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Ponds and lakes are widespread across the rapidly changing permafrost environments. Aquatic systems play an important role in global biogeochemical cycles, especially in greenhouse gas (GHG) exchanges between terrestrial systems and the atmosphere. The source, speciation and emission of carbon released from permafrost landscapes are strongly influenced by local specific conditions rather than general environmental setting. This study reports on GHG ages and emission rates from aquatic systems on Bylot Island in the eastern Canadian Arctic. Dissolved and ebullition gas samples were collected during the summer season from different types of water bodies located in a highly dynamic periglacial valley: polygonal ponds, collapsed ice-wedge trough ponds, and larger lakes overlying unfrozen soils (talik). The results showed strikingly different ages and fluxes depending on aquatic system types. Polygonal ponds were net sinks of dissolved CO2, but variable sources of dissolved CH4. They presented the highest ebullition fluxes, one or two orders of magnitude higher than from other ponds and lakes. Trough ponds appeared as substantial GHG sources, especially when their edges were actively eroding. Both types of ponds produced modern to hundreds of years old (< 550 yr BP) GHG, even if trough ponds could contain much older carbon (> 2000 yr BP) derived from freshly eroded peat. Lakes had small dissolved and ebullition fluxes, however they released much older GHG, including millennium-old CH4 (up to 3500 yr BP) sampled from lake central areas. Acetoclastic methanogenesis dominated at all study sites and there was minimal, if any, methane oxidation in gas emitted through ebullition. These findings provide new insights on the variable role of permafrost aquatic systems as a positive feedback mechanism on climate. [ABSTRACT FROM AUTHOR]

The abrupt warming across the Younger Dryas termination (~11 600 yr before present) was marked by a large increase in the global atmospheric methane mixing ratio. The debate over sources responsible for the rise in methane centers on the roles of global wetlands, marine gas hydrates, and thermokarst lakes. We present a new, higher-precision methane stable carbon isotope ratio (δ13CH4) dataset from ice sampled at Påkitsoq, Greenland that shows distinct 13C-enrichment associated with this rise. We investigate the validity of this finding in face of known anomalous methane concentrations that occur at Påkitsoq. Comparison with previously published datasets to determine the robustness of our results indicates a similar trend in ice from both an Antarctic ice core and previously published Påktisoq data measured using four different extraction and analytical techniques. The δ13CH4 trend suggests that 13C-enriched CH4 sources played an important role in the concentration increase. In a first attempt at quantifying the various contributions from our data, we apply a methane triple mass balance of stable carbon and hydrogen isotope ratios and radiocarbon. The mass balance results suggest biomass burning (42-66% of total methane flux increase) and thermokarst lakes (27-59%) as the dominant contributing sources. Our results do not suggest as large a role for tropical wetlands, boreal peatlands or marine gas hydrates as commonly proposed. [ABSTRACT FROM AUTHOR]

The stable-hydrogen kinetic isotope effects (KIEs) for a series ofn-alkanes in reaction with chlorine atoms in the gas phase were studied in a 25-L PTFE reaction chamber at 298 K. The time dependence of both the stable hydrogen isotope ratios and the concentrations was determined using a gas chromatography pyrolysis isotope ratio mass spectrometry (GC-P-IRMS) system. The following KIE values, in per mil (‰), were obtained: 39.6 ± 2.7 (n-butane), 28.2 ± 0.9 (n-pentane), 24.6 ± 1.0 (n-hexane), 24.0 ± 1.2 (n-heptane), 17.9 ± 3.3 (n-octane), 15.1 ± 0.7 (n-nonane), and 14.9 ± 1.8 (n-decane). The errors given are the ±1s standard errors. These measured values were used to derive structure-reactivity relationship (SRRs), which allow for the calculation of the KIEs for the reaction ofn-alkanes with Cl atoms. The results of the calculations agree with the measurements within few per mil or better. The site specific stable hydrogen isotope fractionation effects for methyl groups are approximately a factor of 3 larger than those for methylene group, a finding which is qualitatively similar to site-specific stable hydrogen isotope effects reported in literature for reactions of alkanes with the OH radical. Becausen-alkanes with close to natural isotope ratios (i.e. neither artificially labeled, nor enriched or depleted) were used, the KIE data are directly applicable to atmospheric studies. Based on these KIE values, the impact of Cl-atom reactions of the stable hydrogen isotope ratio on alkanes are estimated for different levels of Cl-atom concentrations. On average in the troposphere, the impact of Cl-atom reactions of the stable hydrogen isotope ratio ofn-alkanes will be small. However, in regions of the troposphere with high concentrations of Cl atoms, such as the tropospheric ozone depletion episodes during polar sunrise, the impact of Cl-atom reactions is substantial. [ABSTRACT FROM AUTHOR]

We evaluated the utility of vitamin A and E profiles as biomarkers of contaminant exposure in beluga whales (Delphinapterus leucas; n=66) harvested by the Inuvialuit in the Beaufort Sea. Blubber was an important repository for these vitamins, accounting for 76.8±2.6% of the total body store of vitamin A, and 98.5±0.4% of total vitamin E. While the free alcohol form of vitamin A (retinol) appeared highly regulated, the vitamin A esters were influenced by several biological factors including age, body condition and length. Vitamin E concentrations in liver and blubber were related to age, condition, length and feeding ecology, as described δ(15)N and δ(13)C. Despite the influence of these factors, collective results from univariate statistics, best fit multiple regressions, and principal component analysis (PCA) identified polychlorinated biphenyls (PCBs) as important determinants of vitamin concentrations and profiles in beluga tissues. Blubber PCB concentrations best explained variation of the first principal component in a PCA of hepatic vitamins (r(2)=0.13, p=0.014), and regression models found that vitamin A concentrations were negatively correlated with PCB levels in liver (esters: r(2)=0.19, p=0.001), but positively in plasma (retinol: r(2)=0.20, p=0.06) and blubber (retinol: r(2)=0.22, p=0.001, esters: r(2)=0.43, p<0.001). Our analyses provide a basis to propose an integrated toxicity reference value for disruption of vitamin A and E profiles in beluga of 1.6 mg/kg lw PCBs. This disruption of vitamin profiles by moderate levels of PCBs in an arctic cetacean highlights the global reach and impact of these legacy chemicals decades after their peak use., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Methane production by anaerobic digestion of biomass has recently become more attractive because of its potential for renewable energy production. Analytical tools are needed to study and optimize the ongoing processes in biogas reactors. It is considered that optical methods providing continuous measurements at high temporal resolution of carbon isotope ratios of methane (delta(13)C(CH4)) might be of great help for this purpose. In this study we have tested near-infrared laser optical spectrometry and compared it with conventional continuous-flow isotope ratio mass spectrometry (CF-IRMS) using several methane carbon isotope standards and a large number of biogas samples from batch anaerobic reactors. Results from measurements on these samples were used to determine and compare the precision of the two techniques and to quantify for systematic offsets. With pure standards analytical precision of measurements for delta(13)C(CH4) was found to be in the range of 0.33 and 0.48 per thousand, and 0.09 and 0.27 per thousand for the optical method and CF-IRMS, respectively. Biogas samples showed an average mean deviation of delta(13)C(CH4) of 0.38 per thousand and 0.08 per thousand for the optical method and CF-IRMS, respectively. Although the tested laser optical spectrometer showed a dependence of delta(13)C(CH4) on CH(4) mixing ratio in the range of 500 to 8000 ppm this could be easily corrected. After correction, the delta(13)C(CH4) values usually varied within 0.7 per thousand from those measured by conventional CF-IRMS and thus results from both methods agreed within the given analytical uncertainties. Although the precision of the conventional CF-IRMS is higher than the tested optical system, both instruments were well within the acceptable delta(13)C(CH4) precision required for biogas methane measurements. The advantages of the optical system are its simplicity of operation, speed of analysis, good precision, reduced costs in comparison to IRMS, and the potential for field applications.