The geographic and seasonal emission distributions of the major sources and sinks of atmospheric methane were compiled using methane flux measurements and energy and agricultural statistics in conjunction with global digital data bases of land surface characteristics and anthropogenic activities. Chemical destruction of methane in the atmosphere was calculated using three-dimensional OH fields every 5 days taken from Spivakovsky et al. (1990a, b). The signatures of each of the sources and sinks in the atmosphere were simulated using a global three-dimensional tracer transport model. Candidate methane budget scenarios were constructed according to mass balance of methane and its carbon isotopes. The verisimilitude of the scenarios was tested by their ability to reproduce the meridional gradient and seasonal variations of methane observed in the atmosphere. Constraints imposed by all the atmospheric observations are satisfied simultaneously by several budget scenarios. A preferred budget comprises annual destruction rates of 450 Tg by OH oxidation and 10 Tg by soil absorption and annual emissions of 80 Tg from fossil sources, 80 Tg from domestic animals, and 35 Tg from wetlands and tundra poleward of 50°N. Emissions from landfills, tropical swamps, rice fields, biomass burning, and termites total 295 Tg; however, the individual contributions of these terms cannot be determined uniquely because of the lack of measurements of direct fluxes and of atmospheric methane variations in regions where these sources are concentrated.

/pdf/three-dimensional-model-synthesis-of-the-global-methane-lwoiox228k.pdf

Three‐dimensional model synthesis of the global methane cycle

Methane was measured in air samples collected approximately weekly from a globally distributed network of sites from 1983 to 1992. Sites range in latitude from 90°S to 82°N. All samples were analyzed by gas chromatography, with flame ionization detection at the National Oceanic and Atmospheric Administration Climate Monitoring and Diagnostics Laboratory in Boulder, Colorado, and the measurements were referenced against a single calibration scale. The estimated precision of the measurements is ±0.2%. Samples which had clear sampling or analytical errors, or which appeared to be contaminated by local CH4 sources, were identified and excluded from the data analysis. The data reveal a strong north-south gradient in methane with an annual mean difference of about 140 ppb between the northernmost and southernmost sampling sites. Methane time series from the high southern latitude sites have a relatively simple seasonal cycle with a minimum during late summer-early fall, almost certainly dominated by the seasonality in its photochemical destruction. Typical seasonal cycle amplitudes there are about 30 ppb. Seasonal cycles at sites in the northern hemisphere are complex when compared to sites in the southern hemisphere due to the interaction among CH4 sources and sinks, and atmospheric transport. Seasonal cycle amplitudes in the high north are about twice those observed in the high southern hemisphere. Annual mean methane mixing ratios were ∼1% lower at 3397 m than at sea level on the island of Hawaii. Trends were determined at each site in the network and globally. The average increase in the globally averaged methane mixing ratio over the period of these measurements is (11.1±0.2) ppb yr−1. Globally, the growth rate for methane decreased from approximately 13.5 ppb yr−1 in 1983 to about 9.3 ppb yr−1 in 1991. The growth rate of methane in the northern hemisphere during 1992 was near zero. Various possibilities for the long-term, slow decrease in the methane growth rate over the last decade and the rapid change in growth rate in the northern hemisphere in 1992 are given. The most likely explanation is a change in a methane source influenced directly by human activities, such as fossil fuel production.

The growth rate and distribution of atmospheric methane

. Atmospheric greenhouse gas (GHG) concentrations are at unprecedented, record-high levels compared to the last 800 000 years. Those elevated GHG concentrations warm the planet and – partially offset by net cooling effects by aerosols – are largely responsible for the observed warming over the past 150 years. An accurate representation of GHG concentrations is hence important to understand and model recent climate change. So far, community efforts to create composite datasets of GHG concentrations with seasonal and latitudinal information have focused on marine boundary layer conditions and recent trends since the 1980s. Here, we provide consolidated datasets of historical atmospheric concentrations (mole fractions) of 43 GHGs to be used in the Climate Model Intercomparison Project – Phase 6 (CMIP6) experiments. The presented datasets are based on AGAGE and NOAA networks, firn and ice core data, and archived air data, and a large set of published studies. In contrast to previous intercomparisons, the new datasets are latitudinally resolved and include seasonality. We focus on the period 1850–2014 for historical CMIP6 runs, but data are also provided for the last 2000 years. We provide consolidated datasets in various spatiotemporal resolutions for carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), as well as 40 other GHGs, namely 17 ozone-depleting substances, 11 hydrofluorocarbons (HFCs), 9 perfluorocarbons (PFCs), sulfur hexafluoride (SF6), nitrogen trifluoride (NF3) and sulfuryl fluoride (SO2F2). In addition, we provide three equivalence species that aggregate concentrations of GHGs other than CO2, CH4 and N2O, weighted by their radiative forcing efficiencies. For the year 1850, which is used for pre-industrial control runs, we estimate annual global-mean surface concentrations of CO2 at 284.3 ppm, CH4 at 808.2 ppb and N2O at 273.0 ppb. The data are available at https://esgf-node.llnl.gov/search/input4mips/ and http://www.climatecollege.unimelb.edu.au/cmip6 . While the minimum CMIP6 recommendation is to use the global- and annual-mean time series, modelling groups can also choose our monthly and latitudinally resolved concentrations, which imply a stronger radiative forcing in the Northern Hemisphere winter (due to the latitudinal gradient and seasonality).

/pdf/historical-greenhouse-gas-concentrations-for-climate-2lb5hs4i4r.pdf

Historical greenhouse gas concentrations for climate modelling (CMIP6)

A 1-year field program was conducted at South Pole Station in 1992 to measure the downward infrared radiance spectrum at a resolution of 1/ cm over the spectral range 550-1667 cm-'. The atmosphere over the Antarctic Plateau is the coldest and driest on Earth, where in winter, surface temperatures average about -60 C, the total column water vapor is as low as 300 pm of precipitable water, and the clear-sky downward longwave flux is usually less than 80 W/sq m. Three clear-sky test cases are selected, one each for summer, winter, and spring, for which high- quality radiance data are available.as well as ancillary data to construct model atmospheres from radiosondes, ozonesondes, and other measurements. The model atmospheres are used in conjunction with the line-by-line radiative transfer model (LBLRTM) to compare model calculations with the spectral radiance measurements. The high-resolution calculations of LBLRTM (approx. = 0.001/ cm) are matched to the lower-resolution measurements (1/ cm) by adjusting their spectral resolution and by applying a correction for the finite field of view of the interferometer. In summer the uncertainties in temperature and water vapor profiles dominate the radiance error in the LBLRTM calculations. In winter the uncertainty in viewing zenith angle becomes important as well as the choice of atmospheric levels in the strong near-surface temperature inversion. The spectral radiance calculated for each of the three test cases generally agrees with that measured, to within twice the total estimated radiance error, thus validating LBLRTM to this level of accuracy for Antarctic conditions. However, the discrepancy exceeds twice the estimated error in the gaps between spectral lines in the region 1250-1500/ cm, where emission is dominated by the foreign-broadened water vapor continuum.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/97JD02433

Measurements of the downward longwave radiation spectrum over the Antarctic Plateau and comparisons with a line‐by‐line radiative transfer model for clear skies

We have developed a new dry extraction technique to extract air from large pieces of glacial ice. The primary reason for developing this technique was to be able to perform a single extraction and measure a single sample of air from an ice core sample for as many atmospheric constituents as possible. The procedure is modeled after the dry extraction -“cheese grater” design of Etheridge et al. [1988]. Extracted air samples are analyzed for the elemental and isotopic composition of O2 and N2 as well as the CH4 concentration. Extensive experimental work to determine the integrity of the extraction procedure yielded blank values and external precision which are comparable with exiting extraction procedures. Overall external precision for δO2/N2, δ18O of O2, and δ15of N2 analyses is ±2.1‰, ±0.074‰, and ±0.045‰, respectively. Variable δO2/N2 results from ice which is either completely bubbly or clathrated are in good agreement with previous measurements. Variable δO2/N2 results from Greenland Ice Sheet Project (GISP) II ice samples spanning the clathrate formation region (1000–1500 m) are markedly different from previous results obtained with a “wet” extraction procedure. We attribute the differences to variable δO2/N2 ratios in bubbles and clathrates in the clathrate formation region combined with a 21% difference in our extraction efficiency for bubbly versus clathrated ice. The overall uncertainty and blank value for CH4 measurements are ±19 ppb and 16 ppb, respectively. CH4 concentrations for ice between 115 and 140 meters below the surface (mbs) from the GISPII ice core appear to be 4.3% higher than the average value measured by five other laboratories. We attribute our elevated values to uncertainties in the actual concentration of our working standard and small differences in the CH4 concentration of the liberated air relative to the total air trapped in ice. Our corrected CH4 data spanning the last 25 kyr are indistinguishable from the Brook et al. (1996) CH4 record from the same period.

https://agupubs.onlinelibrary.wiley.com/doi/epdf/10.1029/2000JD900335

A modified extraction technique for liberating occluded gases from ice cores

This document presents monthly averages and sampling statistics for atmospheric methane (CH{sub 4}) concentrations (mixing ratios) from the National Oceanic and Atmospheric Administration Climate Monitoring and Diagnostics Laboratory (NOAA/CMDL) global cooperative flask sampling network from 1983 to 1988. The data are derived from a network of 31 stations (27 of which were still active at the end of 1988), which collected air samples in flasks approximately once per week for measurement of both methane and carbon dioxide. The samples were analyzed for atmospheric methane on a gas chromatograph (fitted with a flame ionization detector) at the NOAA/CMDL Laboratory in Boulder, Colorado. These data represent the most spatially comprehensive atmospheric methane record available in the world. They have been used to study the temporal and spatial variations in atmospheric methane concentration and have applications in modeling, projections, and global mass balance calculations. The data consist of station identification code; year; and, for each month, mean monthly methane concentration, standard deviation, and number of samples contributing to the mean. This document provides sample listings of the NOAA/CMDL atmospheric methane data as they appear on magnetic tape, as well as a complete listing of the methane data (statistics excluded) in tabular form. This more » document also offers retrieval program listings, furnishes information on sampling and analysis methods and on data selection, defines limitations and restrictions of the data, and provides reprints of pertinent literature. 1 fig., 4 tabs. « less

L.P. Steele

Papers

Atmospheric methane concentrations---the NOAA/CMDL global cooperative flask sampling network, 1983--1988