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  • 1
    Publication Date: 2005-01-01
    Description: The chemical and isotopic compositions of long-chain (C36–C39) unsaturated ketones (alkenones), a unique class of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have sought to extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe a method for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. The steps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography, exploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurements were highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% for samples containing ≥ 100 μg C. The degree of alkenone unsaturation (U37K′) also varied minimally through the procedure. We also describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-level structural and isotopic determination.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 2
    Publication Date: 2019-09-23
    Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 µg carbon (µgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 µgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 3
    Publication Date: 2018-03-04
    Description: Inland water bodies contain significant amounts of carbon in the form of dissolved inorganic carbon (DIC) derived from a mixture of modern atmospheric and pre-aged sources, which needs to be considered in radiocarbon-based dating and natural isotope tracer studies. While reservoir effects in hardwater lakes are generally considered to be constant through time, a comparison of recent and historical DI14C data from 2013 and 1969 for Lake Constance reveals that this is not a valid assumption. We hypothesize that changes in atmospheric carbon contributions to lake water DIC have taken place due to anthropogenically forced eutrophication in the 20th century. A return to more oligotrophic conditions in the lake led to reoxygenation and enhanced terrigenous organic matter remineralization, contributing to lake water DIC. Such comparisons using DI14C measurements from different points in time enable nonlinear changes in lake water DIC source and signature to be disentangled from concurrent anthropogenically induced changes in atmospheric 14C. In the future, coeval changes in lake dynamics due to climate change are expected to further perturb these balances. Depending on the scenario, Lake Constance DI14C is projected to decrease from the 2013 measured value of 0.856 Fm to 0.54–0.62 Fm by the end of the century.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 4
    Publication Date: 2016-06-24
    Description: The radiocarbon content of dissolved organic carbon (DOC) in rivers, lakes, and other non-saline waters can provide valuable information on carbon cycling dynamics in the environment. DOC is typically prepared for 14C analysis by accelerator mass spectrometry (AMS) either by ultraviolet (UV) oxidation or by freeze-drying and sealed tube combustion. We present here a new method for the rapid analysis of 14C of DOC using wet chemical oxidation (WCO) and automated headspace sampling of CO2. The approach is an adaption of recently developed methods using aqueous persulfate oxidant to determine the δ13C of DOC in non-saline water samples and the 14C content of volatile organic acids. One advantage of the current method over UV oxidation is higher throughput: 22 samples and 10 processing standards can be prepared in one day and analyzed in a second day, allowing a full suite of 14C processing standards and blanks to be run in conjunction with samples. A second advantage is that there is less potential for cross-contamination between samples.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 5
    Publication Date: 2019-06-14
    Description: The radiocarbon (14C) content of simultaneously deposited substrates in lacustrine archives may differ due to reservoir and detrital effects, complicating the development of age models and interpretation of proxy records. Multi-substrate 14C studies quantifying these effects remain rare, however, particularly for large, terminal lake systems, which are excellent recorders of regional hydroclimate change. We report 14C ages of carbonates, brine shrimp cysts, algal mat biomass, total organic carbon (TOC), terrestrial macrofossils, and n-alkane biomarkers from Holocene sediments of the Great Salt Lake (GSL), Utah. 14C ages for co-deposited aquatic organic substrates are generally consistent, with small offsets that may reflect variable terrestrial organic matter inputs to the system. Carbonates and long-chain n-alkanes derived from vascular plants, however, are ∼1000–4000 14C years older than other substrates, reflecting deposition of pre-aged detrital materials. All lacustrine substrates are 14C-depleted compared to terrestrial macrofossils, suggesting that the reservoir age of the GSL was 〉 1200 years throughout most of the Holocene, far greater than the modern reservoir age of the lake (∼300 years). These results suggest good potential for multi-substrate paleoenvironmental reconstruction from Holocene GSL sediments but point to limitations including reservoir-induced uncertainty in 14C chronologies and attenuation and time-shifting of some proxy signals due to detrital effects.
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    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 6
    Publication Date: 2019-04-23
    Description: Speleothem organic matter can be a powerful tracer for past environmental conditions and karst processes. Carbon isotope measurements (δ13C and 14C) in particular can provide crucial information on the provenance and age of speleothem organic matter, but are challenging due to low concentrations of organic matter in stalagmites. Here, we present a method development study on extraction and isotopic characterization of speleothem organic matter using a rapid procedure with low laboratory contamination risk. An extensive blank assessment allowed us to quantify possible sources of contamination through the entire method. Although blank contamination is consistently low (1.7 ± 0.34 – 4.3 ± 0.86 μg C for the entire procedure), incomplete sample decarbonation poses a still unresolved problem of the method, but can be detected when considering both δ13C and 14C values. We test the method on five stalagmites, showing reproducible results on samples as small as 7 μg C for δ13C and 20 μg C for 14C. Furthermore, we find consistently lower non-purgeable organic carbon (NPOC) 14C values compared to the carbonate 14C over the bomb spike interval in two stalagmites from Yok Balum Cave, Belize, suggesting overprint of a pre-aged or even fossil source of carbon on the organic fraction incorporated by these stalagmites.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 7
    Publication Date: 2010-01-01
    Description: The Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS/UCI) has developed protocols for analyzing radiocarbon in samples as small as ∼0.001 mg of carbon (C). Mass-balance background corrections for modern and 14C-dead carbon contamination (MC and DC, respectively) can be assessed by measuring 14C-free and modern standards, respectively, using the same sample processing techniques that are applied to unknown samples. This approach can be validated by measuring secondary standards of similar size and 14C composition to the unknown samples. Ordinary sample processing (such as ABA or leaching pretreatment, combustion/graphitization, and handling) introduces MC contamination of ∼0.6 ± 0.3 μg C, while DC is ∼0.3 ± 0.15 μg C. Today, the laboratory routinely analyzes graphite samples as small as 0.015 mg C for external submissions and ≅0.001 mg C for internal research activities with a precision of ∼1% for ∼0.010 mg C. However, when analyzing ultra-small samples isolated by a series of complex chemical and chromatographic methods (such as individual compounds), integrated procedural blanks may be far larger and more variable than those associated with combustion/graphitization alone. In some instances, the mass ratio of these blanks to the compounds of interest may be so high that the reported 14C results are meaningless. Thus, the abundance and variability of both MC and DC contamination encountered during ultra-small sample analysis must be carefully and thoroughly evaluated. Four case studies are presented to illustrate how extraction chemistry blanks are determined.
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    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 8
    Publication Date: 2018-11-13
    Description: In practice, obtaining radiocarbon (14C) composition of organic matter (OM) in sediments requires first removing inorganic carbon (IC) by acid-treatment. Two common treatments are acid rinsing and fumigation. Resulting14C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on14C content of sedimentary OM, we examine the variability in14C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (RinseHCl) and HCl fumigation (FumeHCl)], we demonstrate that the two acid-treatments can affect14C content differentially. Our findings suggest that, for low-carbonate samples, RinseHClaffects the Fm values due to loss of young labile organic carbon (OC). FumeHClmakes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during RinseHCl, causing the Fm values of remaining OC to increase. FumeHClcan remove thermally labile, usually young, OC and reduce the Fm values. We suggest three factors should be taken into account when using acid to remove carbonate from sediments: IC abundance, proportions of labile and refractory OC, and environmental matrix.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 9
    Publication Date: 2003-01-01
    Description: We have measured the radiocarbon contents of individual, solvent-extractable, short-chain (C14, C16, and C18) fatty acids isolated from Ross Sea surface sediments. The corresponding 14C ages are equivalent to that of the post-bomb dissolved inorganic carbon (DIC) reservoir. Moreover, molecular 14C variations in surficial (upper 15 cm) sediments indicate that these compounds may prove useful for reconstructing chronologies of Antarctic margin sediments containing uncertain (and potentially variable) quantities of relict organic carbon. A preliminary molecular 14C chronology suggests that the accumulation rate of relict organic matter has not changed during the last 500 14C yr. The focus of this study is to determine the validity of compound-specific 14C analysis as a technique for reconstructing chronologies of Antarctic margin sediments.
    Print ISSN: 0033-8222
    Electronic ISSN: 1945-5755
    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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  • 10
    Publication Date: 2005-01-01
    Description: As a result of the growing use of multiple geochemical proxies to reconstruct ocean and climate changes in the past, there is an increasing need to establish temporal relationships between proxies derived from the same marine sediment record and ideally from the same core sections. Coupled proxy records of surface ocean properties, such as those based on lipid biomarkers (e.g. alkenone-derived sea surface temperature) and planktonic foraminiferal carbonate (oxygen isotopes), are a key example. Here, we assess whether 2 different solvent extraction procedures used for isolation of molecular biomarkers influence the radiocarbon contents of planktonic foraminiferal carbonate recovered from the corresponding residues of Bermuda Rise and Cariaco Basin sediments. Although minor Δ14C differences were observed between solvent-extracted and unextracted samples, no substantial or systematic offsets were evident. Overall, these data suggest that, in a practical sense, foraminiferal shells from a solvent-extracted residue can be reliably used for 14C dating to determine the age of sediment deposition and to examine age relationships with other sedimentary constituents (e.g. alkenones).
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    Topics: Archaeology , Energy, Environment Protection, Nuclear Power Engineering , Geosciences
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