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Sequential thermal analysis allows for deconvoluting the refractory nature and complexity of carbon mixtures embedded in mineral matrices for subsequent offline stable carbon and radiocarbon (14C) isotope analyses. Originally developed to separate Holocene from more ancient sedimentary organic matter to improve dating of marine sediments, the Ramped Pyrolysis and Oxidation (RPO) apparatus, or informally, the “dirt burner” is now used to address pressing questions in the broad field of biogeochemistry. The growing interest in the community now necessitates improved handling and procedures for routine analyses of difficult sample types. Here we report on advances in CO2 purification during sample processing, modifications to the instrumentation at the National Ocean Sciences Accelerator Mass Spectrometry (NOSAMS) facility, and introduce sodium bicarbonate procedural standards with differing natural abundance 14C signatures for blank assessment. Measurements from different environmental samples are used to compare the procedure to the different generations of sequential thermal analyses. With this study, we aim to improve the standardization of the procedures and prepare this instrumentation for innovations in online stable carbon isotopes and direct AMS-interface measurements in the future.
Constraining radiocarbon (14C) reservoir age offsets is critical to deriving accurate calendar-age chronologies from 14C dating of materials which did not draw carbon directly from the atmosphere. The application of 14C dating to such materials is severely limited in hydrologically sensitive environments like the Black Sea because of the difficulty to quantify reservoir age offsets, which can vary quickly and significantly through time, due to the dynamics of the biogeochemical cycling of carbon. Here we reconstruct 14C reservoir age offsets (Rshell-atm) of Holocene bivalve shells from the coastal Black Sea relatively to their contemporaneous atmosphere. We show that the 14C reservoir age offset and the stable carbon isotope composition of bivalve shells are linearly correlated in this region. From a biogeochemical standpoint, this suggests that inorganic stable carbon isotope and 14C compositions of Black Sea coastal waters are controlled by the balance between autochthonous primary productivity and heterotrophic respiration of allochthonous pre-aged terrestrial organic matter supplied by rivers. This provided an important implication for Black Sea geochronology as the reservoir age offset of 14C-dated bivalve shell can be inferred from its stable carbon isotope composition. Our results provide a fundamental and inexpensive geochemical tool which will considerably improve the accuracy of Holocene calendar age chronologies in the Black Sea.
We estimate the blank carbon mass over the course of a typical Ramped PyrOx (RPO) analysis (150–1000°C; 5°C×min–1) to be (3.7±0.6) μg C with an Fm value of 0.555±0.042 and a δ13C value of (–29.0±0.1) ‰ VPDB. Additionally, we provide equations for RPO Fm and δ13C blank corrections, including associated error propagation. By comparing RPO mass-weighted mean and independently measured bulk δ13C values for a compilation of environmental samples and standard reference materials (SRMs), we observe a small yet consistent 13C depletion within the RPO instrument (mean–bulk: μ=–0.8‰; ±1σ=0.9‰; n=66). In contrast, because they are fractionation-corrected by definition, mass-weighted mean Fm values accurately match bulk measurements (mean–bulk: μ=0.005; ±1σ=0.014; n=36). Lastly, we show there exists no significant intra-sample δ13C variability across carbonate SRM peaks, indicating minimal mass-dependent kinetic isotope fractionation during RPO analysis. These data are best explained by a difference in activation energy between 13C- and 12C-containing compounds (13–12∆E) of 0.3–1.8 J×mol–1, indicating that blank and mass-balance corrected RPO δ13C values accurately retain carbon source isotope signals to within 1–2‰.
Reservoir age offsets are widely used to correct marine and speleothem radiocarbon age measurements for various calibration purposes. They also serve as a powerful tracer for carbon cycle dynamics. However, a clear terminology regarding reservoir age offsets is lacking, sometimes leading to miscalculations. This note seeks to provide consistent conventions for reporting reservoir 14C disequilibria useful to a broad range of environmental sciences. This contribution introduces the F14R and δ14R metrics to express the relative 14C disequilibrium between two contemporaneous reservoirs and the R metric as the associated reservoir age offset.
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