Compound-specific radiocarbon analysis (CSRA) provides the possibility to date sample material at a molecular level. N-alkanes are considered as specific compounds with high potential to CSRA. As these compounds originate from plant waxes, their radiocarbon (14C) analysis can provide valuable information about the age and origin of organic materials. This helps to reconstruct and understand environmental conditions and changes in vegetation in the past. However, CSRA has two main challenges: The small sample size of CSRA samples, making them extremely sensitive to blank effects, and the input of unknown amounts of extraneous carbon during the analytical procedure. According to the previous study from Sun and co-workers, we used different-sized aliquots of leaves Fagus sylvatica (nC27, nC29) and Festuca rubra agg (nC31, nC33) as modern standards and two commercial standards (nC26, nC28) as fossil standards for blank determination. A third commercial standard (nC27) with predetermined radiocarbon content of F14C = 0.71 (14C age of 2700 BP) serves to evaluate the blank correction. We found that the blank assessment of Sun and co-workers is also applicable to n-alkanes, with a minimum sample size of 15 µg C for dependable CSRA dates. We determined that the blank introduced during the analytical procedure has a mass of (4.1 ± 0.7) µg carrying a radiocarbon content of F14C = 0.25 ± 0.05. Applying the blank correction to a sediment sample from Lake Holzmaar (Germany) shows that all four isolated n-alkanes have similar 14C ages. However, the bulk material of the sediment and branches found in the sediment core are younger than the CSRA dates. We conclude that the disparity between the actual age of analysed organic material and the age inferred from radiocarbon results, which can occur in sediment traps due to delayed deposition, is the reason for the CSRA age.

To elucidate the dynamics of terrestrial leaf waxes in a high-altitude lake system, we performed compound-specific radiocarbon analysis (CSRA) of long-chain n-alkanes in two sediment core sections from Lake Karakul (Pamirs, Tajikistan) and in surface soil samples from the catchment area. We aimed to answer the question whether the n-alkanes are delivered into the lake sediment with substantial delay due to storage in soils, which may cause a potential bias when used as paleoenvironmental proxies. In the surface soils, the CSRA results reveal an age range of n-alkanes from modern to 2278 ± 155 cal BP. In the two sediment core samples, three of the four n-alkane ages fell on the lower ends of the 1σ-uncertainty ranges of modeled ages of the sediments (based on AMS 14C-TOC and OSL dating results). We conclude that sedimentary leaf waxes represent compounds with intermediate turnover time in soils, for example originating from alluvial plains close to the shores. Overall, the results provide evidence that sedimentary leaf wax compounds in this cold and arid setting are potentially older than the conventional age model indicates, but these findings need to be interpreted in context of the generally large uncertainty ranges of such age models.

The analysis of processing standards alongside samples for quality assurance in radiocarbon (14C) analyses is critical. Ideally, these standards should be similar both in nature and age to unknown samples. A new compound-specific approach was developed at the University of Bristol for dating pottery vessels using palmitic and stearic fatty acids extracted from within the clay matrix and isolated by preparative capillary gas chromatography. Obtaining suitable potsherds for use as processing standards in such analyses is not feasible, so we suggest that bog butter represents an ideal material for such purposes. We sampled ca. 450 g from two bog butter specimens and homogenized them by melting. We verified the homogeneity of both specimens by characterization of their lipid composition, δ13C values of individual lipids, and both bulk- and compound-specific radiocarbon analyses on 10 sub-samples of each bog butter specimen. The weighted means of all 14C measurements on the bog butter standards are 3777 ± 4 BP (IB33) and 338 ± 3 BP (IB38), thereby providing age-relevant standards for archaeological and historical fatty acids and ensuring the accuracy of radiocarbon determinations of lipids using a compound-specific approach. These new secondary standards will be subjected to an intercomparison exercise to provide robust consensus values.

At archaeological sites located on islands or near the coast, the potential exists for lipid extracts of potsherds to contain fatty acids (FA) from both aquatic and terrestrial organisms, meaning that consideration must be given to marine reservoir effects (MRE) in radiocarbon (14C) analyses. Here we studied the site of Bornais (Outer Hebrides, UK) where a local MRE, ΔR of –65 ± 45 yr was determined through the paired 14C determinations of terrestrial and marine faunal bones. Lipid analysis of 49 potsherds, revealed aquatic biomarkers in 45% of the vessels, and δ13C values of C16:0 and C18:0 FAs revealed ruminant and marine product mixing for 71% of the vessels. Compound-specific 14C analysis (CSRA) of FAs yielded intermediate 14C ages between those of terrestrial and marine bones from the same contexts, confirming an MRE existed. A database containing δ13C values for FAs from reference terrestrial and marine organisms provided endmembers for calculating the percentage marine-derived C (%marine) in FAs. We show that lipid 14C dates can be corrected using determined %marine and ΔR values, such that pottery vessels from coastal locations can be 14C dated by CSRA of FAs.

The subantarctic island of South Georgia provides terrestrial and coastal marine records of climate variability, which are crucial for the understanding of the drivers of Holocene climate changes in the subantarctic region. Here we investigate a sediment core (Co1305) from a coastal inlet on South Georgia using elemental, lipid biomarker, diatom, and stable isotope data to infer changes in environmental conditions and to constrain the timing of late-glacial and Holocene glacier fluctuations. Because of the scarcity of terrestrial macrofossils and the presence of redeposited and relict organic matter in the sediments, age control for the record was obtained by compound-specific radiocarbon dating of mostly marine-derived n-C16 fatty acids. A basal till layer recovered in Little Jason Lagoon was likely deposited during an advance of local glaciers during the Antarctic cold reversal. After glacier retreat, an oligotrophic lake occupied the site, which transitioned to a marine inlet around 8.0±0.9 ka because of relative sea-level rise. From 7.0±0.6 to 4.0±0.4 ka, reduced vegetation coverage in the catchment, as well as high siliciclastic input and deposition of ice-rafted debris, indicates glacier advances in the terrestrial catchment and likely in the adjacent fjord. A second, less extensive period of glacier advances occurred in the late Holocene, after 1.8±0.3 ka.

One of the difficulties in reporting accurate radiocarbon results from compound-specific radiocarbon analysis (CSRA) is the lack of suitable process standard materials to correct for the amount and 14C content of carbon added during extensive sample processing. We evaluated the use of n-alkanes extracted from modern grass material (1.224±0.006 fraction modern) as process standards for CSRA. The n-alkanes were isolated using preparative capillary gas chromatography (PCGC) from two independent chemical extraction methods applied to the grass. Since this was our first assessment of the 14C content of the grass n-alkanes, we corrected for extraneous carbon derived from PCGC isolation using commercially available single compounds of modern and 14C-free content. Results were consistent across the two extraction methods showing that the C29n-alkane has a fraction modern value that is within 1σ of the bulk value of the grass while C31n-alkane and less abundant n-alkanes have values within 2σ of the bulk value of the grass. C29 and C31n-alkanes were the most abundant n-alkanes in the grass and, as such, the more feasible for collection of sufficient amounts of carbon for accelerator mass spectrometry (AMS) analysis. Our results suggest that choosing a grass n-alkane with an elution time closest to that of the unknowns may be advisable due to possibly greater effect from GC column bleed (14C-free) at later elution times. We conclude that C29 and C31n-alkanes in modern grass of known 14C content can be used as in-house standards to correct for the addition of 14C-free carbon during sample preparation for 14C analysis of n-alkanes.