Radiocarbon (14C) measurements on dissolved inorganic carbon (DIC) are a powerful tool to trace water masses and carbon cycling in the ocean. Existing methodologies to determine the 14C content of seawater DIC requires large volumes of sample (usually >100 mL) and specialized graphitization techniques to achieve the accuracy and precision needed for meaningful data interpretation. The advancement of the CO2 gas ionization accelerator mass spectrometry (AMS) technique today allows routine 14C measurements on small samples (<100 µgC) and may thus permit reducing the sample volumes needed to determine 14C content of seawater DIC to ∼2 mL. The proposed method utilizes the carbonate handling system (CHS), gas interface system (GIS) and MICADAS AMS, and provides good accuracy but reduced precision compared to established methods. Good accuracy is shown by comparing results for a marine in-house DIC standard and a DIC seawater profile from Antarctica between the proposed CHS-GIS-MICADAS approach and reference measurements conducted on the same material at established laboratories (ETH and NOSAMS). Further, two sedimentary porewater profiles from a fjord system in Svalbard are presented. Despite good agreement, the precision of the CHS-GIS-MICADAS approach is reduced, potentially limiting possible interpretations on seawater DIC. Nonetheless, the reduction of sample volumes proves particularly helpful to analyze porewater DIC from sediment cores, where sample material is notoriously limited, reduces the required amounts of toxic HgCl2 and simplifies expedition logistics.

Reliable radiocarbon (14C) ages of foraminifera are a prerequisite to generate robust high-resolution age-depth models or to obtain precise understanding of past carbon cycle dynamics. With the advance of small-scale 14C measurements, instrumental precision and levels of contamination (extraneous carbon introduced during sample pretreatment or analysis) became increasingly important to consider. To reduce the effect of carbon contamination, an attempt can be made to remove it by leaching the surface with weak acids. Alternatively, mathematical corrections (e.g., subtraction) based on processing blanks can be applied. We report on 14C analyses of monospecific foraminifera samples compared between different blank corrections (correction against 14C-free CO2, IAEA-C1 and foraminifera) and sample treatments (i) to examine whether chemical pretreatment and mathematical blank subtraction are comparable, and (ii) to determine limitations hindering reliable 14C dating with ever smaller sample sizes. The data show that chemical pretreatment of foraminifera corrected against IAEA-C1 does remove surface contamination and that the same effect can be achieved for untreated samples that were mathematically corrected for blank values determined from sample size-matched 14C-free foraminifera. Leaching only has a beneficial effect on 14C data for older samples, where the isotopic difference between untreated and chemically pretreated samples exceeds the analytical precision.

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.

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.

Pollen and organic-walled dinoflagellate cyst assemblages from core GeoB 9503-5 retrieved from the mud-belt (∼ 50 m water depth) off the Senegal River mouth have been analyzed to reconstruct short-term palaeoceanographic and palaeoenvironmental changes in subtropical NW Africa during the time interval from ca. 4200 to 1200 cal yr BP. Our study emphasizes significant coeval changes in continental and oceanic environments in and off Senegal and shows that initial dry conditions were followed by a strong and rapid increase in humidity between ca. 2900 and 2500 cal yr BP. After ca. 2500 cal yr BP, the environment slowly became drier again as indicated by slight increases in Sahelian savannah and desert elements in the pollen record. Around ca. 2200 cal yr BP, this relatively dry period ended with periodic pulses of high terrigenous contributions and strong fluctuations in fern spore and river plume dinoflagellate cyst percentages as well as in the fluxes of pollen, dinoflagellate cysts, fresh-water algae and plant cuticles, suggesting “episodic flash flood” events of the Senegal River. The driest phase developed after about 2100 cal yr BP.

Here we provide three new Holocene (11–0 cal ka BP) alkenone-derived sea surface temperature (SST) records from the southernmost Chilean fjord region (50–53°S). SST estimates may be biased towards summer temperature in this region, as revealed by a large set of surface sediments. The Holocene records show consistently warmer than present-day SSTs except for the past ~ 0.6 cal ka BP. However, they do not exhibit an early Holocene temperature optimum as registered further north off Chile and in Antarctica. This may have resulted from a combination of factors including decreased inflow of warmer open marine waters due to lower sea-level stands, enhanced advection of colder and fresher inner fjord waters, and stronger westerly winds. During the mid-Holocene, pronounced short-term variations of up to 2.5°C and a cooling centered at ~ 5 cal ka BP, which coincides with the first Neoglacial glacier advance in the Southern Andes, are recorded. The latest Holocene is characterized by two pronounced cold events centered at ~ 0.6 and 0.25 cal ka BP, i.e., during the Little Ice Age. These cold events have lower amplitudes in the offshore records, suggesting an amplification of the SST signal in the inner fjords.

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.