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Ice cores and snow pits of the cryosphere contain particles that detail the history of past atmospheric air compositions. Some of these particles result from combustion processes and have undergone long-range transport to arrive in the Arctic. Recent research has focused on the separation of particulate matter from ice and snow, as well as the subsequent analysis of the separated particles for 14C with accelerator mass spectrometry (AMS) and for individual particle compositions with laser microprobe mass analysis (LAMMA). The very low particulate concentrations in Arctic samples make these measurements a challenge. The first task is to separate the particles from the ice core. Two major options exist to accomplish this separation. One option is to melt the ice and then filter the meltwater. A second option is to sublimate the ice core directly, depositing the particles onto a surface. This work demonstrates that greater control is obtained through sublimation. A suite of analytical methods has been used for the measurement of the carbon in snow and ice. Total carbon was analyzed with a carbon/nitrogen/hydrogen (CHN) analyzer. AMS was used for the determination of carbon isotopes. Since source identification of the carbonaceous particles is of primary importance here, the use of LAMMA was incorporated to link individual particle molecular-structural patterns to the same group of particles that were measured by the other techniques. Prior to this study, neither AMS nor LAMMA had been applied to particles contained in snow. This paper discusses the development and limitations of the methodology required to make these measurements.
Radiocarbon determinations have been obtained on γ-carboxyglutamic acid [Gla] and α-carboxyglycine (aminomalonate) [Am] as well as acid- and base-hydrolyzed total amino acids isolated from a series of fossil bones. As far as we are aware, Am has not been reported previously in fossil bone and neither Gla nor Am 14C values have been measured previously. Interest in Gla, an amino acid found in the non-collagen proteins osteocalcin and matrix Gla-protein (MGP), proceeds from the suggestion that it may be preferentially retained and more resistant to diagenetic contamination affecting 14C values in bones exhibiting low and trace amounts of collagen. Our data do not support these suggestions. The suite of bones examined showed a general tendency for total amino acid and Gla concentrations to decrease in concert. Even for bones retaining significant amounts of collagen, Gla (and Am extracts) can yield 14C values discordant with their expected age and with 14C values obtained on total amino-acid fractions isolated from the same bone sample.
The object of the study was to assess the effects of a range of pretreatment/extraction schemes on the yields of humic acid and humin obtained from peat and the subsequent radiocarbon ages. We analyzed peat from Flókadalur in northern Iceland, collecting material from a profile containing seven visible tephra horizons in the upper 3 m, whose form and extent indicated little disturbance to the section over the last 4000 yr. The results of a range of pretreatments demonstrated that time rather than the strength of alkali is the more important factor governing the extraction of humic acid. An increase in alkali molarity did not correspond to any systematic increase in yield, whereas an increase in time did, implying that the extraction is kinetically controlled. We found no evidence of variability in 14C age due to pretreatment scheme or between different geochemical fractions of the peat. Further implications from this study are that bog stability and ecological simplicity produce a favorable environment for 14C dating.
We have developed a technique using a single apparatus to recover the inorganic and organic carbon from a small (few milligrams) aliquot of dried marine material for radiocarbon analysis. The main advantages of using a single apparatus are: 1) less sample is required, 2) decreased handling reduces contamination, and 3) less time and materials are used. Blank values of ∼5 μg and 19–44 μg are obtained for the inorganic and organic carbon extractions, respectively. δ14C results from sinking particulate organic and inorganic carbon are presented for samples collected in deep-sea sediment traps deployed for 10–30 day periods at 650 and 100 m above bottom (mab) in the northeast Pacific Ocean.
Chemical and isotopic analyses have been made of pigment samples from two separate rock art sites in Argentina. The purpose of the study has been to establish the feasibility of extracting carbonaceous material from the samples which will permit reliable radiocarbon dates for the time of painting. The two sites, Catamarca and Rio Negro, present quite different problems. Most of the paper is concerned with Catamarca, and here we have shown that the paint pigments contain very little or no organic binder; but they do contain calcium oxalate derived from local cacti, and calcium carbonate derived probably from local plant ash. We describe a method to purify carbon extracted from the calcium oxalate, and present the dates obtained on both components. We show that, though rare, natural deposits containing both calcium oxalate and calcite do occur, but that they are very distinct in both 13C and 14C compositions; and we argue that they are very unlikely to contaminate the pigments to such an extent that the 14C dates are altered. For the Rio Negro site we show that the ground for the paint pigments contains carbon derived from fires burnt inside the cave, and discuss how analytical methods provide information to develop a strategy for extracting material, from both ground and pigment, for more reliable dating.
In a separate study, we conducted a series of high-precision radiocarbon measurements using wood from Britain and New Zealand to investigate interhemispheric offsets and possible temporal variations. To minimize variability associated with different species, the pretreatment of the oak (Quercus patraea) and cedar (Librocedrus bidwilli) was to α-cellulose for both. This study investigates the thoroughness of a range of pretreatment processes by the stable isotope analysis of the products.
Pretreatment of organic samples can be achieved by removal of contaminants, or, alternatively, by isolation of sample-specific components. We discuss the molecular aspects of these two pretreatment types, together with an assessment of their effectiveness in relation to sample type. The main division in sample type is the one between carbohydrates and proteins, leading to opposite chemical strategies for the two sample categories. Recommendations for routine 14C chemistry of organic samples also include the standardization of quality screening procedures using chemical, stable isotope and elemental data that can be collected routinely during the pretreatment of each sample.
One explanation for the radiocarbon dates on the Shroud of Turin being younger than the time of Christ is that the heat from a fire, which scorched a portion of the Shroud, may have affected the 14C content (dates) on the shroud by affecting molecular exchange between the fabric and atmospheric carbon. This report describes a laboratory test on the susceptibility of cellulose, in the form of cotton, to incorporate carbon from CO2 while it is heated in a closed tube with carbon dioxide until the cotton considerably darkened. To maximize the effect of this hypothetical process, we simulated the shroud material with cotton that had a 14C level of 0.55 modern (55 pMC, equivalent to 4800 yr), and the atmosphere with pure CO2, which had a 14C level of 1.3 modern (130 pMC). No measurable 14C transferred from the gas phase to the solid phase. The implication of this test is that scorching is an unlikely mechanism to affect the apparent age of cellulose-like material.
To test the hypothesis that cellulose in linen can be carboxylated at high temperatures in the presence of CO2, water and silver, we heated two aliquots of cellulose extracted from old wood in glass ampoules, adding Ag powder to one to test its potential action as a catalyst for the carboxylation reaction. AMS measurement of the heated aliquots showed no statistically significant difference in 14C content from the “uncarboxylated” cellulose. We conclude that carboxylation is not a systematic source of error in the dating of cellulose-containing materials such as the linen in the Shroud of Turin.
Techniques for making precise and accurate radiocarbon accelerator mass spectrometry (AMS) measurements on samples containing less than a few hundred micrograms of carbon are being developed at the NOSAMS facility. A detailed examination of all aspects of the sample preparation and data analysis process shows encouraging results. Small quantities of CO2 are reduced to graphite over cobalt catalyst at an optimal temperature of 605°. Measured 14C/12C ratios of the resulting targets are affected by machine-induced isotopic fractionation, which appears directly related to the decrease in ion current generated by the smaller sample sizes. It is possible to compensate effectively for this fractionation by measuring samples relative to small standards of identical size. Examination of the various potential sources of background 14C contamination indicates that the sample combustion process is the largest contributor, adding ca. 1 μg of carbon with a less-than-modern 14C concentration.
The accepted state-of-the-art 14C dating method relies on calibration curves to determine initial 14C levels in a sample. The paper reconsiders the basis of 14C dating and offers a possible alternative that eliminates the need to employ calibration curves. The idea is to measure the level of radiogenic nitrogen atoms retained in the sample molecules after 14C β-decay. The practicality of this alternative method still has to be proven.
B. 14C Detection Medium: Preparation and Purification
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.
For very small samples, it is difficult to prepare graphitic targets that will yield a useful and steady sputtered ion beam. Working with materials separated by preparative capillary gas chromatography, we have succeeded with amounts as small as 20 μg C. This seems to be a practical limit, as it involves 1) multiple chromatographic runs with trapping of effluent fractions, 2) recovery and combustion of the fractions, 3) graphitization and 4) compression of the resultant graphite/cobalt matrix into a good sputter target. Through such slow and intricate work, radiocarbon ages of lignin derivatives and hydrocarbons from coastal sediments have been determined. If this could be accomplished as an “online” measurement by flowing the analytes directly into a microwave gas ion source, with a carrier gas, then the number of processing steps could be minimized. Such a system would be useful not just for chromatographic effluents, but for any gaseous material, such as CO2 produced from carbonates. We describe tests using such an ion source.
The carbon concentration in CuO and iron was determined by isolating C. The values were in agreement with results reported in other studies. Contaminating carbon from CuO and Fe was transformed to AMS targets and measured for 14C. C-traces in CuO were shown to be the major contribution to the 14C sample processing blank. In addition, there is a significant variability in the 14C content of CuO observed between different production batches. The combined contamination potential of CuO and Fe was found to be 4.47–8.92 μg recent carbon, whereas the more realistic estimate for AMS-target preparation conditions ranged between 1.63 and 3.24 μg recent carbon, depending on the 14C level in CuO.
Does radioactive decay follow the Poisson distribution?—a fundamental question, to which the theoretical answer seems to be, Yes. On the practical side, the answer to this question impacts the best achievable precision in well-controlled counting experiments. There have been some noteworthy experimental tests of the Poisson assumption, using systems carefully designed for the analysis of individual pulses from stable radioactive sources; thus far, experiment supports theory. For low-level counting, the nature of the background distribution can be of profound practical importance, especially for very long counting experiments where validation by an adequate number of full replicates may be impracticable. One is tempted in such cases to assume that the variance is equal to the mean, in order to estimate the measurement uncertainty. Background radiation, however, has multiple components, only some of which are governed by the laws of radioactive decay.
A specially designed low-level gas counting system at NIST for interactive, retrospective individual pulse shape and time series analysis makes possible the investigation of the empirical distribution function of the background radiation, in a manner similar to the previous empirical distribution studies of radioactive decay. Benefits of individual pulse analysis are that there is no information loss due to averaging and that two independent tests of the Poisson hypothesis can be performed using data from a single, extended measurement period without the need for replication; namely, tests of the distribution of arrival times, expected to be uniform, and the distribution of inter-arrival times, expected to be exponential. For low-level counting the second test has a very interesting and very informative complement: the distribution of coincidence-anticoincidence inter-arrival times.
Key outcomes from the study were that: 1) nonstationarity in the mean background rate over extended periods of time could be compensated by an on-line paired counter technique, which is far preferable to the questionable practice of using an “error-multiplier” that presumes the wandering (nonstationary) background to be random; and 2) individual empirical pulse distributions differed from the ideal GM and Poisson processes by exhibiting giant pulses, a continuum of small pulses, afterpulses, and in certain circumstances bursts of pulses and transient relaxation processes. The afterpulses constituted ca. 8% of the anticoincidence background events, yet they escaped detection by the conventional distributional tests.
The application of traditional gas or liquid scintillation counting (LSC) is necessary for assessing radionuclide activity in countries without operating accelerator mass spectrometry (AMS) facilities. A simple and relatively inexpensive system of mini gas counters for measurement of radiocarbon in archaeological and environmental samples has been set up recently in the Kraków laboratory (Department of Environmental Physics, University of Mining and Metallurgy). The system is composed of a gas purification and counter filling line, three identical 15-mL copper/quartz counters, active and passive shielding, and an electronic unit with data acquisition. One counter measures 22 mg of carbon as CO2 with efficiency >95% at a background reduced to 0.044 cpm by a NaJ(Tl) guard counter and lead shield. The detection limit (1 σ) for a two-week measurement of 48 mL of CO2 is 0.52 pMC. The corresponding counting error of a 100 pMC environmental sample is 1.3 pMC for 22 mgC (one counter) and 0.75 pMC for 66 mgC (three counters filled with the same sample).