Stable isotopic analysis of atmospheric methane by infrared spectroscopy by use of diode laser difference-frequency generation

An infrared absorption spectrometer has been constructed to measure the stable isotopic composition of atmospheric methane samples. The spectrometer employs periodically poled lithium niobate to generate 15 μW of tunable difference-frequency radiation from two near-infrared diode lasers that probe the ν3 rotational-vibrational band of methane at 3.4 μm. To enhance the signal, methane is extracted from 25 l of air by use of a cryogenic chromatographic column and is expanded into the multipass cell for analysis. A measurement precision of 12‰ is demonstrated for both δ13C and δD

What atmospheric oxygen measurements can tell us about the global carbon cycle

This paper explores the role that measurements of changes in atmospheric oxygen, detected through changes in the O2/N2 ratio of air, can play in improving our understanding of the global carbon cycle. Simple conceptual models are presented in order to clarify the biological and physical controls on the exchanges of O2, CO2, N2, and Ar across the air‐sea interface and in order to clarify the relationships between biologically mediated fluxes of oxygen across the air‐sea interface and the cycles of organic carbon in the ocean. Predictions of large‐scale seasonal variations and gradients in atmospheric oxygen are presented. A two‐dimensional model is used to relate changes in the O2/N2 ratio of air to the sources of oxygen from terrestrial and marine ecosystems, the thermal ingassing and outgassing of seawater, and the burning of fossil fuel. The analysis indicates that measurements of seasonal variations in atmospheric oxygen can place new constraints on the large‐scale marine biological productivity. Measurements of the north‐south gradient and depletion rate of atmospheric oxygen can help determine the rates and geographical distribution of the net storage of carbon in terrestrial ecosystems

Atmospheric potential oxygen: New observations and their implications for some atmospheric and oceanic models

Measurements of atmospheric O2/N2 ratios and CO2 concentrations can be combined into a tracer known as atmospheric potential oxygen (APO ≈ O2/N2 + CO2) that is conservative with respect to terrestrial biological activity. Consequently, APO reflects primarily ocean biogeochemistry and atmospheric circulation. Building on the work of Stephens et al. (1998), we present a set of APO observations for the years 1996-2003 with unprecedented spatial coverage. Combining data from the Princeton and Scripps air sampling programs, the data set includes new observations collected from ships in the low-latitude Pacific. The data show a smaller interhemispheric APO gradient than was observed in past studies, and different structure within the hemispheres. These differences appear to be due primarily to real changes in the APO field over time. The data also show a significant maximum in APO near the equator. Following the approach of Gruber et al. (2001), we compare these observations with predictions of APO generated from ocean O2 and CO2 flux fields and forward models of atmospheric transport. Our model predictions differ from those of earlier modeling studies, reflecting primarily the choice of atmospheric transport model (TM3 in this study). The model predictions show generally good agreement with the observations, matching the size of the interhemispheric gradient, the approximate amplitude and extent of the equatorial maximum, and the amplitude and phasing of the seasonal APO cycle at most stations. Room for improvement remains. The agreement in the interhemispheric gradient appears to be coincidental; over the last decade, the true APO gradient has evolved to a value that is consistent with our time-independent model. In addition, the equatorial maximum is somewhat more pronounced in the data than the model. This may be due to overly vigorous model transport, or insufficient spatial resolution in the air-sea fluxes used in our modeling effort. Finally, the seasonal cycles predicted by the model of atmospheric transport show evidence of an excessive seasonal rectifier in the Aleutian Islands and smaller problems elsewhere. Copyright 2006 by the American Geophysical Union

Atmospheric O2/N2 changes, 1993-2002: Implications for the partitioning of fossil fuel CO2 sequestration

Improvements made to an established mass spectrometric method for measuring changes in atmospheric O2/N2 are described. With the improvements in sample handling and analysis, sample throughput and analytical precision have both increased. Aliquots from duplicate flasks are repeatedly measured over a period of 2 weeks, with an overall standard error in each flask of 3-4 per meg, corresponding to 0.6-0.8 ppm O2 in air. Records of changes in O2/N2 from six global sampling stations (Barrow, American Samoa, Cape Grim, Amsterdam Island, Macquarie Island, and Syowa Station) are presented. Combined with measurements Of CO2 from the same sample flasks, land and ocean carbon uptake were calculated from the three sampling stations with the longest records (Barrow, Samoa, and Cape Grim). From 1994-2002, We find the average CO2 uptake by the ocean and the land biosphere was 1.7 ± 0.5 and 1.0 ± 0.6 GtC yr -1 respectively; these numbers include a correction of 0.3 Gt C yr-l due to secular outgassing of ocean O2. Interannual variability calculated from these data shows a strong land carbon source associated with the 1997-1998 El Niño event, supporting many previous studies indicating that high atmospheric growth rates observed during most El Niño events reflect diminished land uptake. Calculations of interannual variability in land and ocean uptake are probably confounded by non-zero annual air sea fluxes of O2. The origin of these fluxes is not yet understood. Copyright 2005 by the American Geophysical Union

Upward revision of global fossil fuel methane emissions based on isotope database

Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions to the total atmospheric methane budget. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.Published88-916A. Geochimica per l'ambienteJCR Journa

Tropical nighttime warming as a dominant driver of variability in the terrestrial carbon sink

The terrestrial biosphere is currently a strong carbon (C) sink but may switch to a source in the 21st century as climate-driven losses exceed CO2-driven C gains, thereby accelerating global warming. Although it has long been recognized that tropical climate plays a critical role in regulating interannual climate variability, the causal link between changes in temperature and precipitation and terrestrial processes remains uncertain. Here, we combine atmospheric mass balance, remote sensing-modeled datasets of vegetation C uptake, and climate datasets to characterize the temporal variability of the terrestrial C sink and determine the dominant climate drivers of this variability. We show that the interannual variability of global land C sink has grown by 50–100% over the past 50 y. We further find that interannual land C sink variability is most strongly linked to tropical nighttime warming, likely through respiration. This apparent sensitivity of respiration to nighttime temperatures, which are projected to increase faster than global average temperatures, suggests that C stored in tropical forests may be vulnerable to future warming

Atmospheric carbon dioxide variability in the Community Earth System Model : evaluation and transient dynamics during the twentieth and twenty-first centuries

Author Posting. © American Meteorological Society, 2013. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 26 (2013): 4447–4475, doi:10.1175/JCLI-D-12-00589.1.Changes in atmospheric CO2 variability during the twenty-first century may provide insight about ecosystem responses to climate change and have implications for the design of carbon monitoring programs. This paper describes changes in the three-dimensional structure of atmospheric CO2 for several representative concentration pathways (RCPs 4.5 and 8.5) using the Community Earth System Model–Biogeochemistry (CESM1-BGC). CO2 simulated for the historical period was first compared to surface, aircraft, and column observations. In a second step, the evolution of spatial and temporal gradients during the twenty-first century was examined. The mean annual cycle in atmospheric CO2 was underestimated for the historical period throughout the Northern Hemisphere, suggesting that the growing season net flux in the Community Land Model (the land component of CESM) was too weak. Consistent with weak summer drawdown in Northern Hemisphere high latitudes, simulated CO2 showed correspondingly weak north–south and vertical gradients during the summer. In the simulations of the twenty-first century, CESM predicted increases in the mean annual cycle of atmospheric CO2 and larger horizontal gradients. Not only did the mean north–south gradient increase due to fossil fuel emissions, but east–west contrasts in CO2 also strengthened because of changing patterns in fossil fuel emissions and terrestrial carbon exchange. In the RCP8.5 simulation, where CO2 increased to 1150 ppm by 2100, the CESM predicted increases in interannual variability in the Northern Hemisphere midlatitudes of up to 60% relative to present variability for time series filtered with a 2–10-yr bandpass. Such an increase in variability may impact detection of changing surface fluxes from atmospheric observations.The CESM project is supported by the National Science Foundation and the Office of Science (BER) of the U.S. Department of Energy. Computing resources were provided by the Climate Simulation Laboratory at NCAR’s Computational and Information Systems Laboratory (CISL), sponsored by the National Science Foundation and other agencies. G.K.A. acknowledges support of a NOAA Climate and Global Change postdoctoral fellowship. J.T.R., N.M.M., S.C.D., K.L., and J.K.M. acknowledge support of Collaborative Research: Improved Regional and Decadal Predictions of the Carbon Cycle (NSF AGS-1048827, AGS-1021776,AGS-1048890). TheHIPPO Programwas supported byNSF GrantsATM-0628575,ATM-0628519, and ATM-0628388 to Harvard University, University of California (San Diego), and by University Corporation for Atmospheric Research, University of Colorado/ CIRES, by the NCAR and by the NOAAEarth System Research Laboratory. Sunyoung Park, Greg Santoni, Eric Kort, and Jasna Pittman collected data during HIPPO. The ACME project was supported by the Office of Biological and Environmental Research of the U.S. Department of Energy under Contract DE-AC02- 05CH11231 as part of the Atmospheric Radiation Measurement Program (ARM), the ARM Aerial Facility, and the Terrestrial EcosystemScience Program. TCCON measurements at Eureka were made by the Canadian Network for Detection of Atmospheric Composition Change (CANDAC) with additional support from the Canadian Space Agency. The Lauder TCCON program was funded by the New Zealand Foundation for Research Science and Technology contracts CO1X0204, CO1X0703, and CO1X0406. Measurements at Darwin andWollongong were supported by Australian Research Council Grants DP0879468 and DP110103118 and were undertaken by David Griffith, Nicholas Deutscher, and Ronald Macatangay. We thank Pauli Heikkinen, Petteri Ahonen, and Esko Kyr€o of the Finnish Meteorological Institute for contributing the Sodankyl€a TCCON data. Measurements at Park Falls, Lamont, and Pasadena were supported byNASAGrant NNX11AG01G and the NASA Orbiting Carbon Observatory Program. Data at these sites were obtained by Geoff Toon, Jean- Francois Blavier, Coleen Roehl, and Debra Wunch.2014-01-0

The CarbonTracker Data Assimilation System for CO2 and delta C-13 (CTDAS-C13 v1.0):retrieving information on land-atmosphere exchange processes

To improve our understanding of the global carbon balance and its representation in terrestrial biosphere models, we present here a first dual-species application of the CarbonTracker Data Assimilation System (CTDAS). The system's modular design allows for assimilating multiple atmospheric trace gases simultaneously to infer exchange fluxes at the Earth surface. In the prototype discussed here, we interpret signals recorded in observed carbon dioxide (CO2) along with observed ratios of its stable isotopologues (CO2)-C-13/(CO2)-C-12 (delta C-13). The latter is in particular a valuable tracer to untangle CO2 exchange from land and oceans. Potentially, it can also be used as a proxy for continent-wide drought stress in plants, largely because the ratio of (CO2)-C-13 and (CO2)-C-12 molecules removed from the atmosphere by plants is dependent on moisture conditions. The dual-species CTDAS system varies the net exchange fluxes of both (CO2)-C-13 and CO2 in ocean and terrestrial biosphere models to create an ensemble of (CO2)-C-13 and CO2 fluxes that propagates through an atmospheric transport model. Based on differences between observed and simulated (CO2)-C-13 and CO2 mole fractions (and thus delta C-13) our Bayesian minimization approach solves for weekly adjustments to both net fluxes and isotopic terrestrial discrimination that minimizes the difference between observed and estimated mole fractions. With this system, we are able to estimate changes in terrestrial delta C-13 exchange on seasonal and continental scales in the Northern Hemisphere where the observational network is most dense. Our results indicate a decrease in stomatal conductance on a continent-wide scale during a severe drought. These changes could only be detected after applying combined atmospheric CO2 and delta C-13 constraints as done in this work. The additional constraints on surface CO2 exchange from delta C-13 observations neither affected the estimated carbon fluxes nor compromised our ability to match observed CO2 variations. The prototype presented here can be of great benefit not only to study the global carbon balance but also to potentially function as a data-driven diagnostic to assess multiple leaf-level exchange parameterizations in carbon-climate models that influence the CO2, water, isotope, and energy balance

Maximum likelihood estimation of covariance parameters for Bayesian atmospheric trace gas surface flux inversions

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/94664/1/jgrd12182.pd