USGS44, a new high-purity calcium carbonate reference material for δ13 C measurements.

RATIONALE: The stable carbon isotopic (δ13 C) reference material (RM) LSVEC Li2 CO3 has been found to be unsuitable for δ13 C standardization work because its δ13 C value increases with exposure to atmospheric CO2 . A new CaCO3 RM, USGS44, has been prepared to alleviate this situation. METHODS: USGS44 was prepared from 8 kg of Merck high-purity CaCO3 . Two sets of δ13 C values of USGS44 were determined. The first set of values was determined by online combustion, continuous-flow (CF) isotope-ratio mass spectrometry (IRMS) of NBS 19 CaCO3 (δ13 CVPDB = +1.95 milliurey (mUr) exactly, where mUr = 0.001 = 1‰), and LSVEC Li2 CO3 (δ13 CVPDB = -46.6 mUr exactly), and normalized to the two-anchor δ13 CVPDB-LSVEC isotope-delta scale. The second set of values was obtained by dual-inlet (DI)-IRMS of CO2 evolved by reaction of H3 PO4 with carbonates, corrected for cross contamination, and normalized to the single-anchor δ13 CVPDB scale. RESULTS: USGS44 is stable and isotopically homogeneous to within 0.02 mUr in 100-µg amounts. It has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr. Single-anchor δ13 CVPDB values of -42.08 ± 0.01 and -41.99 ± 0.02 mUr were determined by DI-IRMS with corrections for cross contamination. CONCLUSIONS: The new high-purity, well-homogenized calcium carbonate isotopic reference material USGS44 is stable and has a δ13 CVPDB-LSVEC value of -42.21 ± 0.05 mUr for both EA/IRMS and DI-IRMS measurements. As a carbonate relatively depleted in 13 C, it is intended for daily use as a secondary isotopic reference material to normalize stable carbon isotope delta measurements to the δ13 CVPDB-LSVEC scale. It is useful in quantifying drift with time, determining mass-dependent isotopic fractionation (linearity correction), and adjusting isotope-ratio-scale contraction. Due to its fine grain size (smaller than 63 µm), it is not suitable as a δ18 O reference material. A δ13 CVPDB-LSVEC value of -29.99 ± 0.05 mUr was determined for NBS 22 oil.

Al-Ansab and the Dead Sea: Mid-MIS 3 archaeology and environment of the early Ahmarian population of the Levantine corridor.

Our field data from the Upper Palaeolithic site of Al-Ansab 1 (Jordan) and from a pollen sequence in the Dead Sea elucidate the role that changing Steppe landscapes played in facilitating anatomically modern human populations to enter a major expansion and consolidation phase, known as the "Early Ahmarian", several millennia subsequent to their initial Marine Isotope Stage 4/3 migration from Africa, into the Middle East. The Early Ahmarian techno-cultural unit covers a time range between 45 ka-37 ka BP. With so far more than 50 sites found, the Early Ahmarian is the first fully Upper Palaeolithic techno-cultural unit exclusively and undisputedly related to anatomically modern human populations. In order to better understand the potentially attractive features of the Early Ahmarian environmental context that supported its persistence for over 8,000 years, we carried out a decennial research program in Jordan and in the Dead Sea. This included (1) a geoscientific and archaeological survey program in the Wadi Sabra (Jordan) with a particular focus on excavations at the Early Ahmarian site of Al-Ansab 1 alongside the detailed analysis of Quaternary sediments from the same area and (2) palaeobotanical research based on Quaternary lake deposits from the Dead Sea. Our pollen data from the Dead Sea indicate slow, low frequency vegetational variation with expanding Artemisia steppe, from 60 to 20 ka BP (MIS 3-2). Here, we see a reciprocal assimilation of southern and northern Levantine vegetation zones thereby enhancing a long-lasting south-to-north steppe corridor. The same integration process accelerated about 40 ka ago, when forested areas retreated in the Lebanese Mountains. The process then extended to encompass an area from Southern Lebanon to the Sinai Peninsula. We argue that, at the same time, the carriers of the Early Ahmarian techno-cultural unit extended their habitat from their original Mediterranean biome (in the North) to the Saharo-Arabian biome (to the South). Our excavation of Al-Ansab 1, a campsite at the eastern margins of the Early Ahmarian settlement area, indicates far reaching annual movements of small, highly mobile hunter-gatherer groups. We assume a low degree of settlement complexity, still allowing for habitat extension of the Early Ahmarian into the margins of the Levantine corridor. Due to our radiometric dates, our combined archaeological and environmental record sheds light on an evolved phase of the Early Ahmarian, around 38 ka ago, rather than the starting phase of this techno-cultural unit. Possible application of our model to the starting phase of the Early Ahmarian remains an aspect of future research.

δ18O anchoring to VPDB: calcite digestion with 18O-adjusted ortho-phosphoric acid.

For anchoring CO(2) isotopic measurements on the δ(18)O(VPD-CO2) scale, the primary reference material (NBS 19 calcite) needs to be digested using concentrated ortho-phosphoric acid. During this procedure, great care must be taken to ensure that the isotopic composition of the liberated gas is accurate. Apart from controlling the reaction temperature to ±0.1 °C, the potential for oxygen isotope exchange between the produced CO(2) and water must be kept to a minimum. The water is usually assumed to reside on the walls in the headspace of the reaction vessel. We demonstrate here that a large fraction of the exchange may also occur with water inside the acid. Our results indicate that both exchange reactions have a significant impact on the results and may have largely been responsible for scale inconsistencies between laboratories in the past. The extent of CO(2)/H(2)O oxygen exchange depends on the concentration (amount of free water) in the acid. For acids with a nominal H(3)PO(4) mass fraction of less than 102%, oxygen isotope exchange can create a substantial isotopic bias during high-precision measurements with the degree of the alteration being proportional to the effective isotopic contrast between the acid and the CO(2) released from the calcite. Water evaporating from the acid at 25 °C has a δ(18)O value of -34.5‰ relative to the isotopic composition of the whole acid. This large fractionation is likely to occur in two steps; by exchange with phosphate, water inside the acid is decreased in oxygen-18 relative to the bulk acid by ∼ -22‰. This water is then fractionated further during evaporation. Oxygen exchange with both water inside the acid and water condensate in the headspace can contribute to the measured isotopic signature depending on the experimental parameters. The system employed for this study has been specifically designed to minimize oxygen exchange with water. However, the amount of altered CO(2) for a 95% H(3)PO(4) at 25 °C still accounts for about 3% of the total CO(2) produced from a 40 mg calcite sample, resulting in a δ(18) O range of about 0.8‰ when varying the δ(18)O value of the acid by 25‰. Least biased results for NBS19-CO(2) were obtained for an acid with a δ(18)O value close to +23‰ vs. VSMOW. In contrast, commercial acids from several sources had an average δ(18)O value of +13‰, amounting to a 10‰ offset from the optimal value. This observation suggests that the well-known scale incompatibilities between laboratories could arise from this difference with measurements that may have suffered systematically from non-optimal acid-δ(18)O values, thus producing variable offsets, depending on the experimental details. As a remedy, we suggest that the δ(18)O of phosphoric acid reacted with calcites for establishing a δ(18)O scale anchor be adjusted, and this should reduce the variability of the δ(18)O of CO(2) evolved in acid digestion to less than ±0.05‰. The adjustment should be made by taking into account the difference in δ(18)O between the calcite-CO(2) and the acid, with a target difference of 16‰. With this strategy, agreement between δ(18)O scales based on water, atmospheric CO(2) , and carbonates as well as data compatibility between laboratories may be substantially improved.

How well do we know VPDB? Variability of delta13C and delta18O in CO2 generated from NBS19-calcite.

In order to generate a local daughter scale from the material defining the international delta13C and delta18O stable isotope ratio scales (NBS19-calcite),1,2 the carbon and oxygen must be liberated to the gas phase, usually as CO2, using acid digestion of the calcite with H3PO4. It is during this conversion step that systematic errors can occur, giving rise to commonly observed discrepancies in isotopic measurements between different stable isotope laboratories. Scale consistency is of particular importance for air-CO2 isotope records where very small differences in isotopic composition have to be reliably compared between different laboratories and quantified over long time periods.3 The information is vital for estimating carbon budgets on regional and global scales and for understanding their variability under the conditions of climate change. Starting from this requirement a number of CO2 preparations from NBS19 were made at Environment Canada (EC) and analyzed in our laboratories together with Narcis II, a set of well-characterized CO2 samples in sealed tubes available from the National Institute for Environmental Studies (NIES).4,5 Narcis II is very homogeneous in delta13C and delta18O with the isotopic composition close to NBS19-CO2. Among our laboratories the results for delta13C agreed to within +/-0.004 per thousand. The same level of agreement in delta13C was obtained when CO2 was generated from NBS19-calcite using different experimental procedures and conditions in the other two laboratories. For delta18O, the corresponding data were +/-0.011 per thousand when using NBS19-CO2 produced at EC, but discrepancies were enhanced by almost one order of magnitude when NBS19-CO2 was prepared by the other laboratories using slightly different reaction conditions (range=0.13 per thousand).In a second series of experiments, larger amounts of CO2 prepared from NBS19 at the Max-Planck-Institut für Biogeochemie (MPI-BGC) were analyzed together with Narcis II and then mixed into CO2-free air. The resulting artificial air samples then were measured by the same three laboratories for the stable isotopic composition of CO2 using locally established extraction and evaluation procedures. Comparison of the results with the prior CO2 values and between the laboratories revealed additional systematic differences owing to the local CO2 extraction processes and standardization procedures. For delta13C the results showed a narrow range of discrepancies of about 0.02 per thousand; for delta18O cumulative disagreements in the range of 0.1 per thousand were observed. From these results the following conclusions are inferred: NBS19-CO2 is a reliable primary anchor to the VPDB delta13C scale. Although prepared by different methods an accuracy of better than +/-0.003 per thousand has been reached. This applies to sample amounts of 5 mg calcite or more.NBS19-CO2 can be used as a general anchor to the VPDB delta18O scale only for accuracy requirements of +/-0.1 per thousand. For a higher scale resolution additional agreements regarding details of the acid digestion reaction will have to be worked out and agreed upon.Narcis II-CO2 comprises an ideal set of test samples for the VPDB scale. The delta13C value is +1.923+/-0.003 per thousand (combined uncertainty); delta18O is between -2.50 and -2.65 per thousand versus VPDB-CO2, with most of the variation in this figure depending on details of the NBS19-CO2 preparation used for the calibration. (Ampoule to ampoule homogeneity is better than 0.01 per thousand.)When mixing NBS19-CO2 into artificial air and using this to test performance between laboratories, the delta13C offsets are small with a remaining discrepancy of only 0.02 per thousand. For delta18O, systematic disagreements are considerably larger than those found for the pure CO2 comparison. Further experimental clarification is required.Artificial air samples such as NBS19-CO2 in air can be used as reliable anchors to create a unified stable isotope scale between different laboratories. An adjustment of local scales based on these air standards appears to be necessary for improving data comparability.

Comparison of 60cobalt and 192iridium sources in high dose rate afterloading brachytherapy.

PURPOSE: (60)Co sources with dimensions identical to those of (192)Ir have recently been made available in clinical brachytherapy. A longer half time reduces demands on logistics and quality assurance and perhaps costs. MATERIAL AND METHODS: Comparison of the physical properties of (60)Co and (192)Ir with regard to brachytherapy. RESULTS: Required activities for the same air kerma rate are lower by a factor of 2.8 for (60)Co. Differential absorption in tissues of different densities can be neglected. Monte Carlo calculations demonstrate that integral dose due to radial dose fall off is higher for (192)Ir in comparison to (60)Co within the first 22 cm from the source (normalization at 1 cm). At larger distances this relationship is reversed. CONCLUSION: Clinical examples for intracavitary and interstitial applications however, show practically identical dose distributions in the treatment volume.

Neural internet: Web surfing with brain potentials for the completely paralyzed.

Neural Internet is a new technological advancement in brain-computer interface research, which enables locked-in patients to operate a Web browser directly with their brain potentials. Neural Internet was successfully tested with a locked-in patient diagnosed with amyotrophic lateral sclerosis rendering him the first paralyzed person to surf the Internet solely by regulating his electrical brain activity. The functioning of Neural Internet and its clinical implications for motor-impaired patients are highlighted.