Tracing human history in west central Africa suffers from a scarcity of historical data and archaeological remains. In order to provide new insight into this problem, we reviewed 733 radiocarbon dates of archaeological sites from the end of the Late Stone Age, Neolithic Stage, and Early and Late Iron Age in Cameroon, Gabon, Central African Republic, Equatorial Guinea, Republic of Congo, and the western Democratic Republic of Congo. This review provides a spatiotemporal framework of human settlement in the forest biome. Beyond the well-known initial spread of Iron Age populations through central African forests from 2500 cal BP, it depicts the geographical patterns and links with the cultural evolution of the successive phases of human expansion from 5000 to 3000 cal BP and then from 3000 to 1600 cal BP, of the hinterland depopulation from 1350 to 860 cal BP, and of recolonization up to 500 cal BP.

Lower Congo rock art is concentrated in a region that stretches from Kinshasa to the Atlantic coast and from northern Angola to southern Congo-Brazzaville. Although Lower Congo rock art was identified as early as the 19th century, it had never been a subject of thorough investigation. Presently inhabited by the Ndibu, one of the Kongo subgroups, the Lovo Massif is situated north of the ancient Kongo Kingdom. With 102 sites (including 16 decorated caves), the massif has the largest concentration of rock art in the entire region. In 2008 and 2010, we were able to collect pigment samples directly on the panels of the newly discovered decorated cave of Tovo. Unlike the Sahara and southern Africa, both extensively prospected, rock art of central Africa is still widely unknown and not dated. Radiocarbon dating of rock art in Africa is a real challenge and only a few direct dates have been obtained thus far. After verifying that the pigment samples were indeed charcoal, we proceeded to 14C date them using accelerator mass spectrometry (AMS). The results indicate dates between cal AD 1480 and 1800, confirming that the occupation of Tovo Cave was contemporaneous with the ancient Kongo Kingdom.

Radiocarbon dating of bones can be very useful in archaeological contexts, especially when dealing with funerary deposits lacking material culture, e.g. pottery vessels. 14C measurements of bone samples are usually performed on the extracted collagen residue. The content and the quality of collagen can vary significantly, mainly depending on bone preservation and diagenesis. Generally speaking, environmental conditions such as low pH level of soils, high temperatures, and percolating groundwaters, typical of arid and tropical zones, can affect the preservation of collagen; at the same time, bones recovered in such environments are more likely to be contaminated with carbon from the surrounding environment. Possible contamination of samples can also occur in temperate zones. While low collagen content is a condition we cannot overcome, we can use several chemical and elemental indicators in order to assess collagen quality. Among these, the C/N atomic ratio is considered a good parameter for detecting low-quality collagen and possibly contaminated samples. In a combustion and graphitization setup like that installed at INFN-LABEC, Florence, measurement can be easily performed using an elemental analyzer when combusting the sample prior to graphitization, thus requiring no extra effort (or extra amount of sample) during the preparation procedure. Bone samples recently 14C dated at INFN-LABEC have confirmed that the measurement of C/N atomic ratios can give some indications of the collagen quality. The bone material was collected from 3 necropoles of the Bronze Age period in Cyprus (Erimi-Laonin tou Porakou, Lophou-Kolaouzou, and Erimi-Kafkalla&Pitharka, along the Kouris Valley), an area characterized by environmental conditions that do not favor bone preservation. Samples were treated to extract collagen and measured by accelerator mass spectrometry (AMS). 14C results have been compared with the archaeological evidence, showing some relationship between measured C/N atomic ratios and collagen quality. In particular, when grouping the measured samples according to their C/N ratio, the agreement between 14C dates and archaeological evidence is good or inconsistent when the C/N ratio clearly falls inside or outside the “recommended” range, respectively, with a still reasonable agreement also when it is slightly above the upper limit of that range.

The aim of this study is to directly radiocarbon date pottery from prehistoric rock-art shelters in the Tassili n'Ajjer (central Sahara). We used a combined geochemical and microscopic approach to determine plant material in the pottery prior to direct 14C dating. The ages obtained range from 5270 ± 35 BP (6276–5948 cal BP) to 8160 ± 45 BP (9190–9015 cal BP), and correlate with the chronology derived from pottery typology. Our results document the transition from pre-Pastoral to Pastoral contexts, dated to the early-mid Holocene transition, and confirm that vegetal temper in pottery can provide reliable 14C ages within Saharan contexts.

To study the effect of ultrafiltration on the radiocarbon ages of relatively poorly preserved bones in Japan, we analyzed the 14C dates of high-molecular-weight (HMW) gelatin samples and compared them with those of other extracted organic fractions, unfiltered gelatin samples extracted from NaOH-treated or NaOH-untreated collagen, and XAD-purified hydrolysates of animal fossil bones (∼4600 BP; gelatin yield of 2–4%) from the Awazu underwater archaeological site, Shiga, Japan. NaOH-treated, unfiltered gelatins and XAD-purified hydrolysates showed statistically similar 14C ages to those of HMW gelatins. The 14C ages of the HMW gelatins were the oldest and similar to those of wood collected from the same layer as the bones, and the NaOH-treated, unfiltered gelatins gave 14C ages within the acceptable margins of error; therefore, ultrafiltration was effective for accurate 14C dating, while NaOH-treated gelatin without ultrafiltration was also sufficient to obtain accurate 14C dates on the animal bones. The 14C ages of human skeletons (∼750 BP; gelatin yield of 2–11%) from 5 individuals excavated from an archaeological site in Yuigahama, Kamakura, Japan, showed statistically the same 14C ages as NaOH-treated, unfiltered gelatins and HMW gelatins within the margins of error, although HMW gelatins were likely to give slightly older ages than unfiltered gelatin with a yield of less than ∼3%. These results indicate that unfiltered gelatins extracted from fossil bones of gelatin yield more than ∼3% can produce accurate 14C ages without the need for ultrafiltration. Ten bone fragments from 3 humans showed the same 14C ages for each individual, suggesting that any bone part from an individual can be used to obtain a representative age. The 14C ages of tooth enamels of 2 individuals were 35 and 70 yr older than their bone ages. Death dates obtained from these age gaps agreed with those determined by morphology.

The ancient Egyptian mummy discovered in the wooden coffin of Ankhpakhered, priest of the god Min, has been studied at CEDAD (Centre for Dating and Diagnostics) at the University of Salento, Italy. The CT scan, performed by the multidisciplinary team of the Mummy Project of Milan, highlighted unusual features of the mummy, suggesting a reuse of the sarcophagus. Furthermore, specimens were taken via endoscopy for accelerator mass spectrometry (AMS) radiocarbon dating and Fourier transform infrared (FTIR) analyses, which have been carried out at CEDAD.

We conducted analyses to identify the most suitable bone pretreatment protocol to be used by the recently established Radiocarbon Laboratory at the University of Cologne, CologneAMS. In 2 sets of analyses, we determined 14C ages for subsamples taken from 3 14C bone standards (Oxford Mammoth, VIRI I, and VIRI H) complemented by age determinations of 12 unknown bone samples. Our results suggest that the strength and duration of the acid and alkali steps and the temperature of gelatinization might have a larger influence on the obtained ages than the presence or absence of ultrafiltration as a pretreatment step.

This paper reports the results of the application of a calcined bone dating protocol to samples collected from the Sanctuary of Zeus on Mt. Lykaion in southern Greece. The site is a mountaintop ash altar rich in anthropogenic sediments, burned bone, and artifacts offered to the god Zeus. Experiments involving time series hydrolysis measurements were conducted on calcined bones from stratified layers throughout the sequence to determine if any of the samples underwent surface contamination from carbonate exchange with the surrounding sedimentary matrix. It was determined that such exchange was unlikely, but samples were acid-etched before pretreatment as a precautionary measure. Paired samples of seeds, charcoal, and calcined animal bone collected from a sediment column in the altar demonstrate the effectiveness of the calcined bone dating technique in this context. The results of dating indicate that the altar was in use from the Mycenaean period through the late Classical period, though samples were not collected from the upper levels of the site due to possible mixing of surface sediments. Fourier transform infrared spectroscopy (FTIR) measurements were taken and crystallinity index values calculated, confirming that the bone samples are indeed calcined. The results presented here correspond with literary accounts of ritual animal sacrifice from historical texts from the 8th century BCE, including the Homeric epics.

This work aims to test the reliability of calcined bones for radiocarbon dating of the Paleolithic. Fifty-five calcined bone samples coming from Aurignacian and Gravettian layers at Abri Pataud (Dordogne, France) were selected based on their macroscopic features. For each sample, the heating state was estimated on the basis of bone crystallinity (splitting factor [SF] using FTIR) and δ13C value. Twenty-seven bone samples (3 unburnt and 24 calcined) from 5 different levels were prepared for 14C dating. The majority (15/24) of the calcined samples had to undergo a sulfix treatment prior to graphitization, probably due to the presence of cyanamide ion in these samples. The comparison between our results and recently published dates on bone collagen for the same levels shows that unburned bone apatite is systematically too young, while a third of the calcined bones fall within or very near the range of expected age. No clear correlation was found between 14C age offset and δ13C value or SF. Most of the sulfixed samples (14/16) yielded ages that were too young, while almost all of the non-sulfixed samples (8/9) gave ages similar or <0.2 pMC from the expected minimum age. Although preliminary, these results suggest that sulfix should be avoided if possible and that clean CO2 gas from well-calcined Paleolithic bones can provide reliable 14C ages.

This paper reports the results from applying the Cryo2SoniC (Cryobreaking, Sonication, Centrifugation) protocol to some lime mortars sampled from the citadel of Shayzar (Syria). The overall aims of this project are 1) to use the properties offered by high-precision accelerator mass spectrometry (AMS) radiocarbon dating for the evaluation of absolute chronology with its typical robust time constraints (i.e. 25 14C yr), and 2) to apply the dating directly to the citadel structures in order to prevent possible biasing effects potentially affecting indirect 14C dating on organic materials found at the study site. The analyses presented in this paper have been mainly performed as a preliminary check of the Cryo2SoniC methodology in order to assess its applicability to this study site by comparing observed mortar results with archaeological expectations about the citadel development phasing and charcoals found encased in mortars. Petrographic and mineralogical thin-section analyses by optical microscopy (TSOM), X-ray powder diffraction (XRD), and scanning electron microscopy plus energy dispersive spectroscopy (SEM/EDS) investigations were carried out for characterization of the mortar samples to verify the occurrence of some features, related to their production technology, which may introduce dating offsets. The resulting 14C calibrated ages were in agreement with the archaeological expectations based on type and stratigraphic site reconstructions, in situ inscriptions, and written sources. Such results showed also a general (with 1 exception) statistical agreement among the charcoals and the analyzed mortars simultaneously, confirming the archaeological expectations for the Shayzar citadel. Results presented in this paper indicate good accuracy for the applied procedure for chronology reconstruction and highlight the capability of Cryo2SoniC to further characterize the Shayzar site.

The Laboratoire des Sciences du Climat et de l'Environnement (LSCE) research program on prehistoric art conducts chronological studies of parietal representations with their associated archaeological context. This multidisciplinary approach provides chronological arguments about the creation period of parietal representations. This article presents chronological investigations carried out in several decorated caves in France (La Grande Grotte, Labastide, Lascaux, La Tête-du-Lion, Villars) and Spain (La Garma, Nerja, La Pileta, Urdiales). Several types of organic materials, collected from different areas of the caves close to the walls and in connection with parietal art, were dated to determine the periods of human presence in the cave, a presence that may have been related to artistic activities. These new radiocarbon results range from 33,000–29,000 (La Grande Grotte) to 16,000–14,000 cal BP (Urdiales).

Theopetra Cave is a unique prehistoric site for Greece, as the Middle and Upper Paleolithic, Mesolithic, and Neolithic periods are present here, bridging the Pleistocene with the Holocene. During the more than 20 yr of excavation campaigns, charcoal samples from hearths suitable for 14C dating were collected from all anthropogenic layers, including the Paleolithic ones. Most of the samples were initially dated using the ABA chemical pretreatment protocol in the Laboratory of Archaeometry of NCSR Demokritos, Greece, and the Radiocarbon Dating and Cosmogenic Isotopes Laboratory of the Weizmann Institute of Science, Israel. The 14C results, which were not always consistent versus depth, showed that the earliest limit of human presence is ∼50,000 yr BP, thus reaching the age limits of the 14C dating method. However, 10 TL-dated burnt flint specimens unearthed from the lower part of the Middle Paleolithic sequence of the cave gave ages ranging between ∼110 and 135 kyr ago. These results are in disagreement with the 14C dates, as they support a much later date for these layers. In order to clarify the situation further, charcoal samples originating from hearths were conventionally dated in the Laboratory of Archaeometry of NCSR Demokritos using the ABA pretreatment. Additionally, hand-picked charcoal fragments also underwent 14C dating by AMS in the Oxford Radiocarbon Accelerator Unit using the acid-base wet oxidation (ABOX-SC) pretreatment protocol. The 14C dates from the cave's Paleolithic layers obtained by both pretreatment protocols suggest a probable charcoal diagenesis affecting the 14C results of these very old samples. However, the dates obtained with ABOX-SC pretreatment are considered more reliable and in the younger stratigraphic part produced consistent results with the TL dating.

The San Lorenzo Cathedral of Alba is a Romanesque church (rebuilt in Gothic epoch) located in northwest Italy. Since 2007, this church has been subjected to renovations and archaeological excavations that led to the finding of the lower part of the basin and the water drainage pipe of a baptismal font of unknown age. Thermoluminescence and radiocarbon dating have been carried out respectively on some ceramic elements and lime mortar samples used in both the pipe and basin of the font. Thermoluminescence results suggest that some of the bricks may have been reused from previous structures while 14C results suggest that the font was built between the 9th and the 11th centuries AD, most probably in the 10th century AD.

Four accelerator mass spectrometry (AMS) facilities undertook an interlaboratory exercise designed to examine the reliability and reproducibility of radiocarbon determinations on bone by dating a sample of elk (Alces alces) from Miesenheim IV. This specimen is derived from a secure geological context directly beneath the Laacher See tephra, which provides a precise terminus ante quern of ∼11,060 yr BP (∼13,050 cal yr BP). Regrettably, the results of the intercomparison exercise were complicated by evident contamination of the bone sample by exogenous organic material. This contaminant, probably humic acid, resulted in a wide span of ages (10,010 ± 30 to 11,100 ± 45 BP). The only method that yielded an accurate determination, consistent with the age of the tephra, was Oxford's single amino acid technique, which targets hydroxyproline. An acid hydrolysis step seems to have been crucial in breaking the bonds between the bone collagen and the contaminant.

The acid-base-acid (ABA) procedure is a common chemical pretreatment used on most organic matter samples. Although this pretreatment is straightforward, there is no consensus among labs about the optimum strength of the chemicals, or even the temperature, to be used for digestions. Comparisons between 14C results obtained by samples undergoing ABA against other wet oxidations, such as acid-base oxidation followed by stepped-combustion (ABOX-SC) or α-cellulose on wood, have sometimes suggested that ABA does not always remove all contaminating carbon. In addition, if not all ABA protocols are the same, could it be said that one procedure is better than others or comparable to wet-oxidation pretreatments, if rigorously applied? To determine whether 14C-free samples showed any fraction modern carbon (FmC) deviations due to pretreatment strategies, 3 experiments were carried out. The first compared 14C results for wood samples at or near the limit of 14C dating, pretreated with a standard ABA protocol used at UC Irvine's Keck Carbon Cycle Accelerator Mass Spectrometry (KCCAMS) facility, with those obtained from ABA- and ABOX-SC-prepared aliquots of the same samples performed at Australian National University (ANU) in 2001. The second experiment subjected wood samples, ranging from ∼12 ka BP to 14C-free, to 5 selected published ABA pretreatments. Third, we evaluated whether the ABA protocol needs a higher-strength final acid step (particularly important for removing CO2 absorption when samples are submerged in alkaline solutions). We are able to show that rigorous ABA treatments exist that can provide robust, reproducible results for many wood samples that are known to be >>50 ka BP, implying that a lack of control over the procedure's outcome might be sample-related, rather than due simply to inadequacies in the chemical pretreatment.

We present a method for the extraction of dissolved organic carbon (DOC) from water. The method is adapted from Burr et al. (2001) using the basic steps: 1) sample filtration; 2) acidification to liberate and remove dissolved inorganic carbon (DIC); 3) evaporation of the sample to isolate salts that include trace quantities of carbon; 4) combustion of the salts; and 5) purification of the CO2. Two significant improvements have been made to the earlier method. The first is to use wet oxidation with potassium permanganate to oxidize organics in place of the combustion step and the second is the development of a reduction/oxidation purification procedure to remove sulfur and nitrogen oxides that may form during the oxidation step. Wet oxidation has a practical advantage over the previous method because it proceeds at low temperature (70 °C). The original method required quartz vessels to oxidize the salts at 900 °C. At this temperature, salts in the samples formed gases that interfered with the isolation of CO2 and the quartz vessels degraded with each combustion, affecting their structural integrity. The expensive quartz vessels could only be used for a limited number of samples, whereas Pyrex vessels used for wet oxidation are inexpensive and can be used indefinitely.

The blank fraction modern carbon (f) and its mass dependence for the refined technique was determined from repeat analyses of salicylic acid produced from petrochemicals. For samples with a mass m above 0.5 mg, F = 0.0083 ± 0.0011. For samples below 0.5 mg, the blank follows a 1/m dependence as observed for other accelerator mass spectrometry (AMS) 14C measurements (Donahue et al. 1990). The reproducibility of the method is demonstrated using repeat measurements from a variety of samples, including a sample measured with the former high-temperature 900 °C combustion technique. The virtues of the wet oxidation method are that it is economical, produces a low blank, and provides good reproducibility.

Buran-Kaya III is a rockshelter located in Crimea (Ukraine). It provides an exceptional stratigraphic sequence extending from the Middle Paleolithic to the Neolithic. Nine Paleolithic layers have been attributed to the Streletskaya or eastern Szeletian, Micoquian, Aurignacian, Gravettian, and Swiderian cultural traditions. Human remains from the richest Gravettian layer (6-1) are radiocarbon dated to 31.9 ka BP, and therefore represent, with Peştera cu Oase (Romania), one of the oldest anatomically modern humans in Europe. The aim of this study is to obtain a controlled stratigraphic sequence of Buran-Kaya III with new 14C dates from faunal and human bones, in their paleoenvironmental context. During our new excavations (2009–2011), sediments, bones, and teeth from the stratigraphical layers were sampled for sedimentological, geochemical, and 14C analyses. Fossil bones from the 2001 excavations were also analyzed. Accelerator mass spectrometry (AMS) 14C dating, including cross-dating, was performed at Groningen, Saclay/Gif-sur-Yvette, and Oxford. Biogeochemical analysis was used to test the integrity of the bone collagen. Dates were modeled using a Bayesian approach. The sedimentological, paleoenvironmental, and chronological data are mutually consistent and show that the Paleolithic human occupations at Buran-Kaya III range from the end of MIS 3 to early MIS 1. These results provide a new chronological and paleoenvironmental framework for the human settlements in eastern Europe during the late Middle and the Upper Paleolithic.

We discuss a radiocarbon study of sediment samples collected from Nanfu terrace in western Taiwan. From these, we extracted humic acids (HA) and humin from the very fine and coarse grain-size fractions using a standard acid-alkali-acid pretreatment. The humin extracts were combusted at 400 and 1100 °C by stepped-combustion, to yield a low-temperature (LT) carbon component and a high-temperature (HT) carbon component. We compare the ages of the LT and HT humin fractions to the HA fractions, in samples collected at 2 depths within the Nanfu terrace. As in previous stepped-combustion studies on sediments, we find that the HA ages are the youngest on average, and overlap the LT ages, and that the carbon contained in the HT fraction is always distinctly older than the LT and HA ages. To better understand the relationship between 14C age and combustion temperature, we conducted an incremental stepped-combustion experiment with one of the samples (1E) using 50 °C steps that ranged from 300 to 1100 °C. The 14C results of the stepped-combustion products show a clear division between 2 isotopically identifiable carbon constituents, from carbon released below 400 °C and carbon released above 550 °C. By comparing the δ13C and 14C results, we find evidence for a third carbon isotopic component in the humin that is released when combusted at ∼500 °C.

A workshop on atmospheric radiocarbon measurements was held in conjunction with the 21st International Radiocarbon conference in July 2012. The main topics were intercomparison of measurements of 14C in atmospheric CO2, the potential for use of gas standards for atmospheric 14C measurements, reporting of uncertainties, and expansion of intercomparison activities to other atmospheric trace gases. This report documents the discussions and conclusions of this workshop.

This article presents results from the first 3 rounds of an international intercomparison of measurements of Δ14CO2 in liter-scale samples of whole air by groups using accelerator mass spectrometry (AMS). The ultimate goal of the intercomparison is to allow the merging of Δ14CO2 data from different groups, with the confidence that differences in the data are geophysical gradients and not artifacts of calibration. Eight groups have participated in at least 1 round of the intercomparison, which has so far included 3 rounds of air distribution between 2007 and 2010. The comparison is intended to be ongoing, so that: a) the community obtains a regular assessment of differences between laboratories; and b) individual laboratories can begin to assess the long-term repeatability of their measurements of the same source air. Air used in the intercomparison was compressed into 2 high-pressure cylinders in 2005 and 2006 at Niwot Ridge, Colorado (USA), with one of the tanks “spiked” with fossil CO2, so that the 2 tanks span the range of Δ14CO2 typically encountered when measuring air from both remote background locations and polluted urban ones. Three groups show interlaboratory comparability within l% for ambient level Δ14CO2. For high CO2/low Δ14CO2 air, 4 laboratories showed comparability within 2%. This approaches the goals set out by the World Meteorological Organization (WMO) CO2 Measurements Experts Group in 2005. One important observation is that single-sample precisions typically reported by the AMS community cannot always explain the observed differences within and between laboratories. This emphasizes the need to use long-term repeatability as a metric for measurement precision, especially in the context of long-term atmospheric monitoring.