezing level during maximal glaciation along the modern lapse rate of − 5.3°C km^− 1, this ΔELA indicates tropical highland cooling of ∼ 5.9 to 7.6 ± 1.2°C. Our data support greater glacial highland cooling than at sea level, implying a high tropical sensitivity to global climate changes. The large magnitude of ELA depression in Guatemala may have been partially forced by enhanced wetness associated with southward excursions of the boreal winter polar air mass.     

Determining accurate temperature-time paths from U-Pb thermochronology: An example from the Kaapvaal craton, southern Africa

Thermochronology has revolutionized our understanding of the establishment and evolution of lithospheric thermal structure. However, many potential benefits provided by the application of diffusion theory to thermochronology have yet to be fully exploited. This study uses apatite (T_c = 450-550 °C) and titanite (T_c = 550-650 °C) U-Pb ID-TIMS thermochronology at the single- to sub-grain scale to separate the variable effects of volume diffusion of Pb from metamorphic (over)growth above and below the T_c of a mineral. Data are presented from two ca. 3227 Ma tonalite samples from north and south of the Barberton Greenstone Belt (BGB), southern Africa. Two distinct populations of apatite from a sample north of the BGB record fast cooling followed by metamorphic growth ∼10 Myr later. Both apatite and titanite dates from south of the BGB show a strong correlation with the grain size and record 100 Myr of post-emplacement cooling. Complex core-rim zoning observed in cathodoluminescence images of apatite is interpreted to reflect metamorphic overgrowth above the T_c. The age and topology of grain size versus date curves from titanite and apatite are used in combination with a finite-difference numerical model to show that slow, non-linear, cooling and not thermal resetting is responsible for the observed distribution. The thermal histories from either side of the BGB are very different and provide unique insight into the BGB’s tectonic evolution: a ∼70 Myr period of apparent stability after ca. 3.2 Ga terrane assembly was followed by fast exhumation south of the BGB that led to lower-crustal melting and intrusion of granitic batholiths ca. 3.14-3.10 Ga.     

Steps toward dating early diagenetic K-feldspar by the Ar-Ar method

Authigenic sedimentary low-temperature K-feldspar separated from Albian-Turonian carbonates in Israel was dated by the step-heating ⁴⁰Ar-³⁹Ar method. In contrast to high-temperature K-feldspars, ca. 90% of the radiogenic Ar was released at temperatures lower than 600 °C and fusion mostly occurred below 750 °C. Though formed under low temperature, Ar loss in all but one sample is estimated to be less than 2%. Nevertheless, the effect of ³⁹Ar recoil is evident in some separates, probably due to their very fine size (4-10 μm). The plateau age of one sample with the highest content of authigenic K-feldspar (93%, 96 Ma) is slightly younger than the assumed stratigraphic age and thus defines the timing of an early diagenetic event within a few million years after deposition. Other samples where a plateau age could be determined yield ages slightly older. Strong acid etching (7 N HNO₃, 85 °C) of the K-feldspar-enriched fraction may have improved the ³⁹Ar-⁴⁰Ar spectra but did not eliminate the presence of minute quantities of detrital K-bearing minerals. Though the present set of data is insufficient for a clear-cut conclusion, the activation energy of the authigenic K-feldspar is in the range of 14-26 kcal mol^− 1 s^− 1, much lower than that of magmatic and hydrothermal K-feldspars and can probably be attributed to the heating schedule and the small crystal size. It is not clear whether the formation at low temperatures (< 50 °C) has any effect on the activation energy.     

Enhanced late gas generation potential of petroleum source rocks via recombination reactions: Evidence from the Norwegian North Sea

Gas generation in the deep reaches of sedimentary basins is usually considered to take place via the primary cracking of short alkyl groups from overmature kerogen or the secondary cracking of petroleum. Here, we show that recombination reactions ultimately play the dominant role in controlling the timing of late gas generation in source rocks which contain mixtures of terrigeneous and marine organic matter. These reactions, taking place at low levels of maturation, result in the formation of a thermally stable bitumen, which is the major source of methane at very high maturities. The inferences come from pyrolysis experiments performed on samples of the Draupne Formation (liptinitic Type II kerogen) and Heather Formation (mixed marine-terrigeneous Type III kerogen), both Upper Jurassic source rocks stemming from the Norwegian northern North Sea Viking Graben system. Non-isothermal closed system micro scale sealed vessel (MSSV) pyrolysis, non-isothermal open system pyrolysis and Rock Eval type pyrolysis were performed on the solvent extracted, concentrated kerogens of the two immature samples. The decrease of C₆₊ products in the closed system MSSV pyrolysis provided the basis for the calculation of secondary gas (C_1-5) formation. Subtraction of the calculated secondary gas from the total observed gas yields a “remaining” gas. In the case of the Draupne Formation this is equivalent to primary gas cracked directly from the kerogen, as detected by a comparison with multistep open pyrolysis data. For the Heather Formation the calculated remaining gas formation profile is initially attributable to primary gas but there is a second major gas pulse at very high temperature (>550 °C at 5.0 K min⁻¹) that is not primary. This has been explained by a recondensation process where first formed high molecular weight compounds in the closed system yield a macromolecular material that undergoes secondary cracking at elevated temperatures. The experiments provided the input for determination of kinetic parameters of the different gas generation types, which were used for extrapolations to a linear geological heating rate of 10⁻¹¹ K min⁻¹. Peak generation temperatures for the primary gas generation were found to be higher for Heather Formation (T_max = 190 °C, equivalent to R_o appr. 1.7%) compared to Draupne Formation (T_max = 175 °C, equivalent to appr. R_o 1.3%). Secondary gas peak generation temperatures were calculated to be 220 °C for the Heather Formation and 205 to 215 °C for the Draupne Formation, respectively, with equivalent vitrinite reflectance values (R_o) between 2.4% and 2.0%. The high temperature secondary gas formation from cracking of the recombination residue as detected for the Heather Formation is quantitatively important and is suggested to occur at very high temperatures (T_max approx. 250 °C) for geological heating rates. The prediction of a significant charge of dry gas from the Heather Formation at very high maturity levels has important implications for petroleum exploration in the region, especially to the north of the Viking Graben where Upper Jurassic sediments are sufficiently deep buried to have experienced such a process.     

Sorptive stabilization of organic matter by amorphous Al hydroxide

Amorphous Al hydroxides (am-Al(OH)₃) strongly sorb and by this means likely protect dissolved organic matter (OM) against microbial decay in soils. We carried out batch sorption experiments (pH 4.5; 40 mg organic C L⁻¹) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO₂ mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH)₃, thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L⁻¹) during sorption. At low SSRs, hence limited am-Al(OH)₃ availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH)₃ more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH)₃ availability, despite constant aromatic C (∼30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral’s occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m⁻²). This study demonstrates that sorption to am-Al(OH)₃ results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby the properties of sorbed OM, and the stability of OM against microbial decay.