Guaciara M. Santos

The Keck Carbon Cycle AMS laboratory, University of California, Irvine: Initial operation and a background surprise

A new radiocarbon accelerator mass spectrometry (AMS) laboratory for carbon cycle studies has been established at the University of California, Irvine. The 0.5MV AMS system was installed in mid-2002 and has operated routinely since October of that year. This paper briefly describes the spectrometer and summarizes lessons learned during the first year of operation. In the process of setting up the system, we identified and largely suppressed a previously unreported (super 14) C AMS background: charge exchange tails from (super 14) N beams derived from nitrogen-containing molecular ions produced near the entrance of the accelerator.

Magnesium Perchlorate as an Alternative Water Trap in AMS Graphite Sample Preparation: A Report on Sample Preparation at KCCAMS at the University of California, Irvine

We present a brief discussion of sample preparation procedures at the Keck Carbon Cycle Accelerator Mass Spectrometer (KCCAMS), University of California, Irvine, and a systematic investigation of the use of Mg(ClO (sub 4) ) (sub 2) as an absorptive water trap, replacing the standard dry ice/ethanol cold finger in graphite sample preparation. We compare high-precision AMS measurement results from oxalic acid I and USGS coal samples using Mg(ClO (sub 4) ) (sub 2) under different conditions. The results obtained were also compared with those achieved using the conventional water removal technique. Final results demonstrate that the use of Mg(ClO (sub 4) ) (sub 2) as an alternative water trap seems very convenient and reliable, provided the Mg(ClO (sub 4) ) (sub 2) is replaced frequently.

Analysis of plutonium isotopes in marine samples by radiometric, ICP-MS and AMS techniques

IAEA reference materials (radionuclides in the marine environment) collected in areas affected by nuclear reprocessing plants and nuclear weapons tests have been analysed by semiconductor alpha-spectrometry (SAS), liquid scintillation spectrometry (LSS) and mass spectrometric techniques (high resolution ICP-MS and AMS) with the aim of developing analytical procedures and to study the geochemical behavior of plutonium in the marine environment. The Pu results obtained by SAS, ICP-MS and AMS were in reasonably good agreement (R2 = 0.99). The mean atom ratios of 240Pu/239Pu in IAEA reference materials, IAEA-134, 135 and 381 were (0.212±0.010), (0.211±0.004) and (0.242±0.004), respectively. IAEA-384 (Fangataufa Lagoon Sediment) gave a 240Pu/239Pu mean atom ratio of 0.051±0.001. The results of 241Pu obtained by ICP-MS and LSS also show reasonable agreement (R2 = 0.91). Pu isotopic signatures were useful in tracing Pu origin and in interpreting biogeochemical processes involving Pu in the marine environment.

AMS 14C Sample Preparation at the KCCAMS/UCI Facility: Status Report and Performance of Small Samples

We present an overview of accelerator mass spectrometry (AMS) radiocarbon sample preparation and measurements, describing the technical upgrades that now allow us to routinely obtain 0.2-0.3% precision for 1-mg carbon samples. A precision of ~1% on samples with 100 g of carbon can also be achieved. We have also developed graphitization techniques and AMS procedures for ultra-small samples (down to 0.002 mg of carbon). Detailed time series are presented for large and small aliquots of standards such as NIST OX-I and OX-II; FIRI-C and -D; IAEA-C6, -C7 and -C8; and 14C-free samples.

A new look at old carbon in active margin sediments

Recent studies suggest that as much as half of the organic carbon (OC) undergoing burial in the sediments of tectonically active continental margins may be the product of fossil shale weathering. These estimates rely on the assumption that vascular plant detritus spends little time sequestered in intermediate reservoirs such as soils, freshwater sediments, and river deltas, and thus only minimally contributes to the extraneously old 14C ages of total organic matter often observed on adjacent shelves. Here we test this paradigm by measuring the Δ14C and δ13C values of individual higher plant wax fatty acids as well as the δ13C values of extractable alkanes isolated from the Eel River margin (California). The isotopic signatures of the long chain fatty acids indicate that vascular plant material has been sequestered for several thousand years before deposition. A coupled molecular isotope mass balance used to reassess the sedimentary carbon budget indicates that the fossil component is less abundant than previously estimated, with pre-aged terrestrial material instead composing a considerable proportion of all organic matter. If these findings are characteristic of other continental margins proximal to small mountainous rivers, then the importance of petrogenic OC burial in marine sediments may need to be reevaluated.

Blank Assessment for Ultra-Small Radiocarbon Samples: Chemical Extraction and Separation Versus AMS

The Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS/UCI) has developed protocols for analyzing radiocarbon in samples as small as ~0.001 mg of carbon (C). Mass-balance background corrections for modern and 14C-dead carbon contamination (MC and DC, respectively) can be assessed by measuring 14C-free and modern standards, respectively, using the same sample processing techniques that are applied to unknown samples. This approach can be validated by measuring secondary standards of similar size and 14C composition to the unknown samples. Ordinary sample processing (such as ABA or leaching pretreatment, combustion/graphitization, and handling) introduces MC contamination of ~0.6 ± 0.3 μg C, while DC is ~0.3 ± 0.15 μg C. Today, the laboratory routinely analyzes graphite samples as small as 0.015 mg C for external submissions and =0.001 mg C for internal research activities with a precision of ~1% for ~0.010 mg C. However, when analyzing ultra-small samples isolated by a series of complex chemical and chromatographic methods (such as individual compounds), integrated procedural blanks may be far larger and more variable than those associated with combustion/graphitization alone. In some instances, the mass ratio of these blanks to the compounds of interest may be so high that the reported 14C results are meaningless. Thus, the abundance and variability of both MC and DC contamination encountered during ultra-small sample analysis must be carefully and thoroughly evaluated. Four case studies are presented to illustrate how extraction chemistry blanks are determined.

Ion Source Development at KCCAMS, University of California, Irvine

The Keck Carbon Cycle accelerator mass spectrometry facility at the University of California, Irvine, operates a National Electronics Corporation 40-sample MC-SNICS ion source. We describe modifications that have increased beam current output, improved reliability, and made the source easier to service.

The Phytolith 14C Puzzle: A Tale of Background Determinations and Accuracy Tests

Over the past decades, analysis of occluded carbon in phytoliths (opaline silica mineral bodies that form in and between plant cells) has become a workhorse of paleoclimate and archaeological studies. Since different plant types exhibit distinctive phytolith morphologies, their assemblages are used in identifying vegetation histories or food culture adaptations. A few direct radiocarbon AMS measurements of phytoliths have been carried out, but these measurements are difficult due to the low concentrations of phytoliths in some plant species, and the small amount of C per phytolith (<2%). In addition, no phytoliths samples of a known 14C age are available to verify measurement accuracy and precision, and to check sample prep- aration protocols. Background corrections are also difficult to address due to the lack of suitable material. In this work, we designed a procedure to quantify a suitable blank using SiO2 powder samples (close to the opal structure, and free of 14C). The full phytolith extraction showed high carbon contamination components: a) ~3 g of modern C and ~2 g of dead C. We also performed accuracy tests on large phytolith-occluded carbon samples extracted from soils and harvested plants. The unex- pected 14C ages in some of the results triggered further investigations of possible sources of carbon contamination.

Radiocarbon dating of the human occupation of Australia prior to 40 ka BP; successes and pitfalls.

Charcoal samples from ancient human occupation sites in Australia have been subjected to a rigorous pretreatment and stepped combustion regime in order to explore the possibility that these sites may be older than previous radiocarbon dating had suggested. In one case, the Devils Lair site in southwest Australia, the methodology has clearly removed vestiges of contamination by more modern carbon and has led to a revised radiocarbon chronology that provides evidence for human occupation of southwest Australia by at least 44 ka BP and probably by 46-47 ka BP. In contrast, charcoal from the Nauwalabila site has been so severely altered that insufficient of the original carbon remains for reliable (super 14) C dating. Finally, where the charcoal is well preserved, such as at the Carpenters Gap site, the new results provide reassurance that earlier (super 14) C results of approximately 40 ka BP are indeed true ages and are not simply at the limit of the (super 14) C technique.

The Keck Carbon Cycle AMS Laboratory, University of California, Irvine : status report

We present a status report of the accelerator mass spectrometry (AMS) facility at the University of California, Irvine, USA. Recent spectrometer upgrades and repairs are discussed. Modifications to preparation laboratory procedures designed to improve sample throughput efficiency while maintaining precision of 2-3‰ for 1-mg samples (Santos et al. 2007c) are presented.