Low-temperature gas from marine shales: wet gas to dry gas over experimental time

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C5, 2% C1) to predominantly light hydrocarbons (56% C1, 8% C5), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results

Position-specific ^(13)C distributions within propane from experiments and natural gas samples

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific ^(13)C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the ^(13)C/^(12)C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ^(13)C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ^(13)C and then increasing in both center and terminal position δ^(13)C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems

Formation temperatures of thermogenic and biogenic methane

Methane is an important greenhouse gas and energy resource generated dominantly by methanogens at low temperatures and through the breakdown of organic molecules at high temperatures. However, methane-formation temperatures in nature are often poorly constrained. We measured formation temperatures of thermogenic and biogenic methane using a “clumped isotope” technique. Thermogenic gases yield formation temperatures between 157° and 221°C, within the nominal gas window, and biogenic gases yield formation temperatures consistent with their comparatively lower-temperature formational environments (<50°C). In systems where gases have migrated and other proxies for gas-generation temperature yield ambiguous results, methane clumped-isotope temperatures distinguish among and allow for independent tests of possible gas-formation models

Impaired postprandial skeletal muscle vascular responses to a mixed meal challenge in normoglycaemic people with a parent with type 2 diabetes

Aims/hypothesis: Microvascular blood flow (MBF) increases in skeletal muscle postprandially to aid in glucose delivery and uptake in muscle. This vascular action is impaired in individuals who are obese or have type 2 diabetes. Whether MBF is impaired in normoglycaemic people at risk of type 2 diabetes is unknown. We aimed to determine whether apparently healthy people at risk of type 2 diabetes display impaired skeletal muscle microvascular responses to a mixed-nutrient meal. Methods: In this cross-sectional study, participants with no family history of type 2 diabetes (FH-) for two generations (n = 18), participants with a positive family history of type 2 diabetes (FH+; i.e. a parent with type 2 diabetes; n = 16) and those with type 2 diabetes (n = 12) underwent a mixed meal challenge (MMC). Metabolic responses (blood glucose, plasma insulin and indirect calorimetry) were measured before and during the MMC. Skeletal muscle large artery haemodynamics (2D and Doppler ultrasound, and Mobil-O-graph) and microvascular responses (contrast-enhanced ultrasound) were measured at baseline and 1 h post MMC. Results: Despite normal blood glucose concentrations, FH+ individuals displayed impaired metabolic flexibility (reduced ability to switch from fat to carbohydrate oxidation vs FH-; p \u3c 0.05) during the MMC. The MMC increased forearm muscle microvascular blood volume in both the FH- (1.3-fold, p \u3c 0.01) and FH+ (1.3-fold, p \u3c 0.05) groups but not in participants with type 2 diabetes. However, the MMC increased MBF (1.9-fold, p \u3c 0.01), brachial artery diameter (1.1-fold, p \u3c 0.01) and brachial artery blood flow (1.7-fold, p \u3c 0.001) and reduced vascular resistance (0.7-fold, p \u3c 0.001) only in FH- participants, with these changes being absent in FH+ and type 2 diabetes. Participants with type 2 diabetes displayed significantly higher vascular stiffness (p \u3c 0.001) compared with those in the FH- and FH+ groups; however, vascular stiffness did not change during the MMC in any participant group. Conclusions/interpretation: Normoglycaemic FH+ participants display impaired postprandial skeletal muscle macro- and microvascular responses, suggesting that poor vascular responses to a meal may contribute to their increased risk of type 2 diabetes. We conclude that vascular insulin resistance may be an early precursor to type 2 diabetes in humans, which can be revealed using an MMC

Position-specific ^(13)C distributions within propane from experiments and natural gas samples

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific ^(13)C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the ^(13)C/^(12)C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ^(13)C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ^(13)C and then increasing in both center and terminal position δ^(13)C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems

Thermal modelling of gas generation and retention in the Jurassic organic-rich intervals in the Darquain field, Abadan Plain, SW Iran

The petroleum system with Jurassic source rocks is an important part of the hydrocarbons discovered in the Middle East. Limited studies have been done on the Jurassic intervals in the 26,500 km2 Abadan Plain in south-west Iran, mainly due to the deep burial and a limited number of wells that reach the basal Jurassic successions. The goal of this study was to evaluate the Jurassic organic-rich intervals and shale gas play in the Darquain field using organic geochemistry, organic petrography, biomarker analysis, and basin modelling methods. This study showed that organic-rich zones present in the Jurassic intervals of Darquain field could be sources of conventional and unconventional gas reserves. The organic matter content of samples from the organic-rich zones corresponds to medium-to-high-sulphur kerogen Type II-S marine origin. The biomarker characteristics of organic-rich zones indicate carbonate source rocks that contain marine organic matter. The biomarker results also suggest a marine environment with reducing conditions for the source rocks. The constructed thermal model for four pseudo-wells indicates that, in the kitchen area of the Jurassic gas reserve, methane has been generated in the Sargelu and Neyriz source rocks from Early Cretaceous to recent times and the transformation ratio of organic matter is more than 97%. These organic-rich zones with high initial total organic carbon (TOC) are in the gas maturity stage [1.5–2.2% vitrinite reflectance in oil (Ro)] and could be good unconventional gas reserves and gas source rocks. The model also indicates that there is a huge quantity of retained gas within the Jurassic organic-rich intervals

Social Perceptions of Forest Ecosystem Services in the Democratic Republic of Congo

The forests of the Albertine Rift are known for their high biodiversity and the important ecosystem services they provide to millions of inhabitants. However, their conservation and the maintenance of ecosystem service delivery is a challenge, particularly in the Democratic Republic of the Congo. Our research investigates how livelihood strategy and ethnicity affects local perceptions of forest ecosystem services. We collected data through 25 focus-group discussions in villages from distinct ethnic groups, including farmers (Tembo, Shi, and Nyindu) and hunter-gatherers (Twa). Twa identify more food-provisioning services and rank bush meat and honey as the most important. They also show stronger place attachment to the forest than the farmers, who value other ecosystem services, but all rank microclimate regulation as the most important. Our findings help assess ecosystem services trade-offs, highlight the important impacts of restricted access to forests resources for Twa, and point to the need for developing alternative livelihood strategies for these communities

Uncovering Ecosystem Service Bundles through Social Preferences

Ecosystem service assessments have increasingly been used to support environmental management policies, mainly based on biophysical and economic indicators. However, few studies have coped with the social-cultural dimension of ecosystem services, despite being considered a research priority. We examined how ecosystem service bundles and trade-offs emerge from diverging social preferences toward ecosystem services delivered by various types of ecosystems in Spain. We conducted 3,379 direct face-to-face questionnaires in eight different case study sites from 2007 to 2011. Overall, 90.5% of the sampled population recognized the ecosystem’s capacity to deliver services. Formal studies, environmental behavior, and gender variables influenced the probability of people recognizing the ecosystem’s capacity to provide services. The ecosystem services most frequently perceived by people were regulating services; of those, air purification held the greatest importance. However, statistical analysis showed that socio-cultural factors and the conservation management strategy of ecosystems (i.e., National Park, Natural Park, or a non-protected area) have an effect on social preferences toward ecosystem services. Ecosystem service trade-offs and bundles were identified by analyzing social preferences through multivariate analysis (redundancy analysis and hierarchical cluster analysis). We found a clear trade-off among provisioning services (and recreational hunting) versus regulating services and almost all cultural services. We identified three ecosystem service bundles associated with the conservation management strategy and the rural-urban gradient. We conclude that socio-cultural preferences toward ecosystem services can serve as a tool to identify relevant services for people, the factors underlying these social preferences, and emerging ecosystem service bundles and trade-offs

Estimation of hydrous-pyrolysis kinetic parameters for oil generation from Baltic Cambrian and Tremadocian source rocks with Type-II kerogen

Determining kinetic parameters for oil generation from a source rock by hydrous pyrolysis requires a considerable amount of sample (kilograms) and laboratory time (several weeks). In an effort to circumvent these requirements, hydrous-pyrolysis (HP) kinetic parameters for oil generation from Upper Cambrian and Tremadocian source rocks of the Baltic region are estimated by two methods: (1) organic sulfur content in kerogen and (2) HP experiments conducted at 330 and 355°C for 72 h. Estimates for the Upper Cambrian source rocks based on organic sulfur contents gave activation energies from 47 to 56 kcal/mole and frequency factors from 1.156 ' 1025>/sup> to 1.078 ' 1028 m.y.-1 . Tremadocian source rocks based on organic sulfur content gave estimated activation energies from 60 to 62 kcal/mole and frequency factors from 1.790 ' 1029 to 1.104 ' 1030 m.y.-1 . The estimates for the Tremadocian source rocks were less affected by thermal maturation because their low kerogen S/(S + C) mole fractions (>gt; 0.018) of the Upper Cambrian source rocks decreased with thermal maturation and resulted in overestimation of the kinetic parameters. The second method was designed to estimate kinetic parameters based on two HP experiments. The assumption that the maximum yield in calculating the rate constant at 330°C (k330°C could be determined by a second hydrous pyrolysis experiment at 355°C for 72 h proved not to be valid. Instead, a previously established relationship between Rock-Eval hydrogen index and maximum HP yield for Type-II kerogen was used to calculate k330°C from oil yields generated by the HP experiment at 330°C for 72 h assuming a first-order reaction. HP kinetic parameters were determined from relationships between k330°C and the HP kinetic parameters previously reported. These estimated HP kinetic parameters were in agreement with those obtained by the first method for immature samples, but underestimated the kinetic parameters for samples at higher thermal maturities. Applying these estimated HP kinetic parameters to geological heating rates of 1 and 10°C/m.y. indicated that the Upper Cambrian source rocks would generate oil notably earlier than the overlying Tremadocian source rocks. This was confirmed in part by available data from two neighboring boreholes in the Polish sector of the Baltic