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

      Santos, Guaciara M.; Southon, John R.; Drenzek, Nicholas J.; Ziolkowski, Lori A.; Druffel, Ellen; Xu, Xiaomei; Zhang, Dachun; Trumbore, Susan; Eglinton, Timothy I.; Hughen, Konrad A. (Department of Geosciences, The University of Arizona, 2010-01-01)
      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 g C, while DC is ~0.3 +/- 0.15 g 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.
    • Buried Ancient Forest and Implications for Paleoclimate since the Mid-Holocene in South China

      Shen, C. D.; Ding, P.; Wang, N.; Yi, W. X.; Ding, X. F.; Fu, D. P.; Liu, K. X.; Zhou, L. P. (Department of Geosciences, The University of Arizona, 2010-01-01)
      The historical evolution of an ancient forest that developed at Gaoyao, south China, can be divided into 4 stages of radiocarbon intervals (1.1-1.5, 2.0-3.5, 3.6-4.0, and 4.3-4.9 ka) in which the last 3 stages all developed in a wetland and formed humic layers of 2.0, 0.5, and 0.7 m depth, respectively. The humic layers were interrupted by 2 white-gray silty clay layers that most likely formed during climate fluctuations. Four drought events were identified during the evolution of the ancient forest, occurring around 4.3, 3.6, 2.0, and 1.1 ka, respectively, with durations of ~1000 14C yr. These events are consistent with other records both in low- and high-latitude areas, in particular with the little ice ages occurring since the mid-Holocene. Precipitation likely increased from 5.0 to 3.6 ka in south China, then decreased, which is probably the main cause for the development as well as the demise of the ancient forest.
    • Centuries of Marine Radiocarbon Reservoir Age Variation within Archaeological Mesodesma donacium Shells from Southern Peru

      Jones, Kevin B.; Hodgins, Gregory W. L.; Etayo-Cadavid, Miguel F.; Andrus, C. Fred T.; Sandweiss, Daniel H. (Department of Geosciences, The University of Arizona, 2010-01-01)
      Mollusk shells provide brief (5 yr per shell) records of past marine conditions, including marine radiocarbon reservoir age (R) and upwelling. We report 21 14C ages and R calculations on small (~2 mg) samples from 2 Mesodesma donacium (surf clam) shells. These shells were excavated from a semi-subterranean house floor stratum 14C dated to 7625 +/- 35 BP at site QJ-280, Quebrada Jaguay, southern Peru. The ranges in marine 14C ages (and thus R) from the 2 shells are 530 and 170 14C yr; R from individual aragonite samples spans 130 +/- 60 to 730 +/- 170 14C yr. This intrashell 14C variability suggests that 14C dating of small (time-slice much less than 1 yr) marine samples from a variable-R (i.e. variable-upwelling) environment may introduce centuries of chronometric uncertainty.
    • Characterization and Dating of Saline Groundwater in the Dead Sea Area

      Avrahamov, Naama; Yechieli, Yoseph; Lazar, Boaz; Lewenberg, Omer; Boaretto, Elisabetta; Sivan, Orit (Department of Geosciences, The University of Arizona, 2010-01-01)
      This work presents an attempt to date brines and determine flow rates of hypersaline groundwater in the extremely dynamic system of the Dead Sea (DS), whose level has dropped in the last 30 yr by ~20 m. The processes that affect the carbon species and isotopes of the groundwater in the DS area were quantified in order to estimate their flow rate based on radiocarbon and tritium methods. In contrast to the conservative behavior of most ions in the groundwater, the carbon system parameters indicate additional processes. The dissolved inorganic carbon (DIC) content of most saline groundwater is close to that of the DS, but its stable isotopic composition (13CDIC) is much lower. The chemical composition and carbon isotope mass balance suggest that the low 13CDIC of the saline groundwater is a result of anaerobic organic matter oxidation by bacterial sulfate reduction (BSR) and methane oxidation. The radiocarbon content (14CDIC) of the saline groundwater ranged from 86 pMC (greater than the ~82 pMC value of the DS in the 2000s) to as low as 14 pMC. The similarity between the 14CDIC value and Na/Cl ratio of the groundwater at the DS shore and that of the 1980s DS brine indicates that the DS penetrated to the aquifer at that time. The low 14CDIC values in some of the saline groundwater suggest the existence of ancient brine in the subaquifer.
    • Comparison of 14C Ages between LSC and AMS Measurements of Choukai Jindai Cedar Tree Rings at 2600 cal BP

      Takahashi, Yui; Sakurai, Hirohisa; Suzuki, Kayo; Sato, Taiichi; Gunji, Shuichi; Tokanai, Fuyuki; Matsuzaki, Hiroyuki; Sunohara, Yoko (Department of Geosciences, The University of Arizona, 2010-01-01)
      Radiocarbon ages of Choukai Jindai cedar tree rings growing in the excess era of 14C concentrations during 2757-2437 cal BP were measured using 2 types of 14C measurement methods, i.e. liquid scintillation counting (LSC) and accelerator mass spectrometry (AMS). The difference between the 2 methods is 3.7 +/- 5.2 14C yr on average for 61 single-year tree rings, indicating good agreement between the methods. The Choukai data sets show a small sharp bump with an average 14C age of 2497.1 +/- 3.0 14C yr BP during 2650-2600 cal BP. Although the profile of the Choukai LSC data set compares well with that of IntCal04, having a 14C age difference of 4.6 +/- 5.3 14C yr on average, the Choukai LSC 14C ages indicate variability against the smoothed profile of IntCal04.
    • Comparison of Depth Profiles of 129I and 14C Concentration in the Surface Layer of Soils Collected from Northeastern Japan

      Matsuzaki, Hiroyuki; Tsuchiya, Yoko Sunohara; Muramatsu, Yasuyuki; Maejima, Yuji; Miyairi, Yosuke; Kato, Kazuhiro (Department of Geosciences, The University of Arizona, 2010-01-01)
      129I/127I and 14C/12C depth profiles were compared for the surface 30-cm layer of soil samples (Andisols) collected from Shimokita Peninsula, northeastern Japan, in November 2005. The 129I/127I and 14C/12C profiles have a clear correlation, even taking into account that the data include samples collected from different sites with different surface histories. These results, and considering that 14C/12C can be regarded as a proxy of the original depth in stable soil, show the diversity of the 129I/127I ratio at the surface among the sites, indicating variations in the thicknesses of the layers recently removed. At one of the sampling sites (P003-1), the ∆14C value measures ~110 near the surface, which is indicative of anthropogenic 14C produced by atmospheric testing of nuclear weapons during the late 1950s and early 1960s. This site has experienced no disturbances for at least the past 50 yr. The relatively high activity of 129I (0.8 mBq/kg) and the 129I/127I ratio (7 x 10^(-9)) observed at the top layer of this site can be considered a 'representative value' when considering the anthropogenic iodine transfer from the atmosphere to the ground. The observations also support 2 separate modes of 129I migration in the soil: i.e. "topmost quick diffusion" and "subsurface relatively slow migration process." Even in the "subsurface relatively slow migration zone," the 129I/127I ratio was still orders higher than the pre-anthropogenic natural level.
    • Compound-Specific Radiocarbon Analyses of Phospholipid Fatty Acids and n-Alkanes in Ocean Sediments

      Druffel, Ellen R. M.; Zhang, Dachun; Xu, Xiaomei; Ziolkowski, Lori A.; Southon, John R.; Dos Santos, Guaciara M.; Trumbore, Susan E. (Department of Geosciences, The University of Arizona, 2010-01-01)
      We report compound-specific radiocarbon analyses of organic matter in ocean sediments from the northeast Pacific Ocean. Chemical extractions and a preparative capillary gas chromatograph (PCGC) were used to isolate phospholipid fatty acids (PLFA) and n-alkanes from 3 cores collected off the coast of California, USA. Mass of samples for accelerator mass spectrometry (AMS) 14C analysis ranged from 13-100 g C. PLFA extracted from anaerobic sediments in the Santa Barbara Basin (595 m depth) had modern ∆14C values (-20 to +54), indicating bacterial utilization of surface-produced, post-bomb organic matter. Lower ∆14C values were obtained for n-alkanes and PLFA from coast (92 m depth) and continental slope (1866 m) sediments, which reflect sources of old organic matter and bioturbation. We present a brief analysis of the blank carbon introduced to samples during chemical processing and PCGC isolation.
    • Decadal Changes of Radiocarbon in the Surface Bay of Bengal: Three Decades after GEOSECS and One Decade after WOCE

      Dutta, Koushik; Prasad, G. V. Ravi; Ray, Dinesh K.; Raghav, Sanjeev (Department of Geosciences, The University of Arizona, 2010-01-01)
      Radiocarbon was measured in the surface seawater dissolved inorganic carbon (DIC) of the Bay of Bengal during November 2006. A meridional transect of the ∆14C in DIC was obtained from measurements in closely spaced samples collected roughly along 88E. The ∆14C of these samples ranged from 44 to 57.7 (mean 51.8 +/- 1.1, n = 12), and 38 at one station in the northern Bay of Bengal. The overall pattern of 14C distribution in DIC of surface Bay of Bengal during 2006 was roughly similar to that during the WOCE expedition of 1995. These results indicate a ∆14C decline rate of ~4 per decade since WOCE in the surface Bay of Bengal, which is much smaller compared to a decline rate of ~25 per decade observed in the 2 decades between the GEOSECS and WOCE expeditions, due to the smaller atmosphere-ocean ∆14C gradient.
    • Development of an Automatic Sampling Unit for Measuring Radiocarbon Content of Groundwater

      Janovics, R.; Molnár, M.; Futó, I.; Rinyu, L.; Svingor, É.; Veres, M.; Somogyi, I.; Barnabás, I. (Department of Geosciences, The University of Arizona, 2010-01-01)
      An automatic water sampling unit was developed to monitor the radioactive emission (radiocarbon and other corrosion and fission products) from nuclear facilities into the groundwater. Automatic sampling is based on the principal of ion exchange using built-in resin columns in the submerging samplers. In this way, even the short-term emissions can be detected. According to our experiments, the 14C activity concentrations and the 13C values of the samples made by the ion exchange method are systematically underestimated compared to the real values. The carbonate adsorption feature of the sampling unit was studied under laboratory and field conditions. For this purpose, a test method was developed. The observed sampling efficiencies and additionally some carbon contamination for the sampling method itself have to be taken into consideration when we estimate the amount of 14C contamination introduced into the groundwater from a nuclear facility. Therefore, a correction factor should be made for the 14C anion exchange sampling. With the help of this correction, the results converge to the expected value.
    • Development of Graphitization of μg-Sized Samples at Lund University

      Genberg, J.; Stenström, K.; Elfman, M.; Olsson, M. (Department of Geosciences, The University of Arizona, 2010-01-01)
      To be able to successfully measure radiocarbon with accelerator mass spectrometry (AMS) in atmospheric aerosol samples, graphitization of small sample sizes ( 50 g carbon) must provide reproducible results. At Lund University, a graphitization line optimized for small samples has been constructed. Attention has been given to minimize the reduction reactor volume and each reactor is equipped with a very small pressure transducer that enables constant monitoring of the reaction. Samples as small as 25 g of carbon have been successfully analyzed, and the mass detection limit of the system has probably not been reached.
    • 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.
    • 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.
    • 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.
    • 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.
    • 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.
    • 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.
    • 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.