By constraining organic carbon (OC) turnover times and ages, radiocarbon (14C) analysis has become a crucial tool to study the global carbon cycle. However, commonly used “bulk” measurements yield average turnover times, masking age variability within complex OC mixtures. One method to unravel intra-sample age distributions is ramped oxidation, in which OC is oxidized with the aid of oxygen at increasing temperatures. The resulting CO2 is collected over prescribed temperature ranges (thermal fractions) and analyzed for 14C content by accelerator mass spectrometry (AMS). However, all ramped oxidation instruments developed to date are operated in an “offline” configuration and require several manual preparation steps, hindering sample throughput and reproducibility. Here we describe a compact, online ramped oxidation (ORO) setup, where CO2 fractions are directly collected and transferred for 14C content measurement using an AMS equipped with a gas ion source. Our setup comprises two modules: (i) an ORO unit containing two sequential furnaces, the first of which holds the sample and is ramped from room temperature to ∼900°C, the second of which is maintained at 900°C and holds catalysts (copper oxide and silver) to ensure complete oxidation of evolved products to CO2; and (ii) a dual-trap interface (DTI) collection unit containing two parallel molecular sieve traps, which alternately collect CO2 from a given fraction and handle its direct injection into the AMS. Initial results for well-characterized samples indicate that 14C content uncertainties and blank background values are like those obtained during routine gas measurements at ETH, demonstrating the utility of the ORO-DTI setup.

While simultaneous radiocarbon and δ13C measurements have been available for organic materials (by accelerator mass spectrometry, AMS, and isotope ratio mass spectrometry, IRMS, respectively), this has not been possible for carbonates until now. Using an existing interface for gas ion source AMS measurements, we developed a prototype for a universal gas interface that allows simultaneous measurement of both carbon isotope ratios from potentially any source of CO2. First results obtained from reference materials (IAEA-C6, OxaII, PhA, IAEA-C1, IAEA-C2, ETH-4) show that for both organic as well as carbonate samples, the precision of radiocarbon measurements in the coupled mode is comparable to routine standalone AMS measurements. For IRMS δ13C measurements, the performance for different materials shows more variation with precisions ranging from 0.07‰ to 0.47‰. However, both organic materials and carbonates can achieve precisions as good as 0.13‰. Once fully automated, the method shows potential for filling the gap of simultaneous carbon isotope measurements for non-organic materials.

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.

The radiocarbon (14C) content of simultaneously deposited substrates in lacustrine archives may differ due to reservoir and detrital effects, complicating the development of age models and interpretation of proxy records. Multi-substrate 14C studies quantifying these effects remain rare, however, particularly for large, terminal lake systems, which are excellent recorders of regional hydroclimate change. We report 14C ages of carbonates, brine shrimp cysts, algal mat biomass, total organic carbon (TOC), terrestrial macrofossils, and n-alkane biomarkers from Holocene sediments of the Great Salt Lake (GSL), Utah. 14C ages for co-deposited aquatic organic substrates are generally consistent, with small offsets that may reflect variable terrestrial organic matter inputs to the system. Carbonates and long-chain n-alkanes derived from vascular plants, however, are ∼1000–4000 14C years older than other substrates, reflecting deposition of pre-aged detrital materials. All lacustrine substrates are 14C-depleted compared to terrestrial macrofossils, suggesting that the reservoir age of the GSL was > 1200 years throughout most of the Holocene, far greater than the modern reservoir age of the lake (∼300 years). These results suggest good potential for multi-substrate paleoenvironmental reconstruction from Holocene GSL sediments but point to limitations including reservoir-induced uncertainty in 14C chronologies and attenuation and time-shifting of some proxy signals due to detrital effects.

Speleothem organic matter can be a powerful tracer for past environmental conditions and karst processes. Carbon isotope measurements (δ13C and 14C) in particular can provide crucial information on the provenance and age of speleothem organic matter, but are challenging due to low concentrations of organic matter in stalagmites. Here, we present a method development study on extraction and isotopic characterization of speleothem organic matter using a rapid procedure with low laboratory contamination risk. An extensive blank assessment allowed us to quantify possible sources of contamination through the entire method. Although blank contamination is consistently low (1.7 ± 0.34 – 4.3 ± 0.86 μg C for the entire procedure), incomplete sample decarbonation poses a still unresolved problem of the method, but can be detected when considering both δ13C and 14C values. We test the method on five stalagmites, showing reproducible results on samples as small as 7 μg C for δ13C and 20 μg C for 14C. Furthermore, we find consistently lower non-purgeable organic carbon (NPOC) 14C values compared to the carbonate 14C over the bomb spike interval in two stalagmites from Yok Balum Cave, Belize, suggesting overprint of a pre-aged or even fossil source of carbon on the organic fraction incorporated by these stalagmites.

In practice, obtaining radiocarbon (14C) composition of organic matter (OM) in sediments requires first removing inorganic carbon (IC) by acid-treatment. Two common treatments are acid rinsing and fumigation. Resulting 14C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on 14C content of sedimentary OM, we examine the variability in 14C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (RinseHCl) and HCl fumigation (FumeHCl)], we demonstrate that the two acid-treatments can affect 14C content differentially. Our findings suggest that, for low-carbonate samples, RinseHCl affects the Fm values due to loss of young labile organic carbon (OC). FumeHCl makes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during RinseHCl, causing the Fm values of remaining OC to increase. FumeHCl can remove thermally labile, usually young, OC and reduce the Fm values. We suggest three factors should be taken into account when using acid to remove carbonate from sediments: IC abundance, proportions of labile and refractory OC, and environmental matrix.

Organic carbon (OC) radiocarbon (14C) signatures in marine surface sediments are highly variable and the causes of this heterogeneity remain ambiguous. Here, we present results from a detailed 14C-based investigation of an Arabian Sea sediment, including measurements on organic matter (OM) in bulk sediment, specific grain size fractions, and OC decomposition products from ramped-pyrolysis-oxidation (RPO). Our results show that 14C ages of OM increase with increasing grain size, suggesting that grain size is an important factor controlling the 14C heterogeneity in marine sediments. Analysis of RPO decomposition products from different grain size fractions reveals an overall increase in age of corresponding thermal fractions from finer to coarser fractions. We suggest that hydrodynamic properties of sediment grains exert the important control on the 14C age distribution of OM among grain size fractions. We propose a conceptual model to account for this dimensionality in 14C variability that invokes two predominant modes of OM preservation within different grain size fractions of Arabian Sea sediment: finer (<63 µm) fractions are influenced by OM-mineral grain aggregation processes, giving rise to relatively uniform 14C ages, whereas OM preserved in coarser (>63 µm) fractions includes materials encapsulated within microfossils and/or entrained fossil (14C-depleted) OC hosted in detrital mineral grains. Our findings highlight the value of RPO for assessment of 14C age variability in sedimentary OC, and for assessing mechanisms of OM preservation in aquatic sediments.

Inland water bodies contain significant amounts of carbon in the form of dissolved inorganic carbon (DIC) derived from a mixture of modern atmospheric and pre-aged sources, which needs to be considered in radiocarbon-based dating and natural isotope tracer studies. While reservoir effects in hardwater lakes are generally considered to be constant through time, a comparison of recent and historical DI14C data from 2013 and 1969 for Lake Constance reveals that this is not a valid assumption. We hypothesize that changes in atmospheric carbon contributions to lake water DIC have taken place due to anthropogenically forced eutrophication in the 20th century. A return to more oligotrophic conditions in the lake led to reoxygenation and enhanced terrigenous organic matter remineralization, contributing to lake water DIC. Such comparisons using DI14C measurements from different points in time enable nonlinear changes in lake water DIC source and signature to be disentangled from concurrent anthropogenically induced changes in atmospheric 14C. In the future, coeval changes in lake dynamics due to climate change are expected to further perturb these balances. Depending on the scenario, Lake Constance DI14C is projected to decrease from the 2013 measured value of 0.856 Fm to 0.54–0.62 Fm by the end of the century.

Studies using carbon isotopes to understand the global carbon cycle are critical to identify and quantify sources, sinks, and processes and how humans may impact them. 13C and 14C are routinely measured individually; however, there is a need to develop instrumentation that can perform concurrent online analyses that can generate rich data sets conveniently and efficiently. To satisfy these requirements, we coupled an elemental analyzer to a stable isotope mass spectrometer and an accelerator mass spectrometer system fitted with a gas ion source. We first tested the system with standard materials and then reanalyzed a sediment core from the Bay of Bengal that had been analyzed for 14C by conventional methods. The system was able to produce %C, 13C, and 14C data that were accurate and precise, and suitable for the purposes of our biogeochemistry group. The system was compact and convenient and is appropriate for use in a range of fields of research.

The radiocarbon content of dissolved organic carbon (DOC) in rivers, lakes, and other non-saline waters can provide valuable information on carbon cycling dynamics in the environment. DOC is typically prepared for 14C analysis by accelerator mass spectrometry (AMS) either by ultraviolet (UV) oxidation or by freeze-drying and sealed tube combustion. We present here a new method for the rapid analysis of 14C of DOC using wet chemical oxidation (WCO) and automated headspace sampling of CO2. The approach is an adaption of recently developed methods using aqueous persulfate oxidant to determine the δ13C of DOC in non-saline water samples and the 14C content of volatile organic acids. One advantage of the current method over UV oxidation is higher throughput: 22 samples and 10 processing standards can be prepared in one day and analyzed in a second day, allowing a full suite of 14C processing standards and blanks to be run in conjunction with samples. A second advantage is that there is less potential for cross-contamination between samples.

The Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS/UCI) has developed protocols for analyzing radiocarbon in samples as small as ∼0.001 mg of carbon (C). Mass-balance background corrections for modern and 14C-dead carbon contamination (MC and DC, respectively) can be assessed by measuring 14C-free and modern standards, respectively, using the same sample processing techniques that are applied to unknown samples. This approach can be validated by measuring secondary standards of similar size and 14C composition to the unknown samples. Ordinary sample processing (such as ABA or leaching pretreatment, combustion/graphitization, and handling) introduces MC contamination of ∼0.6 ± 0.3 μg C, while DC is ∼0.3 ± 0.15 μg C. Today, the laboratory routinely analyzes graphite samples as small as 0.015 mg C for external submissions and ≅0.001 mg C for internal research activities with a precision of ∼1% for ∼0.010 mg C. However, when analyzing ultra-small samples isolated by a series of complex chemical and chromatographic methods (such as individual compounds), integrated procedural blanks may be far larger and more variable than those associated with combustion/graphitization alone. In some instances, the mass ratio of these blanks to the compounds of interest may be so high that the reported 14C results are meaningless. Thus, the abundance and variability of both MC and DC contamination encountered during ultra-small sample analysis must be carefully and thoroughly evaluated. Four case studies are presented to illustrate how extraction chemistry blanks are determined.

We evaluate potential process blanks associated with radiocarbon measurement of microgram to milligram quantities of alkenones at the National Ocean Sciences Accelerator Mass Spectrometry (NOSAMS) facility. Two strategies to constrain the contribution of blanks to alkenone 14C dates were followed: 1) dating of samples of known age and 2) multiple measurements of identical samples. We show that the potential contamination associated with the procedure does not lead to a systematic bias of the results of alkenone dating to either younger or older ages. Our results indicate that alkenones record Δ14C of ambient DIC with an accuracy of approximately 10‰. A conservative estimate of measurement precision is 17‰ for modern samples. Alkenone 14C ages are expected to be reliable within 500 yr for samples younger than 10,500 14C yr.

The chemical and isotopic compositions of long-chain (C36–C39) unsaturated ketones (alkenones), a unique class of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have sought to extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe a method for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. The steps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography, exploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurements were highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% for samples containing ≥ 100 μg C. The degree of alkenone unsaturation (U37K′) also varied minimally through the procedure. We also describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-level structural and isotopic determination.

As a result of the growing use of multiple geochemical proxies to reconstruct ocean and climate changes in the past, there is an increasing need to establish temporal relationships between proxies derived from the same marine sediment record and ideally from the same core sections. Coupled proxy records of surface ocean properties, such as those based on lipid biomarkers (e.g. alkenone-derived sea surface temperature) and planktonic foraminiferal carbonate (oxygen isotopes), are a key example. Here, we assess whether 2 different solvent extraction procedures used for isolation of molecular biomarkers influence the radiocarbon contents of planktonic foraminiferal carbonate recovered from the corresponding residues of Bermuda Rise and Cariaco Basin sediments. Although minor Δ14C differences were observed between solvent-extracted and unextracted samples, no substantial or systematic offsets were evident. Overall, these data suggest that, in a practical sense, foraminiferal shells from a solvent-extracted residue can be reliably used for 14C dating to determine the age of sediment deposition and to examine age relationships with other sedimentary constituents (e.g. alkenones).

We have measured the radiocarbon contents of individual, solvent-extractable, short-chain (C14, C16, and C18) fatty acids isolated from Ross Sea surface sediments. The corresponding 14C ages are equivalent to that of the post-bomb dissolved inorganic carbon (DIC) reservoir. Moreover, molecular 14C variations in surficial (upper 15 cm) sediments indicate that these compounds may prove useful for reconstructing chronologies of Antarctic margin sediments containing uncertain (and potentially variable) quantities of relict organic carbon. A preliminary molecular 14C chronology suggests that the accumulation rate of relict organic matter has not changed during the last 500 14C yr. The focus of this study is to determine the validity of compound-specific 14C analysis as a technique for reconstructing chronologies of Antarctic margin sediments.