Fifteen years of research on accelerator mass spectrometry (AMS) radiocarbon dating of non-hydraulic mortar has now led to the establishment of a chronology for the medieval stone churches of the Åland Islands (Finland), where no contemporary written records could shed light on the first building phases. In contrast to other material for dating, well-preserved mortar is abundantly available from every building stage.

We have gathered experience from AMS dating of 150 Åland mortar samples. Approximately half of them have age control from dendrochronology or from 14C analysis of wooden fragments in direct contact with the mortar. Of the samples with age control, 95% of the results agree with the age of the wood. The age control from dendrochronology, petrologic microscopy, chemical testing of the mortars, and mathematical modeling of their behavior during dissolution in acid have helped us to define criteria of reliability to interpret the 14C results when mortar dating is the only possibility to constrain the buildings in time. With these criteria, 80% of all samples reached conclusive results, and we have thus far been able to establish the chronology of 12 out of the 14 churches and chapels, while 2 still require complementary analyses.

The shape of a distribution of calibrated 14C dates displays spurious peaks and troughs, brought about by changes in the slope of the calibration curve interacting with the spreading effect of the stochastic distribution of counting errors. The distortion results in a positive correlation between the numbers of dates per calendar year and the slopes of the calibration curves, for assemblages of archaeological dates from such widely separated areas as British Columbia, South Australia and New Zealand. The distortion also increases the possibility of date reversals, and increases the overall spread of calibrated 14C dates. After taking into account this systematic distortion and inbuilt age of charcoal and wood samples, we estimate dates for the initial settlement and first appearance of fortifications, and infer a likely trend of population growth for prehistoric New Zealand.

Tree rings from a section of Prumnopitys taxifolia (matai) covering the period ad 1335–1745 have been radiocarbon dated and used to generate a 14C calibration curve for southern hemisphere wood. Comparison of this curve with calibration data for northern hemisphere wood does not show a systematic difference between 14C ages measured in the northern and southern hemispheres. A floating chronology covering 270 yr and terminating at the last Taupo (New Zealand) eruption, derived from a sequence of 10-yr samples of tree rings from Phyllocladus trichomanoides (celery pine, or tanekaha), is also consistent with the absence of a systematic north-south difference, and together with the matai data, fixes the date of the Taupo eruption at ad 232 ± 15.

The University of Waikato, Hamilton, New Zealand and The Queen's University of Belfast, Northern Ireland radiocarbon dating laboratories have undertaken a series of high-precision measurements on decadal samples of dendrochronologically dated oak (Quercus petraea) from Great Britain and cedar (Libocedrus bidwillii) and silver pine (Lagarostrobos colensoi) from New Zealand. The results show an average hemispheric offset over the 900 yr of measurement of 40 ± 13 yr. This value is not constant but varies with a periodicity of about 130 yr. The Northern Hemisphere measurements confirm the validity of the Pearson et al. (1986) calibration dataset.

We have developed accelerator mass spectrometry (AMS) measurement techniques for ultra small-size samples ranging from 0.01 to 0.10 mg C with a new type of MC-SNICS ion source system. We can generate 4 times higher ion beam current intensity for ultra-small samples by optimization of graphite position in the target holder with the new ionizer geometry. CO2 gas graphitized in the newly developed vacuum line is pressed to a depth of 1.5 mm from the front of the target holder. This is much deeper than the previous position at 0.35 mm depth. We measured 12C4+ beam currents generated by small standards and ion beam currents (15–30 μA) from the targets in optimized position, lasting 20 min for 0.01 mg C and 65 min for 0.10 mg C. We observed that the measured 14C/12C ratios are unaffected by the difference of ion beam currents ranging from 5 to 30 μA, enabling measurement of ultra-small samples with high precision. Examination of the background samples revealed 1.1 μg of modern and 1 μg of dead carbon contaminations during target graphite preparation. We make corrections for the contamination from both the modern and background components. Reduction of the contamination is necessary for conducting more accurate measurement.

At the Leibniz radiocarbon lab, art and archaeological objects, often chemically conserved and thus potentially contaminated with respect to their 14C content, are treated using a computer-controlled “Soxhlet”-type series extractor. This device uses a continuous procedure of boiling and condensation of different solvents for extraction and vacuum filtration under constant process conditions. An elutrope sequence of five solvents that dissolve most customary conservation chemicals was selected. A study of these different contaminants applied to reference wood samples with subsequent accelerator mass spectrometry (AMS) measurements demonstrates that their effective removal is dependent on the use of adequate solvents. For many contaminants (e.g. wood glue, methyl cellulose, Klucel®, sugar, and polyethylene glycol), routine acid-alkali-acid (AAA) treatment already yields satisfactory results, whereas for Caparol® and beeswax a relatively “mild” treatment with acetone, methanol, water, and subsequent standard AAA extraction is sufficient. Complete removal of rubber glue, epoxy resin, and paraffin can only be accomplished with our full set of solvents. The latter procedure is also appropriate when no or only incomplete information about the type of conservation material is available. For epoxy resin the contamination appears to be enriched in the alkali residue, and the easily soluble “humic acid” fraction, even after standard AAA treatment, gives satisfactory results. Two case studies on the application of the extraction procedures are presented.

A 6-year and a 2-year record of 14C measurements of soil CO2 in two soils are presented and discussed. The annual 14C variation of soil CO2 is controlled by the seasonally varying contribution of root respiration and of microbial decomposition of organic matter producing soil CO2. The Δ14C soil CO2 difference between summer and winter is ca 50‰ in a soil where turnover of organic matter is fast (τ = 2.5a) and ca 100‰ in a soil of slow turnover (τ = 60a). A simple model describing the movement and turnover of organic matter is derived, giving the depth distributions of organic carbon and of 14C. The model needs a subdivision of the carbon reservoir into at least two reservoirs with residence times of τ1 = la and τ2 = 100a, respectively, and with a vertical transfer velocity in the order of 0.6mm/a.

A theoretical approach towards predicting the carbon isotope composition of carbonate cave deposits is presented. The proposed model simulates time variations of both the chemical and isotopic composition of the carbonate solution and deposited calcite in the course of CaCO3 precipitation. Two phases of the precipitation process are distinguished and treated separately: initial outgassing of the solution until a certain degree of supersaturation of CO3 2- ions is reached and subsequent precipitation of CaCO3 related to further outgassing. Precipitation rates of CaCO3 predicted by the model agree fairly well with literature data. The model predicts δ13C values of deposited calcite within a range of ca −16 to +3‰ depending on temperature, chemical and isotope parameters of the initial solution and actual degree of the precipitation process.

Twenty-two radiocarbon activity measurements were made by accelerator mass spectrometry (AMS) on 2 Holocene stalagmites from Belgium (Han-stm1b) and from southwest France (Vil-stm1b). Sixteen thermal ionization mass spectrometric (TIMS) U/Th measurements were performed parallel to AMS analyses. The past dead carbon proportion (dcp) due to limestone dissolution and old soil organic matter (SOM) degradation is calculated with U/Th ages, measured calcite 14C activity and atmospheric 14C activity from the dendrochronological calibration curves. Results show that the dcp is different for the 2 stalagmites: between 10,800 and 4780 yr from present dcp=17.5% (σ=2.4; n=10) for Han-stm1b and dcp=9.4% (σ=1.6; n=6) between 3070 and 520 yr for Vil-stm1b. Despite a broad stability of the dcp during the time ranges covered by each sample, a slight dcp increase of about 5.0% is observed in the Han-stm1b sample between 8500 and 5200 yr. This change is synchronous with a calcite δ13C increase, which could be due to variation in limestone dissolution processes possibly linked with a vegetation change. The dcp and δ13C of the 2 studied samples are compared with 5 other modern stalagmites from Europe. Results show that several factors intervene, among them: the vegetation type, and the soil saturation leading to variable dissolution process systems (open/closed). The good correlation (R2=0.98) between the U/Th ages and the calibrated 14C ages corrected with a constant dcp validates the 14C method. However, the dcp error leads to large 14C age errors (i.e. 250–500 yr for the period studied), which is an obstacle for both a high-resolution chronology and the improvement of the 14C calibration curves, at least for the Holocene.

The modern water (both pre- and post-atmospheric nuclear testing) of most lakes has an anomalously old apparent radiocarbon age due to what is commonly referred to as the “reservoir effect.” In contrast to marine settings, this 14C-offset phenomenon is primarily caused by pre-aged carbon discharged to lakes by rivers and/or groundwater. In this paper, a 2-component box model based on the principle of 14C mass balance in lake water and in the early diagenesis zone was formulated to address the relative importance of terrestrial inputs, autochthonous production, and biogeochemical processes in the 14C reservoir of a lacustrine system. The model was tested using observed data from Lake Qinghai, the largest inland water body in China. Our inverse modeling using Markov chain Monte Carlo (MCMC) techniques yields best estimates of the δ14C of DIC in river (∼118% modern) and groundwater (∼76% modern), as well as the δ14C of DOC in river water (∼70% modern) during the post-bomb era. Assuming that these parameters remain constant over time, our modeling indicates that both the DIC and DOC pool of this lake have reservoir ages of about 1500 yr for the pre-bomb era, generally consistent with estimates obtained by extrapolation of the age-depth models of 2 sediment cores to the sediment surface.

Bones that have undergone burning at high temperatures (i.e. cremation) no longer contain organic carbon. Lanting et al. (2001) proposed that some of the original structural carbonate, formed during bioapatite formation, survives. This view is based on paired radiocarbon dating of cremated bone apatite and contemporary charcoal. However, stable carbon isotope composition of carbonate in cremated bones is consistently light compared to the untreated material and is closer to the δ13C values seen in C3 plant material. This raises the question of the origin of carbonate carbon in cremated bone apatite. That is, does the isotope signal reflect an exchange of carbon with the local cremation atmosphere and thus with carbon from the burning fuel, or is it caused by isotopic fractionation during cremation?

To study the changes in carbon isotopes (14C, 13C) of bone apatite during burning up to 800 °, a modern bovine bone was exposed to a continuous flow of an artificial atmosphere (basically a high-purity O2/N2 gas mix) under defined conditions (temperature, gas composition). To simulate the influence of the fuel carbon available under real cremation conditions, fossil CO2 was added at different concentrations. To yield cremated bone apatite properties similar to archaeological cremated bones, in terms of crystallographic criteria, water vapor had to be added to the atmosphere in the oven. Infrared vibrational spectra reveal large increases in crystal size and loss of carbonate upon cremation. The isotope results indicate an effective carbon exchange between bone apatite carbonate and CO2 in the combustion gases depending on temperature and CO2 concentration. 14C dates on archaeological cremated bone apatite may thus suffer from an old-wood effect. Paired 13C and 14C values indicate that in addition to this exchange, isotope fractionation between CO2 and carbonate, and admixture of carbon from other sources such as possibly collagen or atmospheric CO2, may play a role in determining the final composition of the apatite carbonate.

After routine accelerator mass spectrometry (AMS) radiocarbon dating had been established at the Leibniz-Labor with the completion of systems for CO2 production, graphitization, and target making, a systematic investigation was conducted to find the sources of 14C concentrations observed in background materials. We quantified the contributions of the AMS-system, the reduction, CO2 production from carbonate, carbonate contamination, and combustion. Carbonate contamination appears to be the dominating factor. Improvements in the pretreatment of foraminifer carbonate have led to the elimination of most of this contamination.

A method for collecting an isotopically representative sample of CO2 from an air stream using a zeolite molecular sieve is described. A robust sampling system was designed and developed for use in the field that includes reusable molecular sieve cartridges, a lightweight pump, and a portable infrared gas analyzer (IRGA). The system was tested using international isotopic standards (13C and 14C). Results showed that CO2 could be trapped and recovered for both δ13C and 14C analysis by isotope ratio mass spectrometry (IRMS) and accelerator mass spectrometry (AMS), respectively, without any contamination, fractionation, or memory effect. The system was primarily designed for use in carbon isotope studies of ecosystem respiration, with potential for use in other applications that require CO2 collection from air.

We have compared accelerator mass spectrometry (AMS) radiocarbon results on wood samples at or near the limit of 14C dating, pretreated with a standard acid-base-acid (ABA) protocol, with those obtained from cellulose prepared from the same samples by several modifications of the Jayme-Wise cellulose extraction method (Green 1963). These tests were carried out to determine the most efficient way to ensure low backgrounds in 14C measurements of well-preserved ancient wood samples.

Data on depth distribution and 14C content of soil organic carbon, and on soil CO2 production in forest ecosystems are presented and discussed. Downward movement and turnover of soil organic matter is estimated from a box chain model. The downward transfer velocity of soil organic material depends on the litter material composition and on the annual rate of microbial decomposition. Depth distribution of 210Pb and 137Cs was measured. The identical transfer velocity of 210Pb and soil organic material suggests that lead transport is due to movement of the organic material itself. Lead in organic-rich soils obviously is bound rather tightly to the organic carrier by ion exchange or organic complexing. 137Cs migration depends on the turnover and downward movement of soil organic material. Results suggest that cesium is not transported only by the downward movement of solid organic matter, but, due to chemical exchange between the organic and hydrous phases, travels faster than organic matter.

Chemical and structural similarities between poorly preserved charcoal and its contaminants, as well as low radiocarbon concentrations in old samples, complicate 14C age determinations. Here, we characterize 4 fossil charcoal samples from the late Middle Paleolithic and early Upper Paleolithic strata of Kebara Cave, Israel, with respect to the structural and chemical changes that occur when they are subjected to the acid-base-acid (ABA) treatment. Differential thermal analysis and TEM show that acid treatment disrupts the structure, whereas alkali treatment results in the reformation of molecular aggregates. The major changes are ascribed to the formation of salt bridges at high pH and the disruption of the graphite-like crystallites at low pH. Weight losses during the treatments are consistently greater for older samples, implying that they are less well preserved. Based on the changes observed in vitro due to pH fluctuations, various methods for removing contamination, as well as a mechanism for preferential preservation of charcoal in nature, are proposed.

New results of radiocarbon dating of ca 100 decadal bristlecone pine samples from 6554 BC to 6084 BC and from 5820 to 5350 BC are presented. Using 3 new 2.5L counters filled to ca 3atm with carbon dioxide, high-precision dating has been performed by this laboratory for more than two years. Demonstration of the precision and accuracy of these counters is presented using ±2‰ measurements from the Spörer minimum period. For the older samples, ±3‰ measurements were made using ca 12-day counting times. Results are presented both as C age bp vs dendro-year BC, particularly for calibration purposes, and as Δ14C vs time.

To create a reliable radiocarbon calibration curve, one needs not only high-quality data but also a robust statistical methodology. The unique aspects of much of the calibration data provide considerable modeling challenges and require a made-to-measure approach to curve construction that accurately represents and adapts to these individualities, bringing the data together into a single curve. For IntCal20, the statistical methodology has undergone a complete redesign, from the random walk used in IntCal04, IntCal09 and IntCal13, to an approach based upon Bayesian splines with errors-in-variables. The new spline approach is still fitted using Markov Chain Monte Carlo (MCMC) but offers considerable advantages over the previous random walk, including faster and more reliable curve construction together with greatly increased flexibility and detail in modeling choices. This paper describes the new methodology together with the tailored modifications required to integrate the various datasets. For an end-user, the key changes include the recognition and estimation of potential over-dispersion in 14C determinations, and its consequences on calibration which we address through the provision of predictive intervals on the curve; improvements to the modeling of rapid 14C excursions and reservoir ages/dead carbon fractions; and modifications made to, hopefully, ensure better mixing of the MCMC which consequently increase confidence in the estimated curve.

Radiocarbon dating at the Arizona accelerator facility has improved substantially in the last three years. Since starting to use graphite targets (see Jull et al, 1986), we have been able to obtain routinely a precision of ca ± 1% (ca 80 yr) for relatively modern material. Our routine technique of tuning and operating the tandem accelerator mass spectrometer (TAMS) and our method of calculating 14C results are discussed in detail. Data on activity ratios of oxalic acid-II/oxalic-I are presented. Examples of the wide variety of projects on which we have collaborated are given. Brief discussions of three such projects are presented for our colleagues who were unable to attend this conference: an Arizona Indian archaeologic project, a study of megafaunal extinctions, and a study of the growth of phosphorite nodules on the sea floor off the Peruvian coast.

During the laboratory pretreatment of samples for radiocarbon dating, small amounts of carbon may be added to a sample. Contamination can be incorporated at any stage: during chemical pretreatment, combustion to CO2, graphitization, or accelerator mass spectrometry (AMS) measurement. Such carbon contamination is often modern in age, and so can have an especially severe effect on samples older than ∼25 ka BP. During the extraction of collagen from bone using the ultrafiltration protocol at the Oxford Radiocarbon Accelerator Unit (ORAU), small amounts of young carbon are added to the sample. Currently, this contamination is poorly characterized when less than 10 mg of collagen is extracted from a bone. Demand to date small collagen samples with 14C concentrations that approach the detection limit of AMS measurement has increased recently with the growing interest in, for example, directly dating Neanderthal remains and Upper Paleolithic bone artifacts. This paper aims to reduce the minimum collagen sample size required to produce a reliable date from 10 to 5 mg by re-examining the combustion background and subsequently the pretreatment background for bone. The average of 136 measurements of directly combusted nylon suggests that 0.0007 ± 0.001 mg of modern carbon is added to each sample, although the distribution is positively skewed. Regression analysis of the measurements of 52 collagen samples extracted from a bone of background age results in a background of just less than 50,000 BP for bone treated at ORAU.