Determination of carbon isotopes in carbonates (calcite, dolomite, magnesite, siderite) by femtosecond laser ablation multi-collector ICP-MS

This study reports a method for in situ determination of stable carbon (δ13C ‰) isotope compositions for calcite, dolomite, magnesite and siderite by femtosecond laser ablation multi-collector inductively coupled plasma...

Evidence from the Changing Carbon Isotopic of Kerogen, Oil, and Gas during Hydrous Pyrolysis from Pinghu Formation, the Xihu Sag, East China Sea Basin

Semi-open hydrous pyrolysis experiments on coal-measure source rocks in the Xihu Sag were conducted to investigate the carbon isotope evolution of kerogen, bitumen, generated expelled oil, and gases with increasing thermal maturity. Seven corresponding experiments were conducted at 335 °C, 360 °C, 400 °C, 455 °C, 480 °C, 525 °C, and 575 °C, while other experimental factors, such as the heating time and rate, lithostatic and hydrodynamic pressures, and columnar original samples were kept the same. The results show that the simulated temperatures were positive for the measured vitrinite reflectance (Ro), with a correlation coefficient (R2) of 0.9861. With increasing temperatures, lower maturity, maturity, higher maturity, and post-maturity stages occurred at simulated temperatures (Ts) of 335–360 °C, 360–400 °C, 400–480 °C, and 480–575 °C, respectively. The increasing gas hydrocarbons with increasing temperature reflected the higher gas potential. Moreover, the carbon isotopes of kerogen, bitumen, expelled oil, and gases were associated with increased temperatures; among gases, methane was the most sensitive to maturity. Ignoring the intermediate reaction process, the thermal evolution process can be summarized as kerogen0(original) + bitumen0(original)→kerogenr (residual kerogen) + expelled oil (generated) + bitumenn+r (generated + residual) + C2+(generated + residual) + CH4(generated). Among these, bitumen, expelled oil, and C2-5 acted as reactants and products, whereas kerogen and methane were the reactants and products, respectively. Furthermore, the order of the carbon isotopes during the thermal evolution process was identified as: δ13C1 < 13C2-5 < δ13Cexpelled oil < δ13Cbitumen < δ13Ckerogen. Thus, the reaction and production mechanisms of carbon isotopes can be obtained based on their changing degree and yields in kerogen, bitumen, expelled oil, and gases. Furthermore, combining the analysis of the geochemical characteristics of the Pinghu Formation coal–oil-type gas in actual strata with these pyrolysis experiments, it was identified that this area also had substantial development potential. Therefore, this study provides theoretical support and guidance for the formation mechanism and exploration of oil and gas based on changing carbon isotopes.

Investigating oxygen and carbon isotopic relationships in speleothem records over the last millennium using multiple isotope-enabled climate models

The incorporation of water isotopologues into the hydrology of general circulation models (GCMs) facilitates the comparison between modelled and measured proxy data in paleoclimate archives. However, the variability and drivers of measured and modelled water isotopologues, and indeed the diversity of their representation in different models are not well constrained. Improving our understanding of this variability in past and present climates will help to better constrain future climate change projections and decrease their range of uncertainty. Speleothems are a precisely datable paleoclimate archive and provide well preserved (semi-)continuous multivariate isotope time series in the lower and mid-latitudes, and are, therefore, well suited to assess climate and isotope variability on decadal and longer timescales. However, the relationship between speleothem oxygen and carbon isotopes to climate variables also depends on site-specific parameters, and their comparison to GCMs is not always straightforward. Here we compare speleothem oxygen and carbon isotopic signatures from the Speleothem Isotopes Synthesis and AnaLysis database version 2 (SISALv2) to the output of five different water-isotope-enabled GCMs (ECHAM5-wiso, GISS-E2-R, iCESM, iHadCM3, and isoGSM) over the last millennium (850–1850 common era, CE). We systematically evaluate differences and commonalities between the standardized model simulation outputs. The goal is to distinguish climatic drivers of variability for both modelled and measured isotopes. We find strong regional differences in the oxygen isotope signatures between models that can partly be attributed to differences in modelled temperatures. At low latitudes, precipitation amount is the dominant driver for water isotope variability, however, at cave locations the agreement between modelled temperature variability is higher than for precipitation variability. While modelled isotopic signatures at cave locations exhibited extreme events coinciding with changes in volcanic and solar forcing, such fingerprints are not apparent in the speleothem isotopes, and may be attributed to the lower temporal resolution of speleothem records compared to the events that are to be detected. Using spectral analysis, we can show that all models underestimate decadal and longer variability compared to speleothems, although to varying extent. We found that no model excels in all analyzed comparisons, although some perform better than the others in either mean or variability. Therefore, we advise a multi-model approach, whenever comparing proxy data to modelled data. Considering karst and cave internal processes through e.g. isotope-enabled karst models may alter the variability in speleothem isotopes and play an important role in determining the most appropriate model. By exploring new ways of analyzing the relationship between the oxygen and carbon isotopes, their variability, and co-variability across timescales, we provide methods that may serve as a baseline for future studies with different models using e.g. different isotopes, different climate archives, or time periods.

Constrain on Oil Recovery Stage during Oil Shale Subcritical Water Extraction Process Based on Carbon Isotope Fractionation Character

In this work, Huadian oil shale was extracted by subcritical water at 365 °C with a time series (2–100 h) to better investigate the carbon isotope fractionation characteristics and how to use its fractionation characteristics to constrain the oil recovery stage during oil shale in situ exploitation. The results revealed that the maximum generation of oil is 70–100 h, and the secondary cracking is limited. The carbon isotopes of the hydrocarbon gases show a normal sequence, with no “rollover” and “reversals” phenomena, and the existence of alkene gases and the CH4-CO2-CO diagram implied that neither chemical nor carbon isotopes achieve equilibrium in the C-H-O system. The carbon isotope (C1–C3) fractionation before oil generation is mainly related to kinetics of organic matter decomposition, and the thermodynamic equilibrium process is limited; when entering the oil generation area, the effect of the carbon isotope thermodynamic equilibrium process (CH4 + 2H2O ⇄ CO2 + 4H2) becomes more important than kinetics, and when it exceeds the maximum oil generation stage, the carbon isotope kinetics process becomes more important again. The δ13CCO2−CH4 is the result of the competition between kinetics and thermodynamic fractionation during the oil shale pyrolysis process. After oil begins to generate, δ13CCO2−CH4 goes from increasing to decreasing (first “turning”); in contrast, when exceeding the maximum oil generation area, it goes from decreasing to increasing (second “turning”). Thus, the second “turning” point can be used to indicate the maximum oil generation area, and it also can be used to help determine when to stop the heating process during oil shale exploitation and lower the production costs.