Stable carbon, nitrogen and sulphur isotope analysis of permafrost preserved human hair from rescue excavations (2009, 2010) at the precontact site of Nunalleq, Alaska

Acknowledgments This work was funded by an Arts and Humanities Research Council (AH/K006029/1) grant awarded to Rick Knecht, Kate Britton and Charlotta Hillerdal (Aberdeen); an AHRC-LabEx award (AH/N504543/1) to KB, RK, Keith Dobney (Liverpool) and Isabelle Sidéra (Nanterre); the Carnegie Trust to the Universities of Scotland (travel grant to KB); and the Max Planck Institute for Evolutionary Anthropology. The onsite collection of samples was carried out by staff and students from the University of Aberdeen, volunteer excavators and the residents of Quinhagak. We had logistical and planning support for fieldwork by the Qanirtuuq Incorporated, Quinhagak, Alaska, and the people of Quinhagak, who we also thank for sampling permissions. Special thanks to Warren Jones and Qanirtuuq Incorporated (especially Michael Smith and Lynn Church), and to all Nunalleq project team members, in Aberdeen and at other institutions, particularly Charlotta Hillerdal and Edouard Masson-Maclean (Aberdeen) for comments on earlier versions of this manuscript, and also to Véronique Forbes, Ana Jorge, Carly Ameen and Ciara Mannion (Aberdeen) for their inputs. Thanks also to Michelle Alexander (York). Finally, thank you to Ian Scharlotta (Alberta) for inviting us to contribute to this special issue, to the Editor, and to three anonymous reviewers, whose suggestions and recommended changes to an earlier version of this manuscript greatly improved the paper.

Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ≈70‰) shifts in δ13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70‰) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

Evolution of the stable carbon isotope composition of atmospheric CO₂ over the last glacial cycle

We present new δ¹³C measurements of atmospheric CO₂ covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in δ¹³C(atm) of 0.5‰ occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in δ¹³C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO₂]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of δ¹³C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.