The importance of studying the radiocarbon content of dissolved inorganic carbon (DI14C) in the oceans has been recognized for decades. Starting with the GEOSECS program in the 1970s, 14C sampling has been a part of most global survey programs. Early results were used to study air-sea gas exchange while the more recent results are critical for helping calibrate ocean general circulation models used to study the effects of climate change. Here we summarize the major programs and discuss some of the important insights the results are starting to provide.

We discuss present and developing techniques for studying radiocarbon in marine organic carbon (C). Bulk DOC (dissolved organic C) Δ14C measurements reveal information about the cycling time and sources of DOC in the ocean, yet they are time consuming and need to be streamlined. To further elucidate the cycling of DOC, various fractions have been separated from bulk DOC, through solid phase extraction of DOC, and ultrafiltration of high and low molecular weight DOC. Research using 14C of DOC and particulate organic C separated into organic fractions revealed that the acid insoluble fraction is similar in 14C signature to that of the lipid fraction. Plans for utilizing this methodology are described. Studies using compound specific radiocarbon analyses to study the origin of biomarkers in the marine environment are reviewed and plans for the future are outlined. Development of ramped pyrolysis oxidation methods are discussed and scientific questions addressed. A modified elemental analysis (EA) combustion reactor is described that allows high particulate organic C sample throughput by direct coupling with the MIniCArbonDAtingSystem.

This study describes a procedural blank assessment of the ultraviolet photochemical oxidation (UV oxidation) method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). A retrospective compilation of Fm and δ13C results for secondary standards (OX-II, glycine) between 2009 and 2018 indicated that a revised blank correction was required to bring results in line with accepted values. The application of a best-fit mass-balance correction yielded a procedural blank of 22.0 ± 6.0 µg C with Fm of 0.30 ± 0.20 and δ13C of –32.0 ± 3.0‰ for this period, which was notably higher and more variable than previously reported. Changes to the procedure, specifically elimination of higher organic carbon reagents and improved sample and reactor handling, reduced the blank to 11.0 ± 2.75 µg C, with Fm of 0.14 ± 0.10 and δ13C of –31.0 ± 5.5‰. A thorough determination of the entire sample processing blank is required to ensure accurate isotopic compositions of seawater DOC using the UV oxidation method. Additional efforts are needed to further reduce the procedural blank so that smaller DOC samples can be analyzed, and to increase sample throughput.

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.

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‰.

In response to the increasing demand for 14C analysis of samples containing less than 25 μg C, ultra-small graphitization reactors with an internal volume of ∼0.8 mL were developed at NOSAMS. For samples containing 6 to 25 μg C, these reactors convert CO2 to graphitic carbon in approximately 30 min. Although we continue to refine reaction conditions to improve yield, the reactors produce graphite targets that are successfully measured by AMS. Graphite targets produced with the ultra-small reactors are measured by using the Cs sputter source on the CFAMS instrument at NOSAMS where beam current was proportional to sample mass. We investigated the contribution of blank carbon from the ultra-small reactors and estimate it to be 0.3 ± 0.1 μg C with an Fm value of 0.43 ± 0.3. We also describe equations for blank correction and propagation of error associated with this correction. With a few exceptions for samples in the range of 6 to 7 μg C, we show that corrected Fm values agree with expected Fm values within uncertainty for samples containing 6–100 μg C.

Compound specific radiocarbon measurements can be made instantaneously using a gas chromatograph (GC) combustion system coupled to a 14C AMS system fitted with a gas ion source. Samples below 10 μg C can be analyzed but the precision is reduced to 5–10% because of lower source efficiency. We modified our GC for CH4 and CO2 analysis and injected samples multiple times to sum data and increase precision. We attained a maximum precision of 0.6% for modern CO2 from 25 injections of 27 μg C and a background of ≃0.5% (40 kyr) for ancient methane. The 14C content of dissolved CO2 and CH4 in water samples collected at a deep-sea hydrothermal vent and a serpentine mud volcano was measured and the results for the vent sample are consistent with previously published data. Further experiments are required to determine a calibration and correction procedure to maximize accuracy.

Radiocarbon analysis of the carbonaceous aerosol allows an apportionment of fossil and non-fossil sources of airborne particulate matter (PM). A chemical separation of total carbon (TC) into its subtractions organic carbon (OC) and elemental carbon (EC) refines this powerful technique, as OC and EC originate from different sources and undergo different processes in the atmosphere. Although 14C analysis of TC, EC, and OC has recently gained increasing attention, interlaboratory quality assurance measures have largely been missing, especially for the isolation of EC and OC. In this work, we present results from an intercomparison of 9 laboratories for 14C analysis of carbonaceous aerosol samples on quartz fiber filters. Two ambient PM samples and 1 reference material (RM 8785) were provided with representative filter blanks. All laboratories performed 14C determinations of TC and a subset of isolated EC and OC for isotopic measurement. In general, 14C measurements of TC and OC agreed acceptably well between the laboratories, i.e. for TC within 0.015–0.025 F14C for the ambient filters and within 0.041 F14C for RM 8785. Due to inhomogeneous filter loading, RM 8785 demonstrated only limited applicability as a reference material for 14C analysis of carbonaceous aerosols. 14C analysis of EC revealed a large deviation between the laboratories of 28–79% as a consequence of different separation techniques. This result indicates a need for further discussion on optimal methods of EC isolation for 14C analysis and a second stage of this intercomparison.

The article reports the first radiocarbon dating of a live African baobab (Adansonia digitata L.), by investigating wood samples collected from 2 inner cavities of the very large 2-stemmed Platland tree of South Africa. Some 16 segments extracted from determined positions of the samples, which correspond to a depth of up to 15–20 cm in the wood, were processed and analyzed by accelerator mass spectrometry (AMS). Calibrated ages of segments are not correlated with their positions in the stems of the tree. Dating results indicate that the segments originate from new growth layers, with a thickness of several centimeters, which cover the original old wood. Four new growth layers were dated before the reference year AD 1950 and 2 layers were dated post-AD 1950, in the post-bomb period. Formation of these layers was triggered by major damage inside the cavities. Fire episodes are the only possible explanation for such successive major wounds over large areas or over the entire area of the inner cavities of the Platland tree, able to trigger regrowth.

A new and unique radiocarbon accelerator mass spectrometry (AMS) facility has been constructed at the Woods Hole Oceanographic Institution. The defining characteristic of the new system is its large-gap optical elements that provide a larger-than-standard beam acceptance. Such a system is ideally suited for high-throughput, high-precision measurements of 14C. Details and performance of the new system are presented.

We report and compare radiocarbon observations made on 2 meridional oceanographic sections along 150°W in the South Pacific in 1991 and 2005. The distributions reflect the progressive penetration of nuclear weapons-produced 14C into the oceanic thermocline. The changes over the 14 yr between occupations are demonstrably large relative to any possible drift in our analytical standardization. The computed difference field based on the gridded data in the upper 1600 m of the section exhibits a significant decrease over time (approaching 40 to 50‰ in Δ14C) in the upper 200–300 m, consistent with the decadal post-bomb decline in atmospheric 14C levels. A strong positive anomaly (increase with time), centered on the low salinity core of the Antarctic Intermediate Water (AAIW), approaches 50–60‰ in Δ14C, a clear signature of the downstream evolution of the 14C transient in this water mass. We use this observation to estimate the transit time of AAIW from its “source region” in the southeast South Pacific and to compute the effective reservoir age of this water mass. The 2 sections show small but significant changes in the abyssal 14C distributions. Between 1991 and 2005, Δ14C has increased by 9‰ below 2000 m north of 55°S. This change is accompanied overall by a modest increase in salinity and dissolved oxygen, as well as a slight decrease in dissolved silica. Such changes are indicative of greater ventilation. Calculation of “phosphate star” also indicates that this may be due to a shift from the Southern Ocean toward North Atlantic Deep Water as the ventilation source of the abyssal South Pacific.

Gas-accepting ion sources for radiocarbon accelerator mass spectrometry (AMS) have permitted the direct analysis of CO2 gas, eliminating the need to graphitize samples. As a result, a variety of analytical instruments can be interfaced to an AMS system, processing time is decreased, and smaller samples can be analyzed (albeit with lower precision). We have coupled a gas chromatograph to a compact 14C AMS system fitted with a microwave ion source for real-time compound-specific 14C analysis. As an initial test of the system, we have analyzed a sample of fatty acid methyl esters and biodiesel. Peak shape and memory was better then existing systems fitted with a hybrid ion source while precision was comparable. 14C/12C ratios of individual components at natural abundance levels were consistent with those determined by conventional methods. Continuing refinements to the ion source are expected to improve the performance and scope of the instrument.

In 2008, a large African baobab (Adansonia digitata L.) from Makulu Makete, South Africa, split vertically into 2 sections, revealing a large enclosed cavity. Several wood samples collected from the cavity were processed and radiocarbon dated by accelerator mass spectrometry (AMS) for determining the age and growth rate dynamics of the tree. The 14C date of the oldest sample was found to be of 1016 ± 22 BP, which corresponds to a calibrated age of 1000 ± 15 yr. Thus, the Makulu Makete tree, which eventually collapsed to the ground and died, becomes the second oldest African baobab dated accurately to at least 1000 yr. The conventional growth rate of the trunk, estimated by the radial increase, declined gradually over its life cycle. However, the growth rate expressed more adequately by the cross-sectional area increase and by the volume increase accelerated up to the age of 650 yr and remained almost constant over the past 450 yr.

To test the hypothesis of an association between schizophrenia and coeliac disease, the sera of 380 chronic schizophrenic in-patients in two mental hospitals in the West of Ireland have been screened for the presence of reticulin antibodies. Antibodies were found in 26 patients. Twenty-one of these patients were further studied by proximal duodenal mucosal biopsy. None of the biopsies showed the morphological and histological features found in untreated coeliac disease. The incidence of reticulin antibodies in schizophrenic patients and controls is similar. The findings of this study lead to the rejection of the hypothesis of a positive genetic relationship between schizophrenia and coeliac disease.

The World Ocean Circulation Experiment, carried out between 1990 and 1997, provided the most comprehensive oceanic survey of radiocarbon to date. Approximately 10,000 samples were collected in the Pacific Ocean by U.S. investigators for both conventional large volume p counting and small volume accelerator mass spectrometry analysis techniques. Results from six cruises are presented. The data quality is as good or better than previous large-scale surveys. The 14C distribution for the entire WOCE Pacific data set is graphically described using mean vertical profiles and sections, and property-property plots.

We explored the reliability of radiocarbon ages obtained on organic carbon phases in opal-rich Southern Ocean sediments. Paired biogenic carbonate and total organic carbon (TOC) 14C analyses for three Southern Ocean cores showed that the TOC ages were systematically younger than the carbonate ages. Carbonate ages were consistent with oxygen isotopic and bio-stratigraphy, indicating error in TOC ages that could be explained by 5–24% of modern carbon contamination of TOC samples. Two possible sources of contamination are: 1) adsorption of atmospheric CO2 or volatile organic compounds to reactive opal surface sites, and 2) fixation of atmospheric CO2 by chemosynthetic bacteria during core storage. In an effort to reduce the modern carbon contamination, diatoms were separated from sediments, purified, and pre-oxidized by concentrated nitric and perchloric acids to permit dating of opal-intrinsic organic carbon (~0.1–0.3% by weight). 14C ages of chemically pre-oxidized opal showed a significant amount of modern carbon contamination, from 11 to 32%, indicating adsorption from the atmosphere of modern carbon onto opal surfaces that were previously cleaned by acid oxidation. Several experiments designed to eliminate the modern C contamination were attempted, but so far we have not been able to obtain a radiocarbon age on 14C-dead Southern Ocean opal-rich sediments, either bulk TOC or purified diatom opal samples, as old as our procedural blank.