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Large carnivores (order Carnivora) are among the world's most threatened mammals due to a confluence of ecological and social forces that have unfolded over centuries. Combining specimens from natural history collections with documents from archival records, we reconstructed the factors surrounding the extinction of the California grizzly bear (Ursus arctos californicus), a once-abundant brown bear subspecies last seen in 1924. Historical documents portrayed California grizzlies as massive hypercarnivores that endangered public safety. Yet, morphological measurements on skulls and teeth generate smaller body size estimates in alignment with extant North American grizzly populations (approx. 200 kg). Stable isotope analysis (δ13C, δ15N) of pelts and bones (n = 57) revealed that grizzlies derived less than 10% of their nutrition from terrestrial animal sources and were therefore largely herbivorous for millennia prior to the first European arrival in this region in 1542. Later colonial land uses, beginning in 1769 with the Mission era, led grizzlies to moderately increase animal protein consumption (up to 26% of diet), but grizzlies still consumed far less livestock than otherwise claimed by contemporary accounts. We show how human activities can provoke short-term behavioural shifts, such as heightened levels of carnivory, that in turn can lead to exaggerated predation narratives and incentivize persecution, triggering rapid loss of an otherwise widespread and ecologically flexible animal.

Using new and published marine fossil radiocarbon (14C/C) measurements, a tracer uniquely sensitive to circulation and air-sea gas exchange, we establish several benchmarks for Atlantic, Southern, and Pacific deep-sea circulation and ventilation since the last ice age. We find the most 14C-depleted water in glacial Pacific bottom depths, rather than the mid-depths as they are today, which is best explained by a slowdown in glacial deep-sea overturning in addition to a "flipped" glacial Pacific overturning configuration. These observations cannot be produced by changes in air-sea gas exchange alone, and they underscore the major role for changes in the overturning circulation for glacial deep-sea carbon storage in the vast Pacific abyss and the concomitant drawdown of atmospheric CO2.

Steller's sea cow, an extinct sirenian and one of the largest Quaternary mammals, was described by Georg Steller in 1741 and eradicated by humans within 27 years. Here, we complement Steller's descriptions with paleogenomic data from 12 individuals. We identified convergent evolution between Steller's sea cow and cetaceans but not extant sirenians, suggesting a role of several genes in adaptation to cold aquatic (or marine) environments. Among these are inactivations of lipoxygenase genes, which in humans and mouse models cause ichthyosis, a skin disease characterized by a thick, hyperkeratotic epidermis that recapitulates Steller's sea cows' reportedly bark-like skin. We also found that Steller's sea cows' abundance was continuously declining for tens of thousands of years before their description, implying that environmental changes also contributed to their extinction.

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon-sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere.

In response to warming climate, methane can be released to Arctic Ocean sediment and waters from thawing subsea permafrost and decomposing methane hydrates. However, it is unknown whether methane derived from this sediment storehouse of frozen ancient carbon reaches the atmosphere. We quantified the fraction of methane derived from ancient sources in shelf waters of the U.S. Beaufort Sea, a region that has both permafrost and methane hydrates and is experiencing significant warming. Although the radiocarbon-methane analyses indicate that ancient carbon is being mobilized and emitted as methane into shelf bottom waters, surprisingly, we find that methane in surface waters is principally derived from modern-aged carbon. We report that at and beyond approximately the 30-m isobath, ancient sources that dominate in deep waters contribute, at most, 10 ± 3% of the surface water methane. These results suggest that even if there is a heightened liberation of ancient carbon-sourced methane as climate change proceeds, oceanic oxidation and dispersion processes can strongly limit its emission to the atmosphere.

The Ice Free Corridor has been invoked as a route for Pleistocene human and animal dispersals between eastern Beringia and more southerly areas of North America. Despite the significance of the corridor, there are limited data for when and how this corridor was used. Hypothetical uses of the corridor include: the first expansion of humans from Beringia into the Americas, northward postglacial expansions of fluted point technologies into Beringia, and continued use of the corridor as a contact route between the north and south. Here, we use radiocarbon dates and ancient mitochondrial DNA from late Pleistocene bison fossils to determine the chronology for when the corridor was open and viable for biotic dispersals. The corridor was closed after ∼23,000 until 13,400 calendar years ago (cal y BP), after which we find the first evidence, to our knowledge, that bison used this route to disperse from the south, and by 13,000 y from the north. Our chronology supports a habitable and traversable corridor by at least 13,000 cal y BP, just before the first appearance of Clovis technology in interior North America, and indicates that the corridor would not have been available for significantly earlier southward human dispersal. Following the opening of the corridor, multiple dispersals of human groups between Beringia and interior North America may have continued throughout the latest Pleistocene and early Holocene. Our results highlight the utility of phylogeographic analyses to test hypotheses about paleoecological history and the viability of dispersal routes over time.

The Ice Free Corridor has been invoked as a route for Pleistocene human and animal dispersals between eastern Beringia and more southerly areas of North America. Despite the significance of the corridor, there are limited data for when and how this corridor was used. Hypothetical uses of the corridor include: the first expansion of humans from Beringia into the Americas, northward postglacial expansions of fluted point technologies into Beringia, and continued use of the corridor as a contact route between the north and south. Here, we use radiocarbon dates and ancient mitochondrial DNA from late Pleistocene bison fossils to determine the chronology for when the corridor was open and viable for biotic dispersals. The corridor was closed after ∼23,000 until 13,400 calendar years ago (cal y BP), after which we find the first evidence, to our knowledge, that bison used this route to disperse from the south, and by 13,000 y from the north. Our chronology supports a habitable and traversable corridor by at least 13,000 cal y BP, just before the first appearance of Clovis technology in interior North America, and indicates that the corridor would not have been available for significantly earlier southward human dispersal. Following the opening of the corridor, multiple dispersals of human groups between Beringia and interior North America may have continued throughout the latest Pleistocene and early Holocene. Our results highlight the utility of phylogeographic analyses to test hypotheses about paleoecological history and the viability of dispersal routes over time.

© 2015 Elsevier Ltd. Several recent studies have used records of the radiocarbon (14C) bomb peak in speleothems to inversely model the soil a 14CO2 and the age distribution of soil organic material (SOM) above caves, in part to investigate the potential of speleothems as sensitive records of past SOM dynamics. The results of these modeling studies have suggested that soil CO2 at karst sites is derived primarily from the decomposition of SOM with turnover times on the order of decades to centuries. This result is in stark contrast with observations of soil a 14CO2 at non-karst sites, which indicate that soil CO2 is derived primarily from root respiration and decomposition of SOM with much shorter turnover times. This discrepancy suggests that SOM in karst settings may have a very different age distribution than sites that have been studied previously and/or that soil CO2 is not the main source of speleothem carbon. To help resolve this discrepancy, we present an improved inverse model which we use to estimate the age of CO2 above several caves. We also present results from a detailed case study of soil carbon dynamics at Heshang Cave, China. This work demonstrates that SOM in karst sites may be much older than SOM in non-karst soils that have been studied previously, but that CO2 produced in the shallow soil zone is unlikely to be the main source of speleothem carbon. A review of the literature suggests that the most likely explanation for the aforementioned discrepancy is that decomposition of down-washed SOM in the vadose zone is the dominant source of speleothem carbon.

Existing radiocarbon ((14)C) dates on American mastodon (Mammut americanum) fossils from eastern Beringia (Alaska and Yukon) have been interpreted as evidence they inhabited the Arctic and Subarctic during Pleistocene full-glacial times (∼ 18,000 (14)C years B.P.). However, this chronology is inconsistent with inferred habitat preferences of mastodons and correlative paleoecological evidence. To establish a last appearance date (LAD) for M. americanum regionally, we obtained 53 new (14)C dates on 36 fossils, including specimens with previously published dates. Using collagen ultrafiltration and single amino acid (hydroxyproline) methods, these specimens consistently date to beyond or near the ∼ 50,000 y B.P. limit of (14)C dating. Some erroneously "young" (14)C dates are due to contamination by exogenous carbon from natural sources and conservation treatments used in museums. We suggest mastodons inhabited the high latitudes only during warm intervals, particularly the Last Interglacial [Marine Isotope Stage (MIS) 5] when boreal forests existed regionally. Our (14)C dataset suggests that mastodons were extirpated from eastern Beringia during the MIS 4 glacial interval (∼ 75,000 y ago), following the ecological shift from boreal forest to steppe tundra. Mastodons thereafter became restricted to areas south of the continental ice sheets, where they suffered complete extinction ∼ 10,000 (14)C years B.P. Mastodons were already absent from eastern Beringia several tens of millennia before the first humans crossed the Bering Isthmus or the onset of climate changes during the terminal Pleistocene. Local extirpations of mastodons and other megafaunal populations in eastern Beringia were asynchrononous and independent of their final extinction south of the continental ice sheets.

Recently, it has been shown that U-Th dated speleothems may provide a valuable archive of atmospheric radiocarbon (14C), but the reliability of these records is dependent upon the stability of the dead carbon proportion (DCP) derived from the soil and bedrock. In order to assess climatic influences on speleothem DCP, we have investigated DCP variability over the Holocene interval where atmospheric 14C is well known based on dendrochronologically dated tree rings by conducting 14C measurements on a U-Th dated stalagmite (HS4) from Heshang Cave, Hubei Province, China (30°27 'N, 110°25 'E; 294 m) spanning 0.5-9.6 ka. We investigated climatic controls on DCP, and found that DCP in HS4 has an average value over the Holocene of 10.3 ± 1.5%, with an average age offset from atmospheric radiocarbon of 875 ± 130 years, and displays a response to both precipitation increases and decreases. HS4 DCP increases during the wetter mid-Holocene interval (~5.5-7.1 ka), likely reflecting a shift to more closed-system dissolution in response to increased soil moisture. DCP decreases during the 8.2 ka event, a time period of dry conditions at Heshang Cave, though the lower amplitude of this shift indicates that DCP may be less sensitive to dry events. Speleothems are potentially valuable archives of atmospheric radiocarbon, especially in older portions of the 14C calibration curve where knowledge of atmospheric 14C is limited, however minor climatic influences on DCP could introduce uncertainties of several hundred years to calibrated ages. © 2014 Elsevier B.V.

The “Christmas Cave”, a cave in the Qidron Valley near the Dead Sea and Qumran, has yielded a complex collection of plant-derived rope and fabric artifacts. Using polymerase chain reaction (PCR) to amplify DNA of the samples, we estimated the sizes and determined restriction patterns and base sequences of chloroplast genes, primarily rbcL (gene for the large subunit of ribulose bisphosphate carboxylase). DNA was successfully extracted from all samples, but was limited to sizes of approximately 200-300 base pairs. As expected, the DNA extracted from the samples was identified as coming primarily from flax (Linum usitatissamum L.), but two samples had a significant fraction, and all samples had at least a trace, of hemp (Cannabis sativa L.) DNA. Artifacts from the Christmas Cave were thought to date from Roman times, but it was thought possible that some could be much older. Accelerator mass spectrometry (AMS)-based 14C dating confirmed that the samples contained representatives from both the Roman and Chalcolithic periods. This paper provides a synthesis of DNA, isotope, and literary analysis to illuminate textile history at the Christmas Cave site.

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.

We report compound-specific radiocarbon analyses of organic matter in ocean sediments from the northeast Pacific Ocean. Chemical extractions and a preparative capillary gas chromatograph (PCGC) were used to isolate phospholipid fatty acids (PLFA) and n-alkanes from 3 cores collected off the coast of California, USA. Mass of samples for accelerator mass spectrometry (AMS) 14C analysis ranged from 13-100 μg C. PLFA extracted from anaerobic sediments in the Santa Barbara Basin (595 m depth) had modern ∆14C values (-20 to +54‰), indicating bacterial utilization of surface-produced, post-bomb organic matter. Lower ∆14C values were obtained for n-alkanes and PLFA from coast (92 m depth) and continental slope (1866 m) sediments, which reflect sources of old organic matter and bioturbation. We present a brief analysis of the blank carbon introduced to samples during chemical processing and PCGC isolation.

Recent studies suggest that as much as half of the organic carbon (OC) undergoing burial in the sediments of tectonically active continental margins may be the product of fossil shale weathering. These estimates rely on the assumption that vascular plant detritus spends little time sequestered in intermediate reservoirs such as soils, freshwater sediments, and river deltas, and thus only minimally contributes to the extraneously old 14C ages of total organic matter often observed on adjacent shelves. Here we test this paradigm by measuring the Δ14C and δ13C values of individual higher plant wax fatty acids as well as the δ13C values of extractable alkanes isolated from the Eel River margin (California). The isotopic signatures of the long chain fatty acids indicate that vascular plant material has been sequestered for several thousand years before deposition. A coupled molecular isotope mass balance used to reassess the sedimentary carbon budget indicates that the fossil component is less abundant than previously estimated, with pre-aged terrestrial material instead composing a considerable proportion of all organic matter. If these findings are characteristic of other continental margins proximal to small mountainous rivers, then the importance of petrogenic OC burial in marine sediments may need to be reevaluated. © 2009 The Geological Society of America.

The 14C reservoir age of the surface ocean was determined for two Holocene periods (4908–4955 and 3008–3066 calendar (cal) B.P.) using U/Th-dated corals from Biscayne National Park, Florida, United States. We found that the average reservoir ages for these two time periods (294 ± 33 and 291 ± 27 years, respectively) were lower than the average value between A.D. 1600 and 1900 (390 ± 60 years) from corals. It appears that the surface ocean was closer to isotopic equilibrium with CO2 in the atmosphere during these two time periods than it was during recent times. Seasonal δ 18O measurements from the younger coral are similar to modern values, suggesting that mixing with open ocean waters was indeed occurring during this coral's lifetime. Likely explanations for the lower reservoir age include increased stratification of the surface ocean or increased Δ14C values of subsurface waters that mix into the surface. Our results imply that a more correct reservoir age correction for radiocarbon measurements of marine samples in this location from the time periods ∼3040 and ∼4930 cal years B.P. is ∼292 ± 30 years, less than the canonical value of 404 ± 20 years.

The sealed tube zinc reduction method for converting CO2 to graphite for AMS 14C measurements was originally developed for rapid production of graphite in biomedical tracer experiments. The method was usually thought to have low precision and a high background. We have modified the zinc reduction method originally outlined in Vogel [J.S. Vogel, Radiocarbon 34 (3) (1992) 344] by carefully controlling the amounts of reagents (zinc, titanium hydride and Co or Fe catalyst) and now routinely obtain a precision of 2-3‰ and a relatively low background of ∼50,000 14C years when analyzing for 14C at the Keck Carbon Cycle AMS facility at UC Irvine. Fractionation of carbon isotopes does occur during graphitization and depends on the graphitization yield, which can be affected by the amounts of reagents used and other conditions. The δ13C of our zinc-reduced graphite is usually lighter by 2-3‰ than the CO2 from which it is made, but this is corrected for in our system by simultaneous measurement of 13C/12C along with 14C/12C by the spectrometer. This method is suitable for 14C enriched samples, as well as natural abundance 14C samples, especially those with modern 14C contents. With improved precision and background, we believe that many disciplines can benefit from this technique because of its low cost and rapid production of graphite. © 2007 Elsevier B.V. All rights reserved.

Radiocarbon levels in annual plants provide a means to map out regional and continental-scale fossil fuel plumes in surface air. We collected corn (Zea mays) across North America during the summer of 2004. Plants from mountain regions of western North America showed the smallest influence of fossil fuel-derived CO2 with a mean Δ14C of 66.3‰ ±1.7‰. Plants from eastern North America and from the Ohio-Maryland region showed a larger fossil fuel influence with a mean Δ14C of 58.8‰ ± 3.9‰ and 55.2‰ ± 2.3‰, respectively, corresponding to 2.7 ppm ± 1.5 ppm and 4.3 ppm ± 1.0 ppm of added fossil fuel CO2 relative to the mountain west. A model–data comparison suggests that surveys of annual plant Δ14C can provide a useful test of atmospheric mixing in transport models that are used to estimate the spatial distribution of carbon sources and sinks.

Radiocarbon levels in annual plants provide a means to map out regional and continental-scale fossil fuel plumes in surface air. We collected corn (Zea mays) across North America during the summer of 2004. Plants from mountain regions of western North America showed the smallest influence of fossil fuel-derived CO2 with a mean Δ14C of 66.3‰ ±1.7‰. Plants from eastern North America and from the Ohio-Maryland region showed a larger fossil fuel influence with a mean Δ14C of 58.8‰ ± 3.9‰ and 55.2‰ ± 2.3‰, respectively, corresponding to 2.7 ppm ± 1.5 ppm and 4.3 ppm ± 1.0 ppm of added fossil fuel CO2 relative to the mountain west. A model–data comparison suggests that surveys of annual plant Δ14C can provide a useful test of atmospheric mixing in transport models that are used to estimate the spatial distribution of carbon sources and sinks.

In this paper, we present an overview of 14C methods, Accelerator Mass Spectrometry (AMS) techniques, and their applications to radiocarbon dating of archaeological sites in South America. We describe sample preparation methods to be applied to archaeological bone samples as well as useful sample selection strategies to help achieve reliable AMS-based 14C results. Application of criteria to determine bone quality (to assess lack of alteration and degradation) before and during sample preparation, and the use of a modified ultrafiltration method to extract collagen from these kinds of materials have enabled us to obtain reliable radiocarbon results. Two applications will be presented to illustrate these issues: a) Paleodietary inferences from isotopic measurements on human bone and teeth from the populations of the central mountains of Argentina, and b) the implication of new 14C determinations obtained from two segments of a single mastodon bone recovered from Monte Verde, that previously differed by more than 5,000 years.

Radiocarbon (∆14C) measurements of monthly samples from a Galapagos surface coral are among the first data sets from the new Keck Carbon Cycle Accelerator Mass Spectrometry laboratory at the University of California, Irvine. An average ∆14C value of -62‰ is obtained for 144 measurements of samples from monthly coral bands that lived from about AD 1760-1771 (±6 yr). High ∆14C values were found during January through March, when upwelling was weak or absent at the Galapagos Islands. Low ∆14C values were obtained mid-year during strong upwelling. The average seasonal variability of ∆14C was 15-25‰, which is greater than that at other tropical and subtropical locations in the Pacific Ocean because of intense seasonal upwelling at this site. Periods of sustained high ∆14C values were found during 1762-1763 and 1766. A spectral analysis revealed that the spectral density for the ∆14C data displays most of its variance at the 5-yr cycle, which is reflective of El Nio periodicity during the 20th century.

A new 14C accelerator mass spectrometry (AMS) laboratory for carbon cycle studies has been established at the University of California, Irvine. The 0.5 MV AMS system was installed in mid-2002 and has operated routinely sinceOctober of that year. This paper briefly describes the spectrometer and summarizes lessons learned during the first year of operation. In the process of setting up the system, we identified and largely suppressed a previously unreported radiocarbonAMS background: charge exchange tails from 14N beams derived from nitrogen-containing molecular ions produced near the entrance of the accelerator.

The role of terrestrial ecosystems as sources or sinks for carbon to the atmosphere and their contribution to inter-annual variations in atmospheric CO2 remain hotly-debated topics. Carbon enters terrestrial ecosystems through a single process, photosynthesis, but it is returned to the atmosphere by the combined metabolic activity of plants, animals, and microbes (Figure l). The largest uncertainties in our understanding of terrestrial carbon cycling are in these return processes, especially how CO2 losses from ecosystems are divided among respiration by living plants—termed autotrophic respiration—versus microbial and faunal decomposition of plant residues—termed heterotrophic respiration (Figure 1); and how seasonal and climatic factors that change plant physiological status and soil conditions influence that partitioning.