Seasonality of precipitation in the southwestern United States during the late Pleistocene inferred from stable isotopes in herbivore tooth enamel

The late Pleistocene was a climatically dynamic period, with abrupt shifts between cool-wet and warmdry conditions. Increased effective precipitation supported large pluvial lakes and long-lived spring ecosystems in valleys and basins throughout the western and southwestern U.S., but the source and seasonality of the increased precipitation are debated. Increases in the proportions of C4/(C4+ C3) grasses in the diets of large grazers have been ascribed both to increases in summer precipitation and lower atmospheric CO2 levels. Here we present stable carbon and oxygen isotope data from tooth enamel of late Pleistocene herbivores recovered from paleowetland deposits at Tule Spring Fossil Beds National Monument in the Las Vegas Valley of southern Nevada, as well as modern herbivores from the surrounding area. We use these data to investigate whether winter or summer precipitation was responsible for driving the relatively wet hydroclimate conditions that prevailed in the region during the late Pleistocene. We also evaluate whether late Pleistocene grass C4/(C4+ C3) was higher than today, and potential drivers of any changes. Tooth enamel δ18O values for Pleistocene Equus, Bison, and Mammuthus are generally low (average 22.0 ± 0.7‰, 2 s.e., VSMOW) compared to modern equids (27.8 ± 1.5‰), and imply lower water δ18O values (-16.1 ± 0.8‰) than modern precipitation (-10.5‰) or in waters present in active springs and wells in the Las Vegas Valley (-12.9‰), an area dominated by winter precipitation. In contrast, tooth enamel of Camelops (a browser) generally yielded higher δ18O values (23.9 ± 1.1‰), possibly suggesting drought tolerance. Mean δ13C values for the Pleistocene grazers (-6.6 ± 0.7‰, 2 s.e., VPDB) are considerably higher than for modern equids (-9.6 ± 0.4‰) and indicate more consumption of C4 grass (17 ± 5%) than today (4 ± 4%). However, calculated C4 grass consumption in the late Pleistocene is strikingly lower than the proportion of C4 grass taxa currently present in the valley (55-60%). δ13C values in Camelops tooth enamel (-7.7 ± 1.0‰) are interpreted as reflecting moderate consumption (14 ± 8%) of Atriplex (saltbush), a C4 shrub that flourishes in regions with hot, dry summers. Lower water δ18O values, lower abundance of C4 grasses, and the inferred presence of Atriplex are all consistent with general circulation models for the late Pleistocene that show enhanced delivery of winter precipitation, sourced from the north Pacific, into the interior western U.S. but do not support alternative models that infer enhanced delivery of summer precipitation, sourced from the tropics. In addition, we hypothesize that dietary competition among the diverse and abundant Pleistocene fauna may have driven the grazers analyzed here to feed preferentially on C4 grasses. Dietary partitioning, especially when combined with decreased pCO2 levels during the late Pleistocene, can explain the relatively high δ13C values observed in late Pleistocene grazers in the Las Vegas Valley and elsewhere in the southwestern U.S. without requiring additional summer precipitation. Pleistocene hydroclimate parameters derived from dietary and floral records may need to be reevaluated in the context of the potential effects of dietary preferences and lower pCO2 levels on the stability of C3 vs. C4 plants

Decadally resolved lateglacial radiocarbon evidence from New Zealand kauri

Author Posting. © The Author(s), 2016. This is the author's version of the work. It is posted here by permission of Arizona Board of Regents on behalf of the University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 58 (2016): 709-733, doi: 10.1017/RDC.2016.86.The Last Glacial-Interglacial Transition (LGIT; 15,000-11,000 cal BP) was characterized by complex spatiotemporal patterns of climate change, with numerous studies requiring accurate chronological control to decipher leads from lags in global paleoclimatic, -environmental and archaeological records. However, close scrutiny of the few available tree-ring chronologies and 14C-dated sequences composing the IntCal13 radiocarbon calibration curve, indicates significant weakness in 14C calibration across key periods of the LGIT. Here, we present a decadally-resolved atmospheric 14C record derived from New Zealand kauri spanning the Lateglacial from ~13,100 - 11,365 cal BP. Two floating kauri 14C time series, curve-matched to IntCal13, serve as a radiocarbon backbone through the Younger Dryas. The floating Northern Hemisphere (NH) 14C datasets derived from the YD-B and Central European Lateglacial Master tree-ring series are matched against the new kauri data, forming a robust NH 14C time series to ~14,200 cal BP. Our results show that IntCal13 is questionable from ~12,200 - 11,900 cal BP and the ~10,400 BP 14C plateau is approximately five decades too short. The new kauri record and re-positioned NH pine 14C series offer a refinement of the international 14C calibration curves IntCal13 and SHCal13, providing increased confidence in the correlation of global paleorecords.This work was part funded by the Foundation for Research, Science and Technology (FRST)—now Ministry for Business, Innovation & Employment (MBIE)-PROP-20224-SFK-UOA), a Royal Society of New Zealand grant, the Australian Research Council (FL100100195 and DP0664898) and the Natural Environment Research Council (NE/H009922/1, NE/I007660/1, NER/A/S/2001/01037 and NE/H007865/1)

Carbonate-hosted microbial communities are prolific and pervasive methane oxidizers at geologically diverse marine methane seep sites

At marine methane seeps, vast quantities of methane move through the shallow subseafloor, where it is largely consumed by microbial communities. This process plays an important role in global methane dynamics, but we have yet to identify all of the methane sinks in the deep sea. Here, we conducted a continental-scale survey of seven geologically diverse seafloor seeps and found that carbonate rocks from all sites host methane-oxidizing microbial communities with substantial methanotrophic potential. In laboratory-based mesocosm incubations, chimney-like carbonates from the newly described Point Dume seep off the coast of Southern California exhibited the highest rates of anaerobic methane oxidation measured to date. After a thorough analysis of physicochemical, electrical, and biological factors, we attribute this substantial metabolic activity largely to higher cell density, mineral composition, kinetic parameters including an elevated Vmax, and the presence of specific microbial lineages. Our data also suggest that other features, such as electrical conductance, rock particle size, and microbial community alpha diversity, may influence a sample's methanotrophic potential, but these factors did not demonstrate clear patterns with respect to methane oxidation rates. Based on the apparent pervasiveness within seep carbonates of microbial communities capable of performing anaerobic oxidation of methane, as well as the frequent occurrence of carbonates at seeps, we suggest that rock-hosted methanotrophy may be an important contributor to marine methane consumption.https://www.pnas.org/content/118/25/e200685711

Accuracy and Practical Considerations for Doubly Labeled Water Analysis in Nutrition Studies Using a Laser-Based Isotope Instrument (Off-Axis Integrated Cavity Output Spectroscopy)

Background: Given the utility of the doubly labeled water (DLW) method for determination of energy expenditure, additional techniques for isotope analysis of the samples are welcome. Laser-based instruments are one such new analytical tool, but their accuracy and feasibility for DLW studies are grossly understudied. Objectives: We assessed the accuracy of laser-based isotope ratio measurements as part of the DLW method for estimation of carbon dioxide production rate (rCO2) and total energy expenditure (TEE), in between-group comparison study designs. Methods: Urine samples from a previous study were analyzed with a laser-based instrument [off-axis integrated cavity output spectroscopy (OA-ICOS)]. In that study, participants consumed a high-, moderate-, or low-carbohydrate diet for 20 wk; urine samples were obtained in weeks 18–20 before and after a 2H- and 18O-enriched water dose. Isotope ratios (δ2H and δ18O), rCO2, and TEE calculated by standard methods were compared to results previously obtained with the standard technique of isotope ratio mass spectrometry (IRMS). Bias, SD, and bias ± 1.96SD bands between IRMS and OA-ICOS were computed. Results: The between OA-ICOS and IRMS rCO2 and TEE trends were equivalent (within 1.2% and 4.1%, respectively), in spite of the differences in measured δ18O values at high enrichment levels. The OA-ICOS δ18O values displayed an increasing offset from the IRMS results as the 18O enrichment increased (mean ± SD 4.6–5.7‰ ± 2‰ offset at the time point with highest 18O enrichment, ∼135‰), whereas the hydrogen isotope ratio (δ2H) differed only slightly between the methods (mean offset −4.9‰ for all time points). The between-diet differences in TEE from the previous study were recapitulated with a smaller subset of participants and time points. Conclusions: OA-ICOS analysis is an accurate and feasible technique for the DLW method. Given the δ18O offset observed at high enrichment, validation of each OA-ICOS instrumental setup against established methods (e.g., IRMS) is recommended

MICROWAVE SPECTRAL, STRUCTURES AND HYPERFINE CONSTANTS OF GOLD(I) HALIDES.

Author Institution: Department of Chemistry, University of British ColumbiaThe microwave rotational spectra of AuF, AuCl, AuBr and AuI have been measured in the frequency range 6-22 GHz, using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by ablating Au metal with a Nd:YAG laser (532) and allowing the vapour to react with a precursor $< 1$ in the Ar or Ne backing gas of the jet. The spectrum of AuF has confirmed that it can be made, in contrast to long-held ideas. The spectra of AuBr and AuI are the first high resolution spectra of any kind reported for these molecules. Equilibrium geometries, vibrational wavenumbers and dissociation energies have been obtained. The Au nuclear quadrupole coupling constants show wide variations between the molecules, which cannot be accounted for with simple theories