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1
Hillaire-Marcel, Claude, and Christiane Causse. "The Late Pleistocene Laurentide Glacier: Th/U Dating of its Major Fluctuations and δ18O Range of the Ice." Quaternary Research 32, no. 2 (September 1989): 125–38. http://dx.doi.org/10.1016/0033-5894(89)90070-7.
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AbstractDirect information on the isotopic composition and timing of the now-vanished Laurentide glacier can be found in subglacial calcite or in early diagenetic concretions from glaciolacustrine deposits. Th/U isotopic measurements on early diagenetic concretions frome Lake Deschaillons varves (St. Lawrence Lowland, Québec) date the early Wisconsinan major ice advance at ca. 80,000 yr (isotopic stage 5a/4 transition). Significant retreat occurred at ca. 46,000 yr (isotopic stage 3) as indicated by Th/U isochrones on early diagenetic concretions from Lake Gayhurst varves in the Appalachian foothills of Québec. During the maximum extension of the ice, which is dated at ca. 22,000 yr by Th/U measurements on subglacial calcite at Cantley (northern margin of the St. Lawrence Lowland), δ18O values (vs PDB) ranging from −16/−19‰ (surficial ice) to ca. −30‰ (basal ice) are inferred for the Laurentide ice isotopic composition. Superimposition of two phases of carbonate precipitation does not prevent the establishment of their respective age and isotopic composition through correlation of independent parameters and calculation of mixing lines.
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Herbert, Timothy D., Rocio Caballero-Gill, and Joseph B. Novak. "A revised mid-Pliocene composite section centered on the M2 glacial event for ODP Site 846." Climate of the Past 17, no. 3 (June 23, 2021): 1385–94. http://dx.doi.org/10.5194/cp-17-1385-2021.
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Abstract. The composite section from ODP Site 846 has provided key data sets for Pliocene stable isotope and paleoclimatic time series. We document here apparent outliers in previously published data sets for stable isotopes and alkenone-derived sea surface temperature (SST) estimates in the Pliocene interval containing the M2 glaciation (ca. 3.290–3.3 Ma) by tying high-resolution core measurements to a continuous downhole conductivity log. We generate a revised sequence of new stable isotopic and alkenone measurements across the M2 event that correlate well to the revised splices of color reflectance and gamma ray attenuation porosity evaluator data from Site 846, and to a new composite section produced at equatorial Pacific ODP Site 850. A new composite splice for Site 846 is proposed, along with composite isotope and alkenone time series that should be integrated into revised Pliocene paleoclimatic stacks.
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Mennekes, David, Michael Rinderer, Stefan Seeger, and Natalie Orlowski. "Ecohydrological travel times derived from in situ stable water isotope measurements in trees during a semi-controlled pot experiment." Hydrology and Earth System Sciences 25, no. 8 (August 23, 2021): 4513–30. http://dx.doi.org/10.5194/hess-25-4513-2021.
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Abstract. Tree water uptake processes and ecohydrological travel times have gained more attention in recent ecohydrological studies. In situ measurement techniques for stable water isotopes offer great potential to investigate these processes but have not been applied much to tree xylem and soils so far. Here, we used in situ probes for stable water isotope measurements to monitor the isotopic signatures of soil and tree xylem water before and after two deuterium-labeled irrigation experiments. To show the potential of the method, we tested our measurement approach with 20-year-old trees of three different species (Pinus pinea, Alnus incana and Quercus suber). They were planted in large pots with homogeneous soil in order to have semi-controlled experimental conditions. Additional destructive sampling of soil and plant material allowed for a comparison between destructive (cryogenic vacuum extraction and direct water vapor equilibration) and in situ isotope measurements. Furthermore, isotope-tracer-based ecohydrological travel times were compared to travel times derived from sap flow measurements. The time to first arrival of the isotope tracer signals at 15 cm stem hight were ca. 17 h for all tree species and matched well with sap-flow-based travel times. However, at 150 cm stem height tracer-based travel times differed between tree species and ranged between 2.4 and 3.3 d. Sap-flow-based travel times at 150 cm stem hight were ca. 1.3 d longer than tracer-based travel times. The isotope signature of destructive and in situ isotope measurements differed notably, which suggests that the two types of techniques sampled water from different pools. In situ measurements of soil and xylem water were much more consistent between the three tree pots (on average standard deviations were smaller by 8.4 ‰ for δ2H and by 1.6 ‰ for δ18O for the in situ measurements) and also among the measurements from the same tree pot in comparison to the destructive methods (on average standard deviations were smaller by 7.8 ‰ and 1.6 ‰ for δ2H and δ18O, respectively). Our study demonstrates the potential of semi-controlled large-scale pot experiments and very frequent in situ isotope measurements for monitoring tree water uptake and ecohydrological travel times. It also shows that differences in sampling techniques or sensor types need to be considered when comparing results of different studies and within one study using different methods.
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Keller, Kathrin M., Sebastian Lienert, Anil Bozbiyik, Thomas F. Stocker, Olga V. Churakova (Sidorova), David C. Frank, Stefan Klesse, et al. "20th century changes in carbon isotopes and water-use efficiency: tree-ring-based evaluation of the CLM4.5 and LPX-Bern models." Biogeosciences 14, no. 10 (May 24, 2017): 2641–73. http://dx.doi.org/10.5194/bg-14-2641-2017.
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Abstract. Measurements of the stable carbon isotope ratio (δ13C) on annual tree rings offer new opportunities to evaluate mechanisms of variations in photosynthesis and stomatal conductance under changing CO2 and climate conditions, especially in conjunction with process-based biogeochemical model simulations. The isotopic discrimination is indicative of the ratio between the CO2 partial pressure in the intercellular cavities and the atmosphere (ci∕ca) and of the ratio of assimilation to stomatal conductance, termed intrinsic water-use efficiency (iWUE). We performed isotope-enabled simulations over the industrial period with the land biosphere module (CLM4.5) of the Community Earth System Model and the Land Surface Processes and Exchanges (LPX-Bern) dynamic global vegetation model. Results for C3 tree species show good agreement with a global compilation of δ13C measurements on leaves, though modeled 13C discrimination by C3 trees is smaller in arid regions than measured. A compilation of 76 tree-ring records, mainly from Europe, boreal Asia, and western North America, suggests on average small 20th century changes in isotopic discrimination and in ci∕ca and an increase in iWUE of about 27 % since 1900. LPX-Bern results match these century-scale reconstructions, supporting the idea that the physiology of stomata has evolved to optimize trade-offs between carbon gain by assimilation and water loss by transpiration. In contrast, CLM4.5 simulates an increase in discrimination and in turn a change in iWUE that is almost twice as large as that revealed by the tree-ring data. Factorial simulations show that these changes are mainly in response to rising atmospheric CO2. The results suggest that the downregulation of ci∕ca and of photosynthesis by nitrogen limitation is possibly too strong in the standard setup of CLM4.5 or that there may be problems associated with the implementation of conductance, assimilation, and related adjustment processes on long-term environmental changes.
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Leavitt, Steven W., and Robert M. Kalin. "A New Tree-Ring Width, δ13C and 14C Investigation of the Two Creeks Site." Radiocarbon 34, no. 3 (1992): 792–97. http://dx.doi.org/10.1017/s0033822200064092.
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We have made isotopic and dendrochronologic measurements on material collected from the Two Creeks site. Radiocarbon dating of outside wood of four logs yielded an average age of 11,760 ± 100 BP, in good agreement with results of Broecker and Farrand (1963) over 25 years ago. The range of 11,640 ± 160 to 11,900 ± 160 BP suggests a period of forest growth of 200–300 years, consistent with a ring-width chronology established by Kaiser (1987). Ring counting of five specimens gave a range of individual tree ages from 110 to 182 years, and width measurements indicate very low year-to-year variation in ring size. However, preliminary cross-dating of five samples produced a 202-year floating chronology. Stable-carbon isotope chronologies on cellulose from five-year ring groups show δ13C scatter among trees typical of that found within modern sites, with some matches of isotopic maxima and minima. Some downward δ13C trends may result from physiological response to rising lake levels (and/or cooling temperatures) at the site, which also produced very narrow rings in the outer ca. 50 ± 20 years.
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Dickinson, Dane, Samuel Bodé, and Pascal Boeckx. "System for <i>δ</i><sup>13</sup>C–CO<sub>2</sub> and <i>x</i>CO<sub>2</sub> analysis of discrete gas samples by cavity ring-down spectroscopy." Atmospheric Measurement Techniques 10, no. 11 (November 22, 2017): 4507–19. http://dx.doi.org/10.5194/amt-10-4507-2017.
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Abstract. A method was devised for analysing small discrete gas samples (50 mL syringe) by cavity ring-down spectroscopy (CRDS). Measurements were accomplished by inletting 50 mL syringed samples into an isotopic-CO2 CRDS analyser (Picarro G2131-i) between baseline readings of a reference air standard, which produced sharp peaks in the CRDS data feed. A custom software script was developed to manage the measurement process and aggregate sample data in real time. The method was successfully tested with CO2 mole fractions (xCO2) ranging from < 0.1 to > 20 000 ppm and δ13C–CO2 values from −100 up to +30 000 ‰ in comparison to VPDB (Vienna Pee Dee Belemnite). Throughput was typically 10 samples h−1, with 13 h−1 possible under ideal conditions. The measurement failure rate in routine use was ca. 1 %. Calibration to correct for memory effects was performed with gravimetric gas standards ranging from 0.05 to 2109 ppm xCO2 and δ13C–CO2 levels varying from −27.3 to +21 740 ‰. Repeatability tests demonstrated that method precision for 50 mL samples was ca. 0.05 % in xCO2 and 0.15 ‰ in δ13C–CO2 for CO2 compositions from 300 to 2000 ppm with natural abundance 13C. Long-term method consistency was tested over a 9-month period, with results showing no systematic measurement drift over time. Standardised analysis of discrete gas samples expands the scope of application for isotopic-CO2 CRDS and enhances its potential for replacing conventional isotope ratio measurement techniques. Our method involves minimal set-up costs and can be readily implemented in Picarro G2131-i and G2201-i analysers or tailored for use with other CRDS instruments and trace gases.
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Bownes, Jessica M., Philippa L. Ascough, Gordon T. Cook, Iona Murray, and Clive Bonsall. "Using Stable Isotopes and a Bayesian Mixing Model (FRUITS) to Investigate Diet at the Early Neolithic Site of Carding Mill Bay, Scotland." Radiocarbon 59, no. 5 (October 2017): 1275–94. http://dx.doi.org/10.1017/rdc.2017.39.
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AbstractWe present δ13C, δ15N, and δ34S measurements on archaeological human and animal bone collagen samples from a shell midden dating to the Neolithic ca. 4000–3500 cal BC, together with measurements on modern fish and shellfish. These data were used in conjunction with the Bayesian mixing model, Food Reconstruction Using Isotopic Transferred Signals (FRUITS), to reconstruct human diet at the site. We demonstrate the importance of using a geographically appropriate faunal baseline in stable isotope paleodietary studies, and suggest that Neolithic individuals at this site consumed up to ca. 21% of dietary protein from marine resources, despite stable isotope ratios that imply a wholly terrestrial diet. This marine resource consumption does not significantly shift the radiocarbon (14C) dates of these individuals, so although we must consider the use of marine resources at the site, the chronology that has previously been established is secure. The δ13C and δ15N measurements from the archaeological herbivore bone collagen indicate that it is unlikely they ate plants enriched with fertilisers such as manure or seaweed. The δ34S values reveal a sea-spray effect; therefore, in this instance, δ34S cannot be used as a dietary indicator but can be used to demonstrate the likely locality of the fauna.
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Sangster, D. F., P. M. Outridge, and W. J. Davis. "Stable lead isotope characteristics of lead ore deposits of environmental significance." Environmental Reviews 8, no. 2 (February 1, 2000): 115–47. http://dx.doi.org/10.1139/a00-008.
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Stable Pb isotopes are increasingly used in environmental science as tracers of natural and anthropogenic Pb sources. This review provides a summary of the recent geological literature concerning Pb isotopes in global Pb ore deposits. The isotopic characteristics of 151 Pb deposits, including 78 20th-century producing mines, have been summarized using the 204Pb-based ratios common to geological science and the 206Pb- and 207Pb-based ratios (i.e., excluding 204Pb) more often employed in environmental studies. A number of current mines, including those exploiting several Australian, Scandinavian, and U.S.A. deposits, have extreme isotopic compositions that provide unique signatures. However, a majority of mines (and unproductive deposits) fall within a relatively narrow range:206Pb/207Pb of 1.15-1.22 and 208Pb/207Pb of 2.42-2.50. In some contexts, unequivocal identification of a source exhibiting one of these common signatures would be difficult, especially with the relatively low precision (ca. 0.2-0.5% RSD) of quadrupole inductively coupled plasma - mass spectrometry (ICP-MS) which has been the most common instrument for environmental Pb isotope measurements. In settings with disparate industrial and natural Pb signatures (i.e., sources withisotopic ratios differing by about 2% or more), ICP-MS precision is adequate for source discrimination. Statistical analyses suggested that while 204Pb is critical for identifying a small proportion of environmental Pb sources, about 86% of the source discrimination power is due to the 206Pb, 207Pb, and 208Pb isotopes. Thus, the requisite analytical precision, rather than a lack of 204Pb data, is the most critical issue with respect to unequivocal identification of Pb sources in most cases. Several factors, especially the increasing dominance of recycling in global Pb production and the international transportation of ore concentrate and refined Pb, may cause unpredictable changes in the isotopic signatures of industrial sources,with a long-term trend towards homogenization. More frequent,comprehensive, and high-precision isotopic characterization of possible point and non-point Pb emitters such as gasoline, smelters, and battery-recycling plants, together with increased efforts to document the origin of constituent leads in industrial sources, would help to address these concerns.Key words: lead isotopes; lead pollution; source identification; lead ore deposits.
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Rodgers, P., C. Soulsby, S. Waldron, and D. Tetzlaff. "Using stable isotope tracers to assess hydrological flow paths, residence times and landscape influences in a nested mesoscale catchment." Hydrology and Earth System Sciences 9, no. 3 (July 22, 2005): 139–55. http://dx.doi.org/10.5194/hess-9-139-2005.
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Abstract. δ18O measurements in precipitation and stream waters were used to investigate hydrological flow paths and residence times at nested spatial scales in the mesoscale (233 km2) River Feugh catchment in the northeast of Scotland over the 2001-2002 hydrological year. Precipitation δ18O exhibited strong seasonal variation, which although significantly damped within the catchment, was reflected in stream water at six sampling sites. This allowed δ18O variations to be used to infer the relative influence of soil-derived storm flows with a seasonally variable isotopic signature, and groundwater of apparently more constant isotopic composition. Periodic regression analysis was then used to examine the sub-catchment difference using an exponential flow model to provide indicative estimates of mean stream water residence times, which varied between approximately 3 and 14 months. This showed that the effects of increasing scale on estimated mean stream water residence time was minimal beyond that of the smallest (ca. 1 km2) headwater catchment scale. Instead, the interaction of catchment soil cover and topography appeared to be the dominant controlling influence. Where sub-catchments had extensive peat coverage, responsive hydrological pathways produced seasonally variable δ18O signatures in runoff with short mean residence times (ca. 3 months). In contrast, areas dominated by steeper slopes, more freely draining soils and larger groundwater storage in shallow valley-bottom aquifers, deeper flow paths allow for more effective mixing and damping of δ18O indicating longer residence times (>12 months). These insights from δ18O measurements extend the hydrological understanding of the Feugh catchment gained from previous geochemical tracer studies, and demonstrate the utility of isotope tracers in investigating the interaction of hydrological processes and catchment characteristics at larger spatial scales.
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Carignan, Jean, Damien Cardinal, Anton Eisenhauer, Albert Galy, Mark Rehkamper, Frank Wombacher, and Nathalie Vigier. "A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials." Geostandards and Geoanalytical Research 28, no. 1 (May 2004): 139–48. http://dx.doi.org/10.1111/j.1751-908x.2004.tb01050.x.
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Hattori, S., S. O. Danielache, M. S. Johnson, J. A. Schmidt, H. G. Kjaergaard, S. Toyoda, Y. Ueno, and N. Yoshida. "Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC<sup>32</sup>S, OC<sup>33</sup>S, OC<sup>34</sup>S and O<sup>13</sup>CS: isotopic fractionation in photolysis and atmospheric implications." Atmospheric Chemistry and Physics Discussions 11, no. 7 (July 19, 2011): 20487–520. http://dx.doi.org/10.5194/acpd-11-20487-2011.
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Abstract. We report measurements of the ultraviolet absorption cross sections of OC32S, OC33S, OC34S and O13CS from 195 to 260 nm. The OCS isotopologues were synthesized from isotopically-enriched elemental sulfur by reaction with carbon monoxide. The measured cross section of OC32S is consistent with literature spectra recorded using natural abundance samples. Relative to the spectrum of the most abundant isotopologue, substitution of heavier rare isotopes has two effects. First, as predicted by the reflection principle, the Gaussian-based absorption envelope becomes slightly more narrow and blue-shifted. Second, as predicted by Franck-Condon considerations, the weak vibrational structure is red-shifted. Sulfur isotopic fractionation constants (33ε, 34ε) as a function of wavelength are not highly structured, and tend to be close to zero on average on the high energy side and negative on the low energy side. Since OCS photolysis occurs in the lower stratosphere, the integrated photolysis rate of each isotopologue at 20 km was calculated. Sulfur isotopic fractionation constants at 20 km altitude are (−3.7 ± 4.5) ‰ and (1.1 ± 4.2) ‰ for 33ε and 34ε, respectively, which is inconsistent with the previously estimated large fractionation of over 73 ‰ in 34ε. This demonstrates that OCS photolysis does not produce sulfur isotopic fractionation of more than ca. 5 ‰, suggesting OCS may be the source of background stratospheric sulfate aerosols. Finally, the predicted isotopic fractionation constant for 33S excess (33E) in OCS photolysis is (−4.2 ± 6.6) ‰, and thus photolysis of OCS is not expected to be the source of the non-mass-dependent signature observed in modern and Archaean samples.
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Hattori, S., S. O. Danielache, M. S. Johnson, J. A. Schmidt, H. G. Kjaergaard, S. Toyoda, Y. Ueno, and N. Yoshida. "Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC<sup>32</sup>S, OC<sup>33</sup>S, OC<sup>34</sup>S and O<sup>13</sup>CS: isotopic fractionation in photolysis and atmospheric implications." Atmospheric Chemistry and Physics 11, no. 19 (October 14, 2011): 10293–303. http://dx.doi.org/10.5194/acp-11-10293-2011.
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Abstract. We report measurements of the ultraviolet absorption cross sections of OC32S, OC33S, OC34S and O13CS from 195 to 260 nm. The OCS isotopologues were synthesized from isotopically-enriched elemental sulfur by reaction with carbon monoxide. The measured cross section of OC32S is consistent with literature spectra recorded using natural abundance samples. Relative to the spectrum of the most abundant isotopologue, substitution of heavier rare isotopes has two effects. First, as predicted by the reflection principle, the Gaussian-based absorption envelope becomes slightly narrower and blue-shifted. Second, as predicted by Franck-Condon considerations, the weak vibrational structure is red-shifted. Sulfur isotopic fractionation constants (33ε, 34ε) as a function of wavelength are not highly structured, and tend to be close to zero on average on the high energy side and negative on the low energy side. The integrated photolysis rate of each isotopologue at 20 km, the approximate altitude at which most OCS photolysis occurs, was calculated. Sulfur isotopic fractionation constants at 20 km altitude are (−3.7 ± 4.5)‰ and (1.1 ± 4.2)‰ for 33ε and 34ε, respectively, which is inconsistent with the previously estimated large fractionation of over 73‰ in 34ε. This demonstrates that OCS photolysis does not produce sulfur isotopic fractionation of more than ca. 5‰, suggesting OCS may indeed be a significant source of background stratospheric sulfate aerosols. Finally, the predicted isotopic fractionation constant for 33S excess (33E) in OCS photolysis is (−4.2 ± 6.6)‰, and thus photolysis of OCS is not expected to be the source of the non-mass-dependent signature observed in modern and Archaean samples.
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Weber, Felix, Christoph Emanuel Düllmann, Vadim Gadelshin, Nina Kneip, Stephan Oberstedt, Sebastian Raeder, Jörg Runke, et al. "Probing the Atomic Structure of Californium by Resonance Ionization Spectroscopy." Atoms 10, no. 2 (May 24, 2022): 51. http://dx.doi.org/10.3390/atoms10020051.
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The atomic structure of californium is probed by two-step resonance ionization spectroscopy. Using samples with a total amount of about 2×1010 Cf atoms (ca. 8.3 pg), ground-state transitions as well as transitions to high-lying Rydberg states and auto-ionizing states above the ionization potential are investigated and the lifetimes of various atomic levels are measured. These investigations lead to the identification of efficient ionization schemes, important for trace analysis and nuclear structure investigations. Most of the measurements are conducted on 250Cf. In addition, the isotope shift of the isotopic chain 249−252Cf is measured for one transition. The identification and analysis of Rydberg series enables the determination of the first ionization potential of californium to EIP=50,666.76(5)cm−1. This is about a factor of 20 more precise than the current literature value.
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Nava-Fernandez, Cinthya, Adam Hartland, Fernando Gázquez, Ola Kwiecien, Norbert Marwan, Bethany Fox, John Hellstrom, et al. "Pacific climate reflected in Waipuna Cave drip water hydrochemistry." Hydrology and Earth System Sciences 24, no. 6 (July 1, 2020): 3361–80. http://dx.doi.org/10.5194/hess-24-3361-2020.
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Abstract. Cave microclimate and geochemical monitoring is vitally important for correct interpretations of proxy time series from speleothems with regard to past climatic and environmental dynamics. We present results of a comprehensive cave-monitoring programme in Waipuna Cave in the North Island of New Zealand, a region that is strongly influenced by the Southern Westerlies and the El Niño–Southern Oscillation (ENSO). This study aims to characterise the response of the Waipuna Cave hydrological system to atmospheric circulation dynamics in the southwestern Pacific region in order to assure the quality of ongoing palaeo-environmental reconstructions from this cave. Drip water from 10 drip sites was collected at roughly monthly intervals for a period of ca. 3 years for isotopic (δ18O, δD, d-excess parameter, δ17O, and 17Oexcess) and elemental (Mg∕Ca and Sr∕Ca) analysis. The monitoring included spot measurements of drip rates and cave air CO2 concentration. Cave air temperature and drip rates were also continuously recorded by automatic loggers. These datasets were compared to surface air temperature, rainfall, and potential evaporation from nearby meteorological stations to test the degree of signal transfer and expression of surface environmental conditions in Waipuna Cave hydrochemistry. Based on the drip response dynamics to rainfall and other characteristics, we identified three types of discharge associated with hydrological routing in Waipuna Cave: (i) type 1 – diffuse flow, (ii) type 2 – fracture flow, and (iii) type 3 – combined flow. Drip water isotopes do not reflect seasonal variability but show higher values during severe drought. Drip water δ18O values are characterised by small variability and reflect the mean isotopic signature of precipitation, testifying to rapid and thorough homogenisation in the epikarst. Mg∕Ca and Sr∕Ca ratios in drip waters are predominantly controlled by prior calcite precipitation (PCP). Prior calcite precipitation is strongest during austral summer (December–February), reflecting drier conditions and a lack of effective infiltration, and is weakest during the wet austral winter (July–September). The Sr∕Ca ratio is particularly sensitive to ENSO conditions due to the interplay of congruent or incongruent host rock dissolution, which manifests itself in lower Sr∕Ca in above-average warmer and wetter (La Niña-like) conditions. Our microclimatic observations at Waipuna Cave provide a valuable baseline for the rigorous interpretation of speleothem proxy records aiming at reconstructing the past expression of Pacific climate modes.
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Retzmann, Anika, Dorothy Walls, Kerri Miller, Michael Wieser, Johanna Irrgeher, and Thomas Prohaska. "Assessing the potential of online ICP–MS analysis to optimize Ca/matrix separation using DGA Resin for subsequent isotopic analysis." Monatshefte für Chemie - Chemical Monthly 152, no. 4 (April 2021): 401–10. http://dx.doi.org/10.1007/s00706-021-02754-2.
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AbstractCa isotopes have gained increasing interest as a diagnostic tool for bone diseases due to the variations in abundances as a consequence of changes in bone-mineral balance. Optimized Ca/matrix separation prior to analysis is a prerequisite for reliable isotope ratio measurements in complex biological matrices such as blood, serum, or urine. The online analysis of analyte/matrix separation by ICP-MS enables direct assessment of elution profiles supporting the optimization process. The integration of transient signals and signal suppression challenge the quantification and interpretation of the elution profiles. Mn and Co remain unretained by the DGA Resin (TrisKem International) from nitric acid. Hence, in the present study, these elements were investigated for their application as standards to monitor signal suppression. Successful analyte quantification was accomplished using a dynamic correction strategy applying a linear gradient of a suppression factor based on Mn and Co intensities. An optimized Ca/matrix separation procedure using DGA Resin is proposed based on the results during online ICP-MS analysis. Graphic abstract
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Benaafi, Mohammed, and Abdulaziz Al-Shaibani. "Hydrochemical and Isotopic Investigation of the Groundwater from Wajid Aquifer in Wadi Al-Dawasir, Southern Saudi Arabia." Water 13, no. 13 (July 3, 2021): 1855. http://dx.doi.org/10.3390/w13131855.
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The Wajid aquifer is considered the main source of water for drinking and irrigation in Wadi Al-Dawasir and Najran, the southern region of Saudi Arabia. This aquifer has been used since the 1960s, and due to the expansion in agricultural activities, the aquifer has been overexploited. The study aims to understand the origin, hydrochemical processes of the groundwater in the shallow unconfined, deep unconfined, and confined parts of the Wajid aquifer in the Wadi Al-Dawasir area. In-situ hydrochemical parameters (pH, temperature, EC, and TDS) were measured in the field, and groundwater samples were collected for major ions and stable isotopes (2H and 18O) measurements in the laboratory. The results show that the groundwater in shallow unconfined, and confined aquifers are of two types; Cl.SO4-Ca. Na and Cl.SO4-Na. Ca; however, groundwater in deep, unconfined aquifers is characterized as HCO3-Ca. Na, and Cl. HCO3-Ca. Na; types of groundwater. The isotopic analysis results reveal that all groundwater samples have values of δ18Oand δ2Hclose to the local and global meteoric water lines, indicating the meteoric origin of Wajid groundwater. Three major hydrochemical processes, including rock weathering, ion exchange, and evaporation, have been identified as key controls on the chemical composition of water in the studied aquifer. The evaporation and ion exchange processes have more influence on the chemical composition of groundwater in the shallow unconfined and confined aquifers. On the contrary, weathering of carbonate minerals affected more the chemistry of groundwater in a deep unconfined aquifer. The unconfined section of the Wajid aquifer shows a reverse pattern of salinity with higher salinity in the recharge area, which is most probably related to the return irrigation water and leaching of salty soil. The open fractures in the upper part of Wajid sandstone most likely act as conduits to percolated saline water to the Wajid aquifer.
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Gupta, Sebanti, John M. Louis, and Robert Tycko. "Effects of an HIV-1 maturation inhibitor on the structure and dynamics of CA-SP1 junction helices in virus-like particles." Proceedings of the National Academy of Sciences 117, no. 19 (April 27, 2020): 10286–93. http://dx.doi.org/10.1073/pnas.1917755117.
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HIV-1 maturation involves conversion of the immature Gag polyprotein lattice, which lines the inner surface of the viral membrane, to the mature capsid protein (CA) lattice, which encloses the viral RNA. Maturation inhibitors such as bevirimat (BVM) bind within six-helix bundles, formed by a segment that spans the junction between the CA and spacer peptide 1 (SP1) subunits of Gag, and interfere with cleavage between CA and SP1 catalyzed by the HIV-1 protease (PR). We report solid-state NMR (ssNMR) measurements on spherical virus-like particles (VLPs), facilitated by segmental isotopic labeling, that provide information about effects of BVM on the structure and dynamics of CA–SP1 junction helices in the immature lattice. Although BVM strongly blocks PR-catalyzed CA–SP1 cleavage in VLPs and blocks conversion of VLPs to tubular CA assemblies, 15N and 13C ssNMR chemical shifts of segmentally labeled VLPs with and without BVM are very similar, indicating that interaction with BVM does not alter the six-helix bundle structure appreciably. Only the 15N chemical shift of A280 (the first residue of SP1) changes significantly, consistent with BVM binding to an internal ring of hydrophobic side chains of L279 residues. Measurements of transverse 15N spin relaxation rates reveal a reduction in the amplitudes and/or timescales of backbone N–H bond motions, corresponding to a rigidification of the six-helix bundles. Overall, our data show that inhibition of HIV-1 maturation by BVM involves changes in structure and dynamics that are surprisingly subtle, but still sufficient to produce a large effect on CA–SP1 cleavage.
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Schleinkofer, Nicolai, David Evans, Max Wisshak, Janina Vanessa Büscher, Jens Fiebig, André Freiwald, Sven Härter, Horst R. Marschall, Silke Voigt, and Jacek Raddatz. "Host-influenced geochemical signature in the parasitic foraminifera <i>Hyrrokkin sarcophaga</i>." Biogeosciences 18, no. 16 (August 20, 2021): 4733–53. http://dx.doi.org/10.5194/bg-18-4733-2021.
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Abstract. Hyrrokkin sarcophaga is a parasitic foraminifera that is commonly found in cold-water coral reefs where it infests the file clam Acesta excavata and the scleractinian coral Desmophyllum pertusum (formerly known as Lophelia pertusa). Here, we present measurements of the trace element and isotopic composition of these parasitic foraminifera, analyzed by inductively coupled optical emission spectrometry (ICP-OES), electron probe microanalysis (EPMA) and mass spectrometry (gas-source MS and inductively-coupled-plasma MS). Our results reveal that the geochemical signature of H. sarcophaga depends on the host organism it infests. Sr / Ca ratios are 1.1 mmol mol−1 higher in H. sarcophaga that infest D. pertusum, which could be an indication that dissolved host carbonate material is utilized in shell calcification, given that the aragonite of D. pertusum has a naturally higher Sr concentration compared to the calcite of A. excavata. Similarly, we measure 3.1 ‰ lower δ13C and 0.25 ‰ lower δ18O values in H. sarcophaga that lived on D. pertusum, which might be caused by the direct uptake of the host's carbonate material with a more negative isotopic composition or different pH regimes in these foraminifera (pH can exert a control on the extent of CO2 hydration/hydroxylation) due to the uptake of body fluids of the host. We also observe higher Mn / Ca ratios in foraminifera that lived on A. excavata but did not penetrate the host shell compared to specimen that penetrated the shell, which could be interpreted as a change in food source, changes in the calcification rate, Rayleigh fractionation or changing oxygen conditions. While our measurements provide an interesting insight into the calcification process of this unusual foraminifera, these data also indicate that the geochemistry of this parasitic foraminifera is unlikely to be a reliable indicator of paleoenvironmental conditions using Sr / Ca, Mn / Ca, δ18O or δ13C unless the host organism is known and its geochemical composition can be accounted for.
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Biriukov, Denys, Hsiu-Wen Wang, Nikhil Rampal, Carmelo Tempra, Patrik Kula, Joerg C. Neuefeind, Andrew G. Stack, and Milan Předota. "The “good,” the “bad,” and the “hidden” in neutron scattering and molecular dynamics of ionic aqueous solutions." Journal of Chemical Physics 156, no. 19 (May 21, 2022): 194505. http://dx.doi.org/10.1063/5.0093643.
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We characterize a concentrated 7.3 m CaCl2 solution, combining neutron diffraction with chloride isotopic substitution (Cl-NDIS) in null water and molecular dynamics (MD) simulations. We elucidate the solution structure, thermodynamic properties, and extent of ion pairing previously suggested as concentration-dependent and often not observed at lower concentrations. Our Cl-NDIS measurements designate the solvent-shared ion pairing as dominant and the contact ion pairing (CIP) as insignificant even under conditions close to the solubility limit. The MD models parameterized against neutron diffraction with calcium isotopic substitution (Ca-NDIS) overestimate CIP despite successfully reproducing most of the Cl-NDIS signal. This drawback originates from the fact that Ca2+–Cl− interactions were primarily “hidden” in the Ca-NDIS signal due to overlapping with Ca2+–Ow and Ca2+–Hw contributions to the total scattering. Contrary, MD models with moderate CIP and possessing generally good performance at high concentrations fail to reproduce the NDIS measurements accurately. Therefore, the electronic polarization, introduced in most of the recent MD models via scaling ionic charges, resolves some but not all parameterization drawbacks. We conclude that despite improving the quality of MD models “on average,” the question “which model is the best” has not been answered but replaced by the question “which model is better for a given research.” An overall “good” model can still be inappropriate or, in some instances, “bad” and, unfortunately, produce erroneous results. The accurate interpretation of several NDIS datasets, complemented by MD simulations, can prevent such mistakes and help identify the strengths, weaknesses, and convenient applications for corresponding computational models.
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Fantle, Matthew S., Heather Tollerud, Anton Eisenhauer, and Chris Holmden. "The Ca isotopic composition of dust-producing regions: Measurements of surface sediments in the Black Rock Desert, Nevada." Geochimica et Cosmochimica Acta 87 (June 2012): 178–93. http://dx.doi.org/10.1016/j.gca.2012.03.037.
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Leavitt, Steven, Li Cheng, David Williams, Talbot Brooks, Bruce Kimball, Paul Pinter, Gerard Wall, et al. "Soil Organic Carbon Isotope Tracing in Sorghum under Ambient CO2 and Free-Air CO2 Enrichment (FACE)." Land 11, no. 2 (February 18, 2022): 309. http://dx.doi.org/10.3390/land11020309.
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As atmospheric carbon dioxide concentrations, [CO2Air], continue their uncontrolled rise, the capacity of soils to accumulate or retain carbon is uncertain. Free-air CO2 enrichment (FACE) experiments have been conducted to better understand the plant, soil and ecosystem response to elevated [CO2], frequently employing commercial CO2 that imparts a distinct isotopic signal to the system for tracing carbon. We conducted a FACE experiment in 1998 and 1999, whereby sorghum (C4 photosynthetic pathway) was grown in four replicates of four treatments using a split-strip plot design: (i) ambient CO2/ample water (365 μmol mol−1, “Control–Wet”), (ii) ambient CO2/water stress (“Control–Dry”), (iii) CO2-enriched (560 μmol mol−1, “FACE–Wet”), and (iv) CO2-enriched/water stressed (“FACE–Dry”). The stable-carbon isotope composition of the added CO2 (in FACE treatments) was close to that of free atmosphere background values, so the subsequent similar 13C-enriched carbon signal photosynthetically fixed by C4 sorghum plants could be used to trace the fate of carbon in both FACE and control treatments. Measurement of soil organic carbon content (SOC (%) = gC/gdry soil × 100%) and δ13C at three depths (0–15, 15–30, and 30–60 cm) were made on soils from the beginning and end of the two experimental growing seasons. A progressive ca. 0.5‰–1.0‰ δ13C increase in the upper soil SOC in all treatments over the course of the experiment indicated common entry of new sorghum carbon into the SOC pools. The 0–15 cm SOC in FACE treatments was 13C-enriched relative to the Control by ca. 1‰, and according to isotopic mass balance, the fraction of the new sorghum-derived SOC in the Control–Wet treatment at the end of the second season was 8.4%, 14.2% in FACE–Wet, 6.5% in Control–Dry, and 14.2% in FACE–Dry. The net SOC enhancement resulting from CO2 enrichment was therefore 5.8% (or 2.9% y−1 of experiment) under ample water and 7.7% (3.8% y−1 of experiment) under limited water, which matches the pattern of greater aboveground biomass increase with elevated [CO2Air] under the Dry treatment, but no parallel isotopic shifts were found in deeper soils. However, these increased fractions of new carbon in SOC at the end of the experiment do not necessarily mean an increase in total SOC content, because gravimetric measurements of SOC did not reveal a significant increase under elevated [CO2Air], at least within the limits of SOC-content error bars. Thus, new carbon gains might be offset by pre-experiment carbon losses. The results demonstrate successful isotopic tracing of carbon from plants to soils in this sorghum FACE experiment showing differences between FACE and Control treatments, which suggest more dynamic cycling of SOC under elevated [CO2Air] than in the Control treatment.
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McCulloch, Malcolm, Mike Cappo, James Aumend, and Wolfgang Müller. "Tracing the life history of individual barramundi using laser ablation MC-ICP-MS Sr-isotopic and Sr/Ba ratios in otoliths." Marine and Freshwater Research 56, no. 5 (2005): 637. http://dx.doi.org/10.1071/mf04184.
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Otoliths preserve a continuous geochemical record of its life history, from the earliest natal stage through to adulthood. Using in situ laser ablation (UV) multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements of Sr isotopic compositions together with elemental abundances (Ca, Sr, Ba and Mg), we show how it is possible to characterise the various types of habitats encountered throughout the lifecycle history of individual barramundi. Unlike trace element concentrations, which can be modulated by physiological processes, Sr isotopic compositions of otoliths provide a direct fingerprint of the water mass in which the fish lived. Elemental abundances, in particular Sr/Ba ratios are, however, shown to be especially sensitive to transitional environments, such as estuaries. The flexibility of the barramundi’s life history is confirmed by the present study, with the existence of both marine and freshwater nurseries, with some individuals spending their entire life cycle in fresh water, some entirely in marine and others moving between freshwater estuarine and marine habitats.
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Howes, Ella L., Karina Kaczmarek, Markus Raitzsch, Antje Mewes, Nienke Bijma, Ingo Horn, Sambuddha Misra, Jean-Pierre Gattuso, and Jelle Bijma. "Decoupled carbonate chemistry controls on the incorporation of boron into <i>Orbulina universa</i>." Biogeosciences 14, no. 2 (January 26, 2017): 415–30. http://dx.doi.org/10.5194/bg-14-415-2017.
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Abstract. In order to fully constrain paleo-carbonate systems, proxies for two out of seven parameters, plus temperature and salinity, are required. The boron isotopic composition (δ11B) of planktonic foraminifera shells is a powerful tool for reconstructing changes in past surface ocean pH. As B(OH)4− is substituted into the biogenic calcite lattice in place of CO32−, and both borate and carbonate ions are more abundant at higher pH, it was suggested early on that B ∕ Ca ratios in biogenic calcite may serve as a proxy for [CO32−]. Although several recent studies have shown that a direct connection of B ∕ Ca to carbonate system parameters may be masked by other environmental factors in the field, there is ample evidence for a mechanistic relationship between B ∕ Ca and carbonate system parameters. Here, we focus on investigating the primary relationship to develop a mechanistic understanding of boron uptake. Differentiating between the effects of pH and [CO32−] is problematic, as they co-vary closely in natural systems, so the major control on boron incorporation remains unclear. To deconvolve the effects of pH and [CO32−] and to investigate their impact on the B ∕ Ca ratio and δ11B, we conducted culture experiments with the planktonic foraminifer Orbulina universa in manipulated culture media: constant pH (8.05), but changing [CO32−] (238, 286 and 534 µmol kg−1 CO32−) and at constant [CO32−] (276 ± 19.5 µmol kg−1) and varying pH (7.7, 7.9 and 8.05). Measurements of the isotopic composition of boron and the B ∕ Ca ratio were performed simultaneously using a femtosecond laser ablation system coupled to a MC-ICP-MS (multiple-collector inductively coupled plasma mass spectrometer). Our results show that, as expected, δ11B is controlled by pH but it is also modulated by [CO32−]. On the other hand, the B ∕ Ca ratio is driven by [HCO3−], independently of pH. This suggests that B ∕ Ca ratios in foraminiferal calcite can possibly be used as a second, independent, proxy for complete paleo-carbonate system reconstructions. This is discussed in light of recent literature demonstrating that the primary relationship between B ∕ Ca and [HCO3−] can be obscured by other environmental parameters.
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Jones, Sam P., Jérôme Ogée, Joana Sauze, Steven Wohl, Noelia Saavedra, Noelia Fernández-Prado, Juliette Maire, Thomas Launois, Alexandre Bosc, and Lisa Wingate. "Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition." Hydrology and Earth System Sciences 21, no. 12 (December 15, 2017): 6363–77. http://dx.doi.org/10.5194/hess-21-6363-2017.
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Abstract. The contribution of photosynthesis and soil respiration to net land–atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8–14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting that this represents a robust approach to assay the activity of CA in soil. As expected, estimates of the δ18O of the soil water that equilibrates with CO2 varied in response to alteration to the δ18O of soil water. However, these estimates were consistently more negative than the composition of the soil water extracted by cryogenic vacuum distillation at the end of the gas measurements with differences of up to −3.94 ‰ VSMOW–SLAP. These offsets suggest that, at least at lower water contents, CO2–H2O isotope equilibration primarily occurs with water pools that are bound to particle surfaces and are depleted in 18O compared to bulk soil water.
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Vardag, S. N., C. Gerbig, G. Janssens-Maenhout, and I. Levin. "Estimation of continuous anthropogenic CO<sub>2</sub>: model-based evaluation of CO<sub>2</sub>, CO, δ<sup>13</sup>C(CO<sub>2</sub>) and Δ<sup>14</sup>C(CO<sub>2</sub>) tracer methods." Atmospheric Chemistry and Physics 15, no. 22 (November 16, 2015): 12705–29. http://dx.doi.org/10.5194/acp-15-12705-2015.
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Abstract. We investigate different methods for estimating anthropogenic CO2 using modeled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that, independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not yet feasible at rural measurement sites due to the low signal-to-noise ratio of anthropogenic CO2 estimates at such settings. The tracers δ13C(CO2) and CO provide an accurate possibility to determine anthropogenic CO2 continuously, only if all CO2 sources in the catchment area are well characterized or calibrated with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We test different calibration strategies for the mean isotopic signature and CO to CO2 ratio using precise Δ14C(CO2) measurements on monthly integrated as well as on grab samples. For δ13C(CO2), a calibration with annually averaged 14C(CO2) grab samples is most promising, since integrated sampling introduces large biases into anthropogenic CO2 estimates. For CO, these biases are smaller. The precision of continuous anthropogenic CO2 determination using δ13C(CO2) depends on measurement precision of δ13C(CO2) and CO2, while the CO method is mainly limited by the variation in natural CO sources and sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. Hypothetical future measurements of continuous Δ14C(CO2) with a precision of 5 ‰ are promising for anthropogenic CO2 determination (precision ca. 10–20 %) but are not yet available. The investigated tracer-based approaches open the door to improving, validating and reducing biases of highly resolved emission inventories using atmospheric observation and regional modeling.
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Godbillot, Camille, Fabrice Minoletti, Franck Bassinot, and Michaël Hermoso. "Parallel between the isotopic composition of coccolith calcite and carbon levels across Termination II: developing a new paleo-CO<sub>2</sub> probe." Climate of the Past 18, no. 3 (March 7, 2022): 449–64. http://dx.doi.org/10.5194/cp-18-449-2022.
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Abstract. Beyond the pCO2 records provided by ice core measurements, the quantification of atmospheric CO2 concentrations and changes thereof relies on proxy data, the development of which represents a foremost challenge in paleoceanography. In the paleoceanographic toolbox, the coccolithophores occupy a notable place, as the magnitude of the carbon isotopic fractionation between ambient CO2 and a type of organic compounds that these photosynthetic microalgae synthesize (the alkenones) represents a relatively robust proxy to reconstruct past atmospheric CO2 concentrations during the Cenozoic. The isotopic composition of coeval calcite biominerals found in the sediments and also produced by the coccolithophores (the coccoliths) have been found to record an ambient CO2 signal through culture and sediment analyses. These studies have, however, not yet formalized a transfer function that quantitatively ties the isotopic composition of coccolith calcite to the concentrations of aqueous CO2 and, ultimately, to atmospheric CO2 levels. Here, we make use of a microseparation protocol to compare the isotopic response of two size-restricted coccolith assemblages from the North Atlantic to changes in surface ocean CO2 during Termination II (ca. 130–140 ka). Performing paired measurements of the isotopic composition (δ13C and δ18O) of relatively large and small coccoliths provides an isotopic offset that can be designated as a “differential vital effect”. We find that the evolution of this offset follows that of aqueous CO2 concentrations computed from the ice core CO2 curve and an independent temperature signal. We interpret this biogeochemical feature to be the result of converging carbon fixation strategies between large and small cells as the degree of carbon limitation for cellular growth decreases across the deglaciation. We are therefore able to outline a first-order trend between the coccolith differential vital effects and aqueous CO2 in the range of Quaternary CO2 concentrations. Although this study would benefit from further constraints on the other controls at play on coccolith geochemistry (growth rate, air–sea gas exchange, etc.), this test of the drivers of coccolith Δδ13C and Δδ18O in natural conditions is a new step in the development of a coccolith paleo-CO2 probe.
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Rodgers, P., C. Soulsby, S. Waldron, and D. Tetzlaff. "Using stable isotope tracers to identify hydrological flow paths, residence times and landscape controls in a mesoscale catchment." Hydrology and Earth System Sciences Discussions 2, no. 1 (January 13, 2005): 1–35. http://dx.doi.org/10.5194/hessd-2-1-2005.
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Abstract. δ18O tracer measurements of precipitation and stream waters were used to investigate hydrological flow paths and residence times at nested spatial scales in the mesoscale (233 km2 River Feugh catchment in the northeast of Scotland over the 2001-2002 hydrological year. Precipitation δ18O exhibited strong seasonal variation, which although significantly damped by catchment mixing processes, was reflected in stream water outputs at six sampling sites. This allowed δ18O variations to be used to infer the relative influence of soil-derived storm flows with a seasonally variable isotopic signature, and groundwater of more constant isotopic composition. Periodic regression analysis was then used to examine the sub-catchment differences in the mixing of these two main hydrological sources processes more quantitatively, using an exponential flow model to provide preliminary estimates of mean stream water residence times, which varied between 0.4-2.9 years. This showed that the effects of increasing scale on estimated mean stream water residence time was minimal beyond the smallest (ca. 1 km2 headwater catchment scale. Instead, the interaction of catchment soil cover and topography acted as the dominant influence. Responsive hydrological pathways, associated with peat soils in the headwater sub-catchments, produced seasonally variable δ18O signatures in runoff with short mean residence times (0.4-0.8 years). In contrast, areas dominated by more freely draining soils and larger groundwater storage in shallow aquifers appear to provide effective mixing and damping of variable precipitation inputs implying longer residence times (1.4-2.9 years). These insights from δ18O measurements extend the hydrological understanding of the Feugh catchment gained from previous geochemical tracer studies, and demonstrate the utility of isotope tracers in investigating the interaction of hydrological processes and catchment characteristics at the mesoscale.
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Ganssen, G., F. Peeters, B. Metcalfe, P. Anand, S. Jung, D. Kroon, and G. J. Brummer. "Quantifying sea surface temperature ranges of the Arabian Sea for the past 20 000 years." Climate of the Past Discussions 6, no. 6 (December 21, 2010): 2795–814. http://dx.doi.org/10.5194/cpd-6-2795-2010.
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Abstract. The oxygen isotopic composition of planktonic foraminifera tests is one of the widest used geochemical tools to reconstruct past changes of physical parameters of the upper ocean. It is common practice to analyze multiple individuals from a mono-specific population and assume that the outcome reflects a mean value of the environmental conditions during calcification of the analyzed individuals. Here we present the oxygen isotope composition of individual specimens of the surface dwelling species Globigerinoides ruber and Globigerina bulloides from sediment cores in the Western Arabian Sea off Somalia inferred as indicators of past seasonal ranges in temperature. Combining the δ18O measurements of individual specimens to obtain temperature ranges with Mg/Ca based mean calcification temperatures allows us to reconstruct temperature extrema. Our results indicate that over the past 20 kyrs the seasonal temperature range has fluctuated from its present value of 16 °C (14 to 30 °C), to 11 °C (15 to 26 °C) during the LGM. The range during the LGM suggests that the maximum temperature was lower, whilst minimum temperature remained approximately constant.
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Tobias, Phillip V., John C. Vogel, H. Dieter Oschadleus, Timothy C. Partridge, and Jeffrey K. McKee. "New Isotopic and Sedimentological Measurements of the Thabaseek Deposits (South Africa) and the Dating of the Taung Hominid." Quaternary Research 40, no. 3 (November 1993): 360–67. http://dx.doi.org/10.1006/qres.1993.1089.
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AbstractEarlier attempts to date the Taung hominid type specimen of Australopithecus africanus Dart yielded conflicting results. Recent faunal studies pointed to an age of 2.3 myr. Radioisotopic results suggested 1.0 myr. New uranium studies reveal that the Thabaseek (the oldest Taung tufa) was not a closed system and that younger uranium entered the tufa after initial deposition, producing an apparent isotopic age younger than the age of deposition. The Thabaseek isotopic dates provide only a terminus ad quem and this technique is therefore not applicable to the older Taung tufas. Delson's dating (2.3 myr) of cercopithecoids from Hrdlicka's pinnacle ca. 50 m from the hominid site provides the best available approximation to the age of the hominid. In our new Taung excavation, stratigraphic analysis indicates that the hominid may somewhat predate most identified fauna. Sedimentologically the hominid matrix proves to be of fluvial deposition, and hence closely resembles one Hrdlicka deposit, both samples differing appreciably from all other Taung samples which bespeak eolian deposition. Thus, the conditions under which the hominid-bearing stratum was deposited were virtually identical to those pertaining to one of the Hrdlicka deposits. The newest results show that Taung was not the youngest South African australopithecine site and eliminate the discrepancy between the relative ages of the Taung A. africanus africanus and the Sterkfontein A. africanus transvaalensis.
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Piotrowska, Natalia, Anna Pazdur, Sławomira Pawełczyk, Andrzej Z. Rakowski, Barbara Sensuła, and Konrad Tudyka. "Human Activity Recorded in Carbon Isotopic Composition of Atmospheric CO2 in Gliwice Urban Area and Surroundings (Southern Poland) in the Years 2011–2013." Radiocarbon 62, no. 1 (August 19, 2019): 141–56. http://dx.doi.org/10.1017/rdc.2019.92.
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ABSTRACTIn this paper, a record of the 14C and 13C isotope content of atmospheric CO2 for Gliwice is presented for samples collected on a weekly basis in the years 2011–2013. In addition, measurements were performed on the early and late wood from the annual rings of pine trees from five sites located 3–6 km from the atmospheric CO2 sampling point. The concentration of 14C in CO2 samples from the air was much lower relative to the concentration of this isotope in “clean air,” indicating a pronounce Suess effect, with a mean Δ14C lower by ca. 60‰ than Jungfraujoch data when the 15% of the highest differences are excluded, which leads to the FFCO2 estimate of 5.8%. In winter, the main source of fossil CO2 was fuel combustion, as confirmed by significant correlations with air pollutants. In the vegetation seasons, the Δ14C was highly variable due to biogenic influence and more variable winds. The isotopic results were also affected by an additional significant CO2 source for the Gliwice air, which was a closed mine shaft. The Δ14C and δ13C in tree rings did not record a strong Suess effect in the years 2008–2013 in woodland areas around Gliwice city.
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Pearson, Ann, Ann P. Mcnichol, Robert J. Schneider, Karl F. Von Reden, and Yan Zheng. "Microscale AMS 14C Measurement at NOSAMS." Radiocarbon 40, no. 1 (1997): 61–75. http://dx.doi.org/10.1017/s0033822200017902.
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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.
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ITO, Motoo, and Scott MESSENGER. "Thermal metamorphic history of a Ca, Al-rich inclusion constrained by high spatial resolution Mg isotopic measurements with NanoSIMS 50L." Meteoritics & Planetary Science 45, no. 4 (April 2010): 583–95. http://dx.doi.org/10.1111/j.1945-5100.2010.01038.x.
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Fletcher, I. R., A. L. Maggi, K. J. R. Rosman, and N. J. McNaughton. "Isotopic abundance measurements of K and Ca using a wide-dispersion multi-collector mass spectrometer and low-fractionation ionisation techniques." International Journal of Mass Spectrometry and Ion Processes 163, no. 1-2 (April 1997): 1–17. http://dx.doi.org/10.1016/s0168-1176(96)04540-5.
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Thomsen, Mette S., and Steinar Gulliksen. "Reduction of CO2-to-Graphite Conversion Time of Organic Materials for 14C AMS." Radiocarbon 34, no. 3 (1992): 330–34. http://dx.doi.org/10.1017/s0033822200063505.
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Graphite is the most common type of target for 14C accelerator mass spectrometry (AMS). It is readily produced by catalytic reduction of CO2, but the presence of a small amount of impurities (e.g., sulfur compounds) may retard the reaction. We have tested some techniques to find a method that reduces the impurity content of CO2 produced by combustion of organic material. We found that using water during combustion reduces the average time for graphite conversion of CO2 from organic matter from >3 h to ca. 2 h. This is the time for graphite production from CO2 obtained by acid hydrolysis of calcite. Measurements of known-age and background samples show that this combustion method neither changes the isotopic ratios nor introduces any additional background.
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Basu, Sourish, Xin Lan, Edward Dlugokencky, Sylvia Michel, Stefan Schwietzke, John B. Miller, Lori Bruhwiler, et al. "Estimating emissions of methane consistent with atmospheric measurements of methane and δ13C of methane." Atmospheric Chemistry and Physics 22, no. 23 (December 5, 2022): 15351–77. http://dx.doi.org/10.5194/acp-22-15351-2022.
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Abstract. We have constructed an atmospheric inversion framework based on TM5-4DVAR to jointly assimilate measurements of methane and δ13C of methane in order to estimate source-specific methane emissions. Here we present global emission estimates from this framework for the period 1999–2016. We assimilate a newly constructed, multi-agency database of CH4 and δ13C measurements. We find that traditional CH4-only atmospheric inversions are unlikely to estimate emissions consistent with atmospheric δ13C data, and assimilating δ13C data is necessary to derive emissions consistent with both measurements. Our framework attributes ca. 85 % of the post-2007 growth in atmospheric methane to microbial sources, with about half of that coming from the tropics between 23.5∘ N and 23.5∘ S. This contradicts the attribution of the recent growth in the methane budget of the Global Carbon Project (GCP). We find that the GCP attribution is only consistent with our top-down estimate in the absence of δ13C data. We find that at global and continental scales, δ13C data can separate microbial from fossil methane emissions much better than CH4 data alone, and at smaller scales this ability is limited by the current δ13C measurement coverage. Finally, we find that the largest uncertainty in using δ13C data to separate different methane source types comes from our knowledge of atmospheric chemistry, specifically the distribution of tropospheric chlorine and the isotopic discrimination of the methane sink.
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DeCarlo, Thomas M., Michael Holcomb, and Malcolm T. McCulloch. "Reviews and syntheses: Revisiting the boron systematics of aragonite and their application to coral calcification." Biogeosciences 15, no. 9 (May 9, 2018): 2819–34. http://dx.doi.org/10.5194/bg-15-2819-2018.
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Abstract. The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B∕Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B∕Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.
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Pazdur, Anna, Mieczyslaw F. Pazdur, Leszek Starkel, and Joachim Szulc. "Stable Isotopes of Holocene Calcareous Tufa in Southern Poland as Paleoclimatic Indicators." Quaternary Research 30, no. 2 (September 1988): 177–89. http://dx.doi.org/10.1016/0033-5894(88)90022-1.
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The isotopic composition of oxygen in freshwater calcareous tufa seems to be a sensitive indicator of past climatic changes. Results of measurements of δc18O and δc13C in tufa samples dated with the 14C method are used to reconstruct Holocene climatic changes in southern Poland. Values of δc18O obtained on tufa samples from four sites (Raclawka, Rzerzuŝnia, Trzebienice, Sieradowice) representing different hydrodynamic conditions of tufa sedimentation seem to form a selfconsistent series. These values, with some simplifying assumptions concerning the course of tufa sedimentation, were therefore used to estimate mean annual temperatures in the interval ca. 9500-2000 yr B.P. When the resulting curve of thermal changes in southern Poland is compared with changes of deposition and erosion of tuffaceous sediments and with results of other methods of reconstruction of paleoclimate in central Europe, a reasonable agreement among the different specific methods is seen.
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Ganssen, G. M., F. J. C. Peeters, B. Metcalfe, P. Anand, S. J. A. Jung, D. Kroon, and G. J. A. Brummer. "Quantifying sea surface temperature ranges of the Arabian Sea for the past 20 000 years." Climate of the Past 7, no. 4 (December 8, 2011): 1337–49. http://dx.doi.org/10.5194/cp-7-1337-2011.
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Abstract. The oxygen isotopic composition of planktonic foraminifera tests is one of the widest used geochemical tools to reconstruct past changes of physical parameters of the upper ocean. It is common practice to analyze multiple individuals from a mono-specific population and assume that the outcome reflects a mean value of the environmental conditions during calcification of the analyzed individuals. Here we present the oxygen isotope composition of individual specimens of the surface-dwelling species Globigerinoides ruber and Globigerina bulloides from sediment cores in the Western Arabian Sea off Somalia, inferred as indicators of past seasonal ranges in temperature. Combining the δ18O measurements of individual specimens to obtain temperature ranges with Mg/Ca based mean calcification temperatures allows us to reconstruct temperature extrema. Our results indicate that over the past 20 kyr the seasonal temperature range has fluctuated from its present value of 16 °C to mean values of 13 °C and 11 °C for the Holocene and LGM, respectively. The data for the LGM suggest that the maximum temperature was lower, whilst minimum temperature remained approximately constant. The rather minor variability in lowest summer temperatures during the LGM suggests roughly constant summer monsoon intensity, while upwelling-induced productivity was lowered.
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Majzlan, Juraj, Maria Brey-Funke, Alexander Malz, Stefan Donndorf, and Rastislav Milovský. "Fluid evolution and mineralogy of Mn-Fe-barite-fluorite mineralizations at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in Germany." Geologica Carpathica 67, no. 1 (February 1, 2016): 3–20. http://dx.doi.org/10.1515/geoca-2016-0001.
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Abstract Numerous small deposits and occurrences of Mn-Fe-fluorite-barite mineralization have developed at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in central Germany. The studied mineralizations comprise the assemblages siderite+ankerite-calcite-fluorite-barite and hematite-Mn oxides-calcite-barite, with the precipitation sequence in that order within each assemblage. A structural geological analysis places the origin of the barite veins between the Middle Jurassic and Early Cretaceous. Primary fluid inclusions contain water vapour and an aqueous phase with NaCl and CaCl2 as the main solutes, with salinities mostly between 24–27 mass. % CaCl2 eq. Th measurements range between 85 °C and 160 °C in barite, between 139 °C and 163 °C in siderite, and between 80 °C and 130 °C in fluorite and calcite. Stable isotopes (S, O) point to the evaporitic source of sulphur in the observed mineralizations. The S,C,O isotopic compositions suggest that barite and calcite could not have precipitated from the same fluid. The isotopic composition of the fluid that precipitated barite is close to the sea water in the entire Permo–Mesozoic time span whereas calcite is isotopically distinctly heavier, as if the fluids were affected by evaporation. The fluid evolution in the siliciclastic/volcanic Rotliegend sediments (as determined by a number of earlier petrological and geochemical studies) can be correlated with the deposition sequence of the ore minerals. In particular, the bleaching of the sediments by reduced Rotliegend fluids (basinal brines) could be the event that mobilized Fe and Mn. These elements were deposited as siderite+ankerite within the Zechstein carbonate rocks and as hematite+Mn oxides within the oxidizing environment of the Permian volcanic and volcanoclastic rocks. A Middle-Jurassic illitization event delivered Ca, Na, Ba, and Pb from the feldspars into the basinal brines. Of these elements, Ba was deposited as massive barite veins.
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Pai, Ashok P., Darren Hillegonds, Primo Lara, Chong-xian Pan, and David Shelton. "Calcium metabolism in patients with castration-resistant prostate cancer: Development of a quantitative urinary assay for extent of bone metastasis." Journal of Clinical Oncology 30, no. 5_suppl (February 10, 2012): 130. http://dx.doi.org/10.1200/jco.2012.30.5_suppl.130.
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130 Background: In patients with metastatic castration-resistant prostate cancer (CRPC), the degree of perturbation from normal bone turnover provides a strong indication of risk for disease progression, skeletal complications and death. Biomarkers of bone cell function and bone collagen degradation provide an integrated index of the underlying disease for patients with bony metastases, but available bone markers are not precise or accurate. In this study, patients with CRPC with bony metastases will consume a single oral calcium-41 dose and the pharmacokinetics of this will be measured over an 18 month period. Participants will also be assessed clinically for time to progression, skeletal related events and death. Methods: Patients with metastatic castration-resistant prostate cancer and bony metastatses, as diagnosed via bone scintigraphy, who were on bisphosphonates were enrolled into the study. 12 consenting research subjects consumed a single 1.2 microgram 41Ca tracer dose and provided 30-250mL urine specimens (single voids) after dose on day 1 (6h after dosing), days 7, 14, 28, 42, 60, and monthly thereafter. Isotope ratios were measured via accelerator mass spectrometry. Results: Urinary 41Ca/Ca was significantly and inversely associated with increased skeletal tumor burdens suggesting that development of an isotopic urine test for bone metastasis extent is feasible, providing a non-invasive and quantitative measure of disease extent. A calculation of the area under the curve of the measurements between day zero and 14 were inversely correlated with disease extent at baseline. Clinical deterioration with worsening bony disease was associated with a significant decrease in the urinary 41Ca/Ca value. We are currently assessing correlations between bone turnover and outcomes such as therapy effectiveness, disease progression, skeletal related events and death. Conclusions: This work is the first direct measurement of long-term calcium metabolism in advanced prostate cancer, providing a basic scientific complement to cellular and collagen-based measures of bone formation and resorption rates as well as a correlation to clinically relevant outcomes.
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Michalska, Danuta, and Andrzej Krzyszowski. "Chronology of multicultural site Sowinki in Greater Poland." Geochronometria 44, no. 1 (March 29, 2017): 30–39. http://dx.doi.org/10.1515/geochr-2015-0047.
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Abstract Sowinki is a village located 35 km south of Poznań, where archaeological research has revealed the remains of settlement from different archaeological periods, ranging from the Mesolithic (ca. six thousand years BC) to the Late Medieval period (ca. 15th century AD). This area, therefore, provides a record of the history of Greater Poland (Poznań) region, tracing back to about seven and a half thousand years ago. Samples of bones and wood were collected from different features, including mostly cellar pits, refuse pits and grave pits. Eight of the samples, all collected from grave pits, were selected for radiocarbon dating. The obtained 14C measurements have confirmed previous findings concerning different cultures registered in the studied area, and additionally, they have helped to clarify chronology of the early medieval cemetery. The presented results are the first isotopic measurements taken for the site of Sowinki. Previously, chronological frameworks of this site were determined on the basis of relative chronology, according to stratigraphy of sediments, examination of metal finds, pottery and flint objects. The deposition depth of the analysed charcoals did not exceed 100 cm below ground level. According to the analysis, all the samples date to the time of the early Piasts’ dynasty. The obtained data have allowed for defining two chronological phases of the early medieval cemetery. This is an important archaeological site both in terms of its spread and the long time of existence. In addition, it provides a valuable background for the study on the emergence of early medieval elites and the formation of the Polish “early feudal” state.
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Ramnarine, R., R. P. Voroney, C. Wagner-Riddle, and K. E. Dunfield. "Carbonate removal by acid fumigation for measuring the δ13C of soil organic carbon." Canadian Journal of Soil Science 91, no. 2 (May 2011): 247–50. http://dx.doi.org/10.4141/cjss10066.
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Ramnarine, R., Voroney, R. P., Wagner-Riddle, C. and Dunfield. K. E. 2011. Carbonate removal by acid fumigation for measuring the δ 13 C of soil organic carbon. Can. J. Soil Sci. 91: 247–250. Complete removal of carbonates from calcareous soil samples is critical for accurate measurement of the quantity and isotopic signature (δ13C) of soil organic carbon (SOC). Carbonates confound SOC and δ13C measurements because they have δ13C values ranging from −10‰ to +2‰, whereas those of soil organic carbon range from −27‰ to −13‰, depending on the source of plant residues. Commonly used methods for removing carbonates involve treatment with acid followed by repeated water washings; however, these methods are time consuming, labour-intensive and lead to losses of acid- and water-soluble organic carbon. Fumigation of soil samples with HCl was evaluated as an alternative method, and the time required for complete carbonate removal was determined in this study. Moistened soil samples, taken from 0- to 10-cm and 30- to 50-cm depths, were exposed to HCl vapours for periods of 0, 6, 12, 24, 48, 72, and 96 h, followed by measurements of total C and δ13C using coupled elemental analyzer-isotope ratio mass spectrometry. The minimum time required to remove all carbonates was ca. 30 h and 56 h for surface and subsurface soils containing 0.80 and 1.94% inorganic C, respectively. Therefore, the fumigation period required is dependent on the total carbonate content of the sample and the nature of the carbonate (pedogenic vs lithogenic). In our study, the rate of removal of inorganic carbon was 0.08–0.10 mg h−1 for soil samples sizes with 2.4 to 5.8 mg of carbonate-C, a rate similar to previous studies on acid fumigation. A “correction factor” was used to account for a change in sample mass due to fumigation and is necessary for accurate determination of SOC concentration using our proposed methodology.
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Guehl, J. M., G. Aussenac, J. Bouachrine, R. Zimmermann, J. M. Pennes, A. Ferhi, and P. Grieu. "Sensitivity of leaf gas exchange to atmospheric drought, soil drought, and water-use efficiency in some Mediterranean Abies species." Canadian Journal of Forest Research 21, no. 10 (October 1, 1991): 1507–15. http://dx.doi.org/10.1139/x91-211.
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The responses of CO2 assimilation rate (A), transpiration rate (E), and leaf conductance (g) to increasing leaf to air water vapor concentration difference (ΔW) were investigated (i) using excised shoots from mature trees of Abiesalba, Abiescephalonica, Abiesmarocana, and Abiesnordmanniana and (ii) in situ on a mature tree of Abiesbornmulleriana. Gas-exchange responses to increasing soil drought were also studied in plants of A. bornmulleriana, A. cephalonica, and Cedrusatlantica. Stable carbon isotope composition measurements were carried out on annual growth rings of A. bornmulleriana to estimate the time-integrated values of the ratio of intercellular leaf (Ci) to ambient (Ca) CO2 concentration. Increasing ΔW around the shoots reduced A and g in such a way that either Ci remained constant or its decrease was not pronounced enough for the changes in A to be accounted for by changes in g only. This suggests a direct effect of ΔW on photosynthesis. The different Abies species showed clear differences in water-use efficiency. Abiescephalonica and A. marocana had lower water costs of CO2 assimilation (E/A) than A. nordmanniana and A. alba. It has also been shown that A. cephalonica and A. marocana are characterized by an optimal stomatal control of leaf gas exchange. Stomata closed very rapidly in A. bornmulleriana in response to water supply being withheld, even prior to there being any important decrease in leaf predawn water potential. The stomatal response in C. atlantica was more gradual. In A. bornmulleriana, drought adaptation appears to be linked to the ability to avoid internal water stress, whereas drought adaptation in C. atlantica involves the ability to tolerate internal water stress. The high stomatal sensitivity mA. bornmulleriana is also supported by the isotopic carbon composition data, as shown by the substantial interannual variations in the estimates of Ci/Ca, ranging from 0.48 for the dryest years to 0.61 for the rainy years.
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Simon, S. A., P. Labarca, and R. Robb. "Activation by saccharides of a cation-selective pathway on canine lingual epithelium." American Journal of Physiology-Regulatory, Integrative and Comparative Physiology 256, no. 2 (February 1, 1989): R394—R402. http://dx.doi.org/10.1152/ajpregu.1989.256.2.r394.
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Responses of isolated canine lingual epithelium in an Ussing chamber to D-glucose and fructose reveal events associated with taste transduction. With the use of isotopic flux studies, together with ion substitution and pharmacological and voltage clamp measurements, it was found that the stimulation of ion transport by D-glucose arises from an increase in the influx of cations through a cation-selective pathway. This influx of cations is completely inhibited by 0.1 mM amiloride. The stimulation of transport by fructose in 0.05 M KCl and by D-glucose in 0.05 M RbCl was also inhibited by amiloride, demonstrating that the saccharide-stimulated entry pathway was specific for neither hexose sugars nor for Na. Saccharide stimulation of canine lingual epithelia does not appear to be modulated by increases in intracellular levels of adenosine 3',5'-cyclic monophosphate, guanosine 3',5'-cyclic monophosphate, or Ca. The Na that enters taste cells on saccharide stimulation exits them via the ouabain inhibitable Na+-K+-adenosinetriphosphatase located in the serosal membranes.
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Ballantyne, A. P., J. Brahney, D. Fernandez, C. L. Lawrence, J. Saros, and J. C. Neff. "Biogeochemical response of alpine lakes to recent changes in dust deposition." Biogeosciences Discussions 7, no. 6 (December 1, 2010): 8723–61. http://dx.doi.org/10.5194/bgd-7-8723-2010.
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Abstract. The deposition of dust has recently increased significantly over some regions of the western US. Here we explore how changes in dust deposition have affected the biogeochemistry of two alpine watersheds in Colorado, US. We first reconstruct recent changes in the mass accumulation rate of sediments and then we use isotopic measurements in conjunction with a Bayesian mixing model to infer that approximately 95% of the inorganic fraction of lake sediments is derived from dust. Elemental analyses of modern dust indicate that dust is enriched in Ca, Cr, Cu, Mg, Ni, and in one watershed, Fe and P relative to bedrock. The increase in dust deposition combined with its enrichment in certain elements has altered the biogeochemisty of these systems. Both lakes showed an increase in primary productivity as evidenced by a decrease in carbon isotopic discrimination; however, the cause of increased primary productivity varies due to differences in watershed characteristic. The lake in the larger watershed experienced greater atmospheric N loading and less P loading from the bedrock leading to a greater N:P flux ratio. In contrast, the lake in the smaller watershed experienced less atmospheric N loading and greater P loading from the bedrock, leading to a reduced N:P flux ratio. As a result, primary productivity was more constrained by N availability in the smaller watershed. N-limited primary productivity in the smaller watershed was partly ameliorated by an increase in nitrogen fixation as indicated by reduced nitrogen isotopic values in more contemporary sediments. This study illustrates that alpine watersheds are excellent integrators of changes in atmospheric deposition, but that the biogeochemical response of these watersheds may be mediated by their physical (i.e. watershed area) and chemical (i.e. underlying geology) properties.
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Ballantyne, A. P., J. Brahney, D. Fernandez, C. L. Lawrence, J. Saros, and J. C. Neff. "Biogeochemical response of alpine lakes to a recent increase in dust deposition in the Southwestern, US." Biogeosciences 8, no. 9 (September 23, 2011): 2689–706. http://dx.doi.org/10.5194/bg-8-2689-2011.
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Abstract. The deposition of dust has recently increased significantly over some regions of the western US. Here we explore how changes in dust deposition have affected the biogeochemistry of two alpine watersheds in Colorado, US. We first reconstruct recent changes in the mass accumulation rate of sediments and then we use isotopic measurements in conjunction with a Bayesian mixing model to infer that approximately 95% of the inorganic fraction of lake sediments is derived from dust. Elemental analyses of modern dust indicate that dust is enriched in Ca, Cr, Cu, Mg, Ni, and in one watershed, Fe and P relative to bedrock. The increase in dust deposition combined with its enrichment in certain elements has altered the biogeochemisty of these systems. Both lakes showed an increase in primary productivity as evidenced by a decrease in carbon isotopic discrimination; however, the cause of increased primary productivity varies due to differences in watershed characteristic. The lake in the larger watershed experienced greater atmospheric N loading and less P loading from the bedrock leading to a greater N:P flux ratio. In contrast, the lake in the smaller watershed experienced less atmospheric N loading and greater P loading from the bedrock, leading to a reduced N:P flux ratio. As a result, primary productivity was more constrained by N availability in the smaller watershed. N-limited primary productivity in the smaller watershed was partly ameliorated by an increase in nitrogen fixation as indicated by reduced nitrogen isotopic values in more contemporary sediments. This study illustrates that alpine watersheds are excellent integrators of changes in atmospheric deposition, but that the biogeochemical response of these watersheds may be mediated by their physical (i.e. watershed area) and chemical (i.e. underlying geology) properties.
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Breemen, O. van, T. D. Peterson, and H. A. Sandeman. "UPb zircon geochronology and Nd isotope geochemistry of Proterozoic granitoids in the western Churchill Province: intrusive age pattern and Archean source domains." Canadian Journal of Earth Sciences 42, no. 3 (March 1, 2005): 339–77. http://dx.doi.org/10.1139/e05-007.
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Hudsonian tectonism in the western Churchill Province of Canada encompassed two periods of granitic plutonism. The Hudson suite plutons represent xenocryst-rich, mainly monzogranitic, near-minimum melts emplaced near their source region in thickened middle crust; the Nueltin syenogranites and Pitz rhyolites were generated by intrusion of basalt into extending crust. Zircons from four Nueltin suite samples and 20 Hudson suite samples were analysed by UPb SHRIMP techniques. Intrusion of the Hudson suite lasted ca. 50 million years, from 1845 to 1795 Ma, with a peak around 1825 Ma, and the Nueltin suite from 1765 to 1750 Ma, following a ca. 30-million-year period of magmatic quiescence. A marked contrast in Th/U ratios was found in igneous zircon from Hudson suite samples south (Th/U = 0.066) and north (Th/U = 1.07) of the northern margin of the Central Hearne domain and is attributed to a difference in the nature of the melting process, with the lower values representing ultrametamorphism and the higher values representing bulk melting resulting from contact with mafic igneous magma. Whole-rock Nd isotopic measurements, with average ε143Nd near 10, indicate a dominant late Archean crustal component in both suites of granites, reflected by numerous inherited zircon ages between 2720 and 2650 Ma in Hudson granites. Further south, along the Manitoba border, inherited zircons of 35003000 Ma, together with previously published UPb data on gneisses and ca. 3 Ga TDM model ages of Hudson granites, indicate the presence of middle to early Archean crust.
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Carbone, S., T. Onasch, S. Saarikoski, H. Timonen, K. Saarnio, D. Sueper, T. Rönkkö, L. Pirjola, D. Worsnop, and R. Hillamo. "Characterization of trace metals with the SP-AMS: detection and quantification." Atmospheric Measurement Techniques Discussions 8, no. 6 (June 11, 2015): 5735–68. http://dx.doi.org/10.5194/amtd-8-5735-2015.
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Abstract. A method to detect and quantify mass concentrations of metals by the Aerodyne Soot Particle – Aerosol Mass Spectrometer (SP-AMS) was developed and evaluated in this study. The generation of monodisperse Regal black (RB) test particles with trace amounts of 13 different metals (Na, Al, Ca, V, Cr, Fe, Mn, Ni, Cu, Zn, Rb, Sr and Ba) allowed the determination of the relative ionization efficiency of each metal (RIEmeas). The ratio RIEtheory / RIEmeas presented values larger than the unity for Na, Rb, Ca, Sr and Ba due to the thermal surface ionization (TSI) on the surface of the RB particles. Values closer to the unity were obtained for the transition metals Zn, Cu, V and Cr. Mn, Fe and Ni presented the lowest RIEtheory / RIEmeas ratio and highest deviation from the unity, which was most likely related to different losses. The RIEmeas values obtained in this study were applied to the data of emission measurements in a heavy fuel oil fired heating station. Emission measurements revealed various fragmentation patterns for sulfate, probably because sulfate was mainly in the form of metallic salts (vanadium sulfate, calcium sulfate, iron sulfate and barium sulfate), which were also identified in the high-resolution mass spectrum. The response of the metals to the laser power was also investigated and the results indicated that a minimum current of 0.6 A was needed in the laser in order to vaporize the metals and the rBC. Isotopic pattern of metals was resolved from high-resolution mass spectra and the mass size distribution information of each individual ion was obtained using the high-resolution particle time-of-flight (HR-PToF).
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Guo, Yi, Dajun Qin, Jie Sun, Lu Li, Fulin Li, and Jiwen Huang. "Recharge of River Water to Karst Aquifer Determined by Hydrogeochemistry and Stable Isotopes." Water 11, no. 3 (March 7, 2019): 479. http://dx.doi.org/10.3390/w11030479.
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The Jinan Karst Spring System in Shandong province, China, has suffered to maintain groundwater level and spring flowing for decades. Recharge of river water to karst aquifer in Jinan is important for the outflowing of four large karst springs in the city center. Field investigations were conducted for two times in May and October, 2015, respectively and water samples were collected for hydrogeochemical and isotopic measurements. Results showed that (a) the water type was predominantly Ca-HCO3-SO4 for karst groundwater, and Ca-Mg-SO4 for river water; (b) the concentration of HCO3− and NO3− in karst groundwater were higher than that in river water, in contrast, the concentration of SO42− and K+ in karst groundwater were lower than that in river water; (c) the δ2H and δ18O values with average of −51.2‰ and −6.6‰ for river water is more enriched than the values in groundwater samples (−59.1‰ and −8.3‰), in that river experienced evaporation in the upstream reservoir; (d) Based on the distribution pattern of δ18O, groundwater near river bank was found to be recharged from river water and found a preferential flow path in karst aquifer situated from Dongkema to Manzizhuang near the river bank. This study provides useful information for understanding of the hydraulic connection between river water and karst aquifer, and benefit the protection and management of water resources.
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Vardag, S. N., C. Gerbig, G. Janssens-Maenhout, and I. Levin. "Estimation of continuous anthropogenic CO<sub>2</sub> using CO<sub>2</sub>, CO, δ<sup>13</sup>C(CO<sub>2</sub>) and Δ<sup>14</sup>C(CO<sub>2</sub>)." Atmospheric Chemistry and Physics Discussions 15, no. 14 (July 24, 2015): 20181–243. http://dx.doi.org/10.5194/acpd-15-20181-2015.
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Abstract. We investigate different methods for estimating anthropogenic CO2 using modelled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not feasible at rural measurement sites due to the low signal to noise ratio of anthropogenic CO2 estimates at such settings. At urban and polluted sites, potential future continuous Δ14C(CO2) measurements with a precision of 5 ‰ or better are most promising for anthropogenic CO2 determination (precision ca. 10–20%), but the insensitivity against CO2 contributions from biofuel emissions may reduce its accuracy in the future. Other tracers, such as δ13C(CO2) and CO could provide an accurate and already available alternative if all CO2 sources in the catchment area are well characterized with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We suggest a strategy for calibrating these source characteristics on an annual basis using precise Δ14C(CO2) measurements on grab samples. The precision of anthropogenic CO2 determination using δ13C(CO2) is largely determined by the measurement precision of δ13C(CO2) and CO2. The precision when using the CO-method is mainly limited by the variation of natural CO sources and CO sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. This allows significant improvement, validation and bias reduction of highly resolved emission inventories using atmospheric observation and regional modelling.