For many of archaeology’s rarest and most enigmatic bone artifacts (e.g. human remains, bone ornaments, worked bone), the destruction of the 500 mg material necessary for direct accelerator mass spectrometry (AMS) dating on graphite targets would cause irreparable damage; therefore many have not been directly dated. The recently improved gas ion source of the MICADAS (MIni CArbon DAting System) offers a solution to this problem by measuring gaseous samples of 5–100 µg carbon at a level of precision not previously achieved with an AMS gas ion source. We present the results of the first comparison between “routine” graphite dates of ca. 1000 µg C (2–3 mg bone collagen) and dates from aliquots of gaseous samples of <100 µg C (<0.2 mg bone collagen), undertaken with the highest possible precision in mind. The experiment demonstrates the performance of the AixMICADAS in achieving reliable radiocarbon measurements from <0.2 mg collagen samples back to 40,000 14C BP. The technique has great implications for resolving chronological questions for key archaeological artifacts.

To achieve a reliable radiocarbon (14C) date for an object, any contamination that may be of a different age must be removed prior to dating. Samples that have been conserved with treatments such as adhesives, varnishes or consolidants can pose a particular challenge to 14C dating. At the Oxford Radiocarbon Accelerator Unit (ORAU), common examples of such substances encountered include shellac, the acrylic polymers Paraloid B-67 and B-72, and vinyl acetate-derived polymers (e.g. PVA). Here, a non-carbon-containing absorbent substrate called Chromosorb® was deliberately contaminated with a range of varieties or brands of these conservation treatments, as well as two cellulose nitrate lacquers. A selection of chemical pretreatments was tested for their efficiency at removing them. While the varieties of shellac and Paraloid tested were completely removed with some treatments (water/methanol and acetone/methanol/chloroform sequential washes, respectively), no method was found that was capable of completely removing any of the vinyl acetate-derived materials or the cellulose nitrate lacquers. While Chromosorb is not an exact analog of archaeological wood or bone, for example, this study suggests that it may be possible to remove aged shellac and Paraloid from archaeological specimens with standard organic solvent-acid-base-acid pretreatments, but it may be significantly more difficult to remove vinyl acetate-derived polymers and cellulose nitrate lacquers sufficiently to provide reliable 14C dates. The four categories of conservation treatment studied demonstrate characteristic FTIR spectra, while highlighting subtle chemical and molecular differences between different varieties of shellac, Paraloid and cellulose nitrate lacquers, and significant differences between the vinyl acetate derivatives.

A new vacuum system for the preparation of graphite samples for radiocarbon (14C) measurement using an accelerator mass spectrometer (AMS) was constructed at the Dendrochronological Laboratory in AGH-UST Kraków. The central part of the system is a manual vacuum line for the production of graphite from carbon dioxide for subsequent AMS measurements. The graphitization system can handle up to five samples simultaneously, and the process lasts for approximately 1 hour. The graphitization line was built to support the preparation of wood samples for a project dedicated to dating a subfossil tree from the Younger Dryas period. For this purpose, the chemical preparation procedure for wood samples was optimized to obtain more reliable results. This includes the extraction of α-cellulose to increase the precision of the age determination. The performance of the system was tested with NIST OxII, IAEA standards (IAEA C3, C5, C6, and C8), and background samples. The results of the 13 samples of subfossil wood were tested and are presented. The methodology gives good reproducibility of results obtained for the samples prepared using this system.

The AixMICADAS facility is in part dedicated to research on radiocarbon (14C) calibration by means of various archives. For this purpose, we are improving upon the capacity to accurately date subfossil wood. In the current study, nine chemical pretreatment protocols are tested on six wood samples of known ages. The optimization based on 14C ages, 13C/12C ratios, carbon % and overall mass yield % leads us to favor the acid-base-acid-bleaching pretreatment (ABA-B). This efficient method is shown to provide a residue of holocellulose with optimal blanks equivalent to an age of 51,300 14C BP with a standard deviation of 1500 yr based on 25 analyses. The seven wood samples from the Sixth International Radiocarbon Intercomparison (SIRI) are then analyzed as a further verification of the accuracy of our method. As a first scientific contribution, we studied two tree-ring sequences from subfossil pines (Barb12 and Barb17) collected in the southern French Alps. New 14C analyses were performed at high resolution (every third year) and are shown to agree well with results obtained previously by high precision β-counting on CO2 from large samples at lower resolution for Barb17 and accelerator mass spectrometry (AMS) data for Barb12. The new 14C series are then matched to the Kauri and YDB chronologies: the new sequence of Barb12-17 tentatively corresponds to the interval between 12,836 and 12,594 cal BP within the Younger Dryas cold period. The 14C comparison between the Barb12-17 sequence from France and the Kauri sequence from New Zealand allows calculating the 14C Inter-Hemispheric Gradient (IHG), with an average value of ca. 57 yr. The IHG stayed relatively high throughout the studied period. Interestingly, the IHG exhibits a transient maximum value (ca. 100 yr) during the period of rapid Δ14C rise (12,750–12,720 cal BP), a behavior that could be due to a delayed response of the Southern Hemisphere.

We present new marine reservoir ΔR correction terms for the central and northern Kuril Islands. We estimate ΔR from a series of archaeological charcoal-shell pairs from two archaeological sites using standard calibration procedures and Monte Carlo simulation. The combined ΔR estimate for all paired samples for the Kuril samples is 508±127 yr. In the context of available North Pacific Rim ΔR estimates, the new Kuril data support the interpretation of a well-mixed, 14C-depleted North Pacific Subarctic Gyre. For the broader subarctic North Pacific region, a ΔR estimate in the range of 440±127 yr is a reasonable correction for any coastal marine shell date, and may be applied to fish and marine mammal dates for taxa known to reside within these waters throughout their life-histories. This generalization fails as one moves south from Hokkaido along the East Asian coast. There, well-equilibrated subtropical water minimize the ΔR offset.

In order to evaluate effects of three land uses on isotopic compositions of CO2 and O2 of soil air to 5 m soil depth, a field study was conducted in the Calhoun Critical Zone Observatory, located in the subtropical climate of the Southern Piedmont of South Carolina, USA. Soil gas reservoirs were installed in ecosystems with three different land uses, each replicated three times: (i) reference hardwood stands that were never cultivated; (ii) currently cultivated plots; (iii) pine stands, which had been used for growing cotton in 19th century but were abandoned in about the 1930s and 1940s when they were regenerated with pines that are today 70–80 yr old. In addition to soil CO2 and O2 concentration measurements, soil gas samples were analyzed for Δ14C, δ13C, and δ18O. Stable carbon isotopic composition becomes lighter with the depth in soils of all three land uses: in the cultivated site δ13C decreases from –18‰ at 0.5 m to –21‰ at 5 m, in pine site from –22 to –25‰, and in hardwood from –21.5 to –24.5‰, respectively. Δ14C increased with depth from 40 to 60‰ in the top 0.5 m to about 80–140‰ at 5 m depending on land use. While surficial soils had relatively similar Δ14C in CO2, between 40 to 60‰ at 0.5 m, at 3 and 5 m, cultivated soils had the highest Δ14C, hardwood the lowest, and pine in between, a pattern that emphasizes the importance of contemporary respired CO2 in hardwood stands. Oxygen isotopic composition of CO2 did not change with depth, whereas free O2 was greatly enriched in lower horizons of forest soils, which we attribute to strong fractionation by respiration.

During the Last Glacial Maximum (LGM) the Tagliamento glacier delivered large amounts of sediment to the Cormor alluvial megafan on the southern Alpine foreland basin. To build a chronology of Late Pleistocene glacier fluctuations and assess the timing of the transition from interstadial to glacial conditions, we have performed radiocarbon (14C) dating on peat and macrofossil samples obtained from a drilling core from the distal Cormor megafan. Our chronology records fluvial and glaciofluvial aggradation from the end of MIS 3 until the end of the LGM. It shows a rapid transmission of signals of environmental change along the Cormor megafan, so that changes in the activity of the Tagliamento glacier directly affect glaciofluvial sedimentation. Our data demonstrate that the intrinsic heterogeneity of peat is most critical for the reliability and reproducibility of the obtained 14C ages. Macrofossil subsamples give evidence for significant mixing of organic components of different ages within single peat samples. Sample heterogeneity is also underlined by the results obtained from testing of different laboratory precleaning methods. Our results suggest that a rigorous ABA pretreatment is sufficient for peat cleaning. In contrast, the chemically stronger ABOX methods appear to rapidly degrade the peat, particularly destroying older organic components.

Radiocarbon (14C) is a key radionuclide in the assessment of the safety of underground geological disposal facilities for radioactive wastes, and the understanding of the 14C behavior in stainless steel may lead to a re-evaluation of the near-surface repository for the disposal of wastes containing this radionuclide in high concentrations. To achieve this objective, leaching experiments were planned for two different scenarios. The first is where the leaching solution, NaOH solution of pH ca. 12 in aerobic conditions, simulates the expected conditions in a cement-based near-surface repository over long time periods. The other one uses an acid solution of 1M H3PO4, which has been proved as a high efficiency chemical removal agent of 14C in graphite. The development of both analytical methods and protocols to measure the release of 14C from the activated steel samples and the speciation in the aqueous and gaseous phase has been undertaken as part of the EC CAST (CArbon-14 Source Term) project. Analytical methods, suitable for identifying and quantifying low molecular weight organic molecules, comprise ion chromatography (IC) and gas chromatography coupled to mass spectrometry (GC-MS); they are described for aqueous and gaseous samples, respectively. In this paper the preparation of leaching experiments to measure the release of 14C and the results obtained are described.

This work focuses on building a high-resolution age-depth model for quantitative palaeoclimate study from the Mohos peat bog, East Carpathian mountains. The investigated core presents a continuous peat profile for the last 12 kyr. The chronology was based on 36 accelerator mass spectrometry radiocarbon (AMS 14C) analyses of the separated Sphagnum samples from different depths of the profile. Dry Sphagnum samples for AMS dating were prepared using the classic acid-base-acid (ABA) method followed with an oxidative bleaching step to get clean cellulose. Sphagnum cellulose samples were measured by AMS using the EnvironMICADAS at the ICER (Debrecen, Hungary). A high-resolution chronology was obtained with the use of Bayesian age-depth modeling. Peat accumulation rate has been calculated and the sections with variable accumulation rate values were observed along the profile.

Carbon-based nanomaterials of different dimensions (1–3D, tubes, bundles, films, papers and sponges, graphene sheets) have been created and their characteristic properties have been discussed intensively in the literature. Due to their unique advantageous, tunable properties these materials became promising candidates in new generations of applications in many research laboratories and, recently, in industries as well. Protein-based bio-nanocomposites are referred to as materials of the future, which may serve as conceptual revolution in the development of integrated optical devices, e.g. optical switches, microimaging systems, sensors, telecommunication technologies or energy harvesting and biosensor applications. In our experiments, we designed various carbon-based nanomaterials either doped or not doped with nitrogen or sulfur during catalytic chemical vapor deposition synthesis. Radio- and isotope analytical studies have shown that the used starting materials, precursors and carriers have a strong influence on the geometry and physico-/chemical characteristics of the carbon nanotubes produced. After determining the 14C isotope constitution 53 m/m% balance was found in the reaction center protein/carbon nanotubes complex in a sensitive way that was prepared in our laboratory. The result is essential in determining the yield of conversion of light energy to chemical potential in this bio-hybrid system.

Lime lumps and bulk mortars show different 14C contamination when analyzed in several CO2 fractions isolated from the effervescence of an ongoing hydrolysis reaction. Age profiles of both materials are therefore highly complementary and together they can provide a reliable date. Furthermore, they can also reveal the complexity of the radiocarbon (14C) distribution within the mortar and thus prevent over-interpretation of the data. The lime lump versus bulk mortar dating data presented here has been collected over 22 years, with only a small fraction of the results so far published internationally. Since there has been an increasing interest in mortar dating over recent years with a special focus on lime lumps, and since many laboratories have just begun mortar dating experiments, we wish to present some of the extensive data that already exist. Previously published data from 15 lime lumps (including 34 14C measurements from sequential dissolution) and 43 new 14C measurements from 17 lime lumps are presented here. The samples are from medieval Finland and Sweden, classical Rome and medieval Italy, and the Roman Jerash (Gerasa), Jordan.

Over the last decade, archaeologists have turned to large radiocarbon (14C) data sets to infer prehistoric population size and change. An outstanding question concerns just how direct of an estimate 14C dates are for human populations. In this paper we propose that 14C dates are a better estimate of energy consumption, rather than an unmediated, proportional estimate of population size. We use a parametric model to describe the relationship between population size, economic complexity and energy consumption in human societies, and then parametrize the model using data from modern contexts. Our results suggest that energy consumption scales sub-linearly with population size, which means that the analysis of a large 14C time-series has the potential to misestimate rates of population change and absolute population size. Energy consumption is also an exponential function of economic complexity. Thus, the 14C record could change semi-independent of population as complexity grows or declines. Scaling models are an important tool for stimulating future research to tease apart the different effects of population and social complexity on energy consumption, and explain variation in the forms of 14C date time-series in different regions.

While the exchange of water through Yucatan Strait is reasonably well known, the age of the deep water in both the Caribbean Sea and Gulf of Mexico is not. We recently measured the radiocarbon (14C) concentrations in deep water in the Gulf of Mexico from a line of stations along 90°30′W. The mean apparent age of water below 900 m, the depth of the Florida Strait sill, was found to be about 740 yr relative to the 1950 14C standard. Depending on how the corrections for biological activity in the upper water are applied, this converts to a “true” age of between 231 ± 28 and 293 ± 74 yr. These ages agree with a previous estimate of the age of the deep water in the Gulf of Mexico based on heat flows, put upper limits on the age of the deep water in the Caribbean Sea, and provide constraints on modelers for the return of deep water from the Gulf of Mexico to the Caribbean. This might be important in the event of a future deep water oil or other chemical spill in the region.

The study of the mechanisms of radiocarbon (14C) release from different types of radioactive waste in final disposal conditions (organic, inorganic species, liquid, or gaseous phase) is an important aspect for the definition of waste acceptance criteria in a repository. The goal of this work is to determine the behavior of activated stainless steel, under standard leaching tests performed at El Cabril laboratory, with the aim of determining the retention capacity of the activated stainless steel, and therefore to assess the treatment and the potential additional barriers necessary for the fulfillment of waste acceptance criteria relevant to the El Cabril surface repository, Spain.

We report marine dissolved organic carbon (DOC) ∆14C from seawater collected from the North central Pacific Ocean (NCP) in 2015. These measurements show DOC ∆14C values averaged –235±5‰ (n=3) in the mixed layer (24–81 m) and –544±5‰ (n=5) in the deep water (1500–5139 m). A comparison of these data with two previously published DOC ∆14C profiles from the NCP in 1985 and 1987 reveals that deep DOC ∆14C values have decreased. We discuss several possible mechanisms that could cause such a shift in DOC ∆14C values, including spatial inhomogeneity and temporal variability due to changes in the dissolution and ∆14C value of surface derived particles in the deep sea. We find that forthcoming profiles of DOC ∆14C results from the NCP will determine the primary mechanisms controlling deep DOC ∆14C distributions, and changes over the past three decades.

Measurements of the radiocarbon (14C) and tritium (3H) activity in a 5.8-m-long ice core from the Saarhalle, Dachstein-Mammoth Cave allowed a substantial revision of previous opinions concerning the age of the ice block, and provide useful experience that may be applied to future 14C dating of cave ice deposits. The stepped combustion technique results in a remarkably older radiocarbon age for the 800°C than for the 400°C fractions of the carbonaceous matter from ice layer samples. The highest tritium activity (37.2±1.2 TU) can be linked to the period of anthropogenically increased tritium activity of atmospheric precipitation at the mid-1960s, providing a well-dated radiochemical reference horizon. Compared the 3H-based extrapolated ages of two shallow samples to the expected atmospheric signal an average 14C reservoir bias of ~1500 BP was obtained for the insoluble organic fraction combusted at 400°C. The conventional 14C age measured for the 400°C fraction of the deeper samples has been corrected with the average reservoir bias. The median calibrated age of the deepest analyzed sample of the ice profile is ~1830 cal BC and a linear extrapolation to the bottom ice layer gave 2590 cal BC, making the Saarhalle ice block among the oldest dated cave ice deposits known in the Alpine domain.

Radiocarbon dates from recent excavations of a range of Angkorian Khmer (~9th–14th CE) stoneware kiln complexes provide a new and independent perspective on the timing and geography of Khmer ceramic production. These data demonstrate a clear two-phase sequence. The first, in the late 9th to late 12th centuries CE, marks a period of intensive production located both to the east of Angkor and to the south at Cheung Ek, south of Phnom Penh. A second shorter phase of production occurred in the late 13th to late 14th CE at more distant provincial settings following the collapse of the Angkorian state.

In order to contribute to the discussion of Holocene climate changes, four sediment cores were collected from the northern Brazilian Amazonia lowland. These cores were studied through pollen analysis and sedimentary features, and the results were discussed within a chronological framework provided by radiocarbon dating. The cores were sampled from fluvial terraces representative of channel, floodplain/lake and crevasse splay deposits formed since the mid-Holocene. The pollen samples derive from floodplain/lake deposits and the pollen grains are mainly composed by families Moraceae, Euphorbiaceae, Caesalpiniaceae, Fabaceae, Rubiaceae, Melastomataceae, Combretaceae, Sapindaceae, Poaceae, Cyperaceae, Aizoaceae, Apiaceae and genus Sebastiana. The pollen data suggest no significant vegetation changes in the study area for the past 4808–4886 cal yr BP. This led to proposing stable climatic conditions since at least the middle Holocene. Such a finding is contrary to the occurrence of a dry period during the middle Holocene. The stabilization of the relative sea level about 6000 cal yr BP along the northern Brazilian littoral may have influenced the water table, and favored the establishment and maintenance of Amazonian lowland forest during the mid- and late Holocene. In addition, this process may have attenuated the impact of that dry period in areas under most fluvial influence.

Carbon-14 (radiocarbon, 14C) is a long-lived radionuclide (5730 yr) of interest regarding the safety for the management of intermediate level wastes (ILW). The present study gives an overview of the release of 14C from irradiated Zircaloy cladding in alkaline media. 14C is found either in the alloy part of Zircaloy cladding due to the neutron activation of 14N impurities by 14N(n,p)14C reaction, or in the oxide layer (ZrO2) formed at the metal surface by the neutron activation of 17O from UO2 or (U-Pu)O2 fuel and water from the primary circuit in the reactor by 17O(n,α)14C reaction. Various irradiated and unirradiated Zircaloys have been studied. The total 14C inventory has been determined both experimentally and by calculations. The results seem to be in good agreement. Leaching experiments were conducted in alkaline media for several time durations. 14C was mainly released as carboxylic acids. Further, corrosion measurements were performed by using both hydrogen measurements and electrochemical measurements. The corrosion rate (CR) ranges from a few nm/yr to 100 nm/yr depending on the surface conditions and the method used for measurement. From a safety assessment point of view, the instant release fraction (IRF) was determined on irradiated Zircaloy-2. The results showed that the 14C inventory in the oxide was significantly below the 20% commonly used in safety case assessments.

Radiocarbon (14C) measurements of foraminifera often provide the only absolute age constraints in marine sediments. However, they are often challenging as their reliability and accuracy can be compromised by reduced availability of adequate sample material. New analytical advances using the MIni CArbon DAting System (MICADAS) allow 14C dating of very small samples, circumventing size limitations inherent to conventional 14C measurements with accelerator mass spectrometry (AMS). Here we use foraminiferal samples and carbonate standard material to assess the reproducibility and precision of MICADAS 14C analyses, quantify contamination biases, and determine foraminiferal 14C blank levels. The reproducibility of conventional 14C ages for our planktic (benthic) foraminiferal samples from gas measurements is 200 (130) yr, and has good precision as illustrated by the agreement between both standards and their reference values as well as between small gas- and larger graphitized foraminiferal samples (within 100±60 yr). We observe a constant contamination bias and slightly higher 14C blanks for foraminifera than for carbonate reference materials, limiting gas (graphite) 14C age determinations for foraminifera from our study sites to ~38 (~42) kyr. Our findings underline the significance of MICADAS gas analyses for 14C on smaller-than-conventional sized foraminiferal samples for paleoclimate reconstructions and dating.