Compound-specific Radiocarbon Analysis Research Articles

Coupling of Dye Analysis and Compound Specific Radiocarbon (14C) Analysis (CSRA) in Heritage Sciences

Natural organic dyes and pigments have been used for millennia to bring colour into our daily lives. Being sourced from a variety of natural sources, they form an extremely varied and large class of compounds, all of which retain the atmospheric 14CO2 of their year of growth. As such these compounds represent ideal candidates for radiocarbon (14C) dating, allowing the identification of or providing information towards the period in which the coloured artefact was created. However, up to now no such analysis has ever been conducted solely on organic colourants within an object. The complex nature of the samples and the sample size limitations with respect to precious and rare art artefacts requires innovative inter- and multidisciplinary approaches. Here we discuss preliminary results in the development of a compound-specific radiocarbon analysis (CSRA) methodology for the analysis of anthraquinone derived red dyes extracted from dyed wool yarns. The aim of this research project is to introduce new routes to date cultural heritage objects, in particular to overcome their intrinsic complexity through the development of CSRA strategies.

Compound-specific radiocarbon analysis of benzene polycarboxylic acids for source apportionment of polyaromatic organic matter in ambient aerosols

Polyaromatic organic matter (POM) is an important group of pollutants and light absorbers in ambient aerosols, which consists of a wide range of chemicals with fused benzene rings. POM in ambient aerosols is mainly derived from the incomplete combustion of fossil fuel and biomass. Source apportionment of POM is crucial for advising efficient mitigation of anthropogenic emissions, but that is a challenge due to the complicated composition of POM and ambient aerosols. Benzene polycarboxylic acids (BPCAs) have recently been introduced as molecular markers of atmospheric POM. Compound-specific radiocarbon analysis of BPCAs is expected to be a powerful tool for apportioning fossil sources and contemporary (i.e., biomass burning) sources of POM in ambient aerosols, yet this application is still lacking. We developed a method for radiocarbon analysis of BPCAs substituted with 3–6 carboxylic groups (B6CA, B5CA, B4CAs and B3CAs). BPCAs were isolated with preparative liquid chromatography with high recoveries (≥85%). The method is validated with reference materials with fossil and contemporary radiocarbon signatures. Successful radiocarbon analysis of BPCAs was achieved for these reference materials after correcting for the presence of average blanks (B6CA: 1.2 ± 0.2 μg, B5CA: 2.3 ± 0.6 μg, individual B4CAs: 2.7 ± 0.2 μg and individual B3CAs: 6.9 ± 0.7 μg). Source apportionment of POM based on radiocarbon analysis of BPCAs was performed for an urban dust reference material, as well as bulk aerosols and water-soluble, methanol-soluble fractions of ambient aerosols from a megacity of southern China. The results show varied contributions of fossil and contemporary sources among different POM fractions.

Compound-Specific Radiocarbon Analysis

Compound-specific radiocarbon analysis has played important role in the methodology applied in radiocarbon dating since the development of modern analytical instrumentation. Thank to this evolution it is nowadays possible to radiocarbon date samples which would be normally considered as undatable due to their heterogenous nature or secondary contamination. The aim of this review is to introduce molecular-specific radiocarbon dating approach and show some particular applications already successfully tested and used in radiocarbon dating.

Compound Specific Radiocarbon (14C) Dating of Our Colorful Past: from Theory to Practice

AbstractFor generations, humanity has preserved customs, places, objects, artistic expressions, and values – our cultural heritage. The use of color on cultural heritage objects is ubiquitous and found on artefacts from prehistoric rock art to present day contemporary artworks. The chemical identification of the colored materials used within an artwork often provides information about the work's origin. At the simplest level, a comparison of the materials present with information on their first date of discovery indicates the earliest possible period in which the colored artefact was created. More precise constraints on the date of creation can be provided by radiocarbon (14C) dating, however until today no such analysis has ever been conducted on the compounds responsible for the object's color. The analysis of natural organic dyes and pigments is challenging, as the limited sampling access, their low concentrations and presence in highly complex matrix, are all major challenges to be overcome. The separation of intermingled carbon sources is without question the most difficult problem, yet feasible with the help of compound specific radiocarbon analysis (CSRA). Here, we discuss the potential of radiocarbon dating isolated natural organic dyes and pigments and explore new routes to date cultural heritage objects.

Carbon-14 release and speciation during corrosion of irradiated steel under radioactive waste disposal conditions

Carbon-14 is a key radionuclide in the safety assessment of deep geological repositories (DGR) for low- and intermediate-level radioactive waste (L/ILW). Irradiated metallic wastes generated during the decommissioning of nuclear power plants are an important source of 14C after their disposal in a DGR. The chemical form of 14C released from the irradiated metallic wastes determines the pathway of migration from the DGR into the environment. In a long-term corrosion experiment with irradiated steel simulating the hyper-alkaline, anoxic conditions of a cement-based DGR, total inorganic (TI14C22TI14C: Total inorganic 14C; TO14C: total organic 14C; TG14C: total gaseous 14C) and organic 14C contents (TO14C) in the liquid and gas phases (TG14C), as well as individual 14C-bearing carbon compounds by compound-specific radiocarbon analysis (CSRA), were quantified using accelerator mass spectrometry (AMS). The AMS-based quantification allows the determination of 14C in the pico- to femtomolar concentration range. An initial increase in TO14C was observed, which could be attributed partially to the release of 14C-bearing oxygenated carbon compounds. In the long term, TO14C and the TI14C remain constant, while TG14C increases over time according to a corrosion rate of steel of 1 nm/yr. In solution, 14C-bearing carboxylic acids (CAs) contribute ~40% to TO14C, and they are the main 14C carriers along with 14C-bearing carbonate (14CO32−). The remaining fraction of TO14C (~ 60%) is likely due to the presence of as yet non-identified polymeric or colloidal organic material. In the gas phase, 14CH4 accounts for more than 80% of the TG14C, while only trace amounts of 14CO, and other small 14C-bearing hydrocarbons have been detected. In a DGR, the release of 14C will be mainly in gaseous form and migrate via the gas pathway from the repository near field to the surrounding host rock and eventually to the environment.

Compound-specific radiocarbon dating of lipid residues in pottery vessels: A new approach for detecting the exploitation of marine resources

Over the last three decades, organic residue analysis has been shown to be especially useful in ancient diet reconstruction; however, it is only recently that the direct radiocarbon dating of lipid residues has become a reliable method for dating pottery vessels and food procurement activities. Here, we applied lipid residue analysis to 29 late Bronze Age pottery vessels from the site of Cliffs End Farm (UK), previously dated by their visible charred residues (carbonised food crusts) and dated four of these vessels by compound-specific radiocarbon analysis (CSRA) of their absorbed lipids. Lipid biomarker detection was limited to only one class of biomarker in four vessels, which indicated that the diet relied mainly on terrestrial animals. Four vessels datable from their absorbed lipids produced 14C measurements significantly older than the published results on the charred residues, suggesting a reservoir effect affecting the dated lipids. Furthermore, the low abundance of pig remains (1–4%) at the site suggests that enriched δ13C16:0 and δ13C18:0 values recorded on the absorbed fatty acids were caused by marine rather than porcine contributions. The percentage of marine products in the CSRA dated vessels was quantified using the δ13C values of individual fatty acids and values from a modern reference database. These percentages of marine products were incorporated in mixed-source radiocarbon calibration using OxCal for the correction of a marine reservoir effect (MRE). Therefore, the combination of lipid compositions, radiocarbon dates and faunal analyses enabled the identification of marine product exploitation at the site. Finally, this allowed the application of MRE corrections to the radiocarbon dates obtained, and comparisons to be made with those of charred residues obtained from the same sherds.

DO RADIOCARBON AGES OF PLANT WAX BIOMARKERS AGREE WITH 14C-TOC/OSL-BASED AGE MODELS IN AN ARID HIGH-ALTITUDE LAKE SYSTEM?

ABSTRACTTo elucidate the dynamics of terrestrial leaf waxes in a high-altitude lake system, we performed compound-specific radiocarbon analysis (CSRA) of long-chain n-alkanes in two sediment core sections from Lake Karakul (Pamirs, Tajikistan) and in surface soil samples from the catchment area. We aimed to answer the question whether the n-alkanes are delivered into the lake sediment with substantial delay due to storage in soils, which may cause a potential bias when used as paleoenvironmental proxies. In the surface soils, the CSRA results reveal an age range of n-alkanes from modern to 2278 ± 155 cal BP. In the two sediment core samples, three of the four n-alkane ages fell on the lower ends of the 1σ-uncertainty ranges of modeled ages of the sediments (based on AMS 14C-TOC and OSL dating results). We conclude that sedimentary leaf waxes represent compounds with intermediate turnover time in soils, for example originating from alluvial plains close to the shores. Overall, the results provide evidence that sedimentary leaf wax compounds in this cold and arid setting are potentially older than the conventional age model indicates, but these findings need to be interpreted in context of the generally large uncertainty ranges of such age models.

The Reservoir Age Effect Varies With the Mobilization of Pre-Aged Organic Carbon in a High-Altitude Central Asian Catchment

Lake sediments provide excellent archives to study past environmental and hydrological changes at high temporal resolution. However, their utility is often restricted by chronological uncertainties due to the “reservoir age effect” (RAE), a phenomenon that results in anomalously old radiocarbon ages of total organic carbon (TOC) samples that is mainly attributed to the contribution of pre-aged carbon from aquatic organisms. Although the RAE is a well-known problem especially in high altitude lakes, detailed studies analyzing the temporal variations in the contribution of terrestrial and aquatic organic carbon (OC) on the RAE are scarce. This is partially due to the complexity of isolating individual compounds for subsequent compound-specific radiocarbon analysis (CSRA). We developed a rapid method for isolating individual short-chain (C16and C18) and long-chain (>C24) saturated fatty acid methyl esters (FAMEs) by using high-pressure liquid chromatography (HPLC). Our method introduces only minor contaminations (0.50 ± 0.22 µg dead carbon on average) and requires only few injections (≤10), therefore offering clear advantages over traditional preparative gas chromatography (prep-GC). Here we show that radiocarbon values (Δ14C) of long-chain FAs, which originate from terrestrial higher plant waxes, reflect carbon from a substantially pre-aged OC reservoir, whereas the Δ14C of short-chain FAs that originate from aquatic sources were generally less pre-aged.14C ages obtained from the long-chain FAs are in closer agreement with14C ages of the corresponding bulk TOC fraction, indicating a high control of pre-aged terrestrial OC input from the catchment on TOC-derived14C ages. Variations in the age offset between terrestrial and aquatic biomarkers are related to changes in bulk sediment log(Ti/K) that reflect variations in detrital input from the catchment. Our results indicate that the chronological offset between terrestrial and aquatic OC in this high-altitude catchment is mainly driven by temporal variations in the mobilization of pre-aged OC from the catchment. In conclusion, to obtain accurate and process-specific lake sediment chronologies, attention must be given to the temporal dynamics of the RAE. Variations in the apparent ages of aquatic and terrestrial contributions to the sediment and their mass balance can substantially alter the reservoir age effect.

Dating Lake Sediments Using Compound‐Specific 14C Analysis of C16 Fatty Acid: A Case Study From the Mount Fuji Volcanic Region, Japan

AbstractLake sediments in volcanic regions contain continuous records of past eruptions and their environmental consequences. However, the frequent scarcity of plant material in lake sediments makes it difficult to provide robust age estimates. In this study, we performed compound‐specific radiocarbon analysis (CSRA) of fatty acids in a sediment core from Lake Kawaguchi in the Mount Fuji volcanic region, Japan, to assess their potential for dating sediments. The C16 fatty acid in the core top sediments exhibits an almost identical age (983 ± 56 years BP) to that of dissolved inorganic carbon in the modern lake surface water, which confirms that the carbon of this compound is derived from lake phytoplankton. Comparison of the 14C age between the C16 fatty acid and a plant leaf at the widespread (Amagi‐Kawagodaira) tephra layer revealed a lake reservoir age of 1,003 ± 73 14C years at ca. 3,150 cal BP, which is consistent with the modern lake reservoir age and the 14C age of the C16 fatty acid in the core top sediments, within error. The reservoir‐corrected 14C age of the C16 fatty acid yielded a modeled age of 2,837 ± 78 cal BP for the Mount Fuji Tephra (Omuro scoria‐fall deposit) in the core. This age is in good agreement with the age determined from plant remains in the same core (2,938 ± 29 cal BP), indicating that CSRA of C16 fatty acid has the potential to date lake sediments after reservoir age correction, even in sediments with limited occurrence of plant macrofossils.

Centennial-scale age offsets of plant wax n-alkanes in Adirondack lake sediments

Lacustrine sediments have the potential to preserve paleoenvironmental proxies such as terrestrial plant waxes at high temporal resolution. The temporal fidelity of plant wax records, however, can be up to several thousand years older than the corresponding sediment, based on compound-specific radiocarbon (14C) analysis. Unfortunately, the factors controlling 14C age offsets between plant waxes and sediments are not well understood. The aims of this study are to quantify and compare plant wax n-alkane 14C age offsets among lakes within the same region, and to determine if drainage and lake basin differences (e.g., size, relief, drainage basin morphology, fluvial inputs) influence these offsets. We collected sediments from five lakes in the Adirondack Mountains, NY, USA that lack petrogenic sources of n-alkanes, and range in drainage basin characteristics. Sediment age models were constructed for each lake using a combination of sediment 210Pb, 137Cs, and macrofossil 14C ages, and compared to 14C ages of long-chain (n-C27, n-C29, n-C31) alkanes sampled from Holocene and Late Glacial aged sediments. The n-alkane 14C ageinitial is a measure of the age offset in n-alkanes relative to the sediment they are deposited in. Across all lakes, the n-alkane 14C ageinitial ranged from penecontemporaneous to 2440 14C yr. This oldest n-alkane 14C ageinitial is significantly outside the distribution of all other samples; when excluded, the overall mean n-alkane 14C ageinitial was 400 ± 255 14C yr (n = 23). The largest n-alkane 14C ageinitial values were observed in the last 1 cal kyr BP (565 ± 180 14C yr (1σ), n = 12)) compared to sediments deposited between 1 and 13 cal kyr BP (220 ± 195 14C yr (1σ), n = 11)). These age offsets develop early after initial lake basin sedimentation and follow a similar pattern in all of the lakes despite differences in lake basin and catchment size, relief, and geomorphology. We speculate that 14C age offsets occur due to reworking of older n-alkanes stored in drainage basin sediments and soils and this mechanism is most effective in the last ∼1 kyr. Regardless, lakes in temperate forested metamorphic bedrock terrains have relatively small and stable n-alkane age offsets compared with lakes with extensive catchment soils or anthropogenic disturbance. By targeting lakes with minimal catchment soils, age offsets may be reduced, thereby minimizing attenuation or age distortion of climate signals in plant wax isotopic records.

Chronological Assessment of the Balta Alba Kurgan Loess-Paleosol Section (Romania) – A Comparative Study on Different Dating Methods for a Robust and Precise Age Model

Loess-paleosol sequences (LPSs) are important terrestrial archives of paleoenvironmental and paleoclimatic information. One of the main obstacles for the investigation and interpretation of these archives is the uncertainty of their age-depth relationship. In this study, four different dating techniques were applied to the Late Pleistocene to Holocene LPS Balta Alba Kurgan (Romania) in order to achieve a robust chronology. Luminescence dating includes analysis of different grain-size fractions of both quartz and potassium feldspar and the best results are obtained using fine-grained quartz blue‐stimulated and polymineral post-infrared infrared-stimulated luminescence measurements. Radiocarbon (14C) dating is based on the analysis of bulk organic carbon (OC) and compound-specific radiocarbon analysis (CSRA). Bulk OC and leaf wax-derived n-alkane 14C ages provide reliable age constraints for the past c. 25–27 kyr. CSRA reveals post-depositional incorporation of roots and microbial OC into the LPS limiting the applicability of 14C dating in older parts of the sequence. Magnetic stratigraphy data reveal good correlation of magnetic susceptibility and the relative paleointensity of the Earth’s magnetic field with one another as well as reference records and regional data. In contrast, the application of paleomagnetic secular variation stratigraphy is limited by a lack of regional reference data. The identification of the Campanian Ignimbrite/Y-5 tephra layer in the outcrop provides an independent time marker against which results from the other dating methods have been tested. The most accurate age constraints from each method are used for two Bayesian age-depth modeling approaches. The systematic comparison of the individual results exemplifies the advantages and disadvantages of the respective methods. Taken as a whole, the two age-depth models agree very well, our study also demonstrates that the multi-method approach can improve the accuracy and precision of dating loess sequences.

Compound-Specific Radiocarbon Analysis of Low Molecular Weight Dicarboxylic Acids in Ambient Aerosols Using Preparative Gas Chromatography: Method Development

Low molecular weight dicarboxylic acids constitute a large fraction of atmospheric organic aerosols, which impact atmospheric radiative forcing and hence Earth’s climate. Radiocarbon (14C) is a unique approach to unambiguously distinguishing the relative contributions of biomass-derived and fossil sources. Here, we developed a compound-specific radiocarbon analysis (CSRA) method for individual dicarboxylic acids in atmospheric particulates. Specifically, the method starts with a dibutyl ester derivatization technique, followed by separation and harvesting of single compounds employing a preparative capillary gas chromatography in sufficient amounts for offline 14C measurement with accelerator mass spectrometry. The optimized preparative steps yielded recoveries of >60% and purities of >99% for target molecules. The radiocarbon isotope compositions determined for reference standards taken through the entire method agree well with the original composition of each standard (R2 = 0.9998). The applicability of the approach was demonstrated with ambient aerosol samples representing contrasting air mass regimes. This yielded two radically different yet system-consistent precursor sources. A minimum size of 50 μg of C of ambient dicarboxylic acids is needed for credible 14C measurement. The established method for CSRA of dicarboxylic acids demonstrates a new analytical dimension for studies of the source and evolution of atmospheric secondary organic aerosols.

Compound‐Specific Radiocarbon Analysis of (Sub‐)Antarctic Coastal Marine Sediments—Potential and Challenges for Chronologies

AbstractIn Antarctic and Subantarctic environments, 14C‐based age determination is often challenging due to unknown reservoir effects, low organic carbon contents of sediments, and high contributions of petrogenic (14C‐free) carbon in ice marginal settings. In this study, we evaluate possible benefits and challenges of compound‐specific radiocarbon analysis (CSRA) as a tool for age determination of marine Antarctic and Subantarctic sediment sequences. We present a comprehensive data set of 14C ages obtained on bulk organic carbon, carbonates, and on fatty acids (FA) from three coastal marine sediment cores from Subantarctic South Georgia and East Antarctica. Low molecular weight (LMW) FA represent the least 14C‐depleted fraction, indicating that the phytoplankton‐derived compounds can be a means of dating sediments. In contrast, vascular plant‐derived high molecular weight FA are systematically depleted in 14C relative to the low molecular weight homologues, reflecting processes such as soil formation/erosion in the catchment. Comparative age‐depth models show significant differences, depending on the material used for the respective models. While the land plant‐derived FA may lead to an overestimation of the actual sediment age, LMW FA reveal complex aquatic reservoir effects. Bulk sedimentary organic carbon 14C ages likely provide appropriate age estimates in settings with low petrogenic carbon input in the Antarctic, whereas CSRA has the potential to produce improved age control in settings with high contributions of petrogenic carbon.

Theoretical Amino Acid-Specific Radiocarbon Content in the Environment: Hypotheses to Be Tested and Opportunities to Be Taken

Tracing of biogeochemical pathways using molecular approaches has advanced our basic understanding of the carbon cycle and life’s legacy in the sedimentary record. To this end, compound-specific radiocarbon analysis has been instrumental in shedding light on the turnover, age, and sources of a range of biomarkers embedded within complex environmental matrices. However, despite their foundational importance for life and their omnipresence throughout geologic space and time, the biogeochemical cycling of amino acids remains largely unexplored. Here, we discuss the potential of using amino acid-specific radiocarbon to deepen our knowledge of the biogeochemistry of food webs and sedimentary organic carbon.

Liquid Chromatographic Isolation of Individual Amino Acids Extracted From Sediments for Radiocarbon Analysis

The “building blocks of life” are found nearly ubiquitously in the environment in the form of proteins, peptides, and single amino acids. To shed light on amino acid sources, cycling, and preservation in sedimentary environments, we present a method using high-pressure liquid chromatography to separate and isolate underivatized amino acids extracted from sediments to conduct compound-specific radiocarbon analysis. This method consists of three main steps including (1) amino acid extraction by hydrofluoric and hydrochloric acids followed by desalting, (2) liquid chromatographic isolation and purification using two complementary column chemistries, and (3) post-purification and measurement by accelerator mass spectrometry. The resulting blank of this procedure is estimated to contain 2.2±1.3 µgC with 0.25±0.09 Fm.

Compound-Specific Radiocarbon Analysis of Organic Compounds from Mount Fuji Proximal Lake (Lake Kawaguchi) Sediment, Central Japan

ABSTRACTDifferential sources of sedimentary organic compounds in a volcanic region were revealed by determining radiocarbon content (Δ14C) of organic compounds in surface sediments from Lake Kawaguchi, at the northern foot of Mount Fuji, central Japan. The Δ14C values of C16 fatty acid (−124‰) and chlorophyll a (Chl a) (−133‰) were similar to the Δ14C of dissolved inorganic carbon (DIC) in surface water (−117‰), suggesting that a significant portion of these compounds originated from modern primary producers with a reservoir age of ~1000 years. On the other hand, a large offset between the Δ14C values of Chl a (−133‰) and those of 132, 173-cyclopheophorbide-a-enol (−169‰) and pheophytin a (−179‰) suggested contributions from older pigments. In addition, the Δ14C of long-chain (C24, C26, and C28) fatty acids (−183 to −75‰) showed a large offset from that of a plant leaf remain (0‰) within sediments, demonstrating that the long-chain fatty acids were affected by substantial contributions from pre-aged terrestrial materials. Overall, the sedimentary organic compounds gave 14C ages older than the plant leaf fragment within sediments; however, the similarity between Δ14C of the C16 fatty acid and DIC implies potential for applying compound-specific radiocarbon analysis as a dating tool in volcanic lake environments.

Determination of ultra-low concentrations of gaseous 14C-bearing hydrocarbons produced during corrosion of irradiated steel using accelerator mass spectrometry.

Compound-specific radiocarbon analysis (CSRA) was developed to identify and quantify gaseous 14C-bearing carbon compounds at the pico- to femtomolar concentration range and employed in a corrosion experiment with small specimens of irradiated steel. The approach is based on gas chromatographic separation of single 14C-bearing carbon compounds, their oxidation to 14CO2, sampling with a custom-made fraction collector and quantification by accelerator mass spectrometry (AMS). In addition to CSRA, a method allowing the quantification of the total 14C content of the gas phase was developed and tested. After validation of the two set-ups with standards, the gaseous 14C-bearing carbon compounds produced during alkaline anoxic corrosion of irradiated steel were quantified. Small hydrocarbons (HCs) like methane (14CH4) and ethane (14C2H6) were the only 14C-bearing compounds identified in the gas phase above the detection limit. 14CH4 was the main species (on average 5.4 × 10-14 mol L-1 gas) and contributed >90% to the total 14C content, whereas the concentration of 14C2H6 was much lower (7.9 × 10-16 mol L-1 gas). To our knowledge, this is the first study reporting CSRA of gaseous 14C-bearing HCs produced during anoxic corrosion of irradiated metallic radioactive waste at ultra-low concentrations.

Dead in the Water: The Vicious Cycle of Blanks During Natural Level 14 C Manipulation of Marine Algal Cultures

Authentic biomarker standards were obtained from algal cultures in an attempt to accurately determine blank C added during sample processing for compound-specific radiocarbon analysis. Emiliania huxleyi and Thalassiosira pseudonana were grown under manipulated Δ14C dissolved inorganic carbon (DIC) levels and chlorophyll a and either alkenones (E. huxleyi) or low molecular weight (LMW) alkanoic acids (T. pseudonana) were isolated from the respective biomass using preparative liquid chromatography (LC), wet chemical techniques or preparative gas chromatography, respectively. DI14C in the seawater medium was determined pre- and post-growth. Biomarker Δ14C values mostly agree within 1-2 analytical uncertainties. In those cases where biomarker Δ14C values differ significantly, chlorophyll a is up to 104‰ more 14C-depleted than alkenones or LMW alkanoic acids, consistent with a larger LC blank compared to the other purification methods. However, in the majority of experimental setups pre- and post-growth DIC Δ14C values seem to be compromised by an unknown and variable blank C contribution. DIC Δ14C values deviate strongly from the anticipated Δ14C values (by up to ca. 560‰), pre- and post-growth Δ14C values differ significantly (by up to ca. 460‰), and changes are not unidirectional. Accordingly, since the substrate Δ14C value cannot unequivocally be constrained, blank C contributions for the different biomarker purification methods cannot be accurately calculated. This study illustrates the challenges and problems of producing authentic standards that are not readily commercially available and exemplifies how a laborious and time-consuming culturing approach may enter a vicious cycle of blank C contamination hampering accurate blank C determination.

Compound-Specific Radiocarbon Analysis of Atmospheric Methane: A New Preconcentration and Purification Setup

ABSTRACTMethane contributes substantially to global warming as the second most important anthropogenic greenhouse gas. Radiocarbon (14C) measurements of atmospheric methane can be used as a source apportionment tool, as they allow distinction between thermogenic and biogenic methane sources. However, these measurements remain scarce due to labor-intensive methods required. A new setup for the preparation of atmospheric methane samples for radiocarbon analysis is presented. The system combines a methane preconcentration line with a preparative gas chromatography technique to isolate pure methane samples for a compound-specific radiocarbon analysis. In order to minimize sample preparation time, we designed a simplified preconcentration line for the extraction of methane from 50 L atmospheric air, which corresponds to 50 µg C as required for a reliable 14C analysis of methane-derived CO2 gas measurement with accelerator mass spectrometry (AMS). The system guarantees a quantitative extraction of methane from atmospheric air samples for 14C analysis, with a good repeatability and a low processing blank. The setup was originally designed for the measurement of samples with low methane concentrations, but it can also be adapted to apportion sources from environmental compartments with high methane levels such as freshwaters or wetlands.

Compound-Specific Radiocarbon Analysis by Elemental Analyzer-Accelerator Mass Spectrometry: Precision and Limitations.

We examine instrumental and methodological capabilities for microscale (10-50 μg of C) radiocarbon analysis of individual compounds in the context of paleoclimate and paleoceanography applications, for which relatively high-precision measurements are required. An extensive suite of data for 14C-free and modern reference materials processed using different methods and acquired using an elemental-analyzer-accelerator-mass-spectrometry (EA-AMS) instrumental setup at ETH Zurich was compiled to assess the reproducibility of specific isolation procedures. In order to determine the precision, accuracy, and reproducibility of measurements on processed compounds, we explore the results of both reference materials and three classes of compounds (fatty acids, alkenones, and amino acids) extracted from sediment samples. We utilize a MATLAB code developed to systematically evaluate constant-contamination-model parameters, which in turn can be applied to measurements of unknown process samples. This approach is computationally reliable and can be used for any blank assessment of small-size radiocarbon samples. Our results show that a conservative lower estimate of the sample sizes required to produce relatively high-precision 14C data (i.e., with acceptable errors of <5% on final 14C ages) and high reproducibility in old samples (i.e., F14C ≈ 0.1) using current isolation methods are 50 and 30 μg of C for alkenones and fatty acids, respectively. Moreover, when the F14C is >0.5, a precision of 2% can be achieved for alkenone and fatty acid samples containing ≥15 and 10 μg of C, respectively.