Four charcoal samples from loess key sites in Austria, Moravia, and western Ukraine were submitted to ABOx (acid-base oxidation) pretreatment to compare results with the classical ABA (acid-base-acid) method. For this purpose, charcoal samples already dated in Groningen laboratory were selected from 3 archaeological sites: Molodova V in western Ukraine (subunit 10–1, ∼32.6 ka BP), Willendorf II in Austria (unit C4, ∼32.1 ka BP and unit C8, ∼38.9 ka BP) and Vedrovice V in Moravia (unit 4, upper part of Bohunice soil, ∼39.5 ka BP). Each selected charcoal sample has been homogenized and divided into 3 subsamples, which were submitted to ABA in Groningen and to ABA and ABOx pretreatments in Oxford. The results show that the ABOx dates are older than the ABA dates. Nevertheless, down to ∼40 ka BP ABOx and Groningen ABA dates appear in good agreement within a time interval of ∼1 millennium at 1σ. However, Groningen ABA pretreatment produces older dates than the Oxford ABA pretreatment. Both Oxford ABOx and Groningen ABA pretreatments provide sets of dates in good agreement with the chronological background of each selected site.

The Artemis accelerator mass spectrometry (AMS) facility, installed in 2003 in Saclay, France, is devoted to radiocarbon measurements. Samples are submitted by scientists in the fields of Quaternary geology, environmental sciences, and archaeology. The entire preparation process, originally optimized for samples with about 1 mg of carbon, has been tested in recent years for samples with a lower carbon content. In particular, we prepared and measured carbonate and organic background and reference samples ranging in mass from 0.01 to 1 mg C. These tests helped define our protocol's practical limits and determine necessary improvements. Furthermore, our experiments demonstrated that satisfactory graphitization yields (80% and higher) and low background values can be obtained with samples down to 0.2 mg of carbon. For handling smaller samples, we developed a specific process. We tested smaller reactors (5 mL in volume) and adapted the reduction parameters (H2 pressure and temperature) accordingly. We also tested the effect of a chemical water trap on graphitization yields and 14C results. This paper presents in detail the aforementioned developments and reports the 14C results obtained for background and standard small samples prepared with the modified reactors.

Δ14Catm has been estimated as 420 ± 80% (IntCal09) during the Last Glacial Maximum (LGM) compared to preindustrial times (0%), but mechanisms explaining this difference are not yet resolved. Δ14Catm is a function of both cosmogenic production in the high atmosphere and of carbon cycling and partitioning in the Earth system. 10Be-based reconstructions show a contribution of the cosmogenic production term of only 200 ± 200% in the LGM. The remaining 220% have thus to be explained by changes in the carbon cycle. Recently, Bouttes et al. (2010, 2011) proposed to explain most of the difference in pCO2atm and Δ13C between glacial and interglacial times as a result of brine-induced ocean stratification in the Southern Ocean. This mechanism involves the formation of very saline water masses that contribute to high carbon storage in the deep ocean. During glacial times, the sinking of brines is enhanced and more carbon is stored in the deep ocean, lowering pCO2atm. Moreover, the sinking of brines induces increased stratification in the Southern Ocean, which keeps the deep ocean well isolated from the surface. Such an isolated ocean reservoir would be characterized by a low Δ14C signature. Evidence of such 14C-depleted deep waters during the LGM has recently been found in the Southern Ocean (Skinner et al. 2010). The degassing of this carbon with low Δ14C would then reduce Δ14Catm throughout the deglaciation. We have further developed the CLIMBER-2 model to include a cosmogenic production of 14C as well as an interactive atmospheric 14C reservoir. We investigate the role of both the sinking of brine and cosmogenic production, alongside iron fertilization mechanisms, to explain changes in Δ14Catm during the last deglaciation. In our simulations, not only is the sinking of brine mechanism consistent with past Δ14C data, but it also explains most of the differences in pCO2atm and Δ14Catm between the LGM and preindustrial times. Finally, this study represents the first time to our knowledge that a model experiment explains glacial-interglacial differences in pCO2atm, Δ13C, and Δ14C together with a coherent LGM climate.

Since installation of the new accelerator at INFN-LABEC in Florence in 2004, the workload has progressively increased in the radiocarbon dating laboratory, requiring a faster sample preparation throughput and greater versatility to allow for a larger variety of treated materials. The “standard” sample preparation line is based on an elemental analyzer (EA) for the combustion of the pretreated samples, and a vacuum line where the CO2 is collected and then converted to graphite. This line has been recently redesigned while maintaining the EA, since this instrument provides us reliable and fast sample combustion and separation of gases. The volumes were optimized and all the mechanical parts (e.g. the fittings) were changed in order to improve the vacuum level, thus decreasing the possibility of contamination; finally, the number of graphitization reactors was doubled (from 4 to 8). In those rare cases involving samples characterized by a complex nearly graphitic structure (e.g. burnt residues), the EA might not guarantee a complete combustion. For these samples, we successfully tested the new sample preparation line that has been recently installed at LABEC and especially dedicated to aerosol samples. This line is equipped with a custom-made combustion oven able to heat to 1000 °C. The subsequent gas separation is accomplished by chemical and thermal traps. As an example, the dating of organic matter collected from an Etruscan bronze statue will be presented and discussed.

Microbial mats (kopara in Polynesian) that develop in shallow brackish to hypersaline ponds on the rims of atolls were investigated for their accumulation process and rate. Two sequences of ∼30-cm-deep kopara, composed of 7 and 5 layers distinguished by their colors and sedimentological facies were collected in 1996 from the Tetiaroa atoll, French Polynesia. The combination of radiocarbon activity measurements on both organic and carbonate constituents, reservoir effect estimation, and comparison with the Southern Hemisphere atmospheric bomb-peak 14C record allowed us to establish a fine chronology of the layer successions documenting the mode of formation, erosion, and restoration of these microbial mat deposits.

We document chemical laboratory procedures and results on international comparison samples at the Hertelendi Laboratory of Environmental Studies, Debrecen, Hungary. We also show results using the new MICADAS system and compare these results to internationally recognized standards and blank materials. The newly developed sample preparation system in HEKAL can handle samples as 1) organic material, 2) cellulose fraction of plant, 3) bones, 4) carbonate and shell, and 5) dissolved inorganic carbon of groundwater. The results of radiocarbon measurements on intercomparison samples confirm the reliability of the sample preparation system at HEKAL Lab and also the good performance of the MICADAS 14C system. The blank levels for each type of sample of 1 mg C carbon content are well reproducible, ∼0.3–0.5 pMC.

The first high-resolution time series of pre- and post-bomb radiocarbon measurements is reported for surface waters in the western Mediterranean Sea. The Δ14C record was obtained from the aragonite skeleton of Cladocora caespitosa using a 50-yr-old corallite collected in the Ligurian Sea in 1998. Laser-ablation ICP measurements of trace elements (Li/Mg and Sr/Ca) show a strong seasonal variability, enabling the chronology of the Δ14C record to be determined at annual timescales. The mean Δ14C of pre-bomb surface water is -56 ± 3%, corresponding to a reservoir age of 262 ± 29 yr. The post-bomb maximum occurs in 1972 with a Δ14C value of 90%, significantly lower than the peak of 150% observed in the North Atlantic. The dilution of the peak-amplitude of Δ14C in western Mediterranean surface waters is attributed to mixing of North Atlantic Central Water inflow with relatively depleted underlying Intermediate Mediterranean and Levantine Intermediate waters. Intensification of this mixing is observed in 1963–1964, consistent with the change in atmospheric circulation from a positive to negative NAO phase (1960–1967). The post-peak Δ14C variability is relatively limited, reflecting mainly local vertical mixing forced by wind stress.

Extraneous carbon (Cex) added during chemical processing and isolation of black carbon (BC) in environmental matrices was quantified to assess its impact on compound specific radiocarbon analysis (CSRA). Extraneous carbon is added during the multiple steps of BC extraction, such as incomplete removal of solvents, and carbon bleed from the gas chromatographic and cation columns. We use 2 methods to evaluate the size and Δ14C values of Cex in BC in ocean sediments that require additional pretreatment using a cation column with the benzene polycarboxylic acid (BPCA) method. First, the direct method evaluates the size and Δ14C value of Cex directly from the process blank, generated by processing initially empty vials through the entire method identically to the treatment of a sample. Second, the indirect method quantifies Cex as the difference between processed and unprocessed (bulk) Δ14C values in a variety of modern and 14C-free or “dead” BC standards. Considering a suite of hypothetical marine sedimentary samples of various sizes and Δ14C values and BC Ring Trial standards, we compare both methods of corrections and find agreement between samples that are >50 μg C. Because Cex can profoundly influence the measured Δ14C value of compound specific samples, we strongly advocate the use of multiple types of process standards that match the sample size to assess Cex and investigate corrections throughout extensive sample processing.

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.

Measurements of the radiocarbon abundance in 5 samples of bis(2–ethylhexyl) phthalate (DEHP) isolated from Stilton cheese were made by accelerator mass spectrometry (AMS) to determine the fraction of carbon originating from contemporary biogenic sources. DEHP is classified as a “priority hazardous substance” by the European Union, a probable human carcinogen by the United States Environmental Protection Agency, and is suspected to be a human endocrine disrupter. Measurement of its 14C abundance in a specific food indicates whether its presence is due to contamination from industrially synthesized DEHP or a naturally inherent component. A method was developed to determine the contemporary carbon fraction of DEHP in a fatty food matrix at concentrations of 0.14 mg/kg. Five 90–μg quantities of DEHP were extracted from 12 kg of Stilton cheese and isolated by silica gel, size exclusion, and high-performance liquid chromatography (HPLC). Masses of samples were determined by gas chromatography mass spectrometry (GC-MS) analyses prior to combustion and manometry afterwards. The purity of DEHP carbon mass in each isolate was determined by multivariate deconvolution of GCMS fragmentation spectra obtained from measurements of standards and isolates, and ranged from 88.0 ± 1.8% to 92.3 ± 1.1% (n = 5, 1σ). Concurrently processed isolation method blanks contained from 0.15 ± 0.04 to 1.52 ± 0.06 μg (n = 3, 1σ) DEHP per sample and significant quantities of pre- and post-chromatographic extraneous carbon contamination. The mean 14C-corrected contemporary carbon fraction of DEHP in the isolates was 0.235 ± 0.073 (1σ; and ± 0.091 at the 95% confidence level), revealing that the majority of DEHP in Stilton cheese results from anthropogenic sources, but with a significant naturally occurring component.

In the 2000s, radiocarbon in dissolved inorganic carbon was measured during 7 revisit cruises along the lines of the World Ocean Circulation Experiment in the Pacific Ocean. Comparison of 14C data along these lines from the 1990s and 2000s revealed decadal changes of 14C concentration in the thermocline, most of which were due to temporal changes in the bomb-produced 14C. Vertical profiles and vertical-integrated inventories of the bomb 14C in the subarctic and equatorial regions did not change appreciably. In the southern subtropical region, 14C decreased in the upper thermocline from the surface to ∼500 m depth. In contrast, 14C increased in the lower thermocline below ∼500 m depth. The opposing directions in 14C change resulted in small temporal changes in the total inventory of bomb 14C. On the other hand, the water-column inventory significantly decreased in the northwestern subtropical region due to the 14C decrease in the upper thermocline. These decadal changes in bomb 14C indicate that the turnover time of thermocline circulation in the northwestern subtropical region is faster than that in the southern subtropical region, and imply an interbasin transport of bomb 14C from the North Pacific to other basins.

It has long been assumed that radiocarbon (Δ14C) content of dissolved inorganic carbon (DIC) is equal to that of particulate organic carbon (POC) in surface seawater; however, little research has been conducted to explicitly test this assumption. Here, we report Δ14C measurements of surface POC samples and compare them with contemporaneous DIC Δ14C measurements from the northeast Pacific Ocean (Hwang et al. 2004; Druffel et al. 2010). Samples were collected from surface waters at Station M off California between 1995 and 2004. The POC Δ14C values decreased 3.2% per year from 1995 to 2004, similar to the decline observed in the DIC Δ14C values during the same period. Overall, our results show no statistical difference between POC and DIC Δ14C—consistent with the assumption that DIC and POC Δ14C values can generally be considered equivalent. However, significant variability was observed for POC Δ14C values during several fall/summer events, where POC Δ14C signatures were lower than DIC Δ14C values. An evaluation of 2 sample pretreatments also suggests that non-homogenized POC samples deviated less from average POC Δ14C values and more closely matched the DIC Δ14C average for the time series. The presence of seasonal POC/DIC Δ14C disagreements, combined with sample processing effects, suggest that infrequent contributions of allochthonous, older carbon may have originated from deeper in the water column, especially during periods when upwelling in this area was prominent.

Dating of the amino acid hydroxyproline from bone collagen has been shown to produce accurate and reliable radiocarbon dates. This article presents further application of the method demonstrating it can be used to obtain dates for both low-collagen and contaminated bones, extending the capability of 14C dating archaeological bone from conventional limits imposed by alternative pretreatment methods. The method therefore has the potential for significantly benefiting the accelerator mass spectrometry (AMS) dating community in the 14C dating of archaeological bone.

When humans consume foods from different radiocarbon reservoirs offset in age to the atmosphere, inaccuracies in the 14C date of bone collagen can occur. Mesolithic human skeletons from the Iron Gates section of the Lower Danube Valley have yielded reservoir offsets of up to ∼500 yr. This has been demonstrated through direct dating of bulk collagen from human bones and the remains of ungulate bone projectile points that were found embedded in them (Cook et al. 2001). We present improvements to a novel HPLC method for the detection and separation of underivatized amino acids using a water-only mobile phase free of organic or inorganic modifiers, ensuring very low carbon backgrounds. Our hypothesis is that direct 14C dating of single essential and non-essential amino acids might allow an improvement in the dating accuracy for reservoir-affected human bones. The method facilitates separation of less polar amino acids (mostly “essential”), currently not possible in the recently published protocol. We discuss methodological developments, demonstrate carbon backgrounds, and present analytical approaches to minimize their effects. We validate the precision and accuracy of the method by accelerator mass spectrometry (AMS) dating relatively modern and 14C-dead, known-age bone standards. Finally, we apply the method to the dating of single amino acids from bone samples with a proven ∼500–yr carbon reservoir effect from Mesolithic burials at the Iron Gates sites. We investigate whether differences can be found in AMS dates for essential and non-essential amino acids since, although contemporaneous, these are expected to derive from dietary sources with differing 14C reservoirs.

In order to evaluate the variability in surface water masses in the Western Pacific Warm Pool, we report high-precision radiocarbon measurements in annual and seasonal bands from Pontes lutea corals collected from the Palau Archipelago (7°N, 134°E). Annual coral bands from 1945 to 2008 and seasonal samples from 1953 to 1957 were analyzed to capture the initial early input of bomb 14C from surface thermonuclear weapons testing in the Marshall Islands. Results show a pre-bomb average δ14C value of-54.9% between 1945 and early 1953. Beginning early in 1954, there is a rapid increase to a maximum of-23.1% at the start of 1955. Values continued to rise after 1957 to a post-bomb peak of 141% by 1976. The large initial rise in δ14C cannot be accounted for by air-sea CO2 exchange. Results therefore suggest that the primary cause of this increase is the lateral advection of fallout-contaminated water from the Marshall Islands to Palau via the North Equatorial Current and then to the North Equatorial Countercurrent.

Mangrove ecosystems are highly productive and play an important role in tropical and global coastal carbon (C) budgets. However, sedimentary organic carbon (SOC) storage and turnover in mangrove forests are still poorly understood. Based on C isotopic measurements of sediment cores of 2 mangrove stands in southern China, SOC density was 431.77 Mg ha−1 at site 1 (a Aegiceras corniculatum-dominated high tidal stand) and 243.65 Mg ha−1 in site 2 (a Bruguiera gymnorrhiza + Kandelia candel-dominated middle tidal stand). SOC δ13C values at both mangrove sites ranged from -29.4% to −26.0%. SOC δ13C was enriched with depth at 20–50 cm at site 1, which possibly resulted from preferential microbial decomposition. SOC δ13C at site 2 experienced frequent tidal flushing, and presented relatively stable values with depth. A bomb-14C-based SOC turnover model indicated that turnover times of SOC at 20–50 cm at site 1 were 4.44–26.04 yr. Modern C input from abundant roots might account for the very short SOC turnover times at these subsurface layers. As a result, our study suggested that tidal processes had a great influence on SOC storage and turnover in mangrove forests.

OxCal is a widely used software package for the calibration of radiocarbon dates and the statistical analysis of 14C and other chronological information. The program aims to make statistical methods easily available to researchers and students working in a range of different disciplines. This paper will look at the recent and planned developments of the package. The recent additions to the statistical methods are primarily aimed at providing more robust models, in particular through model averaging for deposition models and through different multiphase models. The paper will look at how these new models have been implemented and explore the implications for researchers who might benefit from their use. In addition, a new approach to the evaluation of marine reservoir offsets will be presented. As the quantity and complexity of chronological data increase, it is also important to have efficient methods for the visualization of such extensive data sets and methods for the presentation of spatial and geographical data embedded within planned future versions of OxCal will also be discussed.

Bayesian methods have been widely used to address the Iron Age chronological debate in Israel, which has implications for the entire eastern Mediterranean Iron Age chronology. However, a consensus has not been reached. This is largely because radiocarbon dates of materials in this period lie on an oscillation in the calibration curve. This study focuses on the modeling of 14C dates from the Iron I and Iron II periods, discusses the underlying assumptions and limitations of existing Bayesian chronologies, and proposes the use of a more appropriate model that allows for the phase transitions not being instantaneous. The new trapezoidal model sheds light on the probable duration of the transitions between the Iron Age phases.

In April 2001, immediately after bottom water renewal in the Japan/East Sea, 7 vertical profiles of radiocarbon were obtained from the area, including the Japan Basin and the Tsushima/Ulleung Basin. The bottom water Δ14C of the Tsushima/Ulleung Basin increased by 24% during 1979–2001 and was 10–15% higher than the values reported for the Japan Basin and Yamato Basin during 1995–2002. Within the depth interval 800–2000 m, Δ14C values at the southernmost station in the Japan Basin were much higher than at other stations, with the maximum difference in Δ14C values being more than 50%. Based on a combination of physical observations with analysis of the Δ14C data, we concluded that the bottom water, which was formed by the sinking of surface water off Vladivostok, Russia, in late January-early February of 2001, had been widely distributed to depths below 2000 m within the southernmost Japan Basin in a timespan shorter than 2 months. However, there was no evidence that the water had been transported into the Tsushima/Ulleung Basin during the same time interval.

Reconstructions arc presented of past growth rates of 10 Acacia tortilis trees, 5 growing at an arid site (Gebeit, Sudan) and 5 at a hyperarid site (Wadi Nuqrus, Egypt). The reconstructions were made using a free-shape age-depth model based on a series of 14C dates obtained on samples taken along the wood cores retrieved from the trunks of the trees (78 dates in total). In spite of the large difference in annual precipitation between the 2 sites, the range of ages of the trees (60–350 yr) and the variability in their growth rates are quite similar across both sites, whereas within-site growth rates are quite different even for closely spaced individuals. However, the pattern of growth rates of Acacias from the hyperarid Wadi Nuqrus indicates 2 periods of different aridity (the less arid AD 1650–1780 and more arid AD 1780–1930), while at Gebeit no such pattern has been detected.