Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 µg carbon (µgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 µgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.

Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 μg carbon (μgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 μgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.

Description: Sedimentary high molecular weight (HMW) n-alkyl lipids derived from the waxes of terrestrial plants are common target compounds in biogeochemical and paleoenvironmental research. These plant waxes derive predominantly from the epicuticular cover of vascular plant leaves and their relative and absolute abundances and stable isotopic composition can be used as proxies to decipher, e.g., continental climate and land-ocean carbon transfer processes. In marine sediments, however, compound-specific radiocarbon analysis has revealed that plant waxes are often not syn-depositional, but instead are substantially 14C-depleted (‘pre-aged’) upon deposition. This 14C-depletion can be caused by various processes that either promote retention of plant waxes during transport from source to sink such as storage in soils or entrainment in deposition-resuspension loops in rivers and on continental shelves or, alternatively, by processes that add HMW n-alkyl lipids from other sources (e.g., petrogenic inputs). Here, we review the intrinsic and extrinsic processes affecting the sedimentary plant wax 14C composition (ranging from chemical processes to continental-scale environmental conditions), how plant wax 14C compositions translate into mean ages, and which processes control plant wax mean ages in marine sediments. Finally, we use a compilation of available and new compound-specific plant wax 14C data to provide a synthesis and evaluate the major controls on plant wax mean ages in marine sediments at the global scale.

Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Kirkels, F. M. S. A., Zwart, H. M., Usman, M. O., Hou, S., Ponton, C., Giosan, L., Eglinton, T., & Peterse, F. From soil to sea: sources and transport of organic carbon traced by tetraether lipids in the monsoonal Godavari River, India. Biogeosciences, 19(17), (2022): 3979–4010, https://doi.org/10.5194/bg-19-3979-2022.

Description: Monsoonal rivers play an important role in the land-to-sea transport of soil-derived organic carbon (OC). However, spatial and temporal variation in the concentration, composition, and fate of this OC in these rivers remains poorly understood. We investigate soil-to-sea transport of soil OC by the Godavari River in India using glycerol dialkyl glycerol tetraether (GDGT) lipids in soils, river suspended particulate matter (SPM), and riverbed sediments, as well as in a marine sediment core from the Bay of Bengal. The abundance and composition of GDGTs in SPM and sediments in the Godavari River differs between the dry and wet season. In the dry season, SPM and riverbed sediments from the whole basin contain more 6-methyl branched GDGTs (brGDGTs) than the soils. In the upper basin, where mobilisation and transport of soils is limited due to deficient rainfall and damming, contributions of 6-methyl brGDGTs in SPM and riverbed sediments are relatively high year-round, suggesting that they have an aquatic source. Aquatic brGDGT production coincides with elevated values of the isoprenoid GDGT-0  crenarchaeol ratio in SPM and riverbed sediments from the upper basin, indicating low-oxygen conditions. In the wet season, brGDGT distributions in SPM from the lower basin closely resemble those in soils, mostly from the north and east tributaries, corresponding to precipitation patterns. The brGDGT composition in SPM and sediments from the delta suggests that soil OC is only effectively transported to the Bay of Bengal in the wet season, when the river plume extends beyond the river mouth. The sediment geochemistry indicates that also the mineral particles exported by the Godavari River primarily originate from the lower basin, similar to the brGDGTs, suggesting that they are transported together. However, river depth profiles in the downstream Godavari reveal no hydrodynamic sorting effect on brGDGTs in either season, indicating that brGDGTs are not closely associated with mineral particles. The similarity of brGDGT distributions in bulk and fine-grained sediments (≤ 63 µm) further confirms the absence of selective transport mechanisms. Nevertheless, the composition of brGDGTs in a Holocene, marine sediment core near the river mouth appears substantially different from that in the modern Godavari basin, suggesting that terrestrial-derived brGDGTs are rapidly lost upon discharge into the Bay of Bengal and/or overprinted by marine in situ production. The large change in brGDGT distributions at the river–sea transition implies that this zone is key in the transfer of soil OC, as well as that of the environmental signal carried by brGDGTs from the river basin.

Description: This work was supported by the Netherlands Organisation for Scientific Research (NWO) (Veni grant no. 863.13.016 to FP).