<p>Terrestrial ecosystems, including soil and the biosphere, represent important reservoirs of carbon sources and cycling (IPCC, 2000). However, the reaction of terrestrial ecosystems to the changing climate remains poorly constrained. Over the past 20 years, interest in the organic matter (OM) fraction of speleothems, typically comprising 0.01-0.3% of the total carbon (Blyth et al., 2016), has increased due to its potential to offer information about past ecosystems. The sources of speleothem OM are not fully understood and are likely to be a combination of contributions from overlying vegetation, soil, microbial activity within the karst system, and cave fauna. Due to the link that the inner cave environment has with the karst, the signal of non purgeable organic carbon (NPOC) sourced from the overlying soil, vadose zone, or within the cave itself may be preserved within speleothems (Blyth et al., 2013). Hence, the isotopic characterisation (&#120575;<sup>13</sup>C and <sup>14</sup>C) of stalagmite NPOC has the potential to give information about past ecological and climactic state of the surrounding region (Blyth et al., 2013).</p><p>Presented here are the first results of a high-resolution process study of organic and inorganic carbon fluxes in the Milandre cave (Switzerland), whereby the main carbon source reservoirs will be monitored for two years. The total organic carbon content of cave waters ranges from 0.6 -1.3mg/L. The &#120575;<sup>13</sup>C of CO<sub>2</sub> in gas samples from atmospheric air (-9.24 &#8240;), soil air (-12.68 - -27.20&#8240;), gas well air (-24.97- -25.78&#8240;), and cave air (-14.29 - -25.32&#8240;) were analysed. The soil air, well air and cave air have &#120575;<sup>13</sup>C values which range from close to atmospheric &#120575;<sup>13</sup>C to the most &#120575;<sup>13</sup>C depleted cave air end member which suggests differing levels of gas mixing throughout the system. Ultimately, this information will be used to constrain the source of speleothem NPOC and allow the assessment of its suitability as a proxy for ecosystem change. &#160;&#160;</p><p>&#160;</p><p>Blyth, A., Hartland, A. and Baker, A., 2016. Organic proxies in speleothems &#8211; New developments, advantages and limitations. Quaternary Science Reviews, 149, pp.1-17.</p><p>Blyth, A., Smith, C., and Drysdale, R., 2013. A new perspective on the 13C signal preserved in speleothems using LC-IRMS analysis of bulk organic matter and compound specific stable isotope analysis. Quaternary Science Reviews, 75, pp. 143-149.</p><p>IPCC, 2000: Land Use, Land-Use Change and Forestry. (R.Watson, I.Noble, B Bolin, N.H. Ravindranath,D.J. Verardo and D.J. Dokken (eds.)).&#160; Cambridge University Press, UK, pp.375</p><p>&#160;</p>
Abstract. Leaf wax n-alkanes are increasingly used for quantitative paleoenvironmental reconstructions. However, this is complicated in sediment archives with associated hydrological catchments since the stored n-alkanes can have different ages and origins. 14C dating of the n-alkanes yields independent age information for these proxies, allowing their correct paleoenvironmental interpretation. This also holds true for fluvial sediment–paleosol sequences (FSPSs) that integrate two different n-alkane signals: (i) a catchment signal in fluvial sediments and (ii) an on-site signal from local biomass that increasingly dominates (paleo)soils with time. Therefore, the age and origin of n-alkanes in FSPSs are complex: in fluvial sediment layers they can be pre-aged and reworked when originating from eroded catchment soils or from organic-rich sediment rocks in the catchment. In (paleo)soils, besides an inherited contribution from the catchment, they were formed on-site by local biomass during pedogenesis. Depending on the different relative contributions from these sources, the n-alkane signal from an FSPS shows variable age offsets between its formation and final deposition. During this study, we applied compound-class 14C dating to n-alkanes from an FSPS along the upper Alazani in eastern Georgia. Our results show that preheating the n-alkanes with 120 ∘C for 8 h before 14C dating effectively removed the shorter chains (<C25) that partly originate from n-alkanes from Jurassic black clay shales in the upper catchment. The remaining petrogenic contributions on the longer chains (≥C25) were corrected for by using a constant correction factor that was based on the n-alkane concentrations in a black clay shale sample from the upper catchment. Due to different degrees of pre-aging and reworking, the corrected leaf wax n-alkane ages still indicate relatively large age offsets between n-alkane formation and deposition: while intensively developed (paleo)soils showed no age offsets due to a dominance of leaf wax n-alkanes produced on-site, less intensively developed paleosols showed much larger age offsets due to larger proportions of inherited leaf wax n-alkanes from the fluvial parent material. Accordingly, age offsets in nonpedogenic fluvial sediments were largest and strongly increased after ∼4 ka cal BP. The leaf wax n-alkane homolog distribution from intensively developed (paleo)soils indicates a local dominance of grasses and herbs throughout the Holocene, which was most likely caused by anthropogenic activity. The leaf wax n-alkanes from fluvial sediments show a dominance of deciduous trees and shrubs as well as grasses and herbs in different parts of the catchment between ∼8 and ∼5.6 ka cal BP. Since no older deciduous tree- or shrub-derived n-alkanes were dated, this seems to confirm a delayed regional postglacial reforestation of parts of the catchment compared with western and central Europe.
Abstract. Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average 91% of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our set-up, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our set-up were 0.8 ± 0.4 and 0.67 ± 0.34 μg C, respectively, based on multiple measurements of ultra-small samples. The Swiss_4S protocol and the cryo-trapping contributed 0.37 ± 0.18 μg of modern carbon and 0.13 ± 0.07 μg of fossil carbon to the estimated blanks, with consistent estimates obtained for the two laboratories. There was no difference in the background correction between the OC and EC fractions. Our set-up allowed us to efficiently isolate and trap each carbon fraction with the Swiss_4S protocol and to perform 14C analysis of ultra-small OC and EC samples with high accuracy and low 14C blanks.
The University of Bern has set up the new Laboratory for the Analysis of Radiocarbon with AMS (LARA) equipped with an accelerator mass spectrometer (AMS) MICADAS (MIni CArbon Dating System) to continue its long history of 14 C analysis based on conventional counting. The new laboratory is designated to provide routine 14 C dating for archaeology, climate research, and other disciplines at the University of Bern and to develop new analytical systems coupled to the gas ion source for 14 C analysis of specific compounds or compound classes with specific physical properties. Measurements of reference standards and wood samples dated by dendrochronology demonstrate the quality of the 14 C analyses performed at the new laboratory.
Abstract The repeated expansion of East Asian steppe cultures was a key driver of Eurasian history, forging new social, economic, and biological links across the continent. Climate has been suggested as important driver of these poorly understood cultural expansions, but paleo-climate records from the Mongolian Plateau often suffer from poor age control or ambiguous proxy interpretation. Here, we use a combination of geochemical analyses and comprehensive radiocarbon dating to establish the first robust and detailed record of paleo-hydrological conditions for Lake Telmen, Mongolia, covering the past ~4000 years. Our record shows that humid conditions coincided with solar minima, and hydrological modelling confirms the high sensitivity of the lake to paleo-climate changes. Careful comparisons with archaeological and historical records suggest that in the vast semi-arid grasslands of eastern Eurasia, solar minima led to reduced temperatures, less evaporation, and high biomass production, expanding the power base for pastoral economies and horse cavalry. Our findings suggest a crucial link between temperature dynamics in the Eastern Steppe and key social developments, such as the emergence of pastoral empires, and fuel concerns that global warming enhances water scarcity in the semi-arid regions of interior Eurasia.
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