Molecular and Carbon Isotopic Variation during Canister Degassing of Terrestrial Shale: A Case Study from Xiahuayuan Formation in the Xuanhua Basin, North China

Molecular and carbon isotopic variation during degassing process have been observed in marine shale reservoirs, however, this behavior remains largely unexplored in terrestrial shale reservoirs. Here, we investigate the rock parameters of five terrestrial shale core samples from the Xiahuayuan Formation and the geochemical parameters of thirty natural gas samples collected during field canister degassing experiments. Based on these new data, the gas composition and carbon isotope variation during canister degassing are discussed and, further, the relationship between petrophysics and the carbon isotope variation is explored. The results show that methane content first increases and then decreases, the concentrations of carbon dioxide (CO2) and nitrogen gas (N2) peak in the early degassing stage, while heavier hydrocarbons gradually increase over time. Shale gas generated from humic source rocks contains more non-hydrocarbon and less heavy hydrocarbon components than that generated from sapropelic source rocks with similar maturity. Time-series sampling presents an upward increase in δ13C1 value during the degassing process with the largest variation up to 5.7‰, while the variation in δ13C3 and δ13C2 is insignificant compared to δ13C1. Moreover, we find that there is only a small variation in δ13C1 in shale samples with high permeability and relatively undeveloped micropores, which is similar to the limited δ13C1 variation in conventional natural gas. For our studied samples, the degree of carbon isotope variation is positively correlated with the TOC content, micropore volume, and micropore surface, suggesting that these three factors may play a significant role in carbon isotope shifts during shale gas degassing. We further propose that the strong 13C1 and C2+depletion of shale gas observed during the early degassing stage may have resulted from the desorption and diffusion effect, which may lead to deviation in the identification of natural gas origin. It is therefore shale gas of the late degassing stage that would be more suitable for study to reduce analytic deviations. In most samples investigated, significant isotopic variation occurred during the degassing stage at room temperature, indicating that the adsorbed gas had already been desorbed at this stage Our results therefore suggest that more parameters may need to be considered when evaluating the lost gas of shales.

Metabolism is the major driver of hydrogen isotope fractionation recorded in tree-ring glucose of Pinus nigra

- Stable isotope abundances convey valuable information about plant physiological processes and underlying environmental controls. Central gaps in our mechanistic understanding of hydrogen isotope abundances impede their widespread application within the plant and Earth sciences. - To close these gaps, we analysed intramolecular deuterium abundances in glucose of Pinus nigra extracted from an annually resolved tree-ring series (1961 to 1995). - We found fractionation signals at glucose H1 and H2 introduced by closely related metabolic processes. These signals (and thus metabolism) respond to drought and atmospheric CO2 concentration beyond a response change point. They explain ≈60% of the whole-molecule deuterium variability. Altered metabolism is associated with below-average yet not exceptionally low growth. - We propose the signals are introduced at the leaf-level by changes in sucrose-to-starch carbon partitioning and anaplerotic carbon flux into the Calvin-Benson cycle. In conclusion, metabolism can be the main driver of hydrogen isotope variation in plant glucose.

Investigating Hydrogen Isotope Variation during Heating of n-Alkanes under Limited Oxygen Conditions: Implications for Palaeoclimate Reconstruction in Archaeological Settings

This paper reports on a series of heating experiments that focus on n-alkanes extracted from leaf, bark, and xylem tissues of the Celtis australis plant. These lipid biomarkers were analysed for their compound-specific hydrogen isotopic composition (δ2Hwax) under limited oxygen conditions at 150, 250, 350, and 450 °C. Our results reveal isotopic variations in wax lipids of different plant organs during short-term low-temperature combustion. We conclude that, in the absence of a detailed characterisation of the depositional environment in advance of sampling, δ2Hwax values in archaeological or otherwise highly anthropogenic environments should be interpreted cautiously. In addition, we observed that variation in δ2Hwax of leaves is minimal at temperatures ≤ 350 °C, highlighting the potential for δ2Hwax in thermally altered combustion substrates to yield palaeoclimate information, which could allow researchers to investigate links between archaeological and climatic records at a high spatial and temporal resolution.

Monthly mobility inferred from isoscapes and laser ablation strontium isotope ratios in caprine tooth enamel

Strontium isotopic analysis of sequentially formed tissues, such as tooth enamel, is commonly used to study provenance and mobility of humans and animals. However, the potential of 87Sr/86Sr in tooth enamel to track high-frequency movements has not yet been established, in part due to the lack of data on modern animals of known movement and predictive model of isotope variation across the landscape. To tackle this issue, we measured the 87Sr/86Sr in plant samples taken from a 2000 km2 area in the Altai Mountains (Mongolia), and the 87Sr/86Sr in tooth enamel of domestic caprines whose mobility was monitored using GPS tracking. We show that high-resolution, sequential profiles of strontium isotope composition of tooth enamel reliably reflect the high-frequency mobility of domestic livestock and that short-term residency of about 45 days can be resolved. This offers new perspectives in various disciplines, including forensics, ecology, palaeoanthropology, and bioarchaeology.