• Robust Bayesian Analysis, an Attempt to Improve Bayesian Sequencing

      Weninger, Franz; Steier, Peter; Kutschera, Walter; Wild, Eva Maria (Department of Geosciences, The University of Arizona, 2010-01-01)
      Bayesian sequencing of radiocarbon dates deals with the problem that in most cases there does not exist an unambiguous way to define the so-called prior function, which represents information in addition to the result of the 14C measurements alone. However, a random choice of a particular prior function can lead to biased results. In this paper, "robust Bayesian analysis," which uses a whole set of prior functions, is introduced as a more reliable method. The most important aspects of the mathematical foundation and of the practical realization of the method are described. As a general result, robust Bayesian analysis leads to higher accuracy, but paid for with reduced precision. Our investigations indicate that it seems possible to establish robust analysis for practical applications.
    • Radiocarbon Dating of the Last Volcanic Eruptions of Ciomadul Volcano, Southeast Carpathians, Eastern-Central Europe

      Harangi, Sz; Molnár, M.; Vinkler, A. P.; Kiss, B.; Jull, A. J. T.; Leonard, A. G. (Department of Geosciences, The University of Arizona, 2010-01-01)
      This paper provides new accelerator mass spectrometry (AMS) radiocarbon age data for the last volcanic events in the Carpathian-Pannonian region of eastern-central Europe. The eruption ages were determined on charcoal fragments collected from pumiceous pyroclastic flow deposits at 2 localities of the Ciomadul Volcano. Two charcoal samples from the southeastern margin of the volcano (Bixad locality) set the date of the last volcanic eruption to 27,200 +/- 260 yr BP (29,500 +/- 260 cal BC). On the other hand, our data show that the Tusnad pyroclastic flow deposit, previously considered as representing the youngest volcanic rock of the region, erupted at ~39,000 yr BP (~41,300 cal BC). Thus, a period of dormancy more than 10,000 yr long might have elapsed between the 2 volcanic events. The different ages of the Tusnad and Bixad pyroclastic flow deposits are confirmed also by the geochemical data. The bulk pumices, groundmass glass, and the composition of the main mineral phases (plagioclase and amphibole) suggest eruption of slightly different magmas. Considering also the assumed long volcanic history (~600 ka) of the Ciomadul, these data suggest that further detailed studies are necessary on this seemingly inactive volcano in order to evaluate the possible renewal of volcanic activity in the future.
    • Radiocarbon and Stable Carbon Isotope Ratio Data from a 4.7-m-long Sediment Core of Lake Baikal (Southern Siberia, Russia)

      Nara, Fumiko Watanabe; Watanabe, Takahiro; Nakamura, Toshio; Kakegawa, Takeshi; Katamura, Fumitaka; Shichi, Koji; Takahara, Hikaru; Imai, Akio; Kawai, Takayoshi (Department of Geosciences, The University of Arizona, 2010-01-01)
      A sediment core (VER99G12; core length, 4.66 m) was taken from the Buguldeika Saddle of Lake Baikal in 1999. Radiocarbon measurements of total organic carbon (TOC) and pollen concentrate fractions from the VER99G12 core were performed by a Tandetron accelerator mass spectrometry (AMS) system (Model-4130, HVEE) at Nagoya University. The AMS 14C ages showed that the VER99G12 core spans the past ~30 cal ka BP (from the MIS 3 to present), and the average sedimentation rate of this core was calculated to be 13.6 cm/kyr based on the calibrated ages. This means that the time resolution of VER99G12 sediment samples in this study is better than ~70-80 yr/cm. Stable carbon isotope ratios of TOC (13CTOC) in the VER99G12 core varied widely from about 26.6 to 31.3 during the last glacial/post-glacial transition period (about 17-12 cal ka BP). Therefore, a rapid change in the carbon sources in Lake Baikal occurred in the last glacial/post-glacial transition period is concluded.
    • Pre-Bomb Marine Reservoir Variability in the Kimberley Region, Western Australia

      O'Connor, Sue; Ulm, Sean; Fallon, Stewart J.; Barham, Anthony; Loch, Ian (Department of Geosciences, The University of Arizona, 2010-01-01)
      New Delta-R values are presented for 10 known-age shells from the Kimberley region of northwest Australia. Previous estimates of Delta-R for the Kimberley region are based on only 6 individual shell specimens with dates of live collection known only to within 50 yr (Bowman 1985a). Here, we describe the results of our recent attempts to constrain Delta-R variability for this region by dating a suite of known-age pre-AD 1950 shell samples from the Australian Museum and Museum Victoria. A regional Delta-R of 58 +/- 17 14C yr for open waters between Broome and Cape Leveque is recommended based on 7 of these specimens. The criteria used to select shells for dating and inclusion in the regional mean are discussed.
    • Pre-Bomb Marine Reservoir Ages in the Western Pacific

      Yoshida, Kunio; Hara, Tatsuaki; Kunikita, Dai; Miyazaki, Yumiko; Sasaki, Takenori; Yoneda, Minoru; Matsuzaki, Hiroyuki (Department of Geosciences, The University of Arizona, 2010-01-01)
      In this study, molluscan shells housed at the University Museum, the University of Tokyo, provided a new set of region-specific correction values (R) for the western Pacific, in particular for the central part of the main islands in the Japanese Archipelago and the southwest islands of Japan. The values of 40 total samples were calculated from 11 regions. North of the main islands and in the Ryukyu Islands, the mean R values showed comparatively small values, 5-40 14C yr; in the central part of the main islands, these values were 60-90 14C yr.
    • Paleoearthquakes as Anchor Points in Bayesian Radiocarbon Deposition Models: A Case Study from the Dead Sea

      Kagan, Elisa J.; Stein, Mordechai; Agnon, Amotz; Ramsey, Christopher Bronk (Department of Geosciences, The University of Arizona, 2010-01-01)
      The Bayesian statistical method of the OxCal v 4.1 program is used to construct an age-depth model for a set of accelerator mass spectrometry (AMS) radiocarbon ages of organic debris collected from a late Holocene Dead Sea stratigraphic section (the Ein Feshkha Nature Reserve). The model is tested for a case where no prior earthquake information is applied and for a case where there is incorporation of known ages of 4 prominent historical earthquakes as chronological anchor points along the section. While the anchor-based model provided a tightly constrained age-depth regression, the "non-anchored" model still produces a correlation where most of the 68% or 95% age ranges of the 52 seismites can be correlated to historical earthquakes. This presents us with the opportunity for high-resolution paleoseismic analysis and comparison between various sites.
    • New Radiocarbon Dates from the Late Neolithic Tell Settlement of Hódmezővásárhely-Gorzsa, SE Hungary

      Gulyás, Sandor; Sümegi, Pál; Molnár, Mihály (Department of Geosciences, The University of Arizona, 2010-01-01)
      Understanding the internal chronology of the Late Neolithic Tisza culture and the Neolithic of the Tisza region is the subject of debate in both Hungarian and international prehistoric research. The layer sequence of the Late Neolithic Gorzsa tell from SE Hungary offers ideal match points for determining the successive phases of the Tisza culture. According to the results published so far, in the Gorzsa sequence the Tisza culture was divided into 4 main phases with a fifth phase representing the transitional period to the Early Copper Age. Excavations were carried out in 33 profiles covering about 2% of the original area of the entire settlement. The archaeostratigraphy established was based on the identification of microhorizons corresponding to settlement levels. Radiocarbon dates published thus far were created using a pool of various objects of differing microhorizons deriving from different profiles. However, as archaeological results revealed, the settlement was characterized by frequent, minor spatial shifts during its evolution into a tell complex. Here, we present a succession of 7 14C dates deriving from a single profile located at the northeastern flank of the excavation area. The 7 dates span the entire profile from the uppermost microhorizons down to the lowermost ones. The new dates were compared with the existing relative chronology mentioned above. According to our findings, material was deposited in this part of the site mainly during the first 2 phases of evolution of the tell complex. The later phases are either less developed or missing due to possibly a spatial shift of the center of the tell complex resulting first in a deceleration and finally a complete cessation of artifact accumulation to the northwest flanks of the former natural levee. Thus, the previous hypothesis of spatial shifts based on relative chronologies within the site has been corroborated. Furthermore, the congruence between our new dates corrected for any reservoir effect and the previous dates of Hertelendi (1998) may refer to a correct determination of freshwater shell carbonate reservoir effect in the fluvial system of the Tisza River, which may be used in further studies in the area.
    • Optimization of the Graphitization Process at AGE-1

      Němec, Mojmir; Wacker, Lukas; Gäggeler, Heinz (Department of Geosciences, The University of Arizona, 2010-01-01)
      The reaction conditions for the graphitization of CO2 with hydrogen were optimized for a fast production of high-quality carbon samples for accelerator mass spectrometry (AMS) measurement. The iron catalyst in use is first oxidized by heating with air to remove possible carbon and other impurities and then after evacuation reduced back to iron with hydrogen in several flushing steps to remove any iron oxide. The optimum conditions for a fast graphitization reaction were experimentally determined by changing the reaction temperatures and the H2/CO2 ratio. The resulting graphite samples were measured by AMS to find the smallest isotopic changes (13C) at a minimum of molecular fragment formation (13CH current). The improvements are based on thermodynamic data and are explained with Baur-Glaessner diagrams.
    • Modern Radiocarbon Levels for Northwestern Mexico Derived from Tree Rings: A Comparison with Northern Hemisphere Zones 2 and 3 Curves

      Beramendi-Orosco, Laura E.; Gonzalez-Hernandez, Galia; Villanueva-Diaz, Jose; Santos-Arevalo, Francisco J.; Gómez-Martinez, Isabel; Cienfuegos-Alvarado, Edith; Morales-Puente, Pedro; Urrutia-Fucugauchi, Jamie (Department of Geosciences, The University of Arizona, 2010-01-01)
      The radiocarbon variation for northwestern Mexico during the period 1950-2004 was studied by accelerator mass spectrometry (AMS) and liquid scintillation counting (LSC) analyses of tree rings. Two tree-ring sequences of Pseudotsuga menziesii, sampled in a site isolated from urban centers and active volcanoes (26.18 degrees N, 106.3 degrees W, 3000 m asl), were dendrochronologically dated and separated in annual rings prior to 14C analysis. Results obtained show a similar profile to the values reported for the Northern Hemisphere (NH), having significant correlation coefficients with the compilation curves for NH zone 2 (r = 0.987, p < 0.001) and NH zone 3 (r = 0.993, p < 0.001). The maximum peak is centered at 1964.5 with a ∆14C value of 713.15 +/- 9.3‰. The values obtained for the period 1958-1965 are lower than zone 2 values and higher than zone 3 values. For the period 1975-2004, the values obtained are higher than the NH compilation curve and other NH records. We attribute the first divergence to the North American monsoon that may have carried 14C-depleted air from the south during the summer months; the second divergence may be attributable to 14C-enriched biospheric CO2.
    • Is the Consensus Value of ANU Sucrose (IAEA C-6) Too High?

      Xu, Xiaomei; Khosh, Matthew S.; Druffel-Rodriguez, Kevin C.; Trumbore, Susan E.; Southon, John R. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Primary and secondary standards are essential in radiocarbon analyses for the purpose of reporting and comparing data among laboratories, as well as for internal laboratory data quality control. ANU sucrose is one of the IAEA-certified 14C standards (C-6) with a consensus value of 1.5061 +/- 0.0011 fraction modern (Fm). All of our measurements of ANU sucrose (n = 351) as a secondary standard over the last 7 yr result in an average value of 1.5016 +/- 0.0005 Fm (2- standard error). After applying the same outlier tests used for IAEA reference standards, a weighted average value of 1.5016 +/- 0.0002 Fm (n = 294) was calculated. This value is significantly lower than the IAEA C-6 consensus value (t test with unequal variance; p = 0.023). In contrast, our measurements of other secondary standards over the same time period are in excellent agreement with their respective consensus values. Since ANU is the only secondary standard measured in our lab that does not agree with the consensus values, and we have measured a larger number analyses compared to what went into the definition of the consensus value, we suggest that the consensus value of ANU sucrose might be too high by ~0.0045 +/- 0.0011 Fm. Given that some labs routinely use ANU sucrose as a primary standard, our results suggest that revisiting the consensus value of ANU sucrose may be necessary.
    • Hydropyrolysis: Implications for Radiocarbon Pretreatment and Characterization of Black Carbon

      Ascough, P. L.; Bird, M. I.; Meredith, W.; Wood, R. E.; Snape, C. E.; Brock, F.; Higham, T. F. G.; Large, D. J.; Apperley, D. C. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Charcoal is the result of natural and anthropogenic burning events, when biomass is exposed to elevated temperatures under conditions of restricted oxygen. This process produces a range of materials, collectively known as pyrogenic carbon, the most inert fraction of which is known as black carbon (BC). BC degrades extremely slowly and is resistant to diagenetic alteration involving the addition of exogenous carbon, making it a useful target substance for radiocarbon dating particularly of more ancient samples, where contamination issues are critical. We present results of tests using a new method for the quantification and isolation of BC, known as hydropyrolysis (hypy). Results show controlled reductive removal of non-BC organic components in charcoal samples, including lignocellulosic and humic material. The process is reproducible and rapid, making hypy a promising new approach not only for isolation of purified BC for 14C measurement but also in quantification of different labile and resistant sample C fractions.
    • High Contribution of Recalcitrant Organic Matter to DOC in a Japanese Oligotrophic Lake Revealed by 14C Measurements

      Nara, Fumiko Watanabe; Imai, Akio; Uchida, Masao; Matsushige, Kazuo; Komatsu, Kazuhiro; Kawasaki, Nobuyuki; Shibata, Yasuyuki; Amano, Kunihiko; Mikami, Hajime; Hanaishi, Ryuji (Department of Geosciences, The University of Arizona, 2010-01-01)
      Carbon isotopes (14C and 13C) of dissolved organic carbon (DOC) in a Japanese oligotrophic lake (Lake Towada) were measured to study the origin and cycling of dissolved organic matter (DOM) in Lake Towada. Lake water samples were collected at 3 depths (0, 30, and 80 or 85 m) during 4 months (April, June, August, and October) in 2006. 14C measurements of DOC were performed by accelerator mass spectrometry (AMS) at the National Institute for Environmental Studies (NIES-TERRA) in Japan. ∆14C and delta-13C values of DOC in Lake Towada showed light carbon isotopic values ranging from -750 to -514v and -29.0 to -27.8‰, respectively. These values are similar to those of humic substances reported. The very low carbon isotopic values of DOC in Lake Towada suggest a very small contribution of DOC derived from fresh phytoplankton to the lake DOC. There is an extremely high linear relationship between the ∆14C and delta-13C of DOC in Lake Towada when all data points are plotted (r2 = 0.818, p < 0.01), suggesting that the DOC in Lake Towada has 2 specific sources contributing heavy and light carbon isotopes. Although the freshly produced DOC of phytoplankton origin can be decomposed easily, the variation in the autochthonous DOC should influence the carbon isotopic values of DOC in Lake Towada.
    • Frequency Distribution of 14C Ages for Chronostratigraphic Reconstructions: Alaska Region Study Case

      Michczyńska, Danuta J.; Hajdas, Irka (Department of Geosciences, The University of Arizona, 2010-01-01)
      In this study, we test the possibility of using databases of radiocarbon ages to estimate boundaries of climatic chronozones. The Alaska region was chosen and compared with chronozones of 2 European countries: Poland and the Netherlands. The study included setting up a database of 14C ages published for climatic records from Alaska. Some 974 14C determinations on organic samples were selected and used to establish chronozones for the Late Glacial and the Holocene for the Alaska region. The selected data were calibrated and a summed probability density function (PDF) was calculated. The shape analysis of the constructed frequency distribution of 14C dates on calendar timescales together with the assumption about preferential sampling seems to be a useful tool for establishing calendar ages for boundaries of climatic periods, i.e. chronozones.
    • Extraction of In Situ Cosmogenic 14C from Olivine

      Pigati, Jeffrey S.; Lifton, Nathaniel A.; Jull, A. J. Timothy; Quade, Jay (Department of Geosciences, The University of Arizona, 2010-01-01)
      Chemical pretreatment and extraction techniques have been developed previously to extract in situ cosmogenic radiocarbon (in situ 14C) from quartz and carbonate. These minerals can be found in most environments on Earth, but are usually absent from mafic terrains. To fill this gap, we conducted numerous experiments aimed at extracting in situ 14C from olivine ((Fe,Mg)2SiO4). We were able to extract a stable and reproducible in situ 14C component from olivine using stepped heating and a lithium metaborate (LiBO2) flux, following treatment with dilute HNO3 over a variety of experimental conditions. However, measured concentrations for samples from the Tabernacle Hill basalt flow (17.3 +/- 0.3 ka4) in central Utah and the McCarty's basalt flow (3.0 +/- 0.2 ka) in western New Mexico were significantly lower than expected based on exposure of olivine in our samples to cosmic rays at each site. The source of the discrepancy is not clear. We speculate that in situ 14C atoms may not have been released from Mg-rich crystal lattices (the olivine composition at both sites was ~Fo65Fa35). Alternatively, a portion of the 14C atoms released from the olivine grains may have become trapped in synthetic spinel-like minerals that were created in the olivine-flux mixture during the extraction process, or were simply retained in the mixture itself. Regardless, the magnitude of the discrepancy appears to be inversely proportional to the Fe/(Fe+Mg) ratio of the olivine separates. If we apply a simple correction factor based on the chemical composition of the separates, then corrected in situ 14C concentrations are similar to theoretical values at both sites. At this time, we do not know if this agreement is fortuitous or real. Future research should include measurement of in situ 14C concentrations in olivine from known-age basalt flows with different chemical compositions (i.e. more Fe-rich) to determine if this correction is robust for all olivine-bearing rocks.
    • Experiences of Production and Homogeneity Analysis of an AMS 14C Sucrose Standard for High-Activity Measurements

      Sydoff, Marie; Stenström, Kristina (Department of Geosciences, The University of Arizona, 2010-01-01)
      Accurate accelerator mass spectrometry (AMS) measurements rely on standards with well-known isotopic ratios. For radiocarbon measurements, a number of standards with different properties are commercially available, of which the IAEA-C6 sucrose standard with a 14C value of 150.61 pMC is the most active. When analyzing biological samples resulting from studies using 14C-labeled substances, the activity content can be up to 100 times this value. Thus, there is a need for a standard material with higher activity content than IAEA-C6 for making accurate AMS measurements on this type of sample. This paper describes the attempts of producing a standard with an activity content of about 10 times modern carbon. The material chosen has to be chemically inert, preferably non-toxic, commercially available in 14C-labeled form, and the activity must be homogeneously distributed within the material. Two different standard materials were considered: urea and sucrose. Sucrose was chosen for the new standard, since it is non-toxic, inexpensive, and organic and on combustion, forms only carbon dioxide (CO2) and water (H2O). In this paper, we discuss our experience in the production and homogeneity analysis of this material, from the crystallization of the sucrose solution to the graphitization of the samples. When using an online combustion method and a septa-sealed vial reduction method, the AMS measurements indicated that the activity was not homogeneously distributed throughout the material. Contrary to this, measurements of the sucrose solution prior to recrystallization indicated that the activity was more homogeneously distributed before than after the recrystallization. In order to determine whether the inhomogeneity depended on the graphitization method (i.e. the combustion or the reduction method) or on the material itself, 3 different graphitization methods and 2 different methods of recrystallization were tested.
    • Extension of the Southern Hemisphere Atmospheric Radiocarbon Curve, 2120-850 Years BP: Results from Tasmanian Huon Pine

      Zimmerman, Susan; Guilderson, Thomas; Buckley, Brendan; Cook, Edward (Department of Geosciences, The University of Arizona, 2010-01-01)
      Decadal samples of dendrochronologically dated pine (Lagorostrobos franklinii) from the Stanley River basin, Tasmania, have been radiocarbon dated between 2120-850 yr BP. This data set overlaps and extends the current Southern Hemisphere record, which covers the period 110-995 yr BP. There is good agreement between the 2 records between 995-850 yr BP, between sample replicates and with consensus values for standards. As in the younger data set, we find evidence for a distinct but variable offset between the Southern Hemisphere data and IntCal04; although this is likely due to real temporal variability in the interhemispheric offset, further work is planned to rule out possible laboratory or sample preparation differences.
    • Establishment of Chemical Preparation Methods and Development of an Automated Reduction System for AMS Sample Preparation at KIGAM

      Hong, Wan; Park, Jung Hun; Kim, Kyeong J.; Woo, Hyung Joo; Kim, Jun Kon; Choi, Han Woo; Kim, Gi Dong (Department of Geosciences, The University of Arizona, 2010-01-01)
      Many previous studies on the sample preparation of various kinds of radiocarbon dating samples by accelerator mass spectrometry (AMS) have been examined at KIGAM (Korea Institute of Geoscience and Mineral Resources) and our own procedures have been established. Furthermore, an automated reduction system has been developed. The volume of the reduction region was minimized to improve the reduction yield, and air-actuated pneumatic valves and solenoid arrays were used for computer control of the system. Operation of all the valves and vacuum pumps and signals from the temperature sensors and pressure gauges were interfaced to a personal computer with an A/D board. A computer program was also developed to perform automatic operation of the reduction system. This system consistently shows a higher reduction yield than 90%. The reduction time of the system is currently 140 min.
    • Editorial Board

      Department of Geosciences, The University of Arizona, 2010-01-01
    • Effects of Vegetation Switch and Subsequent Change in Soil Invertebrate Composition on Soil Carbon Accumulation Patterns, Revealed by Radiocarbon Concentrations

      Toyota, Ayu; Tayasu, Ichiro; Fujimaki, Reiji; Kaneko, Nobuhiro; Uchida, Masao; Shibata, Yasuyuki; Hiura, Tsutom (Department of Geosciences, The University of Arizona, 2010-01-01)
      Vegetation types strongly affect soil organic carbon (SOC) accumulation in the terrestrial ecosystem through multiple factors such as litter quality and soil biodiversity. However, the roles of soil fauna in SOC accumulation remain unclear. The objectives of this study were to (1) examine how changes in litter types and soil animal communities affect SOC accumulation in continuously forested or vegetation-switched forest areas; and (2) discuss the role of soil animals in SOC accumulation in forest ecosystems. We focused on soils that have accumulated on top of a volcanic ash layer in the 268 yr since a volcanic eruption in 1739. The radiocarbon "bomb spike" in the late 1950s and early 1960s provides a unique isotopic signature of soil carbon age. We investigated the combined effects of litter quality and soil invertebrate function on soil 14C accumulation patterns. To determine the effects of vegetation types on SOC accumulation, we selected 4 types of cool temperate forests, 2 of which had undergone a vegetation switch in about 1960 (conifer to broadleaved forest, CB; broadleaved forest to conifer, BC), and 2 that had continuous forests (conifer forest, CC; broadleaved forest, BB). The ∆14C values at depth intervals in CC were consistent with the expected bomb-14C profile. In contrast, ∆14C patterns in BB, BC, and CB differed from that of CC. Compared to CC, ∆14C values of the other sites showed relatively high 14C concentrations even in deeper soil layers, which suggests the bomb-induced 14C has been transported to a greater depth by soil animals. Current broadleaved forests (BB and CB) had higher biomass of litter-feeding invertebrates than in current coniferous forests (CC and BC). These results suggest that carbon from leaf litter was vertically translocated to deeper soil layers by the abundant soil invertebrates in broad-leaved forests. Disagreement with the expected soil profile in BC suggests that past vegetation (broadleaved forest) has affected the present SOC accumulation pattern.
    • Developments in the Calibration and Modeling of Radiocarbon Dates

      Ramsey, Christopher Bronk; Dee, Michael; Lee, Sharen; Nakagawa, Takeshi; Staff, Richard A. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Calibration is a core element of radiocarbon dating and is undergoing rapid development on a number of different fronts. This is most obvious in the area of 14C archives suitable for calibration purposes, which are now demonstrating much greater coherence over the earlier age range of the technique. Of particular significance to this end is the development of purely terrestrial archives such as those from the Lake Suigetsu sedimentary profile and Kauri tree rings from New Zealand, in addition to the groundwater records from speleothems. Equally important, however, is the development of statistical tools that can be used with, and help develop, such calibration data. In the context of sedimentary deposition, age-depth modeling provides a very useful way to analyze series of measurements from cores, with or without the presence of additional varve information. New methods are under development, making use of model averaging, that generate more robust age models. In addition, all calibration requires a coherent approach to outliers, for both single samples and where entire data sets might be offset relative to the calibration curve. This paper looks at current developments in these areas.